CARBON NANOMATERIALS

SYNTHESIS, STRUCTURE, PROPERTIES AND APPLICATIONS

CARBON NANOMATERIALS
SYNTHESIS, STRUCTURE, PROPERTIES AND APPLICATIONS

RAKESH BEHARI MATHUR

BHANU PRATAP SINGH
SHAILAJA PANDE
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Library of Congress Cataloging‑in‑Publication Data

Names: Mathur, Rakesh Behari, 1952- author. | Singh, Bhanu Pratap (Scientist
in Physics), author. | Pande, Shailaja, author.
Title: Carbon nanomaterials : synthesis, structure, properties and
applications / Rakesh Behari Mathur, Bhanu Pratap Singh, Shailaja Pande.
Description: Boca Raton, FL : CRC Press, Taylor & Francis Group, [2016]
Identifiers: LCCN 2016022639| ISBN 9781498702102 (hardback ; alk. paper) |
ISBN 1498702104 (hardback ; alk. paper) | ISBN 9781498702119 (e-book) |
ISBN 1498702112 (e-book)
Subjects: LCSH: Nanostructured materials. | Carbon. | Nanotubes.
Classification: LCC TA418.9.N35 M52135 2016 | DDC 620.1/15--dc23
LC record available at [Link]

Visit the Taylor & Francis Web site at

[Link]
and the CRC Press Web site at
[Link]
Contents

Preface............................................................................................................................................ xiii
Authors......................................................................................................................................... xvii

1. Introduction to Carbon and Carbon Nanomaterials........................................................ 1

1.1 Introduction....................................................................................................................1
1.1.1 Atomic Structure of Carbon............................................................................3
1.1.2 Carbon Hybridization......................................................................................5
1.1.3 Diamond Structure...........................................................................................5
1.1.4 Graphite Structure............................................................................................6
1.2 Crystal Structure of Graphite.......................................................................................7
1.2.1 Two-Dimensional Lattice Structure: Unit Cell.............................................8
1.2.2 Reciprocal Lattice and Brillouin Zone...........................................................9
1.3 Electronic Band Structure of Graphite...................................................................... 10
1.3.1 Energy Dispersion Relation........................................................................... 10
1.3.2 Density of States.............................................................................................. 11
1.4 Physical Properties of Graphite.................................................................................. 12
1.4.1 Electrical Properties of Graphite.................................................................. 13
1.4.2 Mechanical Properties of Graphite.............................................................. 14
1.4.3 Thermal Properties of Graphite.................................................................... 15
1.4.4 Chemical Properties of Graphite.................................................................. 16
1.5 Nongraphitic Carbons................................................................................................. 17
1.5.1 Carbon Black.................................................................................................... 18
1.5.2 Coal................................................................................................................... 18
1.5.3 Chars................................................................................................................. 18
1.5.4 Graphitizing Carbons..................................................................................... 18
1.5.5 Polycrystalline Graphite................................................................................ 19
1.6 Synthetic Carbon and Graphite................................................................................. 20
1.6.1 Synthetic Graphite: Processing, Properties, and Applications................. 21
1.6.2 Filler.................................................................................................................. 21
1.6.3 Binder...............................................................................................................22
1.6.4 Mesophase Pitch.............................................................................................22
1.6.5 Mixing and Blending..................................................................................... 23
1.6.6 Carbonization.................................................................................................. 23
1.6.7 Graphitization................................................................................................. 24
1.6.8 Structural Analysis of Carbons by X-Ray Diffraction............................... 25
1.7 Pyrolytic Carbon and Graphite.................................................................................. 28
1.7.1 Thermodynamics and Kinetics..................................................................... 28
1.7.2 Isotropic and Laminar Deposits................................................................... 28
1.7.3 Graphitization of Columnar and Laminar Deposits................................. 28
1.8 Nano Forms of Carbon................................................................................................ 29
1.8.1 Quantum Confinement in Carbon Nanomaterials....................................30
1.8.2 Raman Spectroscopy of Nanocarbons......................................................... 32
References................................................................................................................................ 38
Further Reading...................................................................................................................... 39

v
vi Contents

2. Fullerenes................................................................................................................................ 41
2.1 Introduction.................................................................................................................. 41
2.2 Discovery of Fullerenes...............................................................................................42
2.3 Explosion in Fullerenes Research..............................................................................44
2.4 Methods of Synthesis of Fullerenes........................................................................... 45
2.4.1 Laser Vaporization Method........................................................................... 45
2.4.2 Resistive Heating of Graphite Electrodes.................................................... 46
2.4.3 Electric Arc Discharge: Arc Heating or Arc Vaporization
of Graphite Electrodes.................................................................................... 47
2.4.4 Other Methods of Fullerene Synthesis........................................................ 47
[Link] Pyrolysis........................................................................................... 47
[Link] Combustion of Hydrocarbons....................................................... 48
[Link] Fullerene Synthesis Using Coal..................................................... 48
[Link] Electron Beam Irradiation of Graphene
under Transmission Electron Microscopy................................... 48
[Link] Solar Generators.............................................................................. 48
2.5 Purification, Isolation, and Characterization of Fullerenes................................... 49
2.5.1 Purification of Fullerene Soot....................................................................... 49
2.5.2 Isolation of Fullerenes.................................................................................... 50
2.5.3 Characterization of Fullerenes...................................................................... 50
2.6 Formation Mechanism of Fullerenes........................................................................ 53
2.7 Structure of Fullerenes................................................................................................54
2.7.1 Structures of Diamond, Graphite, and C60..................................................54
2.7.2 Electronic Structure of C60 Fullerene........................................................... 56
2.7.3 Structure of Other Fullerenes....................................................................... 57
2.7.4 Structure of Fullerite...................................................................................... 58
2.8 Properties of Fullerenes.............................................................................................. 60
2.8.1 Physical Properties of Fullerenes................................................................. 60
2.8.2 Chemical Properties and Reactions of Fullerenes..................................... 60
[Link] Metal-Doped Fullerenes................................................................. 61
[Link] Endohedral Metallofullerenes....................................................... 62
[Link] Functionalized Fullerenes.............................................................64
2.9 Applications of Fullerenes.......................................................................................... 67
2.9.1 Superconductors............................................................................................. 67
2.9.2 Organic Solar Cells......................................................................................... 68
2.9.3 Biomedical and Personal Care Applications............................................... 68
[Link] Biomedical Applications................................................................ 68
[Link] Personal Care Applications........................................................... 69
2.9.4 Biosensors........................................................................................................ 69
References................................................................................................................................ 69

3. Single-Walled Carbon Nanotubes..................................................................................... 75

3.1 History........................................................................................................................... 75
3.2 Structure of Single-Walled Carbon Nanotube (SWCNT)....................................... 75
3.3 Synthesis of Carbon Nanotubes................................................................................. 76
3.3.1 Arc Discharge.................................................................................................. 76
3.3.2 Laser Ablation................................................................................................. 78
3.3.3 Chemical Vapor Deposition.......................................................................... 78
Contents vii

3.3.4 High-Pressure Carbon Monoxide Process.................................................. 79

3.3.5 Fluidized Bed.................................................................................................. 79
3.4 Growth Mechanism..................................................................................................... 81
3.4.1 Growth Mechanism Based on Chemical Vapor Deposition..................... 81
3.4.2 Mechanism of SWCNT Growth Using Arc Evaporation and Laser
Ablation............................................................................................................ 82
3.5 Properties of SWCNTs.................................................................................................83
3.5.1 Mechanical Properties...................................................................................84
3.5.2 Specific Gravity...............................................................................................84
3.5.3 Thermal Conductivity....................................................................................84
3.5.4 Electrical Conductivity..................................................................................84
3.6 Purification of SWCNTs..............................................................................................85
3.6.1 Acid Treatment................................................................................................85
3.6.2 Air Oxidation...................................................................................................85
3.6.3 High Temperature Annealing.......................................................................85
3.7 Characterization of SWCNTs.....................................................................................85
3.7.1 Raman Spectroscopy......................................................................................85
3.7.2 X-Ray Diffraction............................................................................................ 87
3.7.3 UV/Vis/NIR Spectroscopy of SWCNTs...................................................... 87
3.8 Applications of Single-Walled Carbon Nanotubes................................................. 89
3.8.1 Microelectronics.............................................................................................. 89
[Link] First SWCNT-Based Computer...................................................... 90
3.8.2 Solar Cells........................................................................................................ 91
3.8.3 Hydrogen Storage........................................................................................... 92
3.8.4 Biological and Biotechnological Applications............................................ 92
3.8.5 Space Elevator.................................................................................................. 92
References................................................................................................................................ 93

4. Multiwalled Carbon Nanotubes......................................................................................... 97

4.1 Introduction.................................................................................................................. 97
4.2 Difference between Multiwalled Carbon Nanotubes (MWCNTs),
Single- Walled Carbon Nanotubes (SWCNTs), and Carbon
Nanofibers (CNFs)....................................................................................................... 97
4.3 Synthesis of MWCNTs................................................................................................ 98
4.3.1 Arc Discharge.................................................................................................. 98
4.3.2 Laser Ablation................................................................................................. 99
4.3.3 Chemical Vapor Deposition.......................................................................... 99
4.3.4 Fluidized Bed................................................................................................ 101
4.4 Purification and Functionalization......................................................................... 102
4.5 Characterization......................................................................................................... 103
4.5.1 Scanning Electron Microscopy................................................................... 103
4.5.2 High-Resolution Transmission Electron Microscopy.............................. 103
4.5.3 Raman Spectroscopy.................................................................................... 103
4.5.4 Energy-Dispersive X-Ray Spectroscopy.................................................... 107
4.5.5 Thermal Gravimetric Analysis................................................................... 107
4.6 Applications................................................................................................................ 108
4.6.1 Polymer Nanocomposites for Structural Applications........................... 108
4.6.2 CNT Yarn for Structural Composites........................................................ 109
viii Contents

4.6.3
Electrostatic Discharge and Electromagnetic Interference
Shielding Applications................................................................................. 110
4.6.4 CNTs as Anode Materials for Lithium-Ion Batteries............................... 111
4.6.5 Carbon Nanotubes in Fuel Cells................................................................. 112
4.6.6 Water Purification......................................................................................... 112
4.6.7 Armor Material............................................................................................. 114
4.6.8 CNT as Self-Healing Material..................................................................... 115
4.6.9 CNT-Based Conducting Cables.................................................................. 115
References.............................................................................................................................. 115

5. Carbon Nanofibers and Filaments................................................................................... 121

5.1 Introduction................................................................................................................ 121
5.2 Vapor-Grown Carbon Fibers.................................................................................... 122
5.2.1 Historical Approach..................................................................................... 122
5.3 Growth Mechanism................................................................................................... 123
5.3.1 Growth on Substrate..................................................................................... 124
[Link] Temperature Gradient.................................................................. 125
[Link] Influence of Metal Support Interaction...................................... 126
[Link] Diffusion Rate................................................................................ 126
[Link] Crystallographic Orientation....................................................... 128
[Link] Why the Core Is Hollow............................................................... 128
5.4 Large-Scale Production: Gas Phase Process........................................................... 128
5.5 Morphology................................................................................................................ 131
5.5.1 As-Grown Vapor-Grown Carbon Fiber (VGCF)...................................... 131
5.5.2 Heat-Treated VGCF....................................................................................... 131
5.6 Mechanical Properties of VGCF.............................................................................. 133
5.7 Transport Properties of VGCF.................................................................................. 135
5.7.1 Electrical Conductivity................................................................................ 135
5.7.2 Thermal Conductivity.................................................................................. 136
5.8 Applications of VGCF................................................................................................ 136
5.8.1 Double-Layer Capacitor............................................................................... 137
5.8.2 Intercalation Compounds............................................................................ 137
5.8.3 Carbon Filaments in Reinforcement of Materials.................................... 137
5.9 Graphite Whiskers..................................................................................................... 137
5.9.1 Filaments Prepared from Carbon Arc....................................................... 137
5.10 Carbon Nanofibers (CNFs)....................................................................................... 138
5.10.1 Types of Carbon Nanofibers Available...................................................... 139
5.10.2 Synthesis of Nanofibers............................................................................... 139
5.10.3 Growth and Morphology............................................................................. 141
5.10.4 Heat Treatment.............................................................................................. 142
5.10.5 Intrinsic Fiber Conductivity........................................................................ 142
5.10.6 Mechanical Properties of Nanofibers........................................................ 142
5.11 Applications of Carbon Nanofiber.......................................................................... 143
5.11.1 Carbon Nanofiber Composites................................................................... 143
5.11.2 Conductive Thermoplastic Composites..................................................... 143
5.11.3 Electromagnetic Shielding.......................................................................... 144
5.11.4 Ablation Resistance...................................................................................... 145
5.12 Carbon Microcoils and Nanocoils........................................................................... 145
References.............................................................................................................................. 146
Contents ix

6. Graphene and Graphene Oxide........................................................................................ 149

6.1 Introduction................................................................................................................ 149
6.2 History of Graphene and Its Isolation..................................................................... 150
6.3 Preparative Methods for Graphene......................................................................... 152
6.3.1 Mechanical Exfoliation................................................................................ 152
6.3.2 Chemical Exfoliation of Graphite/Liquid-Phase Exfoliation
of Graphite..................................................................................................... 153
6.3.3 Chemical Exfoliation and Reduction of Exfoliated Graphite Oxide..... 155
[Link] Synthesis of Graphite Oxide........................................................ 156
[Link] Chemical Exfoliation of Graphite Oxide.................................... 156
[Link] Reduction of Graphene Oxide..................................................... 157
6.3.4 Chemical Vapor Deposition (CVD)............................................................ 158
6.3.5 Thermal Decomposition of Silicon Carbide.............................................. 160
6.4 Characterization of Graphene and Graphene Oxide............................................ 161
6.4.1 Optical Microscopy...................................................................................... 161
6.4.2 Atomic Force Microscopy (AFM)............................................................... 161
6.4.3 Transmission Electron Microscopy (TEM)................................................ 163
6.4.4 Raman Spectroscopy.................................................................................... 164
6.4.5 X-Ray Diffraction (XRD).............................................................................. 167
6.5 Structure of Graphene, Graphite Oxide, and Graphene Oxide........................... 167
6.5.1 Structure of Graphene.................................................................................. 167
6.5.2 Structure of Graphite Oxide and Graphene Oxide.................................. 169
6.6 Properties of Graphene and Graphene Oxide........................................................ 169
6.6.1 Electronic Properties of Graphene............................................................. 169
[Link] Band Structure of Graphene........................................................ 170
[Link] Electronic Properties of Graphene.............................................. 171
6.6.2 Mechanical Properties................................................................................. 172
6.6.3 Optical Properties......................................................................................... 173
6.6.4 Thermal Conductivity.................................................................................. 173
6.6.5 Chemical Reactivity of Graphene Oxide................................................... 173
6.7 Applications of Graphene and Graphene Oxide................................................... 176
6.7.1 Electronic Applications................................................................................ 176
6.7.2 Polymer Composites..................................................................................... 177
References.............................................................................................................................. 178

7. Graphene Nanoribbons...................................................................................................... 183

7.1 Introduction................................................................................................................ 183
7.2 Synthesis...................................................................................................................... 183
7.2.1 Cutting from Graphene Using Lithography: Top-Down Approach...... 184
7.2.2 Nanosphere Lithography............................................................................. 185
7.2.3 Graphene Nanoribbon (GNR) Fabrication: Bottom-Up Approach........ 187
7.2.4 Longitudinal Unzipping of Carbon Nanotubes Using Alkali
Metal Vapor................................................................................................... 189
7.2.5 GNR by Unzipping of Carbon Nanotubes through Chemical Route.... 191
7.3 Raman Spectroscopy of GNR................................................................................... 193
7.4 Potential Applications of GNR................................................................................. 194
7.4.1 Electronics...................................................................................................... 195
7.4.2 Graphene Transistors................................................................................... 195
7.4.3 Field-Effect Transistor Physics.................................................................... 196
x Contents

7.4.4 Band Gap Engineering................................................................................. 197

7.4.5 GNR Edges: Where the Action Is............................................................... 198
7.4.6 Band Structure of GNR................................................................................ 199
7.4.7 GNR Interconnects....................................................................................... 201
7.4.8 GNR for Fuel Cells........................................................................................ 201
7.5 Future Challenges...................................................................................................... 201
References.............................................................................................................................. 203

8. Graphene Quantum Dots................................................................................................... 205

8.1 Introduction................................................................................................................ 205
8.2 Structure of Graphene Quantum Dots................................................................... 206
8.2.1 Semiconductor Quantum Dots................................................................... 206
8.2.2 Graphene Quantum Dots............................................................................ 207
8.3 Synthesis of Graphene Quantum Dots................................................................... 208
8.3.1 Top-Down Methods...................................................................................... 208
[Link] Exfoliation Using Acids................................................................ 208
[Link] Electrochemical Exfoliation......................................................... 210
[Link] Hydrothermal/Solvothermal Synthesis..................................... 211
[Link] Microwave and Ultrasonic Routes.............................................. 213
8.3.2 Bottom-Up Methods..................................................................................... 214
[Link] Catalytic Decomposition of Fullerene C60.................................. 214
[Link] Pyrolysis or Carbonization.......................................................... 215
[Link] Organic Synthesis Route.............................................................. 216
8.4 Characterization of Graphene Quantum Dots...................................................... 217
8.5 Properties of Graphene Quantum Dots.................................................................. 220
8.6 Applications of Graphene Quantum Dots.............................................................222
References.............................................................................................................................. 224

9. Amorphous Nanocarbons.................................................................................................. 227

9.1 Introduction................................................................................................................ 227
9.2 Carbon Black............................................................................................................... 228
9.2.1 Mechanism of Carbon Black Formation.................................................... 228
[Link] Theory of Polymerization of Hydrocarbons............................. 229
9.2.2 Manufacture of Carbon Black..................................................................... 229
[Link] Furnace Black Process.................................................................. 229
[Link] Channel Process............................................................................ 231
[Link] Thermal Process............................................................................ 232
9.3 Physical Properties of Carbon Black....................................................................... 232
9.3.1 Particle Size.................................................................................................... 233
9.3.2 Microstructure of Carbon Black................................................................. 233
[Link] Electron Microscopy..................................................................... 235
9.3.3 Surface Area, Porosity, and Adsorption Properties of Carbon Black.... 236
[Link] Surface Area................................................................................... 236
[Link] Porosity........................................................................................... 237
[Link] Surface Activity............................................................................. 237
9.4 Electrical and Thermal Properties........................................................................... 238
9.4.1 Electrical Resistivity..................................................................................... 238
9.4.2 Thermal Conductivity.................................................................................. 238
Contents xi

9.5 Applications of Carbon Black................................................................................... 238

9.5.1 Carbon Black Reinforcement of Elastomers.............................................. 239
9.5.2 Strength.......................................................................................................... 239
9.5.3 Abrasion......................................................................................................... 239
9.5.4 Coloring Agent for Ink and Paints............................................................. 240
9.5.5 Blackness, Tint, and Tone............................................................................. 240
9.5.6 Ultraviolet Protection for Polymers............................................................ 240
9.5.7 Resin and Film Coloring Agents................................................................ 241
9.5.8 Electric Conductive Agent........................................................................... 241
9.5.9 Electronic Equipment Related Material..................................................... 241
9.5.10 Electromagnetic Interference Shielding.................................................... 242
9.5.11 Carbon Black as Catalyst Support.............................................................. 243
9.6 Lampblack................................................................................................................... 243
9.6.1 Production of Lampblack............................................................................ 243
9.6.2 Applications of Lampblack.......................................................................... 244
9.7 Acetylene Black.......................................................................................................... 244
9.7.1 Applications of Acetylene Black................................................................. 244
9.8 Carbon Nanospheres................................................................................................. 245
9.8.1 Growth Model............................................................................................... 245
9.8.2 Synthesis of Carbon Nanospheres.............................................................. 246
[Link] The CVD Route.............................................................................. 246
[Link] Hydrothermal Route..................................................................... 246
[Link] Template Route.............................................................................. 246
9.8.3 Microstructure of Carbon Nanospheres................................................... 247
9.8.4 Applications of Carbon Nanospheres........................................................ 249
9.9 Carbon Nano-Onions................................................................................................ 250
9.9.1 Synthesis Route for Carbon Nano-Onions................................................ 250
9.9.2 Classification, Structure, and Physicochemical Properties
of Carbon Nano-Onions.............................................................................. 251
9.9.3 Applications................................................................................................... 252
References.............................................................................................................................. 252
Further Reading.................................................................................................................... 255
Index.............................................................................................................................................. 257
Preface

Exploring the science of nanostructures has become, in just a few years, a new theme com-
mon to many disciplines in which scientists and engineers are beginning to manipulate
matter at the atomic and molecular scales in order to obtain materials and systems with
significantly improved properties. For decades, microstructures, which are thousands
of times larger than nanostructures, have formed the basis for our current technologies,
including ceramics, composites, fabrication of alloys, and microelectronics. Although
microstructures are small on the scale of direct human experience, their physics largely
remains as much the same as that of macroscopic systems.
Carbon is the unique element in the periodic table that has isomers from zero dimen-
sions to three dimensions. It is interesting that sp2 hybridization leads to different nano-
forms of carbon: a single-atom thick two-dimensional (2D) graphite called graphene, a
planar local structure in the closed polyhedra (0D) of the fullerene family, and the one-
dimensional (1D) cylinders called carbon nanotubes.
Carbon nanomaterials have a unique place in nanoscience owing to their exceptional
thermal, electrical, chemical, and mechanical properties, and have found application
in areas as diverse as superstrong composite materials, energy storage and conversion,
supercapacitors, gas storage, smart sensors, targeted drug delivery, catalyst support, field-­
emission devices, quantum wires, paints, and nanoelectronics. The degree of competitive-
ness in sports has been remarkably impacted by nanotechnology making athletes safer,
comfortable, and more agile than ever. Looking at the broad spectrum of possible applica-
tions there is no doubt that the 21st century belongs to these carbon nanomaterials. This is
a field in which a huge amount of literature has been generated within recent years, and
the number of publications is still increasing every year.
Of late there have been several books about these carbon nanomaterials, focusing mainly
on an individual or selective carbon nanomaterial, and the subject was basically treated like
any other nanomaterial. This book is the first attempt to cover all the existing carbon nano­
materials, namely, carbon nanofibers, vapor-grown carbon fibers (VGCF), graphite nanorib-
bons (GNRs), graphene quantum dots, and amorphous nanocarbons in addition to carbon
nanotubes, fullerenes, and graphene in a single volume. Departing from the conventional
pattern, an attempt has been made to create a platform for the reader to understand the fas-
cinating material carbon in its various manifestations through historical developments,
structure–property relations and so on at an introductory level and finally its transition from
conventional bulk forms to nanocarbons. It is noteworthy that the field of carbon nanomate-
rials is still a gray area of research and therefore an attempt has been made to introduce the
reader to the latest developments on the fundamentals of growth mechanism and synthesis
techniques along with structure property relationships of individual nanomaterials leading to
its application in modern-day technological breakthroughs. More than 500 references are cited
in the book for the benefit of the readers who would like to have deeper insight into the subject.
The book will be very useful not only to experienced scientists and engineers who wish
to broaden their knowledge of the wide-ranging carbon nanomaterials and willing to
develop practical devices, but also to graduate and senior undergraduate students who look
forward to making their mark on nanoscience and technology of carbon materials. It can
also be useful for research and development personnel in industries, working in the area
of conventional carbon materials, to upgrade the technology using carbon nanomaterials.

xiii
xiv Preface

There are more than 10 different carbon nanomaterials addressed in this single book,
which is its unique feature. Some of the results are the authors’ own innovations and expe-
rience with these nanomaterials.
Chapter 1 introduces readers to the element carbon, its existence in various forms (crys-
talline and amorphous), and how carbon science and technology has grown over decades
and centuries. The chapter assumes special significance in familiarizing students with
the general background of the structure, property, and applications of various commonly
used bulk forms of carbons and graphite, including carbon black, carbon fibers, pyrolytic
carbon, synthetic carbon, and graphite. Hybridization in carbon plays a vital role in decid-
ing the physical, chemical, and transport properties of carbons. In order to make the audi-
ence conversant with all these aspects before moving to the next chapters, it was thought
essential to provide a brief background of the subject on the electronic and band structure
of graphite to better correlate the structure and properties of nanoforms of carbon in sub-
sequent chapters. A background of the two very important techniques—x-ray diffraction
and Raman spectroscopy—given in this chapter to characterize carbons in different forms
will prove to be very handy in understanding these aspects in the subsequent chapters.
Special emphasis has been paid to explain the formation of pyrolytic carbon, which forms
the basis of understanding the growth of carbon nanotubes, fullerenes, amorphous, and
filamentous forms of carbons in the following chapters.
Chapter 2 discusses the history and growth mechanism of one of the most important allo-
tropes of carbon in the form of hollow, closed cages of carbon atoms, the fullerenes. The most
popular and stable molecule in the family of fullerenes is the highly symmetrical soccer-
ball-shaped, 60-carbon atom buckminsterfullerene, or C60, which was first detected and
discovered in 1985 at Rice University during laser vaporization experiments on graphite.
Ever since fullerenes have become the subject of intense scientific research, their synthesis,
structure, properties, and applications in materials science and nanotechnology are exten-
sively studied. This chapter presents historical background and an overview of the Nobel
Prize-winning discovery of fullerenes. It explores the methods of synthesis, the electronic
and molecular structure, and the chemical and physical properties of fullerenes. The chapter
also highlights the promising applications of fullerenes in the fields of electronics, materials
science, and biological systems, with special emphasis on health and personal care.
Carbon nanotubes, with their extraordinary mechanical and unique electronic proper-
ties, have garnered much attention in the past decade or so with a broad range of poten-
tial applications, including nanoelectronics, composites, chemical sensors, biosensors,
and nanoelectromechanical systems (NEMS). The scientific community, therefore, is more
motivated than ever to move beyond basic properties and explore the real issues associ-
ated with carbon nanotube-based applications. Chapters 3 and 4 are entirely devoted to
the synthesis and applications of single-walled and multiwalled carbon nanotubes. These
nanotubes are made up of sp2-bonded carbon atoms that can be understood as rolled sheets
of single-layer graphite or graphene with their diameter normally lying in the nanometer
range while their length often exceed microns, thus making them 1D nanostructures. The
chapters provide a brief history of single-walled and multiwalled carbon nanotubes fol-
lowed by discussion of the growth mechanism, structure, and synthesis routes, together
with their exceptional mechanical, electrical, and thermal properties. Different tech-
niques to characterize these carbon nanotubes are discussed, including, scanning electron
microscopy, transmission electron microscopy, Raman spectroscopy, ultraviolet-visible
spectroscopy, and x-ray diffraction. Potential applications and the latest efforts by various
research groups to use these tubes in energy storage, molecular electronics, composites,
Preface xv

and biotechnology are also discussed. The chapters also provide comprehensive and up-
to-date literature citations.
Chapter 5 introduces to the readers various filamentous forms of nanocarbons such as
vapor-grown carbon fibers (VGCFs), graphite whiskers, carbon nanofibers, and nanocoils.
A brief historical approach and the processing conditions for individual nanostructures
is presented with respective applications. A detailed explanation has been provided for
the experimental conditions and growth mechanism, morphology, and fracture behavior.
Different processing parameters to register controlled structures are introduced. Also, the
role of individual materials in particular applications is explained.
Chapter 6 deals with the planar monolayer of carbon atoms known as graphene,
which is the basic building block of all other graphitic forms of carbon such as zero-
dimensional fullerenes, one-dimensional carbon nanotubes, and three-dimensional
graphite. Theoretically known to exist for several decades, graphene was isolated from
graphite in 2004 by Konstantin Novoselov and Andre Geim. Much of the interest in
graphene is due to its unique electronic properties. Graphene is a zero band gap semi-
conductor, wherein its charge carriers effectively behave like massless relativistic par-
ticles. Today graphene is considered as a star among the carbon nanomaterials with
outstanding mechanical, electrical, thermal, and optical properties, and has paved the
way for a variety of potential applications in many areas, such as transistors, trans-
parent and flexible electronics, and nanocomposites. The chapter presents the history
behind the discovery of graphene and explores the methods of synthesis, the electronic
and molecular structure, the physical and chemical properties, and the applications of
graphene especially in the field of electronics, optoelectronics, nanocomposites, and
materials science. Chapter 6 also reviews one of the most important precursor materi-
als for graphene—graphene oxide. Oxidation of graphite by insertion of strong acids
and oxidizing agents within the interlayer space of graphite yields graphite oxide.
Exfoliation of multilayered graphite oxide results in a few layers or individual layers of
exfoliated sheets called graphene oxide. One of the most effective methods of graphene
synthesis in terms of availability, simplicity, cost, yield, and scale-up advantages is the
chemical reduction of graphene oxide.
Chapter 7 introduces one of the latest carbon nanomaterials: graphite nanoribbons
(GNRs). Why and how GNRs can revolutionize the electronics industry in the 21st century
is explained. A brief account behind the three different approaches to produce GNRs—
bottom-up, lithography, and longitudinal unzipping of carbon nanotube (CNT) are intro-
duced. Due to their outstanding properties, GNRs are the major candidate to become the
silicon of the 21st century and open the era of carbon electronics. The science behind engi-
neering the structure of GNRs for efficient field-effect transistors (FETs) is discussed at
length. Narrowing the channel width in FETs, with a high heat dissipation rate and high
current density play an important role together. The chapter also describes various other
applications of GNRs such as in green energy generation and catalyst support.
An alternative, yet remarkable technique to introduce band gaps in graphene is to geo-
metrically confine the size of graphene by producing nanometer-sized pieces of graphene,
called graphene quantum dots. A well-confined shape, which exhibits pronounced quan-
tum confinement and edge effects, leads to novel electrical and optical properties. Chapter 8
is primarily focused on the several synthesis routes of graphene quantum dots followed by
different groups. The chapter also discusses the dependence of its optical behavior on its size
and how its light-emitting powers have been put to good use as smart, luminescent materi-
als with applications in biology as biological tracking agents, biomarkers, and smart sensors.
xvi Preface

Chapter 9 introduces various amorphous nanoforms of carbon. We are aware of carbon

black as an amorphous form of nanocarbon, which is fluffy and lightweight. However,
carbon black itself can manifest into different forms, such as carbon black, thermal black,
acetylene black, and lamp black. Carbon nanospheres and nano-onions are other forms of
polycrystalline forms of carbon. Each form has a different synthesis route with a differ-
ent structure property relationship. The chapter describes structural analysis of different
forms of all these materials following Raman microscopy, electron microscopy, and x-ray
diffraction. An effort has been made to explain how the properties of individual nano-
structures have been exploited in different applications over a period of several decades.
It is the hope of the authors that the present book has brought together a large body of
material in a very coherent fashion that will stimulate further advances in the fascinating
field of science and technology of carbon nanomaterials, both in terms of fundamental
aspects and engineering applications.
I would like to take this opportunity to pay my gratitude to CSIR-National Physical
Laboratory (New Delhi, India), which provided me the platform to build my career on
such a fascinating material, carbon. Special thanks to my colleagues with whom I have
been associated for almost four decades and contributed to the advancement of carbon
science and technology of carbon materials that has motivated me and my colleagues,
Dr. Bhanu Pratap Singh and Dr. Shailaja Pande, to write this book. Above all I want to
thank my wife, Kumkum, for her perseverance, support, and encouragement throughout
the course of writing this book.
Finally, the authors would like to acknowledge the dynamic help and support from
Ms. Aastha Sharma, senior acquisitions editor, CRC Press/Taylor & Francis Group, in com-
pleting this project on schedule.

Rakesh Behari Mathur

Authors

Dr. Rakesh Behari Mathur is scientist emeritus in the department

of physics and the engineering of carbon, CSIR-National Physical
Laboratory, New Delhi, India. He has been instrumental in developing
and commercializing several carbon-based technologies, 160 research
publications, and 12 patents during his more than 38 years of active
research in the field of carbon science and technology. Dr. Mathur
has worked in several reputed institutes and laboratories in Germany,
France, the United Kingdom, the United States, Russia, and Australia, and has established
active scientific collaborations with them.

Dr. Bhanu Pratap Singh is associated with the CSIR-National Physical

Laboratory, New Delhi, India, as a senior scientist in physics and the
engineering of carbon. He specializes in production and application of
carbon nanotubes, graphene, and polymer composites for structural,
electromagnetic interference (EMI) shielding, and energy applications,
and has authored more than 80 publications.

Dr. Shailaja Pande earned her MSc (chemistry) and PhD (solvent extrac-
tion of coal) from the Indian Institute of Technology, Delhi. She was asso-
ciated with the carbon group at CSIR-National Physical Laboratory, New
Delhi, India, as a principal investigator under the Department of Science
and Technology, Ministry of Science and Technology Women Scientists
Scheme (WOS-A), and worked on the development of carbon nanotubes/
polymer network composites for electromagnetic interference shielding
and structural applications. She has written book chapters on polymer
nanotubes and nanocomposites.

xvii
1
Introduction to Carbon and Carbon Nanomaterials

1.1 Introduction
Carbon is the fifteenth most abundant element in the earth’s crust, and the fourth most
abundant element in the universe by mass after hydrogen, helium, and oxygen. Carbon is
also present as a major component in large masses of carbonate rocks, including limestone,
dolomite, and marble. Coal is the largest commercial source of mineral carbon, accounting
for nearly 8 billion tons or almost 80% of fossil carbon fuel. In its elemental form, carbon
(C, atomic number 6) has a valency of 4 and is therefore placed in group IV of the periodic
table along with Si, Ge, Sn, and Pb.
Carbon can exist in both crystalline and amorphous forms. Figure 1.1 shows the three
crystalline allotropes of carbon, that is, with same chemical properties but with different
physical forms. All carbon allotropes are solids under normal conditions, with graphite
being the most thermodynamically stable form. In reality all the allotropes of amorphous
carbons are made of microcrystals of graphite arranged in an irregular fashion. Diamond,
graphite, and fullerenes are crystalline allotropes of carbon. The carbon atoms in diamond
have a three-dimensional (3D) tetrahedral network of covalent bonds, which causes the
electrons to be held tightly. Diamonds are therefore very hard and have high melting and
boiling points. The structure is a closely packed structure and causes diamond to be denser
than graphite. Since all its electrons end up in forming the covalent bonds, therefore it does
not conduct electricity. In graphite only three of the four valence electrons of each carbon
atom are used in bonding, leaving the fourth valence electron as free. Therefore graphite
is a good conductor of electricity.
Diamond is transparent because it has no free electron to absorb radiations and make
a transition in the optical region. Graphite on the other hand has one free electron, which
can absorb all the radiations in the optical region and thus appear black. Figure 1.2 shows
the two contrasting physical forms of naturally occurring allotropes of carbon, which are
used for many industrial applications.
Recently fullerenes have been discovered as the third allotrope of carbon. They are
molecular compounds made entirely of carbon atoms in the form of hollow spheres (C60),
ellipticals (C70), and tubes. Spherical fullerenes are sometimes called buckyballs, and cylin-
drical fullerenes are called buckytubes or nanotubes. The fullerenes might have applica-
tions in synthetic cosmetics, pharmaceuticals, and organic photovoltaics.
Carbon that is deposited on the walls of the reactor during the destructive distillation
of coal is called gas carbon and results into coal tar pitch. Carbon that is deposited on the
walls of the distillation tower during the refining of crude petroleum is called petroleum
coke. Both forms are used for making electrode in dry cells and are good conductors of
electricity.

1
2 Carbon Nanomaterials

Carbon

Crystalline carbon Amorphous carbon

Diamond Graphite Fullerene Coal Charcoal Lamp black

Wood charcoal Sugar charcoal Bone charcoal

Gas carbon: pitch and coke

FIGURE 1.1
Various physical forms of carbon.

Natural graphite lump Diamond crystal

FIGURE 1.2
Physical forms of graphite and diamond crystals.

Wood charcoal is made by the destructive distillation of wood. It is a black, porous,

brittle solid that is a good adsorbent, and good filtering and reducing agent.
Sugar charcoal is obtained by heating sugar in the absence of air. It is the purest form of
amorphous carbon. It can be converted into activated charcoal to increase its adsorption
capacity.
Animal charcoal is also called bone char. It is obtained by destructive distillation of
bones. It contains about 10% to 12% of amorphous carbon.
Carbons have always been the friendliest materials to mankind. Charcoal from wood
was the primitive artist’s crude element for expression and communication as mural on
cave walls. A candle burning with yellow flame would produce soot on an inverted plate
Introduction to Carbon and Carbon Nanomaterials 3

and the black deposit known as soot (lamp black) when mixed with suitable base (water,
oil) created pigments.
The advent of 20th century saw widespread use of graphite crystals as the writing points
for several centuries and has now taken the form of lead in pencils. Printing formed the first
major use of carbon in manufacturing technologies, many of which are still in use today.
Starting in 1940, controlling the processing parameters together with the variety of
choices from carbonaceous materials, individually or in combination led to the develop-
ment of advanced carbon products with contrasting properties. Examples include carbons
that possess the highest thermal conductivity (carbon nanotubes, graphene, carbon–­
carbon composites), but at the same time are thermal insulators (carbon fiber felt/porous car-
bons), completely impervious to gases and fluids (glassy carbon with no open porosity) to
highly porous carbons (activated carbon, surface area ~2000 m2/g), very soft (graphite) and
hardest (diamond), very low coefficient of friction (natural graphite, expanded graphite)
to highly abrasive (hard carbons), low strength (monoliths) to strongest material (carbon
fibers, carbon nanotubes, graphene). Because of such versatility, today carbon has entered
into applications ranging from conventional carbon/graphite electrodes, brushes, clutch
plates, mechanical seals and catalyst support, to highly advanced areas like carbon–­carbon
composites for space re-entry vehicles, aircraft brake discs, and carbon fiber composites for
lightweight, high-strength structures.
The chapter is aimed to provide to the reader a brief idea about the basic structure of
carbon material in the bulk form and how the discovery of the nanostructured forms of
carbon has opened up use of carbon in newer applications. Since the majority of carbon
materials are a result of sp2 hybridization, the structure is explained on the basis of natural
or single-crystal of graphite. This will form the basis of the understanding of electronic
and band structure of nanoforms of carbon presented in the following chapters. X-ray
diffraction and Raman spectroscopy are two important characterization tools that can
give a lot of insight into the structure of various forms of carbon and are widely used by
researchers to understand the novel and newer forms of nanocarbon. An introductory
reference is also provided to x-ray diffraction and Raman spectroscopy used to character-
ize the structure of various forms of carbon and should help the reader in understanding
the difference when we move from bulk to carbon nanomaterials.

1.1.1 Atomic Structure of Carbon

Carbon is a chemical element with the symbol C and atomic number 6 and represented
by the electronic orbital structure illustrated in Figure 1.3. As a member of group IV of
the periodic table, it is obtained in three naturally occurring isotopes, with 12C (6 protons,
6 neutrons, nuclear spin I = 0) and 13C (6 protons and 7 neutrons, nuclear spin I = 1/2) being
stable, whereas 14C (6 protons and 8 neutrons) is radioactive, decaying with a half-life of
about 5700 years. The carbon-12 (12C) isotope forms almost 99% of the carbon on earth,
while carbon-13 (13C) forms the remaining 1%. Though 14C is only found in traces (~10 –12 of
all carbon atoms), due to its long half-life corresponding to reasonable life scale in human
history, measurement on 14C concentration in organic material (e.g., wood) allows one to
date its biological history; this is called carbon dating.
A carbon atom with six electrons has the electron configuration 1s22s22 p1x2 p1y in its
ground state (lowest energy state), as shown in Figure 1.4. Note that there is a large energy
difference between the 1s and 2s orbital and a very small difference in energy between
2s and 2p orbitals. The 1s2 orbital contains two strongly bound core electrons. Four more
weakly bound electrons occupy the 2s22p2 valence orbitals. In the crystalline phase, the
4 Carbon Nanomaterials

6 protons
+ 6 neutrons

Electron

Proton

Neutron
Carbon atom

FIGURE 1.3
Orbital representation of carbon atom.

Ground state Excited state

(~4 eV)

~4 eV
2px 2py 2pz 2px 2py 2pz
Energy

2s 2s

1s 1s

FIGURE 1.4
Electronic configuration for carbon in the ground state and in the excited state.

valence electrons give rise to 2s, 2px, 2py, and 2pz orbitals, which are important in forming
covalent bonds within carbon materials. Because the energy difference between the upper
2p energy levels and the lower 2s in carbon is small (~4 eV) compared to the binding energy
of the chemical bonds, the electronic wave functions for these four electrons can readily
mix with one another, thereby changing the occupation of the 2s and three 2p atomic orbit-
als, so as to enhance the binding energy of a C atom with its neighboring atoms. The general
mixing of 2s and 2p atomic orbitals is called hybridization, whereas the mixing of a single
2s electron with one, two, or three 2p electrons is called spn hybridization with n = 1, 2, 3.
The vertical arrows in Figure 1.5 represent the direction of spin of an electron in the
particular energy state. Notice that the sixth electron is placed in the 2py orbital rather than
being paired with the fifth electron in the 2px orbital. This is the configuration resulting
from Hund’s rule, which states that the most stable arrangement of electrons in orbitals
of equal energy is the one with the greatest number of parallel spins. The 2px and 2py
electrons in the carbon atom are considered to have parallel spins, whereas if they both
occupied the 2px orbital they would have to have opposite spins.
Carbon forms an excited state by promoting one of its 2s electrons into its empty 2pz
orbital and hybridized to the excited state. In the excited state configuration, carbon will
Introduction to Carbon and Carbon Nanomaterials 5

sp3 hybridization of carbon sp2 hybridization of carbon sp hybridization of carbon

Ground Ground Ground

state state state
2s 2p 2s 2p 2s 2p
Promotion
Promotion Promotion of electron
of electron of electron 2s 2p
2s 2p 2s 2p
sp-
sp2- hybridized
sp3-hybridized hybridized state 2py 2pz
orbitals state sp orbitals
2pz
sp2 orbitals

FIGURE 1.5
Hybridization of orbitals of a carbon atom.

be able to form four bonds of equal energy. Since both the 2s and the 2p subshells are half-
filled, the excited state is relatively stable.
The reason why carbon is the only element that can make long chains is not only its
lower atomic number or atomic mass but also the ease with which it can undergo different
hybridization states due to its electronic structure.

1.1.2 Carbon Hybridization
Mixing of two or more atomic orbitals to form a new set of hybrid orbitals is called hybrid-
ization. The element carbon may form virtually an infinite number of compounds. Most
plastics, pharmaceuticals, and food contain long chains of carbon atoms. This is largely
due to the types of bonds carbon can form and the number of different elements it can join
in bonding. Carbon may form single, double, and triple bonds, and the hybridization may
lead to four single bonds (sp3), two single and one double bond (sp2), and one single bond
and one triple bond (sp), as shown in Figure 1.5.
In sp3 hybridization, one electron from the s orbital moves to the empty p orbital to give
four hybridized orbitals of equivalent bonds (energy) of equal strength. In sp2 hybridiza-
tion, one p orbital does not combine with the other three orbitals and one electron is left,
and the orbital looks like a lobe and in plane which is perpendicular to the other three
hybridized orbitals. Together with other hybridized orbitals it makes a double bond, called
the π-bond. In sp hybridization a similar process takes place, but instead two p orbitals
stitch around to form a triple bond. sp3 has the highest electron density, sp2 lesser, and sp
the least electron density. Every first bond made by a carbon atom is a σ bond, followed by
π-bond. The σ bond is always formed by hybridized orbitals, whereas the π-bond is formed
through leftover p orbital. A single bond can rotate, whereas a double bond cannot. Note
that whereas all σ bonds undergo overlapping between the nucleus, the π-bonds overlap
above and below the nucleus. A double bond is stronger than a single bond, but not double
the strength; likewise a triple bond is also stronger than a double bond.

1.1.3 Diamond Structure
It is well known that carbon atoms can form chemical bonds by rearranging the configura-
tion of the outer electrons with hybridization of 2s and 2p electrons. One possible hybrid-
ization scheme is found in diamond where four tetrahedral bonds are formed, each at an
6 Carbon Nanomaterials

+ Diamond

1 s-orbital 3 p-orbitals 4 sp3-orbitals

sp3
109°28ʹ

m
5n
0.7

FIGURE 1.6
Illustration of the electron charge density for a carbon atom with sp3 hybridization and crystal structure of
diamond, showing a cubic cell.

angle of 109°28′. These very strong covalent bonds consist of hybridization of one s state
and three p states (sp3 bonding). The overall symmetry is cubic, as shown in Figure 1.6.

1.1.4 Graphite Structure
Another possible hybridization scheme for the bonding electrons occurs if the carbon
atoms arrange themselves in hexagonal rings. Each layer is itself a giant molecule with
very strong covalent bonds called graphene sheets. This is the case with graphite and
aromatic molecules. Orbitals composed of one 2s and two 2p orbitals (2px and 2py bonds)
are formed. Each carbon atom in graphite is thus sp2 hybridized. These form the strong
covalent bond between carbon atoms in the plane and are known as σ bonds, as shown
in Figure 1.7. The three sp2 hybrid orbitals will arrange themselves in three-dimensional

π-bond side-by-side overlap of p orbitals

Pz Pz
π-bond

sp2 sp2
sp2 sp2
C σ-bond C
sp2 sp2

π-bond

σ-bond head on overlap of hybrid orbitals

FIGURE 1.7
Schematic of the sp2 hybridization of atomic orbitals in graphite with sigma and pi bond overlap in the graphite
lattice.
Introduction to Carbon and Carbon Nanomaterials 7

space to get as far apart as possible. The geometry that achieves this is trigonal planar
geometry, where the bond angle between the hybrid orbitals is 120°. The unmixed pure pz
orbital is perpendicular to this plane, called the π-orbital and provides the weak bonding
between adjacent layers in the graphite structure. This weak interplanar bonding is some-
times referred to as van der Waals bonding.
The overlap of the π-orbitals on adjacent atoms accounts for the carbon–carbon double
bond network in a given plane and is responsible for the high mobility of electrons in
graphite. The pz electron between the layers is delocalized (it is a free electron) and spreads
uniformly over all carbon atoms and resonates between the valence bond structures. These
π-electrons between the layers allow graphite to conduct electricity and heat. The layers
can easily slide over each other making graphite

• Soft and slippery and an excellent lubricant (like oil)

• Account for the tendency of graphite materials to fracture along planes
• Cause the formation of intercalation or charge transfer compounds of graphite

1.2 Crystal Structure of Graphite

In the stable hexagonal layered structure, the carbon atoms are arranged in a honeycomb
lattice with C–C bond separation of 0.142 nm, as shown in Figure 1.8 [1]. The ideal hexago-
nal graphite structure described earlier is composed of theoretically infinite basal planes
with perfect ABAB stacking, with no defects whatsoever. The sheets align such that their
two-dimensional hexagonal lattices are staggered in an ABAB pattern with lattice spacing
between two identical sheets C0 = 6.70 Å. The primed atoms in layer A on one graphene

c
6.70 Å

d
3.35 Å

A
a
1.42 Å

2.46 Å

FIGURE 1.8
The hexagonal crystal structure of graphite. (From J. Bernal, Proceedings of the Royal Society of London. Series A,
Containing Papers of a Mathematical and Physical Character 106, no. 740 (1924): 749–773.)
8 Carbon Nanomaterials

Upper layer (A)

Lower layer (B)

FIGURE 1.9
The crystal structure of graphite showing two adjacent hexagonal layers (top view).

layer are separated by half the orthogonal lattice spacing from the adjacent layer B.
Figure 1.9 shows the positional relationship between two identical graphene planes A and
B, and the graphite structure can be described as an alternate succession of these planes.
The distance between adjacent layer planes (A and B) is 3.35 Å. Strong chemical bonding
forces exist within the intraplanar or layer planes (150–170 kcal/g atom). However, the
bonding energy between the planes is only about 2% of that within the plane (1.3–4 kcal/g
atom). The dashed lines in Figure 1.8 form the three-dimensional unit cell of direct graph-
ite lattice with an in-plane unit cell vector of length 2.46 Å.
Crystal density is 2.254 g/cc as compared to 3.53 g/cc for diamond with sp3 hybridization.
Such an ideal structure is, of course, never found, either in natural or synthetic graphite. By
setting aside the interplanar interactions, the graphite may be treated to a first approxima-
tion as a two-dimensional lattice of a single graphene sheet.
The other form of graphite, called a metastable state, is sometimes present in a rhombo-
hedral structure and has very similar physical properties, except the graphene layers stack
slightly differently in an ABC ABC configuration, wherein layer C is displaced by the same
amount with reference to layer B [1]. The hexagonal graphite may be either flat or buckled.
The hexagonal form can be converted into rhombohedral form through mechanical treat-
ment, and the rhombohedral form reverts to the hexagonal form when it is heated above
1300°C. Studies have shown that natural graphite may contain 15%–20% of the slightly less
stable rhombohedral structure.

1.2.1 Two-Dimensional Lattice Structure: Unit Cell

As already mentioned in the last section, the carbon atoms in two-dimensional graphene
condense in a honeycomb lattice. The honeycomb lattice is not a point lattice because two
neighboring sites are not equivalent and atoms A and B have to move in different direc-
tions to reach the other nearest atom. As illustrated in Figure 1.10a one may view the honey-
comb lattice as a triangular Bravais lattice with a two-atom basis (A and B) [2]. The distance
between any two nearest carbon atoms is 0.142 nm, which is the average of the single (C–C)
and double (C=C) covalent bonds, as in the case of benzene.
The unit cell, Sg, is spanned by the two vectors, a 1 and a 2, and contains two carbon
atoms [2]. The basis vectors (a 1,a 2) have the same length, a = √3 aC–C = 2.46 Å, where
aC–C = 1.42 Å (interatomic distance) and form an angle of π/3. The area of the unit cell,
Sg, is Ag = 3a 2/2.
Introduction to Carbon and Carbon Nanomaterials 9

Carbon Unit cell Σg

Unit cell atom
A ky
y Sg g
b1
a1 4π
A B ΣBZ K 3a0
4π
x Г kx 2π 3a0
O
a2 √3a0
b2
a0 First
Brillouin zone
b

(a) (b)

FIGURE 1.10
Honeycomb or direct lattice of graphite single layer, the structure of graphene. (a) Bravais lattice and (b) recipro-
cal lattice. (From A. Maffucci and G. Miano, Applied Sciences 4, no. 2 (2014): 305–317.)

The primitive unit cell can be considered as equilateral parallelogram with side a =
0.246 nm, where a is the lattice constant of graphene.

1.2.2 Reciprocal Lattice and Brillouin Zone

Every crystal structure has two lattices associated with it: the crystal lattice and the recip-
rocal lattice. An x-ray diffraction pattern of a crystal is a map or image of the reciprocal
lattice of the crystal. Vectors in the direct lattice have the dimensions of length, whereas
vectors in the reciprocal lattice have the dimension of the reciprocal of length (l/length). In
fact the reciprocal lattice is the Fourier transform of the direct lattice so that every position
in Fourier space may be described as a wave. It is much easier to describe the motion of an
electron as a wave of wavelength λ and represent the lattice in terms of wavelength instead
of lattice parameter “a.” The advantage is that it is the motion of charge carriers, knowl-
edge of which is essential for predicting the transport properties of materials. In a direct
lattice the primitive cell contains all information of the physical and mechanical properties
of the material. In a reciprocal lattice all information of wave motion can be understood in
a Brillouin zone or Weigner Seitz cell. The length scale in BZ is smaller, i.e., reciprocal of
“a.” The motion of the electron is represented by the parameter k = 2π/λ, known as wave
vector. It gives the number of waves in length 2π. Further, each plane in the direct lattice is
represented by a vector or a point in the reciprocal lattice. The d-spacings of the planes in
the direct lattice is therefore related to the reciprocal lattice vector as dhkl = 1/|Hhkl|, where
H is the reciprocal lattice vector.
In the reciprocal k-space depicted in Figure 1.10b, the 2D graphene lattice is character-
ized by the unit cell, spanned by the two vectors, b1 and b2, which have the same length
b1 = b2 = 4π √3a and form an angle of 2π/3. The area of the unit cell is given by Bg = 8π2 √3 a2.
The basis vectors of the direct space (a1,a2) and the basis vectors of the reciprocal space (b1,b2)
are related by ai·bj = 2πδij with i,j = 1,2 and the areas, Ag and Bg, are related by AgBg = (2π)2.
The reciprocal lattice of graphene shown in Figure 1.10b is also a hexagonal lattice but
rotated 90° with respect to the direct lattice. Physically, all sites of the reciprocal lattice
represent equivalent wave vectors.
10 Carbon Nanomaterials

1.3 Electronic Band Structure of Graphite

1.3.1 Energy Dispersion Relation
The electrical and magnetic properties of graphite are conveniently explained on the basis
of its band structure based on a two-dimensional model of the lattice since the spacings
of the graphite layers is 0.335 nm, which is very large as compared to the separation to the
individual carbon atoms in the hexagonal layers (0.142 nm). Therefore it appears reasonable
to suppose that the electronic properties of two-dimensional graphite (neglecting inter-
planar effect) would be good approximation for the properties of the three-dimensional
graphite. Moreover, the large anisotropies of the electrical conductivities and magnetic sus-
ceptibilities in and perpendicular to basal planes of graphite make the two-dimensional
model appear as an adequate approximation.
The two-dimensional unit cell for graphite contains two carbon atoms, each carbon
atom having four valence electrons. A tight binding model yields eight bands: four
valence bands and four conduction bands. The two 1s electrons on each atoms are
assumed to have negligible effect on the bonding because of their orbital localization. Of
the four remaining valence electrons on each carbon atom, three sp2 hybridized orbit-
als form the σ valence bands and σ* conduction bands. The remaining pz orbitals of the
carbon atoms, oriented perpendicular to the sheet (z-direction), form the π-valence band
and π*-conduction band. Thus, considering the unit cell, there will be six σ-type energy
bands and two π-type bands.
The four occupied bands are referred to as σ-valence bands and the remaining four are
known as σ* conduction bands. Therefore the problem of the band structure of graphite
sheet conveniently splits into a problem for the σ and σ* bands, and a problem for the π
and π* bands. This approximation is apparently justified by the fact that the π-bands are
more important than σ bands when considering electronic transitions near Fermi energy.

30
M
K´ Г K

Brillouin Conduction
zone ba
nd
Energy (eV)

Fermi energy
0 Dirac point

Valence band

–20
K´ Г M K
Momentum

FIGURE 1.11
The Bloch band description of a single layer of graphene electronic structure; orbital energies depend on the
momentum of charge carriers in the crystal Brillouin zone (inset left). The π and π* bands are decoupled from
the σ and σ* bands and are closer to the Fermi energy. The bands form conical valleys that touch at two of the
high symmetry points, conventionally labeled K and K′ in the Brillouin zone. Near these points the energy var-
ies linearly with the magnitude of the momentum measured from BZ corners. (Reprinted with permission from
Andrey K. Geim and Allan H. Macdonald, Graphene: Exploring carbon flatland, Physics Today, August, 36, Fig.
No. Box-1. Copyright 2007, American Institute of Physics.)
Introduction to Carbon and Carbon Nanomaterials 11

This separation of the π and σ bands in the neighborhood of Fermi energy is shown in
Figure 1.11 [3].
The resulting band structure of graphene is characterized with π and π* bands degener-
ate at the K points in the hexagonal Brillouin zone of the sheet [3]. This degenerate energy
level corresponds to the Fermi energy, which shows that the graphene sheet is a zero gap
semiconductor with a linear E versus K relationship (photon like spectrum) around the
Fermi energy at the K point.
In the neighborhood of each Fermi point, the energy dispersion relation is linear and
may be approximated as

E(±) ≈ ±ħνF|k − k0| (1.1)

where k0 is the wavenumber at a Fermi point, νF ≈ 0.87 × 106 m/s is the Fermi velocity of the
π-electrons, and h is the Planck constant. Such behavior of electrons in graphene makes it
different and unique than any other form of carbon. In general, the band overlap increases
with increasing number of layers. From 10 layers onwards the difference with the band
overlap in bulk graphite (~40 meV) is less than 10%. There is also remarkable difference in
the wave functions at the K point for the levels around the Fermi energy between a single
graphene layer and system consisting of more graphene layers.

1.3.2 Density of States
The electronic density of states for graphite is illustrated in Figure 1.12. There is a large
band gap between the σ orbitals forming bonding and antibonding bands [4]. However,

D(ε)
Ef
σ
П+ σ*
П*

0 E(eV)
(a) ~40 meV

D(ε)

Valence
band Conduction
band
(b) 0 Ef ε0

D(ε)

VB CB

(c) Ef E(eV)

FIGURE 1.12
(a) Sketch of the density of states for graphite. Zero energy is taken at the vacuum level. (b) Density of states for
3D graphite near the region of band overlap. Zero energy is taken at the bottom of the conduction (pi*) band.
(c) Density of states for a single sheet of carbon atoms (2D graphite) near the band touching region. (Adapted from
I.L. Spain, Electronic transport: Properties of graphite, carbons, and related materials, Chemistry and Physics of
Carbon 16 (1981): 119–304.)
12 Carbon Nanomaterials

D(ε)

Eg
~5.3 eV

Valence band Conduction band

0 Ec E(eV)

FIGURE 1.13
Theoretical sketch of the density of states of diamond. Zero energy is taken at the top of the valence or bonding
band. (Adapted from I.L. Spain, Electronic transport: Properties of graphite, carbons, and related materials,
Chemistry and Physics of Carbon 16 (1981): 119–304.)

the π-bands, which just touched at K point for two-dimensional graphite (a single layer
of carbon atoms called graphene shown in Figure 1.11), overlap by ~40 meV for three-
dimensional graphite, as illustrated in Figure 1.12a. This small overlap of bands makes
the graphite semimetal. The density of states near the region of the overlap of the π-band
(valence band) and π*-band (conduction band) is illustrated in Figure 1.12b. Assuming
N number of atoms in the crystal, there are 4N bonding electrons, 3N of which are in σ
band. If the π-bands just touched, as in the 2D graphite (Figure 1.12c) all of the N remain-
ing electrons would lie in the valence band at zero Kelvin and the conduction band would
be empty. However, in 3D graphite, few of the electrons (~10 –4N) lie in the conduction
band, leaving exactly the same number of empty states, called holes, in the valence band.
Any deviation from the ideal graphite lattice can cause a change in the electronic struc-
ture to occur as the lattice becomes more defective resulting in change in the transport
properties. Figure 1.12d shows the shift in Fermi level of boron doped graphite.
In case of diamond crystal lattice, the bonding states are separated from the antibonding
states by approximately 5.3 eV, as shown in Figure 1.13. The pure diamond is therefore a
very good electrical insulator.

1.4 Physical Properties of Graphite

Some of the important properties of the ideal graphite material, that is a material that
most closely corresponds to an infinitely large graphite crystal which is closest to single
crystal graphite, are summarized in Table 1.1. The properties discussed next are either
calculated or based on the actual properties of graphite crystals closely approaching
this ideal structure. As will be seen later in the text, a wide range of materials comes
under the heading of carbon or graphite and these materials often have properties that
are much different from those of the ideal graphite crystal. The material properties are
sometimes confused with the nomenclature “carbon” or “graphite.” Moreover, being a
layered structure, properties of graphite are highly anisotropic, that is, the properties of
the material may vary considerably when measured along the in-plane “ab” directions
or within the plane and in the “c” direction, that is, perpendicular to the planes. Such
anisotropy, especially in electrical and thermal properties, can often be very useful in
several applications.
Introduction to Carbon and Carbon Nanomaterials 13

TABLE 1.1
Important Physical and Chemical Properties of Graphite
Property Graphite
Crystalline form Hexagonal
Lattice parameters a = 0.246 nm, C0 = 0.6708 nm
Color Black
Density at 300 K, 1 atm 2.26 g/cc
Heat of fusion 46.84 kJ/mol
Heat of vaporization to monoatomic gas (estimated) 716.9 kJ/mol
Sublimation point at 1 atm (estimated) 4000 K
Pauling electronegativity 2.5
Atomic volume 5.315 cm3/mol
Triple point (estimated) 4200 K
Boiling point (estimated) 4560 K
Moh’s hardness 1-2

1.4.1 Electrical Properties of Graphite

In electrical conductors such as metals, the attraction between the outer electrons and the
nucleus of the atom is weak; the outer electrons can move readily and, since an electric cur-
rent is essentially a flow of electrons, metals are good conductors of electricity. In electrical
insulators (or dielectrics), electrons are strongly bonded to the nucleus and are not free to
move.
The atomic structure of graphite is such that the highest filled valence band overlaps
the lowest empty conduction band by approximately 40 meV; a few holes and electrons
are always available to carry current. In pure graphite the electron and hole densities are
small and equal, and the carrier effective mass is low. The delocalized π-electrons can
move readily along the basal planes under the influence of electric fields. Consequently,
the electrical resistivity of graphite parallel to the basal planes (ab directions) is low and
the material is a relatively good conductor of electricity. In the perpendicular direction (c
direction), the spacing between planes is comparatively large, and there is no comparable
mechanism for the electrons to move from one plane to another, that is, normal to the
basal planes. As a result the electrical resistivity in that direction is high and the material
is considered an electrical insulator. In some cases, it may be 10,000 times higher than in
the ab directions. Some representative data of resistivity of different forms of graphite is
summarized in Table 1.2 across the range of carbon materials and compared with some
other commercially useful metals and alloys. On the one hand there are just about perfect
crystals of graphite, and on the other there are nearly amorphous carbons like carbon
black. Also, bonding between carbon atoms may differ.
Apart from its scientific interests, the electrical conductivity of carbon-based materials
is of great importance because of its industrial applications. Brushes for electrical motors
are made from polycrystalline graphite because of a combination of electrical and lubri-
cating properties. High-temperature electrodes include furnace cores and electrodes for
metallurgical applications. Carbon resistors are used as electrical components, and auto-
mobile ignition cables are often constructed with carbon cores to maximize suppression
of radio frequency noise. The relationship between structural and electrical characteris-
tics give a characteristic “fingerprint” by which different forms of carbon materials can
be classified.
14 Carbon Nanomaterials

TABLE 1.2
Electrical Resistivity of Various Forms of Carbon and Graphite
along with Important Metals and Alloys
Electrical Resistivity Range
Material (mΩ-cm)
Single crystal graphite 0.03–0.1
Pyrolytic graphite/HOPG 0.020 (ab), 40 (c)
Fine grained/High density (1.8g/cc) graphite 0.9
PAN based carbon fibers (T-300) 1.7
Pitch based carbon fibers (P-120) 0.226
Glassy carbon 4.2
Diamond >1015
Copper 0.0017
Gold 0.002214
Silver 0.0016
Stainless steel 0.069
Aluminum 0.00265
Silicon 6.40 × 107
Silicon carbide 105

1.4.2 Mechanical Properties of Graphite

As mentioned in Section 1.2, the bond between atoms within the basal plane of a graphite
crystal is considerably stronger than the bond between the planes with an anisotropy ratio
of approximately 75. This means that the strength in the ab directions is much higher than
in the c direction. The three important elastic constants in the graphite crystal are given as

C11 = 1060 GPa (a direction)

C33 = 36.5 GPa (c direction)
C44 = 4.5 GPa (parallel to the planes or shear planes)

Young’s modulus of elasticity of the crystal varies up to two orders of magnitude with the
direction. The low value of C44 is the reason for poor interlaminar strength due to easy
shear between basal planes.
It should be noted that such values are those of the ideal graphite crystal. The mechanical
properties of “real” material, such as the molded or synthetic graphite materials and pyro-
lytic graphite, are considerably different since they are controlled by the dominant crystallite
orientation, porosity, structural defects, and other factors. The result is large variations in the
range of these properties, depending on the type of graphite and its manufacturing process.
The theoretical strength of single-crystal, defect-free graphite can be evaluated from the
Orowan-Polanyi equation:

στ = (Eγ γa/ad)1/2 (1.2)

where στ is the breaking stress, Eγ is Young’s modulus (corresponding to elastic constant

C11), γa is the surface energy (i.e., the energy needed to separate two planes in the crystal
per unit area; γa = 4.2 J/m2 for the prismatic bonds [100 plane] in graphite), and ad is the
distance between the plane that is to be separated by the applied tensile stress.
Introduction to Carbon and Carbon Nanomaterials 15

TABLE 1.3
Mechanical Properties of Various Forms of Carbon and Graphite
Material Tensile Strength Young’s Modulus
Single crystal graphite ~100 GPa 1060 GPa (a direction), 36.5 GPa (c direction)
Fine grained/high density (1.8 g/cc) 40 MPa 12 GPa
graphite
Synthetic graphite ~10–30 MPa 6.0 GPa–10 GPa
Diamond 60 GPa 1220 GPa
PAN-based carbon fibers (high strength, 3.53–6.37 GPa 230–295 GPa
type II)
PAN-based carbon fibers (high modulus, 3.92 GPa 580 GPa
type I)
Pitch-based carbon fibers, P-120 2.20 GPa 820 GPa
Carbon–carbon composites 700 MPa 100 GPa
Stainless steel 520 MPa 190 GPa
Titanium 1000 MPa 110 GPa
Aluminum 70 MPa 69 GPa

However, for all practical applications the experimental strength lies well below the the-
oretical limit because of cracks and similar flaws in the carbon materials. Then Equation 1.2
is modified by Griffith’s equation:

στ = (2Eγ γa/πLf)1/2 (1.3)

where Lf is the length of critical flaw that initiates rupture.

Mechanical properties of different forms of graphite including some important metals
and alloys is compared in Table 1.3.

1.4.3 Thermal Properties of Graphite

Like electrical conductivity the acoustic and thermal properties of graphite are highly
anisotropic, since phonons propagate quickly along the tightly bound planes but are
slower to travel from one plane to another. The conductivity ratio in the a and c direction
is around 200, much less than electrical conductivity because phonons also contribute to
thermal conductivity (Ƙ). A large variation in thermal conductivity is found in different
carbon forms and may vary from <50 W/mK for polycrystalline carbons or PAN-based
carbon fibers to ~5000 W/mK for SWCNT (single-walled carbon nanotube) or graphene. A
strong correlation is, however, found between Ƙ and crystalline perfection of the specific
carbon material. The thermal conductivity of the graphite is dominated first by the elec-
tronic contribution, as the temperature is increased from absolute zero, up to the conduc-
tivity peak temperature Tm Ƙ.
In practical applications of the thermal conductivity, it is often conventional to use the
simplified Debye formula:

Ƙ = 1/3 Cʋ ν lɸ (1. 4)

where Cʋ is the specific heat at constant volume, ν is the average phonon group velocity
(i.e., the velocity of sound), and lɸ is the phonon mean free path. In case of highly graphitic
16 Carbon Nanomaterials

TABLE 1.4
Thermal Conductivity of Various Forms of Carbon and Graphite Compared to Metals and Alloys
Material Thermal Conductivity (W/mK)
Single-crystal graphite ~3000 W/mK in ab direction and 65–95 W/mK in c direction
Pyrolytic graphite/HOPG 1700 ± 100 W/(mK) ab direction and 8 ± 1 W/(mK) c direction
Fine grained/high density (1.8 g/cc) graphite 140
PAN-based carbon fibers (T-300) 10
Pitch-based carbon fibers (P-120) 640
Glassy carbon 5.8
Carbon–carbon composites 250–350
Diamond 2000
Copper 112–226
Gold 172
Silver 242
Stainless steel 16
Aluminum 226
Silicon 149
Silicon carbide 120

materials, the heat is carried by phonons and the electronic heat contribution is only negli-
gible. The temperature dependence of the thermal conductivity of graphite obeys a T2.3 law
for temperatures above 30 K and reaches a maximum to about 3000 W/mK around 150 K
and then decreases with a further increase in temperature due to the umklapp phonon–
phonon scattering process.
Thermally conductive polymer composites offer new possibilities for replacing metal
parts in several applications, including power electronics, electric motors, generators,
and heat exchangers. Current interest to improve the thermal conductivity of polymers
is focused on the selective addition of carbon nanofillers with high thermal conductivity.
Unusually high thermal conductivity makes carbon nanotube (CNT) the best promising
candidate material for thermally conductive composites. However, the thermal conductivi-
ties of polymer/CNT nanocomposites are relatively low compared with expectations from
the intrinsic thermal conductivity of CNTs. The challenge primarily comes from the large
interfacial thermal resistance between the CNT and the surrounding polymer matrix,
which hinders the transfer of phonon dominating heat conduction in polymer and CNT.
Carbon–carbon composites are one of the best lightweight (density ~1.8–1.9 g/cc) high tem-
perature thermal conducting materials and can operate at temperatures > 2000°C. They
are used in heat shields for space crafts, nuclear reactors, and aircraft brake discs. Their
thermal conductivity values can be tailored close to copper by using specific carbon fillers
like carbon fibers, VGCF, and CNT. A comparison of the thermal conductivity of the vari-
ous forms of carbon vis-à-vis other important metals and alloys is presented in Table 1.4.

1.4.4 Chemical Properties of Graphite

Pure graphite is one of the most chemically inert materials. It is resistant to most acids,
alkalies, and corrosive gases. However, impurities and imperfections are almost always
present to some degree in both natural and artificial graphites and often have an impor-
tant catalytic effect with a resulting increase in the chemical reactivity. The anisotropy of
the graphite crystal is also reflected in its chemical behavior. The graphite crystal exhibits
Introduction to Carbon and Carbon Nanomaterials 17

large differences in surface energy in the different crystallographic directions; these ener-
gies amount to ~5 J/m2 in the prismatic plane but only about 0.11 J/m2 in the basal plane.
These differences account for the different rate of reaction, that is, slow at the basal plane
and rapid at the edges or at the termination of the basal planes or at defect sites, such as
dislocations, vacancies, and steps. Reaction with gases or vapors occurs preferentially at
“active sites,” that is, the edges of the basal planes of the crystal that are either zigzag or
“arm chair.” Consequently, graphite materials with large crystals and few defects have
the best chemical resistance. The chemical reactivity is also appreciably affected by the
degree of porosity, since high porosity leads to a large increase in surface area with result-
ing increase in reactivity. Obviously, high surface area materials such as activated carbon
are far more reactive than dense, pore-free or closed-pore materials such as glassy carbon.
Therefore there can be considerable differences in reactivity between one form of carbon and
another.
Carbon reacts with oxygen at temperatures around 350°C to 400°C to form gaseous
products like CO and CO2, unlike other refractory materials like oxides and carbides of
metals. Many carbides form a protective layer of oxide when reacted with oxygen and thus
delays oxidation.
Graphite does not react with hydrogen below 1000°C–1500°C and forms CH4. The reac-
tion is, however, catalyzed and may occur at 500°C–600°C in presence of transition met-
als. Highly graphitized carbons like natural graphite or highly oriented pyrolytic graphite
(HOPG) may form intercalation compounds with strong acids and alkali metals. These
species penetrate between the graphene layers by charge transfer and have many useful
properties and applications.

1.5 Nongraphitic Carbons
The relative inability of some carbons to graphitize is believed to be due to the presence
of sp3 cross-linking bonds between entangled graphitic layers, as shown in Figure 1.14a.
At higher temperature the inability of the planes to grow and stack is due to the tangled
arrangement of the planes. Nongraphitizable carbons are mechanically hard, and are
sometimes referred to as hard carbons. These are sometimes also referred to as amorphous

<c>
c

Lc
La

(a) (b)

FIGURE 1.14
Schematic models for the structure of (a) nongraphitizing and (b) graphitizing carbons.
18 Carbon Nanomaterials

carbons. When examined by x-ray diffraction, these materials show only diffuse maxima
at the normal scattering angles. This has been attributed to a random translation and rota-
tion of the layers within the layer planes. This disorder is also referred to as turbostratic
structure. It can be seen that vast differences do exist in graphitizable (preferentially paral-
lel layer planes) microstructure with larger crystallite dimensions (see Figure 1.14b). The
microstructure is directly related to raw materials and processing parameters.

1.5.1 Carbon Black
Carbon blacks are formed by the condensation of carbon from the gas phase into small
spheres containing between ~105–109 atoms with no long-range order corresponding to
the sphere diameter ~2–10 μm. However, aromatic layers are arranged to the surface only.
Accordingly, it is difficult for the spheres to coalesce, and carbon black only partially
graphitizes and is very close to a truly “amorphous carbon.”

1.5.2 Coal
Nature provides an abundant supply of impure carbons in the form of coal. The carboniza-
tion process of the precursor material (rotted vegetation, peat) has taken place over a very
long period of time deep inside the earth crust under conditions in which impurities cannot
easily escape. They also fall into the category of nongraphitizing carbon. A wide variety of
coals can be found and its quality is judged by its coal “ranking” depending upon its car-
bon and energy contents as well as ash contents. Lignite, or brown coal, is the lowest rank
of coal (60%–75% carbon) and used almost exclusively as fuel for electric power generation.
Lignite makes up almost half of our coal reserves. Bituminous coal is used primarily as fuel
in steam-electric power generation, with substantial quantities used for manufacturing and
to make coke. Anthracite, the highest rank of coal (>90% carbon), is a harder, glossy black
coal, with virtually no moisture and volatile contents. It is used primarily for residential
and commercial space heating because of its high-energy contents and smokeless fuel.

1.5.3 Chars
As mentioned earlier, not all aromatic hydrocarbons form coke. Some, such as phenan-
threne and biphenyl, do not graphitize and are considered char formers. These compounds
are branched aromatics (as opposed to the linear structure of the coke-former aromatics)
with a preferred axis of growth. This characteristic prevents the formation of extensive
graphitic planes and of a liquid mesophase. Charcoal is a traditional term used for chars
obtained from wood and other organic related materials. The physical form of the parent
material is retained, with highly developed pore structure. At the microscopic level, the
basic structure is highly disordered with no detectable graphitic properties. Because of
their large surface area and possibility to control the porosity, these are also used as acti-
vated carbons as filters and catalyst support.

1.5.4 Graphitizing Carbons
Most graphitizing carbons are mechanically soft and are sometimes referred to as soft
carbons. These can be readily obtained from soft carbons, such as petroleum coke, by heat-
ing. When the heat treatment temperature is limited to about 1000°C, coke-type materials
are formed. These carbonaceous materials have graphene layers of relatively small extent
Introduction to Carbon and Carbon Nanomaterials 19

(about 1–4 nm), which are stacked in a roughly parallel fashion but with random rotations
and translations between every pair of layers. This type of disorder is given the name
“turbostratic disorder.” As the carbons are heated (HTT, heat treatment temperature) from
1000°C to 2000°C, the lateral extent of the layers grows and the stacking becomes quite
parallel as evidenced by a sharpening of the (002) Bragg reflection. However, at 2000°C
there is still turbostratic disorder. Upon heating above 2000°C the turbostratic disorder is
relieved in a more or less continuous way, the amount of remaining turbostratic disorder
decreasing to zero monotonically after HTT > 3000°C.
Conceptually, graphite is a graphitic carbon with no or very little turbostratic disor-
der. In graphite carbon, the in-plane structure of graphene layers is almost the same as in
graphite, except the lateral extent of the layers increases with heat treatment temperature.

1.5.5 Polycrystalline Graphite
The ideal hexagonal graphite structure described earlier is composed of theoretically infi-
nite basal planes with perfect ABAB stacking, with no defects whatsoever. Such an ideal
structure is, of course, never found, either in natural or synthetic graphite. Graphite mate-
rials, such as pyrolytic graphite, carbon fibers, carbon matrix composites (carbon–­carbon),
vitreous or glassy carbon, carbon black, chars, coke, and many other forms of carbon,
are actually aggregates of graphite crystallites, in other words, polycrystalline graphites.
These crystallites may vary considerably in size. For instance, the apparent crystallite size
perpendicular to the layer planes (Lc) of some vitreous carbons may be as small as 1 to
2 nm, which is the length of a few atoms, or up to 100 nm found in highly ordered pyrolytic
graphite (HOPG). Similarly, the length of crystallite (La) could range from 50 to 1000 nm,
for highly disordered carbon to highly graphitic structure.
Figure 1.15 shows the network of twisted and folded carbon layers in a nongraphitic
structure as a network of polycrystalline or glassy carbon material [5]. Interestingly this

Typical strong confluence

La

Lc

Weak confluence
Lc

La

FIGURE 1.15
The ribbon model of polycrystalline or glassy carbon. (Reproduced with the permission from G. Jenkins,
K.  Kawamura, and L. Ban, Formation and structure of polymeric carbons, Proceedings of the Royal Society of
London A: Mathematical, Physical and Engineering Sciences, The Royal Society, 1972, pp. 501–517.)
20 Carbon Nanomaterials

microstructural model of carbons introduces the concept of curvature of graphene layers

observed in fullerenes and carbon nanotubes.
The layer planes may or may not be perfectly parallel to each other, depending on
whether the material is graphitic or nongraphitic carbon. The aggregates of crystal-
lites also have widely different sizes and properties. Some, such as soot, are extremely
small and contain only a few small crystallites. In such cases, the properties are mostly
related to the surface area. Other aggregates may be relatively large and free of defects
and essentially parallel to each other, in which case the structure and its properties
closely match those of the ideal graphite crystal. Such large aggregates are often found
in pyrolytic graphite. In other aggregates, the crystallites have an essentially random
orientation. This occurs in turbostratic (i.e., showing no evidence of three-dimensional
order) or amorphous carbon. In such cases, the bulk properties are essentially isotro-
pic. Thus in each graphitic material, the size, shape, and degree of imperfection of the
basic crystallite, the general orientation of these crystallites, as well as the bulk char-
acteristics such as porosity and amount of impurities, may vary considerably from one
material to another. As a result, the properties of these various materials may show
considerable differences.
These carbons can be further subdivided into graphitizing and nongraphitizing car-
bons. In general these carbons are classified as soft carbons and hard carbons respectively.
As a guideline, soft carbons are derived from the liquid phase like coal tar or petroleum
pitch, and hard carbons are derived from the solid phase. Other forms of carbon, like car-
bon black or pyrolytic carbon, are obtained from the gas phase.

1.6 Synthetic Carbon and Graphite

The range of materials included under this heading consists of products of pyrolysis of
organic compounds at temperatures above 700°C and molded graphite. These carbons are
largely made up of substantially plane condensed aromatic layers, stacked roughly paral-
lel but may differ from natural crystalline graphite in the following important aspects:

• Interplanar spacing between d002 basal planes and mutual orientation of the layer
planes
• Dimension of the layer planes (La) and stack height (Lc), that is, the number (N) of
basal planes in the stack
• Density
• Missing carbon atoms in the layer planes
• Extrinsic atoms within the layer planes
• Defects in the layer planes, identified with the total pore size and pore volume
between the stacks

These structural differences lead to considerable departure in the properties from those
of single-crystal graphite in terms of electronic properties, transport properties, surface
properties, and chemical reactivity. This, however, offers the opportunity to tailor the
properties of carbon materials to suit the particular application.
Introduction to Carbon and Carbon Nanomaterials 21

Coke (75%–80%) Binder pitch (20%–25%)

Mixing/blending (~150°C)

Forming: include extrusion, molding (110°C–120°C)

Green compact

Baking/carbonization (800°C–1000°C)

Impregnation (impregnating pitch; ~225°C)

Densification

Graphitization (>2700°C)

FIGURE 1.16
The major processing steps in the production of conventional synthetic graphite.

1.6.1 Synthetic Graphite: Processing, Properties, and Applications

The carbon and graphite artifacts prepared by various processes (e.g., molding, extrusion,
chemical vapor deposition) can be defined as synthetic (or artificial) graphitic products. The
compaction process is carried out on a mixture of carbon filler and organic binder, which
is subsequently carbonized and graphitized generally up to a temperature of 1000°C and
>2500°C, respectively, in a vacuum or inert atmosphere. The basic process was invented by
E.G. Acheson, who produced the first molded graphite in 1896. The original applications
of molded graphite were electrodes for electric arc furnaces and cinema arc carbons for
movie projectors. Many improvements have been made over the years, and the applica-
tions have increased considerably in scope. Molded graphite is found in almost every cor-
ner of the industrial world and forms the base of the traditional graphite industry.
The major processing steps in the processing of a conventional polygranular graphite
consists of two phases—a filler material and a binder phase—and the process is summa-
rized schematically in Figure 1.16.

1.6.2 Filler
Carbons heat-treated to a condition where they are relatively pure are often referred to
as cokes. The predominant filler material is petroleum coke made by the delayed coking
process or pitch coke derived from coal tar.
Petroleum coke is the filler of choice in most applications. It is a porous by-product of the
petroleum industry and an almost-pure solid carbon at room temperature. It is produced by
destructive distillation without the addition of hydrogen, either by a continuous process (fluid
coking) or, more commonly, by a batch process (delayed coking). The product of the delayed
coker is green coke, which has seen a maximum temperature of about 450°C and contains a
high percent of volatile materials. This green coke is then calcined (thermally processed), that
22 Carbon Nanomaterials

is, heated to about 1300°C in an inert atmosphere to produce the calcined coke prior to being
crushed and blended. This is one of the most important feedstocks of graphite anode.
Another high-end filler is termed “needle coke.” A by-product of petroleum refining,
this type of coke can be prepared when the precursor pitch has a low concentration of
insoluble particles, so that only a few mesophase spheres are nucleated. A needle coke
initially breaks up into needles when mechanically ground, then into very small platelets
(~100 μ dia) like other coke.

1.6.3 Binder
The most common binder is coal tar pitch, which is a hard, brittle, and glassy material. It
is a by-product of metallurgical-coke production and is obtained by the distillation or heat
treatment of coal tar. Large-scale carbonization of hard coal to produce blast furnace coke
is performed at temperatures between 1000°C and 1200°C and residence time of 14 to 20 hr.
Beside coke as the main product (75 wt.%, relative to feed coal), coke oven gas, water, ben-
zene, ammonia, and crude tar are obtained. The pitch is removed from the tar distillation
plant in liquid form or after solidification after cooling with water. The tar yield accounts
for approximately 3–4 wt.% relative to feed coal. From 35 to 60 kg of pitch are produced
from every metric ton of coal.
Like a polymer or plastic, it has a specific softening point (SP) depending on its molecu-
lar weight. The as-produced pitch has a softening point around 70°C. However, for some
applications, pitches with higher SP are needed; so-called hard pitch, having a SP >150°C
can be produced from soft pitch by air blowing or thermal treatment under pressure and
subsequent removal of low boiling point constituents.
Coal tar pitch has wide molecular weight distribution ranging from approximately 200
to 3000 amu. Approximately 95% of the carbon occurring in coal tar pitch is present in the
form of aromatic compounds.
Both coal tar pitch and petroleum pitch are complex mixtures of numerous organic com-
pounds, predominantly polycyclic aromatic hydrocarbons (PAHs). In addition to PAHs
coal tar pitch also contains hetroaromatic compounds, whereas petroleum pitch is rela-
tively rich in alkyl-substituted PAHs.
The binder helps in plasticizing the filler coke particles so that they can be formed into
the desired shape. Commonly used forming processes include extrusion, molding, and
isostatic pressing. The binder phase is carbonized during the subsequent baking operation
(~1000°C). Mostly, engineering graphite is reimpregnated with impregnating grade pitch
(lower SP) to densify the carbon artifact followed by rebaking. A useful increase in density
and strength are obtained with up to 3–6 impregnation cycles.
The final stage of the manufacturing process is graphitization (2500°C–3000°C) during
which carbon atoms in the baked material migrate to form the thermodynamically more
stable graphite lattice.
The crystals in a manufactured, polygranular graphite are less than perfect with approx-
imately one layer plane in every six constituting a stacking fault.

1.6.4 Mesophase Pitch
Mesophase, a term originally suggested by Friedel, is the anisotropic liquid crystals formed
in the transformation of an isotropic aromatic parent liquid pitch to an anisotropic solid
coke mosaic texture. It is formed by thermal treatment of pitch at temperatures between
400°C and 500°C for 1 to 12 hours. It was Brooks and Taylor [6] and Mochida et al. [7] who
Introduction to Carbon and Carbon Nanomaterials 23

25 µ 25 µ
(a) (b)

FIGURE 1.17
(a) Isolated mesophase spheres in isotropic pitch matrix. (b) Transform of mesophares into pitch coke after heat
treatment to show flow texture.

proposed an explanation of growth of anisotropic features in cokes in terms of liquid crys-

tals shown in Figure 1.17.
In the early stages of formation, mesophase appears as symmetrical spheres (Figure
1.17a) in which planar molecules are arranged in equatorial configuration. The mesophase
spheroids range from about 2 μ to 100 μ. The normal or natural primary quinoline insolu-
ble (QI) concentrate (free carbons or particles) at the interface between mesophase spher-
oids prevents its further growth. However, removal of QI contents allows condensation to
take place, and large polyaromatic molecules are formed with a molecular weight averag-
ing 1000. These polycyclic, spherulitic liquid crystals gradually increase in size to build up
sufficient mutual van der Waals attraction to start promoting their alignment and form
pre-cokes or “green cokes.” The green cokes still retain from 6% to 20% volatile matter at
600°C. These volatiles are gradually removed when the temperature is raised. The coke so
formed shows optical birefringence characteristic of disk-like, nematic liquid crystals. A
typical flow texture of cokes is shown in Figure 1.17b.
The mesophase pitch besides being an important binder material acts as a precursor
to high modulus carbon fibers, mesocarbon microbeads, carbon dots, and high-density
­carbon–carbon composites.

1.6.5 Mixing and Blending

A blend of the proper particle sizes of the petroleum coke and crushed granular pitch is
blended in a mixer. A blend of about 75 wt.% of coke and 25 wt.% of pitch is generally used.
The mixing is carried out at about 150°C before it is fed to die molds or extrusion press
to make green compacts of desired size and shape. The binder coal tar pitch as obtained
from coal tar refining is not a single phase but contains solid dispersed matter, obtained
from gas phase pyrolysis of vapors. These are carbon black particles forming long chains
of agglomerates of 100 particles or 1 micron diameter carbon particles of agglomerates of
10. These primary QI contents (~3%–10%) have influence on rheological properties of pitch
and also on the quality of the baked product. For high-quality graphite products QI-free
(<1% QI) pitch is often used as binder.

1.6.6 Carbonization
Carbonization is basically a heating cycle. The general carbonization mechanism of poly­
aromatic hydrocarbons is relatively simple, since it proceeds by the rupturing of the
24 Carbon Nanomaterials

carbon–hydrogen bonds and the removal of the hydrogen. Some of these hydrocarbons
first go through an intermediate liquid or plastic stage that occurs at temperatures above
approximately 400°C–450°C.
The green molded artifact is heated slowly in a reducing or inert environment, over a
range of temperatures that varies with the nature of the particular binder and may extend
to 1250°C–1300°C. The organic material is decomposed into a carbon residue, and volatile
compounds diffuse out to the atmosphere. The process is complex and several reactions
may take place at the same time such as dehydrogenation, condensation, and isomeriza-
tion. The binder pitch also converts into coke and the carbon content of the residue is a
function of the nature of the precursor and the pyrolysis temperature. It usually exceeds
90 wt.% at 900°C and almost 99 wt.% at 1300°C.
Most of the synthetic graphite production is related to graphite electrodes. These elec-
trodes of a particular diameter (1–2 m) and length (8–10 m) are then carbonized at a very
slow heating rate up to a temperature of >2500°C in electrically heated furnaces. The bak-
ing may take from 20 to 60 days. The electrodes are removed, machined, and packed. After
the aluminum industry, the second largest user of baked carbon and graphite is the steel
industry.

1.6.7 Graphitization
Graphitization occurs in a series of steps that begin as the increasing temperature passes
the carbonization temperature, that is, ~1300°C. Hydrogen, sulfur, and other elements,
which might still be present after carbonization, are gradually removed, and, as the tem-
perature reaches 2000°C, essentially none remains. The weight loss during graphitization
is also attributed to the removal of interlayer chemical species, mostly interstitial carbon.
Over a fairly large range of HTT the interlayer spacing d002 is nearly equal to 0.344 nm,
which is characteristic of well-developed layer planes that are stacked parallel to each
other but are rotated at random with respect to each other, about the c-axis of the crystal-
lite. This random rotational arrangement of planes is termed turbostratic. However, mate-
rials with turbostratic crystallites are not graphite but carbon.
Above 1800°C, the conversion from a turbostratic structure to a graphitic structure
(shown in Figure 1.18) begins slowly at first then more rapidly as the temperature passes
2200°C. The gradual graphitization of the structure is readily confirmed by x-ray diffrac-
tion (Figure 1.18). If HTT exceeds a certain limit, for example, 10–15 minutes of treatment
above 2500°C, the following transformation takes place in the structure: (1) removal of
most defects within each graphite layer plane as well as between the planes, (2) gradual
shifting and growth of the crystallites, (3) removal of cross-linking bonds, (4) beginning of
the planes to stack into regular ABAB sequence of single-crystal graphite, and (5) shifting
of carbon rings or single atoms to fill vacancies and eliminate dislocations. The crystal-
lite size (La) increases from 5 nm, which is a typical size for turbostratic crystallites, to
approximately 100 nm or more [8]. At the same time, the interlayer spacing (d002) is reduced
from 0.344 nm to a minimum of 0.335 nm, which is the spacing of the graphite crystal. The
process is called graphitization.
The carbonization and graphitization processes are kinetic in nature, so the length of
time of application at HTT is also important. Most graphitizable materials (cokes) require
a temperature of 3000°C in order to reach full graphitization with a minimum value
(i.e., 0.3354 nm) of the interlayer spacing. At 3000°C, full graphitization is usually obtained
within 2 to 3 hours. Lower temperatures require considerably more time.
Introduction to Carbon and Carbon Nanomaterials 25

1100°K
1500°K
1700°K

2000°K

FIGURE 1.18
Schematic representation of the structural changes during the pyrolysis of carbonaceous polymers. A heat
treatment temperature beyond 2500°C results in growth of structure from amorphous to polycrystalline to
highly oriented parallel graphite planes with long-range order. (From H. Marsh and G. Griffith. New process
and New Applications. Proc. Int. Symp. on CARBON, Kagaku Gijitsu-sha, Toyohashi, Tokyo, Japan, p. 81, 1982.)

Many types of organic precursors do not graphitize when heat-treated. Even at 3000°C
the layer size, La, may not exceed 5 nm. All thermosetting polymers fall into this cat-
egory, forming disordered carbons with glass-like properties. Normally these materials
are porous because of the large quantity of gases evolved, much of it trapped in the pores.
This class of carbons is referred to as nongraphitizing, and is sometimes characterized as
glassy or vitreous.
Other forms of synthetic carbons are produced from gaseous phase and are termed
pyrolytic carbons. These carbons produced in the range of 1000°C to 1200°C by decompo-
sition of hydrocarbons show the development of faceting upon HTT >3000°C.
The world demand for the synthetic carbons is illustrated in Figure 1.19. The largest con-
sumption of graphite electrodes is in the steel and aluminum industries, whereas several
grades of carbon fibers find application in lightweight, high-strength composites for the
aerospace sector.

1.6.8 Structural Analysis of Carbons by X-Ray Diffraction

X-ray diffraction, the most important of the scattering techniques, has been used as a
dominant tool to study the structure of all types of carbon materials. For example, the line
width of the d002 reflections give the c-axis crystallite size Lc. The a-spacing or the in-plane
crystallite size is provided by study of the (100) diffraction line and its half width at half
maximum intensity. The observation of the (101) and (112) profiles provide information on
the interplanar correlation, since turbostratic graphite does not show well-defined (101)
and (112) diffraction lines, but rather shows “Bragg rods.”
26 Carbon Nanomaterials

Synthetic
graphite
Natural and other
synthetic 11%
graphite
powder
8%
Synthetic
graphite
electrode
Synthetic
42%
graphite
blocks
8% Synthetic
carbon
fibers
31%

% by graphite type

FIGURE 1.19
World graphite market. (From Ashbury Carbons.)

Figure 1.20 shows x-ray powder diffraction photographs showing increase in size of
graphite crystallites in cokes derived from pitch heat-treated at successively increasing
temperature. It is observed that as the crystallite size increases with an increase in HTT,
the corresponding diffraction rings become sharper, and many new lines corresponding
to hkl reflections appear as the graphitization approaches natural graphite.

1000°C

1200°C

1400°C

1600°C

1800°C

>2000°C

Artificial
graphite

Natural
graphite

(002) 100 (101) (102) 004 (103) (110) (112)

FIGURE 1.20
X-ray diffraction photographs of coke heat-treated to different temperatures. (Courtesy of H.P. Rooksby, Hirst
Research Centre, GEC, Wembley.)
Introduction to Carbon and Carbon Nanomaterials 27

Looking at the pattern, the following inferences can be drawn:

• The existence of a line or band near (002) suggests existence of parallel layers.
• Sharpening of this line and appearance of lines (00l) with higher index, i.e., (004)
and (006), suggest growth of crystal.
• Appearance of lines in hkl positions suggests emergence of three-dimensional
ordering

The individual reflection in the powder diffraction photograph in Figure 1.20 is labeled
with reference to x-ray powder diffraction records in Figure 1.21. Figure 1.21 shows the
x-ray diffraction record of the highly graphitized commercial sample [9].
Intensity of the strongest (002) peak is taken as 100% for comparison. Appearance of
the (112) peak at 2θ = 82°46′ suggests the three-dimensional ordering of the graphitic
structure.
The FWHM (B) and peak angles of the (002) and (100) peaks are used in a Scherrer
formula (Equation 1.5) to determine average crystallite thickness and average gra-
phene sheet diameter, respectively. Here t is the crystalline or graphene sheet dimen-
sion, λ is the wavelength of the x-ray source, θ is the scattering angle (in radians), and
κ is a constant:

κλ
t= (1.5)
(B cos θ)

Since there is a large difference in the structure of different carbons and some of the
carbons do not have three-dimensional crystalline state, two different forms of Scherrer
formula are used. For the dimension of turbostratic crystallites perpendicular to the gra-
phene sheets (Lc), (002) data is used and κ equals 0.9. For the dimension in graphene sheet
planes (La), (100) data is used and κ equals 1.84.

1800
002
Intensity (arbitrary units)

004

101

100 110

112
001
103 006 114

0
10 20 30 40 50 60 70 80 90 100 110 120
2θ (degrees)

FIGURE 1.21
X-ray diffraction pattern of heat-treated commercial graphite sample. X-radiation; λ CuKα = 1.5437Å. (From M.S.
Seehra, Interim report, West Virginia University, Morgantown, 1992. With permission.)
28 Carbon Nanomaterials

1.7 Pyrolytic Carbon and Graphite

The chemical vapor deposition (CVD) of carbon materials is not new. Its first practical
use was developed in the 1880s in the production of incandescent lamps to improve the
strength of filaments by carbon deposition and a patent was issued over a hundred years
ago, covering the basis of the CVD of carbon. Pyrolytic graphite is the only graphitic mate-
rial that can be produced effectively as a coating. The coating can be made sufficiently
thick and can be removed from the substrate as a free-standing object. Pyrolytic graphite
is a key element in the technology of coating specialty molded graphites, carbon foam,
carbon fibers, metals, and ceramics. It plays a major role in processing of carbon–carbon
components, such as high temperature crucibles, reentry heat shields, rocket nozzles, and
carbon–carbon brake discs.

1.7.1 Thermodynamics and Kinetics

The CVD of pyrolytic graphite can be optimized by experimentation. The carbon source
(hydrocarbon gas), the method of activating the decomposition reaction (e.g., thermal,
arc discharge or plasma, laser), and the deposition variables (e.g., temperature, pressure,
gas flow) can be changed until a satisfactory deposit is achieved. However, this empirical
approach may be too cumbersome and, for more accurate results, it is sometimes com-
bined with a theoretical analysis or modeling. Basically the CVD process is governed by
two factors: (1) thermodynamics, that is, the driving force that indicates the direction the
reaction is going to proceed; and (2) kinetics, which defines the transport process and is a
rate-determining step, that is, how fast it is going. Chemical thermodynamics is concerned
with the transfer of energy from one chemical system to another in accordance with the
first and second laws of thermodynamics. In the case of CVD, this transfer occurs when
the gaseous compounds, introduced in the deposition chamber, react to form the carbon
deposit and removal of by-products gases. The C/H ratio of the gas mixture (e.g., CH4 and
H2) entering the reaction chamber is an important factor to control the nature of the depo-
sition [10–12].

1.7.2 Isotropic and Laminar Deposits

The isotropic carbon has little graphitic characteristic and essentially no optical activ-
ity. It is composed of very fine grains without observable orientation and for this rea-
son, it is known as isotropic carbon rather than isotropic graphite. It is often obtained
in fluidized-bed deposition, possibly due to continuous surface regeneration by the
mechanical rubbing action of the bed. Generally, isotropic deposits are obtained at
higher temperatures (>1300°C), and laminar and columnar deposits are obtained at
lower temperatures.
It is reported that higher C/H ratios (1/4) favor laminar or columnar deposition, and
lower ratios (1/14) favor isotropic deposition.

1.7.3 Graphitization of Columnar and Laminar Deposits

The columnar and laminar deposits just described generally have a turbostratic structure
in the as-deposited condition, with a large interlayer spacing (~0.344 nm) as revealed by
Introduction to Carbon and Carbon Nanomaterials 29

x-ray diffraction. The material graphitizes readily when heat-treated at 2500°C for 1–2 hr.
The heat treatment at 2500°C causes the reordering of the structure. The various crystallite
imperfections, such as vacancies, stacking faults, dislocations, and rotational disorders,
tend to heal and disappear; the crystallite size La and Lc increases; and the (002) diffrac-
tion peak narrows considerably and becomes close to the position of the ideal graphite
line. The interlayer spacing (d002) decreases to approach that of the ideal graphite crystal
(0.3354 nm).
When columnar or laminar pyrolytic graphites are annealed above 2700°C, usu-
ally under a pressure of several atmospheres, further ordering and stress relieving of
the structure occur within each plane and between planes. The material is known as
highly oriented pyrolytic graphite (HOPG). It is soft and structurally close to the ideal
graphite crystal with an angular spread of the c-axes of crystallites of less than one
degree.
Unlike columnar and laminar pyrolytic deposits, isotropic carbon does not graphitize
readily and is, in this respect, similar to glassy or vitreous carbon. The d-spacing rarely
decreases below 0.344 nm. The crystallite size (Lc) also remains small.

1.8 Nano Forms of Carbon

Though carbon has been known for thousands of years, during the last three decades
three new forms of carbons have been discovered and the inventors of two of them (C60
and graphene) have won the Nobel Prize. Some of the novel nanostructures are illustrated
in Figure 1.22. The classical example of closed shell stabilization of carbon nanostructures
is the formation of C60 molecules and other fullerenes by electric arc evaporation of graph-
ite discovered by Smalley, Kroto, and Curl in the year 1985. Subsequently the team won the
Nobel Prize in chemistry in the year 1996. The diameter of a single C60 fullerene molecule
is 1.4 nm. Here stabilization is achieved by the formation of closed shell structures that
obviate the need for surface heteroatoms to stabilize the dangling bonds, as in the case of
bulk crystals of diamond and graphite.
Other forms of carbon are carbon nanotubes or elongated fullerenes, either closed at
both ends or only at one end. Although various carbon cages were studied, it was only
in 1991 when Iijima observed for the first time tubular carbon structures. The nanotubes
consisted of up to several tens of graphite shells, so-called multiwalled carbon nanotubes

Fullerene Carbon nanotube Graphene Carbon dot Nano-diamond

(CNT) (Cdot) (ND)

FIGURE 1.22
Nanoforms of carbon, from left, o-D fullerene, 1-D carbon nanotube, 2-D graphene, carbon dot, and
nanodiamond.
30 Carbon Nanomaterials

(MWCNTs) with adjacent shell separation of ~0.34 nm, diameters of ~1 nm, and a large
aspect ratio. Two years later Iijima and Ichihashi and Bethune et al. synthesized single-
walled carbon nanotubes (SWCNTs).
Nanocarbons, which have been obtained by controlling the structure in nanometer scale
as well as the bonding nature of carbon atoms, can provide the highly functional advanced
performances, which are difficult to obtain from conventional carbons.
Fullerenes and carbon nanotubes and graphene are unique in the larger family of
nanocarbon-­based materials as interrelated prototypes for zero-dimensional quantum
dots (fullerenes), one-dimensional quantum wires (CNT), and two-dimensional quantum
wells (graphene) (see Figure 1.22).
Likewise carbon nanotubes, which are capped at each end by half of fullerene (Semi
spherical sheet), have aroused great interest in the research community because of
their exotic electrical and mechanical properties. The unique properties of fullerenes
and carbon nanotubes described in the following chapters are expected to be of inter-
est for practical applications.
Early during his pioneering work, Bacon in 1960 synthesized graphite whiskers that he
described as scrolls, using essentially the same conditions as for the synthesis of carbon
nanotubes except for the use of helium pressures higher by an order of magnitude to
synthesize the scrolls. It is believed that the cross-sectional morphology of multiwalled
nanotubes and carbon whisker scrolls is different.
Vapor-grown carbon fibers, which were accidently found inside furnaces containing
hydrocarbon gases and CO for melting metals, are typically several nanometers in diam-
eter, several microns in length with a tubular microstructure. The formation of these fil-
aments at relatively low temperatures <1000°C, in presence of metal catalysts can be a
source of cheap high modulus carbon fibers for reinforcement in composites.
Carbon nano-onions (CNOs), which consist of concentric graphitic shells, represent
another new allotropic nanophase of carbon materials. CNOs have already been shown to
offer a variety of potential applications such as solid lubrication, electromagnetic shield-
ing, fuel cells, heterogeneous catalysis, gas and energy storage, and electro-optical devices
owing to their outstanding chemical and physical properties. According to a recent study,
CNOs can also be used to produce ultrahigh-power micrometer-sized supercapacitors due
to their accessible external surface area for ion adsorption.
Direct current (DC) arc discharge between graphite electrodes is one of the versatile
processes to produce a variety of carbon nanomaterials besides fullerenes and carbon
nanotubes. These include different forms of carbon nanostructures like carbon soot, car-
bon nanoshells, metal encapsulated carbon shells, sea urchins, bucky onions, helical coils,
spinning cones, and nanohorns.
Formation of carbon nanoshells during the arc discharge process demonstrates that
it is possible to encapsulate metal nanoparticles inside the shells for potential applica-
tions in magnetic nanoparticles as data storage, ferrofluids, confinement of radioactive
waste, and targeted drug delivery nanocapsules. A host of publications on this aspect
are available.

1.8.1 Quantum Confinement in Carbon Nanomaterials

In bulk semiconductors the wave vector k can take a very large number of values in gen-
eral. Therefore, available density of states is very large in the directions of kx, ky, and kz.
However, there is quantization of energy levels if one of the dimensions become in the
Introduction to Carbon and Carbon Nanomaterials 31

range of the de Broglie wavelength of thermal electrons, the energy levels transform from
continuum to discrete, and the wavelength λB is given by

h h
λB = = (1.6)
p 2m * E

where h is Planck’s constant, p is the electron momentum, m* is the electron effective mass,
and E is the energy. The wavelength λB is typically on the order of tens of nanometers
for carriers with typical thermal energy. The spatial confinement of the carriers in lower
dimensional semiconductors leads to dramatically different energy–momentum rela-
tions in the directions of confinement, which results in a completely new density of states,
compared to the bulk case, as depicted in Figure 1.23. The density of states is no longer
continuous or quasi-continuous (Figure 1.23a) but becomes quantized, and the energy–
momentum relations dramatically transform into subbands. Therefore, if one of the
dimensions of a semiconductor is comparable to, or less than λB, the electrons will be con-
fined to two dimensions and behave as charge carriers in a quantum well (QW) structure.
In case of graphene, like in thin sheet, the confinement of electron is in z-direction and
the allowed values of k become highly discretized. As shown in Figure 1.23b, for cer-
tain values of kz the density of states remain constant and it follows in steps (conduction
staircase).
In case of carbon nanotubes these can be treated as quantum wire (QWR), which is a
one-dimensional confined structure in the sense that the carrier movement is free in one
dimension (i.e., along the length of the tube) and confined in two others (i.e., along the
diameter of the tube) (x-y graphene plane in an unzipped nanotube). Figure 1.23c shows
the density of states for such structures. These nanotubes are characterized by a number
of singularities where each peak corresponds to a single quantum subband.
Finally, a quantum dot in the present case, is a nanostructure in which the electron and
hole movement is confined in all three dimensions. Quantum dots are thus tiny clusters of
semiconductor material having all three dimensions of only a few nano­meters. In the case
of quantum dots, the charge carriers occupy only a restricted set of energy levels rather
like the electrons in an atom and the valence and conduction bands have sharp energy

Bulk Quantum well Quantum wire Quantum dot

3D 2D 1D 0D
D(E)

D(E)

D(E)

D(E)

Eg E EgE1 E2 E Eg E11 E12 E13 E Eg E111 E112 E113 E

(a) (b) (c) (d)

FIGURE 1.23
Schematic diagram illustrating the representation of the electronic density of states in conduction band depend-
ing on dimensionality. (a) 3D graphite, (b) graphene, (c) carbon nanotubes, and (d) carbon nanodot.
32 Carbon Nanomaterials

levels as shown in Figure 1.23d. For this reason, quantum dots are sometimes referred to
as “artificial atoms.” It is important to stress, however, that quantum dots actually contain
hundreds of thousands of atoms.
The confinement of electrons to lower dimensional structures results in completely new
optoelectronic properties, compared to bulk graphite. Importantly it is basically the den-
sity of states that decides the performance of the device.

1.8.2 Raman Spectroscopy of Nanocarbons

Raman spectroscopy is the inelastic scattering of light by matter. Being highly sensitive to
the physical and chemical properties of the materials, it has become one of the most impor-
tant tools for nanoscience and technology. Raman spectra are very sensitive to changes
that break the translational symmetry. For this reason Raman spectroscopy is most sen-
sitive to highly symmetric covalent bonds with little or no natural dipole moment. The
carbon–­carbon bonds that make up these materials fit this criterion perfectly and as a
result Raman spectroscopy is highly sensitive to these materials and able to provide a
wealth of information about their structure.
Historically the spectroscopy played an important role in the study and characteriza-
tion of graphite materials, being largely used over the last four decades to characterize
pyrolytic graphite, carbon fibers, fullerenes, glassy carbons, nanographite ribbons, and
graphene. For sp2 nanocarbons such as graphene and carbon nanotubes, Raman spectros-
copy can give information about crystallite size, clustering of the sp phase, the presence
of sp2–sp3 hybridization and other crystal disorders, number of graphene layers, nanotube
diameter, chirality, and so on. It can also account for the introduction of chemical impuri-
ties, doping defects, and finally metallic versus conducting behavior.
Every band in the Raman spectrum corresponds directly to a vibrational frequency of a
bond within the molecule. The vibrational frequency and hence the position of the Raman
band is very sensitive to the orientation of the bonds and the weight of the atoms at either
end of the bond.
In the case of diamond, where the material consists of highly uniform C–C bonds in a
tetrahedral crystal structure, the Raman spectrum is very simple (Figure 1.24) [13]. It con-
sists only of a single band because all of the bonds in the crystal are of the same orientation
and strength, resulting in a single vibrational frequency.
The Raman spectrum of crystalline graphite is marked by the presence of strong peaks
due to sp2-bonded carbon in planar sheets in which the bond energy of sp2 is higher than
the sp3 bond in diamond. The two prominent peaks are centered at 1580 and 2700 cm–1 and
known as G and G′ bands, respectively, where the “G” label refers to graphite.
The G band is a first-order Raman allowing feature originating from the zone center
(phonon wave vector q = 0), corresponding to in-plane E2g2 optic modes. The G′ band
(~2700 cm–1) is a second-order (two phonons) feature that allows exploration of q = 0 phonons.
In the Raman spectra obtained with samples with small crystallite size La ~0.5 micro­
meter, that is smaller than the wavelength of light, the presence of an additional dispersive
peak centered at approximately 1350 cm–1 is observed when using lower excitation at
2.1 eV (414 cm–1). The feature is assigned to the breathing of the carbon hexagons that become
Raman active at the border of the crystallite areas owing to the loss of translation symmetry.
The frequency of this feature is about half of the second-order G′ frequency and is related
to the phonon of the first-order process of G′ peak.
Since the peak at ~1350 cm–1 is observed in the presence of defects in an otherwise per-
fect infinite graphite structure, it has been named as the D band (D for defect or disorder).
 Diamond
30,000 Diamond band

20,000

10,000

Raman intensity (cps)

0
800 Graphite on silicon substrate

600 G band—known
Introduction to Carbon and Carbon Nanomaterials

as the graphite or
tangential band
400
Silicon

Raman intensity (cps)

200

3500 3000 2500 2000 1500 1000 500

Raman shift (cm–1)

FIGURE 1.24
Raman spectra of diamond and of a sample of graphite on a silicon substrate. (From J. Hodkiewicz, Thermo Scientific Application Note 51901 (2010).)
33
34 Carbon Nanomaterials

This disorder refers to the crystallite boundary and the ratio ID/IG provides a parameter
that can be used for quantifying disorder.
Another disorder-induced band centered at 1620 cm–1 is usually obtained in the Raman
spectra of disordered graphitic materials, although with smaller intensity than the D band.
This feature has been named the D′ band and also depends on the crystallite size La and
Elaser.
Fullerenes are essentially hollow carbon shells of various size. The most well known of
these is a 60-carbon atom unit called buckminsterfullerene or C60. There are many other
fullerenes with a few to many hundred carbon atoms. Figure 1.25 compares the spectra of
C60 and C70 [13]. The main feature of the C60 spectrum is a relatively sharp line at around
1462 cm–1, known as the pentagonal pinch mode. This tells us that C60 is composed of sp2-
bonded carbon. The sharpness of the band also tells us that the bonds are for the most part
very uniform in nature. In contrast the spectrum of C70 is littered with numerous bands.
These are due to reduction in molecular symmetry, which results in more Raman bands
being active.
Graphene is the fundamental building block of many important carbon materials includ-
ing graphite. Graphite consists of stacks of sp2-bonded planar graphene sheets. When
comparing Raman spectra of graphene and graphite, at first glance the spectra look very
similar. However, there are some signature differences as we can see from Figure 1.26 [13].
The most obvious is the difference in the band at 2700 cm–1, which is known as the G′ band.
It is much more intense than the G band in graphene compared to graphite. The G′ band is
also referred to as the 2D band; both 2D and G′ are accepted names for this band. Upon a
closer look at shape and the position of the G′ band in these two materials one can see that
both the shape of the band and the position are different.
The peak shift in graphite is a result of interaction between the stacked graphene layers,
which has a tendency to shift the bands to higher frequency. The G′ band in a single layer
graphene spectrum fits to a single band, whereas curve fitting reveals several underlying
bands in the graphite spectrum. These bands are a result of the different interlayer interac-
tions that occur at different depths within the graphene.
When the bond lengths and angles of graphene are modified by strain, caused by the
interaction with a substrate or with other graphene layers or due to external perturbations,
the hexagonal symmetry of graphene is broken. The G band is therefore highly sensitive
to strain effects in sp2 nanocarbons and can be used to probe any modification to the flat
geometric structure of graphene, such as the strain induced by external forces.
Curvature effects in carbon nanotubes give rise to multiple peaks in the G band spec-
trum for a SWCNT. Figure 1.27 shows the Raman spectrum of SWCNT in which we can
see well-defined G and G′ bands as they are in graphene and graphite [13]. We also see a
prominent band around 1350 cm–1 from a hybridized vibrational mode associated with
graphene edges and it indicates the presence of some disorder to the graphene structure.
The band is often referred to as the disorder or D band, and its intensity relative to that of
the G band is often used as a measure of the quality of carbon nanotubes.
There is another series of bands appearing at the low frequency end of the spectrum
known as radial breathing mode or RBM bands. The RBM bands are unique to SWCNTs
as the name suggests, corresponding to the expansion and contraction of the tubes. The
frequency of these bands can be correlated to the diameter of the SWCNTs and they can
provide important information on their aggregation state.
MWCNTs have very similar spectra to those of SWCNTs, as is apparent from Figure
1.27. The primary differences are the lack of RBM modes in MWCNTs and a much more
prominent D band. The RBM modes are not present because the outer tubes restrict the
 C60 (buckyballs)
600
500
400
300
200

Raman intensity (cps)

100

120 C70

100
Introduction to Carbon and Carbon Nanomaterials

80

60

40

Raman intensity (cps)

20

2000 1500 1000 500

Raman shift (cm–1)

FIGURE 1.25
Raman spectra of two fullerenes C60 and C70. (From J. Hodkiewicz, Thermo Scientific Application Note 51901 (2010).)
35
 36

Graphene on Si substrate
150

100

50

Raman intensity (cps)

Graphite
600

500 G´ G
400

300

200

Raman intensity (cps)

100

3500 3000 2500 2000 1500

Raman shift (cm–1)

FIGURE 1.26
Comparison of Raman spectra of graphene and graphite. (From J. Hodkiewicz, Thermo Scientific Application Note 51901 (2010).)
Carbon Nanomaterials
 400 SWCNT (1.0–2.5 nm diameter)
300

Int
200
100

DWCNT (~4 nm diameter)

30

20

Int
G D RBM
10

0
Introduction to Carbon and Carbon Nanomaterials

MWCNT (CT 20–30 nm diameter)

Int
50

0
3500 3000 2500 2000 1500 1000 500
Raman shift (cm–1)

FIGURE 1.27
Comparison of Raman spectra of SWCNTs, DWCNTs, and MWCNTs. (From J. Hodkiewicz, Thermo Scientific Application Note 51901 (2010).)
37
38 Carbon Nanomaterials

breathing mode. The more prominent D band in MWCNTs is to be expected to a certain

extent given the multilayer configuration and indicates more disorder in the structure.
Notice that the RBM mode completely disappears as we go to a double wall tube and that
the D band G′ bands get proportionately larger as we add layers to the walls of the tubes.
Nanostructured materials have gained tremendous industrial and academic interest in
the last two decades due to their potential applications in super strong composites, field
emitters, paints, Li battery, fuel cell, super capacitors, hydrogen storage, antibacterial and
drug delivery systems, quantum wires, nanoelectronics, smart sensors, catalyst support,
and fundamental and basic research. However, if this promise is to be realized nothing
less than a complete revolution in the synthetic strategies available for materials produc-
tion may be necessary. This new area of materials science, therefore, presents one of the
greatest technical challenge of the 21st century.

References
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2. A. Maffucci and G. Miano. Electrical properties of graphene for interconnect applications.
Applied Sciences 4, no. 2 (2014): 305–317.
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Introduction to Carbon and Carbon Nanomaterials 39

Further Reading
Following is a partial list of some of the important literature available dealing with the
broad subject of carbon.

Burchell, T.D. ed. Carbon Materials for Advanced Technologies. Elsevier Science Ltd., Oxford, 1999.
Donnet, J.B. and Andries Voet. Carbon Black. Marcel Dekker, New York, 1976.
Donnet, J.B., T.K. Wang, S. Rebouillat, and J.C.M. Peng, eds. Carbon Fibers, 3rd ed. Marcel Dekker,
1998.
Dresselhaus, M.S., G.S. Dresselhaus, K. Sugihara, I.L. Spain, and H.A. Goldberg. Graphite Fibers and
Filaments. Springer-Verlag, New York, 1988.
Figueiredo, J.L., C. Bernardo, R.T.K. Baker, and K.J. Huttinger, eds. Carbon Fibers, Filaments and
Composites. Kluwer Academic, The Netherlands, 1989.
Fischbach, D.B. and A. Pacault. The kinetics and mechanism of graphitization, in Chemistry & Physics
of Carbon, vol. 7. Marcel Dekker.
Fitzer, E. and L.M. Manocha. Carbon Reinforcement and Carbon/Carbon Composites. Springer-Verlag,
New York, 1998.
Jenkins, G.M. and K. Kawamura. Polymeric Carbons. Cambridge Press, Cambridge, 1976.
Kelly, B.T. and R. Taylor. The thermal properties of graphite, in Chemistry & Physics of Carbon, vol. 10.
Marcel Dekker.
Mantell, C.L. Carbon and Graphite Handbook. Interscience, New York, 1968.
Marsh, H., E.A. Heintz, and F. Rodriguez-Reinoso, eds. Introduction to Carbon Technologies. University
of Alicante, Secretariado de Publications, Spain, 1997.
Ruland, W. X-ray diffraction studies of carbon and graphite, in Chemistry & Physics of Carbon, vol. 4.
Marcel Dekker.
Savage, G. Carbon-Carbon Composites. Chapman & Hall, 1993.
Spain, I.L. Electronic transport properties of graphite, carbons and related materials, in Chemistry &
Physics of Carbon, vol. 16. Marcel Dekker.
Zabel, H. and Solin, S.A. eds. Graphite Intercalation Compounds, vols. I and II. Springer 1990 and 1992.
References

1 1: Introduction to Carbon and Carbon

Nanomaterials

1. J. Bernal. The structure of graphite. Proceedings of the

Royal Society of London. Series A, Containing Papers of a
Mathematical and Physical Character 106, no. 740 (1924):
749–773.

2. A. Maffucci and G. Miano. Electrical properties of

graphene for interconnect applications. Applied Sciences
4, no. 2 (2014): 305–317.

3. I.E. Abbott. Graphene: Exploring carbon flatland.

Physics Today 60, no. 8 (2007): 35.

4. I.L. Spain. Electronic transport: Properties of

graphite, carbons, and related materials. Chemistry and
Physics of Carbon 16 (1981): 119–304.

5. G. Jenkins, K. Kawamura, and L. Ban. Formation and

structure of polymeric carbons. Proceedings of the Royal
Society of London A: Mathematical, Physical and Engineering
Sciences, The Royal Society, 1972, pp. 501–517.

6. J. Brooks and G. Taylor. The formation of graphitizing

carbons from the liquid phase. Carbon 3, no. 2 (1965):
185, IN9, 187–186–IN 18–193.

7. I. Mochida, Y. Korai, C.-H. Ku, F. Watanabe, and Y.

Sakai. Chemistry of synthesis, structure, preparation and
application of aromatic-derived mesophase pitch. Carbon 38,
no. 2 (2000): 305–328.

8. H. Marsh and G. Griffith. New process and new

applications. Proc. Int. Symp. on CARBON, Kagaku
Gijitsu-sha, Toyohashi, Tokyo, Japan (1982), p. 81.

9. M.S. Seehra. Interim Report. West Virginia University,

Morgantown, 1992.

10. R. Baker. Catalytic growth of carbon filaments. Carbon

27, no. 3 (1989): 315–323.

11. N.M. Rodriguez. A review of catalytically grown carbon

nanofibers. Journal of Materials Research 8, no. 12
(1993): 3233–3250.

12. G.G. Tibbetts. Why are carbon filaments tubular?

Journal of Crystal Growth 66, no. 3 (1984): 632–638.

13. J. Hodkiewicz. Characterizing carbon materials with

Raman spectroscopy. Thermo Scientific Application Note
51901 (2010).

Further Reading

Following is a partial list of some of the important

literature available dealing with the

broad subject of carbon.

Burchell, T.D. ed. Carbon Materials for Advanced

Technologies. Elsevier Science Ltd., Oxford, 1999.

Donnet, J.B. and Andries Voet. Carbon Black. Marcel Dekker,

New York, 1976.

Donnet, J.B., T.K. Wang, S. Rebouillat, and J.C.M. Peng,

eds. Carbon Fibers, 3rd ed. Marcel Dekker, 1998.

Dresselhaus, M.S., G.S. Dresselhaus, K. Sugihara, I.L.

Spain, and H.A. Goldberg. Graphite Fibers and Filaments.
Springer-Verlag, New York, 1988.

Figueiredo, J.L., C. Bernardo, R.T.K. Baker, and K.J.

Huttinger, eds. Carbon Fibers, Filaments and Composites.
Kluwer Academic, The Netherlands, 1989.

Fischbach, D.B. and A. Pacault. The kinetics and mechanism

of graphitization, in Chemistry & Physics of Carbon, vol.
7. Marcel Dekker.

Fitzer, E. and L.M. Manocha. Carbon Reinforcement and

Carbon/Carbon Composites. Springer-Verlag, New York, 1998.

Jenkins, G.M. and K. Kawamura. Polymeric Carbons. Cambridge

Press, Cambridge, 1976.

Kelly, B.T. and R. Taylor. The thermal properties of

graphite, in Chemistry & Physics of Carbon, vol. 10.
Marcel Dekker.

Mantell, C.L. Carbon and Graphite Handbook. Interscience,

New York, 1968.

Marsh, H., E.A. Heintz, and F. Rodriguez-Reinoso, eds.

Introduction to Carbon Technologies. University of
Alicante, Secretariado de Publications, Spain, 1997.
Ruland, W. X-ray diffraction studies of carbon and
graphite, in Chemistry & Physics of Carbon, vol. 4. Marcel
Dekker.

Savage, G. Carbon-Carbon Composites. Chapman & Hall, 1993.

Spain, I.L. Electronic transport properties of graphite,

carbons and related materials, in Chemistry & Physics of
Carbon, vol. 16. Marcel Dekker.

Zabel, H. and Solin, S.A. eds. Graphite Intercalation

Compounds, vols. I and II. Springer 1990 and 1992.
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Further Reading

Donnet, J.-B. Fifty years of research and progress on

carbon-black. Carbon 32 (1994): 1305–1310.
Donnet, J.-B., R.C. Bansal, and M.-J. Wang. Carbon Black,
2nd ed. Marcel Dekker, 1993.

Harris, P.J.F. New perspectives on the structure of

graphitic carbons. Critical Reviews in Solid State and
Materials Sciences 30 (2005): 235–253.

Harris, S.J. and A.M. Weiner. Chemical kinetics of soot

particle growth. Annual Review of Physical Chemistry 36
(1985): 31–52.

Palmer, H.P. and C.F. Cullis. The formation of carbon from

gases. In Chemistry and Physics of Carbon, vol. 1, edited
by P.L. Walker, 265. Marcel Dekker, 1965.