CARBON SCIENCE AND TECHNOLOGYE docx

CARBON ALLOYS
NOVEL CONCEPTS
TO
DEVELOP CARBON
SCIENCE AND TECHNOLOGY
E. YASUDA,
M.
INAGAKI,
K.
KANEKO,
0,
A. OYA
&
Y. TAN
ELSEVIER


CARBON
ALLOYS
Novel
Concepts to Develop Carbon
Science and Technology
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CARBON
ALLOYS

Novel Concepts
to
Develop
Carbon
Science and Technology
Edited
by
Ei-ichi YASUDA
Michio INAGAKI
Katsumi
KANEKO
Morinobu END0
Asao
OYA
Yasuhiro
TANABE
2003
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V
Contents

Preface

xiii
Part
1
.
Introduction
Chapter
1
.
Introduction

3
1
AShortHistory

3
2
CarbonFamily

5
3
CarbonAlloys

9

References

11
Ei-ichi Yasuda
and
Michio Inagaki
Part
2
.
Space Control in Carbon
Alloys
Chapter
2
.
Hybrid Orbital Control in Carbon Alloys

15
Hybridization in a Carbon Atom

15
2
Defect
StatesandModificationsof
theHybridization

27
Spectroscopies for
sp”
Structure

33
4 Conclusions

38
References

38
Atomic and Molecular Scales

41
1
.
Introduction 41
2
.
Intercalation Compounds 42
Insertion
of
Li Ions into the Disordered Carbon Materials

44
4 Substitution
of
Heteroatoms

46
5
Metal-doped Fullerenes

49

Metal-doped Carbon Nanotubes

50
7 Conclusions

54
Chapter
4
.
Surface and Hidden Surface-controlled Carbon Alloys

57
Materials

57
Carbon Structure
of
Superhigh Surface Area

64
Design of Hidden Surfaces with Alloying

65
Riichiro Saito
1
3
Chapter
3
.
Structural Design and Functions of Carbon Materials by

Alloying
in
Morinobu
Endo. Takuya Hayashi, YoongAhm
Kim.
Hiroaki Ohta and
Sung Wha Hong


3
6
References 54
Katsumi Kaneko
1
2
3

Importance
of
Hidden Surfaces and Confined Spaces
in
Carbon
vi
Contents
4
5
Properties of Hidden Surface-
or
Pore Space-alloyed Carbons

68
Design of New Porous Carbon with Carbon Alloying Technique

76
References

77
Chapter
5
.
Control of Interface and Microstructure in Carbon Alloys

83
1
Introduction

83
2
Interface Control

85
3
Microstructure Control

89
4
Conclusion

93
References

93
Yasuhiro Tanabe and Ei-ichi Yasuda
Part
3
.
Typical Carbon Alloys and Processing
Chapter
6
.
Intercalation Compounds

99
1
Introduction

99
Li-insertion into Carbon Materials

100
Carbon Materials

103
Alkali Metals

104
Boehmite with Layered Structure

105
6

Conclusion

105
References

106
Chapter
7
.
Porous Carbon

109
1
Introduction

109
Control of Pore Structure

110
Performance
of
Advanced Porous Carbon

118
4 Conclusions.

123
References

124

Noboru
Akzuawa
2
3
4
5
New Intercalation Compounds Prepared from Unique
Host
Host Effect on the lntercalation
of
Halogen Molecules and
Physical Properties of MC1,. GICs and Alkyl Derivative
of
Takashi Kyotani
2
3
Chapter
8
.
Polymer Blend Technique €or Designing Carbon Materials

129
Asao
@a
2
.
3
5
1
.

Introduction

129
Porous Carbon Materials

129
4 Carbon Nanofibers and Carbon Nanotubes

133
Other Fibrous Carbon Materials with Unique Shapes

139
6
Conclusions

141
References

141
Preferential Support
of
Metal Particles on Pore Surface

131
Part
4
.
The Latest Characterization Techniques
Chapter
9

.
Computer Simulations

145
Shinji Tsuneyuki
1
Methods.,

145
vii
2 Applications

150
3 Conclusions

156
References

156
Chapter
10
.
X-ray Diffraction Methods to Study Crystallite Size and Lattice
Constants of Carbon Materials

161
1
.
Introduction

161
Measurement Method (JSPS Method)

162
Temperatures

170
References

173
Scattering

175
1
.
Introduction

175
Fundamentals of Small-Angle X-ray Scattering

176
3 Analyses

180
Examples of Structure Determination

183
References

187

Minoru Shiraishi and Michio Znagaki
2
3
Characterization of Carbonized Materials Heat-treated at
Low
Chapter
11
.
Pore Structure Analyses
of
Carbons by Small-Angle X-ray
Keiko Nishikawa
2
.
4
Chapter 12
.
XAFS
Analysis and Applications to Carbons and Catalysts

189
Hiromi Yamashita
1
Introduction

189
2 XAFSAnalysis

190
Applications to Carbon Related Materials and Catalysts

200
XAFS
in the Future

207
References

207
3
4
Chapter 13
.
X-Ray Photoelectron Spectroscopy and its Application to Carbon
.
211
Noboru
Suzuki
2
3
1
Introduction and XPS

211
Cls Binding Energy

212
Application to Carbon Materials

212

References

220
Chapter 14
.
Transmission Electron Microscopy

223
1
Introduction

223
Materials Characterization by Means of TEM

223
Specimen Preparation by FIB

231
In-Situ Heating Experiment

235
References

238
Characterization
of
Carbon Materials

239
1

Introduction

239
Basic Principles of
EELS
and Instrumentation

240
Hiroyasu Saka
2
3
4
Chapter
15
.
Electron Energy-Loss Spectroscopy and its Applications to
Hisako Hirai
2

VI11
Contents
3
4
Applications to Characterizing Carbon Materials

249
5
.
Conclusions: The Future of EELS

254
References

255
The Energy-Loss Spectrum

242
Chapter
16
.
Visualization
of
the Atomic-scale Structure and Reactivity of
Metal Carbide Surfaces Using Scanning Tunneling Microscopy

257
Ken-ichi
Fukui,
Rong-Li Lo and Yasuhiro Iwasawa
1
Introduction

257
2
Principle
of
Scanning Tunneling Microscopy
(STM)

259

3
Preparation
of
Mo, C Surfaces

259
4
Visualization of the Atomic-scale Structure and Reactivity
of
Molybdenum Carbide Surfaces by STM

260
5
Conclusions and Future Prospects

265
References

266
Chapter
17
.
Infra-Red Spectra. Electron Paramagnetic Resonance. and Proton
Magnetic Thermal Analysis

269
Osamu Ito. Tadaaki Ikoma and Richard Sakurovs
1
Infra-Red (IR) Spectra

269
2
EPR

276
3
Proton Magnetic Resonance Thermal Analysis (PMRTA)

281
References

283
Chapter
18
.
Raman Spectroscopy as a Characterization
Tool
for Carbon
Materials

285
Masato Kakihana and Minoru Osada
1
Introduction

285
2
Raman Spectra of Carbon Materials

288

3
Remarks about Raman Measurements

290
4
Recent Raman Studies
of
Carbon Materials

292
References

297
Chapter
19
.
Basics of Nuclear Magnetic Resonance and its Application to
Carbon Alloys

299
Takashi Nishizawa
1
Introduction

299
2
Apparatus

299
3

Basics
of
NMR for Spin
112
Nucleus

300
4
Characterization
of
Pitch

308
5
Solid-state 'Li-NMR

313
References

318
Chapter
20
.
Gas Adsorption

319
Yohko Hanzawa and
Katsumi
&neb
1

Adsorption, Absorption. Occlusion and Storage

319
2
Classification
of
Pores and Porosity

320
3
Selection of an Adsorbate Molecule

321
4
Surface Structure and the Adsorption Isotherm

324
ix
References

331
Chapter 21
.
Electrochemical Characterization of Carbons and Carbon Alloys
.
335
Tsuyoshi Nakajima
1
Introduction

335
2 Characterization Techniques

336
3 Electrochemical Characterization
of
Carbon Alloys

340
4
Conclusions

349
References

349
Mototsugu Sakai
1
Introduction

351
2 Theoretical Considerations

353
3 Experimental Details

360
4 Application to Carbon-related Materials

364

5
Concluding Remarks

380
References

382
Chapter 23
.
Magnetism
of
Nano-graphite

385
Toshiaki Enoki. Bhagvatula
L .
K
Prasad, Yoshiyuki Shibayama.
Kazuyuki Takai and Hirohiko Sat0
1
Introduction

385
2
Conversion from Diamond to Graphite in Nano-scale Dimension
.
.
386
3 Nano-graphite Network

389
4
Fluorinated Nano-graphite

392
References

393
Alloys

395
2
BackgroundfortheMagnetoresistanceMeasurement

395
3 Measurement of Magnetoresistance

400
High-Quality Graphite Film from Aromatic Polyimide Film

403
5
NegativeMagnetoresistanceinBoron-dopedGraphites

409
Chapter 22
.
Mechanical Probe for Micro-mano-characterization

351

Chapter
24
.
Magnetoresistance and its Application to Carbon and Carbon
Yoshihiro Hishiyama
1
Introduction

395
4
Application of Magnetoresistance Technique for Synthesis
of
References

413
Part
5
.
Function Developments and Application Potentials
Chapter 25
.
Applications of Advanced Carbon Materials to the Lithium Ion
Secondary Battery

417
2 Characteristics of Li-ion Secondary Battery

420
Carbon and Graphite Host Materials

420
Lithium/Graphite Intercalation Compounds

421
Voltage Profiles of Carbon Electrodes

424
Effect of Microstructure of Carbon Anode on the Capacity

426
Morinobu Endo and
Yoong
Ahm Kim
1
Introduction

417
3
4
5
6
X
Contents
7
Li Storage Model

430
8
Conclusions

431
References

432
Chapter
26
.
Electrochemical Functions

435
Mikio Miyake
1
2
3
4
Features of Carbon Materials as Electrodes

435
Electrochemical Reactions on Carbon

436
Electrochemical Behavior
of
Various Carbons

439
Application of Carbon Electrodes

441
References

444
Chapter
27
.
Electric Double Layer Capacitors

447
1
Introduction.

447
Capacitance

449
DoubleLayerCapacitanceof
Other CarbonMaterials

454
4
Conclusion

456
References

456
Chapter28
.
FieIdElectronEmissionsfromCarbonNanotubes

459
1
Introduction

459
FEM Study of Nanotubes

460
Nanotube-based Display Devices

465
References

468
Chapter
29
.
Gas Separations with Carbon Membranes

469
Katsuki Kusakabe and Shigeham Morooka
1
Properties
of
Carbon Membranes

469
2
Preparation
of

Carbon Membranes

472
3
PermeancesofMolecularSievingCarbonMembranes

474
4
Oxidation
of
Molecular Sieving Carbon Membranes

478
5
Separation Based on Surface Flow

480
6
Conclusions

481
References

481
Chapter
30
.
Property Control
of
Carbon Materials by Fluorination

485
Hidekazu Touhara
1
Introduction

485
2
Control
of
Carbon Properties by Fluorination

486
3
Alloying by Fluorination

487
References

497
Highly Active Catalyst for Reduction of Nitric Oxide (NO)

499
Kouichi Miura and Hiroyuki Nakagawa
1
Introduction

499
2
Sample Preparation

500
Soshi Shiraishi
2
3
Influence
of
Pore Size Distribution
of
ACFs on Double Layer
Yahachi Saito, Koichi Hata and
Sashiro
Uemura
2
3
The Chemistry of Carbon Nanotubes with Fluorine and Carbon
Chapter
31
.
Preparation of Metal-loaded Porous Carbons and Their Use as a
xi
3 Carbonization Behavior
of
the Resins

501
4 Characterization
of
Metal Loaded Porous Carbons

502
5
Nitric Oxide Decomposition
on
Metal Loaded Porous Carbons

504
6 Conclusions

512
References

512
Chapter32
.
FormationofaSeaweedBedUsingCarbonFibers

515
Minoru
Shiraishi
1
Introduction

515
2 Rapid Fixation
of
Marine Organisms

515
3

Food Chain Through a Carbon Fiber Seaweed Bed

518
4
Formation of an Artificial Bed
of
Seaweed Using Carbon Fibers

519
References

521
Chapter 33
.
Carbodcarbon Composites and Their Properties

523
Tatsuo
Oh
1
Introduction

523
2
Carbon Fibers and Carbon Coils

524
3 Novel Materials and Control
of
Micro-structures

527
4
and Microstructures

531
5
Fracture and its Mechanism

538
6
Microstructure Observation

542
7
Concluding Remarks

542
References

543
Chapter
34
.
Super-hard Materials

545
1
Super-hard Materials

545
2 Diamond-like Carbon

546
3 CarbonNitride

552
Boron Carbonitride (BxCyNz)

556
References

557
Contributing authors

559
Subject index

563
Improvement
of
Properties and Correlation Between Properties
Osamu
Takai
4
5
Conclusion 557


xiii

Carbon is a unique material having diversity
of
structure and property. The concept of
“Carbon Alloys” was initiated in Japan as a national project and is now recognized
internationally. Carbon Alloys are defined as being materials mainly composed
of
carbon materials in multi-component systems, the carbon atoms of each component
having physical andlor chemical interactive relationships with other atoms or
compounds. The carbon atoms of the components may have different hybrid bonding
orbitals to create quite different carbon components. We hope that this bookwill be a
major reference source for those working with carbon alloys.
The book is divided into five parts:
(1)
definitions and approaches to carbon alloys;
(2)
analyses of results in terms of controlling the locations of other alloying elements;
(3)
typical carbon alloys and their preparation;
(4)
characterization
of
carbon alloys;
and
(5)
development and applications of carbon alloys.
Prior to the preparation of this
book,
and as a spin-off from the carbon alloy
project, we published a
Carbon

Dictionary
(in Japanese) with the collaboration
of
Professor
K.
Kobayashi, Professor
S.
Kimura, Mr.
I.
Natsume and Agune-shoufu-sha
Co.,
Ltd.
The book is published with the support
of
a Grant-in-Aid for Publication of
Scientific Research Results
(145309),
provided by the Japan Society for Promotion of
Science (JSPS). All workers in this project are grateful for the receipt
of
aid from the
Grant-in-Aid for Scientific Research on
Priority
Area
(B)
288,
Carbon
Alloys.
We are
also grateful to the sixty-four researchers, eight project leaders and the evaluating

members
of
the team who promoted the Carbon Alloys project (see overleaf). On a
personal note,
I
would like to express my thanks to Ms. K. Marui,
Ms.
M.
Kimura,
Ms.
Y.
Hayashi, Ms.
Y.
Kobayashi and Ms. M. Sasaki for their secretarial roles.
I
must also
thank Professor M. Inagaki for reviewing the manuscripts and Professor
H.
Marsh for
correcting the English
of
all thirty-four chapters of this book.
I
thank Professor
T.
Iseki for his central role leading to the publication
of
the book. Finally, my sincere
thanks go to Elsevier Science Ltd. for publishing this book and for editing the
manuscripts prior to publication.

Ei-ichi Yasuda
Professor
of
Materials
and
Structures Laboratory
To@o
Institute
of
Technology
XiV
Members
of
the
Carbon
Alloys
Project supported by Grant-in-Aid
for
Scientific
Research on Priority Area
(B)
288:
Masahiko Abe (Science Univ.
of
Tokyo), Kazuo Akashi (Science Univ.
of
Tokyo),
Noboru Akuzawa (Tokyo Nut. College
of
Tech.), Norio Arai (Nagoya Univ.), Yong-Bo

Chong
(Res.
Znst.
for
Applied Science), Morinobu Endo (Shinshu Univ.), Toshiaki
Enoki
(Tokyo Znst.
of
Tech.), Mitsutaka Fujita (Univ.
of
Tsukuba), Hiroshi Hatta (The
Znst.
of
Space andAstronaut. Science), Shojun Hino (Chiba Univ.), Hisako Hirai (Univ.
of
Tsukuba), Yoshihiro Hirata (Kagoshima Univ.), Yoshihiro Hishiyama (Musashi
Inst.
of
Tech.), Masaki Hojo (Kyoto Univ.), Hideki Ichinose (The Univ.
of
Tokyo),
Michio Inagaki (Aichi Znst.
of
Tech.), Hiroo Inokuchi (Nut.
Space
Dev. Agency
of
Japan), Masashi Inoue (Kyoto Univ.), Kunio Ito (The Univ.
of
Tokyo), Osamu Ito

(Tohoku Univ.), Shigeru Ito (Science Univ.
of
Tokyo), Hiroshi Iwanaga (Nagasaki
Univ.),
Yasuhiro Iwasawa (The Univ.
of
Tokyo), Kiichi Kamimura (Shinshu Univ.),
Katsumi Kaneko (Chiba Univ.), Tomokazu Kaneko (Tokai Univ.), Teiji Kat0
(Utsunomiya Univ.), Yoshiya Kera (Kink Univ.), Masashi Kijima (Univ.
of
Tsukuba),
Shiushichi Kimura (Yamanashi Univ.), Tokushi Kizuka (Nagoya Univ.), Kazuo Koba-
yashi
(Nagasaki
Univ.), Akira Kojima (Gunma College
of
Tech.), Yozo Korai (Kyushu
Univ.),
Shozo Koyama (Shinshu Univ.), Noriyuki Kurita (Toyohashi Univ.
of
Tech.),
Katsuki Kusakabe (Kyushu Univ.), Takashi Kyotani (Tohoku Univ.), Koji Maeda
(The
Univ.
of
Tokyo), Takeshi Masumoto (Tohoku Univ.), Takashi Matsuda (KitamiInst.
of
Tech.), Michio Matsuhashi (Tohi Univ.), Yohtaro Matsuo (Tokyo
Inst.
of

Tech.),
Michio Matsushita (Tokyo Metropol. Univ.), Yoshitaka Mitsuda
(The
Univ.
of
Tokyo),
Kouichi Miura (Kyoto Univ.), Mikio Miyake (Japan Adv. Znst.
of
Science and Tech.),
Hiroshi Moriyama (Toho Univ.), Seiji Motojima (Gifu Univ.), Tsuyoshi Nakajima
(Kyoto Univ./Aichi Znst.
of
Tech.), Yoshihiro Nakata (Hiroshima Univ.), Yusuke Naka-
yama
(Ehime Univ.), Keiko Nishikawa (Chiba Univ.), Hirokazu Oda (Kansai Univ.),
Zenpachi Ogumi (Kyoto Univ.), Kiyoto Okamura
(Osaka
Pref Univ.), Tatsuo Oku
(Ibuuuki Univ.), Takehiko
Ono
(Osaka
PreJ Univ.), Chuhei Oshima (Waseda Univ.),
Asao Oya (Gunma Univ.), Riichiro Saito (The Univ.
of
Electro-Commun.), Hidetoshi
Saitoh
(Nagaoka
Univ.
of
Tech.), Hiroyasu Saka (Nagoya Univ.), Mototsugu Sakai

(Toyohashi Univ.
of
Tech.), Makoto Sasaki (Muroran Znst.
of
Tech.), Shiro Shimada
(Hokkaido Univ.), Minoru Shiraishi (Tokai Univ.), Takashi Sugino
(Osaka
Univ.),
Kazuya Suzuki (Yokohama Nut. Univ.), Noboru Suzuki (Utsunomiya Univ.), Takashi
Suzuki
(Yamanashi Univ.), Osamu Takai (Nagoya Univ.), Yoshiyuki Takarada (Gun-
ma
Univ.), Yoshio Takasu (Shinshu Univ.), Tsutomu Takeichi (Toyohashi Univ.
of
Tech.), Hisashi Tamai (Hiroshima Univ.), Hajime Tamon (Kyoto Vniv.), Yasuhiro
Tanabe
(Tokyo Inst.
of
Tech.), Takayuki Terai (The Univ.
of
Tokyo), Akira Tomita
(Tohoku Univ.), Hidekazu Touhara (Shinshu Univ.), Norio Tsubokawa (Niigata
Univ.),
Shinji Tsuneyuki (The Univ.
of
Tokyo), Yasuo Uchiyama (Nagasaki Univ.),
Kazumi Yagi (Hokkaido Univ.), Tokio Yamabe (Kyoto Univ.), Osamu Yamamoto
(Kanuguwa Znst.
of
Tech.), Takakazu Yamamoto (Tokyo Inst.

of
Tech.), Hiromi
Yamashita
(Osaka
Pref
Univ.), Toyohiko Yano (Tokyo Znst.
of
Tech.), Eiichi Yasuda
(Tokyo Znst.
of
Tech.).
Part
1
Introduction

3
Chapter
1
Introduction
Ei-ichi
Yasuda' and
Michio
Inagakib
aMaterials and Structures Laboratoiy,
Tokyo
Institute
of
Technology,
Midori-ku,
Yokohama

226-8503,
Japan
bAichi Institute
of
Technology, Yakusa, Toyota
470-0392,
Japan
Abstract:
Carbon materials having a wide range of structure, texture and properties are
classified according to their C-C bonding, based
onsp,
sp2
orsp3 hybrid orbitals. Ashort history
of these carbon materials is divided into basic science, materials development and technology
development. The carbon
family
is composed
of
diamond, graphite, the fulierenes and the
carbynes, each member being unique
in
terms of structure and texture, and also their
ability
to
accept foreign atomslcompounds into their structures. Based on these considerations,
a
new
strategy for
the
development of carbon materials, called

carbon alloys,
has been implemented
in
Japan which has resulted
in
success for developments in carbon science
and
technology.
Keyword:
Carbon materials, Classic carbons, New carbons, Carbon family, Carbon alloys.
1
A
Short
History
Carbon materials have attracted the attention of human beings from prehistoric
times. Carbon materials include charcoals used as heat sources, diamond crystals
used not only as jewels but also for cutting and abrasion, graphite as lubricants and
electrical conductors, and carbon blacks
as
black printing inks. Graphite electrodes,
essential for metal refining, are still produced
in
tonnage quantities. Carbon blacks
of
different sizes have many applications: the small ones for tyres and the large for wet
suits, etc. Activated carbons are important materials for supporting our modern
lifestyle. These three carbon materials (electrode graphites, carbon blacks and
activated carbons) have
a
long history of usage and are called

classic
carbon
materials,
in contrast
to
newly developed carbon materials the so-called
new
carbons.
Carbon materials play
a
part in our daily lives in various ways, many not being that
obvious. For example, among the
new
carbons
there are carbon fibers for reinforcing
rackets and fishing rods, activated carbons as filters for deodorization
in
refrigerators
and for water purification, membrane switches for keyboards
of
computers and other
electronic devices including electrical conductors for automatic pencils, etc.
4
Chapter
1
Table
1
Topics related to carbon materials
Year Basic science Materials development Technology development
1960

1965
1970
1975
1980
1985
1990
1995
Mesophase spheres
Biocompatibility of carbons
High conductivity
of
graphite
intercalation compounds
i-carbon films
Buckminsterfullerene C,
Superconductivity of
K,C,,;
Carbon nanotube single-wall
and multiwall; Proposal of the
concept of “carbon alloys”
Storage of hydrogen in carbon
nanofilaments
Polyacrylonitrile (PAN)-based
carbon
fibers;
Pyrolytic carbons;
Glass-like carbons
Needle-like cokes;
Mesophase-pitch-based carbon
fibers

Vapor-grown carbon fibers
Isotropic high-density graphites
Carbon fiber-reinforced concrete
Electrode for electric
discharge machining
Carbon prostheses
Mesocarbon microbeads
Carbon electrode for fuel cell
First wall for fusion reactor
Carbon anode for lithium ion
rechargeable batteries
Clinging of microorganisms
in
water
to
carbon fibers. Large
capacity for heavy
oil
sorption
by exfoliated graphite
It is interesting to note how
classic carbon
materials are further developed by
researchers every four to five years, and are called
old
but new
materials
[1,2].
Table
1

lists some representative developments since
1960,
grouped under the headings of
basic science, materials development and technology applications.
The year
1960
saw the beginning of the era
of
new carbon materials, because of the
development of carbon fibers from polyacrylonitrile
(PAN),
of pyrolytic carbons and
of glass-like carbons. Carbon fibers, first prepared from polyacrylonitrile, were
extremely attractive materials by reason of their high strength and flexibility.
Developments of other carbon fibers, pitch-based and vapor-grown fibers, followed in
the
1970s.
Japanese researchers made significant contributions to the development of
these carbon fibers: Shindo with PAN-based, Otani with pitch-based, and Koyama
and Endo with vapor-grown carbon fibers. Today, these three types of carbon fibers
are produced on an industrial scale and have wide applications. In contrast, glass-like
carbon, a hard carbon showing conchoidal (glass-like) fracture surfaces with
extremely low gas permeability, found various industrial applications.
A
Japanese
group, represented by Yamada, was deeply involved with these glassy carbons.
Pyrolytic carbons were produced by a non-conventional method, namely that
of
chemical vapor deposition (CVD). The strong anisotropy
of

these pyrolytic carbons
Introduction
5
facilitated several applications, such as the use
of
highly oriented pyrolytic graphite
(HOPG)
as a monochromator in X-ray diffractometers.
In
1964,
the formation
of
optically anisotropic spheres during pitch pyrolysis, the
so-called mesophase spheres and their coalescence were demonstrated. The detailed
studies which followed into the structure
of
these spheres, their growth and
coalescence, and formation of bulk mesophase, promoted the industrial production
of needle-like cokes essential for high-power graphite electrodes, as well as
mesophase-pitch-based carbon fibers with high performance and the mesocarbon
microbeads (MBMC) with several applications.
Around
1970,
a good biocompatibility of carbon materials was found and various
prostheses, such as heart valves, tooth roots,
etc.,
were developed. In about
1980,
industrial technology for producing isotropic high-density graphite materials, using
isostatic pressure, was established. These found applications as jigs for the synthesis

of semiconductor crystals and also electric discharge machining. In about
1985,
a
composite of carbon fibers with cement paste resulted in a pronounced reinforcement
of concrete. Today, not only carbon fiber reinforced concrete but also carbon fibers
themselves are used in various constructions, such as buildings and bridges.
The high electrical conductivity of the AsF,-graphite intercalation compound,
higher than metallic copper, made a strong impact. In
1990,
lithium-ion rechargeable
batteries were developed, where intercalation
of
lithium ions into a graphite anode
was the essential electrochemical reaction. Research currently continues to develop
further practical uses of carbons as anode materials for lithium-ion rechargeable
batteries. Electrical double layer capacitors were also developed using activated
carbons with extremely high surface areas.
The discovery and synthesis
of
buckminsterfullerene
C,
and the superconductivity
of its potassium compound K&, in
1984
and
1990,
respectively, opened up a new
world in carbon materials and created world-wide research activities. Large-sized
fullerenes, such as C,, and C76, some giant fullerenes such as C5po, multi-wall
fullerenes followed. In

1991,
Iijima found single-wall and multi-walled nanotubes
which offered a very promising prospect for modern nanotechnology.
In the
1990s,
marked developments in technology related to applications came
about; Table
1
mentions just
two,
i.e., carbon fibers for water purification and
exfoliated graphite for heavy oil recovery.
The proposal of the idea “Carbon Alloys” by the Japanese Carbon Group in
1992
promoted research activity not only into basic science but
also
the technology which
was related to both material preparation and applications. Most
of
the results of this
research are described in this book.
2
Carbon
Family
It is established that carbon atoms have three different hybrid orbitals,
sp3,
sp2
and
sp,
and have a variety of chemical bonds. This variety in chemical bonding facilitates the

formation
of
an enormous number of organic compounds, and it is the extension of
6
Chapter
1
c,
_

zci
Buckminster-
fullerene
Ce
?
Corannulene
t
1
1
Ovalene
T
f
Polyacety
Fluorene
7
_.

lene
HH
1
-buten-3-yne

(Polyyne)
=c-c=c=~=
(Methylacetylene)
(Cumulene)
Carh yne
Fig.
1.
Organic
compounds
based
on
carbon-carbon bonds usingsp3,sp2 andsp hybrid orbitals
and
inorganic
carbon materials
as
their extension.
these considerations to carbon materials which is shown in Fig.
1
[1,2].
The
C-C
bonds using
sp3
and
sp2
hybrid orbitals result in diamond and graphite, respectively.
The buckminsterfullerene
C,
is

an extension
of
sp2
bonding with the carbynes
utilizing
sp
bonding.
Introduction
7
Carbon
family
Dimensionality
SvuChlral
diversity:
GRAPHlTE
CARBYNE
FULLEREIUZS
thrcc-dimc~onal
two-dimeilsional
onc-dimcnsiod
zero-dimensionul
cubic
&
hcsagonal
hesagowl
&
rhombohedral
cumlllene
buckyballs
to

DIAMOhD
syslems
poylyne
@pes
mhlbes
diamond-likc carbon divcrsity
in
struclun:
diversity
inlength
single-wall
fi
graphitic
to
tuhstratic
L
density
or
chains mdtiwallcd
divemiiy
in
texture
doping in
doping
in
iolerstices
substitution
intercahlion
Fig.
2.

Carbon family, their dimensions,
structural
diversity and possibility
to
accept foreign species.
The family
of
inorganic carbon materials, the
carbon family,
consists of diamond,
graphite, the fuIlerenes and carbynes
[1,2].
Figure
2
summarizes the dimensions of the
distinct structural units
of
each family member and indicates how heteroatoms can be
added to each member.
Diamond consists of
sp3
hybrid orbitals with these covalent chemical bonds
extending
in
three dimensions.
As
a result, diamonds are very hard, isotropic and
electrically insulating. Long-range periodicity of these bonds gives the diamond
crystal. Most diamond crystals are cubic, but some are hexagonal and
so

resemble
zinc-blende and wurtzite, respectively, as in the compounds
ZnS
and
BN.
Where
long-range periodicity is not attained, resulting from the introduction
of
either
structural defects or hydrogen atoms, diamond-like carbon
(DLC)
with an
amorphous structure is formed.
The family members with
spz
bonding as represented by graphite, where the layers
of
carbon atoms, arranged hexagonally are stacked parallel to each other because
of
-electron cloud interactions with a regularity of
ABAB

A
rhombohedral
ABCABC stacking also exists, belonging to the hexagonal crystal system, which
occurs ‘locally’ by introducing stacking faults. Random stacking of imperfect layers is
found in the carbons prepared at temperatures
<
1300°C. Here, the layers are small in
size but where a small number

of
layers are stacked approximately parallel to each
other, then these carbons are described as being
turbostratic.
On
heating these
carbons to temperatures of 3000°C, the size and number of stacked layers increase
and also the regularity of stacking is improved. Hence, a wide range
of
structures can
be obtained from the turbostratic to near-perfect
ABAB
graphitic stacking. Carbons
of intermediate heat treatment temperatures contain variable ratios of turbostratic
and graphitic stacking, with small and large crystallites, depending primarily
on
starting materials (precursors) and heat treatment conditions. The carbon materials
8
RANDOM TEXTURE
ORIENTED
TEXTURE
Chapter
1
PLANAR ORIENTATION
refere
plane
Co-axial
XIAL ORIENTATION
RANDOM
ORIENTATION

-<,.a
:::;t:
Radial
* ,*,;,;.

_I.
5.q*<:<
Concentric
referen$
POINT ORIENTATION
point
Radial
w
Degree
of
orientation
b
Degree
of
graphitization
Heat treatment temperature
Fig.
3.
Microtextures
in
carbon materials related to graphite.
belonging to this carbon family based on graphitic structure are electrically and
thermally conducting and soft mainly because of the presence of -electrons, in sharp
contrast to diamond.
In this

graphite
family
the basic structural unit is a layer of carbon atoms arranged
hexagonally (not necessarily perfectly) giving these materials a strong anisotropy
because the bonding in the layers is covalent and the bonding between the layers is
van der Waals. The way these layers are arranged relative to each other gives diversity
in texture (called
nunotexture).
A
classification based upon a scheme of preferred
orientation of anisotropic layers and its degree is proposed in Fig.
3.
This scheme has
been successfully adopted
[3,4].
From the variety of nanotextures, the existence of
various morphologies in carbon materials with
sp2
hybrid orbitals could be
understood, for example flaky, fibrous and spherical particles.
Amolecule of buckminsterfullerene C,, is made up of carbon atoms arranged as 12
pentagons and 20 hexagons, the C-C bondings being
sp2
hybrid orbitals. Increasing
the number of hexagons beyond C,, separates further the pentagons leading to giant
fullerenes. To separate two groups
of
six
pentagons results in nanotubes. In this
carbon family, the diversity in structure is mainly due to the number of carbon atoms

existing as fullerene particles and the relative location
of
12 pentagons. There are also
variations in the number of layers
so
creating single-walled and multi-walled
nanotubes.
Carbyne is made up of carbon atoms bound linearly by
sp
hybrid bonding, where
two -electrons resonate, giving
two
possibilities, namely an alternative repetition of
single and triple bonds (polyne-type) or a simple repetition of double bonds