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CARBONALLOYS
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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2003
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Printed in The Netherlands.
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 CarbonAlloys
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 CarbonAlloys
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 CarbonAlloys
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 CarbonAlloys 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
[...]... 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, Carbonalloys 1 A Short History Carbon materials have attracted the attention of human beings from prehistoric times Carbon materials include charcoals... compounds 1980 i -carbon films Isotropic high-densitygraphites Carbon fiber-reinforcedconcrete 1985 Buckminsterfullerene C , 1990 Superconductivityof KC, ,,; Carbon nanotube single-wall and multiwall; Proposal of the concept of carbonalloys 1995 Storage of hydrogen in carbon nanofilaments Carbon prostheses Mesocarbon microbeads Carbon electrode for fuel cell First wall for fusion reactor Carbon anode... create quite different carbon components We hope that this bookwill be a major reference source for those working with carbonalloys 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 carbonalloys and their preparation; (4) characterization of carbon alloys; and (5) development... in carbon materials, with such a wide range of structures, textures and properties, and also because of the great demands on materials science from modern technology, a new concept or strategy for the development of carbon materials was needed The Japanese Carbon Group proposed a new strategy, Le., carbonalloys in 1992 [6] The following definition of carbon alloys was tentatively suggested: Carbon alloys. .. proposed for amorphous carbon films in Fig 4 [7] shows that such alloying gives variety in carbon materials Amorphous carbons, which so far have been classified into one category, can be considered as carbonalloys using sp3 and sp2 hybrid orbitals, in addition to bonding with hydrogen In this definition of carbon alloys, porous carbons can be understood as a combination of carbon atoms and nanospaces... alloys, substitutional alloys, intercalation alloys, surfaceand/or hidden surface controlled alloys, and microstructure controlled alloys Special attention was paid to space control and function development by alloying with carbons The formation of carbonalloys may be considered as the filling of space by carbon atoms with different hybrid orbitals and foreign atoms, because sp3 carbon gives three-dimensional... 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... 122-127,1997 Y Tanabe and E Yasuda, Carbonalloys Carbon, 38: 329-334,1995 P.K Bachmann, Ullman’s Encyclopedia of Industrial Chemistry, Vol A26, pp 72-25, 1996 M Inagaki (Ed.) Creation of functional nano- and micro-sized spaces in carbon materials Special issue of Synthetic Metals, 125: 139-266,2002 Part 2 Space Control in CarbonAlloys 15 Chapter 2 Hybrid Orbital Control in CarbonAlloys Riichiro Saito* Department... composed of carbon atoms in multi-component systems, in which each component has physical andlor chemical interactions with each other Here, carbons with different hybrid orbitals account as difierent components Chapter I 10 Polyethyne iC.HJ- Fig 4 Classification diagram for amorphous carbon films [ ] 7 According to this definition, most carbon materials are carbonalloys (homoatomic alloys) , as mentioned... structure and property The concept of CarbonAlloys was initiated in Japan as a national project and is now recognized internationally CarbonAlloys 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 .
and
technology.
Keyword:
Carbon materials, Classic carbons, New carbons, Carbon family, Carbon alloys.
1
A
Short
History
Carbon materials have attracted.
(3)
typical carbon alloys and their preparation;
(4)
characterization
of
carbon alloys;
and
(5)
development and applications of carbon alloys.
Prior