Materials Science and Engineering of Carbon: Characterization 碳材料科学与工程：表征

List of Contributors.................................................................................

Preface ...............................................................................................

Acknowledgments ................................................................................

CHAPTER 1 Introduction............................................................ 1

Michio Inagaki, Feiyu Kang

1.1 Carbon Materials............................................................... 1

1.2 Characterization of Carbon Materials.................................... 3

1.3 Structure of the Present Book.............................................. 5

References.............................................................................. 6

CHAPTER 2 X-ray Powder Diffraction ......................................... 7

Norio Iwashita

2.1 Introduction...................................................................... 7

2.2 X-ray Diffraction Pattern of Carbon Materials........................ 8

2.3 Parameters Determined by X-ray Diffraction.........................10

2.4 Instrumentation ................................................................11

2.5 Specifications for Measurement ..........................................14

2.5.1 Preparation of Sample for X-ray Measurements............ 14

2.5.2 Measurement and Intensity Correction of Diffraction

Profiles.................................................................. 14

2.5.3 Correction of Diffraction Angle With Internal

Standard ................................................................ 16

2.5.4 Determination of Full Width at Half Maximum

Intensity ................................................................ 17

2.5.5 Accuracy of the Values Determined............................ 18

2.6 Degree of Graphitization ...................................................18

2.7 Key Issues for Measurement...............................................21

2.7.1 Diffraction Pattern................................................... 21

2.7.2 Use of Internal Standard........................................... 21

2.7.3 Use of Thin Sample Holder....................................... 22

2.7.4 Indexing the Diffraction Line .................................... 23

2.7.5 Separation into Component Profiles............................ 23

2.8 Concluding Remarks.........................................................24

References.............................................................................24

CHAPTER 3 Small-Angle X-ray Scattering..................................27

Katsuya Fukuyama, Yoshikiyo Hatakeyama

3.1 Introduction.....................................................................27

3.2 Fundamentals ..................................................................28

3.3 Key Issues for the Measurements ........................................33

3.4 Applications for Carbon Materials.......................................35

3.4.1 Porous Carbon Fibers............................................... 35

3.4.2 Glass-Like Carbons ................................................. 36

3.4.3 Mesocellular Foam Carbons (Silica-Templated

Carbons)................................................................ 38

3.4.4 Open Pores Formed by Air Oxidation......................... 40

3.5 Concluding Remarks.........................................................42

References.............................................................................42

CHAPTER 4 Transmission Electron Microscopy..........................45

Sylvie Bonnamy, Agne`s Oberlin

4.1 Introduction.....................................................................45

4.2 Modes of Transmission Electron Microscopy ........................46

4.2.1 Diffracting Mode..................................................... 47

4.2.2 Imaging Modes....................................................... 47

4.3 Key Issues for Observation ................................................48

4.3.1 Object Thickness (Weak Phase Object) ....................... 48

4.3.2 Contrast Transfer Function of the Transmission

Electron Microscope................................................ 49

4.3.3 Diffusion Contrasts.................................................. 54

4.3.4 Fresnel Fringes, ie, Edge Fringes ............................... 54

4.5 Applications for Carbon Materials.......................................56

4.5.1 Transmission Electron Microscopy Modes to Study

Crystallinity of Carbon Materials ............................... 56

4.5.2 Transmission Electron Microscopy Modes in

the Study of Carbonization and Graphitization ............. 62

4.6 Conclusions.....................................................................69

References.............................................................................69

Further Reading......................................................................70

CHAPTER 5 Scanning Electron Microscopy ...............................71

Akira Yoshida, Yutaka Kaburagi, Yoshihiro Hishiyama

5.1 Introduction.....................................................................71

5.2 Instrumentation and Resolving Power ..................................72

5.2.1 Instrumentation....................................................... 73

5.2.2 Magnification and Resolving Power of the

Scanning Electron Microscope................................... 75

5.2.3 Edge Effects Appearing in SE Mode Images................ 76

5.3 Specimen Preparation........................................................77

5.4 Observation With the Out-Lens Objective Lens System ..........79

5.5 Observation With the Snorkel Objective Lens System.............81

5.6 Observation With the In-Lens System..................................82

5.7 Electron Channeling Effect ................................................83

5.7.1 Electron Channeling Effect for Kish Graphite .............. 83

5.7.2 Electron Channeling Pattern for Kish Graphite

and HOPG Specimens.............................................. 86

5.7.3 Mapping and Crystal Grain Size Evaluation................. 88

5.8 Concluding Remarks.........................................................91

References.............................................................................92

CHAPTER 6 Image Analysis ......................................................95

Kyoichi Oshida

6.1 Introduction.....................................................................95

6.2 Image Analysis Methods ...................................................96

6.2.1 Process of Image Analysis ........................................ 96

6.2.2 Analysis of Space Frequency..................................... 97

6.2.3 Three-Dimensional Transmission Electron

Microscopy ...........................................................100

6.2.4 Software for the Analysis ........................................100

6.3 Structure Analysis Through Transmission Electron

Microscopy ................................................................... 101

6.3.1 Cup-Stacked Type Carbon Nanotubes ........................101

6.3.2 Carbon Nanotubes Loaded With Metal Particles ..........104

6.3.3 Thin Graphite ........................................................108

6.3.4 Disordered Carbon .................................................108

6.4 Texture Analysis Through Scanning Electron

Micrographs .................................................................. 113

6.5 Texture Analysis Through Optical Micrographs................... 116

6.6 Concluding Remarks....................................................... 120

References........................................................................... 121

CHAPTER 7 Raman Spectroscopy............................................ 125

Yutaka Kaburagi, Akira Yoshida, Yoshihiro Hishiyama

7.1 Introduction................................................................... 126

7.2 Fundamentals ................................................................ 126

7.3 Key Issues for the Measurements ...................................... 129

7.3.1 Laser Probe Sampling Depth....................................129

7.3.2 Polarization of Laser Light ......................................129

7.3.3 Sampling Area.......................................................131

7.3.4 Temperature ..........................................................132

7.3.5 Elimination of Background Intensity .........................132

7.3.6 Excitation Energy Dependence of D Band..................133

7.3.7 Calibration of Raman Frequency...............................134

7.3.8 Equipment ............................................................136

7.4 As a Measure for Structure Characterization ....................... 138

7.4.1 G Band.................................................................138

7.4.2 D and D0 Bands .....................................................141

7.5 Concluding Remarks....................................................... 149

References........................................................................... 150

CHAPTER 8 X-ray Photoelectron Spectroscopy ........................ 153

Hidetaka Konno

8.1 Introduction................................................................... 153

8.2 Practical Side of Measurements ........................................ 154

8.3 State Analysis................................................................ 156

8.3.1 Determination of Binding Energy..............................156

8.3.2 Background Subtraction ..........................................158

8.3.3 Peak Separation .....................................................159

8.3.4 State Analysis Using Chemical Shift .........................164

8.4 Semiquantitative Analysis................................................ 166

8.5 Concluding Remarks....................................................... 168

References........................................................................... 169

CHAPTER 9 Magnetoresistance............................................... 173

Yoshihiro Hishiyama, Yutaka Kaburagi, Michio Inagaki

9.1 Introduction................................................................... 174

9.2 General Scheme of Dr/r0 Change With Graphitization ......... 174

9.3 Measurement of Magnetoresistance ................................... 178

9.3.1 Specimen Shape.....................................................178

9.3.2 Magnetic Field Orientation Schemes .........................179

9.3.3 Instruments ...........................................................182

9.4 Magnetoresistance Parameters for Coke ............................. 185

9.4.1 Coke B and Gilsonite Coke......................................185

9.4.2 Coke Prepared From Hydrogenated Ethylene

Tar Pitch...............................................................186

9.5 Magnetoresistance Parameters for Carbon Fibers

and Extruded Coke......................................................... 189

9.5.1 Benzene-Derived Vapor-Grown Carbon Fiber

and Extruded Coke.................................................189

9.5.2 Other Carbon Fibers ...............................................191

9.6 Magnetoresistance Parameters for Highly Crystallized

Graphite Materials.......................................................... 192

9.7 Concluding Remarks....................................................... 194

Supplement: Background of the Characterization of Carbon

Materials With Dr/r0 ............................................................ 195

S-1 Origin of the Sign of Dr/r0............................................... 195

S-2 Microtexture .................................................................. 197

S-3 Relationship Between Microtexture and Magnetoresistance.... 199

References........................................................................... 203

CHAPTER 10 Electrochemical Performance............................. 205

Soshi Shiraishi

10.1 Introduction................................................................. 205

10.2 Fundamentals............................................................... 206

10.2.1 Capacitance .......................................................206

10.2.2 Construction of Measurement Cell.........................208

10.2.3 Electrochemically Analytical Mode .......................209

10.2.4 Differential Capacitance and Integral

Capacitance .......................................................211

10.2.5 Definition of Specific Capacitance.........................212

10.3 Measurement Procedure................................................. 214

10.3.1 Measurement Cell...............................................214

10.3.2 Preparation of Carbon Electrode............................216

10.3.3 Aqueous Acid Electrolyte System

(by Three-Electrode Cell).....................................218

10.3.4 Organic Electrolyte System

(by Three-Electrode Cell).....................................219

10.3.5 Organic Electrolyte System

(by Two-Electrode Cell) ......................................221

10.4 Concluding Remarks..................................................... 224

References........................................................................... 224

CHAPTER 11 Gas Adsorption/Desorption Isotherm

for Pore Structure Characterization..................... 227

Yoko Nishi, Michio Inagaki

11.1 Introduction................................................................. 228

11.2 Fundamentals............................................................... 229

11.3 Key Issues for the Measurements and Analyses ................. 232

11.3.1 Sample Amount for the Measurement ....................232

11.3.2 Pretreatment of Sample........................................232

11.3.3 BrunauereEmmetteTeller Method ........................233

11.3.4 as Plot ..............................................................234

11.3.5 BarretteJoynereHalenda Method..........................235

11.3.6 DubinineRadushkevich Method............................237

11.3.7 Density Functional Theory Method........................238

11.4 Application to Carbon Materials ..................................... 239

11.4.1 Microporous Carbons ..........................................239

11.4.2 Mesoporous Carbons...........................................241

11.4.3 Measurements Using Various Gases as Adsorbate ....243

11.4.4 Gravimetric Measurement of Adsorption/

Desorption of CO2 ..............................................244

11.5 Concluding Remarks..................................................... 245

References........................................................................... 246

CHAPTER 12 Thermal Analysis ............................................... 249

Ming-ming Chen

12.1 Introduction................................................................. 249

12.2 Fundamentals in Thermal Analyses ................................. 250

12.3 Key Issues for the Measurements .................................... 252

12.4 Applications of TG and DTG for Carbon Materials ............ 256

12.4.1 Biomasses .........................................................256

12.4.2 Pitches..............................................................258

12.4.3 Organic Polymers ...............................................258

12.4.4 Measurements in Oxygen.....................................263

12.5 Applications of DTA and DSC for Carbon Materials .......... 265

12.5.1 Pitches..............................................................265

12.5.2 Organic Polymers ...............................................267

12.5.3 Intercalation Reactions ........................................269

12.6 Concluding Remarks..................................................... 269

References........................................................................... 270

CHAPTER 13 Titration Method for the Identification

of Surface Functional Groups.............................. 273

Yern Seung Kim, Chong Rae Park

13.1 Introduction................................................................. 273

13.2 Basic Concept of Titration Method.................................. 276

13.3 Instrumentation ............................................................ 279

13.4 Specification for the Methodology................................... 279

13.4.1 Reaction Step.....................................................280

13.4.2 Filtration Step ....................................................281

13.4.3 Titration Step.....................................................281

13.5 Analysis of the Titration Results ..................................... 281

13.6 Key Points for the Titration Measurements ....................... 284

13.6.1 Preparation of the Reaction Mixture for the Reaction

Step..................................................................284

13.6.2 Agitation Method and Period................................284

13.6.3 Titration Condition and End Point Determination.....285

13.7 Concluding Remarks..................................................... 285

References........................................................................... 285

CHAPTER 14 Temperature Programmed Desorption.................. 287

Takafumi Ishii, Takashi Kyotani

14.1 Introduction................................................................. 287

14.2 TPD Experimental Conditions and Apparatus.................... 288

14.3 Assignment of TPD Peaks to Surface Functional

Groups........................................................................ 291

14.4 Secondary Reactions During a TPD Run .......................... 296

14.5 Effect of Air Exposure on TPD Patterns ........................... 299

14.6 Effect of Inorganic Matter in Carbons.............................. 300

14.7 Concluding Remarks..................................................... 302

References........................................................................... 302

Index...................................................................................................307