Industrial Carbon and Graphite Materials

Hubert Jäger received his PhD from the Technical University of Karlsruhe. He started his industrial career in 1986 at SGL Carbon. Since then, he held various positions in R&D, production, technical service and others. Since 2014 he is Professor at the Institut für Leichtbau und Kunststofftechnik (IKL) at the Technical University of Dresden. He is author of several papers in polymer chemistry, SiC-fiber composite technology and carbon fiber surface chemistry. Wilhelm Frohs received his PhD 1989 under the guidance of Prof. Fitzer. In the same year he joined SGL Carbon and has held various R&D positions. His current activities are focused on raw material development. He is author of many papers in the fields of carbon fibers, petroleum, and coal tar pitch coke, coal tar pitch, and graphite electrodes. Since 2010 he is president of the German Carbon Group (Arbeitskreis Kohlenstoff, AKK).

• Volume 1Preface xxiii1 Introduction: The Future of Carbon Materials – The Industrial Perspective 1Hubert Jäger, Wilhelm Frohs, and Tilo Hauke1.1 Overview 11.2 Traditional Carbon and Graphite Materials 21.3 Modern Application of Carbon Materials 121.4 Future Application of Carbon Materials 181.5 Conclusion 202 The Element Carbon 21Wilhelm Frohs and Hubert Jäger2.1 Introduction 212.2 Diamond 282.3 Graphite 282.4 Non-graphitic Carbon 292.5 Carbyne and Chaoite 292.6 Nanoforms of Carbon 30References 30Further Reading 313 History of Carbon Materials 33Gerd Collin3.1 Origin of Elemental Carbon 333.2 Formation and Economic Development of Natural Diamonds 343.3 Formation and Use of Natural Graphite 343.4 History of Charcoal from Wood and Coke from Coal 353.5 History of Carbon Black 353.6 History of Activated Carbon 383.7 Development of Synthetic Graphite 383.8 Development of Synthetic Diamonds 393.9 Development of Carbon Fibers 393.10 Discovery and Inventions of Nanocarbons: Fullerenes, Nanotubes, and Graphene 40References 424 Recommended Terminology for the Description of Carbon as a Solid (© 1995 IUPAC) 45E. Fitzer, K.-H. Köchling, H.P. Böhm, and H. MarshList of Terms 45Description of the Terms 48Acetylene Black 48Description 48Notes 48Acheson Graphite 48Description 48Notes 48Activated Carbon 49Description 49Notes 49Activated Charcoal 49Description 49Agranular Carbon 49Description 49Notes 49Amorphous Carbon 49Description 49Notes 50Artificial Graphite 50Description 50Notes 50Baking 50Description 50Binder 50Description 50Binder Coke 51Description 51Notes 51Brooks and Taylor Structure in the Carbonaceous Mesophase 51Description 51Notes 51Bulk Mesophase 51Description 51Notes 52Calcined Coke 52Description 52Notes 52Carbon 52Description 52Notes 52Carbon Artifact 52Description 52Notes 52Carbon Black 53Description 53Notes 53Carbon–Carbon Composite 53Description 53Carbon Cenospheres 53Description 53Carbon Cloth 53Description 53Notes 54Carbon Electrode 54Description 54Notes 54Carbon Felt 54Description 54Notes 54Carbon Fiber 54Description 54Notes 55Carbon Fiber Fabrics 55Description 55Carbon Fibers Type HM 55Description 55Notes 55Carbon Fibers Type HT 55Description 55Notes 56Carbon Fibers Type IM 56Description 56Notes 56Carbon Fibers Type LM (Low Modulus) 56Description 56Notes 56Carbon Fibers Type UHM 57Description 57Carbon Material 57Description 57Notes 57Carbon Mix 57Description 57Carbon Whiskers 57Description 57Carbonaceous Mesophase 57Description 57Notes 58Carbonization 58Description 58Notes 58Catalytic Graphitization 58Description 58Notes 58Char 59Description 59Notes 59Charcoal 59Description 59Notes 59Coal-Derived Pitch Coke 59Description 59Notes 59Coal-Tar Pitch 60Description 60Notes 60Coalification 60Description 60Notes 60Coke 60Description 60Notes 60Coke Breeze 61Description 61Colloidal Carbon 61Description 61Notes 61Delayed Coke 61Description 61Notes 61Delayed Coking Process 61Description 61Notes 62Diamond 62Description 62Notes 62Diamond by CVD 62Description 62Notes 62Diamond-Like Carbon Films 63Description 63Notes 63Electrographite 63Description 63Exfoliated Graphite 63Description 63Notes 64Fibrous Activated Carbon 64Description 64Notes 64Fibrous Carbon 64Description 64Filamentous Carbon 64Description 64Notes 64Filler 65Description 65Filler Coke 65Description 65Notes 65Fluid Coke 65Description 65Notes 65Fullerenes 66Description 66Notes 66Furnace Black 66Description 66Notes 66Gas-Phase-Grown Carbon Fibers 66Description 66Notes 66Glass-Like Carbon 67Description 67Notes 67Granular Carbon 67Description 67Notes 67Graphene Layer 67Description 67Notes 68Graphite 68Description 68Notes 68Graphite Electrode 68Description 68Graphite Fibers 68Description 68Notes 69Graphite Material 69Description 69Notes 69Graphite Whiskers 69Description 69Notes 69GRAPHITIC CARBON 70Description 70Notes 70Graphitizable Carbon 70Description 70Notes 70Graphitization 70Description 70Notes 70Graphitization Heat Treatment 71Description 71Notes 71Graphitized Carbon 71Description 71Notes 71Green Coke 71Description 71Notes 72Hard Amorphous Carbon Films 72Description 72Hexagonal Graphite 72Description 72Notes 72High-Pressure Graphitization 72Description 72Highly Oriented Pyrolytic Graphite 73Description 73Notes 73Isotropic Carbon 73Description 73Notes 73Isotropic Pitch-Based Carbon Fibers 73Description 73Notes 73Lamp Black 74Description 74Mesogenic Pitch 74Description 74Mesophase Pitch 74Description 74Notes 74Mesophase Pitch-Based Carbon Fibers 74Description 74Metallurgical Coke 75Description 75Notes 75Microporous Carbon 75Description 75Notes 75MPP-Based Carbon Fibers 75Description 75Natural Graphite 75Description 75Notes 76Needle Coke 76Description 76Notes 76Non-graphitic Carbon 76Description 76Notes 76Non-graphitizable Carbon 77Description 77Notes 77Nuclear Graphite 77Description 77Notes 77Pan-Based Carbon Fibers 77Description 77Particulate Carbon 78Description 78Notes 78Petroleum Coke 78Description 78Notes 78Petroleum Pitch 78Description 78Notes 78Pitch 79Description 79Notes 79Pitch-Based Carbon Fibers 79Description 79Notes 79Polycrystalline Graphite 79Description 79Notes 80Polygranular Carbon 80Description 80Notes 80Polygranular Graphite 80Description 80Notes 80Premium Coke 81Description 81Notes 81Puffing 81Description 81Notes 81Puffing Inhibitor 81Description 81Notes 81Pyrolytic Carbon 82Description 82Notes 82Pyrolytic Graphite 82Description 82Notes 82Raw Coke 82Description 82Notes 83Rayon-Based Carbon Fibers 83Description 83Notes 83Regular Coke 83Description 83Notes 83Rhombohedral Graphite 84Description 84Notes 84Semicoke 84Description 84Notes 84Soot 84Description 84Notes 85Spherical Carbonaceous Mesophase 85Description 85Stabilization Treatment of Thermoplastic Precursor Fibers for Carbon Fibers 85Description 85Notes 85Stress Graphitization 85Description 85Notes 86Synthetic Graphite 86Description 86Notes 86Thermal Black 86Description 86References 865 Graphite 89Otto Vohler, Ferdinand von Sturm, Erhard Wege, and Wilhelm Frohs5.1 Graphite Single Crystal 895.2 Natural Graphite 945.2.1 Occurrence and Properties 945.3 Synthetic Graphite 95References 101Further Reading 1036 Industrial Carbons 1056.1 Introduction to Polygranular Carbon and Graphite Materials 106References 1066.1.1 Polygranular Carbon and Graphite Materials 107Hubert Jäger, Wilhelm Frohs, Ferdinand von Sturm, Otto Vohler, and Erhard Wege6.1.1.1 The Relevance of Raw Materials 1076.1.1.1.1 Petroleum Coke 1096.1.1.1.2 Coal-Tar Pitch Coke 1136.1.1.1.3 Anthracite 1146.1.1.1.4 Binder Materials 1156.1.1.1.4.1 Coal-Tar Pitch 1156.1.1.1.4.2 Petroleum Pitch 1176.1.1.1.4.3 Thermosetting Resins 119References 120Further Reading 1216.1.2 Petroleum Coke 122Heinrich Predel and Srini Srivatsan6.1.2.1 Introduction 1226.1.2.2 Physical and Chemical Properties 1226.1.2.2.1 Physical Properties 1226.1.2.2.2 Chemical Properties and Composition 1246.1.2.3 Production 1256.1.2.3.1 Production Processes 1256.1.2.3.1.1 Delayed Coking 1256.1.2.3.1.2 Fluid Coking 1326.1.2.3.1.3 Flexicoking 1346.1.2.3.2 Calcination 1356.1.2.3.2.1 Rotary Kiln Calciner 1376.1.2.3.2.2 Rotary Hearth Calciner 1386.1.2.3.2.3 Shaft Kiln Calciner 1386.1.2.4 Uses and Economic Aspects 1386.1.2.4.1 Green Petroleum Coke 1406.1.2.4.2 Calcined Petroleum Coke 1416.1.2.4.2.1 Anode-Grade Coke (Regular Calcinate) 1416.1.2.4.2.2 Needle Coke 1416.1.2.5 Quality Aspects 1426.1.2.5.1 Green Coke 1426.1.2.5.2 Regular Calcinate 1436.1.2.5.3 Needle Coke 1446.1.2.6 Environmental and Safety Aspects 1456.1.2.6.1 Green Coke 1456.1.2.6.2 Calcined Petroleum Coke 146References 147Further Reading 1496.1.3 Coal-Tar Pitch Coke 150Tetsusei Fukuda6.1.3.1 Introduction 1506.1.3.2 Physical and Chemical Properties 1516.1.3.2.1 Physical Properties 1516.1.3.2.2 Chemical Properties 1516.1.3.3 Production of Pitch Coke 1526.1.3.3.1 Production Process 1526.1.3.3.1.1 Chamber Coking Process 1536.1.3.3.1.2 Delayed Coker and Calciner 1556.1.3.4 Uses 1616.1.3.4.1 Aggregate of Graphite Electrode for Aluminum Smelting 1616.1.3.4.2 Aggregate for Graphite Electrode in Electric Arc Furnace Steelmaking 1616.1.3.5 Environmental and Safety Aspects 162References 1646.1.4 Natural Graphite 165Werner Handl6.1.4.1 Occurrence and Classification 1656.1.4.2 Mining and Cleaning 1656.1.4.3 Applications of Natural Graphite 1696.1.4.4 Economic Aspects 170References 1716.1.5 Tar and Pitch 172Gerd-Peter Blümer, Gerd Collin, and Hartmut Höke6.1.5.1 Origin, Classification, and Industrial Importance of Tars and Pitches 1726.1.5.1.1 Origin and Classification 1726.1.5.1.2 History 1736.1.5.1.3 Industrial Importance 1746.1.5.2 Properties 1746.1.5.3 Processing of Coke-Oven Coal Tar 1846.1.5.3.1 Survey 1846.1.5.3.2 Primary Distillation 1856.1.5.3.3 Processing of Coal-Tar Pitch 1896.1.5.3.3.1 Cooling 1896.1.5.3.3.2 Production of Electrode Pitch 1906.1.5.3.3.3 Production of Special Pitches 1946.1.5.3.4 Processing of Tar Distillates 1966.1.5.3.4.1 Carbon Black Oils 1966.1.5.3.4.2 Impregnating Oils 1966.1.5.3.4.3 Fuel oils 1996.1.5.3.4.4 Diesel Fuels 1996.1.5.3.4.5 Fluxing Oils 1996.1.5.4 Processing of Low-Temperature Coal Tars 1996.1.5.5 Processing of Other Tars and Tarlike Raw Materials 2016.1.5.5.1 Lignite Tars 2016.1.5.5.2 Peat Tars 2016.1.5.5.3 Wood Tars 2026.1.5.5.4 Oil-Shale Tars 2026.1.5.5.5 Pyrolysis Residual Oils 2026.1.5.6 Uses of Tar Products and Their Economic Importance 2036.1.5.7 Toxicology and Ecotoxicology 2046.1.5.7.1 Toxicology 2046.1.5.7.2 Ecotoxicology 2066.1.5.7.3 Classification and Legislation 206References 2076.1.6 Thermosetting Resins 211Josef SurenReferences 2136.2 Manufacturing 214Johann Daimer6.2.1 Grinding and Sizing 2146.2.2 Mixing 2146.2.3 Forming 2156.2.3.1 Molding 2166.2.3.2 Isostatic Molding 2166.2.3.3 Vibration Molding 2176.2.3.4 Other Forming Methods 2176.2.4 Baking 2176.2.4.1 Ring Furnace 2196.2.4.2 Car-Bottom Furnace/Single-Chamber Furnace 2216.2.4.3 Tunnel Kiln 2216.2.4.4 Other Furnaces 2226.2.5 Graphitization 2226.2.5.1 Acheson Furnace 2246.2.5.2 Castner Furnace 2246.2.5.3 Induction Furnace 2256.2.5.4 Radiation Heating 2256.2.6 Purification 2256.2.7 Machining 2266.2.8 Impregnation and Surface Coating 226References 2276.3 Environmental, Health and Safety Aspects of the Production of Carbon and Graphite 230Ruediger Meyer zu Reckendorf6.3.1 Environmental Aspects 2306.3.1.1 Raw Materials 2306.3.1.2 Processes and Energy 2316.3.2 Occupational Safety and Health Aspects 2326.3.2.1 Coal Tar Pitch 2326.3.2.2 Risk Strategy for Benzopyrene 2326.3.2.3 Gases 2336.3.2.4 Electric Current 2346.3.2.5 Dust 2346.3.3 Process Safety 234References 2356.4 Properties of Polygranular Carbon and Graphite Materials 237Marcus Franz, Franz Fendt, and Karl Wimmer6.4.1 Physical Properties 2376.4.2 Chemical Properties 241References 242Further Reading 2426.5 Applications 2436.5.1 Prebaked Anodes for Aluminum Electrolysis 244Jean-Claude Fischer and Raymond Cecil Perruchoud6.5.1.1 Introduction 2446.5.1.2 The Electrolysis Cell 2446.5.1.3 The Role of Anodes in the Pots 2456.5.1.3.1 Current Conductor Aspects 2456.5.1.3.2 Thermal Aspects 2486.5.1.3.3 Anode Failure and Consumption Mechanisms 2496.5.1.3.4 Carbon Consumption Figures 2526.5.1.4 The Cost of Al Production Related to the Anodes 2526.5.1.5 The Anode Manufacture for Large Modern Smelters 2536.5.1.6 The Raw Materials 2546.5.1.7 The Green Mill 2556.5.1.7.1 Dry Aggregate Preparation 2556.5.1.7.2 Paste and Green Block Production 2606.5.1.7.3 The Baking Furnace 2646.5.1.7.4 Anode Slotting 2686.5.1.7.5 Anode Rodding 2696.5.1.7.6 Anode Quality Control 2716.5.1.8 Outlook 271References 2736.5.2 Cathodes for Aluminum Electrolysis 275Frank Hiltmann6.5.2.1 Cathodes in the Aluminum Smelting Process 2756.5.2.2 Cathode Classification 2756.5.2.3 Cathode Lifetime 2776.5.2.4 Wettable Cathodes 2786.5.2.5 Surface-Profiled Cathodes 2796.5.2.6 Spent Potlining 280References 280Further Reading 2806.5.3 Graphite Electrodes for Electric Arc Furnaces 281Daniel Steppich6.5.3.1 Graphite Electrodes for Electric Arc Furnaces 2816.5.3.1.1 Steel Production 2816.5.3.1.1.1 The Era of Iron and Steel 2826.5.3.1.1.2 Steel Recycling in an Electric Arc Furnace 2876.5.3.1.1.3 Steel Market Outlook 2966.5.3.1.2 Graphite Electrodes in the Steel Recycling Process 2986.5.3.1.2.1 Application Requirements 2996.5.3.1.2.2 Wear Mechanisms 3036.5.3.1.2.3 Future Developments 3086.5.3.1.2.4 Graphite Electrode Market Outlook 312References 3146.5.4 Linings and Casting 320Otto Vohler, Ferdinand von Sturm, and Erhard WegeReferences 321Further Reading 3216.5.5 Carbon Electrodes 322Eckhard Escher6.5.5.1 Introduction 3226.5.5.1.1 Raw Materials 3226.5.5.1.2 Manufacturing 3236.5.5.1.3 Typical Properties 3236.5.5.1.4 Dimensions 3246.5.5.1.5 Joint Systems 3246.5.5.1.6 Carbon Electrode Market 325Reference 3256.5.6 Self-Baking Electrodes 326Johann-Christian Leye and Robert Becker6.5.6.1 Raw Materials 3276.5.6.2 Manufacturing 3276.5.6.3 Properties 3286.5.6.4 Operation Mode 3286.5.6.4.1 The Process of Self-Baking Electrodes 328References 3296.5.7 Graphite Process Equipment 331Marcus Franz6.5.7.1 Heat Exchangers 3326.5.7.2 Absorbers, Desorbers, and Distillation Columns 3356.5.7.3 Hydrochloric Acid and Gas Synthesis Units 3356.5.7.4 Reactors 3366.5.7.5 Pumps 3366.5.8 Fine-Grained Graphite 338Werner Richard Hoffmann6.5.8.1 Markets and Applications 3386.5.8.2 Applications in the Electronic Industry 3386.5.8.3 Applications in the Metallurgy 3416.5.8.4 Applications in the Ceramics 3446.5.8.5 Applications in the Glass and Quartz-Glass Production 3456.5.8.6 Applications for Current Transmission 3456.5.8.6.1 Carbon Brushes 3456.5.8.6.2 Current Collectors 3466.5.8.7 Applications in the Analytical Technology 3476.5.9 Synthetic Graphite in Nuclear Applications 349Rainer Schmitt6.5.9.1 Early Graphites in Nuclear Reactor Technology 3496.5.9.2 Requirements for Nuclear Graphite 3506.5.9.3 Radiation Damage in Nuclear Graphite 3516.5.9.3.1 Structure of Polycrystalline Graphite 3516.5.9.3.2 Basic Effects of Radiation on the Graphite Lattice Structure 3536.5.9.3.3 Graphite Property Changes Due to Fast Neutron Irradiation 3556.5.9.3.3.1 Dimensional Changes 3556.5.9.3.3.2 Thermal Expansion Coefficient (CTE) 3556.5.9.3.3.3 Thermal Conductivity and Resistivity 3586.5.9.3.3.4 Young’s Modulus 3586.5.9.3.3.5 Tensile Strength 3596.5.9.3.3.6 Irradiation-Induced Creep 3596.5.9.4 Decommissioning 3616.5.9.5 Outlook 362References 3636.5.10 Expanded Graphite and Graphite Foils 364Martin Christ6.5.10.1 Production 3646.5.10.2 Properties 3656.5.10.3 Applications 3676.5.10.3.1 Sealing Applications 3676.5.10.3.2 Conductive Fillers 3686.5.10.3.3 Latent Heat Storage 3696.5.10.3.4 Other Applications 3706.5.10.4 Economic Aspects 370References 370Further Reading 3716.5.11 Other Classes of Carbon 372Otto Vohler, Ferdinand von Sturm, and Erhard Wege6.5.11.1 Glass-Like Carbon 3726.5.11.2 Pyrocarbon and Pyrographite 3736.5.11.3 Graphite Compounds 3746.5.11.3.1 Surface Complexes 3746.5.11.3.2 Graphite Intercalation Compounds 375References 376Further Reading 3777 Carbon and Graphite for Electrochemical Power Sources 379Mario Wachtler, Oswin Öttinger, and Rüdiger Schweiss7.1 Introduction 3797.2 Primary Batteries 3807.3 Lead Acid Batteries 3817.4 Li-Ion Batteries 3877.4.1 Introduction 3877.4.2 Active Materials: General Concepts 3907.4.2.1 Types of Carbon and Graphite Materials 3917.4.2.2 Mechanism of Charge Storage in Graphitic Materials 3927.4.2.3 Graphitization Degree and Reversible Capacity 3957.4.2.4 The Solid Electrolyte Interphase 3977.4.2.5 Solvent Co-intercalation and Graphite Exfoliation 3987.4.2.6 Further Material Design Aspects 4017.4.2.7 Mechanism of Charge Storage in Amorphous Carbons 4037.4.3 Commercialized Active Materials 4047.4.3.1 Amorphous Carbons (Hard and Soft Carbons) 4067.4.3.2 Graphitized Mesophase Carbon Materials 4097.4.3.3 Natural Graphite 4097.4.3.4 Synthetic Graphite 4117.4.3.5 Carbon/Graphite-Silicon and Composites 4127.4.3.6 Other Anode Materials 4137.4.4 Conductive Additives 4157.4.5 Carbon Coatings 4177.5 “Beyond Li-Ion” Battery Chemistries 4187.5.1 Na-Ion Battery 4187.5.2 Li-Sulfur Battery 4197.5.3 Li-Oxygen/Air Battery 4207.6 Electrochemical Double-Layer Capacitors 4207.6.1 Introduction 4207.6.2 Effect of Porosity on Capacitance 4237.6.3 Carbon-Based Electrode Materials 4257.6.3.1 Activated Carbons 4267.6.3.2 Other Carbon Materials 4277.7 Redox Flow Batteries 4277.7.1 Introduction 4277.7.2 Bipolar Plates 4287.7.3 Electrode Materials 4317.7.3.1 Carbon Felts 4317.7.3.2 Reticulated Vitreous Carbon 4337.7.3.3 Other Electrode Concepts 4347.7.3.4 Relevance of Carbon Materials 4367.8 Fuel Cells 4387.8.1 Introduction 4387.8.2 Bipolar Plates 4397.8.2.1 Manufacturing 4407.8.2.2 Properties 4407.8.3 Gas Diffusion Layers and Electrodes 4407.8.3.1 Gas Diffusion Layer Substrates 4427.8.3.2 Microporous Layers 4447.8.3.3 Gas Diffusion Electrodes and Catalyst Layers 446References 448Further Reading 455Volume 2Preface xv8 Carbon and Graphite for Catalysis 457Dang Sheng Su, Wei Qi, and Guodong Wen9 Activated Carbon 491Klaus-Dirk Henning and Hartmut von Kienle10 Carbon Black 533Conny Oswald Vogler and Manfred Voll11 Carbon Fibers 603Michael Heine12 Carbon Fiber Composites 69712.1 Carbon Fiber Reinforced Polymers 698Klaus Drechsler, Michael Heine, and Peter Mitschang12.2 Carbon Fiber Reinforced Carbon 740Udo Gruber, Oswin Öttinger, Walter Baur, and Ludger Fischer12.3 Carbon Fiber Reinforced Ceramic Composites 825Bernhard Heidenreich and Andreas Kienzle13 Nanocarbons 885Kazunori Fujisawa, Yoong Ahm Kim, Takuya Hayashi, Kenji Takeuchi, Hiroyuki Muramatsu, Shuji Tsuruoka, Takashi Yanagisawa, Mauricio Terrones, and Morinobu EndoIndex 945