Tung sten. Properties, Chemistry, Technology of the Element, Alloys, and Chemical Compounds. Erik Lassner and Wolf-Dieter Schubert

Transcription

1 Tung sten Properties, Chemistry, Technology of the Element, Alloys, and Chemical Compounds Erik Lassner and Wolf-Dieter Schubert Vienna University of Technology Vienna, Austria Kluwer Academie / Plenum Publishers New York, Boston, Dordrecht, London, Moscow

2 Contents CHAPTER 1. The Element Tungsten: Its Properties 1.1. Analogous to Atom Related Physical Properties Nucleus Electron Configuration Spectra Thermodynamic Functions Bulk Tungsten Metal Related Physical Properties Electronic Structure and Bonding Structural Properties Mechanical Properties Thermal Properties Electromagnetic Properties Optical Properties Electron Emission Acoustic Properties Chemical Properties of Tungsten Metal General Remarks Reactions with Nonmetals Reactions with Metals Reactions with Compounds Reactions with Aqueous Solutions Miscellaneous Reactions with Organic Compounds 56 References for Chapter 1 56 CHAPTER 2. Tungsten History: From Genesis to the 20th Century Products 2.1. The Formation of Tungsten Atoms How Tungsten Atoms Came on Earth Average Abundance Geology: Formation of Ore Deposits 65 Ulf

3 xiv CONTENTS 2.5. Minerals Ore Deposits and Reserves Early Discoveries of Ores, Compounds, and of the Element Technically Important Discoveries Industrial Evolution 80 References for Chapter 2 83 CHAPTER 3. Important Aspects of lbngsten Chemistry 3.1. Oxidation of Tungsten Metal by Air or Oxygen Reaction of Tungsten with Water Reduction of Tungsten Oxides by Hydrogen Introduction Thermodynamic Considerations Formation of a Volatile Tungsten Oxide Hydrate [W02(OH)2] Kinetic Considerations Influence of Foreign Elements Reduction of Tungsten Oxides by Carbon or Carbon-Containing Compounds Reduction of Tungsten Halides Introduction Reduction of WF Reduction of WC16 by Hydrogen Reduction of WCI6 by Carbon-Containing Reagents Reaction of Tungsten with Carbon or Carbon-Containing Compounds (Carburization) Carburization of Tungsten Powder by Solid Carbon Formation of Tungsten Carbides in Melts Preparation of Coarse Tungsten Carbide Powder in an Auxiliary Melt Preparation of Tungsten Carbide in Satt Melts Chemistry of Aqueous Tungsten Solutions Electrochemistry of Tungsten Introduction Cathode Reactions Anodic Processes Motten Salts Practical Applications of Electrochemical Processes Electrochromism 126 References for Chapter CHAPTER 4. Tungsten Compounds and Their Application 4.1. Tungsten and Metals: Intermetallic Compounds and Phases Tungsten and Nonmetals 133

4 CONTENTS xv Tungsten and Boron Tungsten and Carbon Tungsten and Silicon Tungsten and Nitrogen Tungsten and Phosphorus Tungsten and Arsenic limgsten and Oxygen Tungsten and Sulfirr 'Ringsten and Selenium Tungsten and Telluriurn ungsten and Fluorine 'Fungsten and Chlorine Tungsten and Bromine Tungsten and Iodine Mixed Ligand and Coordination Compounds of Tungsten Mixed Ligand Compounds Coordination Compounds Organometallic Tungsten Compounds 176 References for Chapter CHAPTER 5. Industrial Production 5.1. Mining and Ore Beneficiation Mining Ore Beneficiation Hydrometallurgy Introduction including Ecological and Economical Considerations Raw Materials and Their Treatment Digestion Dissolution Purification Steps Conversion of Sodium to Ammonium Isopolytungstate Solution Modem Methods in Chinese Plants Ammonium Paratungstate Crystallization The Highly Pure Intermediates Ammonium Paratungstate (APT) Tungsten Trioxide Tungsten Blue Oxide (TBO) Tungstic Acid Ammonium Metatungstate (AMT) Tungsten Metal Powder Production General Push-Type Fumace Rotary Fumace Ttuigsten Powder 225

5 xvi CONTENTS Reduction of Doped Tungsten Oxides Powder Metallurgy Compacting Sintering Fabrication of Tungsten Alternative Processes Electson-Beam Zone Melting Plasma Spraying Chemical Vapor Deposition Physical Vapor Deposition (Sputtering) Special Tungsten Forms and Qualities Globular Tungsten Powder Coarse Tungsten Powder Single Crystals Tungsten Thin Films Porous Tungsten High-Purity Tungsten 247 References for Chapter CHAPTER 6. Tungsten Alloys 6.1. Substitutional Alloys (Solid-Solution Alloys) Tungsten Rhenium Alloys Tungsten Tantalum Alloys Tungsten Titanium Alloys Dispersion-Strengthened and Precipitation-Hardening Alloys Non-Sag Tungsten Alloys with Oxide Dispersoids Alloys with Carbide Dispersoids Tungsten Composites Tungsten Heavy Metal Alloys Tungsten Copper and Twigsten Silver Itingsten-Fiber-Reinforced Composites 278 References for Chapter CHAPTER 7. Tungsten and Tungsten Alloy Products 7.1. Lighting Application Electrical Engineering Electronics High-Temperature Technique Welding, Cutting, Plasma Spraying, Spark Erosion, and Vapor Deposition X-Rays, Radiation, Medical Engineering Mechanical and Engine Engineering 298

6 CONTENTS :vh 7.8. Leisure Time and Sports Equipment Chemical Industry and Metallurgy Space Aviation Military Applications Aviation Laser Technique 304 References for Chapter CHAPTER 8. Tungsten in Meiting Metallurgy 8.1. Tungsten in Steel Introduction Master Alloys Tungsten Alloyed Steels Superalloys Stellite Alloys 318 References for Chapter CIIAPTER 9. Tungsten in Hardmetals 9.1. Introduction Raw Materials Tungsten Carbide Powder Other Carbide Powders Binder Metals Other Materials Hardmetal Production Preparation of Powder Grades Powder Consolidation Sintering Postsinter Treatments Hardmetal Qualities and Applications 353 References for Chapter CHAPTER 10. Tungsten in Cataiysis Metallic Tungsten Survey Hydrodesulfurization and Hydrodenitrogenation Oxides Survey DENOX SCR Catalysts Halides Carbon Compounds 368

7 Miii CONTENTS Survey Preparation of Carbide Catalysts WC W2C Tungsten Carbide Catalysts in Fischer Tropsch Synthesis Organotungsten Compounds: Catalysts in ROMP and ADMET Tungstates Chalkogenides 374 References for Chapter CHAPTER 11. Tungsten Scrap Recycling Introduction and General Considerations Tungsten Recycling Methods Hydrometallurgy Melting Metallurgy Direct Recycling Semidirect Recycling 384 References for Chapter CHAPTER 12. Ecology Introduction Mining and Ore Dressing Chemical Conversion Powder Metallurgy Environmental Considerations about the Substitution of High Speed Steel by Hardmetals 394 References for Chapter CHAPTER 13. Economy Introduction World Mine Production Price of Tungsten Supply and Demand Consumption and Use The "International Tungsten Industry Association" (MA) 406 Referemes for Chapter CHAPTER 14. Tungsten and Living Organisms Introduction Tungsten in Bacteria (Tungsten Enzymes) 410

8 CONTENTS :ix Tungsten and Animals Rats Mice Guinea Pigs Rabbits Tungsten and Humans Important Data Hardmetal Disease Beneficial Influences 414 References for Chapter Index 417