PHYSICAL CHEMISTRY OF METALLURGICAL PROCESSES PHYSICAL CHEMISTRY OF METALLURGICAL PROCESSES M. SHAMSUDDIN B.Sc.(Met.Engg.),M.Sc.(Met.Engg.),Ph.D.(Met.Engg.) ExProfessor andHead,Department of Metallurgical Engineering, Banaras Hindu University, Varanasi, India Copyright©2016byTheMinerals,Metals&MaterialsSociety. Allrightsreserved. PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey. PublishedsimultaneouslyinCanada. Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorbyany means,electronic,mechanical,photocopying,recording,scanning,orotherwise,exceptaspermittedunderSection107or 108ofthe1976UnitedStatesCopyrightAct,withouteitherthepriorwrittenpermissionofTheMinerals,Metals,& MaterialsSociety,orauthorizationthroughpaymentoftheappropriateper-copyfeetotheCopyrightClearance Center,Inc.,222RosewoodDrive,Danvers,MA01923,(978)750-8400,fax(978)750-4470,oronthewebat www.copyright.com.RequeststothePublisherforpermissionshouldbeaddressedtothePermissionsDepartment, JohnWiley&Sons,Inc.,111RiverStreet,Hoboken,NJ07030,(201)748-6011,fax(201)748-6008,oronlineat http://www.wiley.com/go/permissions. LimitofLiability/DisclaimerofWarranty:Whilethepublisherandauthorhaveusedtheirbesteffortsinpreparing thisbook,theymakenorepresentationsorwarrantieswithrespecttotheaccuracyorcompletenessofthecontentsofthis bookandspecificallydisclaimanyimpliedwarrantiesofmerchantabilityorfitnessforaparticularpurpose.Nowarranty maybecreatedorextendedbysalesrepresentativesorwrittensalesmaterials.Theadviceandstrategiescontained hereinmaynotbesuitableforyoursituation.Youshouldconsultwithaprofessionalwhereappropriate.Neitherthe publishernorauthorshallbeliableforanylossofprofitoranyothercommercialdamages,includingbutnotlimited tospecial,incidental,consequential,orotherdamages. Wileyalsopublishesbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmaynotbeavailable inelectronicformats.FormoreinformationaboutWileyproducts,visitthewebsiteatwww.wiley.com.Forgeneral informationonotherWileyproductsandservicesorfortechnicalsupport,pleasecontacttheWileyCustomerCare DepartmentwithintheUnitedStatesat(800)762-2974,outsidetheUnitedStatesat(317)572-3993orfax(317)572-4002. LibraryofCongressCataloging-in-PublicationData: Shamsuddin,M.(Mohammad),1945– Physicalchemistryofmetallurgicalprocesses/M.Shamsuddin. pages cm Includesbibliographicalreferencesandindex. ISBN978-1-119-07833-3(cloth)–ISBN978-1-119-07832-6(oBook)–ISBN978-1-119-07831-9(ePDF)– ISBN978-1-119-07827-2(ePUB) 1. Metallurgy. 2. Chemistry,Physicalandtheoretical. I. Title. TN665.S48252016 669.9–dc23 2015024793 CoverimagecourtesyofM.Shamsuddin. Setin10/12ptTimesbySPiGlobal,Pondicherry,India PrintedintheUnitedStatesofAmerica. 10 9 8 7 6 5 4 3 2 1 1 2016 CONTENTS Preface xi Foreword xvii List of Symbols xix 1 Introduction 1 1.1 Thermodynamic Quantitiesand their Interrelationships, 5 1.1.1 General Thermodynamics, 5 1.1.2 Solution Thermodynamics, 15 Further Reading, 37 2 Roasting of Sulfide Minerals 39 2.1 Methods of Roasting, 40 2.2 Objectives, 41 2.3 Chemistry of Roasting, 42 2.4 Thermodynamics of Roasting, 43 2.5 Kinetics of Roasting, 47 2.6 Predominance Area Diagrams as a Useful Guide in Feed Preparation, 51 2.7 Problems, 53 References, 68 3 Sulfide Smelting 71 3.1 Matte Smelting of Chalcopyrite, 72 3.1.1 Flash Smelting, 74 3.1.2 Submerged Tuyere Smelting, 76 vi CONTENTS 3.1.3 Matte Converting, 76 3.1.4 Ausmelt/Isasmelt:TopSubmergedLancing(TSL)Technology, 80 3.2 Matte Smelting of Galena, 83 3.3 Matte Smelting of Nickel Sulfide, 85 3.3.1 Theory of Direct Conversion of MoltenNickel Sulfide into Nickel, 87 3.4 Continuous Converting, 89 3.4.1 Noranda Continuous Converting Process, 90 3.4.2 Outokumpu FlashConverting Process, 90 3.4.3 Mitsubishi Continuous Converting Process, 91 3.5 Direct Metal Extraction from Concentrates, 92 3.5.1 Outokumpu FlashSmeltingProcess, 93 3.5.2 Mitsubishi Process, 94 3.6 Problems, 96 References, 100 4 Metallurgical Slag 103 4.1 Structure of Oxides, 103 4.1.1 Role of Ion Dimension, 104 4.1.2 Metal–Oxygen Bonds, 106 4.2 Structure of Slag, 108 4.3 Properties of Slag, 110 4.3.1 Basicity of Slag, 110 4.3.2 OxidizingPower of Slag, 112 4.3.3 Sulfide Capacity of Slag, 112 4.3.4 Electrical and Thermal Conductivity, 113 4.3.5 Viscosity, 113 4.3.6 Surface Tension, 117 4.3.7 Diffusivity, 117 4.4 Constitution of Metallurgical Slag, 118 4.4.1 State of Oxidation of Slag, 120 4.5 SlagTheories, 125 4.5.1 Ionic Theories, 126 4.5.2 Molecular Theory, 130 4.6 Problems, 131 References, 143 5 Reduction of Oxides and Reduction Smelting 145 5.1 Reduction Methods, 146 5.2 Thermodynamics of Reduction of Oxides, 147 5.2.1 Metallothermic Reduction, 148 5.2.2 Thermal Decomposition, 154 CONTENTS vii 5.2.3 Reduction with Carbon Monoxide, 155 5.2.4 Reduction with Hydrogen, 159 5.3 Kinetics of Reduction of Oxides, 161 5.3.1 ChemicalReactionwithPorousandNonporousProductFilm, 162 5.4 Commercial Processes, 170 5.4.1 Productionof Iron, 170 5.4.2 Productionof Zinc, 174 5.4.3 Productionof Tungsten andMolybdenum, 177 5.5 Problems, 179 References, 196 6 Interfacial Phenomena 199 6.1 Precipitation, 201 6.2 Nucleation of Gas Bubbles in a Liquid Metal, 205 6.2.1 Role of Interfaces in Slag–Metal Reactions, 208 6.3 Emulsion andFoam, 209 6.4 FrothFlotation, 211 6.5 Other Applications, 213 6.6 Problems, 214 References, 230 7 Steelmaking 233 7.1 Steelmaking Processes, 234 7.1.1 Bessemer Process, 234 7.1.2 Open Hearth Process, 235 7.1.3 Electric Arc Furnace (EAF) Process, 236 7.1.4 Top-Blown Basic Oxygen Converter Process, 236 7.1.5 Rotating Oxygen-Blown Converter Process, 238 7.1.6 Bottom-Blown Oxygen Converter Process, 239 7.1.7 Hybrid/Bath Agitated/Combined-Blown Process, 240 7.2 Physicochemical Principles, 242 7.2.1 Sulfur Reactions, 242 7.2.2 Phosphorus Reactions, 246 7.2.3 Silicon Reactions, 250 7.2.4 Manganese Reactions, 251 7.2.5 Carbon Reactions, 253 7.2.6 Kinetics of Slag–Metal Reactions, 256 7.3 Pre-treatment of Hot Metal, 261 7.3.1 External Desiliconization, 262 7.3.2 External Desulfurization, 262 7.3.3 External Dephosphorization, 262 7.3.4 Simultaneous Removal of Sulfur and Phosphorus, 263 viii CONTENTS 7.4 Chemistry of Refining, 264 7.4.1 Bessemer Process, 264 7.4.2 Open Hearth Process, 266 7.4.3 Electric Arc Furnace (EAF) Process, 266 7.4.4 Top-Blown Basic Oxygen Converter Process, 267 7.4.5 Rotating Oxygen-Blown Converter Process, 272 7.4.6 Bottom-Blown Oxygen Converter Process, 274 7.4.7 Hybrid/BathAgitated/Combined-Blown Process, 276 7.5 Problems, 279 References, 286 8 Secondary Steelmaking 289 8.1 Inert Gas Purging (IGP), 290 8.2 Ladle Furnace (LF), 291 8.3 Deoxidation, 291 8.3.1 Choice of Deoxidizers, 293 8.3.2 Complex Deoxidizers, 294 8.3.3 Vacuum Deoxidation, 299 8.3.4 Deoxidation Practice, 299 8.3.5 Removal of Deoxidation Products, 300 8.4 Stainless Steelmaking, 301 8.4.1 Physicochemical Principles, 302 8.4.2 Stainless Steelmaking Processes, 305 8.5 Injection Metallurgy(IM), 307 8.6 Refining with Synthetic Slag, 309 8.7 Vacuum Degassing, 311 8.7.1 Nitrogen in Iron and Steel, 312 8.7.2 Hydrogen in Iron and Steel, 315 8.7.3 Vacuum Treatmentof Steel, 319 8.8 Problems, 325 References, 348 9 Role of Halides in Extraction of Metals 351 9.1 Preparation of Halides, 354 9.1.1 Complex Fluoride Processes, 354 9.1.2 Halogenation of Oxides, 355 9.1.3 Halogenation of Ferro-Alloys, 359 9.1.4 Crystallization from Aqueous Solution, 360 9.2 Purification of Chlorides, 362 9.2.1 Purificationof Titanium Tetrachloride, 363 9.2.2 Purificationof Columbium Pentachloride, 363 9.2.3 Purificationof Vanadium Tetrachloride, 363