Extractive Metallurgy of Titanium

Dr Zhigang Zak Fang is a Professor in the Powder Metallurgy Research Laboratory of the Faculty of Metallurgical Engineering at the University of Utah, USA. Francis H Froes, Ph.D. has been involved in the Titanium field with an emphasis on Powder Metallurgy (P/M) for more than 40 years. He was employed by a primary Titanium producer-Crucible Steel Company-where he was leader of the Titanium group. He was the program manager on a multi-million dollar US Air Force (USAF) contract on Titanium P/M. He then spent time at the USAF Materials Lab where he was supervisor of the Light Metals group (which included Titanium). This was followed by 17 years at the University of Idaho where he was a Director and Department Head of the Materials Science and Engineering Department. He has over 800 publications, in excess of 60 patents, and has edited almost 30 books-the majority on various aspects of Titanium again with an emphasis on P/M. He gave the key-note presentation at the first TDA (ITA) Conference. In recent years he has co-sponsored four TMS Symposia on Cost Effective Titanium featuring numerous papers on P/M. He is a Fellow of ASM, is a member of the Russian Academy of Science, and was awarded the Service to Powder Metallurgy by the Metal Powder Association. Recently he has been a co-author of three comprehensive papers on the Additive Manufacturing of Titanium. Dr. Ying Zhang is an associate professor in the Institute of Process Engineering, Chinese Academy of Sciences (IPE, CAS), who joined the faculty in 2011 after the graduation. She graduated from Central South University of China with BS degree in 2006, and received her Ph.D degree from the University of Chinese Academy of Sciences in 2011 in the research field of metallurgy. From February 2014 to November 2016, Dr. Zhang joined Prof. Zak Fang’s research group in the University of Utah as a Post-doctor, working on the project of titanium metal powder production under the financial support from the DOE of US. Prior to that, Dr. Zhang was in charge of and participated in a few projects supported by either the Chinese government or industries, including NSFC, the Ministry of Science and Technology of China, Hunan Provincial Science & Technology Department, etc., focusing on the cleaner production of nonferrous metals (including Al, Cr, Zn and Cd). Now she continues her interests in the production of titanium-group metals under the financial support from NSFC as PI. Dr. Zhang has authored/co-authored over 30 publications and over 20 patents.

• ContentsContributors xi1. Introduction to the development of processes for primaryTi metal production 1Zhigang Zak Fang, Hyrum D. Lefler, F.H. Froes, and Ying ZhangReferences 8Part 1 Extractive chemical metallurgy processes 112. A brief introduction to production of titanium dioxideand titanium tetrachloride 13Michael L. Free1. Background 132. Ore sources 133. Processing methods 14References 173. Minerals, slags, and other feedstock for the productionof titanium metal 19Dimitrios Filippou and Guillaume Hudon1. Introduction 192. Ilmenite, rutile, and other natural titanium minerals 213. Ilmenite smelting to titania slag 264. Ilmenite conversion to synthetic rutile 325. Titania slag upgrading to UGS 366. Production of titanium carbide feedstock 377. Conclusions 38Acknowledgments 41References 414. Chemical processes for the production of titanium tetrachlorideas precursor of titanium metal 47Guillaume Hudon and Dimitrios Filippou1. Introduction 472. Titanium tetrachloride 473. Production of titanium tetrachloride 494. Titanium tetrachloride purification 555. Production of pure titanium dioxide 566. Other precursors 59Acknowledgments 60References 60Part 2 Thermochemical reduction of TiCl4 635. Fundamentals of thermochemical reduction of TiCl4 65Toru H. Okabe and Osamu Takeda1. Historical developments in titanium metal production 652. Kroll process 663. Hunter process 714. Fundamentals of titanium reduction process 755. Electrochemical reactions during thermochemical reduction 786. Reduction mechanism of TiCl4 during the Kroll process 817. Past research for new titanium production processes 838. Summary 90References 926. The Kroll process and production of titanium sponge 97Matthew R. Earlam1. Introduction 972. Source of ore 993. Production of TiCl4 1004. Purification of TiCl4 1015. The Hunter process 1026. Armstrong process 1037. Kroll process 1038. Magnesium reduced acid leach (MRAL) (no longer practiced) 1049. Vacuum distillation process TOHO timet 10710. Preparation for melting 110References 1117. A modified Kroll process via production of TiH2 - thermochemicalreductions of TiCl4 using hydrogen and Mg 113Mykhailo Matviychuk, Andrey Klevtsov, and Vladimir S. Moxson1. Introduction 1132. Process description 1143. Experimental results 1204. Role of hydrogen for ADMA process 122References 127Further reading 128Part 3 Thermochemical reduction of TiO2 1298. Metallothermic reduction of TiO2 131Toru H. Okabe1. Introduction 1312. Studies on reduction of titanium oxide before 2000 1343. Studies on reduction of titanium oxide after 2000 1434. Future prospects of metallothermic reduction processes for directproduction of titanium from oxides 1555. Summary 159References 1609. Hydrogen assisted magnesiothermic reduction (HAMR) ofTiO2 to produce titanium metal powder 165Yang Xia, Hyrum D. Lefler, Ying Zhang, Pei Sun, and Zhigang Zak Fang1. Introduction 1652. Fundamentals of the HAMR process 1673. HAMR process description 1724. HAMR product characterization 1735. Summary 176Acknowledgments 176References 17710. Deoxygenation of Ti metal 181Ying Zhang, Zhigang Zak Fang, Pei Sun, Yang Xia, Hyrum D. Lefler,and Shili Zheng1. Introduction 1812. Thermodynamic properties of the TieO solid solutions 1823. Methods of deoxygenation 1864. Concluding remarks 206A. Appendix 207Acknowledgments 220References 220Part 4 Electrochemical reduction of TiO2 and TiOC 22511. Invention and fundamentals of the FFC Cambridge Process 227George Z. Chen and Derek J. Fray1. Background: how the concept of electro-deoxidation came about 2272. Understanding of electro-deoxidation: interactions of the oxide cathodewith molten salts 2303. Understanding of electro-deoxidation: metal/insulator/electrolyte 3PImodels 2354. Understanding of electro-deoxidation: the metal-to-oxide molar volumeratio 2365. Development of an inert anode for electro-deoxidation in calciumchloride based melts 2416. Electro-deoxidation of other metal oxides 2467. Electro-desulfidation of metal sulfides 2578. Electro-deoxidation of mixed metal oxides 2619. Titanium based medical implant materials 27310. Cathodic protection of titanium 27611. Outlook and Prospective 27812. Conclusions 279References 28012. OS process: calciothermic reduction of TiO2 via CaO electrolysisin molten CaCl2 287Ryosuke O. Suzuki, Shungo Natsui, and Tatsuya Kikuchi1. Introduction 2872. Cell design 2963. Thermodynamics of desired salt 2984. Validity of Ca reduction during electrolysis 3035. Conclusion 308References 30913. Titanium production through electrolysis of titanium oxycarbideconsumable anodedthe USTB process 315Hongmin Zhu, Shuqiang Jiao, Jiusan Xiao, and Jun Zhu1. Introduction 3152. Crystalline structure of titanium oxycarbide and titaniumoxycarbonitride 3163. Thermodynamic properties and preparation of titanium oxycarbide fromTiO2 by carbon thermal reduction 3174. Electrochemical dissolution of consumable anode 3205. Electrochemical deposition on the cathode 3256. Scaling up and practices of USTB process 326References 32814. Electrolysis of carbothermic treated titanium oxides to produceTi metal 331James C. WithersReferences 343Further reading 347Part 5 Other processes 34915. Selected processes for Ti production e a cursory review 351Pei Sun, Ying Zhang, and Zhigang Zak Fang1. Introduction 3512. Continuous processes using Mg or Na as the reductant 3523. Processes using low-cost alternatives as reductants 3564. Summary 360Acknowledgments 360References 36016. Recycling of Ti 363Osamu Takeda, Toru H. Okabe1. Introduction 3632. Ti scraps generated in the smelting process 3643. Ti scraps generated in the aircraft industry 3674. Material flow of Ti scraps 3735. Recycling technologies for Ti scraps 3746. Future perspective of recycling technologies 3777. Conclusions and future remarks 382Acknowledgments 383References 38317. Energy consumption of the Kroll and HAMR processes fortitanium production 389Yang Xia, Hyrum D. Lefler, Zhigang Zak Fang, Ying Zhang, and Pei Sun1. Introduction 3892. Review of energy consumption in the Kroll process 3903. Modeling and analysis of energy consumption in the HAMR process 3984. Energy consumption in other emerging processes 4045. Summary and comparison of Kroll and HAMR processes 405Acknowledgments 406References 407Index 411