Contributing Editors
Loren A. Jacobson Robert J. Hanrahan Los Alamos National Laboratory, Retired National Nuclear Security Agency Dennis R. Floyd Richard Alan Patterson Science Applications International Corp. Los Alamos National Laboratory Gilbert London James C. Foley U.S. Naval Air Systems Command, Retired Los Alamos National Laboratory George Fulton Frank Gibbs Lawrence Livermore National Laboratory Colorado School of Mines Don H. Hashiguchi Curtis Salmon Brush Wellman, Inc. Colorado School of Mines Mark N. Emly Angelique Lasseigne Brush Wellman, Inc. Colorado School of Mines Warren Haws Erik A. Pfeif Brush Wellman, Inc. Colorado School of Mines Christopher Dorn Donald J. Kaczynski Brush Wellman, Inc. Brush Wellman, Inc., Retired
About the cover:
The James Webb Space Telescope scheduled to launch in 2013 is a large infrared telescope. The 6.5 m (21 ft) primary mirror contains 18 hexagonal segments made of beryllium. Credit: NASA (www.jwst.nasa.gov) Beryllium Chemistry and Processing
Kenneth A. Walsh Deceased
Edited by Edgar E. Vidal Brush Wellman, Inc. Alfred Goldberg Lawrence Livermore National Laboratory Edward N.C. Dalder Lawrence Livermore National Laboratory David L. Olson Colorado School of Mines Brajendra Mishra Colorado School of Mines
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First printing, July 2009
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Dr. Kenneth A. Walsh
Kenneth Walsh was a scientist, technologist, and corporate leader in the beryllium in- dustry. Dr. Ken Walsh was a South Dakota native who attained the love of chemistry from Dr. Gregg Evans, professor of chemistry at Yankton College in South Dakota. Ken received his A.B. degree in chemistry from Yankton College in 1942. He continued his studies in chemistry at Iowa State University at Ames, Iowa until his education was in- terrupted in 1943 by an invitation to join the Manhattan Project. He started his profes- sional career at Los Alamos where he was working on the task to convert enriched ura- nium from oxide to fluoride which was then reduced to metal. His Los Alamos experiences allowed him to be a contributor to chemical metallurgy at the beginning of the atomic energy age. He also worked on the chemistry of transuranic-metals and compounds. In addition, Ken met his future wife, Dorothy, at Los Alamos. In 1946, he returned to Iowa State University to continue his research for the Atomic Energy Com- mission and finish his Ph.D. degree. He returned to Los Alamos in 1951. During the period from 1957 to 1960, Dr. Walsh did inorganic chemical research for the International Mineral and Chemical Company in Mulberry, Florida. In 1960, Dr. Walsh joined the Brush Wellman Company as Research Manager and focused the rest of his career in the science and engineering of beryllium metal and its compounds and alloys. He made many contributions to the chemical and metallurgical processing of beryl- lium. From his contributions and experiences, he was recognized as an expert in most of the scientific and technology issues associated with production of beryllium. He has numerous publications and patents and was often called upon to give presentations on beryllium to the broader mineral and metallurgical engineering community. He retired as Associate Director of Technology in 1986 and moved to Tyler, Texas. Kenneth A. Walsh 1922–1999 Preface
With the downturn in beryllium production due to changes in the international politi- cal, environmental, health and safety issues, there has been a curtailment in beryllium research and development and a significant loss in beryllium intellectual capacity. Dr. Walsh, knowing that beryllium exhibits unique and advantageous properties as a primary material and as an alloying addition, foresaw that beryllium offers significant advantages that can not be ignored if technology is to advance. Dr. Walsh envisioned a book, which would serve the function as an instructional tool to educate a scientist and engineer as to the chemistry and chemical and metallurgical processing of beryllium. This book should serve as a textbook for a short course or be complete enough to be used by an individual in self-education. This book is, also, to serve as an archive of the tremendous amount of generated knowledge, which does not need to be rediscovered. And finally, this book should offer the user a one stop resource for the necessary chem- ical and physical data that is often required by practitioners of the chemistry and/or chemical processing of beryllium. Dr. Walsh was concerned about the education of young engineers and wanted them to be fully prepared with both beryllium science and technology, but, also, to have cognizance about the health issues and the proper prac- tices to handle and process beryllium ore, metals, chemicals and waste. The book is presented in the manner of an introduction of what beryllium is, its his- tory, and its chemical and physical properties. The mineralogy of beryllium, the preferred sources, and the global source of ore bodies are presented. The identification and specifics of the industrial metallurgical processes used to form oxide from the ore and then metal from the oxide are thoroughly described. The special features of beryllium chemistry are introduced, including analytical chemical practices. Beryllium compounds of industrial interest are identified and discussed. Manufacturing processes of alloying, casting, powder metallurgy processing, forming, metal removal, joining, and others are introduced. The industrially interesting alloys are also identified and specified for their content and applications. The physical metallurgy chapter is offered to bring some con- formity between chemical and physical metallurgical processing of beryllium, metal, al- loys, and compounds. The environmental degradation of beryllium and its alloys both in aqueous and high temperature condition are presented. The health issues are thoroughly presented in one chapter written by experienced professionals. Another chapter is offered to describe the various requirements to handle beryllium in the workplace and the estab- lished practices that are available to meet these continuing requirements. A thorough list of references will assist the user of this book in further investigation. Contributors to this book come from industry, the academic world, and national labo- ratories. Each group provides their insight on beryllium technology. We would like to extend a special note of appreciation for the support of Lawrence Livermore National Laboratories in this project.
David L. Olson Colorado School of Mines Edgar E. Vidal Brush Wellman, Inc. January 2009
vii
Contents
Preface ...... vii
Chapter 1 Introduction ...... 1 1.1 Physical Properties ...... 4 1.2 Chemical Properties ...... 4
Chapter 2 History of Beryllium ...... 7 2.1 Early History...... 7 2.2 Description of the Origin of the Domestic Beryllium Industry...... 8 2.3 Description of Foreign Beryllium Production ...... 12 2.4 Current Status of the Beryllium Industry ...... 17
Chapter 3 Sources of Beryllium ...... 19 3.1 Mineralogy ...... 20 3.2 Geological Outcroppings ...... 22 3.3 Summary Statement ...... 25
Chapter 4 Physical and Nuclear Properties ...... 27 4.1 Introduction ...... 27 4.2 Atomic/Crystal Structure ...... 27 4.3 Elastic Properties ...... 27 4.4 Thermal Properties ...... 32 4.5 Nuclear Properties ...... 42 4.6 Miscellaneous Properties ...... 46
Chapter 5 Thermodynamics of Extraction ...... 55 5.1 Thermodynamic Data...... 55 5.2 Sources of Thermodynamic Data ...... 55 5.3 Reduction of BeO...... 59 5.4 Reduction of Beryllium Halides ...... 61 5.5 Hydrogen Reduction ...... 61
5.6 Thermal Decomposition of BeI2 ...... 62 5.7 Electrolytic Reduction...... 62 5.8 Refining of Beryllium by Distillation ...... 63
ix Chapter 6 Mineral Processing ...... 65 6.1 Bertrandite and Phenacite Flotation ...... 65 6.2 Beryl Concentration from Pegmatitic Gangues and Low-Grade Deposits...... 66 6.3 Concentration of Beryl Using Hydrofluoric Acid Activation ...... 66 6.4 Concentration of Beryllium Ores ...... 66 6.5 Tall Oil Fatty Acid Flotation of Phenacite and Bertrandite ...... 69
Chapter 7 Extractive Metallurgy ...... 71 7.1 Extraction from Beryl ...... 71 7.2 Kjellgren-Sawyer Sulfate Extraction from Beryl ...... 71 7.3 Degussa Extraction of Beryllium from Beryl ...... 73 7.4 Copaux-Kawecki Fluoride Extraction from Beryl...... 74 7.5 Extraction from Bertrandite and Solvent Extraction ...... 78 7.6 Beryllium from Leaching and Settling ...... 78 7.7 Solvent Extraction from Sulfate Solutions ...... 79 7.8 Electrolytic Extraction of Beryllium ...... 85 7.9 Cell Configuration ...... 86 7.10 Theoretical Rate Expression ...... 86 7.11 Electrorefining of Beryllium ...... 90
Chapter 8 Chemistry of Beryllium ...... 93 8.1 General Chemical Character of Beryllium ...... 93 8.2 Solution Chemistry of Hydrated Be2+ Ions...... 97 8.3 Beryllium Fluoride ...... 99 8.4 Chemical Behavior of Beryllium ...... 103
Chapter 9 Analytical Chemistry of Beryllium ...... 107 9.1 Sample Preparation for Beryllium Analysis ...... 107 9.2 Quantitative Procedures for Beryllium Determination...... 107 9.3 Other Methods for Beryllium Separation...... 110 9.4 Radiochemical Separation Procedures ...... 110 9.5 Radiometric Methods of Beryllium Analysis ...... 111 9.6 Spectrometric Methods ...... 112 9.7 Polarographic Methods...... 113
Chapter 10 Beryllium Compounds...... 117 10.1 Beryllium Borides ...... 117 10.2 Beryllium Carbide...... 117 10.3 Beryllium Carbonates ...... 118 10.4 Beryllium Carboxylates...... 118 10.5 Beryllium Halides ...... 118 10.6 Beryllium Hydride ...... 121 10.7 Beryllium Hydroxide ...... 121 10.8 Beryllium Nitrate ...... 121
x 10.9 Beryllium Nitride ...... 122 10.10 Beryllium Oxide ...... 122 10.11 Beryllium Oxide Carboxylates ...... 123 10.12 Beryllium Oxalate ...... 125 10.13 Beryllium Phosphates ...... 125 10.14 Beryllium Perchlorate ...... 126 10.15 Beryllium Sulfate ...... 126 10.16 Beryllium Sulfide ...... 127
Chapter 11 Beryllium Intermetallic Compounds ...... 131 11.1 Background and Historical Information ...... 131 11.2 Structures of the Beryllides ...... 132 11.3 Other Beryllium Intermetallics ...... 133 11.4 Mechanical Properties ...... 134 11.5 Oxidation Behavior ...... 138 11.6 Thermal and Electrical Properties ...... 139 11.7 Sputter Deposition ...... 140 11.8 Diffusion...... 140 11.9 Hydrogen Storage ...... 141 11.10 Fabrication of Beryllides ...... 142 11.11 Conclusions and Future Work ...... 142
Chapter 12 Amorphous Alloys That Contain Beryllium ...... 145 12.1 Introduction ...... 145 12.2 Early Work on Amorphous Alloys ...... 145 12.3 Recent Efforts ...... 147 12.4 Applications ...... 148
Chapter 13 Physical Metallurgy of Beryllium ...... 151 13.1 Beryllium Phases and Phase Transformations ...... 151 13.2 Beryllium Physical Properties ...... 151 13.3 Mechanical Properties ...... 153 13.4 Heat Treatment...... 156 13.5 Alloying ...... 157
Chapter 14 Alloying of Beryllium ...... 163 14.1 Introduction ...... 163 14.2 Alloys and Composites ...... 163 14.3 Beryllium-Aluminum Alloys ...... 164 14.4 Aluminum-Beryllium Production ...... 165 14.5 Beryllium-Antimony Alloys...... 170 14.6 Beryllium-Copper Alloys ...... 171 14.7 Transition Metals ...... 173 14.8 Beryllium-Iron Alloys ...... 173 14.9 Beryllium-Titanium Composites ...... 174
xi Chapter 15 Beryllium Binary Phase Diagrams ...... 179 15.1 Beryllium-Silver (Ag-Be) ...... 179 15.2 Beryllium-Aluminum (Al-Be) ...... 180 15.3 Beryllium-Gold (Au-Be) ...... 180 15.4 Beryllium-Boron (B-Be)...... 180 15.5 Beryllium-Barium (Ba-Be) ...... 181 15.6 Beryllium-Calcium (Be-Ca) ...... 181 15.7 Beryllium-Cobalt (Be-Co) ...... 181 15.8 Beryllium-Copper (Be-Cu) ...... 182 15.9 Beryllium-Iron (Be-Fe) ...... 182 15.10 Beryllium-Gallium (Be-Ga) ...... 183 15.11 Beryllium-Germanium (Be-Ge) ...... 183 15.12 Beryllium-Lithium (Be-Li) ...... 183 15.13 Beryllium-Magnesium (Be-Mg) ...... 183 15.14 Beryllium-Molybdenum (Be-Mo) ...... 183 15.15 Beryllium-Sodium (Be-Na) ...... 186 15.16 Beryllium-Nickel (Be-Ni) ...... 186 15.17 Beryllium-Niobium (Be-Nb) ...... 186 15.18 Beryllium-Plutonium (Be-Pu) ...... 187 15.19 Beryllium-Silicon (Be-Si)...... 187 15.20 Beryllium-Tin (Be-Sn) ...... 187 15.21 Beryllium-Titanium (Be-Ti) ...... 187 15.22 Beryllium-Uranium (Be-U) ...... 188 15.23 Beryllium-Tungsten (Be-W)...... 188 15.24 Beryllium-Yttrium (Be-Y)...... 189 15.25 Beryllium-Zinc (Be-Zn) ...... 189 15.26 Beryllium-Zirconium (Be-Zr)...... 189
Chapter 16 Metallography of Beryllium and Beryllium Alloys...... 199 16.1 Specimen Extraction ...... 199 16.2 Grinding Procedures...... 199 16.3 Polishing Procedures ...... 200 16.4 Etching Procedures ...... 202 16.5 Identification of Constituents ...... 205 16.6 Optical Microscopy ...... 206 16.7 Electron Microscopy...... 206 16.8 Microstructures of Beryllium...... 207 16.9 Toxicity Issues...... 207
Chapter 17 Mechanical Properties of Beryllium ...... 209 17.1 Vacuum Hot-Pressed Block Properties ...... 209 17.2 Hot-Isostatic-Pressed Properties ...... 213 17.3 Yield-Point and Portevin-Le Chatelier Effects ...... 214 17.4 Microyield Properties ...... 217 17.5 Fracture Toughness and Ductile-to-Brittle Transition ...... 219 17.6 Notched-Tensile and Notched-Bend Properties...... 228
xii 17.7 Fatigue Properties ...... 229 17.8 Creep Strength ...... 231 17.9 Grain Size Effects, Recrystallization, and Grain Growth ...... 233 17.10 Control and Effect of Impurities ...... 243 17.11 Hydrostatic Tests...... 246
Chapter 18 Casting of Beryllium ...... 253 18.1 Solidification of Beryllium ...... 253 18.2 Cast Structure ...... 255 18.3 Grain Refinement ...... 255 18.4 Melting Techniques ...... 257 18.5 Metal Purification ...... 262
Chapter 19 Powder Metallurgy ...... 267 19.1 Introduction ...... 267 19.2 Powder Production...... 268 19.3 Powder Consolidation ...... 271 19.4 Sintering ...... 277 19.5 Elevated-Temperature Consolidation...... 280 19.6 Properties of Powder Metallurgy Beryllium...... 285
Chapter 20 Metalworking ...... 295 20.1 Powder Consolidation ...... 295 20.2 Formability ...... 297 20.3 Rolling ...... 300 20.4 Forming ...... 305 20.5 Forging ...... 311 20.6 Extrusion ...... 316 20.7 Wire Drawing...... 322 20.8 Spinning ...... 327 20.9 Near-Net Shaping ...... 328
Chapter 21 Metal Removal ...... 339 21.1 Overview ...... 339 21.2 General Machining Guidelines...... 341 21.3 Machining-Surface Damage ...... 342 21.4 Machining Operations ...... 348
Chapter 22 Beryllium Coating Processes ...... 361 22.1 Beryllium Coatings ...... 361 22.2 Physical Vapor Deposition ...... 363 22.3 Sputtering ...... 370 22.4 Ion Plating ...... 384 22.5 Plasma Arc Spraying...... 387 22.6 Chemical Vapor Deposition ...... 393 22.7 Electroplating (Electrodeposition) ...... 395
xiii Chapter 23 Welding and Joining of Beryllium and Beryllium Alloys ...... 401 23.1 Fusion Welding ...... 401 23.2 Brazing...... 413 23.3 Solid-State Bonding ...... 421 23.4 Soldering ...... 438
Chapter 24 Adhesive Bonding and Mechanical Fasteners ...... 441 24.1 Introduction ...... 441 24.2 Classification of Adhesive Materials ...... 443 24.3 Some Structural-Adhesive Types ...... 445 24.4 Storage Life and Exposure of Adhesives ...... 447 24.5 Surface Preparation ...... 447 24.6 Applying Adhesives ...... 451 24.7 Curing Adhesives ...... 451 24.8 Mechanical Properties ...... 452 24.9 Mechanical Fasteners ...... 453
Chapter 25 Aqueous Corrosion of Beryllium and Beryllium Alloys ...... 459 25.1 Corrosion in Various Environments...... 459 25.2 Corrosion of Beryllium in Rainwater and Seawater ...... 463 25.3 Observations Related to Carbides and Other Inclusions ...... 464 25.4 Polarization Studies ...... 465 25.5 Pitting Corrosion...... 467 25.6 Crystallographic-Orientation Effect on Corrosion ...... 472 25.7 Contamination Sources and Corrosion Prevention ...... 474 25.8 Effect on Mechanical Properties ...... 478
Chapter 26 High-Temperature Corrosion of Beryllium and Beryllium Alloys ...... 485 26.1 Beryllium in Gaseous Atmospheres ...... 485 26.2 High-Temperature Corrosion-Resistant Alloys ...... 490
Chapter 27 Beryllium Waste Recycling ...... 493 27.1 Introduction ...... 493 27.2 Resource Recovery and Process Facility ...... 493 27.3 Summary ...... 498
Chapter 28 Medical Aspects of the Toxicity of Beryllium and Beryllium Alloys ...... 499 28.1 Introduction ...... 499 28.2 Beryllium Diseases ...... 500 28.3 Some Statistical Observations ...... 503 28.4 Contamination Sources...... 506 28.5 First-Aid Procedures and Precautions ...... 508 28.6 Protective and Preventive Actions...... 509 28.7 Acronyms ...... 511
xiv Chapter 29 Hygienic Practices for Handling Beryllium and Its Components ...... 513 29.1 Introduction ...... 513 29.2 Implementation of Handling Practices ...... 513 29.3 Applications ...... 516 29.4 References of Regulations...... 517
Appendix Bibliography ...... 523
Index ...... 561
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