ASM specialty handbook : nickel, cobalt, and their alloys

414 Pages·2000·19.877 MB·English

by  J R Davis, ASM International. Handbook Committee

© 2000 ASM International. All Rights Reserved. www.asminternational.org
ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys (#06178G)
Contents
Introduction to Nickel and Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . .1 Cleaning and Finishing of Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . .273
High-Temperature Coatings for Superalloys. . . . . . . . . . . . . . . . . . . .281
The Nickel Industry: Occurrence, Recovery, and Consumption. . . . . . .3
Uses of Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7 Metallography, Microstructures, and Phase Diagrams of
Wrought Corrosion Resistant Nickels and Nickel Alloys. . . . . . . . . . .14 Nickel and Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .291
Cast Corrosion Resistant Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . .55
Metallography and Microstructures of Nickel, Nickel-Copper, and
Cast Heat Resistant Nickel-Chromium and Nickel-Chromium-Iron
Nickel-Iron Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .293
Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .62
Metallography and Microstructures of Heat Resistant Alloys. . . . . . .298
Superalloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
Phase Diagrams of Binary and Ternary Nickel Systems. . . . . . . . . . .331
Special-Purpose Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Nickel Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .106 Introduction to Cobalt and Cobalt Alloys. . . . . . . . . . . . . . . . . . . .343
Corrosion Behavior of Nickel and Nickel Alloys. . . . . . . . . . . . . . .125 The Cobalt Industry: Occurrence, Recovery, and Consumption. . . . .345
Uses of Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .349
Corrosion Behavior of Nickel Alloys in Specific
Environment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .127 Phase Diagrams of Binary and Ternary Cobalt Systems. . . . . . . . . . .356
Stress-Corrosion Cracking and Hydrogen Embrittlement of Cobalt-Base Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .362
Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .141
Properties and Fabrication Characteristics of
High-Temperature Corrosion Behavior of Nickel Alloys. . . . . . . . . .167
Cobalt and Cobalt Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .371
Fabrication and Finishing of Nickel and Nickel Alloys . . . . . . . . .189
Properties of Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .373
Forming of Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191 Wear Behavior of Cobalt Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . .387
Forging of Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 Corrosion Behavior of Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . .395
Powder Metallurgy Processing of Nickel Alloys. . . . . . . . . . . . . . . . .203 Fabrication and Metallography of Cobalt Alloys. . . . . . . . . . . . . . . . .401
Heat Treating of Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .230
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .407
Machining of Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Welding and Brazing of Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . .245 Alloy Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .422
© 2000 ASM International. All Rights Reserved. www.asminternational.org
ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys (#06178G)

ASM Specialty Handbook
Nickel, Cobalt, and Their Alloys
Edited by
J. R. Davis
Davis & Associates
Prepared under the direction of the
ASM International Handbook Committee
ASM International Staff
Scott D. Henry,Assistant Director of Reference Publications
Bonnie R. Sanders,Manager of Production
Nancy Hrivnak,Copy Editor
Kathleen S. Dragolich,Production Supervisor
Jill A. Kinson and Candace K. Mullet,Production Coordinators
William W. Scott, Jr.,Director of Technical Publications
ASM International
Materials Park, OH 44073
www.asminternational.org
© 2000 ASM International. All Rights Reserved. www.asminternational.org
ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys (#06178G)
Copyright2000
by
ASM International®
All rights reserved
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Comments, criticisms, and suggestions are invited, and should be forwarded to ASM International.
Library of Congress Cataloging-in-Publication Data
ASM specialty handbook: nickel, cobalt, and their alloys / edited by J. R. Davis;
prepared under the direction of the ASM International Handbook Committee.
p. cm.
Includes bibliographical references and index.
1. Nickel—Handbooks, manuals, etc. 2. Nickel alloys—Handbooks, manuals, etc. 3. Cobalt—Handbooks, man-
uals, etc.
4. Cobalt alloys—Handbooks, manuals, etc. I. Davis, J.R. (Joseph R.) II. ASM International. Handbook Com-
mittee.
TA480.N6A282000 620.1’88—dc21 00-059348
ISBN:0-87170-685-7
SAN:204-7586
ASM International®
Materials Park, OH 44073-0002
www.asminternational.org
Printed in the United States of America
© 2000 ASM International. All Rights Reserved. www.asminternational.org
ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys (#06178G)
Contents
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .v Nickel-ChromiumAlloystoResistFuelOilAshCorrosion. . .62
Nickel-Iron-Chromium Alloys . . . . . . . . . . . . . . . . . . . . . . . .63
Introduction to Nickel and Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . .1
Nickel-Chromium-Iron Alloys . . . . . . . . . . . . . . . . . . . . . . . .66
The Nickel Industry: Occurrence, Recovery, and Consumption. . . . . . .3 Superalloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
Elemental Nickel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 General Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .68
Occurrence and Supply. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .73
Extraction and Refining. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Properties and Microstructure. . . . . . . . . . . . . . . . . . . . . . . . .79
End Uses of Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 Environmental Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .85
Uses of Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7 Special-Purpose Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .92
Nickel in Ferrous Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7 Commercially Pure Nickel for Electronic Applications. . . . .92
Nickel and Nickel-Base Alloys. . . . . . . . . . . . . . . . . . . . . . . . .9 Resistance Heating Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . .92
Nickel Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10 Thermocouple Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .94
Nickel in Nonferrous Alloys. . . . . . . . . . . . . . . . . . . . . . . . . .10 Nickel-Iron Soft Magnetic Alloys. . . . . . . . . . . . . . . . . . . . . .94
Nickel Powders. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10 Low-Expansion Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .96
Wrought Corrosion Resistant Nickel and Nickel Alloys. . . . . . . . . . . .14 Nickel-Titanium Shape Memory Alloys. . . . . . . . . . . . . . . .101
Physical Metallurgy of Nickel and Nickel Alloys. . . . . . . . . .14 Nickel-Beryllium Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . .102
Commercial Nickel and Nickel Alloys. . . . . . . . . . . . . . . . . .15 Ordered Intermetallic Alloys of Ni Al . . . . . . . . . . . . . . . . .104
3
Properties of Wrought Nickel and Nickel Alloys . . . . . . . . . . . . .19 Nickel Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .106
Nickel 200. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .19 Nickel Plating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .106
Nickel 201. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .20 Electroforming. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .114
Nickel 270. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21 Electroless Nickel Plating. . . . . . . . . . . . . . . . . . . . . . . . . . .115
Duranickel 301 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22 Thermal Spray Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . .120
Monel 400. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .23 Weld-Overlay Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . .120
Monel R-405. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25 Solid-State Nickel Cladding . . . . . . . . . . . . . . . . . . . . . . . . .122
Monel K-500. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .26
Inconel 600 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .27 Corrosion Behavior of Nickel and Nickel Alloys. . . . . . . . . . . . . . .125
Inconel 622 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .29
Corrosion Behavior of Nickel Alloys in Specific Environments. . . . .127
Inconel 625 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .30
Alloy Characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .127
Inconel 686 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .31
Effects of Major Alloying Elements. . . . . . . . . . . . . . . . . . .129
Inconel 690 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32
Corrosion in Specific Environments. . . . . . . . . . . . . . . . . . .130
Inconel 718 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .33
Corrosion of Nickel and High-Nickel Alloy Weldments . . .137
Inconel 725 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .36
Stress-Corrosion Cracking and Hydrogen Embrittlement
Incoloy 800 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .37
of Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .141
Incoloy 801 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
Physical Metallurgy of Nickel-Base Alloys . . . . . . . . . . . . .141
Incoloy 825 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .39
SCC in Halide Environments . . . . . . . . . . . . . . . . . . . . . . . .143
Hastelloy B-2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .41
SCC in Environments Containing Sulfur Species. . . . . . . . .147
Hastelloy B-3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .42
SCC in High-Temperature Water and Dilute
Hastelloy C-4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .43
Aqueous Solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .152
Hastelloy C-22. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .44
SCC in Caustic Environments. . . . . . . . . . . . . . . . . . . . . . . .154
Hastelloy C-276. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .45
Hastelloy C-2000. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .46 Cracking in Other Environments. . . . . . . . . . . . . . . . . . . . . .157
Hastelloy G . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .47 Hydrogen Embrittlement. . . . . . . . . . . . . . . . . . . . . . . . . . . .157
Hastelloy G-3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .48 SCC Testing Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .160
Hastelloy G-30. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .49 High-Temperature Corrosion Behavior of Nickel Alloys. . . . . . . . . .167
Hastelloy G-50. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .50 Oxidation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .167
Hastelloy N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .51 Carburization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .172
Hastelloy S. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .52 Nitridation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .173
Hastelloy W. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .53 Sulfidation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .176
Hastelloy X . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .53 Halogenation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .177
Cast Corrosion-Resistant Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . .55 Hot Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .182
Standard Grades. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .55 Ash/Salt Deposit Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . .183
Nickel-Base Proprietary Alloys. . . . . . . . . . . . . . . . . . . . . . . .57 Corrosion in Waste Incineration Environments . . . . . . . . . .183
Cast Heat Resistant Nickel-Chromium, Nickel-Iron-Chromium, and Molten Salt Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .184
Nickel-Chromium-Iron Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .62 Molten Metal Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . .186
iii
© 2000 ASM International. All Rights Reserved. www.asminternational.org
ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys (#06178G)
Fabrication and Finishing of Nickel and Nickel Alloys . . . . . . . . .189 Metallography and Microstructures of Nickel and
Nickel-Copper Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . .293
Forming of Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .191
Metallography and Microstructures of Nickel-Iron Alloys. .294
Factors Influencing Formability . . . . . . . . . . . . . . . . . . . . . .191
Metallography and Microstructures of Heat Resistant Alloys. . . . . . .298
Special Considerations for Heat-Resistant Alloys . . . . . . . .191
Specimen Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .298
Lubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .192
Microexamination. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .300
Tools and Equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .192
Microstructures of Wrought Heat Resistant Alloys . . . . . . .301
Shearing, Blanking, and Piercing . . . . . . . . . . . . . . . . . . . . .193
Phases in Wrought Heat Resistant Alloys. . . . . . . . . . . . . . .302
Deep Drawing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .193
Phase Diagrams of Binary and Ternary Nickel Systems. . . . . . . . . . .331
Spinning. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .194
Bending Tube and Pipe. . . . . . . . . . . . . . . . . . . . . . . . . . . . .195 Introduction to Cobalt and Cobalt Alloys. . . . . . . . . . . . . . . . . . . .343
Bending of Plate, Sheet, and Strip. . . . . . . . . . . . . . . . . . . . .196
The Cobalt Industry: Occurrence, Recovery, and Consumption. . . . .345
Expanding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .196
Elemental Cobalt. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .345
Forming of Rod and Bar. . . . . . . . . . . . . . . . . . . . . . . . . . . .196
Occurrence and Supply. . . . . . . . . . . . . . . . . . . . . . . . . . . . .345
Cold Heading and Cold Extrusion. . . . . . . . . . . . . . . . . . . . .197
Extraction and Refining. . . . . . . . . . . . . . . . . . . . . . . . . . . . .345
Straightening. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .197
End Uses of Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .347
Cold-Formed Parts for High-Temperature Service. . . . . . . .197
Uses of Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .349
Forging of Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .198
Metallurgical Uses of Cobalt. . . . . . . . . . . . . . . . . . . . . . . . .349
Die Materials and Lubrication. . . . . . . . . . . . . . . . . . . . . . . .198
Nonmetallurgical Uses of Cobalt . . . . . . . . . . . . . . . . . . . . .354
Heating for Forging. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .198
Phase Diagrams of Binary and Ternary Cobalt Systems. . . . . . . . . . .356
Cooling after Forging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .199
Cobalt-Base Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .362
Forging Practice for Specific Alloys. . . . . . . . . . . . . . . . . . .199
Cobalt-Base Wear Resistant Alloys . . . . . . . . . . . . . . . . . . .363
Thermal-Mechanical Processing (TMP). . . . . . . . . . . . . . . .201
Cobalt-Base Heat Resistant Alloys. . . . . . . . . . . . . . . . . . . .365
Isothermal Forging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .202
Cobalt-Base Corrosion Resistant Alloys. . . . . . . . . . . . . . . .367
Powder Metallurgy Processing of Nickel Alloys . . . . . . . . . . . . . . . .203
Alloy Compositions and Product Forms. . . . . . . . . . . . . . . .368
Production of Nickel Powders. . . . . . . . . . . . . . . . . . . . . . . .203
Properties and Fabrication Characteristics of Cobalt and
Sintering of Nickel and Nickel Alloys . . . . . . . . . . . . . . . . .211
Cobalt Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .371
Roll Compacting of Nickel and Nickel Alloys. . . . . . . . . . .214
Conventional P/M Superalloy Processing. . . . . . . . . . . . . . .215 Properties of Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .373
Specialized P/M Superalloy Processing . . . . . . . . . . . . . . . .220 AiResist 13 (AR-13). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .373
Heat Treating of Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .230 AiResist 213 (AR-213). . . . . . . . . . . . . . . . . . . . . . . . . . . . .373
Types of Heat Treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . .230 AiResist 215 (AR-215). . . . . . . . . . . . . . . . . . . . . . . . . . . . .373
Annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .231 Duratherm 600. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .374
Process Control Factors in Annealing. . . . . . . . . . . . . . . . . .232 Elgiloy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .374
Stress Relieving. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233 FSX-414 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .376
Stress Equalizing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233 Haynes 25 (L-605). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .376
Age Hardening. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .233 Haynes 188 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .377
Thermomechanical Processing . . . . . . . . . . . . . . . . . . . . . . .234 MAR-M 302 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .379
Machining of Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .235 MAR-M 322 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .379
Machinability Categories. . . . . . . . . . . . . . . . . . . . . . . . . . . .235 MAR-M 509 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .379
Basic Principles Applicable to All Machining Operations. .236 MP35N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .380
Recommendations for Machining. . . . . . . . . . . . . . . . . . . . .237 MP159. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .382
Welding and Brazing of Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . .245 Stellite 6B (Haynes 6B). . . . . . . . . . . . . . . . . . . . . . . . . . . . .382
Welding Metallurgy of Corrosion Resistant Alloys . . . . . . .245 Stellite 6K . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .384
Welding Metallurgy of Corrosion Resistant Alloys Ultimet. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .384
Containing Molybdenum. . . . . . . . . . . . . . . . . . . . . . . . . .251 UMCo-50 (Haynes 150) . . . . . . . . . . . . . . . . . . . . . . . . . . . .385
Welding Metallurgy of Heat Resistant Alloys . . . . . . . . . . .255 X-40/X-45. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .386
Consumable Selection, Procedure Development, Wear Behavior of Cobalt Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . .387
and Practice Considerations . . . . . . . . . . . . . . . . . . . . . . .257 Types of Wear. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .387
Brazing of Heat Resistant Nickel-Base Alloys. . . . . . . . . . .267 Wrought Alloy Wear Data. . . . . . . . . . . . . . . . . . . . . . . . . . .388
Cleaning and Finishing of Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . .273 Hot Hardness Values for Wrought Alloys. . . . . . . . . . . . . . .392
Cleaning and Finishing of Corrosion Resistant Wear-Related Applications for Wrought Alloys. . . . . . . . . .393
Nickel Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .273 Wear Behavior of Cobalt-Base Hardfacing Alloys. . . . . . . .393
Cleaning and Finishing of Heat Resistant Nickel Alloys . . .278 Corrosion Behavior of Cobalt Alloys . . . . . . . . . . . . . . . . . . . . . . . . .395
High-Temperature Coatings for Superalloys . . . . . . . . . . . . . . . . . . .281 The Effect of Alloying Elements. . . . . . . . . . . . . . . . . . . . . .395
Coating Requirements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .281 Behavior of Cobalt Alloys in Corrosive
Types of Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .281 Aqueous Environments. . . . . . . . . . . . . . . . . . . . . . . . . . .395
Methods of Applying Diffusion Coatings. . . . . . . . . . . . . . .283 Environmental Embrittlement of Cobalt Alloys. . . . . . . . . .398
Properties of Diffusion Coatings. . . . . . . . . . . . . . . . . . . . . .284 High-Temperature Corrosion of Cobalt Alloys. . . . . . . . . . .399
Practical Applications of Diffusion Coatings. . . . . . . . . . . .286 Fabrication and Metallography of Cobalt Alloys. . . . . . . . . . . . . . . . .401
Methods of Applying Overlay Coatings. . . . . . . . . . . . . . . .287 Heat Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .401
Thermal Barrier Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . .287 Workability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .401
Coating Performance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .288 Joinability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .402
Machinability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .403
Metallography, Microstructures, and Phase Diagrams of
Metallography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .404
Nickel and Nickel Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .291
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .407
MetallographyandMicrostructuresofNickel,Nickel-Copper,
andNickel-IronAlloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .293 Alloy Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .422
iv
© 2000 ASM International. All Rights Reserved. www.asminternational.org
ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys (#06178G)
Preface
The history and development of nickel and cobalt, as well as their arsenical fumes when roasted. The word means a goblin or “ill-natured
alloys,paralleloneanotherinanumberofways.Nickelwasfirstusedby fairy.”ThemoderncobaltindustrydatesbacktotheopeningoftheNew
ancient man in swords and implements fashioned from iron-nickel Caledonia mines in 1875 and the discovery of cobalt-bearing ores in
meteorites. The first authenticated artifact from such a source is what is Africa in the early 20th century. The first cobalt-base alloy was a
believedtobeaportionofadaggerfoundattheSumeriancityofUr(circa cobalt-chromium alloy containing nominally 25% chromium called
3100 B.C.); analysis has shown it to contain 10.9% nickel. The earliest “Stellite,”whichwasdevelopedbyElwoodHaynesandpatentedin1907.
recordeduseofnickelinmoderntimes(i.e.,thelastfewhundredyears) HaynestookthenameStellitefromtheLatinwordforstar,stella,because
was in coins made from “pai-thung,” a white copper-nickel alloy first
ofthealloy’spermanentstarlikeluster.Todaycobaltisusedasacritical
developedinChina.NickelwasfirstidentifiedasanelementbyAlexF.
alloying element in superalloys, cemented carbides, and high-speed tool
Cronstedt in 1751 and named nickel from the ore “kupfernickel,”
steels,asthebaseelementforwear,heat,andcorrosionresistantalloys,in
so-calledbysuperstitiousminerswhobelievedthattheorewasbedeviled.
magneticalloysandcontrolled-expansionalloys,andinvariouselectronic
The modern nickel industry dates back from the opening of the New
components and chemicals.
Caledoniaminesin1875andthoseofSudbury,Ontario,Canada,in1886.
Inrecognitionoftheimportanceoftheseversatileandstrategicmetals,
Thefirstnickel-basealloydevelopedwas“MonellMetal”(nowknownas
ASMdecidedthatthisHandbook,theeighthtobepublishedintheASM
Monelalloy400),anickel-copperalloycontainingnominally67%nickel
Specialty Handbook series, would cover the metallurgy, properties,
withthebalancecopper.Thealloy’soriginwasderivedfromtheoresof
the Sudbury basin in Ontario that contain nickel and copper in fabricationcharacteristics,andapplicationsassociatedwithnickel,cobalt,
approximately the same two-to-one ratio. The trademark for Monel was and their alloys. It is intended to provide the most comprehensive and
firstregisteredin1906.Todaynickeliswidelyusedasakeyconstituentin up-to-date information available on these metals that is suitable for
stainless steels, low-alloy steels, and cast irons, as the base element for engineers, designers, teachers, and students.
many corrosion and heat resistant alloys, as wear or corrosion resistant MuchoftheinformationanddataincludedinthisHandbookhasbeen
coatings, and in special-purpose materials such as magnetic alloys and suppliedbyHaynesInternational,SpecialMetalsCorporation,Carpenter
controlled-expansion alloys. Technology Corporation, Deloro Stellite Inc., Wall Colmonoy
Although isolation of metallic cobalt was first effected by Swedish Corporation, Timken Latrobe Steel, SPS Technologies Aerospace
chemist G. Brandt in 1735, compounds derived from mineral ores Fasteners Group, Elgiloy Specialty Metals, the Cobalt Development
containing cobalt had been used for more than 2000 years as coloring Institute, and the Nickel Development Institute. Gratitude is extended to
agents(blueandgreen)forglassandceramicsinPersiaandEgypt.Cobalt these organizations and to the ASM Editorial and Library staffs, since
was a major coloring agent used by Greek glassworkers about the without these resources it would not have been possible to compile this
beginningoftheChristianera.ChinesepotteryproducedduringtheTang Handbook.
and Ming dynasties (A.D. 600 to 900 and A.D. 1350 to 1650) used cobalt
widely,andVenetianglassproducedintheearly15thcenturyalsoshows
the use of cobalt. The term “kobold” was used applied by miners in Joseph R. Davis
Germany in the 16th century to an ore that did not yield the expected Davis & Associates
copper when reduced by the normal procedure and emitted dangerous Chagrin Falls, Ohio
v
ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys Copyright © 2000 ASM International®
J.R. Davis, editor, p 3-6 All rights reserved.
DOI:10.1361/ncta2000p003 www.asminternational.org
The Nickel Industry: Occurrence,
Recovery, and Consumption
•
NICKELisoneofthemostversatileandim- ingtemperature,fallsapproximatelylinearlyto Hysteresisloss:685J/m3atB=0.6T
portantofthemajorindustrialmetals.Itisavi- 7.0g/cm3at2500K(∼2227°C,or4040°F). • Curietemperature:358°C(676°F)
tal alloying element in cast irons, steels (most Thermal Properties. The melting and boil-
notablyausteniticstainlesssteelscontaining8to ingpointsofnickelare1453°C(2647°F)and TheCurietemperature,inthesamemanneras
35%Ni),andnonferrousalloys.Nickel-baseal- approximately 2730 °C (4946 °C), respec- otherstructure-sensitiveproperties,isdepend-
loys are used in demanding corrosion-resistant tively. Other important thermal properties in- entonpurityandonthepriorhistoryofthesam-
and heat-resistant applications. Nickel-iron al- cludethefollowing: plebutingeneralliesbetween350and360°C
loys have been developed for applications re- (660 and 680 °F) for high-purity nickel (the
quiringcontrolledthermalexpansionorsoftmag- • Coefficient of linear thermal expansion: 358 °C, or 676 °F, previously given value is
neticcharacteristics.Nickelcoatingsandnickel 13.3μm/m·Kat0to100°C(32to212°F) fromVolume2oftheASMHandbook).
•
articles made by electroforming are also tech- Specific heat: 0.471 kJ/kg · K at 100 °C
nologicallyimportant.Nickeland/ornickelcom- (212°F)
• MechanicalProperties
poundsarealsousedincoinage,batteries,cata- Recrystallization temperature: 370 °C
lysts,ceramics,andmagneticsuperconductors. (698°F)
• Thermalconductivity:82.9W/m·Kat100 Tensile Properties. Tensile properties for
annealedhigh-puritynickelhavebeenreported
°C(212°F)
asfollows:
Elemental Nickel
Electrical Properties. The electrical resis- •
Tensilestrength:317MPa(46ksi)
tivity of pure nickel is negligible at extremely •
0.2%offsetyieldstrength:59MPa(8.6ksi)
Although nickel can be produced commer- lowtemperaturesbutincreaseswithincreasing •
Elongationin50mm(2in.):30%
ciallytoapurityof99.99%,mostofthedatare- temperatureandincreasingamountsofimpuri-
portedintheliteratureconcernnickel(plusco- ties.Theresistivityofnickelat20°C(68°F)is
Suitable choice of hot rolling, annealing, and
balt)of99.95%purity.Thisdegreeofpurityis 68.44nΩ·m,andtheelectricalconductivityis
cold drawing or cold rolling can yield tensile
satisfactory for the determination of many 25.2%IACS.
strengthsrangingfrom448to793MPa(65to
properties, but certain properties, for example, Magnetic Properties. Nickel is one of the
115ksi)inrodsandbars,ashighas896MPa
electricalresistivity,areverysensitivetoimpu- three elements (iron and cobalt being the oth-
(130 ksi) in strip, and 1103 MPa (160 ksi) in
ritiesinsolidsolution. ers) that are strongly ferromagnetic at ambient
wire.
Mostofthedatagivenbelowaretakenfrom temperature. Typical normal induction curves
Hardness.Valuesaslowas64HV(35HRB)
Volume 2 of the ASM Handbook (see page of annealed samples of the elements iron,
have been reported for annealed high-purity
1143). More detailed information about the nickel, and cobalt are shown in Fig. 1. Pure
nickel. Cold work and the presence of impuri-
physical, mechanical, and chemical properties nickelisseldomuseditselfasamagneticmate-
tiesincreasethehardness.
ofpurenickelcanbefoundinRef1and2. rialexceptforcertainspecialpurposes,suchas
magnetostriction applications. Many types of
nickel-containing alloys, however, exploit the 20
PhysicalProperties
ferromagnetic properties of nickel. Examples
Fe
includematerialsrangingfromhigh-permeabil-
General. Nickel (symbol Ni) is number 28 ity,softmagneticalloystohigh-coercivity,per-
15
intheperiodictableoftheelements.Thethree manent magnet alloys. Although these alloys
metals—iron, nickel, and cobalt—constitute aregenerallyiron-base,theyfrequentlycontain G
tpheeriotrdaincsittaibolne.gTrohuepaitnomthiecfwoeuirgthhtsoefriensiciknelthies 1sc0ribtoed20in%thNeiarotricmleo“rSe.peScuiaclh-PaulrlpooysseaNreicdkee-l n (B), k 10 Co
58.6934, representing a composite of five sta- Alloys” in this Handbook. Examples of mag- ctio Ni
bleisotopes. neticpropertiesofnickelaregivenbelow: u
d
Crystal Structure. The normal structure of In 5
nickel throughout the entire range of tempera- • Magneticpermeability:μ =1240atB=
max
tures up to the melting point is face-centered 1900G
•
cubic(fcc).Thelatticeconstantofthefccform Coercive force: 167 A·m–1 from H = 4 0
is0.35167nmat20°C(68°F). kA·m–1 0 50 100 150 200
Density.Thedensityofnickelat25°C(77°F) • Saturationmagnetization:0.616Tat20°C Magnetic field strength (H), Oe
is 8.902 g/cm3. The density of liquid nickel at • (68°F) Fig.1 Typical normal induction curves of annealed
itsmeltingpointis7.9g/cm3and,withincreas- Residualinduction:0.300T samplesofiron,nickel,andcobalt.Source:Ref1
4/Introduction to Nickel and Nickel Alloys
ElasticProperties.AveragevaluesofYoung’s Twogeneraltypesofoxideorecanbedistin- fraction is separated into copper sulfide and
modulus of elasticity are 207 GPa (30 × 106 guished: silicate-type ore, in which nickel is nickelsulfideconcentratesbyfrothflotation.
psi)for99.95%Ni.Themodulusofshearis76 contained in the lattice of hydrated magne- The nickel sulfide is converted to granular
GPa(11×106psi).Poisson’sratio,thatis,the sium-iron-silicates, of which garnierite nickeloxidesinterinfluidized-bedreactors.A
ratiooftransversecontractiontolongitudinalex- (Ni,Mg) Si O (OH) is the most common; portionofthisproductismarketeddirectlyfor
6 4 10 8
tensionundertensilestress,is0.31fornickel. and limonitic-type ore, predominantly the hy- alloysteelproduction.Anotherpartofthegran-
drated mineral goethite, (Ni,Fe) ,O ·H O, in ular oxide is treated by chlorination at high
2 3 2
which nickel is dispersed. The chemical com- temperature(1200°C,or2200°F)tolowerits
ChemicalProperties positionofoxideoresvarieswidelyand,inad- copper content to approximately 0.5%, and
ditionto1to3%Ni,maycomprisesignificant then reduced by hydrogen at about 500 °C
amountsofcobaltandchromium.Silicate-type (930 °F) to yield a highly metallized product
Nickel is not an active element chemically ore in New Caledonia analyzes about 2 to 3% (95%Ni)formarket.
anddoesnotreadilyevolvehydrogenfromacid Ni,0.1%Co,2%Cr O ,and10to25%MgO. Two processes are employed to convert the
2 3
solutions;thepresenceofanoxidizingagentis Cubanore,primarilyofthelimonitictype,ana- remainingoxidetopuremetalformarket.One
usuallyrequiredforsignificantcorrosiontooc- lyzesintherangeofabout1.2to1.4%Ni,0.1 involves reduction smelting to metal anodes
cur. Generally, reducing conditions retard cor- to0.2%Co,3%Cr O ,and35to50%Fe. andisfollowedbyelectrolyticrefining,usinga
2 3
rosion,whereasoxidizingconditionsaccelerate sulfate-chloride electrolyte with divided cells
corrosionofnickelinchemicalsolutions.How- and continuous electrolyte purification. The
ever, nickel may also form a protective corro- product of this operation is electrolytic nickel
sion-resistant, or passive, oxide film on expo- Extraction and Refining (Ref 3) cathodes, and the by-products are cobalt and
sure to some oxidizing conditions. Additional preciousmetals.
information is available in the article “Corro- Theotherprocessistheatmospheric-pressure
sionBehaviorofNickelAlloysinSpecificEn- Recovery from Sulfide Ores. Figure 2 il- carbonyl process, which is used in Clydach,
vironments”inthisHandbook. lustratesthemajorprocessesfortheextraction Wales,UnitedKingdom,andinCopperCliff,a
andrecoveryofnickelfromsulfideores.These subdivision of Sudbury, Ontario, Canada. The
oresarefirstcrushedandgroundtoliberatethe nickel oxide sinter is reduced with hydrogen
mineralvaluesandthensubjectedtofrothflota- and treated with carbon monoxide at approxi-
Occurrence and Supply tion to concentrate the valuable constituents mately50°C(120°F)tovolatilizenickelasgas-
and reject the gangue or rock fraction. De- eousnickelcarbonyl.Thiscompoundisdecom-
A large number of nickel-bearing minerals pending on the copper and pyrrhotite (iron) posedatapproximately200°C(390°F)toyield
have been identified, but relatively few are contentsoftheore,itissometimesappropriate high-purity nickel in pellet form. Copper and
abundant enough to be industrially significant. toproduceaseparatecopperconcentrateanda cobalt salts and precious metals are recovered
Nickel materials that are or have been impor- separatepyrrhotiteconcentrate. from the residue. Nickel powder is also pro-
tant are classified as sulfides, laterites (which Selective flotation and magnetic separation ducedatthisplantinapressurecarbonylsystem.
includeoxidesandsilicates),andarsenides.Of may be employed to divide the bulk concen- Thenickel-copperalloyfromthemattesepa-
these, the most important present-day ores are trateintonickel,copper,andiron-richfractions ration step, containing significant platinum-
sulfidesandlaterites. forseparatetreatment(seeprocessAinFig.2). groupmetalvalues,ismeltedinatop-blownro-
Sulfide Ores. Inthesulfideores,nickeloc- Ahigh-gradeironore,nickeloxide,andsulfu- taryconverter,anditssulfurcontentisadjusted
curs chiefly as the mineral pentlandite, ric acid are recovered from the iron concen- by blowing with oxygen at temperatures up to
(Ni,Fe) S , in association with large amounts trate. The nickel concentrate is treated by 1600°C(2900°F).Themetalproductisgranu-
ofpyrrh9ot8ite,Fe S ,andusuallywithasignifi- pyrometallurgicalprocesses.Themajorportion lated with water, and the dried metal granules
cant amount of c7ha8lcopyrite, CuFeS . In addi- undergoes partial roasting in multihearth or are treated in high-pressure (6.7 MPa, or 970
2
tiontonickel,iron,andcopper,theseorescon- fluidized-bed furnaces to eliminate about half psi) reactors with carbon monoxide at 150 °C
tain varying amounts of cobalt and precious ofthesulfurandtooxidizetheassociatediron. (300°F)toformnickelcarbonylandsomeiron
metals: the platinum group metals, gold, and Thehotcalcine,plusflux,issmeltedinnatural carbonyl. The mixed carbonyls are separated
silver. Their chemical composition falls in the gasorcoal-firedreverberatoryfurnacesoperat- byfractionation,andthepurenickelcarbonylis
generalrangeof0.4to3%Ni,0.2to3%Cu,10 ing at about 1200 °C (2200 °F) to produce a decomposedatapproximately200°C(390°F)
to35%Fe,and5to25%S,withthebalancebe- furnace matte that is enriched in nickel and a to yield high-purity nickel pellets and nickel
ingsubstantiallySiO ,Al O ,MgO,andCaO. slag for discard. The furnace matte is trans- powderformarket.
2 2 3
Sulfide ores are generally found in areas ferred to Pierce-Smith converters and blown Thereisasimplerprocedurethatcanbeused
where glacial action has removed much of the with air in the presence of more flux to oxi- toprocessnickelsulfideoreswithlowercopper
overburden of weathered rock. Important dize the remaining iron and associated sulfur, contents.AsshownbyprocessBinFig.2,se-
known deposits are in Sudbury, Ontario, Can- yielding Bessemer matte containing nickel, lective flotation is employed to produce a
ada;intheVoisey’sBaydepositinnortheastern copper,cobalt,smallamountsofpreciousmet- nickel concentrate low in copper and a small
Labrador, Canada; in the Thompson-Moak als, and approximately 22% sulfur. The slag amount of copper concentrate for treatment
Lake area of northern Manitoba, Canada; in thatisgeneratedintheconvertingoperationis elsewhere.Thedewaterednickelconcentrateis
RussiaatNorilskinSiberia;intheKolaPenin- returned to the smelting furnace to recover its fluid-bed-roastedforpartialeliminationofsul-
sula bordering Finland; in western Australia; metalvalues. fur, and the calcine plus flux is smelted in
andinSouthAfrica. The molten Bessemer matte is cast into 25 arc-typeelectricfurnaces.Wastefurnaceslagis
Laterites. The oxide resources of nickel ton molds in which it undergoes controlled granulatedfordisposalwhilethemoltenmatte
(commonly known as laterite ores) are gener- slowcoolingtopromoteformationofrelatively is transferred to Pierce-Smith converters for
ally found in tropical regions, with the largest large,discretecrystalsofcoppersulfide,nickel furtherupgradingtoBessemermatte.Thecon-
deposits being in Cuba, New Caledonia, Indo- sulfide, and a small quantity of a metallic ventionalprocedureoffluxadditionandblow-
nesia, the Philippines, and Central and South phase, a nickel-copper alloy that collects most ingwithairremovesallbuttracesofironfrom
America. These ores formed through weather- of the precious metals. After crushing and thematte,andtheslagproducedisreturnedto
ing processes that resulted in nickel being grinding, the metallics are removed magneti- the electric furnace for recovery of metal val-
leached from surface rock layers and precipi- cally and treated in a refining complex for re- ues.Theconvertermatte,essentiallynickelsul-
tatedatlowerlevels. covery of metal values, and the main sulfide fide (Ni S ), is cast into anodes and electro-
3 2
The Nickel Industry: Occurrence, Recovery, and Consumption/5
Process A Process B Process C
Ore Ore
Comminution Comminution Comminution
Flotation Tailings to
Ctoop cpoeprp ceorn scmeMnetalrtgeanrteetic Tora itloin dgusm top mine backfill Tmorai nitloien dgbusam ctokpfill NFicloktealt Cticoooo ncnpocppeepnr etcrrao stnemceenltterarte Flotation Nickelmo crio ntnoec dbeuanmctrkapftiell
Nickel sceopnacreanttiorante Pcoynrrcheontittreate Iron ore recovery plant Roasting Filtration
Air Sulfur Sulfuric acid Air Sulfur dioxide Drying
dioxide
Roasting Smelting Flux Sulfur dioxide
Smelting Iron Nickel Flux Slag to Air and
Flux Slag to dumpore oxide Furnacdeu mmaptte oxygen Flash smelting
Slag Sdiuolxfuidre ConveFrltuinxg Slag Sdiuolxfuidre ConveFrtliunxg Slag Fmuartnteace FSlulaxg to waste
Air Converter matte Air Air
Converter matte Anode casting Converter matte Converting
into molds
Cooling Comminution
Electrolysis Elemental
Sulfur
sulfur
dioxide Comminution Ammonia Oxygen
Oxygen Flotation Copper sulfide Cobalt oxide, Nickel cathodes Pressure leaching
Granulation Converting to copper smelter precious-metals residue
Water and reverts Nickel-cobalt-copper solution Purification
Nickel CmoantPtvereerstseurre Cnmiocapkgepnleert-ics Mseapganreattiicon Nickel RsuoAlafirisdteing SGuralfnuur ldairo nxiidckeel Ctoo cpoppepr esru slfmideelter Hsuyldfirdoegen
and iron volatilization oxide (75% Ni) Nickel-cobalt solution Pressure reduction
carbonyls Carbon
Fractionation Chlorination Nickel powder Hydrogen
Nickel Carbon
carbonyl monoxide Chlorine Impurities
Anode
casting Cobalt-nickel solution Cobalt-nickel
Reduction precipitation
Electrolysis Nickel-cobalt sulfide Hydrogen
Decomposition Decomposition Hydrogen Water for further treatment sulfide
Ammonium sulfate
solution Evaporation
Iron-nickel Nickel pellets Nickel powder Nickel Precious metals Metalized nickel Ammonium
powder cathode residue, cobalt oxide, granules (95% Ni) sulfate
and reverts
Fig.2 Flowsheetsforthreemethodsofnickelrecoveryfromsulfideores.Seetextforprocessingdetails.Source:Ref3
lyzedtoyieldelementalsulfurattheanodeand Recovery from Laterite Ores. Thebulkof Otherlarge-scaleoperationsarebasedonse-
purenickelatthecathode.Therefiningopera- thenickeloriginatingfromlateriticoresismar- lective reduction of the ore followed by
tion also produces cobalt oxide and pre- keted as ferronickel. The process employed is ammoniacal leaching at atmospheric pressure
cious-metalresidues. basically simple and involves drying and pre- to dissolve the nickel values. The pregnant li-
Intheall-hydrometallurgicalSherrittprocess heatingtheore,usuallyunderreductioncondi- quor is treated to remove impurities and then
(seeprocessCinFig.2),thenickeloreiscon- tions. The hot charge is then further reduced heatedinsuitablevesselstodriveoffammonia
centrated by conventional froth flotation, and and melted in an electric arc furnace, and the and carbon dioxide and to precipitate a basic
thedriednickelconcentrateisflash-smeltedwith crudemetalisrefinedandcastintoferronickel nickelcarbonate.Thismaterialmaybesintered
oxygen-enriched air and flux to produce fur- pigs. A typical operation is shown in Fig. 3 underreducingconditionstoyieldametallized
nace matte and waste slag. The furnace matte (processA). nickel oxide sinter, or the carbonate may be
iscooled,crushed,andfinelygroundasfeed A substantial amount of nickel is produced redissolved in ammoniacal solution and then
for the hydrometallurgical plant, where it is from lateritic ores by the nickel-sulfide matte treated with hydrogen under pressure to yield
leachedunderpressurewithastrongammonia technique.Inthisprocesstheoreismixedwith nickel powder for briquetting. This process is
solutionandairtosolubilizethebasemetalval- gypsum or other sulfur-containing material depicted by process C in Fig. 3. Process D in
ues, with the simultaneous production of am- such as high-sulfur fuel oil, followed by a re- Fig.3depictsaprocesswhereinlimonitic-type
monium sulfate. The pregnant leach liquor is duction and smelting operation to form matte. ores are leached with sulfuric acid at elevated
treatedtoremoveimpuritiesandthenreduced Asinthetreatmentofsulfideconcentrates,the temperature and pressure to solubilize nickel
withhydrogenatelevatedpressure(3MPa, moltenfurnacematteisupgradedineithercon- and cobalt. The pregnant solution is then
or435psi)andtemperature(190°C,or375°F) ventional or top-blown rotary converters to a treated with hydrogen sulfide to precipitate
toyieldagranularnickelpowderproduct.The high-gradematte,whichcanbefurtherrefined mixed nickel-cobalt sulfides. This precipitate
tailliquorfromthisoperationistreatedfurther byroastingandreductiontoametallizedprod- maybetreatedbytheSherrittpressure,ammo-
to recover ammonium sulfate crystals and a uct. An example of this procedure is shown in nia-leach process to yield separate nickel and
mixednickel-cobaltsulfide. Fig.3(processB). cobaltpowders.
6/Introduction to Nickel and Nickel Alloys
Process A Process B Process C Process D End Uses of Nickel
Ore
Limonitic and
Silicate ores Silicate ores silicate ores Limonitic ores
According to the Nickel Development Insti-
Mixing tute, worldwide consumption of nickel can be
Kiln drying Gypsum Kiln drying Sulfuric brokenintothefollowingmarketsegments:
and preheating acid
Pulping
Briquetting Use Nickelconsumption,%
Arsemrdceu flcutitnrinogance Drying Mreudlutichteioanrth Nickel- PleraecshsRiunergesidue SNPtliaacitkninelegl-sbsassteeeallloys 61219...797
Slag to cobalt Alloysteels 9.0
Precipitation
discard Coke, solution Foundryproducts 3.5
Blast limestone Leaching Hydrogen Copper-basealloys 1.4
furnace sulfide Other 1.8
Ladle smelting Sdilsacga trod Spuorluifitcioantion Residue RecycledSsluulrfriyde Transportation
desulfurization to ammonia
Converting Distillation discard Consumption statistics in the United States
Acid
Sand, lime Basic nickel pressure follow similar trends (Table 1), with stainless
Refining Roasting carbonate dissolution steels making up about 55% of all nickel con-
Calcining
Air sumed. According to the American Iron and
Reducing Hydrogen
SteelInstitute,nickel-bearinggradesaccounted
Casting agent Briquetting Ammonia preredsuscutiroen for 63% of the total stainless steel production
Sintering Reduction for1997.Demandforausteniticstainlesssteels
Reduction smelting is expected to continue to drive the world
nickelmarketforatleastanother20years.De-
mandfornickel-bearingsuperalloysisalsoex-
pected to grow. In 1997, U.S. consumption of
Ferronickel Nickel rondelles Nickel Nickel CobaltAmmonium Nickel primary nickel in superalloys increased almost
pigs oxide sinter pig powder sulfate powder
20% because of growing orders in the aero-
Fig.3 Flowsheetsforfourmethodsofnickelrecoveryfromlateriteores.Seetextforprocessingdetails.Source:Ref3 spaceindustry(Table1).
Theuseofprimarynickelbybatterymanufac-
turers is another potential growth market for
nickel. Rechargeable nickel-cadmium and
nickel-metal hydride batteries are used in
handheldpowertools,cellulartelephones,lap-
Table1 ConsumptionofnickelintheUnitedStatesbyenduse top computers, and camcorders. Nickel base
batteries,includingthemorerecentlydeveloped
Form/tonnesofcontainednickel(a)(b)(c) sodiummetal-nickelbatterycalledtheZEBRA
Oxideand Other Total Secondary Grandtotal (ZeroEmissionBatterieResearchActivity),are
Use Metal Ferronickel oxidesinter Chemicals forms primary (scrap) 1997 1996 alsobeingusedinelectricvehiclesandtherap-
Castirons 168 W … 1 45 214 428 642 563 idly growing electric scooter/bicycle market.
Chemicalsandchemical W … W 2,730 … 2,730 … 2,730 5,350 Nickelconsumptionpatternscouldchangesig-
uses nificantly due to tightening oil supplies com-
Electric,magnet, W W … (d) … (d) W W W
binedwithincreasedoilandgasolineprices.The
expansionalloys
Electroplating(sales 15,800 … W 61 1 15,800 … 15,800 16,300 marketforlargeenergy-storagedevicesforna-
toplaters) tionwidecommunicationssystemsandforemer-
Nickel-copperand 2,650 W W … W 2,650 3,390 6,040 7,280 gencypowersupplieswouldalsogrow,further
copper-nickelalloys
encouraging the scale-up of both nickel-metal
Othernickelandnickel 17,000 W W … W 17,000 2,040 19,100 19,300
alloys hydrideandsodiummetal-nickelbatteries.
Steel
Stainlessandheat 26,100 21,000 1,760 … 57 48,900 56,900 106,000 94,100
resistant
Alloys(excludes 5,180 1,090 1,060 (d) W 7,320 1,330 8,650 6,970 REFERENCES
stainless)
Superalloys 18,200 … (d) 1 465 18,700 W 18,700 15,600
1.S.J. Rosenberg, Nickel and Its Alloys, Na-
Other(e) 6,000 410 79 645 1,070 8,210 4,790 13,000 13,300
tionalBureauofStandardsMonograph106,
Totalreported 91,000 22,500 2,890 3,440 1,640 122,000 68,800 190,000 179,000 U.S.DepartmentofCommerce,May1968
Totalallcompanies, NA NA NA NA NA 154,000 38,100 192,000 181,000 2.W. Betteridge, Nickel and Its Alloys, Ellis
apparent
HorwoodLtd.,1984
(a)Dataareroundedtothreesignificantdigitsandmaynotaddtototalsshown.(b)W,withheldtoavoiddisclosingcompanyproprietarydata;in- 3.A.Illis,NickelMetallurgy,McGraw-HillEn-
cludedwith“Other.”.(c)NA,notapplicable.(d)Lessthan12unit.(e)Includesbatteries,catalysts,ceramics,coinage,otheralloyscontainingnickel, cyclopedia of Science and Technology, Vol
anddataindicatedbysymbol“W.”Source:U.S.GeologicalSurvey
11(MET-NIC),7thed.,1992,p711–714