Modern Physical Metallurgy and Materials Engineering About the authors been Vice President of the Institute of Materials and President of the Federated European Materials Soci- eties.Sinceretirementhehasbeenacademicconsultant Professor R. E. Smallman for a number of institutionsboth in theUK and over- seas. After gaining his PhD in 1953, Professor Smallman spentfiveyearsattheAtomicEnergyResearchEstab- lishmentatHarwell,beforereturningtotheUniversity R. J. Bishop of Birmingham where he became Professor of Physi- After working in laboratories of the automobile, calMetallurgyin1964andFeeneyProfessorandHead forging, tube-drawing and razor blade industries oftheDepartmentofPhysicalMetallurgyandScience (1944–59), Ray Bishop became a Principal Scientist of Materials in 1969. He subsequently became Head of the British Coal Utilization Research Association of the amalgamated Department of Metallurgy and (1959–68), studying superheater-tube corrosion and Materials (1981), Dean of the Faculty of Science and mechanisms of ash deposition on behalf of boiler Engineering, and the first Dean of the newly-created manufacturers and the Central Electricity Generating Engineering Faculty in 1985. For five years he was Board. He specialized in combustor simulation of Vice-Principal of the University(1987–92). conditions within pulverized-fuel-fired power station He has held visiting professorship appointments at boilersandfluidized-bedcombustionsystems.Hethen the University of Stanford, Berkeley, Pennsylvania became a Senior Lecturer in Materials Science at (USA),NewSouthWales(Australia),HongKongand the Polytechnic (now University), Wolverhampton, Cape Town and has received Honorary Doctorates acting at various times as leader of C&G, HNC, TEC from the University of Novi Sad (Yugoslavia) and and CNAA honours Degree courses and supervising the University of Wales. His research work has been doctoral researches. For seven years he was Open recognizedbytheawardoftheSirGeorgeBeilbyGold University Tutor for materials science and processing MedaloftheRoyalInstituteofChemistryandInstitute in the West Midlands. In 1986 he joined the ofMetals(1969),theRosenhainMedaloftheInstitute School of Metallurgy and Materials, University of of Metals for contributions to Physical Metallurgy Birminghamasapart-timeLecturerandwasinvolved (1972) and the Platinum Medal, the premier medal of in administration of the Federation of European the Instituteof Materials (1989). Materials Societies (FEMS). In 1995 and 1997 he He was elected a Fellow of the Royal Society gave lecture courses in materials science at the Naval (1986), a Fellow of the Royal Academy of Engineer- Postgraduate School, Monterey, California. Currently ing(1990)andappointedaCommanderoftheBritish he is an Honorary Lecturer at the University of Empire (CBE) in 1992.A former Council Member of Birmingham. theScienceandEngineeringResearchCouncil,hehas Modern Physical Metallurgy and Materials Engineering Science, process, applications Sixth Edition R. E. Smallman, CBE, DSc, FRS, FREng, FIM R. J. Bishop, PhD, CEng, MIM OXFORD AUCKLAND BOSTON JOHANNESBURG MELBOURNE NEWDELHI Butterworth-Heinemann LinacreHouse,JordanHill,OxfordOX28DP 225WildwoodAvenue,Woburn,MA01801-2041 AdivisionofReedEducationalandProfessionalPublishingLtd Firstpublished1962 Secondedition1963 Reprinted1965,1968 Thirdedition1970 Reprinted1976(twice),1980,1983 Fourthedition1985 Reprinted1990,1992 Fifthedition1995 Sixthedition1999 ReedEducationalandProfessionalPublishingLtd1995,1999 Allrightsreserved.Nopartofthispublicationmaybe reproducedinanymaterialform(includingphotocopy- ingorstoringinanymediumbyelectronicmeansand whetherornottransientlyorincidentallytosomeother useofthispublication)withoutthewrittenpermissionof thecopyrightholderexceptinaccordancewiththe provisionsoftheCopyright,DesignsandPatentsAct 1988orunderthetermsofalicenceissuedbythe CopyrightLicensingAgencyLtd,90TottenhamCourt Road,London,EnglandW1P9HE.Applicationsforthe copyrightholder’swrittenpermissiontoreproduceany partofthispublicationshouldbeaddressedtothe publishers BritishLibraryCataloguinginPublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary LibraryofCongressCataloguinginPublicationData AcataloguerecordforthisbookisavailablefromtheLibraryofCongress ISBN0750645644 CompositionbyScribeDesign,Gillingham,Kent,UK TypesetbyLaserWords,Madras,India PrintedandboundinGreatBritainbyBathPress,Avon Contents Preface xi 3 Structuralphases;theirformationand transitions 42 3.1 Crystallization from themelt 42 1 Thestructureandbondingofatoms 1 3.1.1 Freezing of a pure metal 42 1.1 The realm of materials science 1 3.1.2 Plane-front and dendritic 1.2 The free atom 2 solidificationat a cooled 1.2.1 The four electron quantum surface 43 3.1.3 Forms of cast structure 44 numbers 2 1.2.2 Nomenclature for electronic 3.1.4 Gas porosity and segregation 45 states 3 3.1.5 Directional solidification 46 1.3 The Periodic Table 4 3.1.6 Production of metallic single crystals 1.4 Interatomic bonding in materials 7 for research 47 1.5 Bonding and energy levels 9 3.2 Principles and applicationsof phase diagrams 48 3.2.1 The concept of a phase 48 2 Atomicarrangementsinmaterials 11 3.2.2 The Phase Rule 48 2.1 The concept of ordering 11 3.2.3 Stability of phases 49 2.2 Crystal lattices and structures 12 3.2.4 Two-phase equilibria 52 2.3 Crystal directions and planes 13 3.2.5 Three-phase equilibriaand 2.4 Stereographic projection 16 reactions 56 3.2.6 Intermediate phases 58 2.5 Selected crystal structures 18 3.2.7 Limitationsof phase diagrams 59 2.5.1 Pure metals 18 3.2.8 Some key phase diagrams 60 2.5.2 Diamond and graphite 21 3.2.9 Ternary phase diagrams 64 2.5.3 Coordination in ionic crystals 22 3.3 Principles of alloy theory 73 2.5.4 AB-type compounds 24 3.3.1 Primary substitutionalsolid 2.5.5 Silica 24 solutions 73 2.5.6 Alumina 26 3.3.2 Interstitial solidsolutions 76 2.5.7 Complex oxides 26 3.3.3 Types of intermediate phases 76 2.5.8 Silicates 27 3.3.4 Order-disorder phenomena 79 2.6 Inorganic glasses 30 3.4 The mechanism of phase changes 80 2.6.1 Network structures in glasses 30 3.4.1 Kineticconsiderations 80 2.6.2 Classification of constituent 3.4.2 Homogeneous nucleation 81 oxides 31 3.4.3 Heterogeneous nucleation 82 2.7 Polymeric structures 32 3.4.4 Nucleation in solids 82 2.7.1 Thermoplastics 32 2.7.2 Elastomers 35 2.7.3 Thermosets 36 4 Defectsinsolids 84 2.7.4 Crystallinityin polymers 38 4.1 Types of imperfection 84 vi Contents 4.2 Point defects 84 5.3.3 X-ray diffraction methods 135 4.2.1 Point defects in metals 84 5.3.4 Typical interpretativeprocedures for 4.2.2 Point defects in non-metallic diffraction patterns 138 crystals 86 5.4 Analytical electron microscopy 142 4.2.3 Irradiation of solids 87 5.4.1 Interaction of an electron beam with 4.2.4 Point defect concentration and a solid 142 annealing 89 5.4.2 The transmission electron 4.3 Line defects 90 microscope (TEM) 143 4.3.1 Concept of a dislocation 90 5.4.3 The scanning electron microscope 144 4.3.2 Edge and screw dislocations 91 5.4.4 Theoretical aspects of TEM 146 4.3.3 The Burgers vector 91 5.4.5 Chemical microanalysis 150 4.3.4 Mechanisms of slip and climb 92 5.4.6 Electron energy loss spectroscopy 4.3.5 Strain energy associated with (EELS) 152 dislocations 95 5.4.7 Auger electron spectroscopy 4.3.6 Dislocationsin ionicstructures 97 (AES) 154 4.4 Planar defects 97 5.5 Observation of defects 154 4.4.1 Grain boundaries 97 5.5.1 Etch pitting 154 4.4.2 Twin boundaries 98 5.5.2 Dislocationdecoration 155 4.4.3 Extended dislocationsand stacking 5.5.3 Dislocationstrain contrast in faults in close-packed crystals 99 TEM 155 4.5 Volume defects 104 5.5.4 Contrast from crystals 157 4.5.1 Void formation and annealing 104 5.5.5 Imaging of dislocations 157 4.5.2 Irradiation and voiding 104 5.5.6 Imaging of stacking faults 158 4.5.3 Voiding and fracture 104 5.5.7 Applicationof dynamical 4.6 Defect behaviour in some real theory 158 materials 105 5.5.8 Weak-beam microscopy 160 4.6.1 Dislocationvector diagrams and the 5.6 Specialized bombardment techniques 161 Thompson tetrahedron 105 5.6.1 Neutron diffraction 161 4.6.2 Dislocationsand stacking faults in 5.6.2 Synchrotron radiation studies 162 fcc structures 106 4.6.3 Dislocationsand stacking faults in 5.6.3 Secondary ion mass spectrometry cph structures 108 (SIMS) 163 4.6.4 Dislocationsand stacking faults in 5.7 Thermal analysis 164 bcc structures 112 5.7.1 General capabilities of thermal 4.6.5 Dislocationsand stacking faults in analysis 164 ordered structures 113 5.7.2 Thermogravimetric analysis 164 4.6.6 Dislocationsand stacking faults in 5.7.3 Differential thermal analysis 165 ceramics 115 5.7.4 Differential scanning 4.6.7 Defects in crystalline calorimetry 165 polymers 116 4.6.8 Defects in glasses 117 6 Thephysicalpropertiesofmaterials 168 4.7 Stability of defects 117 6.1 Introduction 168 4.7.1 Dislocationloops 117 6.2 Density 168 4.7.2 Voids 119 6.3 Thermal properties 168 4.7.3 Nuclear irradiation effects 119 6.3.1 Thermal expansion 168 6.3.2 Specific heat capacity 170 5 Thecharacterizationofmaterials 125 6.3.3 The specific heat curve and transformations 171 5.1 Tools of characterization 125 6.3.4 Free energy of transformation 171 5.2 Light microscopy 126 6.4 Diffusion 172 5.2.1 Basic principles 126 6.4.1 Diffusion laws 172 5.2.2 Selected microscopical 6.4.2 Mechanisms of diffusion 174 techniques 127 5.3 X-ray diffraction analysis 133 6.4.3 Factors affecting diffusion 175 5.3.1 Production and absorption of 6.5 Anelasticity and internal friction 176 X-rays 133 6.6 Ordering in alloys 177 5.3.2 Diffraction of X-rays by 6.6.1 Long-range and short-range crystals 134 order 177 Contents vii 6.6.2 Detection of ordering 178 7.4.2 Variation of yield stress with 6.6.3 Influence of ordering upon temperature and strain rate 208 properties 179 7.4.3 Dislocationsource operation 209 6.7 Electrical properties 181 7.4.4 Discontinuousyielding 211 6.7.1 Electrical conductivity 181 7.4.5 Yield points and crystal 6.7.2 Semiconductors 183 structure 212 6.7.3 Superconductivity 185 7.4.6 Discontinuousyieldingin ordered alloys 214 6.7.4 Oxidesuperconductors 187 7.4.7 Solute–dislocationinteraction 214 6.8 Magneticproperties 188 7.4.8 Dislocationlocking and 6.8.1 Magneticsusceptibility 188 temperature 216 6.8.2 Diamagnetism and 7.4.9 Inhomogeneity interaction 217 paramagnetism 189 7.4.10 Kinetics of strain-ageing 217 6.8.3 Ferromagnetism 189 7.4.11 Influence of grain boundaries on 6.8.4 Magneticalloys 191 plasticity 218 6.8.5 Anti-ferromagnetism and 7.4.12 Superplasticity 220 ferrimagnetism 192 7.5 Mechanical twinning 221 6.9 Dielectric materials 193 7.5.1 Crystallography of twinning 221 6.9.1 Polarization 193 7.5.2 Nucleation and growth of 6.9.2 Capacitors and insulators 193 twins 222 6.9.3 Piezoelectric materials 194 7.5.3 Effect of impurities on 6.9.4 Pyroelectric and ferroelectric twinning 223 materials 194 7.5.4 Effectofprestrainontwinning 223 6.10 Optical properties 195 7.5.5 Dislocationmechanism of 6.10.1 Reflection, absorptionand twinning 223 transmissioneffects 195 7.5.6 Twinning and fracture 224 6.10.2 Optical fibres 195 7.6 Strengthening and hardening 6.10.3 Lasers 195 mechanisms 224 6.10.4 Ceramic ‘windows’ 196 7.6.1 Point defect hardening 224 6.10.5 Electro-opticceramics 196 7.6.2 Work-hardening 226 7.6.3 Development of preferred 7 Mechanicalbehaviourofmaterials 197 orientation 232 7.1 Mechanical testingprocedures 197 7.7 Macroscopic plasticity 235 7.1.1 Introduction 197 7.7.1 Tresca and von Mises criteria 235 7.1.2 The tensiletest 197 7.7.2 Effective stress and strain 236 7.1.3 Indentation hardness testing 199 7.8 Annealing 237 7.1.4 Impact testing 199 7.8.1 General effects of annealing 237 7.1.5 Creep testing 199 7.8.2 Recovery 237 7.1.6 Fatigue testing 200 7.8.3 Recrystallization 239 7.1.7 Testing of ceramics 200 7.8.4 Grain growth 242 7.2 Elasticdeformation 201 7.8.5 Annealing twins 243 7.2.1 Elasticdeformation of metals 201 7.8.6 Recrystallization textures 245 7.2.2 Elasticdeformation of 7.9 Metalliccreep 245 ceramics 203 7.9.1 Transient and steady-state 7.3 Plastic deformation 203 creep 245 7.3.1 Slip and twinning 203 7.9.2 Grain boundary contributionto creep 247 7.3.2 Resolved shear stress 203 7.9.3 Tertiary creep and fracture 249 7.3.3 Relation of slip to crystal 7.9.4 Creep-resistant alloy design 249 structure 204 7.3.4 Law of critical resolved shear 7.10 Deformation mechanism maps 251 stress 205 7.11 Metallicfatigue 252 7.3.5 Multipleslip 205 7.11.1 Nature of fatigue failure 252 7.3.6 Relation between work-hardening 7.11.2 Engineering aspects of fatigue 252 and slip 206 7.11.3 Structural changes accompanying 7.4 Dislocationbehaviour during plastic fatigue 254 deformation 207 7.11.4 Crack formation and fatigue 7.4.1 Dislocationmobility 207 failure 256 viii Contents 7.11.5 Fatigue at elevated 9.2.6 Mechanically alloyed (MA) temperatures 258 steels 301 9.2.7 Designationof steels 302 9.3 Cast irons 303 8 Strengtheningandtoughening 259 9.4 Superalloys 305 8.1 Introduction 259 9.4.1 Basic alloying features 305 8.2 Strengthening of non-ferrous alloys by 9.4.2 Nickel-based superalloy heat-treatment 259 development 306 8.2.1 Precipitation-hardeningof Al–Cu 9.4.3 Dispersion-hardened alloys 259 superalloys 307 8.2.2 Precipitation-hardeningof Al–Ag 9.5 Titaniumalloys 308 alloys 263 8.2.3 Mechanisms of 9.5.1 Basic alloying and heat-treatment precipitation-hardening 265 features 308 8.2.4 Vacancies and precipitation 268 9.5.2 Commercial titanium alloys 310 8.2.5 Duplex ageing 271 9.5.3 Processing of titaniumalloys 312 8.2.6 Particle-coarsening 272 9.6 Structural intermetallic compounds 312 8.2.7 Spinodal decomposition 273 9.6.1 General properties of intermetallic compounds 312 8.3 Strengthening of steels by 9.6.2 Nickel aluminides 312 heat-treatment 274 8.3.1 Time–temperature–transformation 9.6.3 Titaniumaluminides 314 diagrams 274 9.6.4 Other intermetalliccompounds 315 8.3.2 Austenite–pearlite 9.7 Aluminium alloys 316 transformation 276 9.7.1 Designationof aluminium 8.3.3 Austenite–martensite alloys 316 transformation 278 9.7.2 Applicationsof aluminium 8.3.4 Austenite–bainite alloys 316 transformation 282 9.7.3 Aluminium-lithiumalloys 317 8.3.5 Tempering of martensite 282 9.7.4 Processing developments 317 8.3.6 Thermo-mechanical treatments 283 10 Ceramicsandglasses 320 8.4 Fracture and toughness 284 10.1 Classification of ceramics 320 8.4.1 Griffith micro-crack criterion 284 10.2 General properties of ceramics 321 8.4.2 Fracture toughness 285 10.3 Production of ceramic powders 322 8.4.3 Cleavage and the ductile–brittle 10.4 Selected engineering ceramics 323 transition 288 10.4.1 Alumina 323 8.4.4 Factors affecting brittleness of steels 289 10.4.2 From silicon nitrideto sialons 325 8.4.5 Hydrogen embrittlement of 10.4.3 Zirconia 330 steels 291 10.4.4 Glass-ceramics 331 8.4.6 Intergranular fracture 291 10.4.5 Silicon carbide 334 8.4.7 Ductilefailure 292 10.4.6 Carbon 337 8.4.8 Rupture 293 10.5 Aspects of glass technology 345 8.4.9 Voiding and fracture at elevated 10.5.1 Viscous deformation of glass 345 temperatures 293 10.5.2 Some special glasses 346 8.4.10 Fracture mechanism maps 294 10.5.3 Toughened and laminated 8.4.11 Crack growth under fatigue glasses 346 conditions 295 10.6 The time-dependency of strength in ceramics and glasses 348 9 Modernalloydevelopments 297 9.1 Introduction 297 11 Plasticsandcomposites 351 9.2 Commercial steels 297 11.1 Utilizationof polymeric materials 351 9.2.1 Plain carbon steels 297 11.1.1 Introduction 351 9.2.2 Alloy steels 298 11.1.2 Mechanical aspects of T 351 g 9.2.3 Maraging steels 299 11.1.3 The role of additives 352 9.2.4 High-strengthlow-alloy (HSLA) 11.1.4 Some applicationsof important steels 299 plastics 353 9.2.5 Dual-phase(DP) steels 300 11.1.5 Management of waste plastics 354 Contents ix 11.2 Behaviour of plastics during 13.7.2 Pacemakers 403 processing 355 13.7.3 Artificial arteries 403 11.2.1 Cold-drawing and crazing 355 13.8 Tissuerepair and growth 403 11.2.2 Processing methods for 13.9 Other surgical applications 404 thermoplastics 356 13.10 Ophthalmics 404 11.2.3 Production of thermosets 357 13.11 Drug delivery systems 405 11.2.4 Viscous aspects of melt behaviour 358 14 Materialsforsports 406 11.2.5 Elasticaspects of melt 14.1 The revolution in sports products 406 behaviour 359 14.2 The tradition of using wood 406 11.2.6 Flow defects 360 14.3 Tennis rackets 407 11.3 Fibre-reinforced compositematerials 361 14.3.1 Frames for tennis rackets 407 11.3.1 Introductionto basic structural principles 361 14.3.2 Strings for tennis rackets 408 11.3.2 Types of fibre-reinforced 14.4 Golf clubs 409 composite 366 14.4.1 Kineticaspects of a golf stroke 409 12 Corrosionandsurface 14.4.2 Golf club shafts 410 engineering 376 14.4.3 Wood-typeclub heads 410 12.1 The engineering importance of 14.4.4 Iron-type club heads 411 surfaces 376 14.4.5 Putting heads 411 12.2 Metalliccorrosion 376 14.5 Archery bows and arrows 411 12.2.1 Oxidationat high temperatures 376 14.5.1 The longbow 411 12.2.2 Aqueous corrosion 382 14.5.2 Bow design 411 12.3 Surface engineering 387 14.5.3 Arrow design 412 12.3.1 The coating and modification of 14.6 Bicycles for sport 413 surfaces 387 14.6.1 Frame design 413 12.3.2 Surface coating by vapour 14.6.2 Joiningtechniques for metallic deposition 388 frames 414 12.3.3 Surface coating by particle 14.6.3 Frame assembly using epoxy bombardment 391 adhesives 414 12.3.4 Surface modification with 14.6.4 Composite frames 415 high-energy beams 391 14.6.5 Bicycle wheels 415 13 Biomaterials 394 14.7 Fencing foils 415 13.1 Introduction 394 14.8 Materials for snow sports 416 13.2 Requirements for biomaterials 394 14.8.1 General requirements 416 13.3 Dental materials 395 14.8.2 Snowboarding equipment 416 13.3.1 Cavity fillers 395 14.8.3 Skiing equipment 417 13.3.2 Bridges, crowns and dentures 396 14.9 Safety helmets 417 13.3.3 Dental implants 397 14.9.1 Function and form of safety 13.4 The structure of boneand bone helmets 417 fractures 397 14.9.2 Mechanical behaviourof 13.5 Replacement joints 398 foams 418 14.9.3 Mechanical testingof safety 13.5.1 Hip joints 398 helmets 418 13.5.2 Shoulder joints 399 13.5.3 Knee joints 399 Appendices 420 13.5.4 Fingerjointsandhandsurgery 399 1 SI units 420 13.6 Reconstructive surgery 400 2 Conversion factors, constants and physical 13.6.1 Plastic surgery 400 data 422 13.6.2 Maxillofacialsurgery 401 13.6.3 Ear implants 402 Figure references 424 13.7 Biomaterials for heart repair 402 13.7.1 Heart valves 402 Index 427