Phase Transformations in Metals

and Alloys
SECOND EDITION

D.A. Porter
Rautaruukki Oy
Research Centre
Raahe
Finland
K.E. Easterling
Formerly School of Engineering
University ofExeter
Exeter
UK

London Glasgow Weinheim New York Tokyo Melbourne Madras

Contents

Preface to the second edition

Preface to thefirst edition
1

Thermodynamics and Phase Diagrams

1.1 Equilibrium
1.2 Single Component Systems
1.2.1 Gibbs Free Energy as a Function of Tempcrature
1.2.2 Pressure Effects
1.2.3 The Driving Force for Solidification
1.3 Binary Solutions
1.3.1 The Gibbs Free Energy of Binary Solutions
1.3.2 Ideal Solutions
1.3.3 Chemical Potential
1.3.4 Regulr Solutions
1.3.5 Activity
1.3.6 Real Solutions
1.3.7 Ordered Phases
1.3.8 Intermediate Phases
1.4 Equilibrium in Heterogeneous Systems
1.5 Binary Phase Diagrams
1.5.1 A Simple Phase Diagram
1.5.2 Systems with a Miscibility Gap
1.5.3 Ordered Alloys
1.5.4 Simple Eutectic Systems
1.5.5 Phase Diagrams Containing Intermediate Phases
1.5.6 The Gibbs Phase Rule
1.5.7 The Effect of Temperature on Solid Solubility
1.5.8 Equilibrium Vacancy Concentration
1.6 The Influence of Interfaces on Equilibrium
1.7 Ternary Equilibrium
1.8 Additional Thermodynamic Retationships for Binary Solutio
1.9 The Kinetics of Phase Transformations
References
Further Reading
Exercises

VI

Contents
Diffusion
2.1 Atomic Mechanisms of Diffusion
2.2 Interstitial Diffusion
2.2.1 Interstitial Diffusion as a Random Jump Process
2.2.2 Effect of TemperatureThermal Activation
2.2.3 Steady-State Diffusion
2.2.4 Nonsteady-State Diffusion
2.2.5 Solutions to the Diffusion Equation
Homogenization
The Carburization of Steel
2.3 Substitutional Diffusion
2.3.1 Self-Diffusion
2.3.2 Vacancy Diffusion
2.3.3 Diffusion in Substitutional Atloys
2.3.4 Diffusion in Dilute Substitutional Alloys
2.4 Atomic Mobility
2.5 Tracer Diffusion in Binary Alloys
2.6 Diffusion in Ternary Alloys
2.7 High-Diffusivity Paths
2.7.1 Diffusion along Grain Boundaries and Free Surfaces
2.7.2 Diffusion along Dislocations
2.8 Diffusion in Multiphase Binary Systems
References
Further Reading
Exercises

60
61
63
63
66
69
69
71
71
73
75
75
79
82
91
92
94
96
98
98
102
103
106
106
106

Crystal Interfaces and Microstructure

3.1 Interfacial Free Energy
3.2 Solid/Vapour Interfaces
3.3 Boundaries in Single-Phase Solids
3.3.1 Low-Angle and High-Angle Boundaries
3.3.2 Special High-Angle Grain Boundaries
3.3.3 Equilibrium in Polycrystalline Materials
3.3.4 Thcrmally Activated Migration of Grain Boundaries
3.3.5 The Kinetics of Grain Growth
3.4 Interphase Interfaces in Solids
3.4.1 Interface Coherence
Fully Cohcrent Interfaces
Semicoherent Interfaces
Incoherent Interfaces
Complex Semicoherent Interfaces
3.4.2 Second-Phase Shape: Interfacial Energy Effects
Fully Coherent Precipitates
Partially Coherent Precipitates
Incoherent Precipitates
Precipitates on Grain Boundaries

110
110
112
116
116
122
124
130
139
142
143
143
145
147
148
149
149
151
152
153

Contents
3.4.3

3.5

Second-Phase Shape: Misfit Strain Effects

Fully Coherent Precipitates
Incoherent Inclusions
Plate-Like Precipitates
3.4.4 Coherency Loss
3.4.5 Glissile Interfaces
3.4.6 Solid/Liquid Interfaces
Interface Migration
3.5.1 Diffusion-Controlled and Interface-Controlled Growth
References
Further Reading
Exercises

Solidification
4.1 Nucleation in Pure Metals
4.1.1 Homogeneous Nucleation
4.1.2 The Homogeneous Nucleation Rate
4.1.3 Heterogeneous Nucleation
4.1.4 Nucleation of Melting
4.2 Growth of a Pure Solid
4.2.1 Continuous Growth
4.2.2 Lateral Growth
Surface Nucleation
Spiral Growth
Growth from Twin Intersections
4.2.3 Heat Flow and Interface Stability
4.3 Alloy Solidification
4.3.1 Solidification of Single-Phase Alloys
Equilibrium Solidification
No Diffusion in Sohd, Perfect Mixing in Liquid
No Diffusion in Solid, Diffusional Mixing in Liquid
Cellular and Dendritic Solidification
4.3.2 Eutectic Solidification
Growth of Lamellar Eutectics
4.3.3 Off-Eutectic Alloys
4.3.4 Peritectic Solidification
4.4 Solidification of Ingots and Castings
4.4.1 Ingot Structure
Chili Zone
Columnar Zone
Equiaxed Zone
Shrinkage Effects
4.4.2 Segregation in Ingots and Castings
4.4.3 Continuous Casting
Heat Flow in Welding and Continuous
Casting

VII

154
154
158
160
160
163
168
171
175
180
182
182
185
185
186
190
192
197
197
198
198
200
201
202
203
207
208
208
208
212
214
222
223
229
231
233
233
234
235
236
236
237
238
239

Contents

viii
4.5

4.6
4.7

Solidification of Fusion Welds

Influence of Welding Speed
Geometry of Crystal Growth
Solidification during Quenching from the Melt
Case Studies of some Practical Castings and Welds
4.7.1 Casting of Carbon and Low-Alloy Stcels
4.7.2 Casting of High-Speed Steels
4.7.3 Stainless Steel Weld Metal
References
Further Reading
Exercises

Diffusional Transformations in Solids

5.1 Homogeneous Nucleation in Solids
5.2 Heterogeneous Nucleation
Nucleation on Grain Boundaries
Dislocations
Excess Vacancies
5.2.1 Rate of Heterogeneous Nucleation
5.3 Precipitate Growth
5.3.1 Growth behind Planar Incoherent Interfaces
5.3.2 Diffusion-Controlled Lengthening of Plates or Needles
5.3.3 Thickening of Plate-like Precipitates
5.4 Overall Transformation KineticsTTT Diagrams
5.5 Precipitation in Age-Hardening Atloys
5.5.1 Precipitation in Aluminium-Copper Alloys
GP Zones
Transition Phascs
5.5.2 Precipitation in Aluminium-Silvcr Alloys
5.5.3 Quenched-in Vacancies
5.5.4 Age Hardening
5.5.5 Spinodal Decomposition
5.5.6 Particle Coarsening
Low y
Low Xc
LowD
5.6 The Precipitation of Ferrite from Austenite
5.7 Cellular Precipitation
5.8 Eutectoid Transformations
5.8.1 The Pearlite Reaction in F e - C Alloys
Nucleation of Pearlite
Pearlite Growth
Pearlitc in Off-Eutectoid F e - C Alloys
5.8.2 The Bainite Transformation

243
245
248
249
249
249
251
256
259
260
260

263
265
271
271
274
275
276
279
279
283
285
287
291
291
291
292
302
303
304
308
314
316
316
317
317
322
326
326
327
330
333
334

Contents

ix

Upper Bainite
Lower Bainite
Transformation Shears
5.8.3 The Effect of Alloying Elements on Hardenability
5.8.4 Continuous Cooling Diagrams
5.8.5 Fibrous and Tnterphase Precipitation in Alloy Steels
5.9
Massive Transformations
5.10 Ordering Transformations
5.11 CaseStudies
5.11.1 Titanium Forging Alloys
5.11.2 The Weldability of Low-Carbon and Microalioyed
Roiled Steels
References
Further Reading
Excrcises

334
337
337
338
344
349
349
358
366
366

Diffusionless Transformations
6.1 Characteristics of Diffusionless Transformations
6-1.1 The Solid Solution of Carbon in Iron
6.2 Martcnsite Crystallography
6.2.1 The Bain Model of the fec > bet Transformation
6.2.2 Comparison of Crystallographic Theory with
Experimental Results
6.3 Theories of Martensite Nucleation
6.3.1 Formation of Coherent Nuclci of Martensite
6.3.2 Role of Dislocations in Martensite Nucleation
6.3.3 Dislocation Strain Energy Assisted Transformation
6.4 Martensite Growth
6.4.1 Growth of Lath Martensite
6.4.2 Plate Martensite
6.4.3 Stabilization
6.4.4 Effect of External Stresses
6.4.5 Role of Grain Sizc
6.5 Pre-martensite Phcnomcna
6.6 Tempering of Ferrous Martcnsites
Carbon Segregation
e-Carbide
Cementite
Alloy Carbides
Effect of Retained Austenite
Recovery, Recrystallization and Grain Growth
Temper Embrittlement
6.7 Gase Studies
6.7.1 Carbon and Low-Alloy Quenched and Tempcred Steels
6.7.2 Controllcd Transformation Steels

382
383
385
389
391

372
377
378
379

396
397
398
401
406
409
410
412
415
415
416
416
417
420
421
422
422
426
426
427
428
428
430

Contents
6.7.3

The'Shape-Memory'Metal: Nitinol
References
Further Reading
Exercises

431
437
439
439

Solutions to exercises
Compiled by John C. Ion

441

Index

510