Phase equilibria, phase diagrams and phase transformations: their thermodynamic basis
Gespeichert in:
1. Verfasser: | |
---|---|
Format: | Buch |
Sprache: | English |
Veröffentlicht: |
Cambridge [u.a.]
Cambridge Univ. Press
2009
|
Ausgabe: | 2. ed., repr. |
Schlagworte: | |
Online-Zugang: | Inhaltsverzeichnis Klappentext |
Beschreibung: | XIV, 510 S. graph. Darst. |
ISBN: | 9780521853514 |
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245 | 1 | 0 | |a Phase equilibria, phase diagrams and phase transformations |b their thermodynamic basis |c Mats Hillert |
250 | |a 2. ed., repr. | ||
264 | 1 | |a Cambridge [u.a.] |b Cambridge Univ. Press |c 2009 | |
300 | |a XIV, 510 S. |b graph. Darst. | ||
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Datensatz im Suchindex
_version_ | 1804141177033719808 |
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adam_text | Contents
Preface
to second edition page,
xii
Preface to first edition
xiii
Basic concepts of thermodynamics
1
1.1
External state variables
1
1.2
Internal state variables
3
1.3
The first law of thermodynamics
5
1.4
Freezing-in conditions
9
1.5
Reversible and irreversible processes
10
1.6
Second law of thermodynamics
13
1.7
Condition of internal equilibrium
17
1.8
Driving force
19
1.9
Combined first and second law
21
1.10
General conditions of equilibrium
23
1.11
Characteristic state functions
24
1.12
Entropy
26
Manipulation of thermodynamic quantities
30
2.1
Evaluation of one characteristic state function from another
30
2.2
Internal variables at equilibrium
31
2.3
Equations of state
33
2.4
Experimental conditions
34
2.5
Notation for partial derivatives
37
2.6
Use of various derivatives
38
2.7
Comparison between Cv and CP
40
2.8
Change of independent variables
41
2.9
Maxwell relations
43
Systems with variable composition
45
3.1
Chemical potential
45
3.2
Molar and integral quantities
46
3.3
More about characteristic state functions
48
vi
Contents
3.4
Additivity
of extensive quantities. Free energy and exergy
51
3.5
Various forms of the combined law
52
3.6
Calculation of equilibrium
54
3.7
Evaluation of the driving force
56
3.8
Driving force for molecular reactions
58
3.9
Evaluation of integrated driving force as function of
ΤοτΡ
59
3.10
Effective driving force
60
Practical handling of multicomponent systems
63
4.1
Partial quantities
63
4.2
Relations for partial quantities
65
4.3
Alternative variables for composition
67
4.4
The lever rule
70
4.5
The tie-line rale
71
4.6
Different sets of components
74
4.7
Constitution and constituents
75
4.8
Chemical potentials in a phase with sublattices
77
Thermodynamics of processes
80
5.1
Thermodynamic treatment of kinetics of
internal processes
80
5.2
Transformation of the set of processes
83
5.3
Alternative methods of transformation
85
5.4
Basic thermodynamic considerations for processes
89
5.5
Homogeneous chemical reactions
92
5.6
Transport processes in discontinuous systems
95
5.7
Transport processes in continuous systems
98
5.8
Substitutional diffusion
101
5.9
Onsager s
extrémům
principle
104
Stability
108
6.1
Introduction
108
6.2
Some necessary conditions of stability
110
6.3
Sufficient conditions of stability
113
6.4
Summary of stability conditions
115
6.5
Limit of stability
116
6.6
Limit of stability against fluctuations in composition
117
6.7
Chemical capacitance
120
6.8
Limit of stability against fluctuations of
internal variables
121
6.9
Le
Chatelier s principle
123
Contents
vii
7
Applications of molar Gibbs energy diagrams
126
7.1
Molar Gibbs energy diagrams for binary systems
126
7.2
Instability of binary solutions
131
7.3
Illustration of the Gibbs-Duhem relation
132
7.4
Two-phase equilibria in binary systems
135
7.5
Allotropie
phase boundaries
137
7.6
Effect of a pressure difference on a two-phase
equilibrium
138
7.7
Driving force for the formation of a new phase
142
7.8
Partitionless transformation under local equilibrium
144
7.9
Activation energy for a fluctuation
147
7.10
Ternary systems
149
7.11
Solubility product
151
8
Phase equilibria and potential phase diagrams
155
8.1
Gibbs phase rule
155
8.2
Fundamental property diagram
157
8.3
Topology of potential phase diagrams
162
8.4
Potential phase diagrams in binary and multinary systems
166
8.5
Sections of potential phase diagrams
168
8.6
Binary systems
170
8.7
Ternary systems
173
8.8
Direction of phase fields in potential phase diagrams
177
8.9
Extrémům
in temperature and pressure
181
9
Molar phase diagrams
185
9.1
Molar axes
185
9.2
Sets of conjugate pairs containing molar variables
189
9.3
Phase boundaries
193
9.4
Sections of molar phase diagrams
195
9.5
Schreinemakers rule
197
9.6
Topology of sectioned molar diagrams
201
10
Projected and mixed phase diagrams
205
10.1
Schreinemakers projection of potential phase diagrams
205
10.2
The phase field rule and projected diagrams
208
10.3
Relation between molar diagrams and Schreinemakers
projected diagrams
212
10.4
Coincidence of projected surfaces
215
10.5
Projection of higher-order invariant equilibria
217
10.6
The phase field rule and mixed diagrams
220
10.7
Selection of axes in mixed diagrams
223
viii Contents
10.8
Konovalov s
rule
226
10.9
General
rule for singular equilibria
229
11
Direction of phase boundaries
233
11.1
Use of distribution coefficient
233
11.2
Calculation of
allotropie
phase boundaries
235
11.3
Variation of a chemical potential in a two-phase field
238
11.4
Direction of phase boundaries
240
11.5
Congruent melting points
244
11.6
Vertical phase boundaries
248
11.7
Slope of phase boundaries in isothermal sections
249
11.8
The effect of a pressure difference between two phases
251
12
Sharp and gradual phase transformations
253
12.1
Experimental conditions
253
12.2
Characterization of phase transformations
255
12.3
Microstructural
character
259
12.4
Phase transformations in alloys
261
12.5
Classification of sharp phase transformations
262
12.6
Applications of Schreinemakers projection
266
12.7
Scheil s reaction diagram
270
12.8
Gradual phase transformations at fixed composition
272
12.9
Phase transformations controlled by a chemical potential
275
13
Transformations in closed systems
279
13.1
The phase field rule at constant composition
279
13.2
Reaction coefficients in sharp transformations
for
ρ
=
с +
1 280
13.3
Graphical evaluation of reaction coefficients
283
13.4
Reaction coefficients in gradual transformations
for
ρ
=
с
285
13.5
Driving force for sharp phase transformations
287
13.6
Driving force under constant chemical potential
291
13.7
Reaction coefficients at constant chemical potential
294
13.8
Compositional degeneracies
îorp
=
с
295
13.9
Effect of two compositional degeneracies for
ρ
=
с
— 1 299
14
Partitionless transformations
302
14.1
Deviation from local equilibrium
302
14.2
Adiabatic phase transformation
303
14.3
Quasi-adiabatic phase transformation
305
14.4
Partitionless transformations in binary system
308
Contents ix
14.5
Partial
chemical equilibrium
311
14.6
Transformations in steel under quasi-paraequilibrium
315
14.7
Transformations in steel under partitioning of alloying elements
319
15
Limit of stability and
criticai
phenomena
322
15.1
Transformations and transitions
322
15.2
Order-disorder transitions
325
15.3
Miscibility gaps
330
15.4
Spinodal decomposition
334
15.5
Tri-critical points
338
16
Interfaces
344
16.1
Surface energy and surface stress
344
16.2
Phase equilibrium at curved interfaces
345
16.3
Phase equilibrium at fluid/fluid interfaces
346
16.4
Size stability for spherical inclusions
350
16.5
Nucleation
351
16.6
Phase equilibrium at crystal/fluid interface
353
16.7
Equilibrium at curved interfaces with regard to composition
356
16.8
Equilibrium for crystalline inclusions with regard to composition
359
16.9
Surface segregation
361
16.10
Coherency within a phase
363
16.11
Coherency between two phases
366
16.12
Solute drag
371
17
Kinetics of transport processes
377
17.1
Thermal activation
377
17.2
Diffusion coefficients
381
17.3
Stationary states for transport processes
384
17.4
Local volume change
388
17.5
Composition of material crossing an interface
390
17.6
Mechanisms of interface migration
391
17.7
Balance of forces and dissipation
396
18
Methods of modelling
400
18.1
General principles
400
18.2
Choice of characteristic state function
401
18.3
Reference states
402
18.4
Representation of Gibbs energy of formation
405
18.5
Use of power series in
Γ
407
18.6
Representation of pressure dependence
408
18.7
Application of physical models
410
Contents
18.8 Ideal gas 411
18.9 Real
gases
412
18.10
Mixtures
of
gas
species
415
18.11
Black-body radiation
417
18.12
Electron gas
418
19
Modelling of disorder
420
19.1
Introduction
420
19.2
Thermal vacancies in a crystal
420
19.3
Topological disorder
423
19.4
Heat capacity due to thermal vibrations
425
19.5
Magnetic contribution to thermodynamic properties
429
19.6
A simple physical model for the magnetic contribution
431
19.7
Random mixture of atoms
434
19.8
Restricted random mixture
436
19.9
Crystals with stoichiometric vacancies
437
19.10
Interstitial solutions
439
20
Mathematical modelling of solution phases
441
20.1
Ideal solution
441
20.2
Mixing quantities
443
20.3
Excess quantities
444
Лј.4
Empirical approach to substitutional solutions
445
20.5
Real solutions
448
20.6
Applications of theGibbs-Duhem relation
452
20.7
Dilute solution approximations
454
20.8
Predictions for solutions in higher-order systems
456
20.9
Numerical methods of predictions for higher-order systems
458
21
Solution phases with sublattices
460
21.1
Sublattice
solution phases
460
21.2
Interstitial solutions
462
21.3
Reciprocal solution phases
464
21.4
Combination of interstitial and substitutional solution
468
21.5
Phases with variable order
469
21.6
Ionic solid solutions
472
22
Physical solution models
476
22.1
Concept of nearest-neighbour bond energies
476
22.2
Random mixing model for a substitutional solution
478
22.3
Deviation from random distribution
479
22.4
Short-range order
482
Contents xi
22.5
Long-range order
484
22.6
Long- and short-range order
486
22.7
The compound energy formalism with short-range order
488
22.8
Interstitial ordering
490
22.9
Composition dependence of physical effects
493
References
496
Index
499
Thermodynamic principles are
centrai
to understanding material behaviour, particularly
as the application of these concepts underpin phase equiiibrium, transformation and
state. Whilst this is a complex and challenging area, the use of computational tools has
allowed the materials scientist to model and analyse increasingly convoluted systems
more readily, in order to use and interpret such models and computed results accurately, a
strong understanding of the basic thermodynamics is required.
This fully revised and updated edition covers the fundamentals of thermodynamics, with a
view to the modern computer applications. The theoretical basis of chemical equilibria
and chemical changes is covered with an emphasis on the properties of phase diagrams.
Starting with the basic principles, discussion moves to systems involving multiple phases.
New chapters cover irreversible thermodynamics,
extrémům
principles and the
thermodynamics of surfaces and interfaces. Theoretical descriptions of equilibrium
conditions, the state of systems at equilibrium and the changes as equilibrium is reached,
are all demonstrated graphically. With illustrative examples
-
many computer calculated
-
and exercises with solutions, this textbook is a valuable resource for advanced
undergraduate and graduate students in materials science and engineering.
Additional information on this title, including further exercises and solutions, is available
atwww.cambridge.org/978O52i853514.Thecommercialthermodynamicpackage
Thermo-calť
is used throughout the book for computer applications; a link to a limited
free of charge version can be found at the above website and can be used to solve the
further exercises, in principle, however, a similar thermodynamic package can be used.
Mats Hillert is a Professor Emeritus at
ктн
(Royal Institute of Technology) in Stockholm.
|
any_adam_object | 1 |
author | Hillert, Mats |
author_facet | Hillert, Mats |
author_role | aut |
author_sort | Hillert, Mats |
author_variant | m h mh |
building | Verbundindex |
bvnumber | BV036105258 |
classification_rvk | UG 3800 VE 9500 |
classification_tum | CHE 178f MTA 600f |
ctrlnum | (OCoLC)255897293 (DE-599)BVBBV036105258 |
discipline | Chemie / Pharmazie Physik Chemie |
edition | 2. ed., repr. |
format | Book |
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id | DE-604.BV036105258 |
illustrated | Illustrated |
indexdate | 2024-07-09T22:11:43Z |
institution | BVB |
isbn | 9780521853514 |
language | English |
oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-018995537 |
oclc_num | 255897293 |
open_access_boolean | |
owner | DE-355 DE-BY-UBR DE-19 DE-BY-UBM |
owner_facet | DE-355 DE-BY-UBR DE-19 DE-BY-UBM |
physical | XIV, 510 S. graph. Darst. |
publishDate | 2009 |
publishDateSearch | 2009 |
publishDateSort | 2009 |
publisher | Cambridge Univ. Press |
record_format | marc |
spelling | Hillert, Mats Verfasser aut Phase equilibria, phase diagrams and phase transformations their thermodynamic basis Mats Hillert 2. ed., repr. Cambridge [u.a.] Cambridge Univ. Press 2009 XIV, 510 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier Thermochemie (DE-588)4078260-8 gnd rswk-swf Phasendiagramm (DE-588)4174149-3 gnd rswk-swf Phasengleichgewicht (DE-588)4132145-5 gnd rswk-swf Thermodynamik (DE-588)4059827-5 gnd rswk-swf Thermodynamik (DE-588)4059827-5 s Phasengleichgewicht (DE-588)4132145-5 s Phasendiagramm (DE-588)4174149-3 s DE-604 Thermochemie (DE-588)4078260-8 s Digitalisierung UB Regensburg application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018995537&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis Digitalisierung UB Regensburg application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018995537&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA Klappentext |
spellingShingle | Hillert, Mats Phase equilibria, phase diagrams and phase transformations their thermodynamic basis Thermochemie (DE-588)4078260-8 gnd Phasendiagramm (DE-588)4174149-3 gnd Phasengleichgewicht (DE-588)4132145-5 gnd Thermodynamik (DE-588)4059827-5 gnd |
subject_GND | (DE-588)4078260-8 (DE-588)4174149-3 (DE-588)4132145-5 (DE-588)4059827-5 |
title | Phase equilibria, phase diagrams and phase transformations their thermodynamic basis |
title_auth | Phase equilibria, phase diagrams and phase transformations their thermodynamic basis |
title_exact_search | Phase equilibria, phase diagrams and phase transformations their thermodynamic basis |
title_full | Phase equilibria, phase diagrams and phase transformations their thermodynamic basis Mats Hillert |
title_fullStr | Phase equilibria, phase diagrams and phase transformations their thermodynamic basis Mats Hillert |
title_full_unstemmed | Phase equilibria, phase diagrams and phase transformations their thermodynamic basis Mats Hillert |
title_short | Phase equilibria, phase diagrams and phase transformations |
title_sort | phase equilibria phase diagrams and phase transformations their thermodynamic basis |
title_sub | their thermodynamic basis |
topic | Thermochemie (DE-588)4078260-8 gnd Phasendiagramm (DE-588)4174149-3 gnd Phasengleichgewicht (DE-588)4132145-5 gnd Thermodynamik (DE-588)4059827-5 gnd |
topic_facet | Thermochemie Phasendiagramm Phasengleichgewicht Thermodynamik |
url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018995537&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=018995537&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA |
work_keys_str_mv | AT hillertmats phaseequilibriaphasediagramsandphasetransformationstheirthermodynamicbasis |