Introductory word from the author and acknowledgments ........... 8
Symbols, notations, abbreviations .............................. 13
CHAPTER 1. CRITICAL SURVEY ..................................... 17
1.1 Critical approach to "critical phenomena" ................. 17
1.2 First- and second-order phase transitions ................. 19
1.3 First-order phase transitions cannot have a "critical
point" .................................................... 24
1.4 General considerations on lattice energy, polymorphism
and phase transitions ..................................... 24
1.4.1 Taking into account definitions of a solid phase
and a phase transition ............................. 24
1.4.2 Controlling factor: similarity or lowest energy? ... 25
1.4.3 Why polymorphs sometimes look similar .............. 27
1.5 Other classifications ..................................... 28
1.5.1 Martensitic - and something not martensitic ........ 28
1.5.2 Displacive - and reconstructive .................... 29
1.5.3 Displacive - and order-disorder .................... 31
1.5.4 Phenomenological approach: 1, 21, ... etc. types ... 31
1.5.5 Another phenomenological classification (Pippard) .. 32
1.5.6 Quantum - and classical ............................ 32
1.6 The soft-mode concept ..................................... 32
1.7 The imaginary "incommensurate" solid state ................ 34
1.8 300 mechanisms of one phenomenon .......................... 38
1.9 Ferromagnetism without Weiss-Heisenberg molecular /
exchange field ............................................ 40
CHAPTER 2. THE MOLECULAR MECHANISM OF SOLID-STATE PHASE
TRANSITIONS .................................................... 45
2.1 Summary of the problems ................................... 45
2.2 Crystal growth in a crystal medium: the crystallographic
meaning of interfaces ..................................... 47
2.2.1 The experimental approach .......................... 47
2.2.2 Growth of face-bounded single crystals in crystal
medium ............................................. 49
2.2.4 More on orientations of lattices and interfaces .... 60
2.2.5 The "odd" requirements to the molecular mechanism
of crystal phase transitions ....................... 65
2.3 Edgewise mode of interface motion ......................... 70
2.3.1 Microscopic observation under high optical
resolution ......................................... 70
2.3.2 The implication of the edgewise mechanism .......... 73
2.4 Phase transition at the contact interface ................. 75
2.4.1 Recalling the Hartshorne's effort .................. 75
2.4.2 Designing the contact molecular model of
interface .......................................... 77
2.4.3 Phase transition: molecular relocation at contact
interface .......................................... 78
2.4.4 The solution of the Hartshorne's paradox ........... 80
2.4.5 The coupling at the contact interface .............. 83
2.4.6 General significance and predicting power of the
contact mechanism .................................. 84
2.5 Nucleation in crystals .................................... 88
2.5.1 Problems with the standard interpretation .......... 88
2.5.2 Nucleation in small single crystals ................ 90
2.5.3 Formation of a nucleus: a predetermined act,
rather than a successful random fluctuation ........ 96
2.5.4 The structure of a nucleation site ................. 97
2.6 Temperature of phase transition ........................... 99
2.6.1 Analogy with crystallization from melt ............. 99
2.6.2 The meaning of a recorded transition temperature
Ttr ............................................... 100
2.6.3 The source of typical ambiguities: discrepancies
in the reported temperatures, range of
transition, rounding, and hysteresis of critical
points ............................................ 101
2.6.4 Misplacement of transition temperature -
inevitable misinterpretation of the phase
transition phenomenon ............................. 105
2.6.5 More on hysteresis of solid-state phase
transitions ....................................... 107
2.6.6 Resume and final notes on temperature and
hysteresis of solid-state phase transitions ....... 110
2.6.7 Example No.1: The temperature of phase
transition in p-diiodobenzene (PDI) ............... 111
2.6.8 Example No.2: the "Curie point" in Ni ............. 113
2.7 Order-disorder phase transitions as crystal growth ....... 118
2.7.1 The deceptive "common sense" ...................... 118
2.7.2 Direct microscopic observations of С -- ODC
transitions ....................................... 121
2.7.3 Order-disorder phase transition in CH4: no
ambiguities ....................................... 125
2.8 Epitaxial phase transitions .............................. 127
2.8.1 Oriented and non-oriented crystal growth in
crystal medium .................................... 127
2.8.2 Epitaxial transition in hexamethyl benzene (HMB) .. 128
2.8.3 Epitaxial transition in DL-norleucine (DL-N) ...... 134
2.8.4 Significance of layered structures. Epitaxial
nucleation in the interlayer microcracks .......... 139
2.8.5 Three examples in support of epitaxial crystal
growth ............................................ 142
2.8.6 The origin of domain structures ................... 145
2.8.7 On classification of solid-state phase
transitions ....................................... 146
2.9 Kinetics of solid-state phase transitions ................ 148
2.9.1 Definition; current status; bulk and interface
kinetics .......................................... 148
2.9.2 A more detailed representation of interface
motion ............................................ 151
2.9.3 Ten experimental facts of interface kinetics ...... 153
2.9.4 Revision of a common concept of activation
energy ............................................ 160
2.9.5 Relationships between the controlling parameters .. 161
2.9.6 The "truly out of control" kinetics ............... 163
CHAPTER 3. "LAMBDA-ANOMALIES" AND OTHER APPARENT ANOMALIES .... 165
3.1 The appearance of different physical properties upon
measurement of a heterophase system ...................... 165
3.2 Experimental imitation of a "continuous transition" and
a "λ-anomaly" ............................................ 169
3.3 "λ-Anomaly" of volume coefficient of thermal expansion ... 171
3.4 "λ-Anomaly" of heat capacity ............................. 173
3.4.1 Special role of the heat capacity λ-peaks ......... 173
3.4.2 [Nucleation range] + [Latent heat] =
["λ-Anomaly"] ..................................... 173
3.4.3 Hysteresis of the "heat capacity λ-anomalies" ..... 175
3.4.4 Instructive story of "specific heat λ-anomaly"
in NH4Cl .......................................... 176
3.4.5 Two additional ways to disprove "specific heat
λ-Anomaly" ........................................ 179
3.4.6 Analyzing old literature data ..................... 181
3.4.7 Turning the observed inconsistencies into
harmony ........................................... 182
3.4.8 On linear correlation between specific heat and
coefficient of thermal expansion .................. 183
3.4.9 Summary on the mechanism of phase transition in
NH4Cl ............................................. 184
3.5 "λ-Anomaly" of dielectric constant ....................... 184
3.5.1 The discordant facts .............................. 184
3.5.2 Electric conductance during epitaxial phase
transition ........................................ 185
3.5.3 ε-Peak in (NH4)2SO4 phase transition .............. 189
3.6 "λ-Anomaly" of light scattering .......................... 191
3.6.1 Static source of "critical opalescence" ........... 191
3.6.2 Revealing experiments by Durvasula and Gammon ..... 192
3.6.4 The correct solution has been proposed, but
ignored ........................................... 195
3.6.5 Light scattering in NH4CI and quartz phase
transitions ....................................... 196
3.7 "λ-Anomaly" of neutron scattering ........................ 197
3.8 On solid-state phase transitions, their molecular
mechanism and anomalies - final notes with some
philosophical and psychological overtones ................ 199
CHAPTER 4. FUNDAMENTALS OF FERROMAGNETISM AND
FERROELECTRICITY .............................................. 201
4.1 Unsatisfactory state of the theory and suggested new
solution ................................................. 201
4.2 Ferroelectric and ferromagnetic phase transitions ........ 207
4.2.1 Ferroelectric phase transitions ................... 207
4.2.2 Ferromagnetic phase transitions ................... 210
4.2.3 Ferromagnetic non-second-order non-phase
transition in iron? ............................... 212
4.3 Spontaneous magnetization and spontaneous polarization:
why are they spontaneous? ................................ 215
4.4 "Curie point," a misnomer ................................ 216
4.5 Origin of domain structures .............................. 218
4.6 Two basic components that make a ferroic ................. 222
4.7 Understanding the cause of magnetostriction .............. 223
4.8 Domain interfaces. Tearing down the Bloch wall ........... 228
4.9 Domain equilibrium in ferroic structures ................. 232
4.10 Barkhausen effect as manifestation of crystal growth ..... 236
4.11 Nucleation in single-domain particles .................... 239
4.12 Magnetization stages. Meaning of "easy" and "hard"
directions ............................................... 242
4.13 Origin of magnetic hysteresis and formation of
hysteresis loops. Magnetization as a counterpart of
solid-state phase transition ............................. 248
4.13.1 General remarks ................................... 248
4.13.2 Rectangular hysteresis loops ...................... 250
4.13.3 "Typical" hysteresis loops ........................ 255
4.13.4 Specificity of ferroelectric hysteresis loops ..... 261
4.13.5 Double hysteresis loops ........................... 262
4.14 Crystal rearrangement of antiferromagnet by magnetic
field .................................................... 264
4.15 Summary of the new principles ............................ 265
4.16 A few notes on superconducting phase transitions (SPTs) .. 268
APPENDIX 1: 300 different kinds of solid-state phase
transitions found in literature .......................... 270
APPENDIX 2: Shortcomings of adiabatic calorimetry and an
unnoticed advantage of differential scanning
calorimetry .............................................. 278
APPENDIX 3: Polemic with an anonymous opponent ................ 284
APPENDIX 4: On status of theory of ferromagnetism and
ferroelectricity as stated by experts in the field ....... 291
APPENDIX 5: Review on "light scattering near phase
transitions" ............................................. 295
ADDENDUM A: The theory of phase transitions: history of
distortions and ignorance ................................
ADDENDUM B: Quantum phase transitions: wrong concept .......... 305
ADDENDUM C: No displacements in "displacive" and
"topological" phase transitions .......................... 308
ADDENDUM D: On physics of magnetization ....................... 310
ADDENDUM E: Blending the mechanisms into a pulp ............... 312
ADDENDUM F: Guide to the shape memory effect .................. 314
ADDENDUM G: Incommensurate approach to phase transitions ...... 319
ADDENDUM H: Lesson on Barkhausen effect for Durin and
Zapperi .................................................. 322
ADDENDUM I: Ferromagnetism explained .......................... 323
ADDENDUM J: Magnetocaloric effect in terms of crystal growth .. 326
REFERENCES .................................................... 329
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