Preface	7
	Acknowledgements	10
	Contents	11
	Acronyms	18
	1 Freezing Colloids: Natural and Technological Occurrences	21
	1.1 The Small World of Colloids	21
	1.2 Sea Ice	23
	1.2.1 Brine Channels	23
	1.2.2 Sea Ice and the Emergence of Life on Earth	25
	1.3 Frost Heave	26
	1.4 Life and Liquid Water on Mars	30
	1.5 Biology	32
	1.5.1 Cryosurgery	33
	1.5.2 Cryopreservation of Cells and Tissues	35
	1.5.3 Freezing Resistance of Organisms	38
	1.6 Food Engineering	42
	1.6.1 Cryopreservation of Food	42
	1.6.2 Frozen Dessert and Ice Cream	43
	1.7 Engineering	45
	1.7.1 Water Treatment	45
	1.7.2 Desalination	48
	1.8 Civil Engineering	52
	1.9 Materials Science	53
	1.9.1 Metallurgy	55
	1.9.2 Ice-Templating, Freeze-Casting	59
	1.9.3 Paint	61
	1.10 Conclusions	63
	References	63
	2 Investigating the Freezing of Colloids: Experimental Techniques to Probe Solidification Patterns, Crystal Growth, and Particle Movement	67
	2.1 What Are We Looking For?	67
	2.2 Time and Space Scales	69
	2.3 Solidification Patterns	72
	2.3.1 Field Observations	72
	2.3.2 Optical Microscopy	72
	2.3.3 Scanning Electron Microscopy	78
	2.3.4 Magnetic Resonance Imaging	80
	2.3.5 Near-Infrared Imaging Spectroscopy	81
	2.3.6 Cryomicroscopy	81
	2.4 Crystal Growth: Kinetics, Shape, Crystalline Structure	83
	2.4.1 Optical Interferometry	84
	2.4.2 X-Ray Imaging	85
	2.4.3 Confocal Microscopy	89
	2.4.4 Transmission Electron Microscopy	93
	2.4.5 Electron Backscattered Diffraction	93
	2.4.6 X-Ray Diffraction	96
	2.5 Particle Behaviour	99
	2.5.1 Force Measurements	99
	2.5.2 X-Ray Scattering and Spectroscopy Techniques	102
	2.6 Thermal Measurements	104
	2.7 Conclusions	106
	References	107
	3 Understanding the Freezing of Colloidal Suspensions: Crystal Growth and Particle Redistribution	111
	3.1 Nucleation and Growth	113
	3.1.1 Freezing Point	113
	3.1.2 Homogeneous Nucleation	114
	3.1.3 Heterogeneous Nucleation	115
	3.1.4 Nucleation and Supercooling	117
	3.1.5 Experimental Measures of the Freezing Point	117
	3.1.6 Transient Regime	118
	3.1.7 Role of the Temperature Distribution and Boundary Conditions	121
	3.2 The Water/Ice Interface	122
	3.2.1 Nature of the Water/Ice Interface	122
	3.2.2 Freezing Potential	122
	3.2.3 Stresses Developed During Freezing	124
	3.3 Steady State	125
	3.3.1 Freeze Front Velocity	125
	3.3.2 Morphology of the Interface	128
	3.3.3 Faceted or Dendritic?	129
	3.3.4 Confined Solidification	131
	3.3.5 Solidification Patterns and Their Periodicity	132
	3.3.6 Crystallographic Orientation of the Crystals	137
	3.3.7 Instabilities in Steady State	140
	3.4 Orientation Domains	144
	3.5 Ice Lenses	146
	3.5.1 Formation of Ice Lenses	147
	3.5.2 Consequences of Ice Lens Formation	150
	3.6 Particle Redistribution	152
	3.6.1 Sedimentation	152
	3.6.2 Parallel Between Freezing and Drying	153
	3.6.3 Isolated Particles in Dilute Suspensions	155
	3.6.4 Concentrated Suspensions	164
	3.6.5 Osmotic Pressure and Particle Packing	165
	3.6.6 Soft Objects	166
	3.6.7 Dynamics of Particle Redistribution	172
	3.7 Packing of Particles in the Frozen Structure	174
	3.7.1 Monodisperse, Isotropic Particles	175
	3.7.2 Polydisperse, Isotropic Particles	178
	3.7.3 Anisotropic Particles	179
	3.7.4 Recrystallisation of the Frozen Structure	179
	3.8 The Different Modelling Approaches	182
	3.9 Conclusions	184
	References	185
	4 Ice-Templating: Processing Routes, Architectures, and Microstructures	191
	4.1 Templating Porosity with Ice Crystals: A Brief History	191
	4.1.1 Early Observations	192
	4.1.2 Freezing in Biology	196
	4.1.3 Freezing-Induced Damages in Industrial Applications	198
	4.1.4 Freezing as a Templating Route	198
	4.2 Processing and Shaping Routes	202
	4.2.1 Control of the Freezing Conditions	202
	4.2.2 Freeze Tape-Casting	204
	4.2.3 Ice-Templated Thin Films and Membranes	208
	4.2.4 Assembly of Independently Frozen Pieces	212
	4.2.5 Extrusion and Co-extrusion	212
	4.2.6 Rapid Freezing for Nanofibres Production	216
	4.2.7 Post-freezing Treatments	216
	4.2.8 Emulsions	217
	4.3 Microstructures and Architectures	217
	4.3.1 Orientation Domains of Crystals	218
	4.3.2 Macroporosity	224
	4.3.3 Meso and Microporosity	236
	4.3.4 Aerogels	244
	4.3.5 Fibres	248
	4.3.6 Microparticles	252
	4.4 Reproducibility	257
	4.5 Conclusions	259
	References	260
	5 Ice-Templated Materials: Polymers, Ceramics, Metals and Their Composites	273
	5.1 Dense Ceramics	273
	5.2 Porous Ceramics	274
	5.2.1 Materials	275
	5.2.2 Processing	293
	5.3 Glasses	297
	5.4 Polymers	300
	5.4.1 Materials and Applications	300
	5.4.2 Solvents	303
	5.4.3 Process	304
	5.5 Preceramics Polymers	306
	5.6 Metals	308
	5.6.1 From Metal Particles	308
	5.6.2 From Precursors	311
	5.6.3 Solvents	314
	5.7 Cryogels	315
	5.8 Carbon Materials	319
	5.9 Porous Composites	324
	5.9.1 Ceramic/Polymer Porous Composites	324
	5.9.2 Ceramic/Ceramic Porous Composites	328
	5.9.3 Polymer/Polymer Porous Composites	331
	5.9.4 Carbon-Based Porous Composites	332
	5.9.5 Other Porous Composites	335
	5.10 Dense Composites	336
	5.10.1 Metal/ceramic Composites	337
	5.10.2 Polymer/ceramic Composites	340
	5.10.3 Ceramic/ceramic Composites	341
	5.11 Conclusions	342
	References	343
	6 Ice-Templating and Freeze-Casting: Control of the Processes, Microstructures, and Architectures	371
	6.1 Preparation of the Colloidal Suspensions	371
	6.1.1 Solvent	371
	6.1.2 Particles and Colloids	381
	6.1.3 Formulation and Stability of the Suspensions	391
	6.1.4 Foaming	395
	6.1.5 Emulsions	396
	6.1.6 Additives and Control of Crystal Growth	398
	6.2 Towards a Control of Crystal Growth at the Atomic Level	402
	6.2.1 Freeze-Tolerant Organisms	403
	6.2.2 Zirconium Acetate: A Different Ice-Shaping Compound	403
	6.2.3 Learning from Snowflakes	405
	6.3 Control of the Freezing Conditions	406
	6.3.1 Evaporation	406
	6.3.2 Nucleation and Growth	408
	6.3.3 Design of the Mould	412
	6.3.4 Directionality and Magnitude of the Temperature Gradient	413
	6.3.5 Cooling Rate	421
	6.3.6 Freezing in a Template	428
	6.3.7 Pre-made Ice Templates	429
	6.3.8 Two-Step Freezing	432
	6.3.9 Two-Dimensional Ice-Templating	433
	6.3.10 Application of External Fields	434
	6.4 Recrystallisation	438
	6.5 Sublimation	441
	6.6 Multiple Freeze--Thaw Cycles	444
	6.7 Conclusions	447
	References	447
	7 Properties and Applications of Ice-Templated Materials	459
	7.1 What is the Interest of Ice-Templated Materials?	459
	7.2 Reporting of the Results	461
	7.3 Anisotropy of Properties	462
	7.4 Physical Properties	463
	7.4.1 Porosity	463
	7.4.2 Density	468
	7.4.3 Specific Surface Area	468
	7.4.4 Permeability	469
	7.4.5 Conductivity and Resistivity	477
	7.4.6 Dielectric Properties	478
	7.4.7 Piezoelectric Properties	480
	7.4.8 Thermal Properties	483
	7.4.9 Capacitance	484
	7.4.10 Permittivity	487
	7.4.11 Other Physical Properties	488
	7.5 Structural Properties	488
	7.5.1 Compressive Strength	488
	7.5.2 Reliability	505
	7.5.3 Flexural Strength	507
	7.5.4 Young's Modulus	508
	7.5.5 Toughness	509
	7.6 Functional Properties	514
	7.6.1 Catalytic Properties	514
	7.6.2 Acoustic Properties	515
	7.6.3 Corrosion Resistance	516
	7.7 Applications	517
	7.7.1 Armour and Impact Resistance	517
	7.7.2 Biomedical Applications	517
	7.7.3 Membranes	526
	7.7.4 Adsorption and Depollution	528
	7.7.5 Antifungal Properties	530
	7.7.6 Electrochemical Cells	530
	7.7.7 Batteries, Capacitors, and Supercapacitors	532
	7.7.8 Sensors	534
	7.7.9 Field Emitters	534
	7.7.10 Solar Cells	535
	7.7.11 Thermal Insulation	536
	7.7.12 Thermoresponsive Materials	536
	7.7.13 Shape Memory Materials	537
	7.7.14 Thermal Energy Storage	538
	7.7.15 Phase Change Heat Transfer	540
	7.7.16 Food Engineering	540
	7.7.17 Plasmonic Materials	541
	7.7.18 Antibacterial Material	541
	7.7.19 Chemical Reactions	541
	7.7.20 Model Materials for Physical Studies	544
	7.8 Conclusions: What's Next?	545
	7.8.1 Why Freezing?	546
	7.8.2 Towards Commercial Products?	546
	References	548
	8 Ice-Templating, Freeze-Casting: A Practical Guide to Get Started	569
	8.1 What Do You Want to Do?	569
	8.2 Your Budget	570
	8.3 Materials	571
	8.3.1 Samples Dimensions	576
	8.3.2 Required Cooling Rate	576
	8.4 Freezing	577
	8.4.1 Moulds	577
	8.4.2 Which Coolant?	577
	8.4.3 EHS with Liquid Nitrogen	579
	8.4.4 Freezing Directionality	580
	8.4.5 Directional Freezing	581
	8.4.6 Extracting the Sample from the Mould	586
	8.5 Freeze-Drying	587
	8.5.1 Protecting Your Pump from Solvents	589
	8.5.2 Sample Preparation	589
	8.6 Observing Samples	590
	8.6.1 Describing the Structure	590
	8.6.2 Mercury Porosimetry	591
	8.6.3 Image Analysis in 2D and 3D	592
	8.7 Troubleshooting	595
	8.7.1 My Pores Are Too Large!	595
	8.7.2 My Pores Are Too Small!	596
	8.7.3 The Strength of My Samples Is Too Low!	597
	8.7.4 I Have Defects in the Structure!	598
	8.8 Final Words	603
	References	604
	Index	613