|
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 |
|