Hybrid Materials

Edited by
Guido Kickelbick
1807–2007 Knowledge for Generations
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Hybrid Materials
Synthesis, Characterization, and Applications

Edited by
Guido Kickelbick
The Editor
Prof. Dr. Guido Kickelbick
Technische Universität Wien
Institut für Materialchemie
Getreidemarkt 9/165
1060 Wien
Austria
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ISBN 978-3-527-31299-3
 V

Contents

1 Introduction to Hybrid Materials 1

Guido Kickelbick
1.1 Introduction 1
1.1.1 Natural Origins 1
1.1.2 The Development of Hybrid Materials 2
1.1.3 Definition: Hybrid Materials and Nanocomposites 3
1.1.4 Advantages of Combining Inorganic and Organic Species in One
Material 7
1.1.5 Interface-determined Materials 10
1.1.6 The Role of the Interaction Mechanisms 11
1.2 Synthetic Strategies towards Hybrid Materials 12
1.2.1 In situ Formation of Inorganic Materials 13
1.2.1.1 Sol–Gel Process 14
1.2.1.2 Nonhydrolytic Sol–Gel Process 16
1.2.1.3 Sol–Gel Reactions of Non-Silicates 16
1.2.1.4 Hybrid Materials by the Sol–Gel Process 17
1.2.1.5 Hybrid Materials Derived by Combining the Sol–Gel Approach and
Organic Polymers 19
1.2.2 Formation of Organic Polymers in Presence of Preformed Inorganic
Materials 20
1.2.3 Hybrid Materials by Simultaneous Formation of Both Components 22
1.2.4 Building Block Approach 23
1.2.4.1 Inorganic Building Blocks 24
1.2.4.2 Organic Building Blocks 32
1.3 Structural Engineering 35
1.4 Properties and Applications 39
1.5 Characterization of Materials 41
1.6 Summary 46

2 Nanocomposites of Polymers and Inorganic Particles 49

Walter Caseri
2.1 Introduction 49
2.2 Consequences of Very Small Particle Sizes 53
VI Contents

2.3 Historical Reports on Inorganic Nanoparticles and Polymer

Nanocomposites 63
2.4 Preparation of Polymer Nanocomposites 65
2.4.1 Mixing of Dispersed Particles with Polymers in Liquids 67
2.4.2 Mixing of Particles with Monomers Followed by Polymerization 71
2.4.3 Nanocomposite Formation by means of Molten or Solid Polymers 73
2.4.4 Concomitant Formation of Particles and Polymers 74
2.5 Properties and Applications of Polymer Nanocomposites 75
2.5.1 Properties 75
2.5.2 Applications 78
2.5.2.1 Catalysts 78
2.5.2.2 Gas Sensors 79
2.5.2.3 Materials with Improved Flame Retardance 80
2.5.2.4 Optical Filters 80
2.5.2.5 Dichroic Materials 81
2.5.2.6 High and Low Refractive Index Materials 81
2.6 Summary 83

3 Hybrid Organic/Inorganic Particles 87

Elodie Bourgeat-Lami
3.1 Introduction 87
3.2 Methods for creating Particles 92
3.2.1 Polymer Particles 92
3.2.1.1 Oil-in-water Suspension Polymerization 92
3.2.1.2 Precipitation and Dispersion Polymerizations 93
3.2.1.3 Oil-in-water Emulsion Polymerization 94
3.2.1.4 Oil-in-water Miniemulsion Polymerization 95
3.2.1.5 Oil-in-water Microemulsion Polymerization 95
3.2.2 Vesicles, Assemblies and Dendrimers 95
3.2.2.1 Vesicles 95
3.2.2.2 Block Copolymer Assemblies 96
3.2.2.3 Dendrimers 97
3.2.3 Inorganic Particles 98
3.2.3.1 Metal Oxide Particles 98
3.2.3.2 Metallic Particles 99
3.2.3.3 Semiconductor Nanoparticles 101
3.2.3.4 Synthesis in Microemulsion 102
3.3 Hybrid Nanoparticles Obtained Through Self-assembly
Techniques 103
3.3.1 Electrostatically Driven Self-assembly 103
3.3.1.1 Heterocoagulation 103
3.3.1.2 Layer-by-layer Assembly 107
3.3.2 Molecular Recognition Assembly 109
3.4 O/I Nanoparticles Obtained by in situ Polymerization
Techniques 111
 Contents VII

3.4.1 Polymerizations Performed in the Presence of Preformed Mineral

Particles 111
3.4.1.1 Surface Modification of Inorganic Particles 112
3.4.1.2 Polymerizations in Multiphase Systems 113
3.4.1.3 Surface-initiated Polymerizations 124
3.4.2 In situ Formation of Minerals in the Presence of Polymer
Colloids 130
3.4.2.1 Polymer Particles Templating 130
3.4.2.2 Block Copolymers, Dendrimers and Microgels Templating 134
3.5 Hybrid Particles Obtained by Simultaneously Reacting Organic
Monomers and Mineral Precursors 137
3.5.1 Poly(organosiloxane/vinylic) Copolymer Hybrids 137
3.5.2 Polyorganosiloxane Colloids 140
3.6 Conclusion 142

4 Intercalation Compounds and Clay Nanocomposites 151

Jin Zhu and Charles A. Wilkie
4.1 Introduction 151
4.2 Polymer Lamellar Material Nanocomposites 153
4.2.1 Types of Lamellar Nano-additives 153
4.2.2 Montmorillonite Layer Structure 154
4.2.3 Modification of Clay 154
4.3 Nanostructures and Characterization 156
4.3.1 X-ray Diffraction and Transmission Electron Microscopy to Probe
Morphology 156
4.3.2 Other Techniques to Probe Morphology 158
4.4 Preparation of Polymer-clay Nanocomposites 160
4.4.1 Solution Mixing 161
4.4.2 Polymerization 161
4.4.3 Melt Compounding 163
4.5 Polymer-graphite and Polymer Layered Double Hydroxide
Nanocomposites 164
4.5.1 Nanocomposites Based on Layered Double Hydroxides and Salts 166
4.6 Properties of Polymer Nanocomposites 167
4.7 Potential Applications 168
4.8 Conclusion and Prospects for the Future 169

5 Porous Hybrid Materials 175

Nicola Hüsing
5.1 General Introduction and Historical Development 175
5.1.1 Definition of Terms 177
5.1.2 Porous (Hybrid) Matrices 179
5.1.2.1 Microporous Materials: Zeolites 180
5.1.2.2 Mesoporous Materials: M41S and FSM Materials 182
5.1.2.3 Metal–Organic Frameworks (MOFs) 184
VIII Contents

5.2 General Routes towards Hybrid Materials 185

5.2.1 Post-synthesis Modification of the Final Dried Porous Product by
Gaseous, Liquid or Dissolved Organic or Organometallic Species 185
5.2.2 Liquid-phase Modification in the Wet Nanocomposite Stage or – for
Mesostructured Materials and Zeolites – Prior to Removal of the
Template 187
5.2.3 Addition of Molecular, but Nonreactive Compounds to the Precursor
Solution 188
5.2.4 Co-condensation Reactions by the use of Organically-substituted Co-
precursors 188
5.2.5 The Organic Entity as an Integral Part of the Porous Framework 190
5.3 Classification of Porous Hybrid Materials by the Type of Interaction
192
5.3.1 Incorporation of Organic Functions Without Covalent Attachment to the
Porous Host 192
5.3.1.1 Doping with Small Molecules 192
5.3.1.2 Doping with Polymeric Species 196
5.3.1.3 Incorporation of Biomolecules 199
5.3.2 Incorporation of Organic Functions with Covalent Attachment to the
Porous Host 201
5.3.2.1 Grafting Reactions 201
5.3.2.2 Co-condensation Reactions 203
5.3.3 The Organic Function as an Integral Part of the Porous Network
Structure 209
5.3.3.1 ZOL and PMO: Zeolites with Organic Groups as Lattice and Periodically
Mesostructured Organosilicas 209
5.3.3.2 Metal–Organic Frameworks 213
5.4 Applications and Properties of Porous Hybrid Materials 219

6 Sol–Gel Processing of Hybrid Organic–Inorganic Materials Based on

Polysilsesquioxanes 225
Douglas A. Loy
6.1 Introduction 225
6.1.1 Definition of Terms 226
6.2 Forming Polysilsesquioxanes 228
6.2.1 Hydrolysis and Condensation Chemistry 228
6.2.2 Alternative Polymerization Chemistries 234
6.2.3 Characterizing Silsesquioxane Sol–Gels with NMR 235
6.2.4 Cyclization in Polysilsesquioxanes 237
6.3 Type I Structures: Polyhedral Oligosilsesquioxanes (POSS) 240
6.3.1 Homogenously Functionalized POSS 240
6.3.2 Stability of Siloxane Bonds in Silsesquioxanes 242
6.4 Type II Structures: Amorphous Oligo- and Polysilsesquioxanes 243
6.4.1 Gelation of Polysilsesquioxanes 243
6.4.2 Effects of pH on Gelation 245
 Contents IX

6.4.3 Polysilsesquioxane Gels 246

6.4.4 Polysilsesquioxane–Silica Copolymers 247
6.5 Type III: Bridged Polysilsesquioxanes 248
6.5.1 Molecular Bridges 248
6.5.2 Macromolecule-bridged Polysilsesquioxanes 252
6.6 Summary 252
6.6.1 Properties of Polysilsesquioxanes 253
6.6.2 Existing and Potential Applications 253

7 Natural and Artificial Hybrid Biomaterials 255

Heather A. Currie, Siddharth V. Patwardhan, Carole C. Perry, Paul Roach,
Neil J. Shirtcliffe
7.1 Introduction 255
7.2 Building Blocks 256
7.2.1 Inorganic Building Blocks 256
7.2.1.1 Nucleation and Growth 259
7.2.2 Organic Building Blocks 262
7.2.2.1 Proteins and DNA 262
7.2.2.2 Carbohydrates 264
7.2.2.3 Lipids 266
7.2.2.4 Collagen 266
7.3 Biomineralization 269
7.3.1 Introduction 269
7.3.1.1 Biomineral Types and Occurrence 269
7.3.1.2 Functions of Biominerals 270
7.3.1.3 Properties of Biominerals 270
7.3.2 Control Strategies in Biomineralization 272
7.3.3 The Role of the Organic Phase in Biomineralization 275
7.3.4 Mineral or Precursor – Organic Phase Interactions 276
7.3.5 Examples of Non-bonded Interactions in Bioinspired Silicification 279
7.3.5.1 Effect of Electrostatic Interactions 279
7.3.5.2 Effect of Hydrogen Bonding Interactions 279
7.3.5.3 Effect of the Hydrophobic Effect 280
7.3.6 Roles of the Organic Phase in Biomineralization 280
7.4 Bioinspired Hybrid Materials 281
7.4.1 Natural Hybrid Materials 283
7.4.1.1 Bone 283
7.4.1.2 Dentin 285
7.4.1.3 Nacre 287
7.4.1.4 Wood 287
7.4.2 Artificial Hybrid Biomaterials 289
7.4.2.1 Ancient materials 289
7.4.2.2 Structural Materials 290
7.4.2.3 Non-structural Materials 290
7.4.3 Construction of Artificial Hybrid Biomaterials 291
X Contents

7.4.3.1 Organic Templates to Dictate Shape and Form 291

7.4.3.2 Integrated Nanoparticle–Biomolecule Hybrid Systems 292
7.4.3.3 Routes to Bio-nano Hybrid Systems 292
7.5 Responses 294
7.5.1 Biological Performance 294
7.5.2 Protein Adsorption 295
7.5.3 Cell Adhesion 295
7.5.4 Evaluation of Biomaterials 296
7.6 Summary 298

8 Medical Applications of Hybrid Materials 301

Kanji Tsuru, Satoshi Hayakawa, and Akiyoshi Osaka
8.1 Introduction 301
8.1.1 Composites, Solutions, and Hybrids 301
8.1.2 Artificial Materials for Repairing Damaged Tissues and Organs 306
8.1.3 Tissue–Material Interactions 310
8.1.4 Material–Tissue Bonding; Bioactivity 313
8.1.5 Blood-compatible Materials 318
8.2 Bioactive Inorganic–Organic Hybrids 319
8.2.1 Concepts of Designing Hybrids 319
8.2.2 Concepts of Organic–Inorganic Hybrid Scaffolds and Membranes 321
8.2.3 PDMS–Silica Hybrids 323
8.2.4 Organoalkoxysilane Hybrids 324
8.2.5 Gelatin–Silicate Hybrids 326
8.2.6 Chitosan–Silicate Hybrids 327
8.3 Surface Modifications for Biocompatible Materials 328
8.3.1 Molecular Brush Structure Developed on Biocompatible Materials 328
8.3.2 Alginic Acid Molecular Brush Layers on Metal Implants 329
8.3.3 Organotitanium Molecular Layers with Blood Compatibility 330
8.4 Porous Hybrids for Tissue Engineering Scaffolds and Bioreactors 331
8.4.1 PDMS–Silica Porous Hybrids for Bioreactors 331
8.4.2 Gelatin–Silicate Porous Hybrids 332
8.4.3 Chitosan–Silicate Porous Hybrids for Scaffold Applications 333
8.5 Chitosan-based Hybrids for Drug Delivery Systems 334
8.6 Summary 335

9 Hybrid Materials for Optical Applications 337

Luís António Dias Carlos, R.A. Sá Ferreira and V. de Zea Bermudez
9.1 Introduction 337
9.2 Synthesis Strategy for Optical Applications 339
9.3 Hybrids for Coatings 343
9.4 Hybrids for Light-emitting and Electro-optic Purposes 353
9.4.1 Photoluminescence and Absorption 353
9.4.2 Electroluminescence 359
9.4.3 Quantifying Luminescence 365
 Contents XI

9.4.3.1 Color Coordinates, Hue, Dominant Wavelength and Purity 365

9.4.3.2 Emission Quantum Yield and Radiance 368
9.4.4 Recombination Mechanisms and Nature of the Emitting Centers 372
9.4.5 Lanthanide-doped Hybrids 374
9.4.6 Solid-state Dye-lasers 379
9.5 Hybrids for Photochromic and Photovoltaic Devices 381
9.6 Hybrids for Integrated and Nonlinear Optics 387
9.6.1 Planar Waveguides and Direct Writing 387
9.6.2 Nonlinear Optics 393
9.7 Summary 398

10 Electronic and Electrochemical Applications of Hybrid Materials 401

Jason E. Ritchie
10.1 Introduction 401
10.2 Historical Background 402
10.3 Fundamental Mechanisms of Conductivity in Hybrid Materials 403
10.3.1 Electrical Conductivity 403
10.3.2 Li_ Conductivity 407
10.3.3 H Conductivity 409
10.4 Explanation of the Different Materials 411
10.4.1 Sol–Gel Based Systems 411
10.4.2 Nanocomposites 412
10.4.3 Preparation of Electrochemically Active Films (and Chemically Modified
Electrodes) 414
10.5 Special Analytical Techniques 415
10.5.1 Electrochemical Techniques 415
10.5.2 Pulsed Field Gradient NMR 418
10.6 Applications 419
10.6.1 Electrochemical Sensors 419
10.6.2 Optoelectronic Applications 421
10.6.3 H-conducting Electrolytes for Fuel Cell Applications 423
10.6.4 Li-conducting Electrolytes for Battery Applications 426
10.6.5 Other Ion Conducting Systems 429
10.7 Summary 430

11 Inorganic/Organic Hybrid Coatings 433

Mark D. Soucek
11.1 General Introduction to Commodity Organic Coatings 433
11.2 General Formation of Inorganic/Organic Hybrid Coatings 435
11.2.1 Acid and Base Catalysis within an Organic Matrix 436
11.2.2 Thermally Cured Inorganic/Organic Seed Oils Coatings 443
11.2.3 Drying Oil Auto-oxidation Mechanism 444
11.2.4 Metal Catalysts 445
11.3 Alkyds and Other Polyester Coatings 449
11.3.1 Inorganic/Organic Alkyd Coatings 450
XII Contents

11.4 Polyurethane and Polyurea Coatings 451

11.4.1 Polyurea Inorganic/Organic Hybrid Coatings 452
11.4.2 Polyurethane/Polysiloxane Inorganic/Organic Coating System 455
11.5 Radiation Curable Coatings 459
11.5.1 UV-curable Inorganic/Organic Hybrid Coatings 461
11.5.2 Models for Inorganic/Organic Hybrid Coatings 465
11.5.3 Film Morphology 468
11.6 Applications 470
11.7 Summary 471

Index 477