Encapsulation Nanotechnologies Edited by Vikas Mittal Chemical Engineering Department, The Petroleum Institute, Abu Dhabi, UAE y> Scri\ Scrivener Publishing Wiley
Contents Preface List of Contributors xiii xvii 1 Copper Encapsulation of Multi-Walled Carbon Nanotubes 1 Yong Sun and Boateng Onwona-Agyeman 1.1 Introduction 2 1.2 Preparation of Copper Encapsulated CNTs 3 1.2.1 Arc Discharge 3 1.2.2 Chemical Vapor Deposition 15 1.2.3 Laser Ablation 30 References 37 2 Novel Nanocomposites: Intercalation of Ionically Conductive Polymers into Molybdic Acid 41 Rabin Bissessur, Blakney Hopkins and Douglas C. Dahn 2.1 Introduction 41 2.1.1 Battery Technology 41 2.1.2 The Polymer Electrolyte 43 2.1.3 Intercalation Chemistry 45 2.1.4 Mo03 and Mo03 Derivatives 46 2.2 Experimental 47 2.2.1 Materials 47 2.2.2 Synthesis of POEGO 47 2.2.3 Synthesis of POMOE 48 2.3 Intercalation into Molybdic Acid 48 2.3.1 Intercalation of PEG into Molybdic Acid 48 2.3.2 Intercalation of POEGO into Molybdic Acid 48 2.3.3 Intercalation of POMOE into Molybdic Acid 48 v
vi Contents 2.4 Preparation of Polymer-Lithium Complexes 49 2.4.1 Preparation of POEGO/LiOTf Complexes 49 2.4.2 Preparation of POMOE/LiOTf Complexes 49 2.4.3 Preparation of PEG/LiOTf Complexes 49 2.4.4 Intercalation of Polymer/LiOTf into Molybdic Acid Compounds 50 2.5 Instrumentation 50 2.5.1 Powder X-ray Diffraction 50 2.5.2 Thermogravimetric Analysis 50 2.5.3 Fourier Transform Infrared Spectroscopy 50 2.5.4 Nuclear Magnetic Resonance Spectroscopy 50 2.5.5 AC Impedance Spectroscopy 50 2.6 Results and Discussion 51 2.6.1 Molybdic Acid 51 2.6.2 Polymers 54 2.6.3 Formation of Intercalated Nanocomposites 57 2.6.4 Ionic Conductivity 65 2.7 Conclusions 68 Acknowledgements 68 References 69 3 Fluid-Bed Technology for Encapsulation and Coating Purposes 71 Roman G. Szafran 3.1 Introduction 71 3.2 Principles of Fluidization 74 3.3 Classification of Powders 78 3.3.1 Goossen's Classification of Particles by Archimedes Number 79 3.3.2 Extended Geldart's Classification for Nanopowders 80 3.4 Fluidized Bed Coaters 80 3.4.1 Top-Spray Fluid Bed Coater 81 3.4.2 Conical Bottom-Spray Spouted Bed Coater 83 3.4.3 Spout-Fluid Bed Coater (Wurster Type) 84 3.4.4 Rotor (Tangential) Spray Coater 85 3.4.5 Fast Circulating Spout-FTuid Bed Coater 86 3.5 Fluid-Bed Coating and Encapsulation Processes 88 3.5.1 Fluidized Bed CVD, ALD, MLD 89 3.5.2 Dry Coating of Fine Particles 92
Contents vii 3.6 The Design, Optimization and Scale-Up of the Coating Process and the Apparatus 94 3.7 Numerical Modeling of Fluid-Bed Coating 97 References 101 4 Use of Electrospinning for Encapsulation 107 Rocio Perez-Masid, Maria Jose Fabra, Jose Maria Lagarott and Amparo Lopez-Rubio 4.1 Introduction 107 4.1.1 Generalities About the Electrospinning Technique 107 4.1.2 Advantages of Electrospinning for Encapsulation 109 4.2 Electrospun Structures for the Encapsulation of Bioactive Substances in the Food Area 112 4.2.1 Enzyme Encapsulation 113 4.2.2 Encapsulation of Probiotic Bacteria 114 4.2.3 Antioxidant Encapsulation 115 4.2.4 Encapsulation of Other Food Compounds 116 4.3 Electrospun Encapsulation Structures for Biomedical Applications 117 4.3.1 Post-Spinning Modification 118 4.3.2 Blending and Emulsion Electrospinning 121 4.3.3 "Core-Shell Electrospinning" or "Coaxial Electrospinning" 122 4.4 Other Uses of Electrospinning for Encapsulation 124 4.4.1 Energy Storage Devices 124 4.4.2 Optical and Electronic Devices 127 4.4.3 Biotechnical Plant Protection Systems 129 4.5 Outlook and Conclusions 129 References 130 5 Microencapsulation by Interfacial Polymerization 137 Fabien Salaiin 5.1 Introduction 137 5.2 Generalities 141 5.3 Encapsulation by Heterophase Polymerization 144 5.3.1 Emulsion Polymerization 144 5.3.2 Suspension Polymerization 145 5.3.3 Dispersion Polymerization 147 5.3.4 Miniemulsion Polymerization 148
viii Contents 5.4 Microencapsulation by Poly addition & Polycondensation Interfacial 148 5.4.1 Location of the Film Formation 152 5.4.2 Reaction Rate 152 5.4.3 Shell Formation 153 5.4.4 Influence of the Synthesis Parameters on the Formation of the Shell 156 5.4.5 Influence of the Synthesis Parameters on the Particles Properties 157 5.4.6 Nanoencapsulation by Interfacial Polycondensation 158 5.5 Microencapsulation by In Situ Polymerization 158 5.5.1 Melamine-Formaldehyde Microcapsules 161 5.5.2 Urea-Formaldehyde Microcapsules 164 5.5.3 Silica Microcapsules 165 5.6 Conclusion 166 References 167 6 Encapsulation of Silica Particles by a Thin Shell of Poly(Methyl) Methacrylate 175 Isidora Freris and Alvise Benedetti 6.1 Introduction 176 6.2 Synthesis of Silica (Nano)Particles and Their Surface Modification 178 6.2.1 Silica Synthesis 178 6.2.2 Surface Modification of Silica Particles 179 6.3 Encapsulation of Silica Particles in a Thin PMMA Shell 181 6.3.1 In Situ Conventional Heterophase Radical Polymerization 182 6.3.2 Controlled Living Radical Polymerization 195 6.4 Summary 198 References 199 7 Organic Thin-Film Transistors with Solution-Processed Encapsulation 203 Feng-Yu Tsai and Yu Fu 7.1 Introduction 203 7.2 Environment-Induced Degradations of OTFTs 205 7.2.1 Pentacene-Based OTFTs 206 7.2.2 Polythiophenes-Based OTFTs 208 7.2.3 Requirements of Encapsulation 208
Contents ix 7.3 Encapsulation of OTFTs 209 7.3.1 Polythiophene-Based OTFTs 209 7.3.2 Pentacene-Based OTFTs 216 7.4 Summary and Outlook 221 References 221 8 Tunable Encapsulation Property of Amphiphilic Polymer Based on Hyperbranched Polyethylenimine 225 Decheng Wan and Toshifumi Satoh 8.1 Introduction 226 8.2 Synthesis of PEI-CAMs 228 8.3 Unimolecularity versus Aggregate 8.4 Host-Guest Chemistry of PEI-CAMs 230 of PEI-CAMs 231 8.5 Charge Selective Encapsulation and Separation 233 8.5.1 Charge Selective Encapsulation for Separation of Oppositely Charged Dyes 233 8.5.2 Switchable Charge Selectivity and ph Recycle 8.6 Recognition and Separation Mixtures by Core Engineering 8.6.1 The Core Structure-Guest of the Host 238 of Anionic-Anionic of a CAM 239 Selectivity Relationship 239 8.6.2 Recognition of Similar Guest Molecules in a Mixture 243 8.6.3 The Mechanism of Guest Selectivity in Encapsulation 246 8.7 Modulation of the Guest Release of a CAM 247 8.8 Concluding Remarks 250 Acknowledgements 251 References 251 9 Polymer Layers by Initiated CVD for Thin Film Gas Barrier Encapsulation 255 D.A. Spee, J.K. Rath and R.E.L Schropp 9.1 Introduction 256 9.2 Initiated CVD Polymerization 258 9.2.1 Reaction Mechanism 259 9.2.2 Radical Creation 261 9.2.3 Deposition Rate and Molecular Weight 263 9.2.4 Monomer Adsorption 265
x Contents 9.3 Coating by Initiated CVD 268 9.3.1 Thickness Control 268 9.3.2 Conformality 268 9.3.3 Retention of Functional Groups 270 9.3.4 Tunable Properties by Combining Monomers 270 9.3.5 Barrier Coating by a Single Organic Layer 271 9.4 Advantages of icvd in Hybrid Multilayer Gas Barriers 272 9.4.1 Using Thin Layers for Decoupling 273 9.4.2 Filling of Defects by Polymer 274 9.4.3 Smoothening of the Substrate 275 for the Use in 9.5 Specific Requirements Hybrid Multilayers 276 9.5.1 Planarization 276 9.5.2 Stability 277 9.5.3 High Glass Transition Temperature 279 9.5.4 Adhesion 280 9.6 Multilayer Gas Barriers Containing Polymers by icvd 281 9.6.1 Polymers by icvd with PECVD Inorganics 281 9.6.2 icvd Polymer and HWCVD SiNx 283 9.7 Upscaling and Utilization 285 9.7.1 Roll-to-Roll and Inline Processing 285 9.7.2 Commercial Availability 286 References 287 10 Polymeric Hollow Particles for Encapsulation of Chemical Molecules 291 Jong Myung Park 10.1 Introduction 292 10.2 Colloidosome Approach 295 10.3 Internal Phase Separation/Precipitation Approach 299 10.3.1 Polymerization-Induced Phase Separation 300 10.3.2 Phase Separation by Solvent Evaporation or Displacement 301 10.3.3 Controlled Precipitation Method 304 10.3.4 Other Methods 305
Contents xi 10.4 Self-Assembly of Amphiphilic Copolymers (Copolymer Vesicles) 305 10.4.1 From Amphiphilic Copolymers 306 10.4.2 Crosslinked Polymer Vesicles 307 10.4.3 Vesicular Templating Approach 308 10.5 Layer-by-Layer (L-b-L) Deposition 310 10.5.1 Electrostatic Deposition 311 10.5.2 Hydrogen Bonded L-b-L Deposition 312 10.5.3 L-b-L Deposition on a Liquid Core 314 10.6 Unimolecular Micelles Approach 315 10.6.1 Dendrimer Approach 316 10.6.2 Polymerization of Cucurbituril 318 10.7 Heterophase Polymerization 319 10.7.1 Emulsion Polymerization 319 10.7.2 Interfacial Polycondensation 328 10.8 Key Design Features for Applications of Hollow Polymer Particles 332 10.8.1 Morphology 332 10.8.2 Release Behavior 336 10.8.3 Functionalization 339 10.9 Conclusions 340 References 341 11 Protic Ionic Liquids Confinement in Macro, Meso and Microporous Materials for Proton Conduction 347 A. Eguizdbal and M.P. Pina 11.1 Introduction 348 11.2 Structure and Properties of Materials for Proton Conduction 351 11.2.1 Protic Ionic Liquids 351 11.2.2 Porous Materials: Zeolites, PBI 354 11.3 Encapsulation Procedures and Proton Conduction Performance 365 11.3.1 Encapsulation in Zeolite-Type Materials 365 11.3.2 Encapsulation in Membrane Materials 374 11.4 New Activities and Development Trends 383 References 386
Properties xii Contents 12 Encapsulation Methods with Supercritical Carbon Dioxide: Basis and Applications 391 Soraya Rodriguez-Rojo, Angel Martin and Maria Jose Cocero 12.1 Introduction 391 12.2 Supercritical Fluids - 392 12.3 Particle Engineering and Encapsulation with Supercritical 12.3.1 Supercritical 12.3.2 Supercritical Fluids 394 Fluid as Solvent 394 Fluid as Antisolvent and Related Techniques 401 12.3.3 Supercritical Fluid as Solute 412 12.3.4 Supercritical Fluid as Reaction Media 418 References 419 Index 425