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Part Ⅰ Structure and Organization of Metal Nanoparticles in Polymer Matrices 3

1 Nanoparticles in Materials Chemistry and in the Natural Sciences（Introduction） 3

1.1 Classification of Nanoparticles by Size 5

1.2 Structural Organization of Nanoparticles 9

1.3 Dimensional Phenomena in the Chemistry and Physics of Nanoparticles 9

1.4 Nanoparticles and Materials on their Base 12

References 23

2 Nucleation Mechanism of Nanoparticles and Metal Clusters，their Structure and Chief Properties 25

2.1 Characteristic Features of Nanoparticle Nucleation 26

2.2 Kinetic Features of New Phase Formation 32

2.3 Phase Formation in Chemical Reactions 39

2.4 Self-Organization of Metal-Containing Nanoparticles（Fractal Structures） 43

2.5 Brief Account of Major Production Methods of Metal-Containing Nanoparticles 52

2.6 Metal Clusters as Nanoparticles with Fixed Dimensions 58

References 60

3 Principles and Mechanisms of Nanoparticle Stabilization by Polymers 65

3.1 Stability of Nanoparticles in Solutions 65

3.2 Stabilizing Capability Characteristics of Polymers 68

3.3 Characteristics of Polymer Absorption on Metal Surfaces 71

3.4 Specifics of Polymer Surfactants as Stabilizers 81

3.5 Mechanism of Nanoparticle Stabilization by Polymers 91

3.6 Stabilization of Nanoparticles by Electrolytes 96

3.7 Surface Proofing as a Method of Stabilizing Nanoparticles by Polymers 99

3.8 On the Problem of Matrix Confinement 101

References 106

Part Ⅱ Synthetic Methods for Metallopolymer Nanocomposite Preparation 117

4 Physical Methods of Incorporating Nanoparticles into Polymers 117

4.1 Mechanochemical Dispersion of Precursors Jointly with Polymers 118

4.2 Microencapsulation of Nanoparticles into Polymers 120

4.3 Physical Deposition of Metal Particles on Polymers 124

4.4 Formation of 2D Nanostructures on Polymers 127

4.5 Formation of Metal Nanoparticles in Polymer Matrix Voids（Pores） 130

4.6 Physical Modification and Filling of Polymers with Metal 131

References 132

5 Chemical Methods of Metal-Polymer Nanocomposite Production 135

5.1 Reduction of Polymer-Bound Metal Complexes 136

5.1.1 Reducers and Reduction Processes 136

5.1.2 Reduction in Polymer Solutions 138

5.1.3 Reduction in Block-Copolymers in Solution 145

5.1.4 Formation and Architecture of Metal Nanoparticles in Dendrimers 150

5.1.5 Formation of Nanoparticles in Heterogeneous Polymer Systems 155

5.1.6 Production of Nanocomposites by Reducing with Metals and Organometallic Compounds 160

5.1.7 Bi- and Polymetallic Nanoparticles in Polymers 161

5.2 Nanocomposite Formation by Metal-Containing Precursor Thermolysis 172

5.2.1 Metal Sol Formation in Polymers by Thermal Decomposition of Metal Carbonyls 173

5.2.2 The Features of Metal-Containing Polymer Thermolysis 185

5.2.3 Post-Thermolysis of Other Types of Precursors in Polymer Matrices 190

5.3 Nanocomposite Formation in Monomer-Polymer Mixtures in Thermolysis 193

5.4 Nanocomposites on the Base of Polymer-Immobilized Metalloclusters 196

5.4.1 Monometal-Type Cluster Immobilization 196

5.4.2 Heterometallic Clusters，Chemically Bonded with Polymers 204

5.4.3 Cluster-Containing Monomer Synthesis and Copolymerization as a Way to Produce Metallopolymeric Composites 207

References 222

6 Physico-Chemical Methods of Metal-Polymer Nanocomposite Production 237

6.1 Cryochemical Methods of Atomic Metal Deposition on Polymers 237

6.2 Metal Evaporation Methods on Polymers Localized at Room Temperature 246

6.3 Synthesis of Nanocomposites in a Plasma-Chemical Process 249

6.4 Radiolysis in Polymer Solutions 254

6.5 Photolysis of Metal-Polymer Systems as Means of Obtaining Nanocomposites 256

6.6 Electrochemical Methods of Nanocomposite Formation 261

References 264

Part Ⅲ Hybrid Polymer-Inorganic Nanocomposites 273

7 The Sol-Gel Process in Formation of Hybrid Nanocomposites 273

7.1 General Characteristics of Sol-Gel Reactions 274

7.2 A Combination of Polymerization Reactions and In Situ Sol-Gel Synthesis of Nanocomposites 279

7.3 Sol- Gel Syntheses in the Presence of Polymers 289

7.4 Morphology and Fractal Model of Hybrid Nanocomposites 298

7.5 Nanocomposites Incorporating Multimetallic Ceramics 300

References 311

8 Polymer Intercalation into Porous and Layered Nanostructures 321

8.1 A General Description of the Intercalation Process 321

8.2 Polymerization into the Basal（Interlayer）Space 327

8.3 The Macromolecules Introducing into the Layered Host Lattices 336

8.4 Intercalation Nanocomposites of Polymer/Metal Chalcogenide Type 345

8.5 Langmuir-Blodgett Metallopolymer Films as Self-Organized Hybrid Nanocomposites 351

References 363

9 Nanobiocomposites 377

9.1 Basic Notions of Metal-Containing Protein Systems 378

9.2 Metal Nanoparticles in Imrnunochemistry，Cytochemistry and Medicine 384

9.3 Biosorption，Selective Heterocoagulation and Bacterial Concentration of Metal Nanoparticles 390

9.4 Sol-Gel Process as a Way of Ternplate-Synthesized Nanobioceramics 399

9.5 Biomineralization and Bioinorganic Nanocomposites 403

References 415

Part Ⅳ The Main Applications of Metal-Polymeric Nanocomposites 427

10 Nanoparticle Modifying Action on Polymers 427

10.1 The Control of Physico-Mechanical Properties of Nanocomposites 428

10.2 The Peculiarity of Nanocomposites，Synthesized by Sol-Gel Methods 431

10.3 Polyolefin-Based Nanocomposites 434

10.4 Polymer Matrix Structurization in Nanocomposites 437

10.5 The Physical and Mechanical Properties of Metallopolymer Nanocomposites 442

10.6 Nanocomposites in Adhesion Compounds（Contacts）and Tribopolymers 446

10.7 New Trends in Material Science Connected with Metallopolvmeric Nanocomposites 450

References 453

11 Magnetic，Electrical and Optical Properties of Metal-Polymer Nanocomposites 459

11.1 Metallopolymeric Composites with Magnetic Properties 460

11.2 Electrical Characteristics of Metallopolymer Composites 473

11.3 Optical and Semiconductive Properties of Metal Polymer Nanosystems 486

References 501

12 Metallopolymeric Nanocatalysis 515

12.1 A General Survey of Metallopolymer Catalysis 516

12.2 Hydrogenization Processes 517

12.3 Nanocatalysis of Reactions，Traditionally Perfomed with Homogeneous Metallocomplexes 532

12.4 Nanocatalysis in Polymerization Processes 535

12.5 Polymer-Protected Nanoparticles in Photocatalysis 540

12.6 Metallopolymeric Nanocomposites in Catalysis 543

References 544

13 Conclusion 551

Index 555