Preface xv Acknowledgments xvii List of Most Important Symbols and Abbreviations xix 1 Introduction 1 1.1 Scope 1 1.2 The Importance of Polymer Coatings 2 1.3 The General Constitution of Polymer Coatings 5 1.3.1 Binders and Crosslinkers 6 1.3.2 Pigments and Fillers 8 1.3.3 Additives 12 1.3.4 Solvents 12 1.4 Coating Requirements 14 1.5 Outline and Approach 15 References 16 Further Reading 16 2 Polymers and Network Characteristics 19 2.1 Polymers 19 2.1.1 Polymer Conformations 22 2.1.2 Entanglements 23 2.1.3 Crystallinity 24 2.1.4 Amorphous Polymers 26 2.2 Polymer Formation 30 2.2.1 Step-growth Polymerization 31 2.2.2 Branching and Gelation 33 2.2.3 Limits to the Preparation of Branched Polymers 36 2.2.4 Chain-growth Polymerization 38 2.3 Polymer Networks 41 2.4 Final Remarks 45 References 45 Further Reading 46 3 Thermoset Resins 47 3.1 Petro-based Thermoset Resins 47 3.2 Epoxy Systems 47 3.3 Acrylates and Acrylics 51 3.4 Isocyanates 53 3.5 Polyurethanes 55 3.6 Polyesters 56 3.7 Renewable Raw Materials 57 3.8 Drying Oils 63 3.9 Alkyds 65 References 68 Further Reading 69 4 Basic Coating Formulations 71 4.1 Coating Compositions in General 71 4.2 Solventborne Formulations 72 4.2.1 Solventborne High Solids Formulations 75 4.2.2 Chemistries of Solventborne High Solids Formulations 80 4.3 Waterborne Formulations 85 4.3.1 Chemistries of Waterborne Formulations 90 4.3.2 Challenges and Applications of Waterborne Formulations 93 4.4 Radiation Curing Formulations 96 4.4.1 Photoinitiators 97 4.4.2 Chemistries of Radiation Curing Formulations 99 4.4.3 Chemistries of Powder Coating Formulations 103 4.4.4 Pros and Cons of Radiation Curing 105 4.5 Final Remarks 106 References 108 Further Reading 108 5 Additives and Particulates 109 5.1 Types of Additives 109 5.2 Thickeners 110 5.2.1 Inorganic Thickeners 110 5.2.2 Organic Thickeners 112 5.3 Surface Active Agents 116 5.3.1 Wetting and Dispersing Agents 117 5.3.2 Antifoaming Agents 117 5.3.3 Adhesion Promoters 118 5.4 Surface Modifiers 120 5.5 Leveling and Coalescing Agents 120 5.6 Catalytically Active Additives 121 5.6.1 Dryers 122 5.6.2 Other Catalysts 123 5.7 Special Effect Additives 128 5.8 Particulates 130 References 133 Further Reading 134 6 Application Methods 135 6.1 Conventional Deposition Techniques 135 6.1.1 Brushing and Rolling 135 6.1.2 Spraying 136 6.2 Laboratory and Industrial Methods 138 6.2.1 Doctor Blade Coating 138 6.2.2 Spin Coating 139 6.2.3 Dip Coating 141 6.3 Powder Coating 142 6.4 An Example: Automotive Coatings 147 6.4.1 Electrodeposition 147 6.4.2 The Automotive Coating Buildup 150 6.5 Network Formation Assessment 151 References 152 Further Reading 152 7 Physical–Chemical Aspects 155 7.1 Intermolecular and Mesoscopic Interactions 155 7.1.1 Intermolecular Interactions 155 7.1.2 Mesoscopic Interactions: Continuum Aspects 159 7.1.3 Lifshitz Theory 164 7.1.4 The Derjaguin Approximation 166 7.1.5 Mesoscopic Interactions: Molecular Aspects 167 7.2 Polymer Solubility 170 7.3 Interfacial Aspects 173 7.3.1 Surface Thermodynamics 173 7.3.2 Representative Behavior 178 7.3.3 Wetting of Ideal Surfaces 181 7.3.4 Estimating Surface Helmholtz Energy 184 7.3.5 Wetting of Real Surfaces 189 7.4 Dispersions 193 7.5 Emulsions 196 7.5.1 Basic Types of Emulsions 196 7.5.2 The HLB Concept 198 7.6 Coagulation Kinetics 202 7.6.1 Unhindered Coagulation 202 7.6.2 Hindered Coagulation 204 7.7 Self-assembly 207 7.7.1 SCF Computations 207 7.7.2 An Example: Surfactant Modeling 209 7.7.3 Another Example: Fluorine Segregation 212 7.8 Final Remarks 213 References 213 Further Reading 219 8 Chemical and Morphological Characterization 221 8.1 The Need for Characterization 221 8.2 IR and Raman Spectroscopy 222 8.3 NMR 227 8.4 Functional Group Analysis 236 8.5 XPS, SIMS, and LEIS 239 8.6 SEC 241 8.7 MALDI–MS 242 8.8 XRD 245 8.9 Optical Microscopy 250 8.9.1 Phase Contrast Microscopy 253 8.9.2 Fluorescence Microscopy 254 8.9.3 Confocal Scanning Microscopy 254 8.9.4 Polarized Light Microscopy 255 8.10 Electron Microscopy 256 8.10.1 TEM 256 8.10.2 SEM 259 8.10.3 STEM 260 8.10.4 Sample Preparation and Related Issues 260 8.11 Surface Probe Microscopy 262 8.12 Thickness and Beyond 265 8.13 Final Remarks 266 References 266 Further Reading 271 9 Thermal and Mechanical Characterization 273 9.1 Thermal Characterization 273 9.1.1 DSC 273 9.1.2 TGA 277 9.2 Permeability–Diffusivity–Solubility Analysis 278 9.3 Mechanical Constitutive Behavior 285 9.3.1 Analogous Models 288 9.3.2 Generalization: The Boltzmann Superposition Principle 291 9.3.3 Dynamic Response 293 9.3.4 The Time–Temperature Equivalence 296 9.3.5 The Free Volume and Other Approaches 297 9.4 A Brief Review of Experimental Data 300 9.4.1 Local and Cooperative Processes 301 9.4.2 Chain Motion 303 9.4.3 Mechanisms in Partially Crystalline Materials 306 9.5 Mechanical Characterization 307 9.5.1 DMTA 307 9.6 Hardness 312 9.6.1 Vickers, Knoop, Berkovich, and Brinell Hardness 312 9.6.2 Nanoindentation 314 9.6.3 Estimating the Stress–Strain Curve 315 9.6.4 Empirical Hardness Tests 316 9.7 Internal Stress Analysis 317 9.8 Adherence 319 9.8.1 Thermodynamic Considerations 319 9.8.2 Thermomechanical Considerations: Monoliths 323 9.8.3 Thermomechanical Considerations: Bimaterials 330 9.8.4 Coating Adherence 334 9.8.5 Testing Coating Adherence 337 9.8.6 Practical Tests 341 9.9 Final Remarks 342 References 342 Further Reading 345 10 Rheological Aspects 347 10.1 The Importance of Rheology 347 10.2 Rheological Characterization 348 10.2.1 Hydrodynamic Interactions 352 10.2.2 Dissolvable Polymers 359 10.3 Rheological Control of Paints 362 10.3.1 Powder Coatings 362 10.3.2 Thickening in Waterborne Paints 363 10.4 Viscosity of Paints During Curing 366 References 368 Further Reading 370 11 Appearance 371 11.1 Defects 371 11.2 The Characterization of Color 379 11.2.1 Light Sources 380 11.2.2 Color Sensing, Perception, and Quantification 381 11.2.3 Scattering, Absorption, and Color 384 11.2.4 Addition and Subtraction Systems 387 11.2.5 Color Tolerancing 391 11.3 The Characterization of Feel or Haptic Property 393 11.3.1 QDA of Haptic Coatings: An Example 394 References 397 Further Reading 398 12 Electrically Conductive Coatings 399 12.1 Typical Applications 399 12.2 Electrical Conductivity Measurements 401 12.3 Intrinsically Conductive Polymers 403 12.3.1 Some Conductivity Theory 406 12.3.2 Simple Band Theory 407 12.3.3 Doping 413 12.3.4 Hopping 416 12.4 An Example: P3HT/PCBM Photovoltaics 418 12.5 Conductive Composites 423 12.5.1 A Glimpse of Percolation Theory 423 12.5.2 Other Approaches 428 12.5.3 The Influence of Aspect Ratio 430 12.5.4 Conductive Particles 431 12.6 Some Examples of Conductive Composite Coatings 434 References 438 Further Reading 441 13 Marine Anti-fouling Coatings 443 13.1 Marine Biofouling 443 13.2 Evolution of Marine Coatings toward Green Anti-fouling Approaches 445 13.3 Principles for Preventing Adhesion or Promoting Detachment of Biofoulants 448 13.4 Nontoxic, Non-biocide-release Anti-fouling Coatings 451 13.4.1 Detachment of Biofoulants 451 13.4.1.1 Silicone-based Materials 453 13.4.1.2 Fluorine-based Materials 458 13.4.1.3 Combined Fluorine–Silicone-based Materials 461 13.4.2 Preventing Attachment of Biofoulants 462 13.4.2.1 PEG-based Materials 463 13.4.2.2 Self-assembled Monolayers 465 13.4.2.3 Other Approaches 466 13.5 Recent and Future Approaches 469 13.5.1 Amphiphilic Approach 469 13.5.2 Topographic Approach 472 13.6 Final Remarks 475 References 475 Further Reading 479 14 Self-replenishing and Self-healing Coatings 481 14.1 Self-healing and Self-replenishing: Scope and Limitations 481 14.2 Damage Recovery on Different Length Scales: Preemptive Healing 482 14.3 Approaches to Self-healing Coatings 486 14.3.1 Encapsulated Liquid Binders and Particles 487 14.3.2 Deformation and Recovery in Networks 489 14.3.3 Stress Relaxation in Reversible Networks 493 14.3.4 Reversible Covalent Networks 498 14.4 Industrial Practice 502 14.5 Approaches to Self-replenishing Coatings 504 14.5.1 Barrier and Corrosion Protection 505 14.5.2 Interfacial Bonding Between Dissimilar Materials 506 14.6 Self-replenishing Low Surface Energy Coatings 508 14.6.1 Low Surface Energy (Hydrophobic) Polymeric Coatings 509 14.6.2 Time Recovery of the Surface Self-replenishing 514 14.6.3 Surface-structured Superhydrophobic Polymeric Coatings 515 14.6.4 Further Remarks 521 14.7 Scenarios for Further Options 522 14.7.1 Residual Network Reactivity 522 14.7.2 Segregation of Interactive Chain Ends 523 14.7.3 Multilayer and Graded Coatings 524 14.8 Final Remarks 524 References 525 Further Reading 531 15 What’s Next 533 15.1 Generic Problems and Challenges 533 15.2 What Else? 535 15.3 What’s Next? 537 References 538 Appendix A: Units, Physical Constants, and Conversion Factors 541 Basic and Derived SI Units 541 Physical Constants 541 Conversion Factors for Non-SI Units 542 Prefixes 542 Greek Alphabet 542 Standard Values 543 Appendix B: Data 545 Index 549

A practical guide to polymer coatings that covers all aspects from materials to applications  Polymer Coatings is a practical resource that offers an overview of the fundamentals to the synthesis, characterization, deposition methods, and recent developments of polymer coatings. The text includes information about the different polymers and polymer networks in use, resins for solvent- and water-based coatings, and a variety of additives. It presents deposition methods that encompass frequently used mechanical and electrochemical approaches, in addition to the physical-chemical aspects of the coating process. The author covers the available characterization methods including spectroscopic, morphological, thermal and mechanical techniques. The comprehensive text also reviews developments in selected technology areas such as electrically conductive, anti-fouling, and self-replenishing coatings. The author includes insight into the present status of the research field, describes systems currently under investigation, and draws our attention to yet to be explored systems. This important text: • Offers a thorough overview of polymer coatings and their applications • Covers different classes of materials, deposition methods, coating processes, and ways of characterization • Contains a text that is designed to be accessible and helps to apply the acquired knowledge immediately • Includes information on selected areas of research with imminent application potential for functional coatings Written for chemists in industry, materials scientists, polymer chemists, and physical chemists, Polymer Coatings offers a text that contains the information needed to gain an understanding of the charaterization and applications of polymer coatings.