An integrated collection of case studies providing a concise guide for professionals working with coatings materials in academia and industry
In Applied Coatings: Chemistry, Formulation, and Performance, distinguished scientist Dr. Weih Q. Lee delivers an illuminating collection of case studies designed to connect various elements of applied coatings technology. Going beyond generic discussions, the author describes the fundamental chemistry, formulations, and properties of applied coating materials - including the structural and functional components of structure-property relationships - as well as the foundations of applied cure kinetics and the rheology of epoxy coatings.
Each chapter is self-contained, comprehensive, and can be read individually, while the book remains technically and editorially integrated. Core themes include structure-performance relationships, formulation index driven experiment design, and consolidated thermal analysis. Readers will also find: - A thorough introduction to epoxies and epoxy curing agents, including oxetanes, vinyl esters, glycidyl methacrylate (GMA), isocyanate and silicone crosslinkers, cationic catalysts, acrylate and phenol accelerators, and specialty derivatives - Attentive descriptions of epoxy curing chemistry, including epoxy-phenolic, -polyamide, -active ester, and acid- or base-catalyzed systems in a broader scope - Comprehensive explorations of cure kinetics and rheology, including model-free kinetics (MFK), the nth-order model covering Kissinger plots and the Borchardt - Daniels (BD) approach, the autocatalytic model, executive quantification via curve fitting of DSC (differential scanning calorimetry) exotherms, the rheology of non-reactive fluids, and the viscoelasticity of reactive coatings - Practical discussions of C1S thick-film surface coatings, C2S structural lamination, liquid and powder epoxies, and phenolic coatings, including fluorene monomers, heterocyclic resins, and polymerizable derivatives - Complete treatments of coating characterization, microencapsulation, epoxy hybrids and non-epoxy platforms, adhesion of applied coatings, and adhesion promotion, including reactive and functional silicones
Perfect for formulation and research and development scientists and engineers at any technical level, Applied Coatings will also benefit research professors and students studying coatings, adhesives, composites, electronic materials, and more.
Table of Contents
Preface xi
Abbreviations, Symbols, and Units xiii
Introduction xxix
Part I Materials and Chemistry 1
1 Epoxy Resins, Monomers, and Derivatives 3
1.1 BPA-Based Epoxies (or DGEBAs) 3
1.2 BPF-Based (or DGEBF) and Novolac Epoxies 5
1.3 Modified Epoxies 7
1.4 Poly-functional or Matrix Epoxies 10
1.5 Specialty Epoxies 12
1.6 Aliphatic and UV-Curable Epoxies 14
1.7 Oxetanes 15
1.8 Epoxy Derivatives 16
1.9 BPA-Free Epoxies 17
1.10 Bio-Based Epoxies 18
1.11 Epoxy Diluents and Flexibilizers 19
1.12 Epoxy Vitrimers 19
Debrief A Hydrophobicity 20
Debrief B MWs, EEWs, and functionality (f) 20
Debrief C Synthesis of SERs from LERs 21
Debrief D Oxazolidinones, oxazolidones, oxazolidines, bisoxazolidines, and bis-oxazolines 22
Recaps and Highlights 23
References 25
2 Epoxy Curing Agents 29
2.1 Crosslinkers or Hardeners 29
2.1.1 Primary and secondary amines 29
2.1.2 Phenolics and polyphenols 36
2.1.3 Active esters 41
2.1.4 Mannich bases 42
2.1.5 Anhydrides and carboxylic acids 42
2.1.6 Polysulfides or mercaptans 44
2.1.7 Isocyanates 45
2.1.8 Silicones 47
2.2 Catalysts and Accelerators 48
2.2.1 Catalysts 48
2.2.1.1 Anionic catalysts: tertiary (3∘) amines and imidazoles 48
2.2.1.2 Cationic catalysts 50
2.2.2 Accelerators and modifiers 52
2.2.2.1 Phenol derivatives 52
2.2.2.2 Acrylates 53
2.3 UV Radiation 53
Debrief A Amine and anhydride crosslinkers 54
Debrief B Aromaticity vs. aliphaticity, and hydrophilicity vs. hydrophobicity 54
Debrief C Reactivity and effectiveness of catalysts 56
Recaps and Highlights 57
References 58
3 Epoxy Curing Reactions 63
3.1 Co- and Homo-Polymerizations 63
3.1.1 Epoxy-amine (and -hydrazide) systems 64
3.1.2 Epoxy-phenolic systems 66
3.1.3 Epoxy-ester systems 67
3.1.4 Epoxy-anhydride systems 69
3.2 Cationic and UV-Curing Systems 70
Debrief A Base-catalyzed crosslinking reactions 73
Debrief B Acid-catalyzed crosslinking reactions 75
Debrief C Carbene insertion reactions 77
Debrief D Additional understanding of ring-opening reactions 78
Recaps and Highlights 79
References 81
Part II Methodologies and Characterization 85
4 Concepts, Utilities, Methods, and Techniques 87
4.1 Liquids versus Powders 87
4.1.1 Solvent-based coatings 88
4.1.2 Waterborne (WB) coatings 91
4.1.3 Electro-coatings (E-coatings) 93
4.1.4 Powder coatings 94
4.1.5 UV-curable coatings 95
Debrief A Liquid applications and end uses 95
Debrief B Powder applications and end uses 101
4.2 The Formulation Index 102
4.3 Surface Coatings versus Structural Laminates 103
Debrief C Surface coatings and end uses 105
Debrief D Structural laminates and end uses 107
4.4 Materials and System Properties of Cured Coatings 108
4.5 Characterization of Uncured Coatings 116
Debrief E Illustrations of applied coating technology 120
Debrief F Reverse engineering 122
Recaps and Highlights 125
Appendices 127
A Hydrogen Energy 127
B Power Module 128
C LED Module (Tj ∼120∘ C) 128
References 129
5 Cure Kinetics and Rheology 135
5.1 Cure Kinetics 135
5.1.1 Gel time model 136
5.1.2 Tg model 137
5.1.3 Model-free kinetics 137
5.1.4 nth-order model 139
5.1.4.1 The Kissinger plot 140
5.1.4.2 Borchardt-Daniels (BD) approach 142
5.1.5 Autocatalytic model 143
5.1.6 Comparisons of model-based kinetics 146
Debrief A Thermal and kinetic parameters and their correlations 148
5.1.7 Application of cure kinetics to processing 152
5.1.8 Implementation of cure kinetics in formulation 154
5.1.8.1 Resins 154
5.1.8.2 Crosslinkers 155
5.1.8.3 Catalysts 156
5.1.8.4 Reactive additives 158
5.1.9 Implementation of cure kinetics in 2K liquid epoxy coatings 160
Debrief B Supplemental cure kinetic equations 161
Debrief C Evaluation of latent catalysts by DSC kinetics 161
Recaps and Highlights (I) 164
5.2 Rheology 165
5.2.1 Rheology of non-reactive fluids 166
Debrief D Major rheological phenomena 176
Debrief E Common rheological materials and their characterization 177
5.2.2 Rheology of reactive systems 179
Debrief F Rheological DMA 184
Recaps and Highlights (II) 185
5.3 Kinetics and Rheology Combined 187
Debrief G DMA-DSC consolidation 191
Recaps and Highlights (III) 193
Acknowledgments 194
References 194
Part III Formulations and Applications 199
6 Formulation Case Studies 201
6.1 Liquid Epoxy Coatings and Adhesives 201
6.1.1 One-component (1K) SB epoxy coatings for laminating 201
6.1.2 Two-component (2K) epoxy coatings for surface lining 203
6.1.3 2K epoxy adhesives as thermal interface materials 205
6.2 Functional Epoxy Powder Coatings 206
6.2.1 Formulation index-oriented formulation optimization 206
6.2.2 Crosslinker-free formulations 210
6.2.3 Bisphenol F-based epoxy resins 218
6.2.4 Aliphatic epoxies and silicone-modified amines 222
6.2.5 Active ester crosslinkers 226
6.2.6 Phenylene bis-oxazoline crosslinkers 230
6.2.7 Fluorene monomers for heat-resistant coatings 233
6.2.8 Cationic catalysts and dual cure 242
6.2.9 Specialty and miscellaneous materials and formulations 251
Debrief A Extremely flexible FBE coatings through SDH and BAF amines 253
Debrief B LAT coatings 256
Debrief C Primers, epoxy primers, and epoxy powder primers 267
Debrief D Illustration of first-order reaction (n ≈ 1.0 and m = 0) epoxy formulations 269
Recaps and Highlights 270
Appendices 274
A Comparative Study on Anionic DMS and Cationic BCl3 Amine Complex 274
B Images of Free-Radical Powder Coating-Coated MDF Panels 275
References 276
7 Phenolic Coatings 279
7.1 Phenolic Resins and Derivatives 279
7.1.1 BPA-based phenolic resins 279
7.1.2 Novolac and resole phenolic resins 281
7.1.3 Non-BPA phenolic resins and bio-derivatives 282
7.2 Phenolic-Isocyanate Coatings 287
7.3 Phenolic-BMI Systems 292
7.4 BOXs and BOX-Isocyanate Coatings 295
7.5 BOX-BMI Systems 298
7.6 Quantification of Ph-OHs by UV/Visible 303
Debrief A BMIs and Diels-Alder ring-forming reactions 314
Debrief B UV/visible technique 315
Recaps and Highlights 316
Acknowledgments 317
References 317
Part IV Extended Formulations and Applications 323
8 Microencapsulation 325
8.1 Morphology 325
8.2 Physical Encapsulation 327
8.3 Chemical Encapsulation 329
8.3.1 Core/shell microcapsules via in-situ polymerization 331
8.3.2 Core/shell microcapsules via interfacial polymerization 333
8.4 DOE Example of Microcapsule Formulation and Processing Optimization 335
Debrief A Melamine and amino derivative crosslinkers 340
Debrief B Urea-glyoxal resins and derivatives 344
Debrief C Michael Addition reactions and applications 344
Debrief D Microencapsulation via interfacial polymerization 346
Recaps and Highlights 349
Appendix 350
A Exemplary Carbonless Paper Coatings 350
References 351
9 Hybrids and Non-Epoxy Platforms 355
9.1 Epoxy Hybrids 355
9.1.1 Epoxy-isocyanate systems 355
9.1.2 Epoxy-urethane/urea systems 357
9.1.3 Epoxy-acrylate/BMI systems 357
9.2 Non-Epoxy Systems 364
9.2.1 Polyurethanes and polyols 364
9.2.2 Acrylics and acrylates 367
9.2.3 Polyesters and their monomers 370
9.2.4 Acrylate adhesive case studies 372
9.2.5 Polyurea coating case studies 374
9.2.6 Silicones: silanes, TEOS, PDMS, elastomers 377
9.3 Non-Epoxy Hybrids 389
9.3.1 Phthalonitrile (PN) and BOX-PN hybrids 390
9.3.2 Miscellaneous high-performance polymers 393
Debrief A Silanes, silicates, and PDMSs 394
Debrief B Non-epoxy polymers and hybrids 396
Debrief C Dual UV/thermal curing silicones 399
Recaps and Highlights 400
References 402
Part V Adhesiveness and Adhesion 409
10 Adhesion and Adhesion Promotion 411
10.1 Bulk Adhesives 411
10.1.1 Epoxy structural adhesives 412
10.1.2 Acrylic and PUR structural adhesives 413
10.1.3 One-component (1K) moisture curable PUR and silicone adhesives 415
10.1.4 Anaerobic and instant adhesives 417
10.1.5 Titanate catalysts and formulation tips 419
10.2 Characterization of Adhesives and Adhesion 420
10.2.1 Reactive adhesives 420
10.2.2 Non-reactive adhesives 421
10.2.3 HM adhesives as TIMs: a case study 422
10.3 Substrates and Interfaces 423
10.3.1 Surface energy and surface tension 424
10.3.2 Surface modifications 427
10.3.3 Monomeric and polymeric silanes 428
10.3.4 Other adhesion promoters and adhesive polymers 432
10.4 Adhesion Troubleshooting 437
Debrief A Industrial rheology of adhesives and sealants 438
Debrief B Reactive adhesives 441
Debrief C Organo-functional silanes 442
Debrief D Anticorrosion of coatings on ferrous metals 443
Debrief E Polythiol reactions 446
Recaps and Highlights 447
References 451
11 Closing Remarks 459
Wrap-Ups 459
Outlooks 468
Green and circular 470
Hybrid and smart 471
References 474
Index 479
