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Preface
Symbols and Units
1. What Are Coatings?
1.1. Definitions and Scope / 1
1.2. Composition of Coatings / 4
References / 6
2. Polymerization and Film Formation
2.1. Polymers / 7
2.1.1. Molecular Weight / 9
2.1.2. Morphology / 13
2.2. Polymerization / 17
2.2.1. Chain-Growth Polymerization / 17
2.2.2. Step-Growth Polymerization / 23
2.3. Film Formation / 27
2.3.1. Film Formation by Solvent Evaporation from Solutions of
Thermoplastic Binders / 28
2.3.2. Film Formation from Solutions of Thermosetting Resins / 28
2.3.3. Film Formation by Coalescence of Polymer Particles / 34
General References / 38
References / 39
3. Flow
3.1. Shear Flow / 41
3.2. Types of Shear Flow / 42
3.3. Determination of Shear Viscosity / 46
3.3.1. Capillary Viscometers / 47
3.3.2. Rheometers / 48
3.3.3. Rotating Disk Viscometers / 49
3.3.4. Bubble Viscometers / 50
3.3.5. Efflux Cups / 50
3.3.6. Paddle Viscometers / 51
3.4. Shear Viscosity of Resin Solutions / 52
3.4.1. Temperature Dependence of Viscosity / 53
3.4.2. Dilute Polymer Solution Viscosity / 54
3.4.3. Concentrated Polymer Solution Viscosity / 55
3.5. Viscosity of Liquids with Dispersed Phases / 59
3.5.1. Thickeners for Latex Coatings / 62
3.6. Other Modes of Flow / 63
3.6.1. Turbulent Flow / 63
3.6.2. Normal Force Flow / 64
3.6.3. Extensional Flow / 64
General References / 66
References / 66
4. Mechanical Properties
4.1. Introduction: General Comments on Testing of Coating Films / 68
4.2. Basic Mechanical Properties / 70
4.3. Formability and Flexibility / 74
4.3.1. Fracture Mechanics / 82
4.4. Abrasion and Mar Resistance / 83
4.4.1. Abrasion Resistance / 83
4.4.2. Mar Resistance / 85
4.5. Measurement of Mechanical Properties / 86
4.6. Tests of Coatings on Substrates / 89
4.6.1. Field Exposure Tests / 89
4.6.2. Laboratory Simulation Tests / 89
4.6.3. Empirical Tests / 90
General References / 94
References / 95
5. Exterior Durability
5.1. Photoinitiated Oxidative Degradation / 97
5.2. Photostabilization / 100
5.2.1. UV Absorbers and Excited State Quenchers / 101
5.2.2. Antioxidants / 103
5.2.3. Hindered Amine Light Stabilizers / 104
5.2.4. Pigmentation Effects / 106
5.3. Degradation of Chlorinated Resins / 108
5.4. Hydrolytic Degradation / 109
5.5. Other Modes of Failure on Exterior Exposure / 111
5.6. Testing for Exterior Durability / 112
5.6.1. Accelerated Outdoor Testing / 112
5.6.2. Analysis of Chemical and Mechanical Changes / 114
5.6.3. Accelerated Weathering Devices / 116
General References / 118
References / 118
6. Adhesion
6.1. Surface Mechanical Effects on Adhesion / 121
6.2. Effects of Internal Stress and Fracture Mechanics / 123
6.3. Relationship Between Wetting and Adhesion / 124
6.4. Adhesion to Metal Surfaces / 125
6.4.1. Surface Preparation / 126
6.4.2. Coating–Substrate Interaction / 128
6.4.3. Covalent Bonding to Glass and Metal Substrates / 130
6.5. Adhesion to Plastics and to Coatings / 131
6.6. Testing for Adhesion / 133
General References / 135
References / 135
7. Corrosion Protection by Coatings
7.1. Corrosion of Uncoated Steel / 137
7.2. Corrosion Protection of Metals / 140
7.2.1. Passivation: Anodic Protection / 140
7.2.2. Cathodic Protection / 141
7.2.3. Barrier Protection and Inhibition / 142
7.3. Corrosion Protection by Intact Coatings / 142
7.3.1. Critical Factors / 143
7.3.2. Adhesion for Corrosion Protection / 144
7.3.3. Factors Affecting Oxygen and Water Permeability / 146
7.4. Corrosion Protection by Nonintact Films / 148
7.4.1. Minimizing Growth of Imperfections:
Cathodic Delamination / 149
7.4.2. Primers with Passivating Pigments / 149
7.4.3. Cathodic Protection by Zinc-Rich Primers / 151
CONTE
7.5. Evaluation and Testing / 153
General References / 156
References / 156
8. Acrylic Resins
8.1. Thermoplastic Acrylic Resins / 159
8.2. Thermosetting Acrylic Resins / 160
8.2.1. Hydroxy-Functional Acrylic Resins / 160
8.2.2. Acrylics with Other Functional Groups / 165
8.3. Water-Reducible Thermosetting Acrylic Resins / 166
References / 174
9. Latexes
9.1. Emulsion Polymerization / 177
9.1.1. Raw Materials for Emulsion Polymerization / 178
9.1.2. Emulsion Polymerization Variables / 182
9.1.3. Sequential Polymerization / 186
9.2. Acrylic Latexes / 186
9.3. Vinyl Ester Latexes / 191
9.4. Thermosetting Latexes / 193
General References / 196
References / 196
10. Polyester Resins
10.1. Hydroxy-Terminated Polyester Resins for Conventional
Solids Coatings / 200
10.1.1. Selection of Polyols / 202
10.1.2. Selection of Polyacids / 204
10.2. Polyester Resins for High-Solids Coatings / 205
10.3. Carboxylic Acid–Terminated Polyester Resins / 208
10.4. Carbamate-Functional Polyester Resins / 209
10.5. Water-Reducible Polyester Resins / 209
10.6. Polyester Resins for Powder Coatings / 211
References / 211
11. Amino Resins
11.1. Synthesis of Melamine–Formaldehyde Resins / 214
11.1.1. Methylolation Reaction / 215
11.1.2. Etherification Reaction / 215
11.1.3. Self-Condensation Reactions / 217
11.2. Types of MF Resins / 218
11.3. MF–Polyol Reactions in Coatings / 220
11.3.1. Catalysis of MF–Polyol Reactions / 222
11.3.2. Kinetics and Mechanism of MF–Polyol
Co-condensation / 224
11.3.3. Package Stability Considerations / 226
11.3.4. MF Resin Reactions with Carboxylic Acids, Urethanes,
Carbamates, and Malonate-Blocked Isocyanates / 227
11.4. Other Amino Resins / 227
11.4.1. Urea–Formaldehyde Resins / 228
11.4.2. Benzoguanamine–Formaldehyde Resins / 228
11.4.3. Glycoluril–Formaldehyde Resins / 228
11.4.4. Poly(meth)acrylamide–Formaldehyde Resins / 229
References / 229
12. Binders Based on Polyisocyanates: Polyurethanes
12.1. Reactions of Isocyanates / 232
12.2. Kinetics of Reactions of Isocyanates with Alcohols / 234
12.2.1. Noncatalyzed Reactions / 235
12.2.2. Catalysts / 237
12.2.3. Interrelationships in Catalysis / 241
12.3. Isocyanates Used in Coatings / 242
12.3.1. Aromatic Isocyanates / 242
12.3.2. Aliphatic Isocyanates / 244
12.4. Two Package Solventborne Urethane Coatings / 246
12.4.1. 2K Urea Coatings / 249
12.5. Blocked Isocyanates / 250
12.5.1. Principles of Blocking and Deblocking / 251
12.5.2. Blocking Groups / 254
12.5.3. Catalysis of Blocked Isocyanate Coatings / 258
12.6. Moisture-Curable Urethane Coatings / 259
12.7. Waterborne Urethane Coatings / 261
12.7.1. Polyurethane Dispersions / 261
12.7.2. Acrylic–Polyurethane Dispersions / 262
12.7.3. 2K Waterborne Urethanes / 264
12.8. Hydroxy-Terminated Polyurethanes / 266
References / 267
13. Epoxy and Phenolic Resins
13.1. Epoxy Resins / 271
13.1.1. Bisphenol A Epoxy Resins / 271
13.1.2. Other Epoxy Resins / 275
CO
13.2. Epoxy–Amine Systems / 278
13.2.1. Pot Life and Cure Time Considerations / 279
13.2.2. Toxicity and Stoichiometric Considerations / 281
13.2.3. Graininess and Blushing / 282
13.2.4. T
g Considerations / 283
13.2.5. Other Formulating Considerations / 283
13.2.6. Waterborne Epoxy–Amine Systems / 285
13.3. Other Cross-Linking Agents for Epoxy Resins / 286
13.3.1. Phenols / 286
13.3.2. Carboxylic Acids and Anhydrides / 286
13.3.3. Hydroxyl Groups / 288
13.3.4. Mercaptans / 288
13.3.5. Homopolymerization / 289
13.4. Water-Reducible Epoxy Acrylic Graft Copolymers / 290
13.5. Epoxy Resin Phosphate Esters / 290
13.6. Phenolic Resins / 290
13.6.1. Resole Phenolic Resins / 291
13.6.2. Novolac Phenolic Resins / 292
13.6.3. Ether Derivatives of Phenolic Resins / 293
General References / 293
References / 293
14. Drying Oils
14.1. Composition of Natural Oils / 295
14.2. Autoxidation and Cross-Linking / 297
14.2.1. Nonconjugated Drying Oils / 297
14.2.2. Catalysis of Autoxidation and Cross-Linking / 300
14.2.3. Conjugated Drying Oils / 301
14.3. Synthetic and Modified Drying Oils / 302
14.3.1. Heat-Bodied Oils, Blown Oils, and Dimer Acids / 302
14.3.2. Varnishes / 302
14.3.3. Synthetic Conjugated Oils / 303
14.3.4. Esters of Higher Functionality Polyols / 303
14.3.5. Maleated Oils / 303
14.3.6. Vinyl-Modified Oils / 304
General References / 305
References / 305
15. Alkyd Resins
15.1. Oxidizing Alkyds / 307
15.1.1. Monobasic Acid Selection / 308
15.1.2. Polyol Selection / 310
15.1.3. Dibasic Acid Selection / 311
15.2. High-Solids Oxidizing Alkyds / 312
15.3. Water-Reducible Alkyds / 313
15.4. Nonoxidizing Alkyds / 314
15.5. Synthetic Procedures for Alkyd Resins / 315
15.5.1. Synthesis from Oils or Fatty Acids / 315
15.5.2. Process Variations / 316
15.6. Modified Alkyds / 320
15.7. Uralkyds and Other Autoxidizable Urethanes / 320
15.7.1. Uralkyds / 320
15.7.2. Autoxidizable Polyurethane Dispersions / 322
15.8. Epoxy Esters / 322
General Reference / 324
References / 324
16. Silicon Derivatives
16.1. Silicones / 326
16.1.1. Silicone Rubbers and Resins / 327
16.1.2. Silicone-Modified Resins / 329
16.2. Reactive Silanes / 331
16.3. Orthosilicates / 333
16.3.1. Sol-Gel Coatings / 333
References / 333
17. Other Resins and Cross-Linkers
17.1. Halogenated Polymers / 335
17.1.1. Solution Grade Thermoplastic Vinyl
Chloride Copolymers / 335
17.1.2. Vinyl Chloride Dispersion Copolymers / 336
17.1.3. Chlorinated Rubber, Chlorinated Ethylene Vinyl
Acetate Copolymers, and Chlorinated Polyolefins / 336
17.1.4. Fluorinated Polymers / 337
17.2. Cellulose Derivatives / 338
17.2.1. Nitrocellulose / 338
17.2.2. Cellulose Acetobutyrate / 339
17.3. Unsaturated Polyester Resins / 340
17.4. (Meth)acrylated Oligomers / 342
17.5. 2-Hydroxyalkylamide Cross-Linkers / 342
17.6. Acetoacetate Cross-Linking Systems / 343
17.7. Polyaziridine Cross-Linkers / 345
CONTE
17.8. Polycarbodiimide Cross-Linkers / 346
17.9. Polycarbonates / 347
References / 347
18. Solvents
18.1. Solvent Composition / 349
18.2. Solubility / 351
18.2.1. Solubility Parameters / 351
18.2.2. Three-Dimensional Solubility Parameters / 354
18.2.3. Other Solubility Theories / 356
18.2.4. Practical Considerations / 356
18.3. Solvent Evaporation Rates / 357
18.3.1. Evaporation of Single Solvents / 357
18.3.2. Relative Evaporation Rates / 358
18.3.3. Evaporation of Mixed Solvents / 361
18.3.4. Evaporation of Solvents from Coating Films / 363
18.3.5. Evaporation of Solvents from High-Solids Coatings / 365
18.3.6. Volatile Loss from Waterborne Coatings / 366
18.4. Viscosity Effects / 367
18.5. Flammability / 369
18.6. Other Physical Properties / 370
18.7. Toxic Hazards / 371
18.8. Atmospheric Photochemical Effects / 372
18.9. Regulation of Solvent Emissions from Coatings / 376
18.9.1. Determination of VOC / 376
18.9.2. Regulations / 377
General References / 379
References / 379
19. Color and Appearance
19.1. Light / 383
19.2. Light–Object Interactions / 385
19.2.1. Surface Reflection / 385
19.2.2. Absorption Effects / 387
19.2.3. Scattering / 388
19.2.4. Multiple Interaction Effects / 390
19.3. Hiding / 392
19.4. Metallic and Interference Colors / 393
19.5. The Observer / 394
19.6. Interactions of Light Source, Object, and Observer / 396
19.7. Color Systems / 397
xii CONTENTS
19.8. Color Mixing / 401
19.9. Color Matching / 402
19.9.1. Information Requirements / 402
19.9.2. Color Matching Procedures / 404
19.10. Gloss / 407
19.10.1. Variables in Specular Gloss / 408
19.10.2. Gloss Measurement / 412
General References / 415
References / 415
20. Pigments
20.1. White Pigments / 418
20.1.1. Titanium Dioxide / 418
20.1.2. Other White Pigments / 420
20.2. Color Pigments / 421
20.2.1. Yellow and Orange Pigments / 423
20.2.2. Red Pigments / 425
20.2.3. Blue and Green Pigments / 426
20.2.4. Black Pigments / 427
20.2.5. Metallic, Interference, and Cholesteric Pigments / 428
20.3. Inert Pigments / 430
20.4. Functional Pigments / 431
20.5. Nano-pigments / 432
General References / 433
References / 433
21. Pigment Dispersion
21.1. Dispersion in Organic Media / 435
21.1.1. Wetting / 435
21.1.2. Separation / 436
21.1.3. Stabilization / 436
21.2. Formulation of Non-aqueous Mill Bases / 442
21.2.1. Daniel Flow Point Method / 443
21.2.2. Oil Absorption Values / 444
21.3. Dispersions in Aqueous Media / 445
21.3.1. Stabilization of Aqueous Dispersions / 446
21.4. Dispersion Equipment and Processes / 449
21.4.1. High-Speed Disk Dispersers / 449
21.4.2. Rotor–Stator Mixers / 451
21.4.3. Ball Mills / 451
21.4.4. Media Mills / 453
CONTEN
21.4.5. Three Roll and Two Roll Mills / 455
21.4.6. Extruders / 456
21.4.7. Ultrasound Dispersion / 456
21.5. Evaluation of Dispersion / 456
General References / 459
References / 459
22. Effect of Pigments on Coating Properties
22.1. PVC and CPVC / 461
22.1.1. Factors Controlling CPVC / 462
22.1.2. Determination of CPVC / 463
22.1.3. CPVC of Latex Coatings / 464
22.2. Relationships Between Film Properties and PVC / 466
22.2.1. Mechanical Properties / 466
22.2.2. Effects of Porosity / 470
22.2.3. Effects on Curing and Film Formation / 471
References / 471
23. Application Methods
23.1. Brushes, Pads, and Hand Rollers / 473
23.1.1. Brush and Pad Application / 473
23.1.2. Hand Roller Application / 474
23.2. Spray Application / 475
23.2.1. Air Spray Guns / 476
23.2.2. Airless Spray Guns / 478
23.2.3. Electrostatic Spraying / 479
23.2.4. Hot Spray / 481
23.2.5. Supercritical Fluid Spray / 481
23.2.6. Formulation Considerations for Spray-Applied Coatings /
23.2.7. Overspray Disposal / 484
23.3. Dip and Flow Coating / 484
23.4. Roll Coating / 485
23.5. Curtain Coating / 487
General References / 488
References / 488
24. Film Defects
24.1. Surface Tension / 490
24.2. Leveling / 492
24.3. Sagging and Drip Marks / 496
24.4. Crawling, Cratering, and Related Defects / 499
24.5. Floating and Flooding; Hammer Finishes / 502
24.6. Wrinkling and Wrinkle Finishes / 505
24.7. Bubbling and Popping / 506
24.8. Foaming / 508
24.9. Dirt / 509
General References / 509
References / 509
25. Solventborne and High-Solids Coatings
25.1. Primers / 512
25.1.1. Binders for Primers / 512
25.1.2. Pigmentation of Primers / 513
25.1.3. High-Solids Primers / 514
25.2. Top Coats / 515
25.2.1. Binders for Top Coats / 515
25.2.2. Formulating Solventborne Coatings for Low VOC /
General Reference / 522
References / 522
26. Waterborne Coatings
26.1. Water-Reducible Coatings / 525
26.2. Latex-Based Coatings / 529
26.3. Emulsion Coatings / 532
General References / 533
References / 533
27. Electrodeposition Coatings
27.1. Anionic Electrodeposition Coatings / 536
27.2. Cationic Electrodeposition Coatings / 538
27.3. Effect of Variables on Electrodeposition / 541
27.4. Application of Electrodeposition Coatings / 542
27.5. Advantages and Limitations of Electrodeposition / 544
27.6. Autodeposition Coatings / 545
General Reference / 547
References / 547
28. Powder Coatings
28.1. Binders for Thermosetting Powder Coatings / 548
28.1.1. Epoxy Binders / 550
28.1.2. Hybrid Binders / 550
28.1.3. Polyester Binders / 551
28.1.4. Acrylic Binders / 553
28.1.5. Silicone Binders / 554
28.1.6. UV Cure Powder Coatings / 554
28.2. Binders for Thermoplastic Powder Coatings / 555
28.3. Formulation of Thermosetting Powder Coatings / 555
28.3.1. Low Gloss Powder Coatings / 559
28.4. Manufacture of Powder Coatings / 560
28.4.1. Production / 560
28.4.2. Quality Control / 563
28.5. Application Methods / 564
28.5.1. Electrostatic Spray Application / 564
28.5.2. Other Application Methods / 567
28.6. Advantages and Limitations of Powder Coatings / 569
General References / 571
References / 571
29. Radiation Cure Coatings
29.1. UV Curing / 574
29.2. Free Radical Initiated UV Cure / 578
29.2.1. Unimolecular Photoinitiators / 578
29.2.2. Bimolecular Photoinitiators / 579
29.2.3. Oxygen Inhibition / 580
29.2.4. Vehicles for Free Radical Initiated UV Cure / 581
29.2.5. Waterborne UV Cure Coatings / 584
29.3. Cationic UV Cure / 585
29.3.1. Vehicles for Cationic UV Cure / 585
29.4. Effects of Pigmentation / 586
29.5. Electron Beam Cure Coatings / 588
29.6. Dual UV/Thermal Cure and Selected Applications / 589
29.7. Advantages and Limitations / 591
General References / 593
References / 593
30. Product Coatings for Metal Substrates
30.1. OEM Automotive Coatings / 595
30.1.1. Electrodeposition Coatings and Primer–Surfacers / 596
30.1.2. Top Coats / 597
30.1.3. Factory Repair Procedures / 604
30.2. Appliance Coatings / 605
30.3. Container Coatings / 606
30.3.1. Interior Can Linings / 608
30.3.2. Exterior Can Coatings / 610
30.4. Coil Coating / 611
30.4.1. Advantages and Limitations of Coil Coating / 615
General References / 616
References / 617
31. Product Coatings for Nonmetallic Substrates
31.1. Coatings for Wood / 619
31.1.1. Coatings for Wood Furniture / 619
31.1.2. Panel, Siding, and Flooring Finishes / 626
31.2. Coating of Plastics / 628
31.2.1. In-mold Coating / 628
31.2.2. Post-mold Coating / 629
31.3. Coatings for Glass / 633
General Reference / 634
References / 634
32. Architectural Coatings
32.1. Exterior House Paint / 637
32.2. Flat and Semigloss Paints / 643
32.3. Gloss Enamels / 649
32.3.1. Alkyd Gloss Enamels / 649
32.3.2. Latex Gloss Enamels / 651
General Reference / 655
References / 655
33. Special Purpose Coatings
33.1. Maintenance Paints / 658
33.1.1. Barrier Coating Systems / 659
33.1.2. Systems with Zinc-Rich Primers / 663
33.1.3. Systems with Passivating Pigment Containing Primers / 665
33.2. Marine Coatings / 667
33.3. Automobile Refinish Paints / 670
33.4. Aircraft Coatings / 674
References / 676
34. Perspectives on Coating Design
General References / 687
References / 688
Index
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Preface
Symbols and Units
1. What Are Coatings?
1.1. Definitions and Scope / 1
1.2. Composition of Coatings / 4
References / 6
2. Polymerization and Film Formation
2.1. Polymers / 7
2.1.1. Molecular Weight / 9
2.1.2. Morphology / 13
2.2. Polymerization / 17
2.2.1. Chain-Growth Polymerization / 17
2.2.2. Step-Growth Polymerization / 23
2.3. Film Formation / 27
2.3.1. Film Formation by Solvent Evaporation from Solutions of
Thermoplastic Binders / 28
2.3.2. Film Formation from Solutions of Thermosetting Resins / 28
2.3.3. Film Formation by Coalescence of Polymer Particles / 34
General References / 38
References / 39
3. Flow
3.1. Shear Flow / 41
3.2. Types of Shear Flow / 42
3.3. Determination of Shear Viscosity / 46
3.3.1. Capillary Viscometers / 47
3.3.2. Rheometers / 48
3.3.3. Rotating Disk Viscometers / 49
3.3.4. Bubble Viscometers / 50
3.3.5. Efflux Cups / 50
3.3.6. Paddle Viscometers / 51
3.4. Shear Viscosity of Resin Solutions / 52
3.4.1. Temperature Dependence of Viscosity / 53
3.4.2. Dilute Polymer Solution Viscosity / 54
3.4.3. Concentrated Polymer Solution Viscosity / 55
3.5. Viscosity of Liquids with Dispersed Phases / 59
3.5.1. Thickeners for Latex Coatings / 62
3.6. Other Modes of Flow / 63
3.6.1. Turbulent Flow / 63
3.6.2. Normal Force Flow / 64
3.6.3. Extensional Flow / 64
General References / 66
References / 66
4. Mechanical Properties
4.1. Introduction: General Comments on Testing of Coating Films / 68
4.2. Basic Mechanical Properties / 70
4.3. Formability and Flexibility / 74
4.3.1. Fracture Mechanics / 82
4.4. Abrasion and Mar Resistance / 83
4.4.1. Abrasion Resistance / 83
4.4.2. Mar Resistance / 85
4.5. Measurement of Mechanical Properties / 86
4.6. Tests of Coatings on Substrates / 89
4.6.1. Field Exposure Tests / 89
4.6.2. Laboratory Simulation Tests / 89
4.6.3. Empirical Tests / 90
General References / 94
References / 95
5. Exterior Durability
5.1. Photoinitiated Oxidative Degradation / 97
5.2. Photostabilization / 100
5.2.1. UV Absorbers and Excited State Quenchers / 101
5.2.2. Antioxidants / 103
5.2.3. Hindered Amine Light Stabilizers / 104
5.2.4. Pigmentation Effects / 106
5.3. Degradation of Chlorinated Resins / 108
5.4. Hydrolytic Degradation / 109
5.5. Other Modes of Failure on Exterior Exposure / 111
5.6. Testing for Exterior Durability / 112
5.6.1. Accelerated Outdoor Testing / 112
5.6.2. Analysis of Chemical and Mechanical Changes / 114
5.6.3. Accelerated Weathering Devices / 116
General References / 118
References / 118
6. Adhesion
6.1. Surface Mechanical Effects on Adhesion / 121
6.2. Effects of Internal Stress and Fracture Mechanics / 123
6.3. Relationship Between Wetting and Adhesion / 124
6.4. Adhesion to Metal Surfaces / 125
6.4.1. Surface Preparation / 126
6.4.2. Coating–Substrate Interaction / 128
6.4.3. Covalent Bonding to Glass and Metal Substrates / 130
6.5. Adhesion to Plastics and to Coatings / 131
6.6. Testing for Adhesion / 133
General References / 135
References / 135
7. Corrosion Protection by Coatings
7.1. Corrosion of Uncoated Steel / 137
7.2. Corrosion Protection of Metals / 140
7.2.1. Passivation: Anodic Protection / 140
7.2.2. Cathodic Protection / 141
7.2.3. Barrier Protection and Inhibition / 142
7.3. Corrosion Protection by Intact Coatings / 142
7.3.1. Critical Factors / 143
7.3.2. Adhesion for Corrosion Protection / 144
7.3.3. Factors Affecting Oxygen and Water Permeability / 146
7.4. Corrosion Protection by Nonintact Films / 148
7.4.1. Minimizing Growth of Imperfections:
Cathodic Delamination / 149
7.4.2. Primers with Passivating Pigments / 149
7.4.3. Cathodic Protection by Zinc-Rich Primers / 151
CONTE
7.5. Evaluation and Testing / 153
General References / 156
References / 156
8. Acrylic Resins
8.1. Thermoplastic Acrylic Resins / 159
8.2. Thermosetting Acrylic Resins / 160
8.2.1. Hydroxy-Functional Acrylic Resins / 160
8.2.2. Acrylics with Other Functional Groups / 165
8.3. Water-Reducible Thermosetting Acrylic Resins / 166
References / 174
9. Latexes
9.1. Emulsion Polymerization / 177
9.1.1. Raw Materials for Emulsion Polymerization / 178
9.1.2. Emulsion Polymerization Variables / 182
9.1.3. Sequential Polymerization / 186
9.2. Acrylic Latexes / 186
9.3. Vinyl Ester Latexes / 191
9.4. Thermosetting Latexes / 193
General References / 196
References / 196
10. Polyester Resins
10.1. Hydroxy-Terminated Polyester Resins for Conventional
Solids Coatings / 200
10.1.1. Selection of Polyols / 202
10.1.2. Selection of Polyacids / 204
10.2. Polyester Resins for High-Solids Coatings / 205
10.3. Carboxylic Acid–Terminated Polyester Resins / 208
10.4. Carbamate-Functional Polyester Resins / 209
10.5. Water-Reducible Polyester Resins / 209
10.6. Polyester Resins for Powder Coatings / 211
References / 211
11. Amino Resins
11.1. Synthesis of Melamine–Formaldehyde Resins / 214
11.1.1. Methylolation Reaction / 215
11.1.2. Etherification Reaction / 215
11.1.3. Self-Condensation Reactions / 217
11.2. Types of MF Resins / 218
11.3. MF–Polyol Reactions in Coatings / 220
11.3.1. Catalysis of MF–Polyol Reactions / 222
11.3.2. Kinetics and Mechanism of MF–Polyol
Co-condensation / 224
11.3.3. Package Stability Considerations / 226
11.3.4. MF Resin Reactions with Carboxylic Acids, Urethanes,
Carbamates, and Malonate-Blocked Isocyanates / 227
11.4. Other Amino Resins / 227
11.4.1. Urea–Formaldehyde Resins / 228
11.4.2. Benzoguanamine–Formaldehyde Resins / 228
11.4.3. Glycoluril–Formaldehyde Resins / 228
11.4.4. Poly(meth)acrylamide–Formaldehyde Resins / 229
References / 229
12. Binders Based on Polyisocyanates: Polyurethanes
12.1. Reactions of Isocyanates / 232
12.2. Kinetics of Reactions of Isocyanates with Alcohols / 234
12.2.1. Noncatalyzed Reactions / 235
12.2.2. Catalysts / 237
12.2.3. Interrelationships in Catalysis / 241
12.3. Isocyanates Used in Coatings / 242
12.3.1. Aromatic Isocyanates / 242
12.3.2. Aliphatic Isocyanates / 244
12.4. Two Package Solventborne Urethane Coatings / 246
12.4.1. 2K Urea Coatings / 249
12.5. Blocked Isocyanates / 250
12.5.1. Principles of Blocking and Deblocking / 251
12.5.2. Blocking Groups / 254
12.5.3. Catalysis of Blocked Isocyanate Coatings / 258
12.6. Moisture-Curable Urethane Coatings / 259
12.7. Waterborne Urethane Coatings / 261
12.7.1. Polyurethane Dispersions / 261
12.7.2. Acrylic–Polyurethane Dispersions / 262
12.7.3. 2K Waterborne Urethanes / 264
12.8. Hydroxy-Terminated Polyurethanes / 266
References / 267
13. Epoxy and Phenolic Resins
13.1. Epoxy Resins / 271
13.1.1. Bisphenol A Epoxy Resins / 271
13.1.2. Other Epoxy Resins / 275
CO
13.2. Epoxy–Amine Systems / 278
13.2.1. Pot Life and Cure Time Considerations / 279
13.2.2. Toxicity and Stoichiometric Considerations / 281
13.2.3. Graininess and Blushing / 282
13.2.4. T
g Considerations / 283
13.2.5. Other Formulating Considerations / 283
13.2.6. Waterborne Epoxy–Amine Systems / 285
13.3. Other Cross-Linking Agents for Epoxy Resins / 286
13.3.1. Phenols / 286
13.3.2. Carboxylic Acids and Anhydrides / 286
13.3.3. Hydroxyl Groups / 288
13.3.4. Mercaptans / 288
13.3.5. Homopolymerization / 289
13.4. Water-Reducible Epoxy Acrylic Graft Copolymers / 290
13.5. Epoxy Resin Phosphate Esters / 290
13.6. Phenolic Resins / 290
13.6.1. Resole Phenolic Resins / 291
13.6.2. Novolac Phenolic Resins / 292
13.6.3. Ether Derivatives of Phenolic Resins / 293
General References / 293
References / 293
14. Drying Oils
14.1. Composition of Natural Oils / 295
14.2. Autoxidation and Cross-Linking / 297
14.2.1. Nonconjugated Drying Oils / 297
14.2.2. Catalysis of Autoxidation and Cross-Linking / 300
14.2.3. Conjugated Drying Oils / 301
14.3. Synthetic and Modified Drying Oils / 302
14.3.1. Heat-Bodied Oils, Blown Oils, and Dimer Acids / 302
14.3.2. Varnishes / 302
14.3.3. Synthetic Conjugated Oils / 303
14.3.4. Esters of Higher Functionality Polyols / 303
14.3.5. Maleated Oils / 303
14.3.6. Vinyl-Modified Oils / 304
General References / 305
References / 305
15. Alkyd Resins
15.1. Oxidizing Alkyds / 307
15.1.1. Monobasic Acid Selection / 308
15.1.2. Polyol Selection / 310
15.1.3. Dibasic Acid Selection / 311
15.2. High-Solids Oxidizing Alkyds / 312
15.3. Water-Reducible Alkyds / 313
15.4. Nonoxidizing Alkyds / 314
15.5. Synthetic Procedures for Alkyd Resins / 315
15.5.1. Synthesis from Oils or Fatty Acids / 315
15.5.2. Process Variations / 316
15.6. Modified Alkyds / 320
15.7. Uralkyds and Other Autoxidizable Urethanes / 320
15.7.1. Uralkyds / 320
15.7.2. Autoxidizable Polyurethane Dispersions / 322
15.8. Epoxy Esters / 322
General Reference / 324
References / 324
16. Silicon Derivatives
16.1. Silicones / 326
16.1.1. Silicone Rubbers and Resins / 327
16.1.2. Silicone-Modified Resins / 329
16.2. Reactive Silanes / 331
16.3. Orthosilicates / 333
16.3.1. Sol-Gel Coatings / 333
References / 333
17. Other Resins and Cross-Linkers
17.1. Halogenated Polymers / 335
17.1.1. Solution Grade Thermoplastic Vinyl
Chloride Copolymers / 335
17.1.2. Vinyl Chloride Dispersion Copolymers / 336
17.1.3. Chlorinated Rubber, Chlorinated Ethylene Vinyl
Acetate Copolymers, and Chlorinated Polyolefins / 336
17.1.4. Fluorinated Polymers / 337
17.2. Cellulose Derivatives / 338
17.2.1. Nitrocellulose / 338
17.2.2. Cellulose Acetobutyrate / 339
17.3. Unsaturated Polyester Resins / 340
17.4. (Meth)acrylated Oligomers / 342
17.5. 2-Hydroxyalkylamide Cross-Linkers / 342
17.6. Acetoacetate Cross-Linking Systems / 343
17.7. Polyaziridine Cross-Linkers / 345
CONTE
17.8. Polycarbodiimide Cross-Linkers / 346
17.9. Polycarbonates / 347
References / 347
18. Solvents
18.1. Solvent Composition / 349
18.2. Solubility / 351
18.2.1. Solubility Parameters / 351
18.2.2. Three-Dimensional Solubility Parameters / 354
18.2.3. Other Solubility Theories / 356
18.2.4. Practical Considerations / 356
18.3. Solvent Evaporation Rates / 357
18.3.1. Evaporation of Single Solvents / 357
18.3.2. Relative Evaporation Rates / 358
18.3.3. Evaporation of Mixed Solvents / 361
18.3.4. Evaporation of Solvents from Coating Films / 363
18.3.5. Evaporation of Solvents from High-Solids Coatings / 365
18.3.6. Volatile Loss from Waterborne Coatings / 366
18.4. Viscosity Effects / 367
18.5. Flammability / 369
18.6. Other Physical Properties / 370
18.7. Toxic Hazards / 371
18.8. Atmospheric Photochemical Effects / 372
18.9. Regulation of Solvent Emissions from Coatings / 376
18.9.1. Determination of VOC / 376
18.9.2. Regulations / 377
General References / 379
References / 379
19. Color and Appearance
19.1. Light / 383
19.2. Light–Object Interactions / 385
19.2.1. Surface Reflection / 385
19.2.2. Absorption Effects / 387
19.2.3. Scattering / 388
19.2.4. Multiple Interaction Effects / 390
19.3. Hiding / 392
19.4. Metallic and Interference Colors / 393
19.5. The Observer / 394
19.6. Interactions of Light Source, Object, and Observer / 396
19.7. Color Systems / 397
xii CONTENTS
19.8. Color Mixing / 401
19.9. Color Matching / 402
19.9.1. Information Requirements / 402
19.9.2. Color Matching Procedures / 404
19.10. Gloss / 407
19.10.1. Variables in Specular Gloss / 408
19.10.2. Gloss Measurement / 412
General References / 415
References / 415
20. Pigments
20.1. White Pigments / 418
20.1.1. Titanium Dioxide / 418
20.1.2. Other White Pigments / 420
20.2. Color Pigments / 421
20.2.1. Yellow and Orange Pigments / 423
20.2.2. Red Pigments / 425
20.2.3. Blue and Green Pigments / 426
20.2.4. Black Pigments / 427
20.2.5. Metallic, Interference, and Cholesteric Pigments / 428
20.3. Inert Pigments / 430
20.4. Functional Pigments / 431
20.5. Nano-pigments / 432
General References / 433
References / 433
21. Pigment Dispersion
21.1. Dispersion in Organic Media / 435
21.1.1. Wetting / 435
21.1.2. Separation / 436
21.1.3. Stabilization / 436
21.2. Formulation of Non-aqueous Mill Bases / 442
21.2.1. Daniel Flow Point Method / 443
21.2.2. Oil Absorption Values / 444
21.3. Dispersions in Aqueous Media / 445
21.3.1. Stabilization of Aqueous Dispersions / 446
21.4. Dispersion Equipment and Processes / 449
21.4.1. High-Speed Disk Dispersers / 449
21.4.2. Rotor–Stator Mixers / 451
21.4.3. Ball Mills / 451
21.4.4. Media Mills / 453
CONTEN
21.4.5. Three Roll and Two Roll Mills / 455
21.4.6. Extruders / 456
21.4.7. Ultrasound Dispersion / 456
21.5. Evaluation of Dispersion / 456
General References / 459
References / 459
22. Effect of Pigments on Coating Properties
22.1. PVC and CPVC / 461
22.1.1. Factors Controlling CPVC / 462
22.1.2. Determination of CPVC / 463
22.1.3. CPVC of Latex Coatings / 464
22.2. Relationships Between Film Properties and PVC / 466
22.2.1. Mechanical Properties / 466
22.2.2. Effects of Porosity / 470
22.2.3. Effects on Curing and Film Formation / 471
References / 471
23. Application Methods
23.1. Brushes, Pads, and Hand Rollers / 473
23.1.1. Brush and Pad Application / 473
23.1.2. Hand Roller Application / 474
23.2. Spray Application / 475
23.2.1. Air Spray Guns / 476
23.2.2. Airless Spray Guns / 478
23.2.3. Electrostatic Spraying / 479
23.2.4. Hot Spray / 481
23.2.5. Supercritical Fluid Spray / 481
23.2.6. Formulation Considerations for Spray-Applied Coatings /
23.2.7. Overspray Disposal / 484
23.3. Dip and Flow Coating / 484
23.4. Roll Coating / 485
23.5. Curtain Coating / 487
General References / 488
References / 488
24. Film Defects
24.1. Surface Tension / 490
24.2. Leveling / 492
24.3. Sagging and Drip Marks / 496
24.4. Crawling, Cratering, and Related Defects / 499
24.5. Floating and Flooding; Hammer Finishes / 502
24.6. Wrinkling and Wrinkle Finishes / 505
24.7. Bubbling and Popping / 506
24.8. Foaming / 508
24.9. Dirt / 509
General References / 509
References / 509
25. Solventborne and High-Solids Coatings
25.1. Primers / 512
25.1.1. Binders for Primers / 512
25.1.2. Pigmentation of Primers / 513
25.1.3. High-Solids Primers / 514
25.2. Top Coats / 515
25.2.1. Binders for Top Coats / 515
25.2.2. Formulating Solventborne Coatings for Low VOC /
General Reference / 522
References / 522
26. Waterborne Coatings
26.1. Water-Reducible Coatings / 525
26.2. Latex-Based Coatings / 529
26.3. Emulsion Coatings / 532
General References / 533
References / 533
27. Electrodeposition Coatings
27.1. Anionic Electrodeposition Coatings / 536
27.2. Cationic Electrodeposition Coatings / 538
27.3. Effect of Variables on Electrodeposition / 541
27.4. Application of Electrodeposition Coatings / 542
27.5. Advantages and Limitations of Electrodeposition / 544
27.6. Autodeposition Coatings / 545
General Reference / 547
References / 547
28. Powder Coatings
28.1. Binders for Thermosetting Powder Coatings / 548
28.1.1. Epoxy Binders / 550
28.1.2. Hybrid Binders / 550
28.1.3. Polyester Binders / 551
28.1.4. Acrylic Binders / 553
28.1.5. Silicone Binders / 554
28.1.6. UV Cure Powder Coatings / 554
28.2. Binders for Thermoplastic Powder Coatings / 555
28.3. Formulation of Thermosetting Powder Coatings / 555
28.3.1. Low Gloss Powder Coatings / 559
28.4. Manufacture of Powder Coatings / 560
28.4.1. Production / 560
28.4.2. Quality Control / 563
28.5. Application Methods / 564
28.5.1. Electrostatic Spray Application / 564
28.5.2. Other Application Methods / 567
28.6. Advantages and Limitations of Powder Coatings / 569
General References / 571
References / 571
29. Radiation Cure Coatings
29.1. UV Curing / 574
29.2. Free Radical Initiated UV Cure / 578
29.2.1. Unimolecular Photoinitiators / 578
29.2.2. Bimolecular Photoinitiators / 579
29.2.3. Oxygen Inhibition / 580
29.2.4. Vehicles for Free Radical Initiated UV Cure / 581
29.2.5. Waterborne UV Cure Coatings / 584
29.3. Cationic UV Cure / 585
29.3.1. Vehicles for Cationic UV Cure / 585
29.4. Effects of Pigmentation / 586
29.5. Electron Beam Cure Coatings / 588
29.6. Dual UV/Thermal Cure and Selected Applications / 589
29.7. Advantages and Limitations / 591
General References / 593
References / 593
30. Product Coatings for Metal Substrates
30.1. OEM Automotive Coatings / 595
30.1.1. Electrodeposition Coatings and Primer–Surfacers / 596
30.1.2. Top Coats / 597
30.1.3. Factory Repair Procedures / 604
30.2. Appliance Coatings / 605
30.3. Container Coatings / 606
30.3.1. Interior Can Linings / 608
30.3.2. Exterior Can Coatings / 610
30.4. Coil Coating / 611
30.4.1. Advantages and Limitations of Coil Coating / 615
General References / 616
References / 617
31. Product Coatings for Nonmetallic Substrates
31.1. Coatings for Wood / 619
31.1.1. Coatings for Wood Furniture / 619
31.1.2. Panel, Siding, and Flooring Finishes / 626
31.2. Coating of Plastics / 628
31.2.1. In-mold Coating / 628
31.2.2. Post-mold Coating / 629
31.3. Coatings for Glass / 633
General Reference / 634
References / 634
32. Architectural Coatings
32.1. Exterior House Paint / 637
32.2. Flat and Semigloss Paints / 643
32.3. Gloss Enamels / 649
32.3.1. Alkyd Gloss Enamels / 649
32.3.2. Latex Gloss Enamels / 651
General Reference / 655
References / 655
33. Special Purpose Coatings
33.1. Maintenance Paints / 658
33.1.1. Barrier Coating Systems / 659
33.1.2. Systems with Zinc-Rich Primers / 663
33.1.3. Systems with Passivating Pigment Containing Primers / 665
33.2. Marine Coatings / 667
33.3. Automobile Refinish Paints / 670
33.4. Aircraft Coatings / 674
References / 676
34. Perspectives on Coating Design
General References / 687
References / 688
Index
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