Preface	5
	Contents	7
	Part I: Network Formation and Modeling	9
	Chapter 1: Role of Distributions in Binders and Curatives and Their Effect on Network Evolution and Structure	10
	Introduction	10
	Distributions-Description and Transformation	11
	Distributions in Coatings Binders	12
	Distributions in Commercial Starting Components	13
	Functionality Distribution in Polyisocyanates	13
	Functionality and Molecular Weight Distributions in Telechelics	15
	Distributions Generated by Side Reactions	15
	Two-Stage Reactive Systems-Preparation of a Precursor in the First Stage and Its Cross-Linking in the Second Stage	16
	Functional Copolymers	17
	Hyperbranched Polymers	20
	Off-Stoichiometric (Highly Branched) Copolyadducts	24
	Systems with Distributions of Groups of Different Reactivities	28
	Chain-Extended Systems	30
	Multistage Network Formation Processes	34
	Conclusions	36
	Appendix	37
	Definitions of Distributions and Their Transform Using the Formalism of Probability Generating Functions	37
	Probability Generating Functions	37
	Degree of Polymerization and Molecular Weight Distributions	39
	Functionality Distributions	41
	Distribution of Reaction States of Building Units in the Branching Process	41
	References	42
	Chapter 2: Heterogeneity in Crosslinked Polymer Networks: Molecular Dynamics Simulations	45
	Introduction	45
	Background	46
	Model and Simulation Method	48
	Heterogeneities in Network Polymers	51
	Local-Scale Heterogeneities	53
	Extended Heterogeneities	56
	Swelling and Voids	60
	Summary	67
	References	69
	Chapter 3: Rigidity Percolation Modeling of Modulus Development During Free-Radical Crosslinking Polymerization	72
	Introduction	72
	Network Load-Displacement Relationship	76
	Modeling Method	80
	Results and Discussion	85
	Stress Distribution	86
	Effect of Initiation Rate Constant	89
	Effect of Primary Cyclization Rate Constant	92
	Conclusions	93
	References	94
	Part II: Coating Film Formation and Properties	98
	Chapter 4: Rheology Measurement for Automotive Coatings	99
	Introduction	99
	Viscosity in Simple Shear	100
	Viscometers Used in Coatings Industry	102
	Structures Causing Non-Newtonian Behavior	103
	Viscometry Test Practices	104
	Viscometry Applied to Paint Formulations	111
	Dynamic Oscillatory Rheology	112
	Nonlinear Dynamic Oscillatory Rheology	116
	Summary/Outlook	116
	References	117
	Chapter 5: Magnetic Microrheology for Characterization of Viscosity in Coatings	118
	Introduction	118
	Magnetic Microrheometry for In Situ Characterization of Coating Viscosity	120
	Magnetic Microrheometer Designed for Coatings	120
	Coating Viscosity as a Function of Time and Position	123
	Magnetic Microrheology of a Coating Used in Tissue Making	126
	Experimental Methods	127
	Magnetic Microrheometer Setup	127
	Coating Formulations	128
	Probe Particles	128
	Imaging, Data Collection, and Analysis	131
	Comparison with Traditional Rheology	132
	Results and Discussion	132
	Noncrosslinking PAE (NX PAE) Solutions	132
	Plasticizer Concentration in NX PAE	134
	Effect of Crosslinking Potential	136
	Summary	137
	References	138
	Chapter 6: CryoSEM: Revealing Microstructure Development in Drying Coatings	140
	Introduction	140
	Scanning Electron Microscopy	141
	Cryogenic Scanning Electron Microscopy (cryoSEM)	142
	Vitrification	142
	Cryo-fracture	145
	Sublimation	146
	Artifacts of CryoSEM Sample Preparation	147
	Examples of CryoSEM Characterization in Coatings Research	149
	Conclusions	153
	References	154
	Chapter 7: Film Formation Through Designed Diffusion Technology	156
	Introduction	156
	Model and Mechanism of Designed Diffusion Technology	158
	Design and Synthesis of the Designed Diffusion Polymers	159
	Physical and Analytical Results and Discussion	160
	Acceleration of Hardness Development	160
	VOC Reduction Without Compromising Film Formation	161
	Coalescent (Texanol) Partitioning between Polymer A and Designed Diffusion Polymer DD	162
	Percolation Threshold and Accelerated Diffusion or Permeation Pathways	164
	Effect of Coalescent Boiling Point	165
	Ultimate Hardness of the Dominant Phase Polymer A as a Function of its Tg	166
	Tg Effect of Designed Diffusion Polymer DD	167
	Application Results and Discussion	168
	Conclusions	170
	References	171
	Chapter 8: In Situ FTIR Study of Cure Kinetics of Coatings with Controlled Humidity	172
	Background	172
	Experimental	175
	Materials	175
	Sample Preparation	175
	Humidity Control System	177
	FTIR Kinetic Study	179
	Results and Discussion	179
	FTIR with Humidity Control	179
	Bubbler DI Water Temperature Effect	179
	Temperature Control and Condensation	180
	Background Collection	181
	Humidity Control	182
	Kinetics of HDI Trimer Reacting with Water	182
	Kinetics of HDI Trimer Reacting with Acrylic Polyol	187
	Conclusions	193
	References	194
	Chapter 9: Shrinkage in UV-Curable Coatings	197
	Introduction	197
	Fundamentals and Applications of UV-Curable Coatings	197
	Character and Influence of Shrinkage on UV-Curable Coatings	198
	Measurement and Evaluations of Shrinkage in UV-Curable Coatings	200
	Dilatometry Method	200
	Pycnometer Method	201
	Buoyancy Method	203
	Bonded-Disk Method	204
	Interferometer Method	205
	Laser Displacement Method	206
	Laser Scanning Method	207
	Video-Imaging Device Method	208
	Linometer and NIR Spectroscopy Combination Method	209
	Photorheometry and NIR Spectroscopy Combination Method	209
	Methods of Controlling the Shrinkage	210
	The Condition of Photopolymerization	211
	Addition of Inert Component	212
	Adjusting the Structure of Monomers	212
	The Density of Functional Groups	212
	Structure Rigidity and Steric Hindrance	214
	Ring-Opening Polymerization	214
	Thiol-Containing System	216
	Hybrid System	218
	Solid-State Photopolymerization	219
	Summary and Developing Prospects of Shrinkage Research in UV Curing	220
	References	221
	Chapter 10: Measurements of Stress Development in Latex Coatings	226
	Introduction	226
	Experimental	230
	Stress Measurement	230
	Minimum Film Formation Temperature	232
	Latex	233
	Results and Discussion	234
	Effect of MFFT on Stress Development	234
	Effect of Coalescing Aids on Film Stress Development	236
	Conclusions	238
	References	240
	Chapter 11: Stress Development in Reactive Coatings	242
	Introduction	242
	Stress Measurement	245
	Experimental	249
	Synthesis of Acrylic Polyols	249
	Molecular Weight	250
	Coating Solutions	251
	NCO Conversion	251
	Glass Transition Temperature	252
	Pendulum Hardness	252
	Coating Stress	252
	Results and Discussion	253
	Effect of Monomer Type in Acrylic Polyols	253
	Effect of Molecular Weight of Acrylic Polyol	257
	Effect of Crosslink Density	257
	Effect of Addition of Low-Tg Polyester	261
	Effect of Solvent Addition	263
	Effect of Baking During Film Formation	264
	Conclusions	265
	References	266
	Part III: Coating Film Properties and Applications	269
	Chapter 12: Swelling of Coating Films	270
	Introduction	270
	Degree of Swelling and Its Determination	271
	Evolution of Network Structure	272
	Theoretical Models of Equilibrium Swelling of Cross-Linked Polymers	274
	Swelling of Networks of Gaussian Chains	275
	Considering Finite Extensibility of Network Chains	277
	Swelling of Adhering Coating Film	278
	Effect of Constraints During Film Formation on Swelling of Detached Film	278
	Effect of the Polymer-Solvent Interaction Parameter	280
	Effect of Structural Parameters of the Network on Swelling and the Swell Test	282
	The Swell Test as a Measure of Changes in Cross-Link Density or Solvent Quality	284
	Correlations with Experiment	284
	Pitfalls of the Swell Test	288
	Conclusions	288
	References	289
	Chapter 13: Chemical Depth Profiling of a Multilayer Coating System Using Slab Microtomy and FTIR-ATR Analysis	291
	Background	291
	Experimental	293
	Sample Preparation	293
	Optical Microscope Imaging	293
	Microtoming	294
	FTIR-ATR	295
	Indentation Hardness	295
	Results and Discussion	296
	Summary	308
	References	309
	Chapter 14: Characterization of Component Distributions in Acrylic Latex and Paint Films Containing an Alkali-Soluble Resin (A...	311
	Introduction	311
	Experimental	313
	Materials	313
	Latex Film Analyses	314
	Water Contact Angle	314
	Atomic Force Microscopy (AFM)	314
	Confocal Raman Microscopy (CRM)	314
	Paint Film Analyses	315
	Paint Formulation and Film Preparation	315
	Results and Discussion	316
	WaterContact Angle on Acrylic Polymer and ASR/AL Blends	316
	Film Morphology and ASR Distribution	317
	ASR Distribution in Latex Films	318
	ASR Distribution in Paint Films	321
	Surfactant Enrichment on Paint 1 Film	324
	Conclusions	327
	References	327
	Chapter 15: Advances in NanoScratch Testing of Automotive Clearcoats	330
	Introduction	330
	Experimental Methodology	332
	Materials	332
	Test Procedure	333
	Scratch Test Conditions	335
	Scratching Coefficient of Friction	335
	Scratch Morphology	336
	Optical Microscope	336
	Atomic Force Microscopy	336
	Results and Discussion	336
	Indenter Characterization	337
	Determination of Fracture Threshold	339
	Measurement of Plastic Resistance	339
	Measurement of Scratch Recovery	340
	Scratch Visibility	343
	Statistical Comparison Between Materials	346
	Conclusion	351
	Appendix MATLAB and Kornucopia ML Analysis of Scratch Data	352
	References	356
	Chapter 16: Scratch and Mar Resistance of Automotive Coatings	357
	Introduction	357
	Experimental	359
	Scratch and Mar Resistance Test Methods	359
	Crockmeter-2mum	360
	Crockmeter-9mum	361
	Amtec Kistler Car Wash	361
	Nano Scratch	361
	Results and Discussion	363
	Effect of Crosslink Density on Scratch and Mar Resistance	363
	Chain Elasticity vs. Scratch and Mar Resistance	364
	Aging and Weathering Effect on Scratch and Mar Resistance	366
	Nanotechnology	368
	Conclusions	371
	References	372
	Chapter 17: Appearance of Automotive Coatings	373
	Introduction	373
	Experimental	376
	Results and Discussion	377
	Film Formation: Low- vs. High-Bake Coatings	377
	Flow and Leveling	379
	Substrate Telegraphing	385
	Gradients of Drying and Curing	388
	Multi-Layer Compatibility	390
	Consolidated Systems	394
	Conclusions	397
	References	397
	Chapter 18: Craters and Other Coatings Defects: Mechanisms and Analysis	399
	Introduction	399
	Surface Tension-Driven Defects	399
	Craters	400
	General	400
	Surface Flow	401
	Crater Formation Time	403
	Crater Size and Contaminant Volume	404
	Causes of Craters	404
	Crater Prevention	405
	Wetting and Dewetting	406
	Picture Framing (Fat Edges)	407
	Telegraphing	408
	Convection Flow Defects	409
	Wrinkling	411
	Volatile-Related Defects	412
	Popping	413
	Gassing	415
	Air Entrapment	417
	Defects Related to Flow or Lack of It	418
	Sagging	418
	Poor Leveling and Orange Peel	418
	Conclusions	419
	References	420
	Chapter 19: Degradation of Polymer Coatings in Service: How Properties Deteriorate Due to Stochastic Damage	422
	Introduction	422
	Background	423
	Opportunities for Degradation	423
	Statistics of Random Events	425
	Intrinsic Defects in Crosslinked Networks	426
	Degradation Kinetics of Physical Properties	427
	Gloss	429
	Toughness	432
	Other Degradation Kinetics	435
	Nonsimultaneous Degradation	438
	Summary	441
	References	443
	Chapter 20: Long-Term Mechanical Durability of Coatings	446
	Introduction	446
	Fracture Mechanics	447
	Crack Initiation	447
	Crack Propagation	449
	Stresses in Organic Coatings	450
	Long-Term Resistance to Cracking in Coatings	452
	Evolution of Cracking Patterns	455
	Conclusions	456
	References	457
	Chapter 21: Automotive Paint Application	459
	Introduction	459
	The Evolution of Automotive Coating Application from 1980 to Today	460
	Typical Automotive Coating Sequence	463
	Conversion Coating	463
	Electrocoat	464
	Primer, Basecoat, and Clearcoat	464
	Practical Application	465
	Uniform Film	465
	Predicting Deposited Film Thickness from Application Parameters	471
	Flow Rate Calculation Example	472
	Transfer Efficiency Example Calculation	475
	Wet Film Nonvolatiles	476
	Atomization	477
	Pneumatic Atomization	478
	Rotary Atomization	482
	Electrostatic Deposition by Rotary Atomizer	488
	Summary	489
	References	489
	Index	491