Wen / Dusek / Dušek Protective Coatings

Film Formation and Properties
1. Auflage 2017
ISBN: 978-3-319-51627-1
Verlag: Springer Nature Switzerland
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 504 Seiten

This book focuses on characterization of organic coatings by different testing methods and understanding of structure formation and materials properties. The knowledge of protective organic coatings and current test methods is based largely on empirical experience. This book aims at explaining the coating property changes during film drying and curing in terms of chemical and physical transformations. Current test methods are reviewed with emphasis on understanding their physical basis and expressing the test results in terms of comparable physical quantities. In general, this book provides readers a deeper understanding of the binder design, coating film formation process, properties build-up, appearance and defect formation, and automotive paint application. It also suggests manifold ways to improving the coatings performance.This book is designed for coating professionals to gain deeper understanding of characterization techniques and to select the right ones to solve their coating problems. It is ideal for both experienced and early career scientists and engineers. Also, it is useful for graduate students in the general area of protective coatings.


Mei Wen is a Research Associate at Axalta Coating Systems, located at the Coatings Technology Center in Wilmington, Delaware.  She has worked in the chemical industry for fifteen years, with her primary focus being directed toward organic coatings.  Since joining Axalta Coating Systems in 2013, she has worked on clearcoats for Automotive Coatings and leads an academic collaboration between Axalta and the Institute of Macromolecular Chemistry, Prague, Czech Republic on coatings film formation.  Prior to her current work, Dr. Wen worked at Arkema for ten years on acrylic, polyurethane, epoxy, marine antifoulant, mesoporous titanium oxide, and transparent conductive oxide coatings.   She served as a Director on the Board for the International Society of Coating Science and Technology (ISCST) from 2008 to 2012.  She was selected to attend the National Academy of Engineering's U.S. Frontiers of Engineering Symposium in 2007.  In 2005 she received an R&D 100 award on Marine Antifoulant Coating binders with her colleagues and was an invited speaker at Gordon Research Conference for Coatings and Films. Prior to her time at Arkema, Dr. Wen also worked for Applied Materials on electroplating of copper. She has published 26 technical papers. She received her B.S. and M.S. degrees of Chemical Engineering from Tsinghua University in 1987 and 1995, respectively, and her Ph.D. degree of Chemical Engineering from University of Minnesota in 2001.
Karel Dušek is at present Emeritus Professor of Institute of Macromolecular Chemistry (IMC), Academy of Sciences of the Czech Republic. He served for this institution since 1965 in various positions, since 1973 as Principal Scientist and Head of Department of Mechanical Properties and Polymer Networks; in the period 1975-1991 he headed the joint Department of Polymer Physics. He obtained his PhD degree from Institute of Physical Chemistry, Czechoslovak Academy of Sciences in 1958, and worked for SYNPO Research Establishment in Pardubice, CZ, until 1965. His educational and research activities included polymer physics and chemistry at Charles University in Prague, University of Pardubice, and visiting professorships at Technical University, Delft (The Netherlands), University of Essex (UK), University of Massachusetts in Amherst (USA), Kyoto Institute of Technology (Japan), University of Pau and INSA Lyon (France). Since 1997, he is Adjunct Professor of Bioengineering Department of University of Utah in Salt Lake City. In 1997, he was honored by the Doctor Honoris Causa degree by Wroclaw Technical University (Poland). Other honors and awards included State Prize of Czechoslovak Republic in 1988, Silver Medal of City of Paris in 1990, Heyrovský Medal for Merits in Chemical Sciences in 2000, P.J. Flory Polymer Research Award in 2004; he was awarded three times by Annual Prize of the Academy of Sciences. Prof. Dušek is Founding Member of Polymer Networks Group (1974), served as Chairman, Vice-Chairman, and Treasurer and organized three of the biennial meetings.  He is also Founding Member of Learned Society of the Czech Republic. He served as Editor in seven scientific journals. On European Union scene, Prof. Dušek served as Coordinator of Area of Excellence 'Structure-Property Relationships' of Network of Excellence Nanostructured Multifunctional Polymer-Based Materials and Nanocomposites and as Coordinator of Czech representation in this Network. By January 2013, he published about 300 scientific papers with over 7700 citations and his H-index was 43.

Autoren/Hrsg.

Wen, Mei

Dusek, Karel

Dušek, Karel

Inhaltsverzeichnis

1;Preface;5
2;Contents;7
3;Part I: Network Formation and Modeling;9
3.1;Chapter 1: Role of Distributions in Binders and Curatives and Their Effect on Network Evolution and Structure;10
3.1.1;Introduction;10
3.1.2;Distributions-Description and Transformation;11
3.1.3;Distributions in Coatings Binders;12
3.1.3.1;Distributions in Commercial Starting Components;13
3.1.3.1.1;Functionality Distribution in Polyisocyanates;13
3.1.3.1.2;Functionality and Molecular Weight Distributions in Telechelics;15
3.1.3.2;Distributions Generated by Side Reactions;15
3.1.3.3;Two-Stage Reactive Systems-Preparation of a Precursor in the First Stage and Its Cross-Linking in the Second Stage;16
3.1.3.3.1;Functional Copolymers;17
3.1.3.3.2;Hyperbranched Polymers;20
3.1.3.3.3;Off-Stoichiometric (Highly Branched) Copolyadducts;24
3.1.3.3.4;Systems with Distributions of Groups of Different Reactivities;28
3.1.3.3.5;Chain-Extended Systems;30
3.1.3.4;Multistage Network Formation Processes;34
3.1.4;Conclusions;36
3.1.5;Appendix;37
3.1.5.1;Definitions of Distributions and Their Transform Using the Formalism of Probability Generating Functions;37
3.1.5.2;Probability Generating Functions;37
3.1.5.3;Degree of Polymerization and Molecular Weight Distributions;39
3.1.5.4;Functionality Distributions;41
3.1.5.5;Distribution of Reaction States of Building Units in the Branching Process;41
3.1.6;References;42
3.2;Chapter 2: Heterogeneity in Crosslinked Polymer Networks: Molecular Dynamics Simulations;45
3.2.1;Introduction;45
3.2.2;Background;46
3.2.3;Model and Simulation Method;48
3.2.4;Heterogeneities in Network Polymers;51
3.2.4.1;Local-Scale Heterogeneities;53
3.2.4.2;Extended Heterogeneities;56
3.2.4.3;Swelling and Voids;60
3.2.5;Summary;67
3.2.6;References;69
3.3;Chapter 3: Rigidity Percolation Modeling of Modulus Development During Free-Radical Crosslinking Polymerization;72
3.3.1;Introduction;72
3.3.2;Network Load-Displacement Relationship;76
3.3.3;Modeling Method;80
3.3.4;Results and Discussion;85
3.3.4.1;Stress Distribution;86
3.3.4.2;Effect of Initiation Rate Constant;89
3.3.4.3;Effect of Primary Cyclization Rate Constant;92
3.3.5;Conclusions;93
3.3.6;References;94
4;Part II: Coating Film Formation and Properties;98
4.1;Chapter 4: Rheology Measurement for Automotive Coatings;99
4.1.1;Introduction;99
4.1.2;Viscosity in Simple Shear;100
4.1.3;Viscometers Used in Coatings Industry;102
4.1.4;Structures Causing Non-Newtonian Behavior;103
4.1.5;Viscometry Test Practices;104
4.1.6;Viscometry Applied to Paint Formulations;111
4.1.7;Dynamic Oscillatory Rheology;112
4.1.8;Nonlinear Dynamic Oscillatory Rheology;116
4.1.9;Summary/Outlook;116
4.1.10;References;117
4.2;Chapter 5: Magnetic Microrheology for Characterization of Viscosity in Coatings;118
4.2.1;Introduction;118
4.2.2;Magnetic Microrheometry for In Situ Characterization of Coating Viscosity;120
4.2.2.1;Magnetic Microrheometer Designed for Coatings;120
4.2.2.2;Coating Viscosity as a Function of Time and Position;123
4.2.3;Magnetic Microrheology of a Coating Used in Tissue Making;126
4.2.3.1;Experimental Methods;127
4.2.3.1.1;Magnetic Microrheometer Setup;127
4.2.3.1.2;Coating Formulations;128
4.2.3.1.3;Probe Particles;128
4.2.3.1.4;Imaging, Data Collection, and Analysis;131
4.2.3.1.5;Comparison with Traditional Rheology;132
4.2.3.2;Results and Discussion;132
4.2.3.2.1;Noncrosslinking PAE (NX PAE) Solutions;132
4.2.3.2.2;Plasticizer Concentration in NX PAE;134
4.2.3.2.3;Effect of Crosslinking Potential;136
4.2.4;Summary;137
4.2.5;References;138
4.3;Chapter 6: CryoSEM: Revealing Microstructure Development in Drying Coatings;140
4.3.1;Introduction;140
4.3.2;Scanning Electron Microscopy;141
4.3.3;Cryogenic Scanning Electron Microscopy (cryoSEM);142
4.3.3.1;Vitrification;142
4.3.3.2;Cryo-fracture;145
4.3.3.3;Sublimation;146
4.3.3.4;Artifacts of CryoSEM Sample Preparation;147
4.3.4;Examples of CryoSEM Characterization in Coatings Research;149
4.3.5;Conclusions;153
4.3.6;References;154
4.4;Chapter 7: Film Formation Through Designed Diffusion Technology;156
4.4.1;Introduction;156
4.4.2;Model and Mechanism of Designed Diffusion Technology;158
4.4.3;Design and Synthesis of the Designed Diffusion Polymers;159
4.4.4;Physical and Analytical Results and Discussion;160
4.4.4.1;Acceleration of Hardness Development;160
4.4.4.2;VOC Reduction Without Compromising Film Formation;161
4.4.4.3;Coalescent (Texanol) Partitioning between Polymer A and Designed Diffusion Polymer DD;162
4.4.4.4;Percolation Threshold and Accelerated Diffusion or Permeation Pathways;164
4.4.4.5;Effect of Coalescent Boiling Point;165
4.4.4.6;Ultimate Hardness of the Dominant Phase Polymer A as a Function of its Tg;166
4.4.4.7;Tg Effect of Designed Diffusion Polymer DD;167
4.4.5;Application Results and Discussion;168
4.4.6;Conclusions;170
4.4.7;References;171
4.5;Chapter 8: In Situ FTIR Study of Cure Kinetics of Coatings with Controlled Humidity;172
4.5.1;Background;172
4.5.2;Experimental;175
4.5.2.1;Materials;175
4.5.2.2;Sample Preparation;175
4.5.2.3;Humidity Control System;177
4.5.2.4;FTIR Kinetic Study;179
4.5.3;Results and Discussion;179
4.5.3.1;FTIR with Humidity Control;179
4.5.3.1.1;Bubbler DI Water Temperature Effect;179
4.5.3.1.2;Temperature Control and Condensation;180
4.5.3.1.3;Background Collection;181
4.5.3.1.4;Humidity Control;182
4.5.3.2;Kinetics of HDI Trimer Reacting with Water;182
4.5.3.3;Kinetics of HDI Trimer Reacting with Acrylic Polyol;187
4.5.4;Conclusions;193
4.5.5;References;194
4.6;Chapter 9: Shrinkage in UV-Curable Coatings;197
4.6.1;Introduction;197
4.6.2;Fundamentals and Applications of UV-Curable Coatings;197
4.6.3;Character and Influence of Shrinkage on UV-Curable Coatings;198
4.6.4;Measurement and Evaluations of Shrinkage in UV-Curable Coatings;200
4.6.4.1;Dilatometry Method;200
4.6.4.2;Pycnometer Method;201
4.6.4.3;Buoyancy Method;203
4.6.4.4;Bonded-Disk Method;204
4.6.4.5;Interferometer Method;205
4.6.4.6;Laser Displacement Method;206
4.6.4.7;Laser Scanning Method;207
4.6.4.8;Video-Imaging Device Method;208
4.6.4.9;Linometer and NIR Spectroscopy Combination Method;209
4.6.4.10;Photorheometry and NIR Spectroscopy Combination Method;209
4.6.5;Methods of Controlling the Shrinkage;210
4.6.5.1;The Condition of Photopolymerization;211
4.6.5.2;Addition of Inert Component;212
4.6.5.3;Adjusting the Structure of Monomers;212
4.6.5.3.1;The Density of Functional Groups;212
4.6.5.3.2;Structure Rigidity and Steric Hindrance;214
4.6.5.3.3;Ring-Opening Polymerization;214
4.6.5.3.4;Thiol-Containing System;216
4.6.5.3.5;Hybrid System;218
4.6.5.4;Solid-State Photopolymerization;219
4.6.6;Summary and Developing Prospects of Shrinkage Research in UV Curing;220
4.6.7;References;221
4.7;Chapter 10: Measurements of Stress Development in Latex Coatings;226
4.7.1;Introduction;226
4.7.2;Experimental;230
4.7.2.1;Stress Measurement;230
4.7.2.2;Minimum Film Formation Temperature;232
4.7.2.3;Latex;233
4.7.3;Results and Discussion;234
4.7.3.1;Effect of MFFT on Stress Development;234
4.7.3.2;Effect of Coalescing Aids on Film Stress Development;236
4.7.4;Conclusions;238
4.7.5;References;240
4.8;Chapter 11: Stress Development in Reactive Coatings;242
4.8.1;Introduction;242
4.8.2;Stress Measurement;245
4.8.3;Experimental;249
4.8.3.1;Synthesis of Acrylic Polyols;249
4.8.3.2;Molecular Weight;250
4.8.3.3;Coating Solutions;251
4.8.3.4;NCO Conversion;251
4.8.3.5;Glass Transition Temperature;252
4.8.3.6;Pendulum Hardness;252
4.8.3.7;Coating Stress;252
4.8.4;Results and Discussion;253
4.8.4.1;Effect of Monomer Type in Acrylic Polyols;253
4.8.4.2;Effect of Molecular Weight of Acrylic Polyol;257
4.8.4.3;Effect of Crosslink Density;257
4.8.4.4;Effect of Addition of Low-Tg Polyester;261
4.8.4.5;Effect of Solvent Addition;263
4.8.4.6;Effect of Baking During Film Formation;264
4.8.5;Conclusions;265
4.8.6;References;266
5;Part III: Coating Film Properties and Applications;269
5.1;Chapter 12: Swelling of Coating Films;270
5.1.1;Introduction;270
5.1.2;Degree of Swelling and Its Determination;271
5.1.2.1;Evolution of Network Structure;272
5.1.3;Theoretical Models of Equilibrium Swelling of Cross-Linked Polymers;274
5.1.3.1;Swelling of Networks of Gaussian Chains;275
5.1.3.2;Considering Finite Extensibility of Network Chains;277
5.1.3.3;Swelling of Adhering Coating Film;278
5.1.3.4;Effect of Constraints During Film Formation on Swelling of Detached Film;278
5.1.3.5;Effect of the Polymer-Solvent Interaction Parameter;280
5.1.4;Effect of Structural Parameters of the Network on Swelling and the Swell Test;282
5.1.5;The Swell Test as a Measure of Changes in Cross-Link Density or Solvent Quality;284
5.1.5.1;Correlations with Experiment;284
5.1.5.2;Pitfalls of the Swell Test;288
5.1.6;Conclusions;288
5.1.7;References;289
5.2;Chapter 13: Chemical Depth Profiling of a Multilayer Coating System Using Slab Microtomy and FTIR-ATR Analysis;291
5.2.1;Background;291
5.2.2;Experimental;293
5.2.2.1;Sample Preparation;293
5.2.2.2;Optical Microscope Imaging;293
5.2.2.3;Microtoming;294
5.2.2.4;FTIR-ATR;295
5.2.2.5;Indentation Hardness;295
5.2.3;Results and Discussion;296
5.2.4;Summary;308
5.2.5;References;309
5.3;Chapter 14: Characterization of Component Distributions in Acrylic Latex and Paint Films Containing an Alkali-Soluble Resin (A...;311
5.3.1;Introduction;311
5.3.2;Experimental;313
5.3.2.1;Materials;313
5.3.2.2;Latex Film Analyses;314
5.3.2.2.1;Water Contact Angle;314
5.3.2.2.2;Atomic Force Microscopy (AFM);314
5.3.2.2.3;Confocal Raman Microscopy (CRM);314
5.3.2.3;Paint Film Analyses;315
5.3.2.3.1;Paint Formulation and Film Preparation;315
5.3.3;Results and Discussion;316
5.3.3.1;WaterContact Angle on Acrylic Polymer and ASR/AL Blends;316
5.3.3.2;Film Morphology and ASR Distribution;317
5.3.3.3;ASR Distribution in Latex Films;318
5.3.3.4;ASR Distribution in Paint Films;321
5.3.3.5;Surfactant Enrichment on Paint 1 Film;324
5.3.4;Conclusions;327
5.3.5;References;327
5.4;Chapter 15: Advances in NanoScratch Testing of Automotive Clearcoats;330
5.4.1;Introduction;330
5.4.2;Experimental Methodology;332
5.4.2.1;Materials;332
5.4.2.2;Test Procedure;333
5.4.2.2.1;Scratch Test Conditions;335
5.4.2.2.2;Scratching Coefficient of Friction;335
5.4.2.3;Scratch Morphology;336
5.4.2.3.1;Optical Microscope;336
5.4.2.3.2;Atomic Force Microscopy;336
5.4.3;Results and Discussion;336
5.4.3.1;Indenter Characterization;337
5.4.3.2;Determination of Fracture Threshold;339
5.4.3.3;Measurement of Plastic Resistance;339
5.4.3.4;Measurement of Scratch Recovery;340
5.4.3.5;Scratch Visibility;343
5.4.3.6;Statistical Comparison Between Materials;346
5.4.4;Conclusion;351
5.4.5;Appendix MATLAB and Kornucopia ML Analysis of Scratch Data;352
5.4.6;References;356
5.5;Chapter 16: Scratch and Mar Resistance of Automotive Coatings;357
5.5.1;Introduction;357
5.5.2;Experimental;359
5.5.3;Scratch and Mar Resistance Test Methods;359
5.5.3.1;Crockmeter-2mum;360
5.5.3.2;Crockmeter-9mum;361
5.5.3.3;Amtec Kistler Car Wash;361
5.5.3.4;Nano Scratch;361
5.5.4;Results and Discussion;363
5.5.4.1;Effect of Crosslink Density on Scratch and Mar Resistance;363
5.5.4.2;Chain Elasticity vs. Scratch and Mar Resistance;364
5.5.4.3;Aging and Weathering Effect on Scratch and Mar Resistance;366
5.5.4.4;Nanotechnology;368
5.5.5;Conclusions;371
5.5.6;References;372
5.6;Chapter 17: Appearance of Automotive Coatings;373
5.6.1;Introduction;373
5.6.2;Experimental;376
5.6.3;Results and Discussion;377
5.6.3.1;Film Formation: Low- vs. High-Bake Coatings;377
5.6.3.2;Flow and Leveling;379
5.6.3.3;Substrate Telegraphing;385
5.6.3.4;Gradients of Drying and Curing;388
5.6.3.5;Multi-Layer Compatibility;390
5.6.3.6;Consolidated Systems;394
5.6.4;Conclusions;397
5.6.5;References;397
5.7;Chapter 18: Craters and Other Coatings Defects: Mechanisms and Analysis;399
5.7.1;Introduction;399
5.7.2;Surface Tension-Driven Defects;399
5.7.2.1;Craters;400
5.7.2.1.1;General;400
5.7.2.1.2;Surface Flow;401
5.7.2.1.3;Crater Formation Time;403
5.7.2.1.4;Crater Size and Contaminant Volume;404
5.7.2.1.5;Causes of Craters;404
5.7.2.1.6;Crater Prevention;405
5.7.2.2;Wetting and Dewetting;406
5.7.2.3;Picture Framing (Fat Edges);407
5.7.2.4;Telegraphing;408
5.7.2.5;Convection Flow Defects;409
5.7.2.6;Wrinkling;411
5.7.3;Volatile-Related Defects;412
5.7.3.1;Popping;413
5.7.3.2;Gassing;415
5.7.3.3;Air Entrapment;417
5.7.4;Defects Related to Flow or Lack of It;418
5.7.4.1;Sagging;418
5.7.4.2;Poor Leveling and Orange Peel;418
5.7.5;Conclusions;419
5.7.6;References;420
5.8;Chapter 19: Degradation of Polymer Coatings in Service: How Properties Deteriorate Due to Stochastic Damage;422
5.8.1;Introduction;422
5.8.2;Background;423
5.8.2.1;Opportunities for Degradation;423
5.8.2.2;Statistics of Random Events;425
5.8.2.3;Intrinsic Defects in Crosslinked Networks;426
5.8.3;Degradation Kinetics of Physical Properties;427
5.8.3.1;Gloss;429
5.8.3.2;Toughness;432
5.8.3.3;Other Degradation Kinetics;435
5.8.3.4;Nonsimultaneous Degradation;438
5.8.4;Summary;441
5.8.5;References;443
5.9;Chapter 20: Long-Term Mechanical Durability of Coatings;446
5.9.1;Introduction;446
5.9.2;Fracture Mechanics;447
5.9.2.1;Crack Initiation;447
5.9.2.2;Crack Propagation;449
5.9.3;Stresses in Organic Coatings;450
5.9.4;Long-Term Resistance to Cracking in Coatings;452
5.9.5;Evolution of Cracking Patterns;455
5.9.6;Conclusions;456
5.9.7;References;457
5.10;Chapter 21: Automotive Paint Application;459
5.10.1;Introduction;459
5.10.2;The Evolution of Automotive Coating Application from 1980 to Today;460
5.10.3;Typical Automotive Coating Sequence;463
5.10.3.1;Conversion Coating;463
5.10.3.2;Electrocoat;464
5.10.3.3;Primer, Basecoat, and Clearcoat;464
5.10.4;Practical Application;465
5.10.4.1;Uniform Film;465
5.10.5;Predicting Deposited Film Thickness from Application Parameters;471
5.10.5.1;Flow Rate Calculation Example;472
5.10.5.2;Transfer Efficiency Example Calculation;475
5.10.5.3;Wet Film Nonvolatiles;476
5.10.6;Atomization;477
5.10.6.1;Pneumatic Atomization;478
5.10.6.2;Rotary Atomization;482
5.10.6.3;Electrostatic Deposition by Rotary Atomizer;488
5.10.7;Summary;489
5.10.8;References;489
6;Index;491