Polymer Interface and Adhesion

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1 Polymer Interface and Adhesion SOUHENG WU E. I. du Pont de Nemours &.Company Wilmington, Delaware MARCEL DEKKER, INC. New York and Basel

Preface Acknowledgments 1. INTERFACIAL THERMODYNAMICS 1 1.1 Formulation of Interfacial Thermodynamics 1 1.2 Work of Adhesion and Work of Cohesion 4 1.3 Interfacial and Hydrostatic Equilibrium 5 1.

2 Preface Acknowledgments 1. INTERFACIAL THERMODYNAMICS Formulation of Interfacial Thermodynamics Work of Adhesion and Work of Cohesion Interfacial and Hydrostatic Equilibrium Effect of Curvature on Vapor Pressure and Surface Tension Spreading Pressure and Spreading Coefficient Contact Angle Equilibrium: Young Equation Contact Angle Hysteresis 15 References MOLECULAR INTERPRETATIONS Microscopic Theories of van der Waals Forces Additivity and Fractional Contributions of Various Types of Molecular Forces Approximations for Unlike Molecules Lennard-Jones Potential Energy Function Attraction Between Macroscopic Bodies Macroscopic Theory of van der Waals Forces: The Lifshitz Theory 54 References 62 IX

3. INTERFACIAL AND SURFACE TENSIONS OF POLYMER MELTS AND LIQUIDS 67 3.1 Surface Tensions of Polymer Melts and Liquids 67 3.2 Interfacial Tensions Between Polymers 96 References 129 U.

3 3. INTERFACIAL AND SURFACE TENSIONS OF POLYMER MELTS AND LIQUIDS Surface Tensions of Polymer Melts and Liquids Interfacial Tensions Between Polymers 96 References 129 U. CONTACT ANCLES OF LIQUIDS ON SOLID POLYMERS Equilibrium Spreading Pressure Spreading Coefficient Effect of Temperature on Contact Angle Effect of Primary and Secondary Transitions Contact Angle and Heat of Wetting Polarity of Liquids Prediction of Contact Angles Effect of Solute Adsorption on Contact Angle Tabulation of Equilibrium Contact Angle Distortion of Liquid Surfaces: Marangoni Effect Spreading of Partially Submerged Drops 164 References SURFACE TENSION AND POLARITY OF SOLID POLYMERS Determination of Surface Tension and Polarity Surface Tension and Polarity of Organic Pigments Constitutive Effect on Surface Tension Morphological Effect on Surface Tension Effects of Additives, Polymer Blends, Copolymers, Conformation, and Tacticity on Surface Tension 209 References WETTING OF HICH-ENERCY SURFACES Introduction Spreading on High-Energy Surfaces Effect of Water and Organic Contaminations Kinetics of Surface-Energy Variation 229 References 231

xi 7. DYNAMIC CONTACT ANCLES AND WETTING KINETICS 235 7.1 Introduction 235 7.2 Kinetics of Spontaneous Motion 236 7.3 Kinetics of Forced Motion 247 References 254 8.

4 xi 7. DYNAMIC CONTACT ANCLES AND WETTING KINETICS Introduction Kinetics of Spontaneous Motion Kinetics of Forced Motion 247 References EXPERIMENTAL METHODS FOR CONTACT ANGLES AND INTERFACIAL TENSIONS Measurements of Contact Angles Measurements of Interfacial and Surface Tensions of Polymer Liquids and Melts 266 References MODIFICATIONS OF POLYMER SURFACES: MECHANISMS OF WETTABILITY AND BONDABIL1TY IMPROVEMENTS Chemical Treatments Flame and Thermal Treatments Plasma Treatments Photochemical Treatments Crystalline Modifications of Polymer Surfaces Miscellaneous Modifications 327 References ADHESION: BASIC CONCEPT AND LOCUS OF FAILURE Definitions Basic Concept of Adhesive Bond Strength Locus of Failure 344 References FORMATION OF ADHESIVE BOND Elementary Processes in Adhesive Bond Formation Wetting and Adhesion Diffusion and Adhesion Chemical Adhesion Mechanical Adhesion 434 References

xii Contents 12. WEAK BOUNDARY LAYERS 449 12.1 Weak-Boundary-Layer Theory 449 12.2 Examples of Weak Boundary Layers 450 12.3 Critique of Weak-Boundary-Layer Theory 456 References 460 13.

5 xii Contents 12. WEAK BOUNDARY LAYERS Weak-Boundary-Layer Theory Examples of Weak Boundary Layers Critique of Weak-Boundary-Layer Theory 456 References EFFECT OF INTERNAL STRESS ON BOND STRENGTH Shrinkage of a Coating Adhering to a Substrate Free Thickness Contraction in a Butt Joint No Thickness Contraction in a Sandwich Structure No Thickness Contraction in a Long, Narrow Adhesive Layer in an Annulus 472 References FRACTURE OF ADHESIVE BOND 475 Part I. Fundamentals of Fracture Mechanics Linear Elastic Fracture Mechanics Local Plastic Flow Generalization of Flaw Theory to Viscoelastic Materials: Rivlin and Thomas Theory Properties of Fracture Energy 488 Part II. Analysis and Testing of Adhesive Bonds Tensile Tests (Butt Joints) Shear Tests (Lap Joints) Peel Tests (Peel Joints) Cantilever Beam Tests Other Fracture Energy Tests 560 References CREEP, FATIGUE, AND ENVIRONMENTAL EFFECTS 571 Part I. Creep and Fatigue of Adhesive Joints Creep Fracture Fatigue Fracture 579

Part II. Environmental Effects 586 15.3 Spontaneous Separation 589 15.4 Effect of Interfacial Chemical Bonds 593 15.

6 Part II. Environmental Effects Spontaneous Separation Effect of Interfacial Chemical Bonds Stress Corrosion Cracking and Fatigue in Wet Environment 603 References 609 Appendix I: Calculation of Surface Tension and Its Nonpolar and Polar Components from Contact Angles by the Harmonic-Mean and the Geometric-Mean Methods 613 Appendix II: Unit Conversion Tables 619 Index 621

Introduction to Joining Processes

Introduction to Joining Processes 4. TEST METHODS Joints are generally designed to support a load, and must be tested to evaluate their load-supporting capabilities. However, it is also important to evaluate, not the joint, but rather