Adhesion: Current Research and Applications

Contents


            Preface   V

                                    X MII
            List o f Contributors

           The lnterfacial Chemistry of Adhesion:
1
           Novel Routes to the Holy Grail? 1
           J . F. Watts
           Abstract 1
1.1        Introduction 1
1.2        Development of a Model Interphase 3
1.3        The Buried Interface 8
1.4        Conclusion 15
           Acknowledgments 15
           References 15

2          Modeling Fundamental Aspects o f the Surface Chemistry
           of Oxides and their lnteractions with Coupling Agents 1 7
           P. Schrffels, M. Amkreutz, A. T: B lumenau, T: Krüger, B. Schneider,
           T: Frauenheim, a nd 0 . - D. H ennemann
           Abstract 17
2.1        Introduction: Atomistic Simulations in Adhesion 1 7
2.2        Prediction of Surface Properties: Ideal Reconstructions
           on a-Si02(0001) 19
           Organic Components of the Adhesive and Substrate-Adhesive
2.3
           Interaction 23
2.4        Conclusion and Outlook 29
           References 3 0

3                                                                 33
           Adhesion at the Nanoscale: an Approach by AFM
           M. Brogly, 0 N oel, C . Castelein, a nd J . Schultz
                       .
           Abstract 33
3.1        [ntroduction 34
3.2        Materials and Methods        34

Adhesion - Current Research and Application. Wulff Possart
Copyright 0 2005 WILEY-VCH Verlag GmbH & Co. KGaA, W einheim
ISBN: 3-527-31263-3
        I
V lll       Contents

                       Preparation of Oxidized Silica Surface 35
                       Grafting of Functionalized SAMs onto Silicon Wafer 35
                       Crosslinking and Functionalization of PDMS Networks 35
                       Characterization of the SAMs 36
                       Results and Discussion 37
                       Force-Distance Cume Measurements and AFM Calibration 37
                       Force-Distance Cume Features 37
                       The DD Curve (Contact Mode) 37
                       AFM Calibration 38
                       Determination of the Spring Constant of the Cantiiever 38
                       Nonlinearity of the Quadrant of Photodiodes 38
                       Scan Rate of the Cantilever 38
                       Systematic Check 39
                       Force-Distance Curves on Rigid Systems of Controlled Surface
                       Chemistry 39
                       Force-Distance Measurements on Polymers 40
                       Force-Indentation Measurements on Polymers 40
                       Force-Indentation Cumes on Systems of Controlled Surface
                       Chemistry and Controlled Mechanical Properties 42
                       Conclusion 45
                       References 45

                       Organization of PCL-b-PMMA Diblock Thin Films:
                                                                            47
                       Relationship to the Adsorption Substrate Chemistry
                       T: Elzein, M. Brogly, and J . Schultz
                       Abstract 47
                       Introduction 47
                       Materials and Methods 48
                       PCL-b-PMMA Diblocks 48
                       Infrared Spectroscopy 49
                       Transmission 49
                       Polarization-Modulation infrared Reflection-Absorption Spectroscopy
                       (PM-IRRAS) 49
                       Atomic Force Microscopy (AFM) 50
                       Results and Discussion 50
                       PCL-b-PMMA Bulk Characterization 50
                       PCL-b-PMMA Thin Films on OH-Functionalized Cold Substrates 51
                       PCL-b-PMMA Thin Films on Gold Substrates 55
                       Conclusion 56
                       References 57
Adhesion and Friction Properties of Elastomers at Macroscopic
and Nanoscopic Scales 59
5. Bistac and A. Calliano
Abstract 59
Introduction 59
Materials and Methods 60
Results and Discussion 62
Adherence Energy 62
Macroscale Fnction 64
Nanoscale Friction and Adhesion   65
Conclusion 68
References 69

Chemical Structure Formation and Morphology
in Ultrathin Polyurethane Films on Metals 71
C. Wehlack and W. Possart
Abstract 71
Introduction 71
Materials and Methods 72
Sample Preparation 72
Experimental Characterization 74
IR Spectra Calculation 74
IR Band Assignment 75
Results and Discussion 76
Curing at Room Temperature 76
Morphology of Thin Films 79
Chemical Structure of Cured Films 80
Conclusion 85
Acknowledgments 86
References 87

Properties of the lnterphase Epoxy-AmineIMetal:
lnfluences from the Nature of the Amine and the Metal 89
M . Aufay and A. A. Roche
Abstract 89
Introduction 89
Materials and Methods 90
Materials 90
Thermal Analysis (DSC) 91
Micro-Infrared Spectroscopy (P-FTIR) 91
Fourier Transform Near-Infrared Spectroscopy (FT-NIR) 92
Inductively Coupled Plasma Spectroscopy (ICP) 92
X-Ray Diffraction (XRD) 92
Polarized Optical Microscopy (POM) Coupled with a Hot Stage
Apparatus 92
    I
X       Contents

                   Results and Discussion 93
                   lnterphase Formation Mechanisms 93
                   Formation of New Networks 94
                   Crystallization of "Modified" IPDA 94
                   Modification of Mechanical Properties 95
                   Comparison of Coatings and Metal-Bulk Interphases 97
                   Influence of the Stoichiometric Ratio 100
                   Conclusion 101
                   Acknowledgrnents 102
                   References 102

                   Mapping Epoxy lnterphases 103
                   M . Munz, J . Chung, and G. Kalinka
                   Abstract 103
                   Introduction 104
                   Stiffness Mapping by Indentation Techniques 106
                   SFM-Based Stiffness Mapping in Force Modulation Microscopy
                   (FMM) Mode 106
                   Depth-Sensing Micro-indentation (DSI) 108
                   Some Fundamental Aspects of Interphase Mapping by Indentation
                   Techniques I 10
                   Artifacts Induced by Topography 110
                   Artifacts induced by the Extent of the Stress Field Beneath
                   the Indenter 114
                   Two Cases of Mapped Epoxy Interphases 116
                   The Cu/Epoxy Interphase 116
                   The PVP/Epoxy Interphase 118
                   Conclusion 121
                   Acknowledgments 122
                   References 122

                   Mechanical lnterphases in Epoxies as Seen by Nondestrudive
                   High-Performance Brillouin Microscopy 125
                   J. K. Krüger, U . M üller. R. Bactavatchalou, D. Liebschner, M . Sander.
                   W. Possart, C . Wehlack, J. Baller, a nd D. Rouxel
                   Abstract 125
                    Introduction 125
                   Brillouin Spectroscopy on Thermal Phonons and Other Elementary
                   Excitations 126
                   An Introduction to the Physics of Classical Brillouin
                   Spectroscopy 126
                   The Kinematic View of Brillouin Spectroscopy 129
                   Scattenng Geometries and Other Pitfalls 129
                   Brillouin Microscopy 132
                   Mechanical Interphases at Polymer-Substrate Interfaces 134
The Polymer Model System 134
Epoxy/Silicone Rubber Interphase 134
Epoxy/Metal Interphases 136
Technical Bulk Metals: Cu, Al 137
Thin Evaporated Meta1 Substrates: Al, Cu, Au, Mg        138
Discussion 141
Conclusion 142
Acknowledgments 142
References 142

                                              143
Structure Formation in Barnacle Adhesive
M. Wiegemann
Abstract 143
Introduction 143
Barnacles 144
General Aspects of Bamacle Settlement 144
Biochemical Characterization of Bamacle Cement 145
Substrate-Specific Formation of Bamacle Adhesive 146
Substrate-Specific Morphology of Bamacle Base 147
Phenomenological Approach to Adhesive Structure Formation
and Morphology Changes 148
Homologous ( ?) Structure Formation of Biological Adherates
on Hydrophobic Surfaces 150
Theoretical Colloid Approach to Structure Formation in Bamacle
Adhesive 152
Conclusions 154
Acknowledgments 154
References 154

Adhesion Molecule-Modified Cardiovascular Prostheses:
Characterization of Cellular Adhesion in a Cell Culture Model
and by Cellular Force Spectroscopy 157
U . Bakowsky, C. Ehrhardt, C. Loehbach, P. Li, C. Kneuer. D. Jahn,
D. Hoekstra, and C.-M. Lehr
Abstract 157
Introduction 158
Materials and Methods 160
Chemicals for the Modification 160
Implant Materials 160
Modification of the PTFE Surface 160
Scanning Force Microscopy 162
Fourier Transform lnfrared Spectroscopy 163
Environmental Scanning Electron Microscopy 163
Confocal Laser Scanning Microscopy (CLSM) 163
Isolation and Culture of HUVECs 164
      I
XI1       Contents

                     Endothelialization of PTFE Films 164
                     Results and Discussion 165
                     Wet-Chemical Modification of PTFE Polymer Film       165
                     Ce11 Adhesion Experiments 166
                     Adhesion and Cultivation in Static Culture 166
                     Perfusion Experiments 166
                     Cell Adhesion Force Measurements 167
                     Conclusion 169
                     Acknowledgments 170
                     References 171

                     Surface Engineering by Coating o f Hydrophilic Layers:
                     Bioadhesion and Biocontarnination 175
                     C. Legeay and F. Poncin-Epaillard
                     Abstract 175
                     Introduction 175
                     The Need for Bioadhesion of Biomaterials 175
                     Mechanism of Bioadhesion 176
                     Surface Engineering 177
                     Surface Preparation 177
                     Surface Sterilization 178
                     Results and Discussion 178
                     Hydrophobic Cold Plasma Treated Surfaces in Ophthalmology 178
                     Hydrophilic Cold Plasma Treated Surfaces Based
                     on Polyvinylpyrrolidone (PVP) or Natural Derivative Coatings 179
                     Grafting of Monomer onto Plasma-Pretreated Surfaces 180
                     Coating with Commercial Native or Synthetic Polymers 181
                     Examples 183
                     With Different Biomolecules, i.e., Proteins 184
                     Implantation ( ex in vivo) 184
                     In vivo Implantation 185
                     Conclusion 186
                     References 187

                                                                                     189
                     New Resins and Nanosysterns for High-Performance Adhesives
                     R. Mülhaupt
                     Abstract 189
                     Introduction 190
                     Tailor-Made Polymers and Properties on Demand 190
                     Controlled Polymerization and Catalysis 191
                     Functional Polymers from the Life Sciences 192
                     Reactive Extrusion and Isocyanate-Free Polyurethane Chemistry   193
                     Nanosystems 194
                     The Nano Challenge 194
                     Nanophase Separation 196
Nanomolecules as Molecular Nanoparticles      298
POSS and Nanocomposites 200
Conclusion 201
Acknowledgments 202
References 202

lnfluence of Proton Donon on the Cationic Polymerization
of Epoxides 205
A. Hartwig, K Koschek, and A. Lühring
Abstract 205
Introduction 206
Initiators for the Cationic Polymerization of Epoxides 207
Influence of Moisture on the Polymerization Kinetics 209
Modification of the Polymerization Behavior by the Addition
of Alcohols 212
Conclusion 215
Acknowledgrnents 215
References 215

                                                                    217
Novel Adhesion Promoten Based on Hyperbranched Polymers
A. Buchman, H . Dodiuk-Kenig, T: Brand, Z. Cold, and 5. Kenig
Abstract 217
Introduction 218
Experimental 219
Bulk Hyperbranch Incorporation 219
HB Polymers as Adhesion Promoters 220
Results and Discussion 221
Conclusion 227
References 228

                                                              229
Rheology o f Hot-Melt PSAs: lnfluence o f Polymer Structure
C. Derail and C. M ann
Abstract 229
Introduction 229
Main Features of the Viscoelastic Behavior of the Pure Components,
Blends, and Full Adhesive Formulations 231
Rheological Experiments 231
Rheological Behavior of the Pure Components: [SI], [SIS],
and Pure Blends 231
Rheological Behavior of the Full Adhesive Formulations 233
A Model of the Rheological Behavior 236
A Model for the Pure Copolymers 236
A Model for the Blends [SIS-SI] 239
A Model for the Full Adhesive Formulations [SIS-SI-Resin] 239
Discussion 240
       I
X IV       Contents


                      Molecular Design 240
                      On the Variation of the Secondary Elastic Plateau Modulus 241
                      Conclusions 245
                      Adtnowledgments 247
                      References 247

                      Preparation and Characterization
                                                                        249
                      of UV-Gosslinkable PressureSensitive Adhesives
                      H.-S. Do, S.-E. Kim, a nd H.-J. K im
                      Abstract 249
                      Introduction 249
                      Materials and Methods 252
                      Preparation of UV-Crosslinkable Acrylic PSA 252
                      Preparation of PSA Samples and UV Curing 253
                      FTIR-ATR Spectroscopy 253
                      DSC Measurement 254
                      PSA Performance 254
                      Results and Discussion 254
                      FTIR-ATR Measurements 254
                      PSA Performance 258
                      Probe Tack 258
                      Peel Strength 260
                      Shear Adhesion Failure Temperature (SAFT) 261
                      Conclusions 263
                      References 263

                      Contribution o f Chemical lnteractions to the Adhesion Between
                      Evaporated Metals and Functional Groups o f Different Types
                      at Polymer Surfaces 265
                      J. Friedrich, R. Mix, a nd C . K ühn
                      Abstract 265
                      lntroduction 266
                      Interactions Between Meta1 Atoms and Functional Groups
                      at Polymer Surfaces 266
                      Preparation of the Plasma-Modified Polymer Surfaces 267
                      Interactions Between Evaporated Al and Functional Groups 269
                      Adhesive Bond Strength and Concentration of Functional
                      Groups 269
                      Materials and Methods 270
                      Materials 270
                      Plasma Pretreatment of Polymers 271
                      Deposition of Adhesion-Promoting Plasma Polymer Layers 271
                      Surface Analysis 271
                      Labeling of Functional Groups 272
                      Contact Angle Measurements 272
Meta1 Deposition 272
Peel Strength Measurements 273
Results 273
Production of Polymer Surfaces Containing Functional Groups 273
Surface Free Energy Measurements 275
Peel Strength Measurements of Al-Plasma Modified
PP Systems 276
Peel Strength of Al-Plasma-Produced Homopolymer-PP
Systems 277
Peel Strength of Al-Plasma Copolymer-PP Systems 277
Plasma Pretreatment of PTFE Surfaces 279
Peel Strength Measurements of AI-PTFE Systems 281
Hydrogen Plasma Pretreatrnent of PTFE 281
Hydrogen Plasma Pretreatment of PTFE and Deposition
of Plasma Polymer Layers 281
Discussion 282
Contribution of Chemical Bonds to the Resulting Adhesion
Strength 282
Dependence of Adhesion Strength on Concentration of Functional
Groups at the Polymer S 284
Conclusion 285
References 286

Alkene Pulsed Plasma Functionalized Surfaces:
An Interfacial Diels-Alder Reaction Study 289
F. Sr@er, J. Schultz, and V . Roucoules
Abstract 289
Introduction 289
Materials and Methods 290
Results and Discussion 292
Interfacial Chemistry 292
Cycloaddition 294
Kinetics 295
Monolayers 295
Plasma Polymer Thin Films 298
Comparison of Surface Reaction in Monolayers and Plasma Polymer
Thin Films 299
Conclusion 302
References 303

Laser Surface Treatment of Composite Materials
to Enhance Adhesion Properties 305
Q. Bknard, M. Fois, M. Crisel, and P. Laurens
Introduction 305
Why Treat a Composite Surface? 305
      I   Contents
XVI

                     Available Treatments for Composite Surfaces 305
                     Materials and Methods 307
                     Composite Materials 307
                     Surface Analyses 307
                     Single Lap Shear Tests 308
                     Results and Discussion 308
                     Why Excimer Laser Treatment? 308
                     Excimer Laser Surface Treatment 310
                     Surface Charactenzation 310
                     Mechanical Tests 312
                     Conclusion 317
                     References 318

                     Effects o f the lnterphase on the Mechanical Behavior
                     o f Thin Adhesive Films - a Modeling Approach 319
                     S. Diebels, H. Steeb, und W. Possart
                     Abstract 319
                     Introduction 319
                     Theoretical Framework 322
                     Applications and Examples 325
                     Uniaxial Tension Test 326
                     Simple Shear Test 330
                     Conclusion 330
                     References 333

                     Effect o f the Diblock Content on the Adhesive and Deformation
                     Properties o f PSAs Based on Styrenic Block Copolymers 337
                     C . Creton, A. Roos, and A. Chiche
                     Introduction 337
                     Block Copolymer Based Adhesives 339
                     Effect of the Diblock Content on Adhesive and Deformation
                     Properties 348
                     Understanding the Structure of the Extended Foam 350
                     Interfacial Fracture 356
                     Summary 360
                     Acknowledgrnents 361
                     References 361

                     Contact Mechanics and Intetläcial Fatigue Studies
                     Between Thin Semicrystalline and Classy Polymer Films. 365
                     R. L. M cSwain, A. R. Markowitz, und K. R. Shull
                     Abstract 365
                     Introduction 365
                     Materials and Methods 369
                     Materials and Sarnple Preparation 369
Pull-Off Test 371
Cyclic Interfacial Fatigue Test 374
Results 374
Discussion 381
Wetting Behavior and PEO/TMPC Miscibility 381
PEO/TMPC Interfacial Width and Adhesion 3 82
PDMS Rupture 3 84
Conclusion 3 85
Acknowledgments 385
References 385

Local and Global Aspects o f Adhesion Phenornena
in Soft Polymers 3 87
M . - F. Vallat
Abstract 3 87
Introduction 3 87
The Molecular Interphase 388
Autohesion of Polyisoprene 3 89
Autoadhesion of EPDM 393
Macroscopic Interphases 3 95
Vulcanized Elastomers 3 95
Polyurethane Joints 3 98
Conclusion 400
References 401

Calibration and Evaluation o f Nonlinear Ultrasonic Transmission
Measurernents o f Thin-Bonded Intetläces 403
5. Hirsekorn, A. Koka, 5 . Kurzenhäuser, and W Arnold
Abstract 403
Introduction 403
Experimental and Calibration Procedure 4 04
Calibrated Ultrasonic Transmission Measurements 406
Ultrasonic Measurement and Destructive Tests 4 10
Conclusion 4 18
Acknowledgments 41 8
References 41 9

Debonding o f Pressure-Sensitive Adhesives:
A Cornbined Tack and Ultra-Small Angle X-Ray Scattering Study      421
E. Maurer, 5. Loi, and P. Müller-Buschbaum
Abstract 421
Introduction 421
In-Situ Small Angle Scattering Using Synchrotron Radiation      4 23
Microscopically Inaccessible Substructures 426
Conclusion 4 32
        I   Contents
XVlll

                       Acknowledgments 433
                       References 433

                       Nondestructive Testing of Adhesive Curing in Class-Metal
                       Cornpounds by Unilateral NMR 435
                       K. Kremer, B. Blümich, F.-P. Schmitz, and J . Seitzer
                       Abstract 435
                       Introduction 436
                       Nuclear Magnetic Resonance (NMR) and the NMR-MOUSE 436
                       Quality Control 437
                       Application 438
                       Conclusion and Outlook 442
                       Acknowledgments 442
                       References 443

                       Chernical Processes During Aging in Ultra-thin Epoxy Films
                       on Metals 445
                       A. Meise6 C. Wehlack, and W. Possart
                       Abstract 445
                       Introduction 445
                       Experimental 447
                       Sample Preparation 4 47
                       Aging Conditions 447
                       Results and Discussion 448
                       Crosslinking 448
                       Additional Aging Effects 451
                       Band Assignment and Chemical Aging Processes 458
                       Condusion 462
                       Acknowledgments 463
                       References 463

                       Depth-Resolved Analysis of the Aging Behavior
                       of Epoxy Thin Films by Positron Spectroscopy 465
                       J . Kanzow, F. Faupel, W. Egger, P. Sperr, C . Kögel, C. Wehlack, A. Meiser,
                       and W. Possart
                       Abstract 465
                        Introduction 465
                        Materials and Methods 466
                        Results 467
                        PALS Investigation of an Unaged Epoxy Film 468
                        PALS Investigation of Aged Epoxy Films 469
                        Further Investigations of Aged Epoxy Films 471
                        Discussion and Conclusion 474
                       Acknowledgments 476
                        References 476
Epoxies on Stainless Steel - Curing and Aging   479
D. Fata, C. Bockenheimer, a nd W Possart
Abstract 479
lntroduction 480
Materials and Methods 481
Materials 481
Sample Preparation 482
Aging Experiments 482
Characterization of Aged Specimens 483
Results and Discussion 484
The RT Curing Epoxy System (EP1) 484
Curing of EPl 484
Thermal Aging of EP1 afier Post-Curing at 4 0 C 487
Hydro-thermal Aging of EPl 492
The Hot-Curing Epoxy System (EP2) 495
Curing of EP2 495
Thermal Aging of EP2 498
Hydro-thermal Aging of EP2 500
Conclusion 503
Acknowledgment 505
References 505

Scanning Kelvin Probe Studies of Ion Transport
and De-adhesion Processes at Polymer/Metal Interfaces   507
K. Wapner a nd C . c rundmeier
Abstract 507
lntroduction 508
Theory and Experimental S et-up of a Scanning Kelvin Probe 509
Applications of Scanning Kelvin Probe Studies in Adhesion
Science 514
Diffusion of Ions into Metal/Adhesive Interfaces 514
Corrosive Degradation of the Polymer/Metal lnterface 516
Cathodic Delamination on Adhesive-Coated Iron 516
Anodic Delamination (Filiform Corrosion)
on Coated Aluminum 518
Detection of Wet Debonding 520
A New Scanning Kelvin Probe Blister Test 521
Acknowledgrnent 523
References 523
     I   Contents
XX

                    Advanced Mass Transport Applications with Elastic Bonding
                    o f Sandwich Cornponents 525
                    S. Koch, A. Starlinger, and X. Wang
                    Abstract 5 25
                    I ntrodu~tion 525
                    Stress Distribution in Different Joints 526
                    Stress Distribution in Bolted Joints 527
                    Stress Distribution in a Stiff Adhesive Joint 5 28
                    Stress Distribution in an Elastic Adhesive Joint 5 29
                    Applications of Flexible Adhesives in Mass Transportation
                    Systems 5 29
                    GRP Front Cab 5 30
                    Application in Tram Design 5 30
                    Methods of Modeling Flexible Adhesives 531
                    Modeling Methods for Detailed Local Analysis 5 32
                    Modeling Methods for Large Global Structural Analysis 533
                    Cornparison of the TR08 Results from FE Analysis
                    and frorn Measurernent on Lathen Test Track 5 34
                    Joint Design, Production, and Testing 535
                    Production of Adhesive Joints 536
                    Joint Testing 536
                    Conclusion 537
                    References 537

                    Adhesive Jointsfor Modular Cornponents
                    in Railway Applicatiom 539
                    C. Nagel, M . Brede, M. Calomjirescu,J. Sauer, E .A. Ullrich, T: Fertig,
                    and 0 . - D. Hennemann
                    Abstract 5 39
                    Introduction 5 39
                    Adhesives and Adherends 5 40
                    Surface Pretreatrnent 541
                    Mechanical Behavior of Adhesives and Joints 5 42
                    Elastic-Plastic Properties of Structural Adhesive Systems 543
                    Hyperelastic Properties of Flexible Adhesive Systems 5 44
                    Creep Behavior of Adhesive Joints 545
                    Fatigue Properties of Adhesive Joints 547
                    Environmental Influences and Design of Structures 5 50
                    Conclusion 553
                    Acknowledgment 553
                    References 5 54
Behavior o f Dismantlable Adhesives
                                              555
lncluding Thermally Expansive Microcapsules
Y Nishiyamo and C. Sato
Abstract 555
introduction 555
Materials and Methods 557
Materials 557
Volume Expansion of the Cured B dk Adhesive 558
Dismantlability of Joints Bonded with the Dismantlable
Adhesive 559
Bond Strength of the Dismantlable Adhesive 559
PVT (Pressure-Volume-Temperature)Tests 560
Resdts and Discussion 561
Volume Expansion of the Cured Bulk Adhesive 561
Dismantlability of Joints Bonded with the Dismantlable
Adhesive 562
Bond Strength of the Dismantlable Adhesive 564
PVT Relationship of Microcapsules and Dismantlable Adhesive 565
Discussion 567
Conclusion 567
References 568

                569
Subject Index