<p> Preface xi</p> <p><b>1 High-Performance Metal–Polymer Composites: Chemical Bonding, Adhesion, and Interface Design 1</b></p> <p>1.1 Introduction 1</p> <p>References 10</p> <p><b>2 Interpretation of Adhesion Phenomena – Review of Theories 13</b></p> <p>2.1 General 13</p> <p>2.2 Mechanical Interlocking 20</p> <p>2.2.1 Mechanical Interlocking in a Macroscopic Scale 20</p> <p>2.2.2 Mechanical Adhesion on a Microscale 20</p> <p>2.2.3 Mechanical Anchoring on a Molecular Scale 21</p> <p>2.3 Interdiffusion 23</p> <p>2.3.1 Diblock Copolymers for Interface-Crossing Adhesion Promotion 23</p> <p>2.3.2 Interdiffusion andWelding 23</p> <p>2.3.3 Diffusion of Metals into Polymers 25</p> <p>2.4 Interphase Formation 28</p> <p>2.4.1 Polymer–Polymer Blends 28</p> <p>2.4.2 Nanoparticle Composites 29</p> <p>2.4.3 Transcrystalline Layers 29</p> <p>2.4.4 Redox Reactions across the Metal–Polymer Interface 30</p> <p>2.4.5 Reactions of Transition Metals with Aromatic Polymers 32</p> <p>2.4.6 Loss in Anisotropic Orientation of Polymers Caused by Pretreatment or by Contact to Metals 34</p> <p>2.4.7 Weak Boundary Layer 36</p> <p>2.5 Weak Molecular Interactions (Cohesive Forces) 38</p> <p>2.5.1 Thermodynamic Adsorption,WettingModel 38</p> <p>2.5.2 Contact Angle, Surface Properties, and Adhesion 39</p> <p>2.5.3 Contact Angle Measurement 40</p> <p>2.5.4 Advancing and Receding Contact Angles, Contact Angle Hysteresis 42</p> <p>2.5.5 Real Surfaces 43</p> <p>2.5.6 Critical Surface Tension – Zisman Plot 44</p> <p>2.5.7 Surface TensionTheories 46</p> <p>2.5.8 Polar and Dispersive Components of Surface Tension 47</p> <p>2.5.9 Acid–Base Interactions 48</p> <p>2.5.10 Rheological Model 51</p> <p>2.5.11 Summary 51</p> <p>2.6 Electrostatic Attraction 52</p> <p>2.7 Contaminations, Role ofWater, or Humidity 54</p> <p>2.8 Coupling Agents 55</p> <p>2.9 Use of Glues (Adhesives) 59</p> <p>2.10 Hydrophobic Recovery 70</p> <p>References 72</p> <p><b>3 Interactions at Interface 89</b></p> <p>3.1 Composites and Laminates 89</p> <p>3.2 Laminate Processing 90</p> <p>3.3 Polymers as Substrate or as Coating 92</p> <p>3.4 Chemical Reactions at Surfaces 92</p> <p>3.4.1 Chemisorption 92</p> <p>3.5 Reactions of Metal Atoms with Polyolefins 97</p> <p>3.6 Reaction of Metal Atoms with O-Functional Groups at Polymer Surfaces 97</p> <p>3.7 Reactions of Metal Atoms with Amino Groups on Polymer Surfaces 105</p> <p>3.8 Silane and Siloxane Adhesion-Promoting Agents 105</p> <p>References 107</p> <p><b>4 Chemical Bonds 113</b></p> <p>4.1 Bonds in Polymers 113</p> <p>4.1.1 Covalent C—H and C—C Bonds in Polymers 113</p> <p>4.1.2 C—C Double, Triple, Conjugated, and Aromatic Bonds 116</p> <p>4.1.3 C—O, C=O, O—C=O, and O=CO—O Bonds in Polymers 117</p> <p>4.1.4 N-Containing Functional Groups 118</p> <p>4.1.5 Chemical Bonds in Other Materials 119</p> <p>4.2 Reactions of Chemical Bonds during Pretreatment 119</p> <p>4.2.1 Aliphatic Chains 119</p> <p>4.2.2 Preformed Degradation Products and Preferred Rearrangement Processes 121</p> <p>4.3 Chemical Bonds at Interface 122</p> <p>4.3.1 Polymer–Polymer Linking 122</p> <p>4.3.2 Carbon–Metal Bonds 123</p> <p>4.3.3 Covalent Bonds between Oxides and Polymers 126</p> <p>4.3.4 Interface between Polymers and Transition Metals 127</p> <p>References 130</p> <p><b>5 Functional Groups at Polymer Surface and Their Reactions 135</b></p> <p>5.1 OH Groups at Surface 135</p> <p>5.2 Primary Amino Groups at Polymer Surfaces 140</p> <p>5.3 Carboxylic Groups as Anchor Points for Grafted Molecules 143</p> <p>5.4 Bromination 146</p> <p>5.5 Silane Bonds 147</p> <p>5.6 Click Chemistry 148</p> <p>5.7 ATRP 150</p> <p>5.8 Grafting 152</p> <p>5.8.1 Grafting of Fluorescence Markers onto Functional Groups at Polyolefin Surfaces 153</p> <p>5.8.2 Covalent Linking of Spacer Bonded Dye Sensors onto Polyolefin Surfaces 154</p> <p>5.8.3 Covalent Linking of Spacer Bonded Dye Sensors onto Polyolefin Surfaces Supported by a Cucurbituril Jacket 155</p> <p>5.8.4 Grafting of Polyglycerols onto Polyolefin Surfaces for Introducing Antifouling Property 156</p> <p>5.8.5 Summary of Complex Structures Covalently Grafted onto Polyolefin Surfaces 159</p> <p>5.9 Polymers Deposited onto Silicon or Glass 162</p> <p>5.10 Molecular Entanglement of Macromolecules of Coating and Substrate at Polymer Surfaces (Interpenetrating Network at Interface) 162</p> <p>References 165</p> <p><b>6 Pretreatment of Polyolefin Surfaces for Introducing Functional Groups 173</b></p> <p>6.1 Situation at Polyolefin Surfaces 173</p> <p>6.2 Physical and Chemical Attacks of Polyolefin Surfaces 173</p> <p>6.3 A Few General Remarks to the Pretreatment of Polyolefins 179</p> <p>6.4 Introduction of Functional Groups to polyolefin Surfaces 184</p> <p>6.5 Usual Pretreatment Processes and Their Advantages and Disadvantages 186</p> <p>6.5.1 Oxygen Plasma Exposure 186</p> <p>6.5.2 Structural Degradation of Polymer on Exposure to Oxygen Plasma 187</p> <p>6.5.3 Degradation of Polymers by Exposure to Oxygen Plasma 192</p> <p>6.5.4 Cross-linking of Polymers by Plasma-Emitted UV Radiation 198</p> <p>6.6 Surface Oxidation by Atmospheric-Pressure Plasmas (Dielectric Barrier Discharge-DBD, Atmospheric Pressure Glow Discharge-APGD or Corona Discharge, Spark Jet, etc.) 201</p> <p>6.7 Flame Treatment 204</p> <p>6.8 Silicoater Process (Pyrosil) 205</p> <p>6.9 Laser Ablation 205</p> <p>6.10 UV Irradiation with Excimer Lamps 206</p> <p>6.12 Mechanical Pretreatment 213</p> <p>6.13 Cryogenic Blasting 214</p> <p>6.14 Skeletonizing 214</p> <p>6.15 Roughening for Mechanical Interlocking and Increasing of Surface Area by Plasma and Sputter Etching 215</p> <p>6.16 Solvent Cleaning 215</p> <p>6.17 SolventWelding 217</p> <p>6.18 Chemical Treatment by Chromic Acid and Chromo-Sulfuric Acid 218</p> <p>6.19 Chemical Etching and Functionalizing of Fluorine-Containing Polymers 220</p> <p>6.20 Oxyfluorination 221</p> <p>6.21 Sulfonation 222</p> <p>6.22 Sputtering for Film Deposition 223</p> <p>6.23 Cross-linking as Adhesion Improving Pretreatment (CASING) 225</p> <p>6.24 Monosort Functionalization and Selective Chemical Reactions 226</p> <p>6.24.1 Well-Defined Functionalization of Polymer Surfaces by Classic Organic Chemistry 226</p> <p>6.24.2 Selective Monosort Functionalization of Polymer Surfaces by Oxygen Plasma Exposure and Post-Plasma Chemical Treatment for Producing OH Groups 227</p> <p>References 237</p> <p><b>7 Adhesion-Promoting Polymer Layers 259</b></p> <p>7.1 General 259</p> <p>7.2 Historical Development 261</p> <p>7.3 Influence of Plasma Wattage on Chemical Structure of Plasma Polymers 263</p> <p>7.4 Pulsed-Plasma Polymerization 265</p> <p>7.5 Pressure-Pulsed Plasma 267</p> <p>7.6 Copolymerization in Pulsed Plasmas 271</p> <p>7.7 Some Additional Details to the Mechanisms of Plasma Polymerization 275</p> <p>7.8 Often-Observed Abnormal Side Reactions Occurring in the Plasma Only 278</p> <p>7.9 Structure of Plasma Polymers 281</p> <p>7.10 Use of Plasma Polymers as Adhesion-Promoting Layers 286</p> <p>7.11 Adhesion Promotion of VeryThick Layers 289</p> <p>7.12 Summary 290</p> <p>References 290</p> <p><b>8 Monosort Functional Groups at Polymer Surfaces 299</b></p> <p>8.1 Introduction 299</p> <p>8.2 Bromination of Polyolefin Surface by Exposure to the Br2 Plasma 305</p> <p>8.3 Bromoform as Precursor 309</p> <p>8.4 Deposition of Plasma Polymers Carrying C—Br Groups 312</p> <p>8.5 Loss in BromineGroups byWet-Chemical Processing 313</p> <p>8.6 Other Halogenations 314</p> <p>8.6.1 Chlorination 315</p> <p>8.6.2 Fluorination 317</p> <p>8.6.3 Iodination 317</p> <p>8.6.4 Measuring the Electron Temperature in Haloform Plasmas 317</p> <p>8.6.5 Comparison of Halogenation Processes 318</p> <p>8.7 C—Br as Anchoring Point for Grafting 319</p> <p>8.7.1 Changing the C—Br Functionalization into NH2 Functionalization 319</p> <p>8.7.2 Other Functional Groups 321</p> <p>8.7.3 Grafting onto C—Br Groups 322</p> <p>8.8 Underwater Capillary Discharge Plasma or Glow Discharge Electrolysis (GDE) 323</p> <p>8.9 Conclusions 323</p> <p>References 332</p> <p><b>9 Chemical Grafting ontoMonosort Functionalized Polyolefin Surfaces 337</b></p> <p>9.1 General Aspects 337</p> <p>9.2 Grafting of Spacers onto Radicals 344</p> <p>9.3 Grafting of Spacers and Oligomers by Reaction with C—OH Groups at the Polyolefin Surface 346</p> <p>9.4 Grafting of Linear Spacers and Oligomers onto C—Br Groups 347</p> <p>9.5 Introduction of Spacers with Siloxane Cages (POSS) 349</p> <p>9.6 Grafting via Click Reaction 350</p> <p>9.7 Influence of Spacers on the Metal–Polymer Adhesion 351</p> <p>9.8 Summary 352</p> <p>References 353</p> <p><b>10 Conclusions and Outlook to the New Interface Design 357</b></p> <p>10.1 Introduction 357</p> <p>10.2 Physical Effects Produced by Covalent Bonding of Metal to Polymer 360</p> <p>10.3 Introduction of Functional Groups onto Polyolefin Surfaces Associated with Damaging of Polymer Structure Near Surface 363</p> <p>10.4 Thermal Expansion Coefficients of Metals and Polymers 365</p> <p>10.5 Differences between Al–Polyolefin and Polyolefin–Al Laminates 366</p> <p>10.6 Protection of CovalentMetal–Polymer Bonds along the Interface 367</p> <p>10.7 Reaction Pays for Grafting Spacer Molecules onto Polyolefin Surfaces 368</p> <p>10.8 Special Requirements for Metal Deposition Especially Aluminum 370</p> <p>10.9 UsedWays to Introduce Spacers for Maximum Adhesion 372</p> <p>10.9.1 Spacer Attachment onto NH2 Groups 372</p> <p>10.9.2 Spacer Grafting onto OH-Groups at Polymer Surface 375</p> <p>10.9.3 Spacer Anchoring onto C—Br Groups 376</p> <p>10.9.4 Silane Attachment 376</p> <p>10.9.5 Silane Hydrolysis and Subsequent Partial Cross-linking 377</p> <p>10.9.6 Adhesion Strength Measurements 381</p> <p>10.9.7 Summary and Conclusions 383</p> <p>References 388</p> <p><b>11 Short Treatise on Analysis Chemical Features 395</b></p> <p>11.1 General 395</p> <p>11.2 Bulk Analysis 395</p> <p>11.2.1 Infrared Spectroscopy 396</p> <p>11.2.2 UV–vis Spectroscopy 400</p> <p>11.2.3 NMR Spectroscopy 401</p> <p>11.2.4 MALDI- and ESI-ToF-MS 403</p> <p>11.2.5 HPLC and GPC/SEC 405</p> <p>11.3 Surface Analysis 406</p> <p>11.3.1 Sampling Depth 406</p> <p>11.3.2 XPS 408</p> <p>11.3.3 ToF-SIMS 410</p> <p>11.3.4 SEIRA and IRRAS 412</p> <p>References 414<br /><br />Index 415</p>