<p>Introduction xiii</p> <p><b>1 The Surface of Polymers </b><b>1<br /> </b><i>Rosica Mincheva and Jean-Marie Raquez</i></p> <p>1.1 Introduction 1</p> <p>1.2 The Surface of Polymers 2</p> <p>1.2.1 Definition of a Polymer Surface 2</p> <p>1.2.2 Factors Determining a Polymer Surface 3</p> <p>1.2.2.1 Internal Factors 3</p> <p>1.2.2.2 External Factors 4</p> <p>1.2.3 The Polymer Surface at a Microscopic Level 11</p> <p>1.3 Properties of Polymer Surfaces at Interfaces 12</p> <p>1.3.1 Surface Wettability 13</p> <p>1.3.2 Surface Thermal Properties 15</p> <p>1.3.2.1 Surface<i> T</i><sub>g </sub>15</p> <p>1.3.2.2 Surface Crystallization 17</p> <p>1.4 Experimental Methods for Investigating Polymer Surfaces at Interfaces 21</p> <p>1.5 Conclusions 21</p> <p>References 21</p> <p><b>Part I Gas Phase Methods </b><b>31</b></p> <p><b>2 Surface Treatment of Polymers by Plasma </b><b>33<br /> </b><i>Pieter Cools, Laura Astoreca, Parinaz Saadat Esbah Tabaei, Monica Thukkaram, Herbert De Smet, Rino Morent, and Nathalie De Geyter</i></p> <p>2.1 Plasma: An Introduction 33</p> <p>2.1.1 Definition 33</p> <p>2.1.2 Thermal Versus Nonthermal Plasma 34</p> <p>2.1.3 The Formation of Nonthermal Plasma 35</p> <p>2.1.4 Plasma Generation and Operating Conditions 37</p> <p>2.1.4.1 Different Methods of Plasma Generation 37</p> <p>2.1.4.2 DC Discharges 38</p> <p>2.1.4.3 DC Pulsed Discharges 38</p> <p>2.1.4.4 RF and MW Discharges 38</p> <p>2.1.4.5 Dielectric Barrier Discharge (DBD) 39</p> <p>2.1.4.6 Atmospheric Pressure Plasma Jet (APPJ) 40</p> <p>2.1.4.7 Gliding Arc 41</p> <p>2.1.5 Nonthermal Plasma for Polymer Surface Treatment 41</p> <p>2.2 Applications of Plasma Surface Activation of Polymers 43</p> <p>2.2.1 Adhesion Improvement 43</p> <p>2.2.2 Packaging and Textile Applications 47</p> <p>2.2.2.1 Printability Enhancement 47</p> <p>2.2.2.2 Dyeability Improvement 47</p> <p>2.2.2.3 Mass Transfer Changes 49</p> <p>2.2.3 Biomedical Applications 50</p> <p>2.2.3.1 Inert Synthetic Polymers 50</p> <p>2.2.3.2 Biodegradable Polymers 53</p> <p>2.3 Plasma Grafting 56</p> <p>2.4 Hydrophobic Recovery 59</p> <p>2.5 Conclusion 61</p> <p>References 61</p> <p><b>3 A Joint Mechanistic Description of Plasma Polymers Synthesized at Low and Atmospheric Pressure </b><b>67<br /> </b><i>Damien Thiry, François Reniers, and Rony Snyders</i></p> <p>3.1 Introduction 67</p> <p>3.2 Plasma Polymerization 69</p> <p>3.2.1 Plasma Fundamentals 70</p> <p>3.2.2 Growth Mechanism 72</p> <p>3.3 Probing the Plasma Chemistry 83</p> <p>3.3.1 Optical Emission Spectroscopy 84</p> <p>3.3.2 Mass Spectrometry 87</p> <p>3.4 Conclusions 96</p> <p>References 97</p> <p><b>4 Organic Surface Functionalization by Initiated CVD (iCVD) </b><b>107<br /> </b><i>Karen K. Gleason</i></p> <p>4.1 Introduction 107</p> <p>4.2 Mechanistic Principles of iCVD 108</p> <p>4.3 Functional, Surface Reactive, and Responsive Organic Films Prepared by iCVD 113</p> <p>4.4 Interfacial Engineering with iCVD: Adhesion and Grafting 127</p> <p>4.5 Reactors for Synthesizing Organic Films by iCVD 128</p> <p>4.6 Summary 129</p> <p>References 130</p> <p><b>5 Atomic Layer Deposition and Vapor Phase Infiltration </b><b>135<br /> </b><i>Mark D. Losego and Qing Peng</i></p> <p>5.1 Atomic Layer Deposition Versus Vapor Phase Infiltration 135</p> <p>5.2 Atomic Layer Deposition (ALD) on Polymers 138</p> <p>5.2.1 Chemical Mechanisms of ALD 138</p> <p>5.2.2 ALD on Polymers with Dense –OH Groups: Cellulose and Poly(vinyl alcohol) 140</p> <p>5.2.3 ALD onto “Unreactive” Polymer Substrates 141</p> <p>5.2.4 Applications of ALD Coated Polymers 143</p> <p>5.2.4.1 ALD Coated Cotton Fibers 143</p> <p>5.2.4.2 Applications for ALD Coatings on Other Polymers 144</p> <p>5.3 Vapor Phase Infiltration of Polymers 145</p> <p>5.3.1 Processing Thermodynamics and Kinetics of VPI 145</p> <p>5.3.1.1 Thermodynamics of Vapor-Phase Precursor Sorption into Polymers 145</p> <p>5.3.1.2 Kinetics of Precursor Diffusion During VPI 147</p> <p>5.3.1.3 VPI Processes Incorporating Both Penetrant Diffusion and Reaction 148</p> <p>5.3.1.4 Measuring the Thermodynamics and Kinetics of a VPI Process 149</p> <p>5.3.2 Applications of Vapor Phase Infiltrated Polymers 150</p> <p>5.3.2.1 Altering Mechanical Performance 150</p> <p>5.3.2.2 Contrasting Agent for Multi-phase Polymer Imaging 152</p> <p>5.3.2.3 Improved Chemical Resistance 152</p> <p>5.3.2.4 Patterning for Microsystems 153</p> <p>5.3.2.5 Vapor Diffusion Barriers 154</p> <p>5.3.2.6 Conducting Polymers and Hybrid Photovoltaic Cells 154</p> <p>5.3.2.7 Other Application Spaces 155</p> <p>5.4 Summary and Future Outlook for ALD and VPI on Polymers 156</p> <p>References 156</p> <p><b>Part II UV and Related Methods </b><b>161</b></p> <p><b>6 Photoinduced Functionalization on Polymer Surfaces </b><b>163<br /> </b><i>Kazuhiko Ishihara</i></p> <p>6.1 Introduction 163</p> <p>6.2 Improving the Surface Properties of Polymeric Materials by Photoirradiation 165</p> <p>6.3 Photoreaction of Polymers with Other Polymers 166</p> <p>6.3.1 Photoinduced Chemical Reaction Between Polymers 166</p> <p>6.3.2 Photoinduced Grafting at the Polymer Surface 168</p> <p>6.3.3 Preparation of High-functionality Surface by Photoinduced Graft Polymerization 169</p> <p>6.3.4 Application of Photoinduced Grafting Process to Artificial Organs 172</p> <p>6.4 Self-initiated Photoinduced Graft Polymerization 174</p> <p>6.4.1 Poly(ether ketone) as Photoinitiator for Graft Polymerization 174</p> <p>6.4.2 Effects of Inorganic Salts on Photoinduced Graft Polymerization in an Aqueous System 178</p> <p>6.5 Conclusion and Future Perspective 180</p> <p>References 181</p> <p><b>7 </b><b>𝜸-Rays and Ions Irradiation </b><b>185<br /> </b><i>Alejandro Ramos-Ballesteros, Victor H. Pino-Ramos, Felipe López-Saucedo,</i><i>Guadalupe G. Flores-Rojas, and Emilio Bucio</i></p> <p>7.1 𝛾-Rays and Ions Irradiation 185</p> <p>7.2 Ionizing Radiation Sources 186</p> <p>7.3 𝛾-Ray-Induced Modifications 186</p> <p>7.3.1 Grafting Modifications 186</p> <p>7.3.1.1 Radiation-induced Grafting Methods 188</p> <p>7.3.1.2 Ionic Grafting 192</p> <p>7.3.1.3 RAFT-graft Polymerization 193</p> <p>7.3.1.4 Applications 194</p> <p>7.3.2 Cross-linking 197</p> <p>7.3.2.1 𝛾-Ray Cross-linking Modifications 199</p> <p>7.3.2.2 Cross-linking with Additives 200</p> <p>7.3.2.3 Industrial Applications 201</p> <p>7.4 Heavy Ion-Induced Modifications 202</p> <p>7.4.1 Polymers 204</p> <p>7.5 Conclusions 205</p> <p>Acknowledgments 206</p> <p>References 206</p> <p><b>Part III Chemical Methods </b><b>211</b></p> <p><b>8 Functionalization of Polymers by Hydrolysis, Aminolysis, Reduction, Oxidation, and Some Related Reactions </b><b>213<br /> </b><i>Dardan Hetemi and Jean Pinson</i></p> <p>8.1 Hydrolysis and Aminolysis 213</p> <p>8.1.1 PLA and Polyesters 213</p> <p>8.1.2 Hydrolysis 214</p> <p>8.1.3 Aminolysis 214</p> <p>8.1.4 PCL 215</p> <p>8.1.5 PET 216</p> <p>8.1.6 PMMA 216</p> <p>8.1.7 Cellulose 217</p> <p>8.2 Chemical Reduction 220</p> <p>8.2.1 PEEK 220</p> <p>8.2.2 PET 225</p> <p>8.2.3 PMMA 227</p> <p>8.2.4 PC 227</p> <p>8.2.5 PTFE 229</p> <p>8.3 Chemical Oxidation 231</p> <p>8.4 Non-covalent Surface Modification 234</p> <p>8.5 Conclusion 235</p> <p>References 236</p> <p><b>9 Functionalization of Polymers by Reaction of Radicals, Nitrenes, and Carbenes </b><b>241<br /> </b><i>Jean Pinson</i></p> <p>9.1 Functionalization of Polymers by Reaction of Radicals 241</p> <p>9.1.1 Peroxides as Radical Initiators 241</p> <p>9.1.2 Hydrogen Peroxides as Radical Initiator 244</p> <p>9.1.3 Persulfates as Radical Initiators 246</p> <p>9.1.4 Oxygen as Radical Initiator 248</p> <p>9.1.5 Azo Compounds as Radical Initiator 249</p> <p>9.1.6 Diazonium Salts as Radical Initiator 250</p> <p>9.1.6.1 Polypyrrole 251</p> <p>9.1.6.2 Polyaniline 251</p> <p>9.1.6.3 Poly(3,4-ethylenedioxythiophene)–Poly(styrenesulfonate) (PEDOT:PSS) 253</p> <p>9.1.6.4 Polymethylmethacrylate (PMMA) 254</p> <p>9.1.6.5 Polypropylene (PP) 255</p> <p>9.1.6.6 Polyvinyl Chloride 255</p> <p>9.1.6.7 Cyclic Olefin Copolymers (COC) 256</p> <p>9.1.6.8 Polyetheretherketone (PEEK) 256</p> <p>9.1.6.9 PET (Polyethylene Terephthalate) 257</p> <p>9.1.6.10 Polysulfone Membranes 258</p> <p>9.1.6.11 Cation Exchange Membranes 258</p> <p>9.1.6.12 Fluoro Polymers 259</p> <p>9.1.6.13 Natural Polymers 260</p> <p>9.1.7 Alkyl Halides as Radical Initiator 260</p> <p>9.2 Surface Modification of Polymers with Carbenes and Nitrenes 260</p> <p>9.2.1 Carbenes 261</p> <p>9.2.2 Nitrenes 264</p> <p>9.3 Conclusion 267</p> <p>References 268</p> <p><b>10 Surface Modification of Polymeric Substrates with Photo- and Sonochemically Designed Macromolecular Grafts </b><b>273<br /> </b><i>Fatima Mousli, Youssef Snoussi, Ahmed M. Khalil, Khouloud Jlassi, Ahmed Mekki, and Mohamed M. Chehimi</i></p> <p>10.1 Introduction 273</p> <p>10.1.1 Context 273</p> <p>10.1.2 Scope of the Chapter 274</p> <p>10.2 Surface-confined Radical Photopolymerization of Insulating Vinylic and Other Monomers 274</p> <p>10.2.1 Type I and Type II Photoinitiation Systems 275</p> <p>10.2.2 Simultaneous Photoinduced Electron Transfer and Free Radical Polymerization Confined to Surfaces 282</p> <p>10.2.3 Surface-initiated Photo<i>iniferter</i> 284</p> <p>10.2.4 “Brushing Up from Anywhere” Using Polydopamine Thin Adhesive Coatings 284</p> <p>10.2.5 Recent Trends in Surface-confined Photopolymerization (CRP) 287</p> <p>10.3 Surface-confined Photopolymerization of Conjugated Monomers 289</p> <p>10.3.1 Polypyrrole 290</p> <p>10.3.1.1 Mechanisms of Photopolymerization of Pyrrole 290</p> <p>10.3.1.2 Substrates for in Situ Photoinduced Polymerization of Pyrrole and Potential Applications 291</p> <p>10.3.2 Polyaniline 294</p> <p>10.3.2.1 Mechanisms of Photopolymerization of Aniline 294</p> <p>10.3.2.2 Substrates for in Situ Photoinduced Polymerization of Aniline 298</p> <p>10.4 Surface-confined Sonochemical Polymerization of Conjugated and Vinylic Monomers 298</p> <p>10.4.1 Insights into Sonochemistry: Origin of the Phenomenon and Mechanism of Polymer Synthesis 298</p> <p>10.4.2 Ultrasound-assisted Polymerization or Polymer Deposition over Organic Polymeric Substrates 303</p> <p>10.4.2.1 Sonopolymerization 303</p> <p>10.4.2.2 Ultrasonic Spray 303</p> <p>10.4.3 Sonopolymerization over Miscellaneous Types of Surface: Inorganic Polymeric Substrates 305</p> <p>10.5 Conclusion 306</p> <p>Acknowledgments 307</p> <p>References 307</p> <p><b>Part IV Applications </b><b>317</b></p> <p><b>11 Surface Modification of Nanoparticles: Methods and Applications </b><b>319<br /> </b><i>Gopikrishna Moku, Vijayagopal Raman Gopalsamuthiram, Thomas R. Hoye, and Jayanth Panyam</i></p> <p>11.1 Introduction 319</p> <p>11.2 Polymers Used in the Preparation of Nanoparticles 320</p> <p>11.3 Common Biodegradable Polymers for Nanoparticle Fabrication 320</p> <p>11.3.1 Albumin 320</p> <p>11.3.2 Alginate 320</p> <p>11.3.2.1 Chitosan 321</p> <p>11.3.3 Gelatin 322</p> <p>11.3.4 Poly(lactide-<i>co</i>-glycolide) (PLGA) and Polylactide (PLA) 322</p> <p>11.3.5 Poly-ε-caprolactone (PCL) 323</p> <p>11.4 Fabrication of Nanoparticles 323</p> <p>11.5 Linker Chemistry for Attaching Ligands on Polymeric Nanoparticles 324</p> <p>11.5.1 Hydrazone Bond Formation 327</p> <p>11.5.2 Non-covalent Attachment 328</p> <p>11.6 Surface-functionalized Polymeric Nanoparticles for Drug Delivery Applications 328</p> <p>11.6.1 Polysaccharides 329</p> <p>11.6.2 Lipids 329</p> <p>11.6.3 Aptamers 332</p> <p>11.6.4 Antibodies 332</p> <p>11.6.5 Peptides 333</p> <p>11.6.5.1 Polyethylene Glycol (PEG) 334</p> <p>11.7 Characterization of Surface-modified Nanoparticles 336</p> <p>11.7.1 Particle Size 336</p> <p>11.7.2 Dynamic Light Scattering (DLS) 337</p> <p>11.7.3 Scanning Electron Microscopy (SEM) 337</p> <p>11.7.4 Transmission Electron Microscopy (TEM) 339</p> <p>11.7.5 Surface Charge 339</p> <p>11.7.6 Surface Hydrophobicity 340</p> <p>11.7.7 Fourier Transform IR (FTIR) Spectroscopy 341</p> <p>11.8 Summary/Conclusion 342</p> <p>References 342</p> <p><b>12 Surface Modification of Polymers for Food Science </b><b>347<br /> </b><i>Valentina Siracusa</i></p> <p>12.1 Introduction 347</p> <p>12.2 Physical and Chemical Methods 348</p> <p>12.2.1 Gas Phase and Radiation 349</p> <p>12.2.1.1 Gas Phase 349</p> <p>12.2.1.2 Radiation 350</p> <p>12.2.2 Liquid and Bulk Phase Methods 352</p> <p>12.2.2.1 Adsorption Methods 352</p> <p>12.2.2.2 Desorption Method 352</p> <p>12.2.3 Interfacial Adhesion of Polymers 353</p> <p>12.2.4 Grafting and Polymerization 354</p> <p>12.3 Mechanical Method 354</p> <p>12.4 Biological Method 354</p> <p>12.5 Surface Modification of Polymer for Food Packaging 355</p> <p>12.5.1 Applications 355</p> <p>12.5.1.1 Surface Sterilization 355</p> <p>12.5.1.2 Printing 355</p> <p>12.5.1.3 Mass Transfer 356</p> <p>12.5.2 Polymers 356</p> <p>12.6 Conclusion 358</p> <p>References 359</p> <p><b>13 Surface Modification of Water Purification Membranes </b><b>363<br /> </b><i>Anthony Szymczyk, Bart van der Bruggen, and Mathias Ulbricht</i></p> <p>13.1 Introduction 363</p> <p>13.2 Irradiation-Based Direct Polymer Modification 365</p> <p>13.2.1 Plasma Treatment 365</p> <p>13.2.2 UV Irradiation 366</p> <p>13.2.3 Irradiation with High Energy Sources 368</p> <p>13.3 Coatings 369</p> <p>13.3.1 Coatings from Gas Phase 369</p> <p>13.3.2 Coatings from Wet Phase 371</p> <p>13.4 Grafting Methods 378</p> <p>13.4.1 Grafting-to 378</p> <p>13.4.2 Grafting-from 381</p> <p>13.4.2.1 Plasma-Induced Graft Polymerization 381</p> <p>13.4.2.2 UV-Induced Grafting 383</p> <p>13.4.2.3 Grafting Induced by High Energy Radiations 385</p> <p>13.4.2.4 Grafting Initiated by Chemical/Electrochemical Means 385</p> <p>13.4.3 Controlled Grafting-from 389</p> <p>13.5 Conclusion 392</p> <p>References 394</p> <p><b>14 Surface Modification of Polymer Substrates for Biomedical Applications </b><b>399<br /> </b><i>P. Slepicka, N. Slepičková Kasálková, Z. Kolská, and V. Švor</i><i>čík</i></p> <p>14.1 Introduction 399</p> <p>14.2 Plasma Treatment 400</p> <p>14.3 Laser Modification 411</p> <p>14.3.1 Interaction with Cells 411</p> <p>14.3.2 Sensor Construction 412</p> <p>14.4 Conclusion 416</p> <p>Acknowledgments 417</p> <p>References 417</p> <p>Index 427</p>