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