Surface Modification of Polymers

Jean Pinson, PhD, is Professor Emeritus of the Université Paris Diderot. He is interested in the functionalization and modification of polymer surfaces and the surface chemistry of diazonium salts. Damien Thiry, PhD, is Senior Researcher at the University of Mons (Chimie des Interactions Plasma-Surface (ChIPS)), Belgium.

• Introduction xiii1 The Surface of Polymers 1Rosica Mincheva and Jean-Marie Raquez1.1 Introduction 11.2 The Surface of Polymers 21.2.1 Definition of a Polymer Surface 21.2.2 Factors Determining a Polymer Surface 31.2.2.1 Internal Factors 31.2.2.2 External Factors 41.2.3 The Polymer Surface at a Microscopic Level 111.3 Properties of Polymer Surfaces at Interfaces 121.3.1 Surface Wettability 131.3.2 Surface Thermal Properties 151.3.2.1 Surface Tg 151.3.2.2 Surface Crystallization 171.4 Experimental Methods for Investigating Polymer Surfaces at Interfaces 211.5 Conclusions 21References 21Part I Gas Phase Methods 312 Surface Treatment of Polymers by Plasma 33Pieter Cools, Laura Astoreca, Parinaz Saadat Esbah Tabaei, Monica Thukkaram, Herbert De Smet, Rino Morent, and Nathalie De Geyter2.1 Plasma: An Introduction 332.1.1 Definition 332.1.2 Thermal Versus Nonthermal Plasma 342.1.3 The Formation of Nonthermal Plasma 352.1.4 Plasma Generation and Operating Conditions 372.1.4.1 Different Methods of Plasma Generation 372.1.4.2 DC Discharges 382.1.4.3 DC Pulsed Discharges 382.1.4.4 RF and MW Discharges 382.1.4.5 Dielectric Barrier Discharge (DBD) 392.1.4.6 Atmospheric Pressure Plasma Jet (APPJ) 402.1.4.7 Gliding Arc 412.1.5 Nonthermal Plasma for Polymer Surface Treatment 412.2 Applications of Plasma Surface Activation of Polymers 432.2.1 Adhesion Improvement 432.2.2 Packaging and Textile Applications 472.2.2.1 Printability Enhancement 472.2.2.2 Dyeability Improvement 472.2.2.3 Mass Transfer Changes 492.2.3 Biomedical Applications 502.2.3.1 Inert Synthetic Polymers 502.2.3.2 Biodegradable Polymers 532.3 Plasma Grafting 562.4 Hydrophobic Recovery 592.5 Conclusion 61References 613 A Joint Mechanistic Description of Plasma Polymers Synthesized at Low and Atmospheric Pressure 67Damien Thiry, François Reniers, and Rony Snyders3.1 Introduction 673.2 Plasma Polymerization 693.2.1 Plasma Fundamentals 703.2.2 Growth Mechanism 723.3 Probing the Plasma Chemistry 833.3.1 Optical Emission Spectroscopy 843.3.2 Mass Spectrometry 873.4 Conclusions 96References 974 Organic Surface Functionalization by Initiated CVD (iCVD) 107Karen K. Gleason4.1 Introduction 1074.2 Mechanistic Principles of iCVD 1084.3 Functional, Surface Reactive, and Responsive Organic Films Prepared by iCVD 1134.4 Interfacial Engineering with iCVD: Adhesion and Grafting 1274.5 Reactors for Synthesizing Organic Films by iCVD 1284.6 Summary 129References 1305 Atomic Layer Deposition and Vapor Phase Infiltration 135Mark D. Losego and Qing Peng5.1 Atomic Layer Deposition Versus Vapor Phase Infiltration 1355.2 Atomic Layer Deposition (ALD) on Polymers 1385.2.1 Chemical Mechanisms of ALD 1385.2.2 ALD on Polymers with Dense –OH Groups: Cellulose and Poly(vinyl alcohol) 1405.2.3 ALD onto “Unreactive” Polymer Substrates 1415.2.4 Applications of ALD Coated Polymers 1435.2.4.1 ALD Coated Cotton Fibers 1435.2.4.2 Applications for ALD Coatings on Other Polymers 1445.3 Vapor Phase Infiltration of Polymers 1455.3.1 Processing Thermodynamics and Kinetics of VPI 1455.3.1.1 Thermodynamics of Vapor-Phase Precursor Sorption into Polymers 1455.3.1.2 Kinetics of Precursor Diffusion During VPI 1475.3.1.3 VPI Processes Incorporating Both Penetrant Diffusion and Reaction 1485.3.1.4 Measuring the Thermodynamics and Kinetics of a VPI Process 1495.3.2 Applications of Vapor Phase Infiltrated Polymers 1505.3.2.1 Altering Mechanical Performance 1505.3.2.2 Contrasting Agent for Multi-phase Polymer Imaging 1525.3.2.3 Improved Chemical Resistance 1525.3.2.4 Patterning for Microsystems 1535.3.2.5 Vapor Diffusion Barriers 1545.3.2.6 Conducting Polymers and Hybrid Photovoltaic Cells 1545.3.2.7 Other Application Spaces 1555.4 Summary and Future Outlook for ALD and VPI on Polymers 156References 156Part II UV and Related Methods 1616 Photoinduced Functionalization on Polymer Surfaces 163Kazuhiko Ishihara6.1 Introduction 1636.2 Improving the Surface Properties of Polymeric Materials by Photoirradiation 1656.3 Photoreaction of Polymers with Other Polymers 1666.3.1 Photoinduced Chemical Reaction Between Polymers 1666.3.2 Photoinduced Grafting at the Polymer Surface 1686.3.3 Preparation of High-functionality Surface by Photoinduced Graft Polymerization 1696.3.4 Application of Photoinduced Grafting Process to Artificial Organs 1726.4 Self-initiated Photoinduced Graft Polymerization 1746.4.1 Poly(ether ketone) as Photoinitiator for Graft Polymerization 1746.4.2 Effects of Inorganic Salts on Photoinduced Graft Polymerization in an Aqueous System 1786.5 Conclusion and Future Perspective 180References 1817 ;;-Rays and Ions Irradiation 185Alejandro Ramos-Ballesteros, Victor H. Pino-Ramos, Felipe López-Saucedo,Guadalupe G. Flores-Rojas, and Emilio Bucio7.1 ;;-Rays and Ions Irradiation 1857.2 Ionizing Radiation Sources 1867.3 ;;-Ray-Induced Modifications 1867.3.1 Grafting Modifications 1867.3.1.1 Radiation-induced Grafting Methods 1887.3.1.2 Ionic Grafting 1927.3.1.3 RAFT-graft Polymerization 1937.3.1.4 Applications 1947.3.2 Cross-linking 1977.3.2.1 ;;-Ray Cross-linking Modifications 1997.3.2.2 Cross-linking with Additives 2007.3.2.3 Industrial Applications 2017.4 Heavy Ion-Induced Modifications 2027.4.1 Polymers 2047.5 Conclusions 205Acknowledgments 206References 206Part III Chemical Methods 2118 Functionalization of Polymers by Hydrolysis, Aminolysis, Reduction, Oxidation, and Some Related Reactions 213Dardan Hetemi and Jean Pinson8.1 Hydrolysis and Aminolysis 2138.1.1 PLA and Polyesters 2138.1.2 Hydrolysis 2148.1.3 Aminolysis 2148.1.4 PCL 2158.1.5 PET 2168.1.6 PMMA 2168.1.7 Cellulose 2178.2 Chemical Reduction 2208.2.1 PEEK 2208.2.2 PET 2258.2.3 PMMA 2278.2.4 PC 2278.2.5 PTFE 2298.3 Chemical Oxidation 2318.4 Non-covalent Surface Modification 2348.5 Conclusion 235References 2369 Functionalization of Polymers by Reaction of Radicals, Nitrenes, and Carbenes 241Jean Pinson9.1 Functionalization of Polymers by Reaction of Radicals 2419.1.1 Peroxides as Radical Initiators 2419.1.2 Hydrogen Peroxides as Radical Initiator 2449.1.3 Persulfates as Radical Initiators 2469.1.4 Oxygen as Radical Initiator 2489.1.5 Azo Compounds as Radical Initiator 2499.1.6 Diazonium Salts as Radical Initiator 2509.1.6.1 Polypyrrole 2519.1.6.2 Polyaniline 2519.1.6.3 Poly(3,4-ethylenedioxythiophene)–Poly(styrenesulfonate) (PEDOT:PSS) 2539.1.6.4 Polymethylmethacrylate (PMMA) 2549.1.6.5 Polypropylene (PP) 2559.1.6.6 Polyvinyl Chloride 2559.1.6.7 Cyclic Olefin Copolymers (COC) 2569.1.6.8 Polyetheretherketone (PEEK) 2569.1.6.9 PET (Polyethylene Terephthalate) 2579.1.6.10 Polysulfone Membranes 2589.1.6.11 Cation Exchange Membranes 2589.1.6.12 Fluoro Polymers 2599.1.6.13 Natural Polymers 2609.1.7 Alkyl Halides as Radical Initiator 2609.2 Surface Modification of Polymers with Carbenes and Nitrenes 2609.2.1 Carbenes 2619.2.2 Nitrenes 2649.3 Conclusion 267References 26810 Surface Modification of Polymeric Substrates with Photo- and Sonochemically Designed Macromolecular Grafts 273Fatima Mousli, Youssef Snoussi, Ahmed M. Khalil, Khouloud Jlassi, Ahmed Mekki, and Mohamed M. Chehimi10.1 Introduction 27310.1.1 Context 27310.1.2 Scope of the Chapter 27410.2 Surface-confined Radical Photopolymerization of Insulating Vinylic and Other Monomers 27410.2.1 Type I and Type II Photoinitiation Systems 27510.2.2 Simultaneous Photoinduced Electron Transfer and Free Radical Polymerization Confined to Surfaces 28210.2.3 Surface-initiated Photoiniferter 28410.2.4 “Brushing Up from Anywhere” Using Polydopamine Thin Adhesive Coatings 28410.2.5 Recent Trends in Surface-confined Photopolymerization (CRP) 28710.3 Surface-confined Photopolymerization of Conjugated Monomers 28910.3.1 Polypyrrole 29010.3.1.1 Mechanisms of Photopolymerization of Pyrrole 29010.3.1.2 Substrates for in Situ Photoinduced Polymerization of Pyrrole and Potential Applications 29110.3.2 Polyaniline 29410.3.2.1 Mechanisms of Photopolymerization of Aniline 29410.3.2.2 Substrates for in Situ Photoinduced Polymerization of Aniline 29810.4 Surface-confined Sonochemical Polymerization of Conjugated and Vinylic Monomers 29810.4.1 Insights into Sonochemistry: Origin of the Phenomenon and Mechanism of Polymer Synthesis 29810.4.2 Ultrasound-assisted Polymerization or Polymer Deposition over Organic Polymeric Substrates 30310.4.2.1 Sonopolymerization 30310.4.2.2 Ultrasonic Spray 30310.4.3 Sonopolymerization over Miscellaneous Types of Surface: Inorganic Polymeric Substrates 30510.5 Conclusion 306Acknowledgments 307References 307Part IV Applications 31711 Surface Modification of Nanoparticles: Methods and Applications 319Gopikrishna Moku, Vijayagopal Raman Gopalsamuthiram, Thomas R. Hoye, and Jayanth Panyam11.1 Introduction 31911.2 Polymers Used in the Preparation of Nanoparticles 32011.3 Common Biodegradable Polymers for Nanoparticle Fabrication 32011.3.1 Albumin 32011.3.2 Alginate 32011.3.2.1 Chitosan 32111.3.3 Gelatin 32211.3.4 Poly(lactide-co-glycolide) (PLGA) and Polylactide (PLA) 32211.3.5 Poly-ε-caprolactone (PCL) 32311.4 Fabrication of Nanoparticles 32311.5 Linker Chemistry for Attaching Ligands on Polymeric Nanoparticles 32411.5.1 Hydrazone Bond Formation 32711.5.2 Non-covalent Attachment 32811.6 Surface-functionalized Polymeric Nanoparticles for Drug Delivery Applications 32811.6.1 Polysaccharides 32911.6.2 Lipids 32911.6.3 Aptamers 33211.6.4 Antibodies 33211.6.5 Peptides 33311.6.5.1 Polyethylene Glycol (PEG) 33411.7 Characterization of Surface-modified Nanoparticles 33611.7.1 Particle Size 33611.7.2 Dynamic Light Scattering (DLS) 33711.7.3 Scanning Electron Microscopy (SEM) 33711.7.4 Transmission Electron Microscopy (TEM) 33911.7.5 Surface Charge 33911.7.6 Surface Hydrophobicity 34011.7.7 Fourier Transform IR (FTIR) Spectroscopy 34111.8 Summary/Conclusion 342References 34212 Surface Modification of Polymers for Food Science 347Valentina Siracusa12.1 Introduction 34712.2 Physical and Chemical Methods 34812.2.1 Gas Phase and Radiation 34912.2.1.1 Gas Phase 34912.2.1.2 Radiation 35012.2.2 Liquid and Bulk Phase Methods 35212.2.2.1 Adsorption Methods 35212.2.2.2 Desorption Method 35212.2.3 Interfacial Adhesion of Polymers 35312.2.4 Grafting and Polymerization 35412.3 Mechanical Method 35412.4 Biological Method 35412.5 Surface Modification of Polymer for Food Packaging 35512.5.1 Applications 35512.5.1.1 Surface Sterilization 35512.5.1.2 Printing 35512.5.1.3 Mass Transfer 35612.5.2 Polymers 35612.6 Conclusion 358References 35913 Surface Modification of Water Purification Membranes 363Anthony Szymczyk, Bart van der Bruggen, and Mathias Ulbricht13.1 Introduction 36313.2 Irradiation-Based Direct Polymer Modification 36513.2.1 Plasma Treatment 36513.2.2 UV Irradiation 36613.2.3 Irradiation with High Energy Sources 36813.3 Coatings 36913.3.1 Coatings from Gas Phase 36913.3.2 Coatings from Wet Phase 37113.4 Grafting Methods 37813.4.1 Grafting-to 37813.4.2 Grafting-from 38113.4.2.1 Plasma-Induced Graft Polymerization 38113.4.2.2 UV-Induced Grafting 38313.4.2.3 Grafting Induced by High Energy Radiations 38513.4.2.4 Grafting Initiated by Chemical/Electrochemical Means 38513.4.3 Controlled Grafting-from 38913.5 Conclusion 392References 39414 Surface Modification of Polymer Substrates for Biomedical Applications 399P. Slepicka, N. Slepièková Kasálková, Z. Kolská, and V. Švorèík14.1 Introduction 39914.2 Plasma Treatment 40014.3 Laser Modification 41114.3.1 Interaction with Cells 41114.3.2 Sensor Construction 41214.4 Conclusion 416Acknowledgments 417References 417Index 427