The plasma chemistry of polymer surfaces: advanced techniques for surface design

This book illustrates plasma properties, polymer characteristics, surface specifics, and how to purposefully combine plasma and polymer chemistry. In so doing, it covers plasma polymerization, surface functionalization, etching, crosslinking, and deposition of monotype functional-group-bearing plasma polymers.It explains different techniques and plasma types, such as pressure-pulsed, remote, low-wattage plasmas and plasma polymerization in liquids. Finally, among the numerous applications discussed are plasmas for chemical synthesis, industrial processes or the modification of membranes and papers, adhesion promotion, corrosion protection, fire retardency, and as ion-exchangers and biomaterials as well as DNA chips, nanoparticle modifiers, and solar cells. INDICE: Preface XI1 Introduction 1References 92 Interaction between Plasmaand Polymers 112.1 Special Features of Polymers 112.2 Processes on Polymer Surfaces during Plasma Exposure 142.3 Influence of Polymer Type 232.4 Methods, Systematic, and Definitions 242.4.1 Surface Modifi cation (Functionalization) 252.4.2 Coating of Polymer Surfaces with Functional Group-Bearing Plasma Polymers 262.4.2.1 Plasma-Chemical Polymerization 262.4.2.2 Pulsed-Plasma Polymerization 272.4.3 Other Polymer Process 282.4.3.1 Polymer Etching 282.4.3.2 Crosslinking 292.5 Functional Groups and Their Interaction with Other Solids 29References 313 Plasma 353.1 Plasma State 353.2 Types of Low-Pressure Glow Discharges453.3 Advantages and Disadvantages of Plasma Modification of Polymer Surfaces483.4 Energetic Situation in Low-Pressure Plasmas 493.5 Atmospheric and Thermal Plasmas for Polymer Processing 503.6 Polymer Characteristics 513.7 Chemically Active Species and Radiation 53References 534 Chemistry and Energetics in Classic and Plasma Processes 554.1 Introduction of Plasma Species onto Polymer Surfaces 554.2 Oxidation by Plasma Fluorination and by Chemical Fluorination 644.3 Comparison of Plasma Exposure, Ionizing Irradiation, and Photo-oxidation of Polymers 65References 675 Kinetics of Polymer Surface Modification 695.1 Polymer Surface Functionalization 695.1.1 Kinetics of Surface Functionalization 695.1.2 Unspecific Functionalizations by Gaseous Plasmas 725.2 Polymer SurfaceOxidation 725.2.1 Polyolefins 725.2.2 Aliphatic Self-Assembled Monolayers 735.2.3 Polyethylene 755.2.4 Polypropylene 785.2.5 Polystyrene 795.2.6 Polycarbonate 855.2.7 Poly(ethylene terephthalate) 865.2.8 Summary of Changes at PolymerSurfaces on Exposure to Oxygen Plasma 945.2.9 Categories of General Behavior of Polymers on Exposure to Oxygen Plasma 975.2.10 Role of Contaminations at Polymer Surfaces 1005.2.11 Dependence of Surface Energy on Oxygen Introduction 1025.3 Polymer Surface Functionalization with Amino Groups 1035.3.1 Ammonia Plasma Treatment for Introduction of Amino Groups 1035.3.2 Side Reactions 1095.3.3 Instability Caused by Post-Plasma Oxidation 1105.3.4 Exposure of Self-Assembled (SAM) and Langmuir-Blodgett (LB)Monolayers to Ammonia Plasma 1115.3.5 XPS Measurements of Elemental Compositions 1125.3.6 ToF-SIMS Investigations 1145.3.7 ATR-FTIR 1155.3.8 CHN Analysis 1175.3.9 NMR 1185.3.10 Discussion of Hydrogenation and Amination of Polyolefi ns byAmmonia Plasma 1205.4 Carbon Dioxide Plasmas 1235.5 SH-Forming Plasmas 1265.6 Fluorinating Plasmas 1265.7 Chlorination 1345.8 Polymer Modifi cation by Noble Gas Plasmas 136References 1396 Bulk, Ablative, and Side Reactions 1456.1 Changes in Supermolecular Structure of Polymers 1456.2 Polymer Etching 1516.3 Changes in Surface Topology 1556.4 Plasma Susceptibility of Polymer Building Blocks 1586.5 Plasma UV Irradiation 1606.6 Absorption of Radiation by Polymers 1626.7 Formation of Unsaturations 1656.8 Formation of Macrocycles 1696.9 Polymer Degradation and Supermolecular Structureof Polymers 1716.10 Crosslinking versus Degradation of Molar Masses 1756.11 Radicals and Auto-oxidation 1776.12 Plasma-Induced Photo-oxidations of Polymers 1816.13 Different Degradation Behavior of Polymers on Exposure toOxygen Plasma1816.14 Derivatization of Functional Groups for XPS 185References 1937 Metallization of Plasma-Modifi ed Polymers 1977.1 Background 1977.2 Polymer Plasma Pretreatment for Well AdherentMetal-Polymer Composites 1987.2.1 Surface Cleaning by Plasma for Improving Adhesion 1997.2.2 Oxidative Plasma Pretreatment of Polymers for Adhesion Improvement 2027.2.3 Reductive Plasma Pretreatment of Perfluorinated Polymers 2077.2.4 Adhesion Improvement Using Homo- and Copolymer Interlayers 2107.3 New Adhesion Concept 2137.4 Redox Reactions along the Interface 2207.5 Influence of Metal-Polymer Interactions on Interface-Neighbored Polymer Interphases 2247.6 Metal-Containing Plasma Polymers 2277.7 Plasma-Initiated Deposition of Metal Layers 2287.8 Inspection of Peeled Surfaces 2287.9 LifeTime of Plasma Activation 229References 2348 Accelerated Plasma-Aging of Polymers 2398.1 Polymer Response to Long-Time Exposure to Plasmas 2398.2 Hydrogen Plasma Exposure 2448.3 Noble Gas Plasma Exposure, CASING 247References 2479 Polymer Surface Modifi cations with Monosort Functional Groups 2499.1 Various Ways of Producing Monosort Functional Groups at Polyolefin Surfaces 2499.2 Oxygen Plasma Exposure and Post-Plasma Chemical Treatment for Producing OH Groups 2519.3 Post-Plasma Chemical Grafting of Molecules, Oligomers, or Polymers 2569.3.1 Grafting onto OH Groups 2569.3.2 Grafting onto NH2 Groups 2579.3.3 Grafting onto COOH-Groups 2589.4 Selective Plasma Bromination for Introduction of Monosort C-Br Bonds to Polyolefin Surfaces 2589.4.1 General Remarks 2589.4.2 History of the Plasma Bromination Process 2609.4.3 Theoretical Considerations on the Plasma Bromination Process 2609.4.4 Bromination Using Bromoform or Bromine Plasmas 2659.4.5 Bromination Using Allyl Bromide Plasma 2699.4.6 Grafting ontoBromine Groups 2719.4.7 Yield in Density of Grafted Molecules at Polyolefin Surfaces 2729.4.8 Change of Surface Functionality 2779.4.9 Surface Bromination of Polyolefins: Conclusions 2799.4.10 Bromination of Poly(ethylene terephthalate) 2809.5 Functionalization of Graphitic Surfaces 2819.5.1 Bromination with Bromine Plasma 2819.5.2 Dependence of Bromination Rate on Plasma Parameters 2869.5.3 Alternative Plasma Bromination Precursors 2879.5.4 Efficiency in Bromination of Carbon and Polymer Materials 2889.5.5 Grafting of Amines to BrominatedSurfaces 2889.5.6 Refunctionalization to OH Groups 2899.5.7 NH2 Introduction onto Carbon Surfaces 2899.6 SiOx Deposition 2929.7 Grafting onto Radical Sites2949.7.1 Types of Produced Radicals 2959.7.2 Grafting onto C-Radical Sites 2959.7.3 Post-Plasma Quenching of Radicals 2969.7.4 Grafting on Peroxide Radicals 2969.7.5 Plasma Ashing 297References 29710 Atmospheric-Pressure Plasmas 30310.1 General 30310.2 Dielectric Barrier Discharge (DBD) Treatment 30410.3 Polymerization by Introduction of Gases, Vapors, or Aerosols into a DBD 31110.4 Introduction of Polymer Molecules into the Atmospheric-Pressure Plasma and Their Deposition as Thin Polymer Films (Aerosol-DBD) 31210.5 DBD Treatment of Polyolefi n Surfaces for Improving Adhesion in Metal-Polymer Composites 32010.6 Electrospray Ionization (ESI) Technique 32110.6.1 ESI + Plasma 32710.6.2 ESI without Plasma 32810.6.3 Comparison of Aerosol-DBD and Electrospray 32910.6.4 Topography 33010.6.5 Electrophoretic Effect of ESI 333References 33311 Plasma Polymerization 33711.1 Historical 33711.2 General Intention and Applications 34011.3 Mechanism of Plasma Polymerization 34111.3.1 Plasma-Induced Radical Chain-Growth Polymerization Mechanism 34211.3.2 Ion-Molecule Reactions 34411.3.3 Fragmentation-(Poly)recombination (Plasma Polymerization) 34411.4 Plasma Polymerization in Adsorption Layer or Gas Phase 34511.5 Side-Reactions 34611.6 Quasi-hydrogen Plasma 34811.7 Kinetic Models Based on Ionic Mechanism 35111.8 Kinetic Models of Plasma-Polymer Layer Deposition Based on a Radical Mechanism 35311.9 Dependence on Plasma Parameter 35811.10 Structure of Plasma Polymers 36111.11 Afterglow (Remote or Downstream) Plasmas 36411.12 Powder Formation 36611.13 Plasma Catalysis 36711.14 Copolymerization in Continuous-Wave Plasma Mode 368References 37012 Pulsed-Plasma Polymerization 37712.1 Introduction 37712.2 Basics37712.3 Presented Work on Pulsed-Plasma Polymerization 38112.4 Role of Monomers in Pulsed-Plasma Polymerization 38212.5 Dark Reactions 38412.6 Pressure-Pulsed Plasma 38512.7 Differences between Radical and Pulsed-Plasma Polymerization 38912.8 Surface Structure and Composition of Pulsed-Plasma Polymers 39112.9 Plasma-Polymer Aging and Elimination of Radicals in Plasma Polymers 40112.10 Functional Groups Carrying Plasma-Polymer Layers 40312.10.1 Allyl Alcohol 40312.10.2 Allylamine 41312.10.3 Acrylic Acid 41612.10.4 Acrylonitrile 42112.11 Vacuum Ultraviolet (VUV) Induced Polymerization 42212.12 Plasma-Initiated Copolymerization 42412.12.1 Reasons for Copolymerization 42412.12.2 Copolymer Kinetics 42712.12.3 Allyl Alcohol Copolymers with Ethylene, Butadiene, and Acetylene 42712.12.4 Allyl Alcohol Copolymers with Styrene 43412.12.5 Acrylic Acid 44312.12.6 Copolymers with Allylamine 44512.13 Graft Polymerization 44712.14 Grafting onto Functional Groups 450References 451Index 457

• ISBN: 978-3-527-31853-7
• Editorial: Wiley-VCH
• Encuadernacion: Cartoné
• Páginas: 473
• Fecha Publicación: 25/04/2012
• Nº Volúmenes: 1
• Idioma: Inglés