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The Plasma Chemistry of Polymer Surfaces: Advanced Techniques for Surface Design

ISBN: 978-3-527-31853-7
473 pages
May 2012
The Plasma Chemistry of Polymer Surfaces: Advanced Techniques for Surface Design (3527318534) cover image
More than 99% of all visible matter in the universe occurs as highly ionized gas plasma with high energy content. Electrical low- and atmospheric-pressure plasmas are characterized by continuous source of moderate quantities of energy or enthalpy transferred predominantly as kinetic energy of electrons. Therefore, such energetically unbalanced plasmas have low gas temperature but produce
sufficient energy for inelastic collisions with atoms and molecules in the gas phase, thus producing reactive species and photons, which are able to initiate all types of polymerizations or activate any surface of low reactive polymers. However, the broadly distributed energies in the plasma exceed partially the binding energies in polymers, thus initiating very often unselective reactions and polymer degradation. The intention of this book is to present new plasma processes and new plasma reactions of high selectivity and high yield.

This book aims to bridge classical and plasma chemistry, particularly focusing on polymer chemistry in the bulk and on the surface under
plasma exposure. The stability of surface functionalization and the qualitative and quantitative measurement of functional groups at polymer
surface are featured prominently, and chemical pathways for suppressing the undesirable side effects of plasma exposure are proposed
and illustrated with numerous examples. Special attention is paid to the smooth transition from inanimate polymer surfaces to modified bioactive polymer surfaces. A wide range of techniques, plasma types and applications are demonstrated.
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Preface XI

1 Introduction 1

References 9

2 Interaction between Plasma and Polymers 11

2.1 Special Features of Polymers 11

2.2 Processes on Polymer Surfaces during Plasma Exposure 14

2.3 Influence of Polymer Type 23

2.4 Methods, Systematic, and Definitions 24

2.4.1 Surface Modifi cation (Functionalization) 25

2.4.2 Coating of Polymer Surfaces with Functional Group-Bearing Plasma Polymers 26

2.4.2.1 Plasma-Chemical Polymerization 26

2.4.2.2 Pulsed-Plasma Polymerization 27

2.4.3 Other Polymer Process 28

2.4.3.1 Polymer Etching 28

2.4.3.2 Crosslinking 29

2.5 Functional Groups and Their Interaction with Other Solids 29

References 31

3 Plasma 35

3.1 Plasma State 35

3.2 Types of Low-Pressure Glow Discharges 45

3.3 Advantages and Disadvantages of Plasma Modification of Polymer Surfaces 48

3.4 Energetic Situation in Low-Pressure Plasmas 49

3.5 Atmospheric and Thermal Plasmas for Polymer Processing 50

3.6 Polymer Characteristics 51

3.7 Chemically Active Species and Radiation 53

References 53

4 Chemistry and Energetics in Classic and Plasma Processes 55

4.1 Introduction of Plasma Species onto Polymer Surfaces 55

4.2 Oxidation by Plasma Fluorination and by Chemical Fluorination 64

4.3 Comparison of Plasma Exposure, Ionizing Irradiation, and Photo-oxidation of Polymers 65

References 67

5 Kinetics of Polymer Surface Modification 69

5.1 Polymer Surface Functionalization 69

5.1.1 Kinetics of Surface Functionalization 69

5.1.2 Unspecific Functionalizations by Gaseous Plasmas 72

5.2 Polymer Surface Oxidation 72

5.2.1 Polyolefins 72

5.2.2 Aliphatic Self-Assembled Monolayers 73

5.2.3 Polyethylene 75

5.2.4 Polypropylene 78

5.2.5 Polystyrene 79

5.2.6 Polycarbonate 85

5.2.7 Poly(ethylene terephthalate) 86

5.2.8 Summary of Changes at Polymer Surfaces on Exposure to Oxygen Plasma 94

5.2.9 Categories of General Behavior of Polymers on Exposure to Oxygen Plasma 97

5.2.10 Role of Contaminations at Polymer Surfaces 100

5.2.11 Dependence of Surface Energy on Oxygen Introduction 102

5.3 Polymer Surface Functionalization with Amino Groups 103

5.3.1 Ammonia Plasma Treatment for Introduction of Amino Groups 103

5.3.2 Side Reactions 109

5.3.3 Instability Caused by Post-Plasma Oxidation 110

5.3.4 Exposure of Self-Assembled (SAM) and Langmuir–Blodgett (LB)

Monolayers to Ammonia Plasma 111

5.3.5 XPS Measurements of Elemental Compositions 112

5.3.6 ToF-SIMS Investigations 114

5.3.7 ATR-FTIR 115

5.3.8 CHN Analysis 117

5.3.9 NMR 118

5.3.10 Discussion of Hydrogenation and Amination of Polyolefi ns by

Ammonia Plasma 120

5.4 Carbon Dioxide Plasmas 123

5.5 SH-Forming Plasmas 126

5.6 Fluorinating Plasmas 126

5.7 Chlorination 134

5.8 Polymer Modifi cation by Noble Gas Plasmas 136

References 139

6 Bulk, Ablative, and Side Reactions 145

6.1 Changes in Supermolecular Structure of Polymers 145

6.2 Polymer Etching 151

6.3 Changes in Surface Topology 155

6.4 Plasma Susceptibility of Polymer Building Blocks 158

6.5 Plasma UV Irradiation 160

6.6 Absorption of Radiation by Polymers 162

6.7 Formation of Unsaturations 165

6.8 Formation of Macrocycles 169

6.9 Polymer Degradation and Supermolecular Structure

of Polymers 171

6.10 Crosslinking versus Degradation of Molar Masses 175

6.11 Radicals and Auto-oxidation 177

6.12 Plasma-Induced Photo-oxidations of Polymers 181

6.13 Different Degradation Behavior of Polymers on Exposure to

Oxygen Plasma 181

6.14 Derivatization of Functional Groups for XPS 185

References 193

7 Metallization of Plasma-Modified Polymers 197

7.1 Background 197

7.2 Polymer Plasma Pretreatment for Well Adherent

Metal–Polymer Composites 198

7.2.1 Surface Cleaning by Plasma for Improving Adhesion 199

7.2.2 Oxidative Plasma Pretreatment of Polymers for Adhesion Improvement 202

7.2.3 Reductive Plasma Pretreatment of Perfluorinated Polymers 207

7.2.4 Adhesion Improvement Using Homo- and Copolymer Interlayers 210

7.3 New Adhesion Concept 213

7.4 Redox Reactions along the Interface 220

7.5 Influence of Metal–Polymer Interactions on Interface-Neighbored Polymer Interphases 224

7.6 Metal-Containing Plasma Polymers 227

7.7 Plasma-Initiated Deposition of Metal Layers 228

7.8 Inspection of Peeled Surfaces 228

7.9 Life Time of Plasma Activation 229

References 234

8 Accelerated Plasma-Aging of Polymers 239

8.1 Polymer Response to Long-Time Exposure to Plasmas 239

8.2 Hydrogen Plasma Exposure 244

8.3 Noble Gas Plasma Exposure, CASING 247

References 247

9 Polymer Surface Modifications with Monosort Functional Groups 249

9.1 Various Ways of Producing Monosort Functional Groups at Polyolefin Surfaces 249

9.2 Oxygen Plasma Exposure and Post-Plasma Chemical Treatment for Producing OH Groups 251

9.3 Post-Plasma Chemical Grafting of Molecules, Oligomers, or Polymers 256

9.3.1 Grafting onto OH Groups 256

9.3.2 Grafting onto NH2 Groups 257

9.3.3 Grafting onto COOH-Groups 258

9.4 Selective Plasma Bromination for Introduction of Monosort C–Br Bonds to Polyolefin Surfaces 258

9.4.1 General Remarks 258

9.4.2 History of the Plasma Bromination Process 260

9.4.3 Theoretical Considerations on the Plasma Bromination Process 260

9.4.4 Bromination Using Bromoform or Bromine Plasmas 265

9.4.5 Bromination Using Allyl Bromide Plasma 269

9.4.6 Grafting onto Bromine Groups 271

9.4.7 Yield in Density of Grafted Molecules at Polyolefin Surfaces 272

9.4.8 Change of Surface Functionality 277

9.4.9 Surface Bromination of Polyolefins: Conclusions 279

9.4.10 Bromination of Poly(ethylene terephthalate) 280

9.5 Functionalization of Graphitic Surfaces 281

9.5.1 Bromination with Bromine Plasma 281

9.5.2 Dependence of Bromination Rate on Plasma Parameters 286

9.5.3 Alternative Plasma Bromination Precursors 287

9.5.4 Efficiency in Bromination of Carbon and Polymer Materials 288

9.5.5 Grafting of Amines to Brominated Surfaces 288

9.5.6 Refunctionalization to OH Groups 289

9.5.7 NH2 Introduction onto Carbon Surfaces 289

9.6 SiOx Deposition 292

9.7 Grafting onto Radical Sites 294

9.7.1 Types of Produced Radicals 295

9.7.2 Grafting onto C-Radical Sites 295

9.7.3 Post-Plasma Quenching of Radicals 296

9.7.4 Grafting on Peroxide Radicals 296

9.7.5 Plasma Ashing 297

References 297

10 Atmospheric-Pressure Plasmas 303

10.1 General 303

10.2 Dielectric Barrier Discharge (DBD) Treatment 304

10.3 Polymerization by Introduction of Gases, Vapors, or Aerosols into a DBD 311

10.4 Introduction of Polymer Molecules into the Atmospheric-Pressure Plasma and Their Deposition as Thin Polymer Films (Aerosol-DBD) 312

10.5 DBD Treatment of Polyolefi n Surfaces for Improving Adhesion in Metal–Polymer Composites 320

10.6 Electrospray Ionization (ESI) Technique 321

10.6.1 ESI + Plasma 327

10.6.2 ESI without Plasma 328

10.6.3 Comparison of Aerosol-DBD and Electrospray 329

10.6.4 Topography 330

10.6.5 Electrophoretic Effect of ESI 333

References 333

11 Plasma Polymerization 337

11.1 Historical 337

11.2 General Intention and Applications 340

11.3 Mechanism of Plasma Polymerization 341

11.3.1 Plasma-Induced Radical Chain-Growth Polymerization Mechanism 342

11.3.2 Ion–Molecule Reactions 344

11.3.3 Fragmentation–(Poly)recombination (“Plasma Polymerization”) 344

11.4 Plasma Polymerization in Adsorption Layer or Gas Phase 345

11.5 Side-Reactions 346

11.6 Quasi-hydrogen Plasma 348

11.7 Kinetic Models Based on Ionic Mechanism 351

11.8 Kinetic Models of Plasma-Polymer Layer Deposition Based on a Radical Mechanism 353

11.9 Dependence on Plasma Parameter 358

11.10 Structure of Plasma Polymers 361

11.11 Afterglow (Remote or Downstream) Plasmas 364

11.12 Powder Formation 366

11.13 Plasma Catalysis 367

11.14 Copolymerization in Continuous-Wave Plasma Mode 368

References 370

12 Pulsed-Plasma Polymerization 377

12.1 Introduction 377

12.2 Basics 377

12.3 Presented Work on Pulsed-Plasma Polymerization 381

12.4 Role of Monomers in Pulsed-Plasma Polymerization 382

12.5 Dark Reactions 384

12.6 Pressure-Pulsed Plasma 385

12.7 Differences between Radical and Pulsed-Plasma Polymerization 389

12.8 Surface Structure and Composition of Pulsed-Plasma Polymers 391

12.9 Plasma-Polymer Aging and Elimination of Radicals in Plasma Polymers 401

12.10 Functional Groups Carrying Plasma-Polymer Layers 403

12.10.1 Allyl Alcohol 403

12.10.2 Allylamine 413

12.10.3 Acrylic Acid 416

12.10.4 Acrylonitrile 421

12.11 Vacuum Ultraviolet (VUV) Induced Polymerization 422

12.12 Plasma-Initiated Copolymerization 424

12.12.1 Reasons for Copolymerization 424

12.12.2 Copolymer Kinetics 427

12.12.3 Allyl Alcohol Copolymers with Ethylene, Butadiene, and Acetylene 427

12.12.4 Allyl Alcohol Copolymers with Styrene 434

12.12.5 Acrylic Acid 443

12.12.6 Copolymers with Allylamine 445

12.13 Graft Polymerization 447

12.14 Grafting onto Functional Groups 450

References 451

Index 457

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Jörg Florian Friedrich was born in 1948, in Erkner, near Berlin. From 1967 to 1972, he studied chemistry at Humboldt University in Berlin. In 1972 he began his PhD studies at the German Academy of Sciences in Berlin in the Institute for Macromolecular Chemistry. His graduation
followed in the years 1974/1975 as PhD resp. Dr. rer. nat., and in 1981/1982 he obtained his habilitation (lecture qualifi cation). He continued his career in the Federal Institute for Materials Research and Testing (BAM) from 1995 on as head of the Division 'Analysis and Structure of Polymers' and later on 'Polymer Surfaces'. He was appointed to professor (and director) in 1996 and to professor at Technical University of Berlin, in 2007.
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