Contents
Preface XV
List of Contributors XIX
List of Contacts XXIII
Part I Introduction to Plasma Technology for Surface
Functionalization 1
1 Introduction to Plasma and Plasma Technology 3
Massimo Perucca
1.1 Plasma: the Fourth State of Matter 3
1.2 Historical Highlights 4
1.3 Plasma Fundamentals 6
1.3.1 Free Ideal Gas 7
1.3.2 Interacting Gas 8
1.3.3 The Plasma as a Fluid 11
1.3.4 Waves in Plasmas 12
1.3.5 Relevant Parameters that Characterize the State of Plasma 14
1.4 Classification of Technological Plasmas 17
1.4.1 Hot (Thermal) Plasmas and Their Applications 18
1.4.2 Cold (Nonthermal) Plasmas and Their Applications 19
1.5 Reactive Plasmas 22
1.5.1 Elementary Plasma–Chemical Reactions 22
1.5.2 Elastic Scattering and Inelastic Thomson Scattering: Ionization
Cross-section 24
1.5.3 Molecular Ionization Mechanisms 25
1.5.4 Stepwise Ionization by Electron Impact 26
1.6 Plasma Sheaths 28
1.7 Summary 31
References 31
2 Plasma Systems for Surface Treatment 33
Guy Buyle, Joachim Schneider, Matthias Walker, Yuri Akishev, Anatoly
Napartovich, and Massimo Perucca
2.1 Introduction 33
2.2 Low Pressure Plasma Systems 34
2.2.1 Microwave Systems 35
2.2.1.1 Introduction 35
2.2.1.2 Standard Microwave System for Textile Treatment 36
2.2.1.3 Example: Duo-Plasmaline–a Linearly Extended Plasma Source 36
2.2.1.4 Electron Cyclotron Resonance Heated Plasmas 40
2.2.2 Capacitively Coupled Systems 43
2.2.2.1 Introduction 43
2.2.2.2 Capacitive Coupled Plasma for Biomedical Applications 44
2.2.3 Physical Vapor Deposition Plasma: LARC 45
2.2.3.1 Background 45
2.2.3.2 Cathodic Arc PVD Systems 45
2.2.3.3 Example: Treatment of Food Processing Tools by LARC
PVD System 48
2.3 Atmospheric Pressure Plasma Systems 49
2.3.1 Corona-type Surface Treatment 51
2.3.1.1 Standard Corona Treatment 51
2.3.1.2 Controlled Atmosphere Corona Treatment–Aldyne Treatment 52
2.3.1.3 Liquid Deposition 52
2.3.2 Remote Surface Treatment 54
2.3.2.1 Plasma Sources Used for Modeling 55
2.3.2.2 Example: AcXys Plasma Jet 57
2.4 Summary 58
Acknowledgment 59
References 59
3 Plasma-surface Interaction 63
Domenico D’Angelo
3.1 Introduction 63
3.2 Polymer Etching 65
3.3 Plasma Grafting 66
3.4 Chemical Kinetics 68
3.4.1 Chain Polymerization 68
3.4.2 Plasma Polymerization 70
3.5 Example: Plasma Polymerization 71
3.5.1 Plasma Polymerization of HEMA 72
3.5.1.1 Theoretical Background 72
3.5.1.2 Example: Polymerization of HEMA on PET Fabric 73
3.5.2 Plasma Polymerization of HDMSO 75
3.6 Conclusion 76
References 77
4 Process Diagnostics by Optical Emission Spectroscopy 79
Giacomo Piacenza
4.1 Introduction 79
4.2 Optical Emission Spectroscopy 79
4.2.1 Theory of Optical Emission 80
4.2.2 Spectroscopy 82
4.2.3 OES Bench and Set-up 83
4.3 Optical Absorption Spectroscopy 85
4.3.1 Actinometry 86
4.4 Laser Induced Fluorescence (LIF) 87
4.5 Conclusion 88
References 88
5 Surface Analysis for Plasma Treatment Characterization 91
Amandine David, Yves de Puydt, Laurent Dupuy, S´everine Descours,
Fran¸coise Sommer, Minh Duc Tran, and Jocelyn Viard
5.1 Introduction to Surface Characterization Techniques 91
5.2 X-ray Photoelectron Spectroscopy (XPS) or Electron Spectroscopy
for Chemical Analysis (ESCA) 94
5.2.1 Principles of XPS 95
5.2.2 XPS Core Level Chemical Shift 96
5.2.3 Quantitative Analysis 97
5.2.4 Quantitative Analysis of Nitrogen Plasma-Treated Polypropylene 98
5.2.5 Angle-Resolved XPS Depth Profiling and Surface Sensitivity
Enhancement by Grazing Angle XPS Detection 100
5.2.6 Determination of Thin Coating Thickness by Angle-Resolved
XPS 100
5.2.7 Mapping 104
5.2.8 Summary of XPS 105
5.3 Static Secondary Ion Mass Spectrometry by Time of Flight
(ToF-SSIMS) 106
5.3.1 Principles of ToF-SSIMS 106
5.3.1.1 Secondary Ion Emission 107
5.3.1.2 Static and Dynamic Modes 107
5.3.1.3 Molecular SIMS 107
5.3.2 Applications of ToF-SSIMS 107
5.3.2.1 Spectrometry Mode 108
5.3.2.2 Secondary Ion Imaging 108
5.3.2.3 Depth Profiling 108
5.3.2.4 Data Treatment by Multivariate Methods: Multi-Ion SIMS 108
5.3.2.5 Examples 109
5.3.2.5.1 Poly(ethylene terephthalate) Tissue 109
5.3.2.5.2 Polypropylene Packaging 109
5.3.2.5.3 SiOx Barner Coating on PET 111
5.3.2.5.4 Anti-UV Additive qualification on PET Films 112
5.4 Atomic Force Microscopy 114
5.4.1 Operating Modes in AFM 114
5.4.1.1 Contact Mode 115
5.4.1.1.1 Constant Force Mode 115
5.4.1.2 Resonant Modes 117
5.4.1.2.1 The Contact –No Contact Mode 118
5.4.1.2.2 Phase Contrast Mode 118
5.4.1.3 Other Modes 119
5.4.2 Summary and Outlook 119
5.5 Scanning Electron Microscopy (SEM) 121
5.5.1 Principles of SEM 121
5.5.2 Imaging in SEM 122
5.5.3 New Generation of SEM 122
5.5.4 Chemical Analysis 123
5.5.5 Sample Preparation and Applications 124
5.6 Transmission Electron Microscopy (TEM) 124
5.6.1 Principles of TEM 124
5.6.2 Resolution 126
5.6.3 Image Contrast 126
5.6.4 Chemical Analysis 126
5.6.5 Typical Applications of TEM 127
5.6.6 Sample Requirements 127
5.7 Contact Angle Measurement 129
5.7.1 Surface Energy Calculation 130
5.7.1.1 Owens and Wendt Model for Surface Energy Calculation 130
5.7.1.2 Good and Van Oss Model for Surface Energy Calculation 131
5.8 Conclusions 132
References 132
Part II Hyperfunctional Surfaces for Textiles, Food and Biomedical
Applications 133
6 Tuning the Surface Properties of Textile Materials 135
Guy Buyle, Pieter Heyse, and Isabelle Ferreira
6.1 Introduction 135
6.1.1 Potential Impact of Plasma on the Textile Industry 135
6.1.2 Plasma Basics 137
6.1.3 Fundamental Advantage of Plasma Processing 138
6.1.4 Classification of Plasmas from the Textile Viewpoint 138
6.1.4.1 Pressure-based 140
6.1.4.2 Substrate-based 141
6.2 Plasma Treatment of Textile Materials 142
6.2.1 Overview of Functionalizations 142
6.2.2 Effect of Plasma Treatment on Textile Substrates 143
6.2.2.1 Interaction of Active Plasma Species with a Surface 143
6.2.2.2 Basic Plasma Effect on Substrate 143
6.2.2.3 Aging 144
6.3 Integration of Plasma Processes into the Textile Manufacturing
Chain 146
6.3.1 Fiber Level 147
6.3.2 Filament Level 148
6.3.3 Yarn Level 149
6.3.3.1 Natural Materials 149
6.3.3.1.1 Cotton 149
6.3.3.1.2 Wool 149
6.3.3.1.3 Other Natural Fibers 149
6.3.3.2 Non-natural Materials 150
6.3.4 Fabric Level 150
6.3.4.1 Woven Textiles 151
6.3.4.1.1 Natural Materials 151
6.3.4.1.2 Non-natural Materials 152
6.3.4.2 Knitted Textiles 152
6.3.4.3 Non-wovens 153
6.3.5 Intermediate/Finished Textile Material 154
6.4 Specific Requirements for the Textile Industry 155
6.4.1 Chemical Composition 155
6.4.2 Surface Cleanliness 155
6.4.3 Three-dimensional Structure of Textiles 156
6.4.4 Large Surface Area 157
6.4.5 Moisture Regain and Air Adsorption 158
6.5 Case Studies 158
6.5.1 Assessing the Surface Energy of Textiles 158
6.5.1.1 Introduction to Methods for Evaluating the Surface Energy and
Wetting of Textiles 159
6.5.1.1.1 Wilhelmy Method 159
6.5.1.1.2 Washburn Method 160
6.5.1.2 Evaluation of Methods for Measuring Hydrophilic Properties 161
6.5.1.2.1 Wilhelmy Method 161
6.5.1.2.2 Washburn Method 162
6.5.1.2.3 Summary of Evaluation 163
6.5.1.3 Tests and Standards for Evaluating Hydrophobic/Oleophobic
Properties 163
6.5.1.3.1 Water Repellency: Spray Test 164
6.5.1.3.2 Water/Alcohol Repellency 165
6.5.1.3.3 Oil Repellency 166
6.5.2 Hydrophilic Properties Imparted by Plasma 167
6.5.2.1 Plasma Experiments at Low Pressure 167
6.5.2.1.1 First Screening of Precursors 168
6.5.2.1.2 Aging of the Samples 169
6.5.2.2 Plasma Experiments at Atmospheric Pressure (Aldyne System) 170
6.5.3 Hydrophobic/Oleophobic Properties Imparted by Plasma 171
6.5.3.1 Preliminary Experiments 171
6.5.3.2 Washing Durability 172
6.5.3.3 Abrasion Durability 173
6.5.3.4 Summary of Oleophobic Properties 174
6.6 Transferring Plasma Technology to Industrial Processes 174
6.6.1 Textile Sector Related Issues 175
6.6.2 Fundamental Aspects Regarding Industrialization 176
6.7 Summary 177
References 178
7 Preventing Biofilm Formation on Biomedical Surfaces 183
Virendra Kumar, Hubert Rauscher, Fr´ed´eric Br´etagnol, Farzaneh
Arefi-Khonsari, Jerome Pulpytel, Pascal Colpo, and Fran¸cois Rossi
7.1 Bacterial Adhesion to Biomaterials: Biofilm Formation 183
7.1.1 ‘Biofilm’ and Its Implications in the Biomedical Field 184
7.1.2 Mechanism for Bacterial Adhesion to Surfaces 184
7.1.3 Biofilm Formation – a Multistep Process 186
7.1.4 Factors Influencing Biofilm Formation 187
7.1.4.1 Role of the Conditioning Film 187
7.1.4.2 Material Surface Characteristics 188
7.1.4.3 Micro-organism Characteristics 190
7.1.4.4 Environmental Factors 191
7.2 Biofilm Prevention Strategies 192
7.2.1 Pre-surgery Precautionary Approach 192
7.2.2 Antimicrobial-releasing Biomaterials 193
7.2.3 Surface-engineering Approach 193
7.2.3.1 High Surface Energy Approach 194
7.2.3.2 Low Surface Energy Approach 195
7.2.3.3 Surfaces with Bound Tethered Antimicrobial Agents 196
7.2.4 ‘Antibiofilm’ Approach 197
7.3 Role of Plasma Processing in Biofouling Prevention 198
7.3.1 Plasma Surface Functionalization 199
7.3.2 Plasma-Induced Grafting 199
7.3.3 Plasma Polymerization 200
7.3.4 Plasma Sterilization 201
7.4 Case Study: Plasma-deposited Poly(ethylene oxide)-like Films
for the Prevention of Biofilm Formation 202
7.4.1 PEO Films and Plasma Deposition 202
7.4.2 Plasma Polymerization by Continuous Wave Plasma 203
7.4.2.1 Retention of the PEO Character and Film Stability 203
7.4.2.2 Protein Adsorption 205
7.4.2.3 Cell Attachment and Proliferation 206
7.4.2.4 Aging 208
7.4.3 Plasma Polymerization in Pulsed Mode 208
7.4.4 Sterilization of PEO-like Films 210
7.4.5 Composite Films: Ag Nanoparticles in a PEO-like Matrix 211
7.4.5.1 Synthesis of Ag Nanoparticles and Deposition on Surfaces 212
7.4.5.2 Composite AgNP/PEO Surfaces and Their Antibacterial Activity 213
7.5 Summary 216
References 217
8 Oxygen Barriers for Polymer Food Packaging 225
Joachim Schneider and Matthias Walker
8.1 Introduction 225
8.2 Fundamentals of Gas Diffusion through Polymers 225
8.2.1 Diffusion, Solubility, and Permeability of Polymers 227
8.2.2 Diagnostic Methods 230
8.2.3 Barrier Concepts 233
8.3 Case Study: Plasma Deposition of SiOx Barrier Films on Polymer
Materials Relevant for Packaging Applications 234
8.3.1 Materials and Measurements 234
8.3.1.1 Selection of Two-dimensional and Three-dimensional Polymer
Substrates 234
8.3.1.2 Measurement of the Steady-state O2 Particle Flux 235
8.3.1.3 Measurement of the Coating Thickness 235
8.3.2 SiOx Barrier Films on PET Foil 236
8.3.2.1 SiOx Barrier Films Deposited from O2: HMDSOGas Mixtures 236
8.3.2.1.1 O2 Permeation Measurements: Determination of the Diffusion
Coefficient 237
8.3.2.1.2 O2 Permeation Measurements: Variation of the O2: HMDSO Gas
Mixture Ratio 238
8.3.2.1.3 FTIR Analysis: Chemical Composition of the Surface of the SiOx
Barrier Films Deposited from Different O2: HMDSO Gas
Mixtures 239
8.3.2.2 SiOx Barrier Films Deposited from O2 : HMDSN Gas Mixtures 243
8.3.2.2.1 O2 Permeation Measurements: Variation of the O2: HMDSN Gas
Mixture Ratio 243
8.3.2.2.2 FTIR Analysis: Comparing Best Performing SiOx Barrier Films
Deposited from O2 : HMDSOand fromO2 : HMDSN Gas
Mixtures 245
8.3.2.2.3 O2 Permeation Measurements: Variation of the Film Thickness 246
8.3.3 SiOx Barrier Films on PP Foil 247
8.3.3.1 ECR Plasma Source: Comparing the Barrier Properties of SiOx Films
Deposited on PP and on PET Foil by Variation of the O2 : HMDSOGas
Mixture Ratio 247
8.3.3.2 Duo-Plasmaline Plasma Source: SiOx Barrier Films Deposited from
O2: HMDSNGas Mixtures 249
8.3.4 ECR Plasma Deposition of SiOx Barrier Films on Polymer Trays
Designed for Food Packaging 251
8.3.4.1 ECR Plasma Deposition of SiOx Barrier Films Without Directed Gas
Supply and Customized Magnet Configuration: Variation of the
Plasma Deposition Time and of the Distance between Sample and
Plasma 252
8.3.4.2 Achieving Industrially Relevant Plasma Deposition Times by Directed
Gas Supply and Customized Magnet Configuration 255
8.4 Conclusions 258
Acknowledgments 259
References 259
9 Anti-wear Coatings for Food Processing 263
Maddalena Rostagno and Federico Cartasegna
9.1 Introduction 263
9.2 Recent Developments in PVD Coatings 264
9.3 Coatings Trends and Market Share 267
9.4 Coatings Application in the Food Processing Sector 268
9.5 Coating Requirements in the Food Sector 269
9.5.1 Wear Resistance 270
9.5.2 Coefficient of Friction (COF) 271
9.6 Selection of Methodologies for Effective Characterization of Coatings
for the Food Sector 271
9.6.1 Chemical and Structural Characterization 273
9.6.1.1 Scanning Electron Microscopy (SEM) 273
9.6.1.1.1 Application to Anti-wear Coatings for Food Processing Tools 273
9.6.1.2 Energy Dispersive X-ray Spectrometry (EDX) 274
9.6.1.2.1 Application to Anti-wear Coatings 274
9.6.1.3 Calotest and Optical Microscopy (OM) 275
9.6.1.3.1 Application to Anti-wear Coatings for Food Processing Tools 276
9.6.2 Mechanical Characterization 276
9.6.2.1 Hardness 276
9.6.2.1.1 Application to Anti-wear Coatings for Food Processing Tools 277
9.6.2.2 Pin-on-disk 279
9.6.2.2.1 Application to Anti-wear Coatings for Food Processing Tools 280
9.6.3 Atoxicity and Corrosion Characterization 280
9.6.3.1 Food Compatibility: Heavy Metals Release 280
9.6.3.2 Food Compatibility: Oxidation Test 280
9.6.3.3 Salt Spray Test 280
9.7 Case Studies: Development and Characterization of Ceramic Coatings
for Food Processing Applications 281
9.7.1 Relevant Substrates and Functionalities Required for Cutting
Applications 281
9.7.2 Technical Analysis and Choice of the Proper Coating Chemistry and
Technique 282
9.7.3 Coating Development 285
9.7.4 Case Study: PVD Coating of Saw Blades 288
9.7.5 Case Study: PVD Coating of Hammers for Food Treatment 291
9.8 Conclusions 294
References 294
10 Physics and Chemistry of Nonthermal Plasma at Atmospheric Pressure
Relevant to Surface Treatment 295
Yuri Akishev, Anatoly Napartovich, Michail Grushin, Nikolay Trushkin,
Nikolay Dyatko, and Igor Kochetov
10.1 Introduction 295
10.2 Discharge Modeling 297
10.2.1 Full Kinetic Models and Reduced Model for Technological
Plasma 297
10.2.2 Electron Kinetics 299
10.2.3 Plasma Chemistry 301
10.2.4 Experimental UV, Optical, and Near Infra-red Emission Spectra 302
10.2.4.1 Air-based Discharges 302
10.2.4.2 Nitrogen-based Discharges 306
10.2.4.3 CF4-based Discharges 309
10.2.5 Influence of Impurities on Composition of Gas Activated by
Nonthermal Plasma 310
10.3 Kinetic Model for Chemical Reactions on a Polypropylene Surface in
Atmospheric Pressure Air Plasma 314
10.3.1 Description of Kinetic Model 314
10.3.1.1 Description of Chemical Reaction Modeling 314
10.3.1.2 Description of Surface Concentration Modeling 320
10.3.1.2.1 Abstraction of H Atoms from H-sites by OH Radicals 320
10.3.1.2.2 Abstraction of H Atoms from H-sites by Alkoxy Radicals 321
10.3.1.2.3 Chain Backbone Scission Due to Interaction of Alkoxy Radicals with
the Polymer Backbone 321
10.3.2 Results of Modeling and Comparison with Experimental Data 321
10.4 Conclusions 328
Acknowledgement 328
References 328
Part III Economical, Ecological, and Safety Aspects 333
11 Economic Aspects 335
Elisa Aimo Boot
11.1 Market Analysis: an Overview 335
11.1.1 Textile Market Analysis 335
11.1.1.1 General 335
11.1.1.2 Technical Textiles 336
11.1.1.3 Hydrophobic and Oleophobic Textile Market 336
11.1.2 Biomedical Market Perspective 337
11.1.3 Food Packaging Market Potential 339
11.2 Case Study: Up-Scaling of the Plasma Treatment of Hammers
for Meat Milling 340
11.2.1 Analysis of the Reference Scenario 341
11.2.2 Analysis of Scenario 2 – Outsourcing 341
11.2.3 Analysis of Scenario 3 – In-house 342
11.2.4 Investment and Operating Cost 343
11.2.5 Comparative Analysis of All Three Scenarios 344
11.2.6 Final Considerations 345
References 346
12 Environment and Safety 347
Massimo Perucca and Gabriela Benveniste
12.1 Introduction to LCA 347
12.2 Environmental Impact of Traditional Surface Processing: the Reason
for Developing Innovative Solutions Supported by Dedicated LCA 350
12.3 LCA Applied to Plasma Surface Processing: Case Studies 353
12.3.1 Scope, Functional Unit, and System Boundaries 354
12.3.2 Life Cycle Inventory (LCI) and Hypothesis 356
12.3.3 Inventory Data and Results 360
12.3.3.1 The Anti-corrosion Process 361
12.3.3.2 Textile Processes 364
12.3.3.2.1 Total Energy Requirement 364
12.3.3.2.2 Output of the Oleophobic PET Processes 366
12.3.3.2.3 Output of the Hydrophobic PET/Cotton Processes 367
12.3.4 Impact Assessment 369
12.3.5 Sensitivity Analysis 371
12.3.5.1 Managing Uncertainties 371
12.3.5.2 Example 1: General Sensitivity Analysis for the LCA Study of the Textile Processes 371
12.3.5.3 Example 2: Design of Plasma Processes via LCA 375
12.3.6 Concluding Considerations on LCA Study 375
12.4 Process Safety for the Working Environment 378
12.4.1 Atmospheric Pressure Plasma Unit: Standard Configuration 379
12.4.2 Devising Safe Processes for Industrial Applications Maintaining the
Semi-continuous Feeding 381
12.4.3 Final Considerations on Process Safety 388
References 389
Index 391