An indispensable volume detailing the current and potential applications of atmospheric pressure plasma treatment by experts practicing in fields around the world

Polymers are used in a wide variety of industries to fabricate legions of products because of their many desirable traits. However, polymers in general (and polyolefins, in particular) are innately not very adhesionable because of the absence of polar or reactive groups on their surfaces and concomitant low surface energy. Surface treatment of polymers, however, is essential to impart reactive chemical groups on their surfaces to enhance their adhesion characteristic. Proper surface treatment can endow polymers with improved adhesion without affecting the bulk properties.

A plethora of techniques (ranging from wet to dry, simple to sophisticated, vacuum to non-vacuum) for polymer surface modification have been documented in the literature but the Atmospheric Pressure Plasma (APP) treatment has attracted much attention because it offers many advantages vis-a-vis other techniques, namely uniform treatment, continuous operation, no need for vacuum, simplicity, low cost, no environmental or disposal concern, and applicability to large area samples.

Although the emphasis in this book is on the utility of APP treatment for enhancement of polymer adhesion, APP is also applicable and effective to modulate many other surface properties of polymers: superhydrophilicity, superhydrophobicity, anti-fouling, anti-fogging, anti-icing, cell adhesion, biocompatibility, tribological behavior, etc.

The key features of Atmospheric Pressure Plasma Treatment of Polymers:

• Address design and functions of various types of reactors
• Bring out current and potential applications of APP treatment
• Represent the cumulative wisdom of many key academic and industry researchers actively engaged in this key and enabling technology

Michael Thomas is the head of the Department of Atmospheric Pressure Processes at the Fraunhofer Institute for Surface Engineering and Thin Films (IST), Germany, and has more than 15 years' experience in surface technology. Trained as a chemist, his work is focused on fundamental and industrial projects of surface treatment and coatings in the area of plasma processes at atmospheric pressure, with specific interest in adhesion using dielectric barrier discharge and microplasma-based processes. He has published more than 30 technical papers and professional articles and holds 10 patents on the topic of atmospheric pressure plasma technology.

Kashmiri Lal Mittal was employed by the IBM Corporation from 1972 through 1993. Currently, he is teaching and consulting worldwide in the broad areas of adhesion as well as surface cleaning. He has received numerous awards and honors including the title of doctor honoris causa from Maria Curie-Skłodowska University, Lublin, Poland. He is the editor of more than 110 volumes dealing with adhesion measurement, adhesion of polymeric coatings, polymer surfaces, adhesive joints, adhesion promoters, thin films, polyimides, surface modification, surface cleaning, and surfactants.

Preface xiii

Acknowledgements xvii

Part 1: Fundamental Aspects 1

1 Combinatorial Plasma-based Surface Modifi cation of Polymers by Means of Plasma Printing with Gas-Carrying Plasma Stamps at Ambient Pressure 3
Alena Hinze, Andrew Marchesseault, Stephanus Büttgenbach, Michael Thomas and Claus-Peter Klages

1.1 Introduction 4

1.2 Experimental 7

1.3 Results and Discussion 18

1.4 Conclusions 23

Acknowledgements 23

References 24

2 Treatment of Polymer Surfaces with Surface Dielectric Barrier Discharge Plasmas 27
Marcel Šimor and Yves Creyghton

2.1 Introduction 28

2.2 A General Overview of Surface Modification Results Obtained with Surface DBDs 32

2.3 An Overview of Selected Results Obtained at TNO by the SBD 41

2.4 Conclusions 73

References 74

3 Selective Surface Modification of Polymeric Materials by Atmospheric-Pressure Plasmas: Selective Substitution Reactions on Polymer Surfaces by Different Plasmas 83
Norihiro Inagaki

3.1 Introduction 84

3.2 Defl uorination of Poly(tetrafl uoroethylene) Surfaces 86

3.3 Selective Modifi cation of Polymeric Surfaces by Plasma 102

3.4 Summary 120

References 121

4 Permanence of Functional Groups at Polyolefi n Surfaces Introduced by Dielectric Barrier Discharge Pretreatment in Presence of Aerosols 131
R. Mix, J. F. Friedrich and N. Inagaki

4.1 Introduction 131

4.2 Experimental 135

4.3 Results 137

4.4 Discussion 151

4.5 Summary 153

Acknowlegdements 153

References 153

5 Achieving Nano-scale Surface Structure on Wool Fabric by Atmospheric Pressure Plasma Treatment 157
C.W. Kan, W.Y.I. Tsoi, C.W.M. Yuen, T.M. Choi and T.B. Tang

5.1 Introduction 158

5.2 Experimental 159

5.3 Results and Discussion 160

5.4 Conclusions 171

Acknowledgements 171

References 172

6 Deposition of Nanosilica Coatings on Plasma Activated Polyethylene Films 175
D. D. Pappas, A. A. Bujanda, J. A. Orlicki, J. D. Demaree, J. K. Hirvonen, R. E. Jensen and S. H. McKnight

6.1 Introduction 175

6.2 Experimental 177

6.3 Results and Discussion 179

6.4 Conclusions 194

Acknowledgement 194

References 195

7 Atmospheric Plasma Treatment of Polymers for Biomedical Applications 199
N. Gomathi, A. K. Chanda and S. Neogi

7.1 Introduction 199

7.2 Plasma for Materials Processing 200

7.3 Atmospheric Plasma Sources 202

7.4 Effects of Plasma on Polymer Surface 206

7.5 Atmospheric Plasma in Biomedical Applications 208

7.6 Conclusion 212

References 212

Part 2 Adhesion Enhancement 217

8 Atmospheric Pressure Plasma Polymerization Surface Treatments by Dielectric Barrier Discharge for Enhanced Polymer-Polymer and Metal-Polymer Adhesion 219
Maryline Moreno-Couranjou, Nicolas D. Boscher, David Duday, Rémy Maurau, Elodie Lecoq and Patrick Choquet

8.1 Introduction 220

8.2 Atmospheric Plasma Polymerization Processes 221

8.3 Atmospheric Plasma Surface Modification for Enhanced Adhesion 223

8.4 Applications of Adhesion Improvement Using Atmospheric Pressure Plasma Treatments 240

8.5 Conclusion 246

References 246

9 Adhesion Improvement by Nitrogen Functionalization of Polymers Using DBD-based Plasma Sources at Ambient Pressure 251
Michael Thomas, Marko Eichler, Kristina Lachmann, Jochen Borris, Alena Hinze and Claus-Peter Klages

9.1 Introduction 252

9.2 Amino Functionalization with Nitrogen-Containing Gases 253

9.3 Adhesion Promotion by Amino Functionalization with Nitrogen-Containing Gases 262

9.4 Conclusion 270

Acknowledgements 271

References 271

10 Adhesion Improvement of Polypropylene through Aerosol Assisted Plasma Deposition at Atmospheric Pressure 275
Marjorie Dubreuil, Erik Bongaers and Dirk Vangeneugden

10.1 Introduction 276

10.2 Experimental 278

10.3 Results and Discussion 283

10.4 Conclusions 295

Acknowledgments 296

References 296

11 The Effect of Helium-Air, Helium-Water Vapor, Helium-Oxygen, and Helium-Nitrogen Atmospheric Pressure Plasmas on the Adhesion Strength of Polyethylene 299
Victor Rodriguez-Santiago, Andres A. Bujanda, Kenneth E. Strawhecker and Daphne D. Pappas

11.1 Introduction 300

11.2 Experimental Approach 301

11.3 Results and Discussion 304

11.4 Conclusion 311

Acknowledgements 312

References 312

12 Atmospheric Plasma Surface Treatment of Styrene-Butadiene Rubber: Study of Adhesion and Ageing Effects 315
Cátia A. Carreira, Ricardo M. Silva, Vera V. Pinto, Maria José Ferreira, Fernando Sousa, Fernando Silva and Carlos M. Pereira

12.1 Introduction 316

12.2 Experimental 319

12.3 Results and Discussion 320

12.4 Conclusions 325

Acknowledgements 325

References 326

13 Atmospheric Plasma Treatment in Extrusion Coating: Part 1 Surface Wetting and LDPE Adhesion to Paper 329
Mikko Tuominen, J. Lavonen, H. Teisala, M. Stepien and J. Kuusipalo

13.1 Introduction 330

13.2 Experimental 332

13.3 Results and Discussion 336

13.4 Conclusions 350

Acknowledgements 351

References 351

14 Atmospheric Plasma Treatment in Extrusion Coating: Part 2 Surface Modification of LDPE and PP Coated Papers 355
Mikko Tuominen, J. Lavonen, J. Lahti and J. Kuusipalo

14.1 Introduction 356

14.2 Experimental 359

14.3 Results and Discussion 363

14.4 Conclusions 377

Acknowledgements 379

References 379

15 Achieving Enhanced Fracture Toughness of Adhesively Bonded Cured Composite Joint Systems Using Atmospheric Pressure Plasma Treatments 383
Amsarani Ramamoorthy, Joseph Mohan, Greg Byrne, Neal Murphy, Alojz Ivankovic and Denis P. Dowling

15.1 Introduction 384

15.2 Materials and Methods 385

15.3 Characterisation Techniques 387

15.4 Results and Discussion 388

15.5 Conclusions 393

Acknowledgement 393

References 393