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Polymer Brushes

ISBN: 978-3-527-31033-3
501 pages
September 2004
Polymer Brushes (3527310339) cover image


Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".
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Table of Contents


List of Contributors.

Polymer Brushes: On the Way to Tailor-Made Surfaces (Jürgen Rühe).

1 Growth of Polymer Molecules at Surfaces: Introductory Remarks.

2 Coatings: From First Principles to High-Tech Applications.

3 Surface-Coating Techniques.

4 Surface-Attached Polymers.

5 Polymer Brushes: General Features.

6 Theory of Polymer Brushes.

7 Synthesis of Polymer Brushes.

8 Polymer Brushes as Functional Materials.

9 Microstructured Polymer Brushes.

10 Surface-Initiated Polymerization: The Overall Picture.

Part I Synthesis.

1 Recent Advances in Polymer Brush Synthesis (Anthony M. Granville and William J. Brittain).

1.1 Introduction.

1.2 “Grafting To” Synthesis Technique.

1.3 “Grafting From” Synthesis Technique.

2 Polymer Brushes by Atom Transfer Radical Polymerization (Jeffrey Pyun, Tomasz Kowalewski, and Krzysztof Matyjaszewski).

2.1 Introduction.

2.2 Polymer Brushes on Flat Surfaces.

2.3 Polymer Brushes from Particles.

2.4 Molecular Brushes.

3 Polymer Brushes by Atom Transfer Radical Polymerization Initiated from Macroinitiator Synthesized on the Surface (Viktor Klep, Bogdan Zdyrko, Yong Liu, and Igor Luzinov).

3.1 Introduction.

3.2 Experimental.

3.3 Results and Discussion.

4 Synthesis of Polypeptide Brushes (Henning Menzel and Peter Witte).

4.1 Introduction.

4.2 Preparation of Peptide Brushes by “Grafting To”.

4.3 Preparation of Peptide Brushes by Grafting From Polymerization.

4.4 Preparation of Peptide Brushes by Living Grafting From Polymerization.

5 Bottle Brush Brushes: Ring-Opening Polymerization of Lactide from Poly(hydroxyethyl methacrylate) Surfaces (Jong-Bum Kim, Wenxi Huang, Chun Wang, Merlin Bruening, and Gregory L. Baker).

5.1 Introduction.

5.2 Synthesis of PHEMA-g-PLA.

5.3 Conclusions and Implications for Future Studies.

5.4 Experimental Section.

6 Preparation of Well-Defined Organic-Inorganic Hybrid Nanostructures using Living Cationic Surface-Initiated Polymerization from Silica Nanoparticles (Il-Jin Kim, Su Chen, and Rudolf Faust).

6.1 Introduction.

6.2 Experimental Section.

6.3 Results and Discussion.

7 Photoinitiated Polymerization from Self-Assembled Monolayers (Daniel J. Dyer, Jianxin Feng, Charles Fivelson, Rituparna Paul, Rolf Schmidt, and Tongfeng Zhao).

7.1 Introduction.

7.2 Substrates.

7.3 Photoinitiated Radical Polymerization Mechanisms.

7.4 Polymerization from AIBN-type SAMs.

7.5 Conclusions and Future Studies.

7.6 Experimental.

8 Recent Advances in the Synthesis and Rearrangement of Block Copolymer Brushes (Stephen G. Boyes, Anthony M. Granville, Marina Baum, Bulent Akgun, Brian K. Mirous, and William J. Brittain).

8.1 Introduction and Background.

8.2 Controlled/“Living” Free Radical Polymerization.

8.3 Synthesis of Block Copolymer Brushes.

8.4 Rearrangement of Block Copolymer Brushes.

9 Surface-Grafted Hyperbranched Polymers (Hideharu Mori and Axel H. E. Müller).

9.1 Introduction.

9.2 “Grafting To” Approach.

9.3 Multi-Step Grafting Approach.

9.4 “Grafting From” Approach.

Part II Characterization.

10 The Analysis and Characterization of Polymer Brushes: From Flat Surfaces to Nanoparticles (Rigoberto C. Advincula).

10.1 Introduction.

10.2 Characterization of Ultrathin Polymer Films and Polymer Brushes.

10.3 Investigating Polymer Brush Systems.

10.4 The Importance of Characterizing Particles and Nanoparticles.

10.5 Characterization and Analysis Methods for Polymer Brushes on Particles.

11 Characterization of Polymer Brushes on Nanoparticle Surfaces (Thomas A. P. Seery, Mark Jordi, Rosette Guino, and Dale Huber).

11.1 Introduction.

11.2 Experimental.

11.3 Results and Discussion.

12 Spherical Polyelectrolyte Brushes (Matthias Ballauff).

12.1 Introduction.

12.2 Synthesis and Characterization.

12.3 Experimental Verification of Theoretical Predictions.

12.4 Flow Behavior.

12.5 Applications.

13 Weak Polyelectrolyte Brushes: Complex Formation and Multilayer Build-up with Oppositely Charged Polyelectrolytes (Rupert Konradi, Haining Zhang, Markus Biesalski, and Jürgen Rühe)

13.1 Introduction.

13.2 Synthesis and Data Evaluation.

13.3 Swelling Behavior of Weak Polyelectrolyte Brushes in Aqueous Environments.

13.4 Interaction Between Polyelectrolyte Brushes and Oppositely Charged Polyelectrolytes in Solution.

14 Structure and Properties of High-Density Polymer Brushes (Yoshinobu Tsujii, Muhammad Ejaz, Shinpei Yamamoto, Kohji Ohno, Kenji Urayama, and Takeshi Fukuda).

14.1 Introduction.

14.2 Controlled Synthesis of High-Density Polymer Brush by ATRP.

14.3 Structure and Properties of High-Density PMMA Brushes.

14.4 Application of High-Density Polymer Brushes.

15 Behavior of Surface-Anchored Poly(acrylic acid) Brushes with Grafting Density Gradients on Solid Substrates (Tao Wu, Jan Genzer, Peng Gong, Igal Szleifer, Petr Vlček, and Vladimír Šubr)


15.1 Introduction.

15.2 Experimental Section.

15.3 Theory Section.

15.4 Experimental Results.

15.5 Discussion.

16 Kinetics of Polymer Brush Formation With and Without Segmental Adsorption (Lynn S. Penn, Heqing Huang, Roderic P. Quirk, and Tae H. Cheong).

16.1 Introduction.

16.2 Experimental.

16.3 Results and Discussion.

Part III Applications.

17 Applications of Polymer Brushes and Other Surface-Attached Polymers (Kenneth C. Caster).

17.1 Introduction.

17.2 Surface Modification and Functionalization.

17.3 Applications.

17.4 Future Prospects.


18 Polymer Brushes: Towards Applications (Gregory L. Whiting, Tamer Farhan, and Wilhelm T. S. Huck).

18.1 Introduction.

18.2 Experimental.

18.3 Results and Discussion.

19 Polymerization, Nanopatterning and Characterization of Surface-Confined, Stimulus-Responsive Polymer Brushes (Marian Kaholek, Woo-Kyung Lee, Bruce LaMattina, Kenneth C. Caster, and Stefan Zauscher).

19.1 Introduction.

19.2 Experimental.

19.3 Results and Discussion.

20 Mixed Polymer Brushes: Switching of Surface Behavior and Chemical Patterning at the Nanoscale (Sergiy Minko, Marcus Müller, Valeriy Luchnikov, Mikhail Motornov, Denys Usov, Leonid Ionov, and Manfred Stamm).

20.1 Introduction.

20.2 Theory of Mixed Polymer Brushes.

20.3 Synthesis of Mixed Brushes.

20.4 Experimental Study of Phase Segregation in Mixed Brushes.

20.5 Adaptive Responsive Behavior: Regulation of Wetting and Adhesion.

20.6 Patterning of Mixed Brushes.

21 Local Chain Organization of Switchable Binary Polymer Brushes in Selective Solvents (Melbs C. LeMieux, Denys Usov, Sergiy Minko, Manfred Stamm, and Vladimir V. Tsukruk).

21.1 Introduction.

21.2 Experimental.

21.3 Results and Discussion.

22 Motion of Nano-Objects Induced by a Switchable Polymer Carpet (Svetlana Prokhorova, Alexey Kopyshev, Ayothi Ramakrishnan, and Jürgen Rühe).

22.1 Introduction.

22.2 Materials.

22.3 Results and Discussion.

23 Photochemical Strategies for the Preparation and Microstructuring of Densely Grafted Polymer Brushes on Planar Surfaces (Oswald Prucker, Rupert Konradi, Martin Schimmel, Jörg Habicht, In-Jun Park, and Jürgen Rühe).

23.1 Introduction.

23.2 General Features of Surface-Initiated Polymerization from Monolayers of Azo Initiators.

23.3 Photolithographic Procedures for the Generation of Microstructured Polymer Brushes on Planar Surfaces.

23.4 Multifunctional Patterns.

23.5 Applications of Photostructured Polymer Brushes.


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Author Information

Rigoberto C. Advincula is currently Associate Professor at the Department of Chemistry of the University of Houston. He obtained his bachelor's degree from the University of the Philippines in 1987 and his PhD in Chemistry at the University of Florida seven years later.
He was Alexander von Humboldt Research Fellow at the Max Planck Institute for Polymer Research in 1995 and the following year a Research Fellow at the Department of Chemical Engineering, Stanford University. In 2003, Dr. Advincula was one of the recipients of the Arthur K. Doolittle Award given by the Polymer Materials Science and Engineering division of the American Chemical Society. His current research interests are in the area of organic and polymer materials as applied to nanoscale building blocks and phenomena, with applications focusing on electro-optical properties, biofunctional systems, and surface modifiers.

William J. Brittain is currently Professor at the University of Akron, Department of Polymer Science. He obtained his bachelor's degree from the University of Northern Colorado in 1977 and his PhD in Chemistry at the California Institute of Technology in 1982.

Kenneth C. Caster is currently Senior Research Scientist within the Center for Biologically Inspired Materials and Materials Systems at the Pratt School of Engineering, Duke University. He obtained his bachelor's degree from Stetson University in 1979 and his PhD in Chemistry from Duke University in 1983. He was a National Institutes of Health Postdoctoral Fellow at the University of Florida from 1983 to 1985, thereafter he spent 18 years in industrial R&D, first at Union Carbide Corporation in new product development and catalysis research, followed by 9 years at Lord Corporation, as principle investigator of new materials research in the Lord Materials Division. In 1998, Dr. Caster was joint-winner of the Lord Corporation Chemical Products Division Technical Achievement Award for innovation and development of Contact Metathesis Polymerization. He has extensive experience from basic R&D to process development, and his areas of expertise include ring-opening metathesis polymerization, organophosphorus chemistry, catalysis, ligand design and synthesis, heterocyclic chemistry, and small molecule molecular modeling.

Jürgen Rühe has been Professor for Chemistry and Physics of Interfaces at the University of Freiburg since 1999 and since 2001 he is also director of the Institute for Microsystems Technology. Prior to this, he was associate professor at the Max-Planck-Institute for Polymer Research. He has been visiting scientist at the IBM Almaden Laboratories, at the RIKEN Institute in Tokyo, Japan, the Cavendish Laboratories of Physics, Stanford University and Georgia Institute for Technology. Professor Rühe has won the prize for Chemistry awarded by the Academy of Sciences in Göttingen (1999) and the DECHEMA award 2001. His research interests are directed towards the development of new methods for the generation of tailor-made surfaces and the use of polymers in nanosciences and microsystems technology.

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"…this book will appeal to a variety of people working with surface modifications of materials for many types of applications." (IEEE Electrical Insulation Magazine, September/October 2006)

"... a good investment for scientists active in this modern field of research or for those who would like to enter this exciting interdisciplinary field."
—Rainer Jordan, Lehrstuhl für Makromolekulare Stoffe (Advanced Materials, Vol. 17, No. 9, May 2, 2005)

"…a valuable reference for scientists, technologists, and engineers with an interest in this field and is recommended for academic and industrial libraries." (Polymer News, May 2005)

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