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- Herausgeber: Wiley-VCH
- Kategorie: Fachliteratur
- Sprache: Englisch
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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Seitenzahl: 614
Veröffentlichungsjahr: 2012
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Table of Contents
Cover
Related Titles
Title page
Copyright page
Preface
1 Introduction
2 Interaction between Plasma and Polymers
2.1 Special Features of Polymers
2.2 Processes on Polymer Surfaces during Plasma Exposure
2.3 Influence of Polymer Type
2.4 Methods, Systematic, and Definitions
2.5 Functional Groups and Their Interaction with Other Solids
3 Plasma
3.1 Plasma State
3.2 Types of Low-Pressure Glow Discharges
3.3 Advantages and Disadvantages of Plasma Modification of Polymer Surfaces
3.4 Energetic Situation in Low-Pressure Plasmas
3.5 Atmospheric and Thermal Plasmas for Polymer Processing
3.6 Polymer Characteristics
3.7 Chemically Active Species and Radiation
4 Chemistry and Energetics in Classic and Plasma Processes
4.1 Introduction of Plasma Species onto Polymer Surfaces
4.2 Oxidation by Plasma Fluorination and by Chemical Fluorination
4.3 Comparison of Plasma Exposure, Ionizing Irradiation, and Photo-oxidation of Polymers
5 Kinetics of Polymer Surface Modification
5.1 Polymer Surface Functionalization
5.2 Polymer Surface Oxidation
5.3 Polymer Surface Functionalization with Amino Groups
5.4 Carbon Dioxide Plasmas
5.5 SH-Forming Plasmas
5.6 Fluorinating Plasmas
5.7 Chlorination
5.8 Polymer Modification by Noble Gas Plasmas
6 Bulk, Ablative, and Side Reactions
6.1 Changes in Supermolecular Structure of Polymers
6.2 Polymer Etching
6.3 Changes in Surface Topology
6.4 Plasma Susceptibility of Polymer Building Blocks
6.5 Plasma UV Irradiation
6.6 Absorption of Radiation by Polymers
6.7 Formation of Unsaturations
6.8 Formation of Macrocycles
6.9 Polymer Degradation and Supermolecular Structure of Polymers
6.10 Crosslinking versus Degradation of Molar Masses
6.11 Radicals and Auto-oxidation
6.12 Plasma-Induced Photo-oxidations of Polymers
6.13 Different Degradation Behavior of Polymers on Exposure to Oxygen Plasma
6.14 Derivatization of Functional Groups for XPS
7 Metallization of Plasma-Modified Polymers
7.1 Background
7.2 Polymer Plasma Pretreatment for Well Adherent Metal–Polymer Composites
7.3 New Adhesion Concept
7.4 Redox Reactions along the Interface
7.5 Influence of Metal–Polymer Interactions on Interface-Neighbored Polymer Interphases
7.6 Metal-Containing Plasma Polymers
7.7 Plasma-Initiated Deposition of Metal Layers
7.8 Inspection of Peeled Surfaces
7.9 Life Time of Plasma Activation
8 Accelerated Plasma-Aging of Polymers
8.1 Polymer Response to Long-Time Exposure to Plasmas
8.2 Hydrogen Plasma Exposure
8.3 Noble Gas Plasma Exposure, CASING
9 Polymer Surface Modifications with Monosort Functional Groups
9.1 Various Ways of Producing Monosort Functional Groups at Polyolefin Surfaces
9.2 Oxygen Plasma Exposure and Post-Plasma Chemical Treatment for Producing OH Groups
9.3 Post-Plasma Chemical Grafting of Molecules, Oligomers, or Polymers
9.4 Selective Plasma Bromination for Introduction of Monosort C–Br Bonds to Polyolefin Surfaces
9.5 Functionalization of Graphitic Surfaces
9.6 SiOx Deposition
9.7 Grafting onto Radical Sites
10 Atmospheric-Pressure Plasmas
10.1 General
10.2 Dielectric Barrier Discharge (DBD) Treatment
10.3 Polymerization by Introduction of Gases, Vapors, or Aerosols into a DBD
10.4 Introduction of Polymer Molecules into the Atmospheric-Pressure Plasma and Their Deposition as Thin Polymer Films (Aerosol-DBD)
10.5 DBD Treatment of Polyolefin Surfaces for Improving Adhesion in Metal–Polymer Composites
10.6 Electrospray Ionization (ESI) Technique
11 Plasma Polymerization
11.1 Historical
11.2 General Intention and Applications
11.3 Mechanism of Plasma Polymerization
11.4 Plasma Polymerization in Adsorption Layer or Gas Phase
11.5 Side-Reactions
11.6 Quasi-hydrogen Plasma
11.7 Kinetic Models Based on Ionic Mechanism
11.8 Kinetic Models of Plasma-Polymer Layer Deposition Based on a Radical Mechanism
11.9 Dependence on Plasma Parameter
11.10 Structure of Plasma Polymers
11.11 Afterglow (Remote or Downstream) Plasmas
11.12 Powder Formation
11.13 Plasma Catalysis
11.14 Copolymerization in Continuous-Wave Plasma Mode
12 Pulsed-Plasma Polymerization
12.1 Introduction
12.2 Basics
12.3 Presented Work on Pulsed-Plasma Polymerization
12.4 Role of Monomers in Pulsed-Plasma Polymerization
12.5 Dark Reactions
12.6 Pressure-Pulsed Plasma
12.7 Differences between Radical and Pulsed-Plasma Polymerization
12.8 Surface Structure and Composition of Pulsed-Plasma Polymers
12.9 Plasma-Polymer Aging and Elimination of Radicals in Plasma Polymers
12.10 Functional Groups Carrying Plasma-Polymer Layers
12.11 Vacuum Ultraviolet (VUV) Induced Polymerization
12.12 Plasma-Initiated Copolymerization
12.13 Graft Polymerization
12.14 Grafting onto Functional Groups
Index
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The Author
Prof. Dr. Jörg Friedrich
BAM – Bundesanstalt für
Material forschung u. -prüfung
Unter den Eichen 87
12205 Berlin
All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.
© 2012 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Print ISBN: 978-3-527-31853-7
ePDF ISBN: 978-3-527-64803-0
oBook ISBN: 978-3-527-64800-9
ePub ISBN: 978-3-527-64802-3
mobi ISBN: 978-3-527-64801-6
Preface
Some 40 years experience with plasmas applied to polymers and the special view of a polymer chemist are the motivation for writing this book. The rapid growth of applications of plasma processes on an industrial scale is connected with the pioneering work of engineers. Basic research into plasmas and their properties is associated with plasma and astrophysics. Pure plasmas of noble gases under well-defined conditions in exactly determined geometries are traditional objects of plasma physics. Thus, chemical processes are out of view. However, in such simple systems the chemistry of irradiation and release of degradation products also play an important role, as do the polymer surface, near-surface layers, plasma boundary layer, and plasma bulk. Organic and polymer chemistry often dominate the use of molecular plasmas for polymer surface treatment and modification. A much more complicated and complex situation is found for plasma polymerization processes, which can often be described only by formal kinetics as the elementary and chemical processes are not known in exact detail. Electrical low- and atmospheric-pressure plasmas are characterized by a surplus in energy and enthalpy needed for simple chemical processes. The chemistry of excess energy allows endothermic reactions to be performed because the dose rate exceeds all necessary enthalpies of reaction pathways known in chemistry or even in radiation chemistry. Thus, random, statistic, and exotic processes dominate and, therefore, the reaction products are most often chemically irregular in terms of structure and composition. Additionally, the polymer products are unstable because of plasma-produced metastable radicals that are trapped in the polymer bulk and which subsequently remain capable of undergoing oxidation on exposure to oxygen from air. Therefore, the plasma product is unstable and changes continuously during storage. A nice example may illustrate such a “terrible” plasma. At the beginning of my work, in the early 1970s, I had scraped plasma polymers from the wall of the plasma reactor for infrared analysis. The plasma polymer flakes were collected, cooled with liquid nitrogen, and then ground for production of polymer powder. This powder was disseminated in KBr powder, which is necessary for KBr disk preparation. After evaporation of nitrogen the sample begun to smolder and became black. The technical assistant was stunned and did not want to continue his work with other samples. The behavior of the sample was, in fact, due to the fast reaction of radicals that came into contact with oxygen from the air after the plasma polymer layer was disintegrated. Peroxide formation and undefined auto-oxidation were initiated.
Organic chemists or polymer chemists turn away from such “black box chemistry,” labeling it as impure chemistry, far from regular chemistry, that does not follow a defined chemical mechanism. Thus, the pure chemist is shocked and all his knowledge is superfluous. If a polymer chemist must accept that chemically inert gases, such as methane or benzene, can be polymerized or polymers exposed to plasmas are destroyed, degraded, etched, and so on, any previous thinking, any knowledge, is of no help.
The task of this book is to bring together physicists, engineers, chemists, and polymer researchers, looking preferentially from the chemical and especially from the polymer chemical point of view into plasma processes and the reactions in the polymer body. Here, a new type of plasma chemist, who treats and produces polymers, is created or, better, a plasma polymer chemist is born.
Forty years of experience with plasma and polymer chemistry, analysis, and polymer degradation have been concentrated in this book. It discusses important findings in this field from all parts of the world.
Jörg Friedrich
Berlin, 20th September 2011
