Advances in Polymer Science - QUT
46
Advances in
Polymer Science
Fortschritte der Hochpolymeren-Forschung
Editors: H.-J. Cantow, Freiburg i. Br. ? G. Dall'Asta, Colleferro ? K. Dusek, Prague ? J. D. Ferry, Madison ? H. Fujita, Osaka ? M. Gordon, Colchester J. P. Kennedy, Akron ? W. Kern, Mainz ? S. Okamura, Kyoto C. G. Overberger, Ann Arbor ? T. Saegusa, Kyoto ? G. V. Schulz, Mainz W. P. Slichter, Murray Hill ? J. K. Stille, Fort Collins
Behavior of Macromolecules
With Contributions by R. C. Arridge P.J. Barham M. Kawaguchi J.Kolarik A.Takahashi
With 60 Figures Gardens Point A23205962B Behavior of macromolecules
Springer-Verlag Berlin Heidelberg New York 1982
Editors
Prof. Hans-Joachim Cantow, Institut fur Makromolekulare Chemie der Universitat, Stefan-Meier-Str. 31, 7800 Freiburg i,Br,, BRD
Prof. Gino Dall'Asta, SNIA VISCOSA - Centra Studi Chimico, Colleferro (Roma), Italia
Prof. Karel Dusek, Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, 16206 Prague 616, CSSR
Prof. John D. Ferry, Department of Chemistry, The University ofWisconsin, Madison, Wisconsin 53706, U.S.A.
Prof. Hiroshi Fujita, Department of Macromolecular Science, Osaka University, Toyonaka, Osaka, Japan
Prof. Manfred Gordon, Department of Chemistry, University of Essex, Wivenhoe Park, Colchester C043 SQ, England
Prof. Joseph P. Kennedy, Institute of Polymer Science, The University of Akron, Akron, Ohio 44325, U.S.A.
Prof. Werner Kern, Institut fur Organische Chemie der Universitat, 6500 Mainz, BRD Prof. Seizo Okamura, No. 24, Minami-Goshomachi, Okazaki, Sakyo-Ku, Kyoto 606,
Japan Prof. Charles G. Overberger, Department of Chemistry, The University of Michigan,
Ann Arbor, Michigan 48104, U.S.A. Prof. Takeo Saegusa, Department of Synthetic Chemistry, Faculty of Engineering,
Kyoto University, Kyoto, Japan Prof. Giinter Victor Schulz, Institut fur Physikalische Chemie der Universitat,
6500 Mainz, BRD Dr. William P. Slichter, Chemical Physics Research Department, Bell Telephone
Laboratories, Murray Hill, New Jersey 07971, U.S.A. Prof. John K. Stille, Department of Chemistry, Colorado State University, Fort Collins,
Colorado 80523, U.S.A.
I
A23205962B
ISBN-3-540-11640-0 Springer-Verlag Berlin Heidelberg New York ISBN-0-387-11640-0 Springer-Verlag New York Heidelberg Berlin
Library of Congress Catalog Card Number 61-642
This work is subject to copyright. AH rights are reserved, whether the whole or part of the material is concerned, specifically thoseof translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under ? 54 of the German Copyright Law where copies are made for other than private use, a fee is payable to the publisher, the amount to "Verwertungsgesellschaft Wort", Munich.
? Springer-Verlag Berlin Heidelberg 1982 Printed in Germany
The use of general descriptive names, trademarks, etc. in this publication, even if the former are not especially identified, is not to be taken as a sign that such names, as understood by the Trade Marks and Merchandise Marks Act, may accordingly be used freely by anyone. Typesetting and printing: Schweninger Verlagsdruckerei. Bookbinding: Bruhlsche Universitatsdruckerei, GieBen. 2152/3140-543210
Table of Contents
The Structure of Macromolecules Adsorbed on Interfaces
A. Takahashi and M. Kawaguchi
1
Polymer Elasticity - Discrete and Continuum Models
R. C. Arridge and P. J. Barham
67
Secondary Relaxations in Glassy Polymers - Hydrophilic Polymethacrylates
J.Kolarik
119
Author Index Volumes 1-46
163
The Structure of Macromolecules Adsorbed on Interfaces
Akira Takahashi and Masami Kawaguchi
Department of Industrial Chemistry, Faculty of Engineering, Mie University, Tsu, Mie 514, Japan
This article reviews recent advances in polymer adsorption both in theory and experiment. The adsorption of macromolecules on interfaces plays an essential role in the diversity of practical problems in industry, technology and biology such as adhesion, flocculation and stabilization of colloid particles, chromatography, reinforcement, and artifical organs in medicine.
This review appeals to researchers in the above mentioned fields and helps not only experimentalists but also theoreticians who are interested in polymer adsorption.
A. Introduction
3
B. Theories
of
Polymer
Adsorption
4
B.l Isolated Polymer Chains
5
B.2 Number of Configurations of a Tail and a Loop
6
B.3 Interacting Non-Ionic Polymer Chains
6
B.3.1
The
Theory
of
Hoeve
6
B.3.1.1 Adsorption Isotherms
6
B.3.1.2 Segment Distribution Function for Loops
8
B.3.1.3 Excluded Volume Effect
10
B.3.2 The Theory of Silberberg
11
B.3.3 The Theory of Scheutjens and Fleer
16
B.3.4 Root-Mean-Square Thicknesses of Loops and Tails
25
B.3.4.1 Root-Mean-Square Thickness of Loops
25
B.3.4.2 Root-Mean-Square Thickness of Tails
26
B.3.5 Diffusion Equation Approach
26
B.3.6 The Scaling Theory
28
B.4 Theories of the Adsorption of Polyelectrolytes 30
B.4.1 The Theory of Frisch and Stillinger 30
B.4.2 The Theory of Hesselink
30
B.5 Summary
34
C. Experimental Techniques
35
C.l Adsorption Isotherms
35
C.2 Thickness of the Adsorbed Layer
35
C.2.1 Hydrodynamic Methods
35
C.2.2 Ellipsometry
35
Advances in Polymers Science 46 ? Springer-Verlag Berlin Heidelberg 1982
2
A. Takahashi and M. Kawaguchi
C.2.3 TheATRMethod
36
C.3 Fraction of Adsorbed Segments and Fraction of Occupied Surface Sites .
36
C.4
Heat
of
Adsorption
37
D. Experimental Results
37
D.l Adsorption of Flexible Non-Ionic Polymers
37
D.l.l Ellipsometric Studies
37
D.l.1.1 Adsorption at the Theta Point
37
D.l. 1.2 Adsorption from Good Solvents 42
D.l.2 Hydrodynamic Studies
44
D.1.3 Other Approaches
46
D.l. 4 Attachment of Train Segments to Active Sites 47
D.1.5
Heats
of
Adsorption
52
D.2 Adsorption of Branched Polymers
52
D.3
Adsorption
of
Block
Copolymers
53
D.4 Adsorption of Polyelectrolytes
54
D.5
Adsorption
of
Block
Polyelectrolytes
59
D.6 Adsorption of Polyampholytes
60
D.7 Adsorption of Rod-Like Macromolecules
60
E. Conclusions
61
F. References
62
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