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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