Table Of ContentSeries: Impact of Award
Chain mobility
and Progress in Medicine,
Pharmaceutical, and
Polymer Science and Technology
George Wypych
Toronto 2020
Published by ChemTec Publishing
38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada
© ChemTec Publishing, 2019
ISBN 978-1-927885-65-9 (hardcopy); 978-1-927885-66-6 (epub)
Cover design: Anita Wypych
All rights reserved. No part of this publication may be repro-
duced, stored or transmitted in any form or by any means without
written permission of copyright owner. No responsibility is
assumed by the Author and the Publisher for any injury or/and
damage to persons or properties as a matter of products liability,
negligence, use, or operation of any methods, product ideas, or
instructions published or suggested in this book.
Library and Archives Canada Cataloguing in Publication
Title: Chain mobility and progress in medicine, pharmaceutical, and polymer science
and technology / George Wypych.
Names: Wypych, George, author.
Description: Series statement: Impact of award | Includes bibliographical references
and index.
Identifiers: Canadiana (print) 20190144955 | Canadiana (ebook) 2019014498X
| ISBN 9781927885659 (hardcover) | ISBN 9781927885666 (PDF)
Subjects: LCSH: Materials. | LCSH: Matter-Properties.
Classification: LCC TA403 .W97 2020 | DDC 620.1/129-dc23
Printed in United States, United Kingdom, France, and Australia
Table of Contents iii
Table of Contents
1 Introduction. Nobel Prize Justification for Pierre-Gilles de Gennes 1
2 Analysis of Existing Publications 3
3 Mechanisms of Chain Motion of Macromolecular Substances 5
3.1 Bead-chain 5
3.2 Bond fluctuation model 6
3.3 Brill transition 8
3.4 Chain diffusion 10
3.5 Chain orientation 13
3.6 Chemo-responsive 17
3.7 Coarse-grained 18
3.8 Fluorescence blob 19
3.9 Intra- vs. inter-chain 20
3.10 Light-activated 23
3.11 Magnetic-activated 24
3.12 Microwave 25
3.13 Rod chain 26
3.14 Rouse 28
3.15 Shape memory 29
3.16 Slip-link 33
3.17 Strain-induced 35
3.18 Tube models 37
3.19 Summary 43
4 Parameters (Conditions) of Chain Movement 47
4.1 Activation energy 47
4.2 Annealing 49
4.3 Chain adsorption 50
4.4 Chain scission 51
4.5 Compaction pressure 52
4.6 Configuration 53
4.7 Confinement dimensions 54
4.8 Crosslinks 55
4.9 Crystallization 56
4.10 Dynamic ratio 58
4.11 Electrostatic interaction 59
4.12 Entanglements 60
4.13 Free surface 62
iv Table of Contents
4.14 Free volume 63
4.15 Glass transition temperature 64
4.16 Hydrophilicity 66
4.17 Interaction length 67
4.18 Interface layer 68
4.19 Layer thickness 69
4.20 Microstructure 70
4.21 Miscible and immiscible blends 72
4.22 Molecular weight 75
4.23 Nanoparticles 76
4.24 Packing density 78
4.25 Presence of low molecular compounds 80
4.26 Pressure 82
4.27 Relaxation time 83
4.28 Rotational motion 85
4.29 Segmental dynamics 86
4.30 Side chains 89
4.31 Temperature 90
4.32 Time of chain movement 93
4.33 Summary 94
5 The Effect of Chain Movement on the Properties of Materials 97
5.1 Chain alignment 97
5.2 Chain orientation 101
5.3 Creation of free volume 102
5.4 Crystallization 104
5.5 Dimensional stability 107
5.6 Formation of porous structures 108
5.7 Ionic transport 109
5.8 Mechanical properties 110
5.9 Polar groups 112
5.10 Polymer blends 113
5.11 Polymer redistribution 115
5.12 Proton transfer 116
5.13 Release rate of low molecular compounds 117
5.14 Reinforcement 118
5.15 Self-healing 119
5.16 Sound attenuation 121
5.17 Steric hindrance 122
5.18 Storage modulus 123
5.19 Swelling 124
5.20 Thermal expansion 126
5.21 Thermal stability 127
Table of Contents v
5.22 Wear 129
5.25 Summary 131
6 Significant Analytical Methods of Study 133
6.1 Atomic force microscopy 133
6.2 In situ synchrotron X-ray 134
6.3 NMR imaging 136
6.4 NMR mouse 136
6.5 NMR solid-state 137
6.6 Positron annihilation spectroscopy 139
6.7 WAXD and SAXS 139
7 Chain Mobility in Different Polymers 141
7.1 Acrylonitrile-butadiene-styrene 141
7.2 Cellulose 142
7.3 Cellulose acetate 143
7.4 Carrageenan 144
7.5 Chitosan 145
7.6 Ethyl cellulose 147
7.7 Epoxy 148
7.8 Ethylene-propylene diene terpolymer 150
7.9 Ethylene-co-tetrafluoroethylene 151
7.10 Ethylene-vinyl acetate copolymer 152
7.11 Ethylene-vinyl alcohol copolymer 153
7.12 Gelatin 154
7.13 High-density polyethylene 155
7.14 Low-density polyethylene 156
7.15 Polyamide 157
4.15.1 Polyamide 46 157
4.15.2 Polyamide 6 157
4.15.3 Polyamide 11 158
7.15.4 Polyamide 12 158
7.16 Poly(acrylic acid) 160
7.17 Polyacrylamide 161
7.18 Polyacrylonitrile 162
7.19 Polyarylate 163
7.20 Polybutadiene 164
7.21 Poly(butylene terephthalate) 165
7.22 Polycarbonate 166
7.23 Poly(ε-caprolactone) 167
7.24 Polydimethylsiloxane 168
7.25 Poly(ester carbonate) 169
7.26 Polyetheretherketone 170
vi Table of Contents
7.27 Poly(ethylene oxide) 171
7.28 Poly(ethylene terephthalate) 172
7.29 Polyethylene, silane-crosslinkable 173
7.30 Poly(3-hydroxybutyrate) 174
7.31 Polyimide 175
7.32 Poly(lactic acid) 178
7.33 Polymethylmethacrylate 181
7.34 Polypropylene 183
7.35 Poly(p-phenylene sulfide) 186
7.36 Poly(propylene terephthalate) 187
7.37 Poly(1,4-phenylene vinylene) 188
7.38 Polystyrene 189
7.39 Polysulfone 191
7.40 Polytetrafluoroethylene 192
7.41 Poly(trimethylene terephthalate) 193
7.42 Polyurethane 194
7.43 Poly(vinyl alcohol) 196
7.44 Poly(vinyl chloride) 198
7.45 Poly(vinylidene fluoride) 199
7.46 Poly(vinyl methyl ether) 200
7.47 Poly(styrene-co-butadiene) 201
7.48 Styrene-ethylene-butylene-styrene triblock copolymer 202
7.49 Starch 203
7.50 Ultrahigh molecular weight polyethylene 204
7.51 Summary 206
8 Comparison of Justification of Nobel Prize by the Selection
Committee with Actual Results of Research Reported 207
Index 209
1
Introduction.
Nobel Prize Justification for
Pierre-Gilles de Gennes
The Royal Swedish Academy of Sciences awarded the 1991 Nobel Prize in Physics to
Professor Pierre-Gilles de Gennes, College de France, Paris, France for discovering that
methods developed for studying order phenomena in simple systems can be generalized to
more complex forms of matter, in particular to liquid crystals and polymers.1
A bulk of de Gennes work was aimed at the description of how polymer chains and
their individual segments can move, known as polymer dynamics.1 Using neutron-scatter-
ing techniques, it is possible to distinguish how individual parts of a polymer chain move.1
The results of measurements have helped to confirm de Gennes’ models for polymer chain
motion.1 The “reptation” model, which describes the serpentine motion of a polymer chain
within a “tangle” of surrounding polymer chains was proposed by de Gennes.1
Prof. de Gennes published 422 papers between 1956 to 1995.2 His work was recog-
nized by numerous organizations including Hollweck Prize from the Joint French-British
Physical Society in 1968: Prix Cognac-Jay in 1970; Prix Ampere from the French Acad-
emy of Science in 1977; Gold Medal from Centre National de Recherche Scientifique
(CNRS), France in 1981; Matteucci Medal from the Italian Science Academy in 1987;
Harvey Prize from Technion Israel in 1988; Polymer Award from American Physical
Society as well as American Chemical Society in 1988; Wolf Prize for Physics from Israel
in 1990; Lorentz Medal from the Dutch Academy of Arts and Sciences in 1991.2 The anal-
ysis of his scientific contribution can be found elsewhere.2
The justification of Wolf Prize included the following achievements: “Among his
important contributions to many different parts of condensed matter physics, including
magnetism, superconductivity and scattering studies, Professor Pierre-Gilles de Gennes
has provided fundamental concepts for the development of macromolecular science.
These have provided a firm foundation for analyzing complicated but important processes.
He analyzed the dynamics of correlated motions of polymers in their complex environ-
ment and predicted their critical phenomena by extending the use of path-integral meth-
ods, developing applications of scaling ideas and introducing the concept of reptation.
This work has stimulated many experiments which have confirmed his concepts and their
relevance. It has energized the whole field of the physics of long chained macromolecules,
much of the new work being done by former students and young colleagues. These
achievements also hold promise for future applications to biological systems.”3
2 Introduction. Nobel Prize Justification for Pierre-Gilles de Gennes
Chain movement affects many physical properties of materials such as orientation,
creation of free volume, crystallization, dimensional stability, steric hindrance, ionic trans-
port, reaction to external forces, self-healing, thermal expansion, vibration damping, etc.,
and factors affecting mechanical performance such as storage modulus, mechanical prop-
erties, wear, etc. Prediction and simulation of chain mobility require well designed models
and principles.
After receiving the Nobel Prize in 1991, de Gennes gave talks on science, innova-
tion, and common sense, to high school students.1 He visited around 200 high schools
during 1992-1994.1 This story is summarized in a book (Les objets fragiles, Plon, Paris
1994, also available in English translation under the title Fragile Objects: Soft Matter,
Hard Science, and the Thrill of Discovery).1
This book revisits the theoretical work of Pierre-Gilles de Gennes in the area of
chain movement and compares findings with the status of currently applied methods of
study.
References
1 Royal Swedish Academy of Science. Press release. 16 October 1991.
2 Kalyane, VL; Sen, BK, Malaysian J. Libr. Inf. Sci., 1, 2, 13-26, 1996.
3 Pierre-Gilles de Gennes Winner of Wolf Prize in Physics - 1990. The 1990 Wolf Foundation Prize in
Physics.
2
Analysis of
Existing Publications
The French word reptation translated to
English means the crawling, creep, creep-
ing motion, or the act of crawling. The rep-
tiles (class Reptilia) includes tetrapod
animals such as crocodiles, lizards, snakes,
etc. It is, therefore, an excellent combina-
tion of meaning and profoundly ingrained
image of a certain kind of movement com-
monly recognized. The application of this
word in science is not new. In 1939, Griggs
used this term to describe movement of
rocks, in 1968, Breed applied it in discus-
sion of the movement of microorganism,
and finally in 1971, Yelon used the word of
reptation in field of interaction of multi-
layer magnetic fields, as well as, de Gennes
Figure 2.1. Frequency of publication of articles contain-
ing word reptation based on the Science Direct database adapted reptation to describe movement of
of publications. polymer chains.1
Figure 2.1 shows a yearly number of publications in the area of polymer chemistry
which contained the word of reptation. The current number of papers published recently
oscillates around 140 which is small when compared with graphene which has also been
awarded Nobel Prize (about 5000 publications per year).2 Analyzing Figure 2.1, one may
notice that there was no characteristic spike of interest (very prominent in the case of
graphene) after Nobel Prize was awarded. Several years later, the present frequency of
publication was achieved and stabilized.
There is a small number of patents which have used word of reptation to discuss the
process of formation of coatings, compression moldings, composite self-healing systems,
solute migration, etc. The total number of such patents up-to-date is less than 200 (com-
pared with several thousand patents obtained for graphene applications per year). This
means that reptation has a stronger influence on evaluation and discussion of scientific
findings (e.g., random thermal motion, entanglements, friction, maximum relaxation time,
etc.) than on the practical, technological developments. The growing interest in the self-
healing materials may contribute to the modification of these trends.
