Table Of ContentA. Teramoto, M. Kobayashi, T. Norisuye (Eds.)
Ordering in
Macromolecular Systems
Proceedings of the OUMS'93
Toyonaka, Osaka, Japan, 3-6 June 1993
With 250 Figures and 20 Tables
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Hong Kong Barcelona Budapest
Professor Akio Teramoto
Professor Masamichi Kobayashi
Professor Takashi N orisuye
Department of Macromolecular Science
Osaka University
Faculty of Science
Toyonaka,5600saka,Japan
ISBN-13: 978-3-642 -78895-6 e-ISBN-13 :978-3-642 -78893-2
DOl: 10.1007/978-3-642-78893-2
Library of Congress Cataloging-in-Publication Data
OUMS'93 (1993: Osaka, Japan) Ordering in macromolecular systems: proceedings of the
OUMS' 93, Toyonaka, Osaka, Japan, 3 - 6 June 19931 A. Teramoto, M. Kobayashi,
T. Norisuye (eds.) p. em. Includes bibliographical references and index.
ISBN-13 :978-3-642 -78895-6
I. Polymers-Structure-Congresses. 2. Crystalline polymers-Congresses. 3. Polymer liquid
crystals-Congresses. l. Teramoto, A. 1933-. II. Kobayashi, M. (Masamichi), 1933- .
III. Norisuye, T. (Takashu), 1943-. IV. Osaka Daigaku. V. Title.
QD381.9.S87096 1993 547.7'0442--dc20 94-8717 CIP
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Preface
This volume summarizes the papers presented at the First Osaka University
Macromolecular Symposium OUMS'93 on "Ordering in Macromolecular Systems",
which was held at Senri Life Science Center, Osaka, Japan, on June 3 through June 6,
1993. The symposium covered the three topics, (1) Crystallization and Phase
Transitions, (2) Polymer Liquid Crystals and (3) Block Copolymers, Polymer Blends
and Surfaces, and invited leading scientists in these fields. At present any of these
topics is a hot issue in itself and frequently taken up separately in many occasions. It is
noted however that all these topics are correlated with each other with the keyword
"Ordering" and their combination provides a unique feature of the present symposium
in reflecting the interactions among investigators working in these important fields with
the common ground expressed by the keyword "Ordering". Nineteen invited lectures
and 40 posters of both experiment and theory were presented at the symposium, and
the eighteen lectures and ten poster presentations contribute to this volume.
In the first topic crystal structures and their transitions were discussed from
kinetic as well as static points of view; attention was paid to give a molecular-level
interpretation of the structure, phase transition and physical properties, using theories
and simulations. The second topic was mainly concerned with static structures and
thermodynamic properties of polymer liquid crystals including phase behaviours. It
was shown that the structures and properties related to lyotropic liquid crystals are
explained theoretically on the basis of simple molecular models; here were discussed
not only nematic but also columnar and smectic phases. The final topic was concerned
with various microscopic as well as macroscopic structures formed with block
copolymers and polymer blends, which exhibit unique features in bulk and at surface.
In all these topics both general insight and particular issues were included. The
program of the symposium was arranged so that the three topics were properly mixed,
encouraging discussions among these slightly different fields and with a particular
emphasis on the interplay between experiment and theory. In some cases they are
explained well theoretically, and in other cases either experiment or theory needs to be
followed by the other. The papers contributed to this volume also should reflect the
outcome from such interactions at the meeting. Thus we believe this volume will be
useful for specialists working in these related fields on one hand, and serve as a
reference book for those who wish to get familiar with these fields on the other hand.
VI
The present symposium was sponsored by the Osaka University International
Exchange Program in Macromolecular Science. Thus a brief account of this program
may be pertinent here. In 1989 the Department of Macromolecular Science, Osaka
University, celebrated the 30th anniversary and has founded in the Macromolecular
Science Course, the Graduate School of Science, Osaka University, the Osaka
University International Exchange Program in Macromolecular Science, with the
generous support of many companies and individuals. The main purpose of the
Program is to promote the international exchange in macromolecular science through
international symposium and personnel exchange. The OUMS'93 symposium is the
first of such symposiums. This symposium was supported in part by the Society of
Polymer Science, Japan, to which acknowledgement is made.
January 1994 Akio Teramoto
Masamichi Kobayashi
Takashi Norisuye
Contents
A Unifying Scheme for Polymer Crystallization Based on Recent Experiments
with Wider Implications for Phase Transfonnations
A. Keller, M. Hikosaka, S. Rastogi, A. Toda and P. I. Barham ............. 1
Order-Disorder Transitions in Crystalline Polymers with Characteristic Mechanical
and Electric Properties
K. Tashiro and M. Kobayashi ......................................... 17
Computer Simulation of Macromolecular Crystals and Their Defects
B. Wunderlich, B. G. Sumpter, D. W. Noid and G. L. Liang ............... 35
AFM Observation of Surface Morphology for Oriented PET Films
Y. Sasaki, X. I. Shao, T. Suzuki and H. Ishihara ......................... 51
Characterization of Polymer Interface by Micro Raman Spectroscopy
S. Hosoda, S. Hoshi, K. Kojima, A. Uemura, H. Yamada
and M. Kobayashi ................................................... 59
Supramolecular Assemblies of Cyclodextrins with Polymers and Preparation
of Polyrotaxanes
A. Harada, I. Li and M. Kamachi ....................................... 69
Case II Diffusion in Polystyrene Fiber: In-situ Measurement of a Moving
Sharp Front
M. Fukuda .......................................................... 79
"Liquid Crystallization" Mechanism of Liquid Crystalline Polymers
M. Hikosaka, K. Mabuchi, K. Yonetake, T. Masuko, G. Ungar
and V. Percec ........................................................ 89
Thennotropic Liquid Crystals in Polypeptides
I. Watanabe ......................................................... 99
Study on the Orientational Order of the Main Chain Liquid Crystalline Polymers
D.-W. Kim, I.-K. Park and K.-S Hong ................................ 115
Statistical Theory of Liquid Crystalline Orderings in Hard Rod Fluids
- Nematic, Cholesteric, Smectic and Columnar Phases -
H. Kimura .......................................................... 125
Phase Diagram and Molecular Ordering of Dimer Liquid Crystals Dissolved
in a Simple Nematic Solvent
A. Abe, R. N. Shimizu and H. Furuya ................................. 139
vm
Phase Equilibria in Liquid Crystalline Polymer Solutions:
Theory and Experiment
T. Sato and A. Teramoto ............................................. 155
Light Scattering Studies of a Nematic to Smectic-A Phase Transition in
Rigid Rod Polymer Solutions
J.-H. Wang, F. Lonberg, X. Ao and R. B. Meyer ....................... 171
Collective and Molecular Dynamics in Ferroelectric Liquid Crystals:
From Low Molar to Polymeric and Elastomeric Compounds
F. Kremer and A. Schonfeld ......................................... 181
The Rheology of PBLG Liquid Crystalline Polymers at High Concentrations
R. G. Larson, J. Promislow, S.-G. Baek and J. J. Magda. .. . . . . .. .. .. .. 191
Microdomain Structures of Triblock Copolymers of the ABC Type
I. Noda, Y. Matsushita and Y. Mogi ................................... 203
Evolution of Ordering in Thin Films of Symmetric Diblock Copolymers
T. P. Russell, A. M. Mayes and M. S. Kunz ............................ 217
Rheology of Polymeric Materials with Mesoscopic Domain Structure
M. Doi, 1. Harden and T. Ohta ........................................ 225
Rheology, Dielectric Relaxation, and Adhesion of Thermodynamically
Confined Diblock Copolymer Chains
H. Watanabe and T. Kotaka ....................................... ; .. 241
Crystallization Kinetics and Microdomain Structures for Blends of
Amorphous-Crystalline Block Copolymers with Amorphous Homopolymers
K. Sakurai, D. J. Lohse, D. N. Schulz, J. A. Sissano, M. Y. Lin,
M. Agamalyan and W. J. MacKnight .................................. 253
Reversible Heteropolymer Gelation - Phase Diagrams of Mixed Networks -
F. Tanaka .......................................................... 263
SANS Studies of Early Stage Spinodal Decomposition
T. Hashimoto, H. Jinnai, H. Hasegawa and C. C. Han .................. 273
Dynamic Interplay between Wetting and Phase Separation in Geometrically
Confined Polymer Mixtures
H. Tanaka . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 291
Wetting of Grafted Polymer Surfaces by Compatible Chains
L. Leibler, A. Ajdari, A. Mourran, G. Coulon and D. Chatenay ........... 301
Surface Segregation and Wetting from Polymer Mixtures
U. Steiner, E. Eiser, A. Budkowski, L. Fetters and J. Klein .............. 313
IX
Interfacial Properties of Mixed Polymer Films Spread at the Air / Water Interface
M. Kawaguchi ..................................................... 323
Polymer Monolayer Dynamics
H. Yu ............................................................. 333
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
Subject Index ............................................... 351
A Unifying Scheme for Polymer Crystallization Based
on Recent Experiments with Wider Implications for Phase
Transformations
A. Keller, M. Hikosakat ,5. Rastogitt, A. Todcttt and P.J. Barham
HH Wills Physics Laboratory, University of Bristol
Tyndall Avenue, Bristol BS8lTL
Abstract: This lecture is aimed to link the "main stream" subject of chain folded
polymer crystallization to the "speciality stream" of extended chain crystallization,
the latter as typified by the crystallization of polyethylene under pressure. This is
achieved through a scheme based on some new experimental material comprising
the recognition of thickening growth as a primary growth process of lamellae and
of the prominence of metastable phases, specifically of the mobile hexagonal
phase in polyethylene. The scheme relies on the consideration of crystal size as a
stability determining factor, namely on melting point depression, which in
general is different for different polymorphs. It is shown that under specificable
conditions phase stabilities can invert with size, i.e. a phase which is metastable
for infinite size can become the stable one when the phase is sufficiently small.
When applying this condition to crystal growth it follows that a crystal in such a
situation will appear and grow in a phase that is different from that in its state of
ultimate stability, maintaining this state as a metastable one or transforming into
the ultimate stable state during growth according to circumstances. The
consequences of such deliberations, of potential significance to all phase
transformations also beyond polymer crystallization, are being developed
throughout the paper.
INTRODUCTION
The material of the present paper has emerged from varied and far ranging
experimental works on polymer crystallization as initiated by one of us (MH) in
Tokyo and currently pursued in Yamagata, subsequently extended in association
with the Bristol Polymer Laboratory. While the individual works are being
reported separately elsewhere (1-4) the experimental results have led to the
t Prermanent address: Department of Materials Science, Yamagata University, Yonezawa, Japan
tt Permanent address: Department of Polymer Technology, Eindhoven Technical University,
Eindhoven, The Netherlands
ttt Permanent address: Department of Physics, Kyoto University, Kyoto, Japan
A. Terall1olo. \1. Kobayashi, T. Norisujc (Eds.)
Ordering in Macromolecular Systems
2
recognition of some new themes which promise to be of general relevance to
polymer crystallization, to crystallization beyond the polymer field, and even to
wider issues of phase transformation in general. It is these themes which we are
trying to convey in the present paper with some references to the underlying
works themselves
In broadest generality two factors have emerged in the course of the experimental
works which have controlling influence on the crystallization process in those
experiments. In the first instance metastable phases as the primary products of
crystallisation, and secondly, the size dependence of phase stability. Neither of
these are new in themselves yet their combination leads to new considerations
which are the subject of the present paper. The role of metastability in phase
transformations was recognised in the last century and is embodied in Ostwald's
Rule of Stage (5). The role of phase sizes is of course familiar in the form of
melting point, boiling point etc. depressions due to limited phase dimensions as
expressed quantitatively by the Thomson-Gibbs equation. Such a phase of small
dimension is metastable with respect to the one of infinite size. In the scheme to
be developed in this paper we invoke a combination of the two kinds of
metastability: that determined by phase type (e.g. different polymorphs of the
same crystal phase) and that by the limited dimension of a given phase. As will
be seen this will prove to be particularly helpful in envisaging the process of
phase transformations in terms of phase type of competing stability.
In the case of polymer crystallization in particular it provides a unifying umbrella
for two, so far largely separate areas of the subject: chain folded crystallization,
the most widely studied form of crystallization here to be termed "main stream",
and extended chain type crystallization, in the case of polyethylene (PE) - the
model substance for such studies - arising at elevated pressure, here to be termed
"speciality stream".
SOME BASIC FACTS
The factual material leading to the new perspectives to be presented fall into the
two groups already stated: metastability and lamellar thickness. Taking lamellar
thickness first it will be recalled that in the "main stream" subject of chain folded
crystallization the crystals are thin platelets containing the chains in a folded
conformation with the lamellar thickness corresponding (or closely related) to the
fold length (6). The lamellae being uniformly thick crystal growth is envisaged
as occurring only in the lateral direction with unaltered thickness, the
