mechanical properties of polymers based on nanostructure and morphology, 2005, p.738

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Mechanical Properties
of Polymers Based on
Nanostructure and Morphology
© 2005 by Taylor & Francis Group.
DK4635_title 4/26/05 11:02 AM Page 1
Mechanical Properties
of Polymers Based on
Nanostructure and Morphology
edited by
G. H. Michler
F. J. Baltá-Calleja
Boca Raton London New York Singapore
A CRC title, part of the Taylor & Francis imprint, a member of the
Taylor & Francis Group, the academic division of T&F Informa plc.
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Mechanical properties of polymers based on nanostructure and morphology / edited by G.H.
Michler and F.J. Baltá-Calleja.
p. cm.

Includes bibliographical references and index.
ISBN 1-57444-771-8 (alk. paper)
1. Composite materials. 2. Nanostructure materials. 3. Polymers. I. Michler, Goerg H. (Goerg
Hannes) II. Baltá-Calleja, F.J. III. Title.
TA418.9C6M397 2005

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Preface

The mechanical behavior of polymers has been the subject of con-
siderable research in the past. Mechanical properties are, indeed,
of relevance for all applications of polymers in industry, medicine,
household, and others. The improvement of properties in general
and the better fitting of specific properties to defined applications
is a continuous goal of polymer research. Of particular interest is
not only the improvement of the special properties themselves,
such as stiffness, strength or toughness, but also the combined
improvement of usually contradictory mechanical properties (like
strength and toughness) in combination with other physical prop-

erties (e.g., transparency, flame resistance, conductivity, etc.). The
outstanding role of the mechanical properties applies, as well, to
many of the applications of polymers in which other properties are
those playing the primary role, such as in medicine, optics, elec-
tronics, micro-system techniques and others. The defined improve-
ment of the mechanical properties demands a better understanding
of the multiple dependence between molecular structure, morphol-
ogy, polymerization and processing methods on the one hand, and
ultimate mechanical properties, on the other; i.e., structure-prop-
erty correlations. The bridge between the structure, the morphol-

DK4635_C000.fm Page v Tuesday, April 19, 2005 9:17 AM
© 2005 by Taylor & Francis Group.

ogy and the mechanical properties is the micromechanical pro-
cesses or mechanisms occurring at microscopic level: the so-called
field of micromechanics.
Polymeric systems become increasingly complicated and multi-
functional if they entail a larger level of structural complexity. In
the last two decades the level of interest has gradually shifted from
the µm-scale to the nm-scale region. Systems with at least one
structural size below 100 nm are considered nowadays as new
classes of materials: the so-called

nanostructured polymers, nano-
polymers or nanocomposites

. However, nanomaterials in the form of
rubber carbon black composites have existed already for nearly one
century, and biomedical materials such as bone, teeth, and skin also

have been known for millions of years. Thus, although, the class of
nanomaterials is not totally new, rapid development of research
activity aiming for a better understanding of the basic mechanisms
contributing to the properties of this class of remarkable systems
has been recently observed. Natural materials, like human bone or
seashell (abalone), reveal more and more very complex hierarchical
structures with highly specific functions that have been optimized
during bio-evolution over very long periods of time. Far-off these
biomaterials, in most synthetic polymer blends and composites the
hierarchical structure is most often created accidentally during syn-
thesis or processing. Therefore, the mechanical properties of these
man-made polymers must be better understood by examining the
length scale, architecture and interactions occurring in these syn-
thetic materials.
This volume focuses on selected results concerning the mechan-
ical properties of polymers as derived from the improved knowledge
of their structures at the µm- and nm-scale as well as from the
interactions (micro- and nanomechanisms) between the complex
hierarchical structures and functional requirements. The interest
in the topic for this volume arose at the 1998 Europhysics Confer-
ence on Macromolecular Physics “Morphology and Micromechanics
of Polymers” that was held in Merseburg (Germany) (see special
volume of the

Journal of Macromolecular Science-Physics,

Vol. B38,
1999). Several authors of this book contributed as main lecturers
to the success of the conference.
The structure of the book is organized as follows:

In the first part, “Structural and Morphological Characteriza-
tion,” the main aspects of the morphology of semicrystalline poly-
mers, as revealed by electron microscopy (

Bassett

) and x-ray scat-
tering techniques (

Hsiao

) are highlighted. Emphasis on the

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© 2005 by Taylor & Francis Group.

nanostructure of amorphous block copolymers and blends (

Adhikari,
Michler

) is also given.
The second part, “Deformation Mechanisms at Nanoscopic
Levels,” is devoted to describing the main micro- and nanomicro-
scopic effects and mechanisms occurring in different classes of poly-
mers. First, the influence of molecular variables on crazing and
fracture behavior is discussed in the case of amorphous polymers
(

Kausch, Halary

). Then, the physical elementary mechanisms
including strength, crystal plasticity, orientation processes, and dif-
ferent modes of deformation are illustrated for selected semicrys-
talline polymers (

Galeski

) and complemented with results from elec-
tron microscopic microdeformation tests (

Plummer; Henning,
Michler

). Recent results on micromechanical properties, as derived
from microindentation hardness studies in different polymers and
correlated to nanostructural parameters, are presented (

Baltá-
Calleja, Flores, Ania

). Basic aspects of toughness enhancement for
particle-modified semicrystalline polymers using model analysis are
considered (

van Dommelen, Meijer

). This part ends with an overview
about nano- and micromechanical effects in heterogeneous poly-
mers, partly known in industry, partly new or up until now only

theoretical possibilities (

Michler

).
The third part, “Mechanical Properties Improvement and Frac-
ture Behavior,” offers selected examples of heterogeneous polymers
with improved mechanical properties and fracture behavior. Struc-
ture-property relationships and mechanisms of toughness enhance-
ment are discussed for rubber-modified amorphous polymers (

Heck-
mann, McKee, Ramsteiner

) and semicrystalline polymers (

Harrats,
Groeninckx

). New aspects of manufacturing, structure development
and properties of practical relevance in nanoparticle-filled thermo-
plastic polymers are given (

Karger-Kocsis, Zhang

) and the state of
the art of carbon nanotube and nanofiber-reinforced polymer sys-
tems is emphasized (

Schulte, Nolte

). Additionally, novel unusual
methods of polymer modifications are based on micro- and nanolay-
ered polymers (

Bernal-Lara, Ranade, Hiltner, Baer

) and hot-com-
paction of oriented fibers and tapes are also presented (

Ward, Hine

).
In addition to the wide spectrum of properties present in the
above polymers, toughness enhancement is a particular aim of many
of the discussed modifications. In the different chapters the usual
routes of rubber-toughening of amorphous and semicrystalline poly-
mers are completed by effects of toughness enhancement due to
nanoparticle and nanofiber modification, micro- and nanolayer pro-
duction and hot compaction of oriented polymers.

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© 2005 by Taylor & Francis Group.

The book is directed particularly at polymer scientists in
research institutes and in industry, and should serve as a link
between more practical aspects of polymers and the knowledge
about the influence of the different levels of structure and morphol-
ogy on properties. It additionally aims to provide a better under-
standing on new effects and new possibilities to improve mechanical

properties of polymer systems. Therefore, the book will be also
helpful for students of polymer physics, chemistry and engineering,
as well as those researchers interested in materials science.

F. J. Baltá-Calleja
G.H. Michler

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© 2005 by Taylor & Francis Group.

Acknowledgment

The editors gratefully acknowledge the generous support of the
Alexander von Humboldt Foundation, Bonn, during the preparation
of the present volume.

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© 2005 by Taylor & Francis Group.

The Editors

Francisco J. Baltá-Calleja, Ph.D.,

received his B.Sc. degree in
physics at the University of Madrid in 1958. He then started his
research work at the University of the Sorbonne in Paris on pio-
neering NMR studies of organic liquids relating to intermolecular
effects. In 1959 he joined the H.H. Wills Physics Laboratory in
Bristol, with a Ramsay Memorial Fellowship, to work on crystalli-
zation and morphology of synthetic polymers. In 1962 he received

a Ph.D. in physics at the University of Bristol. In 1963 he was
appointed adjoint professor of electricity and magnetism at the
University of Madrid. He spent many years as a research associate
and visiting professor in various international institutions, includ-
ing the Fritz Haber Institute of the Max Planck Society in Berlin;
Camille Dreyfus Laboratory, Research Triangle Institute, North
Carolina, USA; J.J. Thomson Physical Laboratory, University of
Reading; Abt. Experimentelle Physik, University of Ulm; University
of Hamburg; University of Leeds; University of Shizuoka, etc. In
1970 he established the Macromolecular Physics Laboratory at the
Spanish Research Council, a department for basic polymer research,
collaborating with university, industry and international research
laboratories. Presently, he is professor of physics at the Institute for

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© 2005 by Taylor & Francis Group.

Structure of Matter, CSIC, Madrid, and has been director of this
institute (1986–2003) and founder and director of the Centre of
Physics (1996–2003), CSIC in Madrid. His research interests focus
on interrelating structure, processing and dynamic changes in poly-
mers, by means of x-ray diffraction methods using synchrotron radi-
ation, and properties (micromechanical, electrical, electro-optical,
dielectric and magnetic properties) of advanced polymers, liquid
crystalline systems and composites. He is the author of about 350
papers and several books (

X-ray Scattering of Synthetic Polymers

,

Elsevier, 1989;

Microhardness of Polymers,

Cambridge University
Press, 2000;

Block Copolymers

, Marcel Dekker, 2000; etc). He has
also been active in organizing several major international meetings
in Europe. Recognition of his activities has been considerable,
among the most notable being his election in 1988 as chairman of
the Solid State Physics group of the Spanish Royal Society of Phys-
ics, his election in 1994 as chairman of the Macromolecular Board
of the European Physical Society and his election in 1999 as a
member of the Royal Academy of Sciences in Barcelona. He has also
received the DuPont Research Award in 1994 and the Humboldt
Research Award (Germany) in 1995. He is a member of the editorial
boards of several international journals including

Journal of Mac-
romolecular Science-Physics, Journal of Polymer Engineering, Inter-
national Journal of Polymeric Materials,

and

Journal of Applied
Polymer Science

. He is a member of the American Physical Society,
the European Physical Society, and the Materials Research Society,
US. He has also been a consultant to DuPont de Nemours (Luxem-
bourg) and Exxon Mobil (Texas).

Goerg Hannes Michler, Ph.D.,

received his M.Sc. degree in phys-
ics at the University of Halle-Wittenberg in 1968. He then started
his work on the morphology of polymers as a research scientist at
the Institute of Solid State Physics and Electron Microscopy of the
Academy of Sciences in Halle/Saale in cooperation with the chemical
industry, first at the Department of Polymer Research, Leuna
Werke, Germany (1969–1981), and then as head of the Polymer
Physics Group, Chemische Werke Buna, Schkopau, Germany
(1981–1990). In 1978 he received a Ph.D. in physics at the Univer-
sity of Halle-Wittenberg and in 1987 the Habilitation and venia
legendi. In 1990 he was appointed professor of experimental physics
at the Technical University of Merseburg. Presently, he is professor
of general materials science at the University of Halle-Wittenberg,
founder and director of the Institute of Polymeric Materials and vice

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© 2005 by Taylor & Francis Group.

director of the Polymer Service GmbH, Merseburg. His research
interests focus on the structure-property correlations of materials,
especially amorphous and semicrystalline polymers, blends, copol-
ymers, composites, and biomedical materials by means of electron
and atomic force microscopy. His special field of interest is the study

of toughness enhancement and of the mechanisms of deformation
and fracture in polymers based on nanostructure and morphology
(micro- and nanomechanics). He has headed several interdiscipli-
nary research projects at the university and between the university
and chemical industry on new polymeric materials, polymers with
improved mechanical properties, sustainable development of mate-
rials and biomedical polymers. He is a consultant to Dow Chemical
Germany and Sasol Polymers, South Africa. He is author of more
than 190 papers and several books (

Kunststoff-Mikromechanik: Mor-
phologie, Deformations- und Bruchmechanismen

, Hanser, 1992;

Ultramikrotomie in der Materialforschung

, Hanser, 2004). He has
also been active in organizing annual symposia and workshops on
electron microscopy in materials science and ultramicrotomy in
materials science and several major international meetings. His
work has been awarded with the Alexander von Humboldt – J.C.
Mutis Prize (2002, Ministry of Science and Technology, Spain) and
the Paul J. Flory Polymer Research Prize (2003, University of North
Texas, USA). He is a member of several international committees
including the Scientific Committee of Polymer Physics of the Ger-
man Physical Society (since 1991), IUPAC Macromolecular Division
IV.2 (since 1997), and Macromolecular Board of the European Phys-
ical Society (since 1998). He is also a member of the American
Chemical Society, the European Physical Society, German Physical

Society, and Society of German Engineers.

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Contributors

Rameshwar Adhikari

Institute of Materials Science
Martin-Luther-University
Halle-Wittenberg
Merseburg, Germany

F. Ania

Department of Macromolecular
Physics
Instituto de Estructura de la
Materia
CSIC
Madrid, Spain

E. Baer

Department of Macromolecular
Science and Engineering, and
Center for Applied Polymer
Research
Case Western Reserve

University
Cleveland Ohio

David C. Bassett

JJ Thomson Physical
Laboratory
University of Reading
Reading, United Kingdom

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© 2005 by Taylor & Francis Group.

Francisco J. Baltá-Calleja

Department of Macromolecular
Physics
Instituto de Estructura de la
Materia
CSIC
Madrid, Spain

T.E. Bernal-Lara

Department of Macromolecular
Science and Engineering, and
Center for Applied Polymer
Research
Case Western Reserve
University

Cleveland Ohio

A. Flores

Department of Macromolecular
Physics
Instituto de Estructura de la
Materia
CSIC
Madrid, Spain

Andrzej Galeski

Center for Molecular and
Macromolecular Studies
Polish Academy of Sciences
Lodz, Poland

G. Groeninckx

Division of Molecular and
Nanomaterials
Katholieke Universiteit Leuven
Heverlee, Belgium

J.L. Halary

Ecole Supérieure de Physique et
Chimie Industrielles del la
Ville de Paris

Paris, France

Charef Harrats

Division of Molecular and
Nanomaterials
Katholieke Universiteit Leuven
Heverlee, Belgium

W. Heckmann

Polymer Research Laboratory
BASF Aktiengesellschaft
Ludwigshafen, Germany

Sven Henning

Institute of Materials Science
Martin-Luther-University
Halle-Wittenberg
Merseburg, Germany

A. Hiltner

Department of Macromolecular
Science and Engineering, and
Center for Applied Polymer
Research
Case Western Reserve
University

Cleveland Ohio

P. J. Hine

IRC in Polymer Science and
Technology
School of Physics and
Astronomy
University of Leeds
Leeds, United Kingdom

Benjamin S. Hsiao

Chemistry Department
State University of New York at
Stony Brook
Stony Brook, New York

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© 2005 by Taylor & Francis Group.

József Karger-Kocsis

Institute for Composite Materials
Kaiserslautern University of
Technology
Kaiserslautern, Germany

Hans-Henning Kausch

c/o Science de Base
École Polytechnique Fédérale
de Lausanne
Lausanne, Switzerland

G.E. McKee

Polymer Research Laboratory
BASF Aktiengesellschaft
Ludwigshafen, Germany

Goerg H. Michler

Institute of Materials Science
Martin-Luther-University
Halle-Wittenberg
Merseburg, Germany

H.E.H. Meijer

Department of Mechanical
Engineering
Eindhoven University of
Technology
Eindhoven, Netherlands

M.C.M. Nolte

Polymer Composites Section
Technische Universität

Hamburg-Harburg
Hamburg, Germany

Christopher J.G. Plummer

Laboratoire de Technologie des
Composites et Polymères
École Polytechnique Fédérale
de Lausanne
Lausanne, Switzerland

F. Ramsteiner

Polymer Research Laboratory
BASF Aktiengesellschaft
Ludwigshafen, Germany

Aditya Ranade

Department of Macromolecular
Science and Engineering, and
Center for Applied Polymer
Research
Case Western Reserve
University
Cleveland Ohio

Karl Schulte

Polymer Composites Section

Technische Universität
Hamburg-Harburg
Hamburg, Germany

J.A.W. van Dommelen

Department of Mechanical
Engineering
Eindhoven University of
Technology
Eindhoven, Netherlands

I.M. Ward

IRC in Polymer Science and
Technology
School of Physics and
Astronomy
University of Leeds
Leeds, United Kingdom

Z. Zhang

Institute for Composite
Materials
Kaiserslautern University of
Technology
Kaiserslautern, Germany

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© 2005 by Taylor & Francis Group.

Contents

PART I Structural and Morphological
Characterization

Chapter 1

The Morphology of Crystalline Polymers

D.C. Bassett

Chapter 2

Nanostructure Development in Semicrystalline
Polymers during Deformation by Synchrotron
X-Ray Scattering and Diffraction Techniques

Benjamin S. Hsiao

Chapter 3

Nanostructures of Two-Component Amorphous
Block Copolymers: Effect of Chain
Architecture

Rameshwar Adhikari and Goerg H. Michler

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© 2005 by Taylor & Francis Group.

PART II Deformation Mechanisms at
Nanoscopic Level

Chapter 4

Crazing and Fracture in Amorphous Polymers:
Micromechanisms and Effect of Molecular
Variables

H.H. Kausch and J.L. Halary

Chapter 5

Strength and Toughness of Crystalline Polymer
Systems

Andrzej Galeski

Chapter 6

Microdeformation and Fracture in
Semicrystalline Polymers.

Christopher J.G. Plummer

Chapter 7

Micromechanical Deformation Mechanisms in

Polyolefins: Influence of Polymorphism and
Molecular Weight.

Sven Henning and Goerg H. Michler

Chapter 8

Micro-Indentation Studies of Polymers Relating
to Nanostructure and Morphology

F. J. Baltá-Calleja, A. Flores, and F. Ania

Chapter 9

Micromechanics of Particle-Modified
Semicrystalline Polymers: Influence of
Anisotropy Due to Transcrystallinity
and/or Flow

J. A. W. van Dommelen and H. E. H. Meijer

Chapter 10

Micromechanical Mechanisms of Toughness
Enhancement in Nanostructured Amorphous
and Semicrystalline Polymers

Goerg H. Michler

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PART III Mechanical Properties
Improvement and Fracture
Behavior

Chapter 11

Structure-Property Relationship in Rubber
Modified Amorphous Thermoplastic Polymers

W. Heckmann, G.E. McKee, and F. Ramsteiner

Chapter 12

Deformation Mechanisms and Toughness
of Rubber and Rigid Filler Modified
Semicrystalline Polymers.

C. Harrats and G. Groeninckx

Chapter 13

Structure-Property Relationships in
Nanoparticle/Semicrystalline Thermoplastic
Composites.

J. Karger-Kocsis and Z. Zhang

Chapter 14

Carbon Nanotube and Carbon
Nanofiber-Reinforced Polymer Composites

K. Schulte and M.C.M. Nolte

Chapter 15

Nano- and Microlayered Polymers: Structure
and Properties.

T.E. Bernal-Lara, A. Ranade, A. Hiltner and E. Baer

Chapter 16

High Stiffness and High Impact Strength
Polymer Composites by Hot Compaction of
Oriented Fibers and Tapes

P. J. Hine and I.M. Ward


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Part I

Structural and Morphological
Characterization

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1

The Morphology of Crystalline Polymers

D.C. BASSETT

University of Reading, UK

CONTENTS

I. Introduction
II. Crystalline Polymers
III. Polymer Lamellae
IV. Spherulites
V. Banded Spherulites
VI. Crystallization under Stress or Flow
VII. Future Challenges
References

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I. INTRODUCTION

The wide variation in properties of a given polymer according
to its processing conditions reflects differences in internal
organization. Polymer morphology is the study of this internal

organization, primarily by microscopy but complemented by
other techniques [1]. It has been and continues to be respon-
sible for establishing the principal elements in our under-
standing of macromolecular self-organization and thence to
establishing structure–property relationships. Its central
position in polymer science arises essentially from three
causes. First microscopy identifies specific locations of interest
and is not restricted, as are nonmicroscopic techniques, to
average values. Second, microscopic information is much more
detailed and so potentially more informative than that from
other sources. Third, the morphological record is particularly
rich in crystalline polymers, more so than in other materials,
because, in large measure, the long molecules remain where
they were placed during crystallization and subsequent treat-
ments such as deformation, allowing the sample’s history to
be read whereas in atomic and small-molecular solids this
information is usually lost.

II. CRYSTALLINE POLYMERS

Polymer morphology is mostly, but not entirely, concerned with
crystalline polymers, partly because of their rich record as
mentioned but also because the two most economically impor-
tant synthetic polymers, polyethylene and polypropylene, are
built from the two monomers of most fundamental interest.
Polyethylene is the closest approach to the ideal linear chain
and can be modified to introduce branches through copolymer-
ization while polypropylene is the first

α

-polyolefine and intro-
duces stereospecificity into the polymer chain.
Crystalline polymers are not uniform solids. In the polar-
izing optical microscope they reveal polycrystalline textures
(Figure 1) which are infinite in their variety, no two specimens
being the same. For polymers crystallized from a quiescent
melt, these textures are commonly described as spherulitic

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because, provided there are not too many growth centers
(primary nuclei), little spheres (spherulites) are an interme-
diate stage of development before objects impinge. Prior to
attaining a spherical envelope, objects starting at a point or
short line commonly pass through embryonic forms which
may be sheaflike or polygonal depending on the viewing direc-
tion. Especially in circumstances of reduced branching, at low
supercoolings, such immature objects are known as axialites
and hedrites, respectively. Whether these early forms can
mature into spherical entities depends upon there being suf-
ficient space to allow the development, which is controlled by
the concentration of primary nuclei: more nuclei mean smaller
objects. But whatever stage is reached, the underlying process
of spherulitic growth is the same and all objects are con-
structed on the same principles.
Polymer spherulites are typically constructed on a frame-
work of individual radial lamellae, called dominant, which
branch repetitively then diverge at angles ~20°, increasing

for thinner lamellae. This repetitive divergence of dominant
lamellae is the fundamental reason why an initial single

Figure 1

Spherulites of i-polypropylene growing from the melt
viewed optically between crossed polars. (From Bassett DC. Phil
Trans Roy Soc Lond A 1994; 348:29–43. With permission.)

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