Polymers: Molecular Structure and Dynamics

592 Pages·1980·9.43 MB·iii-xxii, 1-590\592

by  R.A. Fava (Eds.)

Volume 16
Polymers
PART A: Molecular Structure and Dynamics
Edited by
R. A. FAVA
ARC0 Polymers, Inc.
Monroeville, Pennsylvania
@
I980
ACADEMIC PRESS
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Library of Congress Cataloging in Publication Data
Main entry under title:
Polymer physics.
(Methods of experimental physics ; v. 16)
Includes bibliographical references and index.
CONTENTS: pt. A. Molecular structure and
dynamics, edited by R. A. Fava.
1. Polymers and polymerization.
I. Fava, Ronald A. 11. Series.
QD3 81. P6 12 547'.84 7 9- 26 343
ISBN 0-12-475916-5
PRINTED IN THE UNITED STATES OF AMERICA
80 81 82 83 9 8 7 6 5 4 3 2 1
CONTRIBUTORS
Numbers in parentheses indicate the pages on which the authors’ contributions begin.
C. V. BERNEYD, epartment of Nuclear Engineering, Massachusetts tn-
stitute of Technology, Cambridge, Massachusetts 02139 (205)
L. LAWRENCCEH APOYt, nstituttet for Kemiindustri, The Technical Uni-
versity of Denmark, 2800 Lyngby, Denmark (404)
DONALDB . DuPRE, Department of Chemistry, University of Louisville,
Louisville, Kentucky 40208 (404)
R. A. FAVAA, RCO Polymers, Inc., 440 College Park Drive, Monroeville,
Pennsylvuniu 15146 (1)
J. S. KING,N uclear Engineering Department, University of Michigan,
Ann Arbor, Michigan 48109 (480)
ROBERTF . KRATZ,ARCOP olymers, tnc., Research and Development De-
partment, P.O. Box 208, Monaca, Pennsylvania 15061 (13)
PHILIPL . KUMLERD, epartment of Chemistry, State University of New
York, College of Fredonia, Fredonia, New York 14063 (442)
J. R. LYERLAt,B M Reserrrch Laboratories, San Jose, California 95193
(241)
G. D. PATTERSONB,e ll Telephone Laboratories, Murray Hill, New Jersey
07974 (170)
DOROTHYJ . POLLOCKA, RCO Polymers, tnc., Research and Develop-
ment Department, P.O. Box 208, Monaca, Pennsylvania 15061 (13)
R. G. SNYDERW,e stern Regional Research Center, Science and Educa-
tion Administration, US.D epartment of Agriculture, Berkeley, Cali-
fornia 94710 (73)
J. R. STEVENDS,e partment of Physics, University of Guelph, Guelph,
Ontario, NIG 2WI, Canuda (371)
H. W. WHITED, epartment qf’Physics, University of Missouri, University
Park, Columhiu, Missouri 65211 (149)
T. WOLFRAMD,e partment of Physics, University of Missouri, University
Piirk, Colirmbin, Missouri 6521 1 (149)
SIDNEYYI P,D epartment of Nuclear Engineering, Massuchusetts tnsti-
tute qf Technology, Cambridge, Massachusetts 02139 (205)
xi
FOREWORD
The thoroughness and dedication of Ronald Fava in preparing these
volumes may be verified by this work’s impressive scope and size. This
is the first time Merhods of Experimental Physics has utilized three volumes
in the coverage of a subject area.
The volumes, in part, indicate the future development of this publica-
tion. Solid state physics was covered in Volumes 6A and 6B (edited by
K. Lark-Horovitz and Vivian A. Johnson) in 1959. Rather than attempt
a new edition of these volumes in a field that has experienced such rapid
growth, we planned entirely new volumes, such as Volume 11 (edited by
R. V. Coleman), published in 1974. We now appreciate the fact that future
coverage of this area will require more specialized volumes, and Polymer
Physics exemplifies this trend.
To the authors and the Editor of this work, our heartfelt thanks for
a job well done.
L. MARTON
C. MARTON
PREFACE
A polymer must in many ways be treated as a separate state of matter
on account of the unique properties of the long chain molecule. There-
fore, although many of the experimental methods described in these three
volumes may also be found in books on solid state and molecular physics,
their application to polymers demands a special interpretation. The
methods treated here range from classical, well-tried techniques such as
X-ray diffraction and infrared spectroscopy to new and exciting applica-
tions such as those of small-angle neutron scattering and inelastic electron
tunneling spectroscopy. It is convenient to present two types of chapters,
those dealing with specific techniques and those in which all techniques
applied in measuring specific polymer properties are collected. The pres-
entation naturally divides into three parts: Part A describes ways of inves-
tigating the structure and dynamics of chain molecules, Part B more spe-
cifically deals with the crystallization of polymers and the structure and
morphology of the crystals, while in Part C those techniques employed
in the evaluation of mechanical and electrical properties are enumerated.
It should be emphasized, however, that this is not a treatise on the proper-
ties of polymeric materials. The authors have introduced specific polymer
properties only incidentally in order to illustrate a particular procedure
being discussed. The reader is invited to search the Subject Index wherein
such properties may be found listed under the polymer in question.
I have endeavored to arrange chapters in a logical and coherent order
so that these volumes might read like an opera rather than a medley of
songs. The authors are to be commended for finishing their contributions
in timely fashion to help achieve this end. I also wish to acknowledge
with thanks the support of ARC0 Polymers, Inc. and the use of its fa-
cilities during the formative stages of the production.
R. A. FAVA
CONTRIBUTORS TO VOLUME 16, PARTS 6 AND C
Part 6
EDWARDS . CLARKP,o lymer Engineering, University of Tennessee, Knox-
ville, Tennessee 37916
LOISJ . FROLENN,a tional Measurement Laboratory, National Bureau of
Standurds, Wushington, D.C. 20234
IAN R. HARRISONC,o llege of Earth and Mineral Sciences, The Pennsyl-
vania State University, University Park, Pennsylvania 16802
G. N. PATELC, orporate Research Center, Allied Chemical Corporation,
Morristown, New Jersey 07960
GAYLONS . Ross, National Measurement Laboratory, National Bureau
of Stundards, Washington, D.C. 20234
JAMES RUNT,C ollege of Earth and Materials Science, The Pennsylvania
State University, University Purk, Pennsylvania 16802
JOSEPH E. SPRUIELLP,o lymer Engineering, University of Tennessee,
Knoxville, Tennessee 37916
RICHARDG . VADIMSKYBe, ll Telephone Laboratories, Murray Hill, New
Jersey 07974
JING-I WANG,C ollege of Earth and Mineral Sc,iences, The Pennsylvania
State University, University Park, Pennsylvania 16802
Part C
RICHARDH . BOYD,D epartment of Materials Science and Engineering,
University of Utah, Salt Lake City, Utah 84112
NORMANB ROWN,D epartment of Materials Science and Engineering,
University of Pennsylvania, Philadelphia, Pennsylvania 191 74
D. KEITHD AVIESE, lectrical Research Association Limited, Letrtherhead,
Surrey, KT22 7SA, England
xxi
xxii CONTRIBUTORS TO VOLUME 16, PARTS B AND c
R. M. FELDERD, epcirtnient of Chemical Engineering, North Curolititr
State University, Rcrleigh, North Curolina 27650
BRUCEH ARTMANNN, uveil Surfuce Weapons Center, White Ocrk, Sillvr
Spring, Mrrryland 20910
IAN L. HAY, Celmese Resecirch Company, Summit Lcrborcrtory, Summit,
New Jersey 07901
G. S. HUVARDD, eperrtment of Chetniccil Engineering. North Carolinrr
State University, Rcrleigh, North Carolinti 27607
TOSHIH~KN AOG AMURA," DCJprirtmento j' Mechcrnical crnd Industrial En-
gineering, Deptrrtment of Mcitericils Scic.nce cind Enginc.ering.
College of Engineering, University of Utrih, Sirlt Lake City, Utcrh
841 12
DONALJD. PLAZEK, Drpcrrtment ofMrtullurgica1 and Mritericris Enginrer-
ing , Uni \ te rsity of Pittsburgh , Pittsburgh , Pen nsy 1L W ii ia I526 I
J. ROOVERS, Division of Chemistry, Ncrtional Reserirch Corrncil of
Cei ncidcr , Otter wcr , On tcrrio KIA 0 R9 Cer n acl~r
I
JOHN L. RUTHERFORDK, eLirJbtt Division, The Singer Comprrny, Little
Fcills, New Jersey 07424
B. R. VARLOWE, lectrictrl Etigineering Lcrboratory, Uniiyersity of' Mein-
Chester, Meinchester MI3 9PL, England
R. W. WARFIELDN, avcil Sirr-uce Wecrpons Center, White Otrk, Sihver
Spring, Mriryleind 20910
.' Present address: Department of Organic Synthesis, Faculty of Engineering, Kyushu
University. Higashi-ku, Fukuoka 812, Japan.
1. INTRODUCTION
By R. A. Fava
1. laH istoric Development
The possibility of joining small molecular units together to form long-
chain macromolecules, or polymers, must have occurred to chemists long
before polymer science became a subject in its own right. With the
knowledge we have today we can, in fact, trace back through the litera-
ture many instances of polymerization reported unknowingly by various
authors. For example, Regnault' in 1838 described the development of
turbulence and the deposition of small quantities of a white noncrystalline
powder when vinylidene chloride was stored in sunlight. In the following
year, Simon2 reported extracting a volatile oil from a commercial sub-
stance known as Storax. This oil thickened after several months to a
viscous mass no longer soluble in alcohol or ether. Then, in 1872, Bau-
mann3 described the effect of sunlight on vinyl chloride. A white powder
was formed with the same elemental analysis as the starting material.
Baumann described this as an isomer of vinyl chloride. It is almost cer-
tain, however, that what he really saw was the polymer of vinyl chloride,
i.e., poly(viny1 chloride) or PVC. Similarly, we can deduce that Regnault
had probably synthesized poly(viny1idene chloride), another important
commercial polymer, and Simon's volatile oil was styrene that he polym-
erized to polystyrene.
The experimental techniques were not then available to characterize
such substances, nor had the theoretical understanding of chemical
bonding been sufficiently well developed.
By the early twentieth century such curious reactions of some mole-
cules to heat and light had become an important branch of organic chemis-
try. Standard procedures of organic chemistry such as molecular weights
by osmometry and freezing-point depression, melting-point measure-
M. V. Regnault, Ann. Chim. Phys. [2] 69, 151 (1838).
* E. Simon, Ann. Pharm. (Lemgo, Ger.)3 1, 265 (1839).
E. Baumann, Ann. Chem. Pharm. 163, 308 (1872).
Copyright @ 1980 by Academic Ress. Inc.
METHODS OF EXPERIMENTAL PHYSICS, VOL. 16A All rights of reproduction in any form reserved.
ISBN 0-12-475916-5
2 1. INTRODUCTION
ments, crystal structure by X-ray diffraction, solution viscosity and other
solution measurements were used to analyze the products. From observa-
tions of their colloidal nature it was concluded that the products were
loose agglomerates (micelles) of small molecules held together by second-
ary valence forces. The forces were believed to be associated with the
unsaturation in those molecules which contained covalent double bonds,
for example:
,H /H
vinyl chloride: ,C=C
H ‘ c1
H, /C’
vinylidene chloride: ,C=C
H ‘ c1
,H /H
styrene: ,C=C,
H CaH,
The micelle theory began to crumble after Staudinger and Fritschi4
found that if natural rubber (polyisoprene) is hydrogenated the molecules
still remain of colloidal size. The micelle theory would predict that the
agglomerated isoprene molecules, saturated by the hydrogenation, would
dissociate and form a highly volatile liquid.
A new theory, developed in classic publications of Sta~dingerp,o~s tu-
lated that polymers are made up of small molecules held together by pri-
mary valence forces (covalent bonding). The history of the development
of this now-accepted model of the structure of polymers is well docu-
mented in Staudinger’s collected works.6
Suffice to say, it was some time before these new ideas were fully ac-
cepted. One of the nagging drawbacks was the fact that polymers dis-
played crystallinity and the X-ray diffraction pattern suggested a unit cell
similar in size to that of the small molecular unit. As early as 1926, how-
ever, it was hinted by Sponsler,’ with reference to cellulose fibers, that
the small molecules from which polymers are built form repeat units along
the polymer chain and the unit cell is formed by this and the juxtaposition
of adjacent parallel chains (see also Chapter 6.1, this volume, Part B).
‘
H. Staudinger and J. Fntschi, Helv. Chim. Acta 5, 785 (1922).
H. Staudinger. Bey. Drsch. Chem. Ces. 53, 1073, (1920); 59, 3019 (1926).
H. Staudinger, “From Organic Chemistry to Macromolecules,” Wiley (Interscience),
New York, 1961.
’
0. L. Sponsler, J. Gen. Physiol. 9, 677 (1926).
1.2. DEFINITIONS 3
1.2. Definitions
The International Union of Pure and Applied Chemistry (IUPAC)*h as
defined internationally agreed nomenclature in the field of polymer sci-
ence. The term macromolecule is an all-embracing term covering all
large molecules, while a high polymer is restricted to structures that are at
least approximately multiples of a low-molecular-weight unit (a
monomer). A high polymer may be further specified as follows:
homopolymer: a single monomer type,
copolymer: two different monomer units in irregular sequence, e.g.,
poly(ethy leneco-propylene),
terpolymer (etc.): three (etc.) units in irregular sequence,
alternating copolymer: two units in alternating sequence, e.g.,
poly(ethy1ene-alr-carbon monoxide),
block copolymer: a sequence of one unit followed by a sequence of a
secorid unit in the same chain, e.g., poly(styrene-b-butadiene),
pol y (sty rene-b-isoprene-b-syt rene).
Due to the statistical nature of the polymerization process the polymer
chains are not all the same length and very often contain defects in the
form of short or long branches. A special kind of branch containing a dif-
ferent molecular unit may be synthesized subsequent to the main-chain
polymerization. Such a polymer is called a graft copolymer, e.g.,
poly(butadiene-g-styrene). If branches bridge two chains a cross-linked
network is formed.
Another type of defect occurs in polymers built from monomer units
that are asymmetric with respect to the chain axis. If the covalent bonds
are not freely rotating by virtue of double bonds or steric hindrances,
neighboring molecular units may be permanently joined in parallel or anti-
parallel sequences. This quality is called tacricity. If the sequence is
random the polymer is called atactic and will not generally crystallize.
Regular tacticity in a polymer chain is illustrated below with two monomer
units of polypropylene:
y S
syndiotactic:
International Union of Pure and Applied Chemistry, J. Polym. Sci. 8, 257 (1952).