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SECOND EDITION
FUNDAMENTALS
OF
POLYMER
SCIENCE
AN INTRODUCTORY TEXT
SECOND EDITION
FUNDAMENTALS
OF
POLYMER
SCIENCE
AN INTRODUCTORY TEXT
PAUL C. PAINTER
MICHAEL M. COLEMAN
The Pennsylvania State University
Boca Raton London New York Washington, D.C.

Library of Congress Cataloging-in-Publication Data
Main entry under title:

Fundamentals of Polymer Science: An Introductory Text — Second Edition
Full Catalog record is available from the Library of Congress
This book contains information obtained from authentic and highly regarded sources.
Reprinted material is quoted with permission, and sources are indicated. A wide variety of
references are listed. Reasonable efforts have been made to publish reliable data and infor
mation, but the author and the publisher cannot assume responsibility for the validity of all
materials or for the consequences of their use.
Neither this book nor any part may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, microfilming, and recording, or by any
information storage or retrieval system, without prior pennission in writing from the publisher.
The consent of CRC Press LLC does not extend to copying for general distribution, for
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Direct all inquiries to CRC Press LLC, 2000 N.W. Corporate Blvd., Boca Raton, Florida
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and are used only for identification and explanation, without intent to infringe.
Visit the CRC Press Web site at www.crcpress.com
© 1997 by CRC Press LLC

Originally Published by Technomic Publishing
No claim to original U.S. Government works '

International Standard Book Number 1-36676-339-5
Library of Congress Card Number 97-60315
DEDICATION AND ACKNOWLEDGEMENT
This is the book that we swore we would never write after we finished our
last book. But now that we have written it and the frustrations have passed, we
gratefully dedicate the book to our fathers, Charles Painter and Ronald Coleman,
whose lives were and much more difficult than ours and who sacrificed many
things to give us a start.
TABLE OF CONTENTS
Preface to the Second Edition ........................................................................ xi

Preface to the First Edition ............................................................................. xiii
1. The Nature of Polymeric M aterials
A WHAT ARE POLYMERS—WHAT IS POLYMER SCIENCE? ......................... 1

B. SOME BASIC DEFINITIONS—THE ELEMENTS OF POLYMER
MICROSTRUCTURE .............................................................................................. 3
C. MOLECULAR WEIGHT-SOME INITIAL OBSERVATIONS .......................... 16
D. STUDY QUESTIONS .............................................................................................25
E. SUGGESTIONS FOR FURTHER READING .......................................................26
F. APPENDIX : CHEMICAL STRUCTURES OF SOME
COMMON POLYMERS ........................................................................................ 26
2. Polymer Synthesis 29
A INTRODUCTION ................................................................................................... 29
B. STCP-GROWTH POLYMERIZATION ..................................................................31
C. CHAIN OR ADDITION POLYMERIZATION .......................................................40
D. POLYMERIZATION PROCESSES .......................................................................54
E. STUDY QUESTIONS .............................................................................................60
F. SUGGESTIONS FOR FURTHER READING .......................................................61
3. Kinetics of Step-Growth and Addition Polymerization 63

A INTRODUCTION ................................................................................................... 63
B. THE KINETICS OF STEP-GROWTH POLYMERIZATION ...............................64
C. KINETICS OF FREE RADICAL POLYMERIZATION .......................................68
D. STUDY QUESTIONS .............................................................................. 79
E. SUGGESTIONS FOR FURTHER READING .......................................................81
4. Statistics of Step-Growth Polymerizations 83

A INTRODUCTION ................................................................................................... 83
B. THE STATISTICS OF LINEAR POLYCONDENSATION .............................. 84
v ii
viii Table o f Contents
C. MOLECULAR WEIGHT DISTRIBUTIONS IN LINEAR

CONDENSATION POLYMERS ............................................................................. 89
D. MULTICHAIN CONDENSATION POLYMERS .................................................... 93
E. THEORY OF GELATION .......................................................................................96
F. RANDOM BRANCHING WITHOUT NETWORK FORMATION .......................103
G. STUDY QUESTIONS ............................................................................................105
H. SUGGESTIONS FOR FURTHER READING ........................................................ 106
5. Copolymerization 107
A. GENERAL OVERVIEW .......................................................................................107
B. THE COPOLYMER EQUATION ....................................................................... 109
C. REACTIVITY RATIOS AND COPOLYMER COMPOSITION ........................ 113
D. COPOLYMER SEQUENCE DISTRIBUTION AND THE
APPLICATION OF PROBABILITY THEORY ....................................................119
E. STUDY QUESTIONS ........................................................................................... 141
F. SUGGESTIONS FOR FURTHER READING ..................................................... 143
6 . Spectroscopy and the Characterization of Chain Structure 145

A. INTRODUCTION ..................................................................................................145
B. FUNDAMENTALS OF SPECTROSCOPY .......................................................145
C. BASIC INFRARED SPECTROSCOPY ...............................................................150
D. CHARACTERIZATION OF POLYMERS BY
INFRARED SPECTROSCOPY ............................................................................155
E. BASIC NMR SPECTROSCOPY ..........................................................................173
F. CHARACTERIZATION OF POLYMERS BY
NMR SPECTROSCOPY ....................................................................................180
G. STUDY QUESTIONS ........................................................................................... 204
H. SUGGESTIONS FOR FURTHER READING .....................................................2 06
7. Structure 207
A. INTRODUCTION ................................................................................................. 207
B. STATES OF MATTER AND BONDING IN POLYMER MATERIALS ........... 208
C. THE CONFORMATIONS OR CONFIGURATIONS OF
POLYMER CHAINS .............................................................................................. 218
D. RANDOM WALKS, RANDOM FLIGHTS AND DISORDERED
POLYMER CHAINS .............................................................................................. 224
E. POLYMER MORPHOLOGY ................................................................................237
F. FINAL WORDS— A BRIEF COMMENT ON SIZE ........................................... 255
H. SUGGESTIONS FOR FURTHER READING ......................................................257
8 . Crystallization, Melting and the Glass Transition 259

A. OVERVIEW AND GENERAL APPROACH ...................................................... 259
B. SOME FUNDAMENTALS ...................................................................................260
C. CRYSTALLIZATION AND MELTING: SOME EQUILIBRIUM
Table o f Contents ix
CONSIDERATIONS .............................................................................................273
D. THE KINETICS OF POLYMER CRYSTALLIZATION .....................................278
E. THE CRYSTALLINE MELTING TEMPERATURE ......................................... 283
F. THE GLASS TRANSITION TEMPERATURE ................................................... 290
H. SUGGESTIONS FOR FURTHER READING .....................................................305
9. Thermodynamics of Polymer Solutions and Blends 307

A INTRODUCTION.....................................................................................................307
B. THE FREE ENERGY OF MIXING................................................................ 308
C. THE PHASE BEHAVIOR OF POLYMER SOLUTIONS AND BLENDS ........321
D. DILUTE SOLUTIONS, EXCLUDED VOLUME AND THE
THETA TEMPERATURE .....................................................................................330
E. STUDY QUESTIONS ........................................................................................... 335
F. SUGGESTIONS FOR FURTHER READING .....................................................337
10. Molecular Weight and Branching 339

A INTRODUCTION.....................................................................................................339
B. OSMOTIC PRESSURE AND THE DETERMINATION OF
NUMBER AVERAGE MOLECULAR WEIGHT ............................................... 341
C. LIGHT SCATTERING AND THE DETERMINATION OF
WEIGHT AVERAGE MOLECULAR WEIGHT ................................................. 352
D. SOLUTION VISCOMETRY AND THE VISCOSITY AVERAGE
MOLECULAR WEIGHT .....................................................................................363
E. SIZE EXCLUSION (OR GEL PERMEATION) CHROMATOGRAPHY ........... 373
F. SEC AND THE DETERMINATION OF LONG CHAIN BRANCHING .......... 381
H. SUGGESTIONS FOR FURTHER READING .....................................................394
11. Mechanical and Rheological Properties 395

A INTRODUCTION AND OVERVIEW ................................................................... 395
B. A BRIEF REVIEW OF SOME FUNDAMENTALS ........................................... 396
C. DEVIATIONS FROM IDEAL BEHAVIOR ......................................................... 404
D. INTRODUCTION TO VISCOELASTICITY ........................................................416
E. MECHANICAL AND THEORETICAL MODELS OF
VISCOELASTIC BEHAVIOR .............................................................................. 4 3 0
F. NON-LINEAR MECHANICAL AND RHEOLOGICAL BEHAVIOR ................. 449
G. ULTIMATE PROPERTIES ...................................................................................459
H. STUDY QUESTIONS ........................................................................................... 467
L SUGGESTIONS FOR FURTHER READING .....................................................469
Index 471
PREFACE TO THE SECOND EDITION
Writing a book, particularly a textbook, can take a lot out of you:

W ritin g a book is an a d v en tu re: it begins as an am usem ent, then it becom es
a m istress, then a m aster and finally a ty ra n t.
W inston S. C hurchill
Things get particularly hard near the end, when you are confronted by the
tedious tasks of preparing an index, editing and proof reading; especially when
you look out the window, the sun is shining and you would rather be playing
golf.
All m orning I w orked on the p ro o f o f one of my poem s, an d I took o u t a
com m a; in the aftern o o n I p u t it back.
O scar Wilde
So it is perhaps inevitable that your attention slips and errors creep in. You
don't realize this until later, of course, when you start to find some minor typo's
or garbled sentences. This is not too bad and you can always blame your
publishers:
It is w ith p u b lish ers as w ith wives: one alw ays w ants som ebody else's.
Norman D ouglass
But if your book is used as a text, each and every mistake will be found by
your students and the number of revealed errors becomes daunting. Even worse,
these errors are often brought to your attention in a manner that you believe
reflects a large measure of glee:
T h ere a re those w ho notice m istakes in passing and those w ho buy books fo r
the sole p urpose o f finding them .
A . K. Dewdney
It is particularly galling when your so-called friends participate in the

criticism:
501 Preface to the Second Edition
O f all plagues, good heaven, thy wrath can send,

Save me, oh save me from the candid friend.
George C anning
Naturally, your first instinct is to attribute their comments to mere envy:

Nothing is more hum iliating than to see idiots succeed in enterprises we
have failed in.
G ustave F laubert
This base emotional response is quickly replaced by denial:

If at first you don't succeed, destroy all evidence that you have tried.
A nonym ous
But in the end a measure of objectivity returns and you start to make a list of
corrections. You then also notice that there are certain topics that you really made
a mess of:
I know you believe you understand what you think I said, but I am not sure
you realize that what you heard is not what I meant.
A n onym ou s
So you end up writing a second edition. You hopefully fix all the errors in
the first edition, modify a little here and there to improve clarity, add some study
questions (for those idle teachers who cannot be bothered to make them up!) and
end up totally rewriting and reorganizing two chapters. But you no longer have
the illusion that your efforts will be remotely error-firee; you just hope to get
some minor satisfaction from your work:
Some day I hope to write a book where the royalties will pay for the copies
I give away.
Clarence Darrow
February 1997 PAUL PAINTER

MIKE COLEMAN
PREFACE TO THE FIRST EDITION
If you, dear reader, ever write a book, you will eventually find that having
labored long and hard to write down and give shape to your view of a subject, an
effort that can result in hundreds of pages of text and figures that perhaps (if you
are lucky) only a few hundred people might ever read, you are then faced with
the oppressive but suddenly daunting task of writing a preface. This is where
you are supposed to explain what the book is about and why you wrote it in the
first place. The problem is that you no longer remember.
But a preface has its uses. It can give readers a w hiff o f the author's prose
style and an indication of his potential as an inducer o f tedium , thus
enabling them to m oderate their enthusiasm , lower their sigh ts, and so
prepare themselves for the main body o f the work.
Frank M uir (An Irreverent and Thoroughly Incom plete
Social H istory o f A lm ost Everything)
In addition, you are by now tired and fed up with the whole enterprise;
How unfit, and how unworthy a choice I have made of myself, to undertake a
work of this mixture.
S ir W alter Raleigh
and you are starting to suspect that your explanation of what you know reveals
even more about what you don’t know;
A person who publishes a book w illfully appears before the populace with
his pants down.
Edna St. Vincent M illay
Even worse, you find that if your scribblings have been a collaborative effort
you might no longer be on speaking terms with your co-author and one-time
friend;
I have known two professors of Greek who ceased speaking to one another
because o f divergent views on the pluperfect subjunctive.
Stephen L eacock
xiii
xiv Preface to the First Edition
Fortunately, you realize that this too will pass and you must save your
disagreements for more vital matters;
I've seen lifelong friends drift apart over golf just because one could play
better, but tbe other counted better.
Stephen Leacock
What really happens is that if you teach, then at some point you become so
frustrated with what you perceive as the shortcomings of the available texts that
you decide to write your own. And that is what happened to us. Of course, you
then find that the books you were using were not so bad after all, its just that you
wanted to emphasize or include subjects that perhaps others found uninteresting
or irrelevant, but which to you are of consuming interest and central to the whole
field.
So, here is our effort; the essential parts of what we teach in two courses to
juniors, seniors and some first-year graduate students that have drifted into
polymers from other fields. It is an introduction and survey of the subject based
on a refinement of what we have taught over the last ten years. As with all books
of this type, it is difficult to know what to assume as prior knowledge. We
naturally suppose that the student has digested some fundamentals of organic
chemistry.
Organic chemistry is the study of organs; inorganic chemistry is the study of
the insides o f organs.
M ax Shulman
and has enough physics and physical chemistry to be comfortable with basic
molecular concepts;
M O L E C U L E ,a . The ultimate, indivisible unit of matter. It is distinguished
from the corpuscle, also the ultimate, indivisible unit o f m atter, by a closer
resem blance to the atom , also the u ltim ate, indivisible unit o f m atter.
Three great scien tific theories o f the structure o f the universe are the
molecular, the corpuscular and the atom ic. A fourth affirm s, with Haeckel,
the condensation or precipitation o f matter from eth er-w h ose existence is
proved by the condensation or precipitation. The present trend o f scientific
thought is toward tbe theory o f ions. Tbe ion differs from the molecule, tbe
corpuscle and tbe atom in that it is an ion. A fifth theory is held by idiots,
but it is doubtful if they know any more about the matter than the others.
A m brose Bierce
(The D evil's D ictionary)
However, it has been our experience that the average student has only
imperfectly digested certain fundamentals before starting their studies of
polymers, so in our lectures and in this book we attempt to start at a simple level
with brief reviews of what should be (but usually isn't) well-known material. Of
course, we have to guard against canying this to extremes and we have tried to
overcome a tendency to ovcr-explain;
Preface to First Edition XV
I am standing on the threshold about to enter a room. It is a complicated

business. In the first place I must shove against an atm osphere pressing
with a force of fourteen pounds on every square inch o f my body. I must
make sure of landing on a plank travelling at twenty miles a second round
the su n -a fraction o f a second too early or too late, the plank would be
miles away. I must do this whilst hanging from a round planet head outward
into space, and with a wind o f aether blowing at no one knows how many
m iles a second through every interstice o f my body. The plank has no
solidity of substance. To step on it is like stepping on a swarm o f (lies.
Shall I not slip through? No, if I make the venture one of the flies hits me
and gives a boost up again; I fall again and am knocked upwards by another
fly, and so on. I may hope that the net result will be that I remain about
steady; but if unfortunately I should slip through the floor or be boosted too
violently up to the ceiling, the occurrence would be, not a violation o f the
laws o f N ature, but a rare coincidence. These are som e of the m inor
d ifficulties. I ought really to look at the problem four-dim ensionally as
concerning the intersection o f my world-line with that o f the plank. Then
again it is necessary to determine in which direction the entropy o f the world
is increasing in order to make sure that my passage over the threshold is an
entrance not an exit.
Verily, it is easier for a camel to pass through the eye o f a needle that for a
scientific man to pass through a door.
S ir A rthur Eddington
(The Nature o f the Physical World)
Keeping this warning in mind, we have tried to say what we have to say
simply;
Don't quote Latin; say what you have to say, and then sit down.
A rth u r W ellesley
D uke o f W ellington
and in so doing we have deliberately adopted a conversational tone to our

writing. Some might find this irritating and unrigorous;
This is the sort o f English up with which I will not put.
W inston S. C hurchill
but in the final analysis this is the way we like to write and if you don't like it,
write your own damned book!
February 1994 PAUL PAINTER

MIKE COLEMAN
CHAPTER 1
The Nature of Polymeric Materials

"He fixed thee mid this dance
o f plastic circumstance"
—Robert Browning
A. WHAT ARE POLYMERS—WHAT IS POLYMER SCIENCE?
Simply stated, polymers are very large molecules (macromolecules) that are
comprised or built up of smaller units or monomers. The arrangements of these
units, the various types of chains that can be synthesized and the shapes that
these chains can bend themselves into, result in a class of materials that are
characterized by an enormous and intriguing range of properties. Some of these
are unique to polymers (e.g., rubber elasticity) and, as we shall see, are simply a
consequence of their size and chain-like structure.
Polymer science is also a relatively new discipline and one that is
characterized by extraordinary breadth. It involves aspects of organic chemistry,
physical chemistry, analytical chemistry, physics (particularly theories of the
solid state and solutions), chemical and mechanical engineering and, for some
special types of polymers, electrical engineering. Clearly, no one person has an
in-depth knowledge of all these fields. Most polymer scientists seek a broad
overview of the subject that is then usually supplemented by a more detailed
knowledge of a particular area. This book is a first step towards the former and
to give a flavor for the diversity of this subject matter we will commence with an
outline of some of the areas we will cover.
Polymer Synthesis
Many polymer scientists think that it is unlikely that we will ever again see
any new thermoplastic take the world by storm (i.e., achieve levels of production
comparable to polyethylene or polystyrene), but it should be kept in mind that
similar things were being said round about 1950, just before high density
polyethylene and isotactic polypropylene made their debut (some of this
terminology will be defined shortly). Today, there are two good reasons to think
they may be right, however. First, all the monomers that can be readily
polymerized already have been; second, commercializing a new commodity
plastic would probably cost more than $1 billion (The Economist, May 1980).
This is not promising in an industry that has become infected by MBA's with a
1
2 THE NATURE OF POLYMERIC MATERIALS
six month time-horizon. Fortunately, this does not mean that polymer synthetic
chemists are out of business. There is considerable interest in using new
catalysts (for example) to produce commodity plastics more cheaply, or in
producing better defined chain structures to give controlled properties;
synthesizing "specialty" polymers such as those with stiff chains and strong
intermolecular attractions to give thermal resistance and high strength; or chains
with the types of delocalized electronic structures that result in unusual electrical
and optical properties. These materials would be produced in smaller quantities
than "bulk" plastics, but can be sold at a much higher price. Our intention is only
to give you a start in this area, however, so you won't find any discussion of
advanced synthetic methods in this book. In chapter 2 we simply cover the
basics of polymer synthesis, but this is enough for you to grasp the essentials of
how the majority of commercial polymers are produced.
Polymer Characterization
What a chemist thinks he or she has made is not always the stuff that is lying
around the bottom of his or her test tube. Accordingly, there is an enormous
field based on characterization. This is now a particularly exciting area because
of recent advances in instrumentation, particularly those interfaced with high-
powered yet small and relatively cheap dedicated computers. These novel
analytical techniques are not only useful in studying new materials, but
answering questions that have intrigued polymer scientists for decades. For
example, spectroscopic techniques are used to examine "local" chemical structure
and interactions in polymer systems. Electron and other microscopies and the
scattering of electromagnetic radiation are used to characterize overall structure or
morphology; i.e., how components of a system phase separate into various types
of structures; how chains fold into crystals; and the shape of an individual chain
in a particular environment. Some techniques are so expensive that national
facilities are required, e.g., synchotron radiation and neutron scattering. Our
focus in this book will be on the basics, and in particular we will discuss the
measurement of molecular weight and the use of molecular spectroscopy to
characterize chain structure.
Polymer Physical Chemistry
Paul Flory was awarded the Nobel Prize in Chemistry for his work in this
area and we will mention his name often in this book. Polymer physical
chemistry is a subject that demands a knowledge of theory and the ability to
perform carefully controlled experiments, often using the types of instruments
mentioned above. (The areas of characterization and polymer physical chemistry
overlap considerably and they are artificially separated here merely to illustrate
the different types of things polymer scientists do.) The simplest way to get a
"feel" for this subject is get a copy of Flory's book Principles o f Polymer
Chemistry, still a classic after forty years, and scan the chapters on, for example,
the theories of rubber elasticity, solution thermodynamics, phase behavior, etc.
Polymer Microstructure
This subject is still attracting enormous interest, and there has been much recent
emphasis on polymer blends or alloys and polymer liquid crystals.
Polymer Physics
Polymer physics and polymer physical chemistry are overlapping disciplines

that are not, in many cases, easily delineated. Historically, however, it is
possible to point to an enormous impact by theoretical physicists starting in the
late 1960's and early 1970's. Until then most theory was based on almost
classical physical chemistry, but a number of leading physicists (notably
de Gennes and Edwards) started to apply modem theories of statistical physics to
the description of long chain molecules. The result has been a revolution in
polymer theory, one that is not easily assimilated by "traditional" polymer
scientists and is still ongoing.
Polymer physics is not confined to theory, however. Experimental polymer
physics continues to focus on areas such as chain conformation, viscoelastic and
relaxation properties, phenomena at interfaces, kinetics of phase changes and
electrical and piezoelectric properties. In our discussions of polymer physics and
physical chemistry we will focus on chain conformation and morphology
(structure), thermal properties (crystallization, melting and the glass transition),
solution properties and the determination of molecular weight.
Polymer Engineering
Last, but by no means least, there is a vast area that is involved with chemical
engineering (the processing of polymers) and mechanical engineering (studies of
strength, fatigue resistance, etc.) as applied to polymeric materials. For example,
there is enormous interest in producing ultra-high strength polymer fibers. It
turns out that even "common or garden" polymers like polyethylene or
polypropylene can be processed to give "high-tech" properties. The trick is to
align the chains as perfectly as possible; not an easy task. Once made of course,
the mechanical properties of these materials have to be determined. This involves
more than stretching a fiber until it breaks. The mechanical properties of
polymers are complicated by all sorts of factors (defects, relaxation processes,
etc.) and the field is an intriguing combination of mechanical measurements,
structural characterization and theory. The last chapter in this book will deal with
mechanical properties of polymers.
B. SOME BASIC DEFINITIONS - THE ELEMENTS OF

POLYMER MICROSTRUCTURE
It may seem a bit like putting the cart before the horse, but we will first
describe some basic molecular characteristics of the chain structure of polymers
before we consider the chemistry of how these materials are produced. By
arranging the subject matter in this manner it immediately becomes clear why
certain synthetic methods have become important and how polymer chemistry
can now be used (in principle) to obtain designed materials, with particular types
of molecular groups arranged in a chosen pattern.
In many texts it is also customary to introduce various classification schemes
at this point Many of these are quite arbitrary and the subject has outgrown
them. There is one that is both descriptive and remains widely used, however,
and this divides polymers into thermoplastics and thermosets. As the names
suggest the former flow or, more precisely, flow more easily, when squeezed,
pushed or stretched by a load, usually at elevated temperatures. Most of them
hold their shape at room temperature, but can be reheated and formed into
different shapes. Thermosets are like concrete, they flow and can be molded
when initially constituted, but then become set in their shape, usually through the
action of heat and (often) pressure, this process is often called "curing".
Reheating a "cured" sample serves only to degrade and generally mess-up the
article that has been made. This difference in behavior is, of course, a direct
consequence of the various types of arrangements of units in polymer chains
(polymer microstructure) and we will now take a look at these structures.
Linear, Branched and Cross-Linked Polymers
The simplest type of polymer is a linear homopolymer, by which we mean a

chain that is made up of identical units (except for the end groups) arranged in a
linear sequence. If we could see such a chain under a microscope of some kind it
would appear, relative to small roughly spherical molecules such as HzO, like a
tangled up kite string or fishing line. Polymers where there are different types of
units in the same chain are called copolymers and we will describe these in more
detail shortly.
An example of a polymer that can be synthesized in the form of a linear chain
is polyethylene (usually denoted PE). A part of a typical chain is shown in figure
1.1. Normally, commercial samples of this polymer are very long (have a high
molecular weight), so that figure 1.1 only shows a small part of such a chain.
It is usual to represent such a polymer in terms of its chemical repeat unit, as
follows:
-(CH2 -C H 2)n-
where n can be very large. The chemical repeat units of a few common polymers
are listed at the end of this chapter.
It turns out that when polyethylene was first synthesized on an industrial
scale (in the 1930's) a high pressure process was used (at low pressures ethylene
does not polymerize at all) and for various reasons (that we will consider when
we discuss synthesis) branched polymers were produced. The chemical
structure of a branched polyethylene is also illustrated in figure 1.1. It wasn't
until various catalytic processes were discovered (in the early 1950's) that linear
polyethylene was synthesized*.
* The history o f these discoveries and the interplay of the personalities involved is both
fascinating and intriguing. We will discuss some of the history in chapter 2 and the interested
reader should consult the references listed in that chapter.
Polymer Microstructure 5
(A) Part of a Linear Polyethylene Molecule
(B) Part of a Branched Polyethylene Molecule
Figure 1.1 "Ball and stick" and space filling models o f polyethylene.
The difference in chemical structure between linear and branched

polyethylene appears to be quite small and localized to those units that form the
branch points. Such differences can have a profound affect on properties,
however. Because linear chains can pack in a regular three dimensional fashion,
they form a crystalline phase (while part of it stays tangled up in an amorphous
phase). A highly branched polymer is incapable of doing this, because the
random location and varying lengths of the branches prevent regular packing.
At low degrees of branching, however, there is a degree of crystallinity, but
it is lower than that found in samples of linear polyethylene. Because of the
regular arrangement and hence tighter packing of the chains in the crystalline
regions, linear polyethylene is often called high density polyethylene (HDPE),
while slightly branched material is called low density polyethylene (LDPE).
(Highly branched and hence completely amorphous samples are not (presently)
of any commercial significance.)
Properties such as stiffness, strength, optical clarity, etc. are profoundly
affected by the changes in crystallinity that me a consequence of branching.
Obviously, crystallization in polymers is a broad and extensive subject in its own
right and one we will return to later. The point that should be grasped here is the
effect chain structure has on properties and hence the importance of having a firm
understanding of these first principles and definitions.
The types of random short chain branches described above are not the only
type that occur. Various reactions lead to long chain branches and it is also
possible to synthesize comb-like or star-shaped polymers (illustrated in figure
1.2). Certain types of monomers form highly branched structures at the onset of
polymerization. This is illustrated in figure 1.3, where Y or X shaped monomers
are shown combining to give what usually becomes a very complicated three
dimensional structure known as a network. The Y and X shaped molecules are
trifunctional or tetrqfunctional molecules (have 3 or 4 chemical groups that are
capable of reacting with one another to form a covalent bond).
A network, where every unit is interconnected through various tortuous
pathways, is only formed at a certain point in the reaction and always remains
SHORT LONG STAR
Figure 12 Schematic diagram depicting short, long and star branching.

NETWORK FORMATION
Figure 1 3 Schematic diagram depicting the development o f branched chains and networks.
Figure 1.4 Schematic diagram depicting the cross-linking o f linear polymer chains.
mixed with monomers and other small molecules, unless the reaction is driven to
ultimate completion (i.e., all the original functional groups are reacted). This
type of network is typical of various thermosets.
As the old saying has it, there is more than one way to skin a cat, and
networks can also be formed by taking linear polymer chains and chemically
linking them together, as illustrated in figure 1.4. This process is called cross-
linking (or vulcanization) and is crucial in forming various types of elastomeric
materials. If all the chains become interconnected by such reactions, then a so-
called infinite network is formed.
Homopolymers and Copolymers: A Question of Semantics?
Synthetic polymers have traditionally been named for their respective

monomeric precursors; for example, polyacrylonitrile [-CH2-CHCN-]n from
acrylonitrile CH2=CHCN; poly(vinylidene chloride) [-CH2-CCl2-]„ from
vinylidene chloride CH2=CC12; polystyrene [-CH2-CH(C6H5)-]n from styrene
CH2=CH(C6Hj); ethylene-co-vinyl acetate copolymers from ethylene CH2=CH2
and vinyl acetate CH^CHCOCOCHj) etc. To reiterate, polymers synthesized

from a single monomer are commonly referred to as homopolymers but, as we
shall see, this term is not necessarily an adequate description of such polymers
and may lead to serious misconceptions. The term copolymer is usually used to
describe a polymer derived from two or more monomers, as in the case of
ethylene-co-vinyl acetate mentioned above.
The problem is that many polymers synthesized from a single monomer
might be better described as "pseudo-copolymers”. For example, we mentioned
above that polyethylene may be synthesized from ethylene via a number of
techniques including high-pressure, free radical and catalytic methods (Ziegler-
Natta and supported metal oxides). A range of polyethylenes, usually denoted in
terms of density (i.e., low, medium and high density), are commercially
available. There are large differences in the physical and mechanical properties
of these polyethylenes which may be primarily attributed to variations in the
polymer chain microstructure. During the polymerization of ethylene, structural
units other than methylene groups are incorporated into the polymer backbone.
These structural irregularities or defects, are alkyl substituted groups (-CH2CHR;
where R = methyl, ethyl etc.), which are the short-chain branches described
above. Thus, if the term homopolymer implies a polymer chain containing
identical structural units, it follows that polyethylenes can be, at best, only
loosely described as homopolymers. In fact, it might be better to describe
polyethylene in terms of a copolymer of ethylene and other a-olefins. It is
interesting to note that "actual" copolymers of ethylene and butylene, synthesized
at relatively low pressures using Ziegler-Natta catalysts, have been commercially
introduced and called "linear low density polyethylenes" (LLDPE). This is
somewhat confusing, but there is a degree of logic in naming the polymer as
such, as it is analogous to low density polyethylene (LDPE). The main
difference being that short chain branching units are incorporated either by
polymerization conditions using a single monomer, or by the deliberate
copolymerization of a second comonomer.
Isomerism in Polymers
Just because a polymer is synthesized from a pure monomer, where all the
molecules are initially identical, does not mean that the final product consists of
chains of regularly arranged units. We have already seen that branching can
occur in a polymer such as polyethylene and it turns out that if we start with an
asymmetric monomer we can obtain a variety of microstructures consisting of
various geometric and stereo isomers. The most important types are sequence
isomerism, stereoisomerism and structural isomerism.
Sequence Isomerism
When a monomer unit adds to a growing chain it usually does so in a

preferred direction. Polystyrene, poly(methyl methacrylate) and poly(vinyl
chloride) are only a few examples of common polymers where addition is almost
exclusively head-to-tail. However, for several specific polymers there are
significant numbers of structural units that arc incorporated "backwards" into the
chain leading to head-to-head and tail-to-tail placements. This is referred to as
sequence isomerism. Classic examples include poly(vinyl fluoride),
poly(vinylidine fluoride), polyisoprene and polychloroprene.
In the general case of a vinyl monomer CH2=CXY, the head of the unit is
arbitarily defined as the CXY end while the tail is defined as the CH2 end. A
unit may add onto the chain in two ways:
r
j y r - c h 2-c x y * = (TH)
R* + CH=CXY
T H R-CXY-CH* = (HT)
y
For convenience we will define "normal” addition as (TH) and "backward"
addition as (HT). In poly(vinyl chloride) (X = H, Y = Cl), poly(methyl
methacrylate) (X = CH3, Y = COOCH3) or polystyrene (X = H, Y = Q H j), for
example, the units are arranged almost exclusively in a head-to-tail fashion, thus:
Some polymers, e.g. poly(vinyl fluoride) (X = H, Y = F) or poly(vinylidine

fluoride) (X = Y = F), have a significant number of units incorporated
"backwards" into the chain, giving head to head and tail to tail placements:
Stereoisom erism
Continuing with our discussion of polymers derived from a single monomer,

let us now consider another major facet of polymer microstructure, namely
stereoisomerism. Polymerization of a vinyl monomer, CH2=CHX, where X
may be a halogen, alkyl or other chemical moiety except hydrogen, leads to
polymers with microstructures that are described in terms of tacticity. The
substituent placed on every other carbon atom has two possible arrangements
relative to the chain and the next X group along the chain. At one extreme, the
monomer unit, which contains an asymmetric carbon atom, may be incorporated
into the polymer chain in a manner such that each X group is meso to the
preceding X group (i.e., on the same side of the extended chain - see figure 1.5).
This polymer is described as isotactic.
Conversely, at the other extreme, addition of a monomer unit to the growing
polymer chain may be directed to yield a polymer in which each successive X
group is racemic to the preceding one (i.e., on the opposite side of the stretched
out chain—again, see figure 1.5). This is called a syndiotactic polymer.
Polypropylene (X=CH3), for example, may be synthesized to yield an essentially
isotactic or syndiotactic polypropylene by varying the polymerization conditions.
These structures are illustrated in figure 1.6 for an extended polypropylene chain.
(Because of steric repulsions the isotactic chain does not like this zig-zag shape,
but would prefer to fold into a helix. We will consider such conformations
later). Between these two extremes there is an enormous number of polymer
chain microstructures based on different distributions of meso and racemic
placements of structural repeating units. If there is no preferred direction to the
addition of a monomer to the growing chain, Le.f the monomers are incorporated
randomly with respect to the stereochemistry of the preceding unit, an atactic
polymer is formed. Commercial polystryene, used for the manufacture of clear
plastic beer glasses, and poly(methyl methacrylate), or Plexiglas®, are examples
of a commonly encountered atactic polymers. In common with our general
theme, it is also possible to conceive of vinyl homopolymers in terms of
"copolymers" in which the comonomers are represented by the meso and racemic
placements of the structural units of the polymer chain. This will prove a useful
approach when we apply statistical methods to the description of microstructure
in chapters 4 and 5.
Structural Isomerism— The Microstructure of Polydienes
Another outstanding example of the complex polymer chain microstructure

that can result from the polymerization of a single monomer is seen in the
synthesis of polydienes from conjugated dienes. Isoprene, for example, may be
H H H H H H H H
racemic diad meso diad

r m
Figure 1.5 Schematic diagram depicting racemic and meso diads.

(A) P art of an Isotactic Polypropylene Molecule
(B) Part of a Syndiotactic Polypropylene Molecule
Figure 1.6 Side view "ball and stick" and top view space filling models o f extended chain
isotactic and syndiotactic polypropylenes.
polymerized to polyisoprene by a variety of techniques including free radical,

ionic and Ziegler-Natta catalysis. Mother Nature also synthesizes "natural"
polyisoprenes, Heavea (Natural Rubber) and Gutta Percha, but uses trees instead
of round bottom flasks as polymerization vessels. The way in which isoprene is
incorporated into a growing polymer chain is dependent upon the method of
polymerization and the precise experimental conditions. Three common
examples of diene monomers can be represented by the general formula:
1 2 3 4
CH2 = CX - CH = CH2
where:
X = H butadiene
X = CH3 isoprene
X = Q chloroprene
We have numbered the carbon atoms for reasons that will soon be apparent.
Many common elastomers are polydienes and therefore important polymer
materials, but they're often regarded with fear and loathing by new students of
polymer science because a description of their chain structure requires learning
some nomenclature. The geometric and stereoisomers that are found in poly
dienes are a result of the configuration of the double bond and whether the poly
merization has proceeded by opening both monomer double bonds or just one.
Four major structural isomers, shown schematically in figure 1.7, are
possible. The so-called 1,4 polymers are formed by linking carbon atom 4 of one
monomer to carbon atom 1 of the next, and so on. The arrangement of the
substituent carbon atoms relative to the double bond in 1,4 polymers can be in
either the cis or trans configuration. The 1,2 or 3,4 polymers are formed when
incorporation into the polymer chain occurs through either the first or second
double bond, respectively. These have the same configurational properties as
vinyl polymer chains and may occur in isotactic or syndiotactic sequences.
— CH^
c=c
— Ch2 / — CH2 /
c sC s
c h 3/ sc - h H C -C H o
II II 3
ch2 ch2
Figure 1.7 Schematic representation o f the structural isomers o f polyisoprene.

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Bernard then draws a minute parallel, more curious than admirable, between the cross
and the trials of life,――likening the four difficulties in the way of holiness, to the four ends
of the cross; bodily fear being the foot-piece; open assaults and temptations, the right arm-
piece; secret sins and trials, the left hand-piece; and spiritual pride, the head-piece. Or, as
he briefly recapitulates, the four virtues attached to the four horns of the cross, are
these:――continence, patience, prudence, and humility. A truly forcible figure, and one not
without its effect, doubtless, on the hearers. This arrangement of the cross, moreover,
seems to prove, that in the time of Bernard, the idle story about Andrew’s cross being
shaped like the letter X, was entirely unknown; for it is evident that the whole point of the
allusion here consists in the hearers supposing that Andrew was crucified on a cross of the
common shape,――upright, with a transverse bar and head-piece.
In conclusion of all this fabulous detail, may be appropriately quoted the closing passage
of the second discourse of Bernard, the spirit of which, though coming from a Papist, is not
discordant with the noblest essential principles of truly catholic Christianity, seldom indeed,
found so pure in the Romish church, as in this “Last of the Fathers,” as he has been justly
styled. This, with all the passages above quoted, may be found by those who can enjoy the
original, in his works. (Divi Bernardi Opera Omnia Joh. Picard. Antwerp, 1609, folio;
columns 322‒333.)
So accordant are these words with the spirit which it becomes this work to inculcate, that
I may well adopt them into the text, glad to hang a moral to the end of so much falsehood,
though drawn from such a theme, that it seems like “gathering grapes of thorns, or figs of
thistles.”
Bernard has in this part of his discourse been completing all the details of his parallel
between the cross and the Christian’s life, and in this conclusion, thus crowns the simile, by
exhorting his saintly hearers to cling, each to his own cross, in spite of all temptation to
renounce it; that is, to persevere in daily crucifying their sins, by a pure deportment through
life.
Happy the soul that glories and triumphs on this cross, if it only
persevere, and do not let itself be cast down in its trials. Let every
one then, who is on this cross, like the blessed Andrew, pray his
Lord and Master, not to let him be taken down from it. For what is
there which the malign adversary will not dare? what will he not
impiously presume to try? For what he thought to do to the disciple
by the hands of Aegeas, the same he once thought to do to the
Master by the scornful tongues of the Jews. In each instance alike,
however, driven by too late experience of his folly, he departed,
vanquished and confounded. O may he in like manner depart from
us, conquered by Him who triumphed over him by Himself, and by
His disciple. May He cause, that we also may attain the same happy
end, on the crosses which we have borne, each one in his own
peculiar trials, for the glory of His name, “who is God over all,
blessed forever.”
JAMES BOANERGES;
THE SON OF ZEBEDEE.
his rank and character.
Whatever may have been the peculiar excellences of this

apostle’s character, as recognized by the searching eye of Him who
knew the hearts of all men, the early close of his high career has
prevented the full development of energies, that might, in the course
of a longer life, have been made as fruitful in works of wonder and
praise, as those of the other members of the elect trio, his friend
and his younger brother; and his later years, thus prolonged, might
have left similar recorded testimonies of his apostolic zeal. Much too,
that truly concerns his brief life, is swallowed up in the long narrative
of the eminent chief of the twelve, whose superiority was on all
occasions so distinctly marked by Jesus, that he never imparted to
this apostle any exalted favor in which Peter did not also share, and
in the record of which his name is not mentioned first. In the first
call,――in the raising of the daughter of Jairus to life,――at the
transfiguration,――and on the apostolic roll,――James is uniformly
placed after Peter; and such too, was the superior activity and
talkative disposition of Peter, that whenever and wherever there was
anything to be said, he was always the first to say it,――cutting off
the sons of Zebedee from the opportunity, if they had the disposition,
to make themselves more prominent. Yet the sons of Zebedee are
not entirely unnoticed in the apostolic history, and even the early-
martyred James may be said to have a character quite decidedly
marked, in those few passages in the sacred record, where facts
concerning him are commemorated. In the apostolic list given by
Mark, it is moreover mentioned, that he with his brother had received
a name from Jesus Christ, which being given to them by him,
doubtless with a decided reference to their characters, serves as a
valuable means of ascertaining their leading traits. The name of
“Boanerges,”――“sons of thunder,” seems to imply a degree of
decided boldness, and a fiery energy, not exactly accordant with the
usual opinions of the characters of the sons of Zebedee; but it is an
expression in the most perfect harmony with the few details of the
conduct of both, which are given in the New Testament.
Boanerges.――This word is one, whose composition and derivation, (as is the case
with many other New Testament proper names,) have caused great discussion and
difference of opinion among the learned. It occurs only in Mark iii. 17, where it is incidentally
mentioned in the list of the apostles, as a new name given to the sons of Zebedee by Jesus.
Those who are curious, can find all the discussion in any critical commentator on the
passage. Poole’s Synopsis, in one heavy folio column and half of another, gives a complete
view of all the facts and speculations concerning this matter, up to his time; the amount of
all which, seems to be, that, as the word now stands, it very nearly sets all etymologies at
defiance,――whether Hebrew, Syriac, Chaldee or Arabic,――since it is impossible to say
how the word should be resolved into two parts, one of which should mean “sons,” and the
other “thunder;” so that it is well for us we have Mark’s explanation of the name, since
without it, the critics would probably have never found either “son” or “thunder” in the word.
As to the reason of the name’s being appropriated to James and John, conjectures equally
numerous and various may be found in the same learned work; but all equally
unsatisfactory. Lampe also is very full on this point. (Prolegomena to a Johannine Theology
cap. I. lib. ii. §§ 9‒15.
his family and call.
Of the first introduction of this apostle to Jesus, it may be

reasonably conjectured, that he formed an acquaintance with him at
the same time with his brother John and the sons of Jonah, as
already commemorated in the former lives, from the brief record in
the first chapter of John’s gospel. After this, he and his brother, as
well as Peter and Andrew, returned quietly to their honest business
of fishing on the lake of Gennesaret, on whose shore, no doubt, was
their home,――perhaps too, in Bethsaida or Capernaum, as their
intimacy and fellowship with the sons of Jonah would seem to imply
a vicinity of residence; though their common occupation might bring
them frequently together in circumstances where friendly assistance
was mutually needed; and the idea of their residence in some other
of the numerous villages along the northern end of the lake, on either
side, is not inconsistent with any circumstance specified in their
history. In their occupation of fishing, they were accompanied by
their father Zebedee, who it seems, was not so far advanced in
years as to be unable to aid his sons in this very laborious and
dangerous business; which makes it quite apparent that James and
John being the sons of so active a man, must themselves have but
just attained manhood, at the time when they are first mentioned.
Respecting the character of this brisk old gentleman, unfortunately
very few data indeed are preserved; and the vagueness of the
impression made by his name, though so often repeated in
connection with his sons, may be best conceived by reference to that
deeply enigmatical question, with which grave persons of mature
age are sometimes wont to puzzle the inquisitive minds of young
aspirants after Biblical knowledge, “Who was the father of Zebedee’s
children?”――a query which certainly implies a great deficiency of
important facts, on which the curious learner could found a definite
idea of this somewhat distinguished character. Indeed “the mother of
Zebedee’s children” seems to posses in the minds of most readers
of the gospels a much more prominent place than “the father of
them;” for the simple occasion on which she presents herself to
notice, is of such a nature as to show that she was the parent from
whom the sons inherited at least one prominent trait,――that of high,
aspiring ambition, with which, in them as well as in her, was joined a
most decidedly comfortable degree of self-esteem, that would not
allow them to suspect that other people could be at all behind them
in appreciating those talents, which in their own opinion, and their
fond mother’s, showed that they were “born to command.” Indeed it
appears manifest, that there was much more “thunder” in her
composition, than in her husband’s, and it is but fair to suppose, from
the decided way in which she put herself forward in the family affairs,
on at least one important occasion, without any pretension whatever
on his part, to any right of interference or decision, that she must
have been in the habit of having her own way in most matters;――a
peculiar prominence in the domestic administration, very naturally
resulting from the ♦circumstance, that her husband’s frequent long
absences from home must have left the responsibilities of the family
often upon her alone, and he, like a prudent man, on his return, may
have valued domestic quiet above the maintenance of any very
decided supremacy. If the supposition may be adopted, however,
that Zebedee died soon after the call of his sons, the silence of the
sacred record respecting him is easily accounted for, and the above
conclusion as to his domestic management, may be considered
unnecessarily derogatory to his dignity of character.
♦ “cirstance” replaced with “circumstance”
Sprung from such parents, and brought up by them on the shores

and waters of Gennesaret, James had learned the humble business
of his father, and was quietly devoting himself to the labors of a
fisherman, probably never dreaming of an occasion that should ever
call forth his slumbering energies in “thunder,” or hold up before his
awakened ambition, the honors of a name that should outlast the
wreck of kingdoms, and of the brightest glories of that age. But on
the morning, when the sons of Jonah received the high call and
commission to become “fishers of men,” James and his brother
too,――at the solemn command, “Follow me,”――laid down their
nets, and left the low labors and amusements of the fishing, to their
father, who toiled on with his servants, while his sons went forth
through Galilee, following him who had called them to a far higher
vocation. No acts whatever are commemorated, as performed by
them in this first pilgrimage; and it was not until after their return from
the north of Galilee, and the beginning of their journey to Jerusalem,
that the occasion arose, when their striking family trait of ambition
was most remarkably brought out.
his ambitious claims.
Their intellectual and moral qualities being of a comparatively high

order, had already attracted the very favorable attention of Jesus,
during the first journey though Galilee; and they had already, on at
least two occasions, received most distinguishing marks of his
regard,――they alone of all the twelve, sharing in the honor of being
present with Peter at the raising of the daughter of Jairus, and being
still more highly favored by the view of the solemn events of the night
of the transfiguration, amid the thunders of Hermon. On that
occasion, the terrors of the scene overcame even their aspiring
souls; and when the cloud burst over them, they both sunk to the
earth, in speechless dread, along with Peter, too, who had previously
manifested so much greater self-command than they, in daring to
address in complaisant words the awful forms before them; while
they remained silent with terror at a phenomenon for which their
views of their Master’s character had but poorly prepared them.
From all these prostrating terrors they had since, however, fully
recovered, and were now completely restored to their former
confidence in themselves, and were still rooted in their old views of
the Messiah’s earthly glories,――in this particular, however, only
sharing the common error of the whole twelve. In this state of mind,
looking upon Jesus Christ only as an ambitious man, of powerful
mind, vast knowledge, divine consecration, and miraculous gifts,
which fitted him for the subversion of the Roman dominion, and the
erection of a kingdom of his own,――their thoughts were all the
while running on the division of the spoils and honors, which would
be the reward of the chief followers of the conqueror; and in this
state of mind, they were prepared to pervert all the declarations of
Jesus, so as to make them harmonize with their own hopes and
notions. While on this journey southward, to Jerusalem, after they
had passed into the eastern sections of Judea, beyond the Jordan,
Jesus was one day, in answer to an inquiry from Peter, promising his
disciples a high reward for the sacrifices they had made in his
service; and assuring them, that in return for houses or lands or
relatives or friends, left for his name’s sake, they should all receive a
return, a hundred-fold greater than the loss. Especially were their
fancies struck by a vivid picture, which he presented to their minds,
of the high rewards accruing to all the twelve, declaring that after the
completion of the change which he was working, and when he had
taken his own imperial throne, they should sit around him on twelve
thrones, judging the twelve tribes of Israel. Here was a prospect,
enough to satisfy the most aspiring ambition; but along with the
hopes now awakened, arose also some queries about the
preference of places in this throned triumph, which were not easily
settled so as to satisfy all at once. In the proposed arrangement, it
was perfectly evident, that of the whole circle of thrones, by far the
most honorable locations would be those immediately on the right
and left of the Messiah-king; and their low ambition set them at once
contriving how to get these pre-eminent places for themselves. Of all
the apostolic band, none could so fairly claim the right hand throne
as Peter; already pronounced the Rock on which the church should
be founded, and commissioned as the keeper of the keys of the
kingdom. But Peter’s devotion to his Master seems to have been of
too pure a character, to let him give any thought to the mere rewards
of the victory, so long as he could feel sure of the full return of that
burning affection to his Lord, with which his own ardent soul glowed;
and he left it to others to settle points of precedency and the division
of rewards. On no occasion throughout his whole life, is there
recorded any evidence of the slightest disposition to claim the mere
honors of a pre-eminence, though his superior force of character
made the whole band instinctively look to him for guidance, on all
times of trouble and danger, after the ascension. His modest,
confiding, disinterested affection for his Master, indeed, was the
main ground of all the high distinctions conferred on him so
unsparingly by Jesus, who would have been very slow to honor thus,
one who was disposed to grow proud or overbearing under the
possession of these favors. But this very character of modesty and
uncalculating affection, gave occasion also to the other disciples, to
push themselves forward for a claim to those peculiar exaltations,
which his indifference to personal advancement seemed to leave
unoccupied, for the more ambitious to assume. In this instance,
particularly, James and John were so far moved with the desire of
the enviable distinction of this primacy, that they made it a matter of
family consultation, and accordingly brought the case before their
fondly ambitious mother, who instantly determined that the great
object should be achieved before any one else could secure the
chance for the place; and resolved to use her influence in favor of
her darling sons. On the first favorable opportunity she therefore
went with them to Jesus; and, as it would appear by the combination
of the accounts of Matthew and Mark, both she and they presented
the request at once and together,――James and John, however,
prefacing the declaration of their exact purpose by a general petition
for unlimited favor,――“Master, we would that thou shouldst do for
us whatever we desire?” To this modest petition, Jesus replied by
asking, “What would ye that I should grant?” They, with their mother,
falling down at his feet in fawning, selfish worship, then urged their
grand request:――“Grant,” said the ambitious Salome, “that these
my two sons may sit, the one on thy right hand, and the other on thy
left, when thou reignest in thy glory.” Jesus, fully appreciating the
miserable state of selfish ignorance which inspired the hope and the
question, in order to show them their ignorance, and to make them
express their minds more fully, assured them that they knew not the
meaning of their own request, and asked them whether they were
able to drink of the cup that he should drink of, and be baptized with
the baptism that he should be baptized with? With unhesitating self-
conceit, they answered, “We are able.” But Jesus replied in such a
tone as to check all further solicitation of this kind from them, or from
any other of his hearers. “Ye shall drink indeed of my cup, and be
baptized with the baptism that I am baptized with; but to sit on my
right hand and on my left, is not mine to give; but it shall be given to
them for whom it is prepared by my father.”――“The cup of sorrow,
and suffering, and agony,――the baptism of spirit, fire, and
blood,――of these you shall all drink in a solemn and mournful
reality, which you are now far from conceiving; but the high places of
the kingdom which I come to found, are not to be disposed of to
those who think to forestall my personal favor; they are for the
blessed of my father, who, in the time appointed in his own good
pleasure, will give it to them, in the end of days.” The disappointed
family of Zebedee retired, quite confounded with the rejection of their
petition, and with the darkly told prophecy that accompanied it,
dooming them to some mysterious fate of which they could form no
idea whatever. The rest of the twelve, hearing of the ambitious
attempt of the sons of Zebedee to secure the supremacy, by a secret
movement, and by family influence, were moved with great
indignation against the intriguing aspirants, and expressed their
displeasure so decidedly, that Jesus called them around him, to
improve this manifestation of folly and passion, to their advantage;
and said, “You know that the nations are governed by princes and
lords, and that none exercise authority over them but the great ones
of the land. Now it shall not be so among you; but he who will be
great among you, must be your servant; and he who shall be your
chief, shall be the slave of all the rest. For even the Son of Man
himself came not to make others his slaves, but to be himself a slave
to many, and even to sacrifice his life in their service.”
Salome.――The reason for the supposition that this was really the name of the mother
of James, consists in the comparison of two corresponding passages of Matthew and Mark.
In Matthew xxvii. 56, it is said that among the women present at the crucifixion, were “Mary
Magdalene, Mary, the mother of Joses, and the mother of Zebedee’s children.” In the
parallel passage, Mark xv. 40, they are mentioned as “Mary Magdalene, Mary, the mother of
James and Joses, and Salome.” In Mark xvi. 1, Salome is also mentioned among those who
went to the sepulcher. This is not proof positive, but it is reasonable ground for the
supposition, more especially as Matthew never mentions Salome by name, but repeatedly
speaks of “the mother of Zebedee’s children.”
If, as is probable then, Salome and the mother of Zebedee’s children were identical, it is
also reasonable to suppose, as Lampe does, that Zebedee himself may have died soon
after the time when the call of his sons took place. For Salome could hardly have left her
husband and family, to go, as she did, with Jesus on his journeys, ministering to his
necessities,――but if her husband was really dead, she would have but few ties to confine
her at home, and would therefore very naturally be led, by her maternal affection, and
anxiety for her sons, to accompany them in their wandering life. The supposition of
Zebedee’s death is also justified by the circumstance, that John is spoken of in his own
gospel, (John xix. 27,) as possessing a house of “his own,” which seems to imply the death
of his father; since so young a man would hardly have acquired property, except by
inheritance.
Thus he laid out before them all the indispensable qualities of the
man who aspired to the dangerous, painful and unenviable primacy
among them,――humility, meekness and laborious industry. But vain
were all the earnest teachings of his divine spirit. Schemes and
hopes of worldly eminence and imperial dominion, were too deeply
rooted in their hearts, to be displaced by this oft-repeated view of the
labors and trials of his service. Already, on a former occasion too,
had he tried to impress them with the true spirit of the apostleship.
When on the way to Capernaum, at the close of this journey through
Galilee, they had disputed among themselves on the question, which
of them should be the prime minister of their Messiah-king, when he
had established his heavenly reign in all the dominions of his father
David. On their meeting with him in the house at Capernaum, he
brought up this point of difference. Setting a little child before them,
(probably one of Peter’s children, as it was in his house,) and taking
the little innocent into his arms, he assured them that unless they
should become utterly changed in disposition and in hope, and
become like that little child in simplicity of character, they should
have no share whatever, in the glories of that kingdom, which was to
them an object of so many ambitious aspirations. But neither this
charge nor the repetition of it, could yet avail to work that necessary
change in their feelings. Still they all lived on in vain and selfish
hope, scheming for personal aggrandizement, till the progress of
events bringing calamity and trial upon them, had purified their
hearts, and fully fitted them for the duties of the great office to which
they had so unthinkingly devoted themselves. Then indeed, did the
aspiring James receive, in a deeper sense than he had ever
dreamed of, the reward for which he now longed and
begged;――drinking first of the cup of agony, and baptized first in
blood, he ascended first to the place on the right hand of the
Messiah in his eternal kingdom. But years of toil and sorrow, seen
and felt, were his preparation for this glorious crown.
James has also been made the subject of a long series of fables, though the early
termination of his apostolic career would seem to leave no room whatever, for the insertion
of any very great journeys and labors upon the authentic history. But the Spaniards, in the
general rage for claiming some apostle as a national patron saint, long ago got up the most
absurd fiction, that James, the son of Zebedee, during the period intervening between
Christ’s ascension and his own execution at Jerusalem, actually performed a voyage over
the whole length of the Mediterranean, into Spain, where he remained several years,
preaching, founding churches, and performing miracles, and returned to Jerusalem in time
for the occurrence of the concluding event, as recorded in the twelfth chapter of Acts. This
story probably originated in the same manner as that suggested to account for the fables
about Andrew; that is,――that some preacher of Christianity, of this name, in a later age,
actually did travel into Spain, there preaching the gospel, and founding churches; and that
his name being deservedly remembered, was, in the progress of the corruptions of the truth,
confounded with that of the apostle James, son of Zebedee,――this James being selected
rather than the son of Alpheus, because the latter had already been established by tradition,
as the hero of a story quite inconsistent with any Spanish journey, and being also less
dignified by the Savior’s notice. Be that as it may, Saint James (Santo Jago) is to this day
esteemed the patron saint of Spain, and his tomb is shown in Compostella, in that kingdom;
for they will have it, that, after his decapitation by Herod Agrippa, his body was brought all
the way over the sea, to Spain, and there buried in the scene of his toils and miracles. A
Spanish order of knighthood, that of St. Jago de Compostella, takes its name from this
notion.
The old romancer, Abdias Babylonius, who is so rich in stories about Andrew, has much
to tell about James, and enters at great length into the details of his crucifixion; crowning the
whole with the idle story, that when he was led to death, his accuser, Josiah, a Pharisee,
suddenly repenting, begged his forgiveness and professed his faith in Christ,――for which
he also was beheaded along with him, after being baptized by James in some water that
was handed to him by the executioner, in a calabash. (Abdias Babylonius, History of the
Apostolical Contest, IV. § 9.)
From the time of this event, there occurs no mention whatever of

any act of James, until the commemoration of the occasion of his
exit; and even this tragic circumstance is mentioned so briefly, that
nothing can be learned but the mere fact and manner of his death.
On the occasion fully described above, in the life of Peter, Herod
Agrippa I. seized this apostle, and at once put him to death by the
executioner’s sword. The particular grounds, on which this act of
bloody cruelty was justified by the tyrant and his friends, are wholly
unknown. Probably there was a pretence at a set accusation of
some crime, which would make the act appear less atrocious at the
time, than appears from Luke’s silence as to the grounds of the
proceeding. The remarkable prominence of James, however, was
enough to offer a motive to the popularity-seeking Agrippa, whose
main object, being to “please the Jews,” led him to seize those who
had most displeased them, by laboring for the advancement of the
Nazarene heresy. And that this actually was his governing principle
in selecting his victims, is made further apparent by the circumstance
that Peter, the great chief of the band, was next marked for
destruction. Though no particular acts of James are recorded as
having made him prominently obnoxious to the Jews, yet there is
every reason to believe, that the exalted ardor and now chastened
ambition of this Son of Thunder, had made him often the bold
assaulter of sophistry and hypocrisy,――a heroism which at once
sealed his doom, and crowned him with the glory of THE
APOSTOLIC PROTO-MARTYR.
JOHN;
THE SON OF ZEBEDEE.
his character.
This other son of Zebedee and of “thunder,” whenever any

description of the apostles has been given, has been by most
religious writers generally characterized as a mild, amiable person,
and is thus figured in strong contrast with the bold and often bitter
spirit of Peter. The circumstance that he is described as “the disciple
whom Jesus loved,” has doubtless done much to cause the almost
universal impression which has prevailed, as to the meekness of his
disposition. But this is certainly without just reason; for there is no
ground for supposing that any peculiar softness was essential to the
formation of the character for which the Redeemer could feel a
strong affection. On the contrary, the almost universal behavior of the
apostolic band, seems to show that the natural characteristics which
he marked as betraying in them the deeper qualities that would best
fit them for his service, and qualify them as the sharers of his
intimate instruction and affection, were more decidedly of the stern
and fiery order, than of the meek and gentle. Nor is there any
circumstance recorded of John, whether authentic or fabulous, that
can justify the supposition that he was an exception to these general,
natural characteristics of the apostles; but instances sufficiently
numerous are given in the gospels, to make it clear, that he was not
altogether the soft and gentle creature, that has been commonly
presented as his true image.
It has been commonly supposed that he was the youngest of all

the apostles; nor is there any reason to disbelieve an opinion
harmonizing, as this does, with all that is recorded of him in the New
Testament, as well as with the undivided voices of all tradition. That
he was younger than James, may be reasonably concluded from the
circumstance that he is always mentioned after him, though his
importance in the history of the foundation of the Christian faith might
seem to justify an inversion of this order; and in the life of James, it
has already been represented as probable, that he too must have
been quite young, being the son of a father who was still so much in
the freshness of his vigor, as to endure the toils of a peculiarly
laborious and dangerous business. On this point, also, the opinion
even of tradition is entitled to some respect, on the ground taken by
an author quoted in the life of Peter,――that though we consider
tradition as a notorious liar, yet we may give some attention to its
reports, because even a liar may sometimes speak the truth, where
he has no object in deceiving us.
The youngest of the disciples.――All that can be said on this opinion is, that it is
possible, and if the testimony of the Fathers were worth the slightest consideration on any
historical question concerning the apostles, it might be called even probable; but no early
writer alludes to his age at all, till Jerome, who very decidedly calls John, “the youngest of
all the apostles.” Several later Fathers make the same assertion, but the voice of antiquity
has already been shown to be worth very little, when it is not heard within three centuries of
the events on which it offers its testimony. But at any rate the assertion of John’s juniority is
not improbable.
A great deal of violent discussion has been lavished on the almost equally important
question, whether John was ever married. The earliest established testimony on this point is
that of Tertullian, who numbers John among those who had restrained themselves from
matrimony for the sake of the kingdom of heaven. Testimony as late as the third century,
however, on an opinion which favored monastic views, is worth nothing. But on the strength
of this, many Fathers have made great use of John, as an instance of celibacy, accordant
with monastic principles. Epiphanius, Jerome and Augustin allude frequently to the
circumstance, the latter Father in particular insisting that John was engaged to be married
when he was called, but gave up the lady, to follow Jesus. Some ingenious modern
theologians have even improved upon this so far as to maintain that the marriage of Cana in
Galilee was that of John, but that he immediately left his wife after the miracle. (See Lampe,
Prolegomena, I. i. 13, notes.)
his family and business.
The authentic history of the life of this apostle must also

necessarily be very brief; most of the prominent incidents which
concern him, having already been abundantly described in the
preceding lives. But there are particulars which have not been so
fully entered into, some of which concern this apostle exclusively,
while in others he is mentioned only in conjunction with his brother
and friends; and these may all, with great propriety, be more fully
given in this life, since his eminence, his writings, and long
protracted labors, make him a proper subject for a minute
disquisition.
Being the son of Zebedee and Salome, as has already been

mentioned in the life of his brother, he shared in the low fortunes and
laborious life of a fisherman, on the lake of Gennesaret. This
occupation indeed, did not necessarily imply the very lowest rank in
society, as is evident from the fact that the Jews held no useful
occupation to be beneath the dignity of a respectable person, or
even a learned man. Still the nature of their business was such, as to
render it improbable that they had adopted it with any other view
than that of maintaining themselves by it, or of enlarging their
property, though perhaps not of earning a support which they had no
other means whatever of procuring. It has been said, that doubtless,
there were many other inhabitants of the shores of the lake, who
occasionally occupied themselves in fishing, and yet were by no
means obliged to employ themselves constantly in that avocation.
But the brief statement of circumstances in the gospels is enough to
show that such an equipage of boats and nets, and such steady
employment all night, were not indicative of anything else than a
regular devotion of time to it, in the way of business. Yet that
Zebedee was not a man in very low circumstances, as to property, is
quite manifest from Mark’s statement, that when they were called,
they left their father in the vessel, along with the “servants,” or
workmen,――which implies that they carried on their fishing
operations, on so extended a scale, as to have a number of men in
their service, and probably had a vessel of considerable size, since it
needed such a plurality of hands to manage it, and use the
apparatus of the business to advantage; a circumstance in which
their condition seems to have been somewhat superior to that of
Peter and Andrew, of whom no such particulars are specified,――all
accounts representing them as alone, in a small vessel, which they
were able to manage of themselves. The possession of some family
estate is also implied, in numerous incidental allusions in the
gospels; as in the fact that their mother Salome was one of those
women who followed Jesus and “ministered to him of their
substance” or possessions. She is also specified among those
women who brought precious spices for embalming the body of
Jesus. John is also mentioned in his own gospel, as having a house
of his own, in which he generously supported the mother of Jesus,
as if he himself had been her son, throughout the remainder of her
life; an act of friendly and pious kindness to which he would not have
been competent, without the possession of some property in addition
to the house.
his education.
There is reason to suppose, that in accordance with the

established principles of parental duty among the Jews, he had
learned the rudiments of the knowledge of the Mosaic law; for a
proverbial sentence of the religious teachers of the nation, ranked
among the vilest of mankind, that Jew, who suffered a son to grow
up without being educated in the first principles, at least, of his
national religion. But that his knowledge, at the time when he first
became a disciple of Jesus, extended beyond a barely respectable
degree of information on religious matters, there is no ground for
believing; and though there is nothing which directly contradicts the
idea that he may have known the alphabet, or have made some
trifling advances in literary knowledge,――yet the manner in which
he, together with Peter, was spoken of by the proud members of the
Sanhedrim, seems to imply that they did not pretend to any
knowledge whatever of literature. And the terms in which both Jesus
and his disciples are constantly alluded to by the learned scribes and
Pharisees, seem to show that they were all considered as utterly
destitute of literary education, though, by reason of that very
ignorance, they were objects of the greatest wonder to all who saw
their striking displays of a religious knowledge, utterly unaccountable
by a reference to anything that was known of their means of arriving
at such intellectual eminence. Indeed, there seems to have been a
distinct design on the part of Christ, to select for his great purpose,
men whose minds were wholly free from that pride of opinion and
learned arrogance, almost inseparable from the constitutions of
those who had been regularly trained in the subtleties of a slavish
system of theology and law. He did not seek among the trained and
drilled scholars of the formal routine of Jewish dogmatism, for the
instruments of regenerating a people and a world,――but among the
bold, active, and intelligent, yet uneducated Galileans, whose
provincial peculiarities and rudeness, moreover, in a high degree
incapacitated them from taking rank among the polished scholars of
the Jewish capital. Thus was it, that on the followers of Christ, could
never he put the stigma of mere theological disputants; and all the
gifts of knowledge, and the graces of mental power, which they
displayed under his divine teachings, were totally free from the
slightest suspicion of any other than a miraculous origin. Some have,
indeed, attempted to conjecture, from the alleged elegance of John’s
style in his gospel and epistles, that he had early received a finished
education, in some one of the provincial Jewish colleges; and have
even gone so far as to suggest, that probably Jairus, “the ruler of the
synagogue” in Capernaum, or more properly, “the head of the school
of the law,” had been his instructor,――a guess of most remarkable
profundity, but one that, besides lacking all sort of evidence or
probability, is furthermore made totally unnecessary, by the
indubitable fact, that no signs of any such perfection of style are
noticeable in any of the writings of John, so as to require any
elaborate hypothesis of this kind to explain them. The greatest
probability is, that all his knowledge, both of Hebrew literature and
the Greek language, was acquired after the beginning of his
apostolic course.
his name.
The Jews were accustomed, like most of the ancient nations of

the east, to confer upon their children significant names, which were
made to refer to some circumstance connected with the person’s
prospects, or the hopes of his parents respecting him. In their son’s
name, probably Zebedee and Salome designed to express some
idea auspicious of his progress and character in after life. The name
“John,” is not only common in the New Testament, but also occurs in
the Hebrew scriptures in the original form “Johanan,” which bears
the happy signification of “the favor of Jehovah,” or, “favored by
Jehovah.” They probably had this meaning in mind when they gave
the name to him, and on that account preferred it to one of less
hopeful religious character; but to suppose, as some commentators
have, that in conferring it, they were indued with a prophetic spirit,
which for the moment directed them to the choice of an appellation
expressive of the high destiny of a chosen, favored herald of the
grace of God, to Israel and to the Gentiles,――is a conjecture too
absurdly wild to be entertained by a sober and discreet critic for a
moment. Yet there are some, who, in the rage for finding a deep
meaning in the simplest matters, interpret this simple, common
name, as prophetically expressive of the beginning of the reign of
grace, and of the abrogation of the formal law of Moses, first
announced by John the Baptist, whose testimony was first fully
recorded in the gospel of John the Apostle. Such idle speculations,
however, serve no useful purpose, and only bring suspicion upon
more rational investigations in the same department.
his call and discipleship.
The first introduction of John to Jesus, appears to be distinctly,

though modestly, described by himself, in the first chapter of his
gospel, where he has evidently designated himself in the third
person, as “the other disciple” of John the Baptist, who accompanied
Andrew on his first visit to Jesus. After this introduction above
narrated, he seems to have remained near the newly found Messiah
for some days, being of course, included among those disciples who
were present at the marriage in Cana. He appears to have returned,
soon after, to his avocation on the lake, where he, for some time,
appears to have followed the business in which he had been brought
up, till the word of his already adopted Master came to summon him
to the actual duties of the discipleship. On the journeys that followed
this call, he was engaged in no act of importance, in which he was
not also associated with those disciples, in whose lives these
incidents have been already fully described. On one occasion
however, a solitary instance is recorded by Luke, of a remark made
by John, during a conversation which took place in Capernaum, after
the return from the mission through Galilee, and not long before the
great journey to Jerusalem. It seems to have been at the time when
Jesus was inculcating a child-like simplicity, as an essential
characteristic of his followers; and the remark of John is, both by
Mark and Luke, prefaced with the words,――“and John answered
and said,”――though no very clear connection can be traced
between what he said and the preceding words of Jesus. The
passage however is interesting, as showing that John was not
always most discreet in his regard for the peculiar honors of his
Master,――and in the case which he refers to, had in his restrictive
zeal, quite gone beyond the rules of action, by which Jesus expected
him to be guided. The remark of John on this occasion
was,――“Master, we saw one casting out devils in thy name, and we
forbade him, because he followeth not with us.” This confession
betrays a spirit still strongly under the influence of worldly feelings,
manifesting a perfectly natural emotion of jealousy, at the thought of
any intrusion, upon what he deemed the peculiar and exclusive
privilege of himself and his eleven associates in the fellowship of
Christ. The high commission of subduing the malign agencies of the
demoniac powers, had been specially conferred on the elect twelve,
when they first went forth on the apostolic errand. This divine power,
John had supposed utterly above the reach of common men, and it
was therefore with no small surprise, and moreover with some
indignant jealousy, that he saw a nameless person, not enrolled in
the sacred band, nor even pretending to follow in any part of their
train, boldly and successfully using the name of Jesus Christ, as a
charm to silence the powers of darkness, and to free the victims of
their evil influences. This sort of feeling was not peculiar to John, but
occurs wherever there arises a similar occasion to suggest it. It has
been rife among the religious, as well as the worldly, in all ages; and
not a month now passes when it is not openly manifested, marring
by its low influences, the noblest schemes of Christian benevolence,
as well as checking the advances of human ambition. So many there
are who, though imbued in some degree with the high spirit of
apostolic devotion, yet, when they have marked some great field of
benevolence for their efforts, are apt to regard it as their own
peculiar province, and are disposed to view any action in that
department of exertion as an intrusion and an encroachment on their
natural rights. This feeling is the worst characteristic of ultra-
sectarianism,――a spirit which would “compass sea and land,” not
merely “to gain one proselyte,” but also to hinder a religious rival
from the attainment of a similar purpose,――a spirit which in its
modes of manifestation, and in its results, is nearer to that of the
demon it aspires to expel, than to that of Him in whose name it
professes to work. But that such was not the spirit of Him who went
about doing good, is seen in the mild, yet earnest reply with which he
met the manifestation of this haughty and jealous exclusiveness in
his beloved disciple. “Forbid him not; for there is no man who can do
a miracle in my name, who will lightly speak evil of me. For he who is
not against us is on our part.” And then referring to the previous train
of his discourse, he went on to say,――“For he who shall give you a
cup of water in my name, because you belong to Christ, I tell you,
indeed, he shall not lose his reward.” So simple were the means of
manifesting a true regard for Christ, and so moderate were the
services which would constitute a claim to his remembrance, and to
a participation in the rights of his ministry. If the act of kindness or of
apostolic ministration had been done in his name, and had answered
its good purpose, this was enough to show that he who performed it
was such a friend as, so far from speaking evil of Jesus, would
insure the best glory of his name, though he had not attached
himself in manner and form to the train of regular disciples. Jesus
Christ did not require a formal profession of regular discipleship, as
essential to the right of doing good in his name, or to the surety of a
high and pure reward. How many are there among his professed
followers in these times, who are “able to receive this saying?” There

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Preface to the Second Edition ........................................................................ xi

1. The Nature of Polymeric M aterials

A WHAT ARE POLYMERS—WHAT IS POLYMER SCIENCE? ......................... 1

3. Kinetics of Step-Growth and Addition Polymerization 63

4. Statistics of Step-Growth Polymerizations 83

C. MOLECULAR WEIGHT DISTRIBUTIONS IN LINEAR

6 . Spectroscopy and the Characterization of Chain Structure 145

8 . Crystallization, Melting and the Glass Transition 259

9. Thermodynamics of Polymer Solutions and Blends 307

10. Molecular Weight and Branching 339

11. Mechanical and Rheological Properties 395

Writing a book, particularly a textbook, can take a lot out of you:

It is particularly galling when your so-called friends participate in the

O f all plagues, good heaven, thy wrath can send,

Naturally, your first instinct is to attribute their comments to mere envy:

This base emotional response is quickly replaced by denial:

February 1997 PAUL PAINTER

I am standing on the threshold about to enter a room. It is a complicated

and in so doing we have deliberately adopted a conversational tone to our

February 1994 PAUL PAINTER

The Nature of Polymeric Materials

A. WHAT ARE POLYMERS—WHAT IS POLYMER SCIENCE?

Polymer Physical Chemistry

Polymer physics and polymer physical chemistry are overlapping disciplines

B. SOME BASIC DEFINITIONS - THE ELEMENTS OF

Linear, Branched and Cross-Linked Polymers

The simplest type of polymer is a linear homopolymer, by which we mean a

(A) Part of a Linear Polyethylene Molecule

(B) Part of a Branched Polyethylene Molecule

The difference in chemical structure between linear and branched

SHORT LONG STAR

Figure 12 Schematic diagram depicting short, long and star branching.

Homopolymers and Copolymers: A Question of Semantics?

Synthetic polymers have traditionally been named for their respective

and vinyl acetate CH^CHCOCOCHj) etc. To reiterate, polymers synthesized

When a monomer unit adds to a growing chain it usually does so in a

Some polymers, e.g. poly(vinyl fluoride) (X = H, Y = F) or poly(vinylidine

Continuing with our discussion of polymers derived from a single monomer,

Structural Isomerism— The Microstructure of Polydienes

Another outstanding example of the complex polymer chain microstructure

racemic diad meso diad

Figure 1.5 Schematic diagram depicting racemic and meso diads.

(A) P art of an Isotactic Polypropylene Molecule

(B) Part of a Syndiotactic Polypropylene Molecule

polymerized to polyisoprene by a variety of techniques including free radical,

Figure 1.7 Schematic representation o f the structural isomers o f polyisoprene.