Does Quantum Magic Impinge on

Polymer Physics?
JOHN W. S. HEARLE

Department of Textiles
UMIST
Manchester,England

Penrose states that quantum effects can occur even in relatively large systems
when energy differences remain small. This is just the situation with polymer
materials. A quantum description by Penrose of the formation of quasi-crystals
can be rewritten to apply to polymer crystallization. The implications of the need to
take account of quantum effects are discussed. Another approach based on the
quantization of energy levels in clusters of atoms offers a possible explanation of
heat setting in nylon and polyester fibers. Finally some problems of the interpreta-
tion of quantum theory are discussed.

INTRODUCTION that it was basically relevant but impossible to apply

n a paper celebrating the achievements of Paul
I Lindenmeyer, it seems appropriate to venture into
a field of speculation that is really out of one’s depth!
I know little of Paul’s early work on cellulose, but I
believe it was definitive, practical, and useful. I first
met him in 1963when he introduced P. J. Stevenson
and me to present our work on the mechanics of
nonwoven fabrics. In many visits to the Chemstrand
Research Center over the next seven years, I came to
admire the work of Paul and his group on polymer
crystallization. I recently read a comment-I think by
Gell-Mann-to the effect, “never believe an experi-
mental result until it is confirmed by theory.” Linden-
meyer’s simple theoretical treatment of the energies
of single polymer molecules with varying numbers of
folds convinced me of the reality of chain folding, and,
in my view, is still the best way to present the subject
to students. Many others (McCullough, Holland, Pe-
tersen, Zaukelies, Bell, Dumbleton, . ..) from the
Chemstrand group made great contributions in that
golden age of polymer physics, but Lindenmeyer was
a source of ideas and inspiration and Buchdahl saw
that the research was supported.
I met Paul Lindenmeyer again towards the end of
the 1970s. when we both lectured at a small meeting
on fibers organized by the U S . Army Research Office.
This was when I first heard his account of the appli-
cation of Prigogine’s nonlinear irreversible thermody-
namics to melt spinning of fibers (1). I was out of my
depth with the detail of the mathematics, but my
reaction was that there was a 45% chance that this
was of major importance and utility, a 45% chance
in an informative way, and a 10%chance that it was
all wrong. A few years later, I obtained a Royal Society
Senior Visiting Fellowship for Paul at UMIST, so that
he could follow his ideas further. Unfortunately, we
did not manage to bridge the gap between the vision
in Paul’s mind and any practical calculations or s u p
portive experiments. He thought that the structural
response of fibers to thermomechanical treatments
would be different with oscillating parameters, which
seemed a reasonable suggestion on other grounds,
but he was unable to give any clue as to what fre-
quency or amplitude might be necessary. The subse-
quent support by Boeing of more theoretical research
by Bullough did not yield any way of reducing Linden-
meyer’s ideas to practice (2).
Subsequently, in general reading, I have found pri-
gogine’s theories mentioned along with other new
ideas. on the science of complexity: chaos, fractals,
nonlinear systems, and kinetics of nonhomogeneous
processes. All of these seem relevant in principle to
polymer physics, but one cannot see how to apply
them in practice (3): What one might term the Lin-
denmeyer syndrome defeats us. The above concepts
are applicable to classical physics, but, in the same
contexts, interpretations of quantum physics are d i s
cussed, and it is the impact of a particular sentence
that has led me to this paper.
QUANTUM MAGIC AND QUANTUM MYSTERY
Many Energy Levels
“Quantum Magic and Quantum Mystery” is the
title of Chapter 6 of Penrose’s book The Emperor’s

260 POLYMER ENGINEERING AND SCIENCE, FEBRUARY 1994, Yo/. 34, No. 4
 Does QuantumMagic Impinge on Polymer Physics?
New M i n d (4).On page 296,we read:
Recall, first of all, that the descriptions of quan-
tum theory appear to apply sensibly (usefuily?)
[not] only at the so-called quantum level
-of molecules, a t o m s , or subatomic
particles-but also at larger dimensions, so long
as ener@ differences between alternative possi-
bilities remain very small.
But that is just the situation with the many ways in
which polymer molecules can pack together. For
amorphous polymers, the different arrangements will
tend to have the same properties. But, in semicrys
tallhe polymers, such as nylon and polyester fibers,
the many possible structures with a density midway
between crystal and amorphous may behave very
differently. There will be subtle differences in m e
chanical properties, probably greater differences in
the poorly understood behavior in heat setting, and
differences of major technological importance in dye
diffusion. Do we need to consider how the develop
ment of structure, and the changes in heat treat-
ments, differ if they are viewed as a quantum process
and not a classical one?
In Chapter 8, “In Search of Quantum Gravity”(page
367h Penrose goes on to speculate that the reduction
[Rl of the state vector, from the linear superposition
[Ul of many quantum states to a single classical state,
might be a gravitational phenomenon. Penrose ad-
mits the technical dmculties of quantum gravity the-
ory, but suggests that the reduction might occur if
the linear rules of quantum superposition break down
when the masses involved are large enough to cause
appreciable space-time curvature. This would happen
when the measure of curvature was of the order of
one graviton. Penrose comments:
The idea is that the “one-graviton”level should
lie comfortably between the “quantum level,” of
atoms, molecules, etc., where the linear rules (U)
of ordinary quantum theory hold good, and the
“classicallevel” of our everyday experiences.
He states that the controlling factor is not just physi-
cal size but is really the mass and energy distribu-
tion. However, as a f i s t crude estimate, he takes the
Planck mass of lop5gram,adding that this is larger
than one would wish. Despite the many obscurities
and ambiguities, Penrose tries to be more explicit,
and a very rough calculation leads to a value of
gram as appropriate to a cloud-chamber experiment.
Even this figure of gram seems extraordinarily
large: At a typical polymer density of 1 g/cm3, it
corresponds to lo5 (pmI3, which is a linear dimen-
sion of about 50 pm, greater than most fiber diame-
ters and about 5000 times larger than the typical
scale of fine structure of crystalline and amorphous
regions. There is ample scope to reduce the estimate
of size and still leave quantum effects as relevant to
polymer crystallization and related phenomena.
Quantum-Mechanical Crystallization
Later in the book (page 4341,Penrose introduces,
as part of an argument in another context, a particu-
POLYMER ENGlNEERtNG AND SCIENCE, FEBRUARY 1994, Vol. 34,No. 4
lar example of crystallization, which can be adapted
to the realities of polymer crystallization.Severalyears
earlier, Penrose had made some mathematical stud-
ies of aperiodic tiling, in which a quasi-periodic struc-
ture had a five-fold symmetry. In classical crystalle
graphic terms, such a form would be forbidden. Sub
sequently, “crystalline” alloys of aluminum-
manganese and aluminum-lithium-copperwith five-
fold symmetry were discovered. In three dimensions,
this is a forbidden icosahedral symmetry. These are
now called quasi-crystals, and can grow up to 1 mm
across.
Penrose’s account of how he thinks these quasi-
crystals form can be rewritten to apply to the forma-
tion of the fine structure of semicrystalline polymers,
especially under the rapid quenching found in melt-
spinning of fibers. As discussed later, it fits In with
indications that a super-lattice may be present. In
the extracts following, words in bold are my changes,
and those in [italics1 complete the original Penrose
text.
Now, a remarkable feature of the quasicrys-
talline polymer W e structures [tiling patterns]
that I have been describing is that their assembly
is necessarily non-local. That is to say in assem-
bling the structures [patterns],it is necessary,
from time to time, to examine the state of the
structure [pattern]many, many “atoms” away
from the point of assembly, if one is to be sure of
not making a serious error when putting the
pieces together.. . Thls kind of feature is an in-
gredient of a considerable controversy that sur-
rounds the question of quasi-crystal structure
and growth at the present time, and it would be
unwise to attempt to draw deftnitive conclusions
until some of the outstanding issues are resolved.
Nevertheless, one may speculate: and I shall ven-
ture my own opinion. First, I believe that some of
these quasicrystaIline substances are indeed
highly organized, [and their atomic arrangements
are rather close in structure to the tiling patterns
that I haw been considering].Second, I a m of the
(more tentative) opinion that their assembly can-
not reasonably be achieved by the local adding of
polymer segments [atoms] one at a time, in
accordance with the classical picture of crystal
growth, but instead there must be a non-local
essentially quantum-mechanical ingredient to
their assembly.
The way I picture this growth as taking place is
that, instead of having polymer stgments
[atoms] coming individually and attaching them-
selves a t a continually moving growth line (classi-
cal crystal growth), one must consider an evolv-
ing quantum linear superposition of many differ-
ent alternative arrangements of attaching seg
ments {atoms] by the quantum procedure (U).
Indeed this is what quantum mechanics tells us
must (almost always) be occurring! There is not
just one thing that happens: many alternative
molecular [ atomic] arrangements must coexist
261
 John W. S. Hearle
in complex linear superposition. A few of these
superposed alternatives will grow to very much
bigger conglomerations and, at a certain point,
the difference between the gravitational fields of
some of the alternatives will reach the one-gravi-
ton level (or whatever is appropriate: see Chapter
8, p. 367). At this stage one of the alternative
arrangements-or more likely, still a superposi-
tion, but a somewhat reduced superposition-will
become singled out as the “actual” arrangement
(quantum procedure R). This superposed assem-
bly, together with reductions to more definite
arrangements, would continue at a larger and
larger scale until a reasonable-sized fine struc-
ture [ quasi-crystal] is formed.
Normally, when Nature seeks out a crystalline
configuration, she is searching for a configura-
tion of lowest energy (taking the background tem-
perature to be zero). I am envisaging a similar
thing with quasi-crystal growth, the difference
being that this state of lowest energy is much
more difficult to find, and the “best” arrangement
of the polymer segments [atoms] cannot be d i s
covered simply by adding segments [atoms] one
at a time in the hope that each individual seg-
ment [atom] can get away with just solving its
own minimizing problem. Instead, we have a
global problem to solve. I t must be a cooperative
effort among a large number of segments [atoms]
all at once. Such a cooperation, I a m maintain-
ing, must be achieved quantum mechanically:
and the way that this is done is by many different
combined arrangements of segments [ atoms] be-
ing “tried” simultaneously in linear superposi-
tion.. . The selection of an appropriate (though
probably not the best) solution to the minimizing
problem must be achieved as the one-graviton
criterion (or appropriate alternative) is
reached-which would presumably occur when
the physical conditions are just right.
Polymer Fine Structure
If the validity-in general terms, even if not in every
detail-of Penrose’s views is accepted, the following
comments can be made in regard to polymer crystal-
lization and the formation of fine structure. In-
evitably, it is necessary to start by presenting the
discussion in current terms, although in reality the
proper concepts might be quite different.
The multiplicity of close energy levels is not in
question: and it is also certain that the determination
of energy levels is non-local. In contrast to the drop
ping of a small molecule into a crystal lattice from a
neighboring disordered state, which has little effect at
a distance greater than a few atoms, the incorpora-
tion of a polymer segment tightens the associated
length of tie-molecule, puts stresses on the next crys-
talline entity, changes its energy level, and so on for a
considerable distance.
The same point can be expressed in another way.
HOWlarge a volume of polymer must be considered in
262 POLYMER ENGINEERING AND SCIENCE, FEBRUARY 1994, Vol. 34, No. 4
order to get realistic estimates of minimum energy
levels? One would estimate that this would have to
contain at least 100 crystallites, so that if the total
structure was built up by repetition of a single cell,
any crystallite was about 5 crystallites away from its
repetition (without any freedom for independent
structural adjustment). Changes within such a cell
would certainly have an effect over the whole cell, so
that Penrose’s arguments would apply. This is a scale
of about 50 nm, but even this may well be too small
for sufficiently accurate calculations of energy levels.
There thus appear to be convincing arguments that
the formation of the semicrystalline polymer fine
structure should be treated in quantum terms. This
implies a superposition of quantum states, until one
state has achieved a dominant position and reduc-
tion of the state vector occurs. There is also the
possibility that the quantum situation is reactivated
when a rise in temperature alters the distribution of
energy levels.
What would be the consequences of treating the
problem in quantum terms? This is a difficult ques-
tion to answer. The Lindenmeyer syndrome comes in,
because of the difficulty of giving a mathematically or
computationally adequate description of the state of a
piece of polymer fine structure containing millions of
atoms-not to mention solving the wave equation for
such a system! Some clever conceptual and theoreti-
cal approaches are needed. However, one can hazard
a few suggestions.
The coexistence of many states opens up the vari-
ety of forms of fine structure to be considered. Almost
all of the states will really be in transition between
the clearly defined structures, which we try, not very
successfully, to describe. The transitions between
states will be easier. They will not be blocked by high
energy barriers, because, to use an older terminology,
quantum tunneling can occur. Movement of defects
and other structural changes, which would be forbid-
den in a classical system, could thus occur.
The freedom given in this way removes what has
always seemed to me to be a difficulty. In classical
terms, it is not easy to envisage how the structure
can evolve, except in minor ways, once some crystal-
lization has taken place. With atoms or small
molecules, or even with small polymer repeat units as
in polyethylene, changes can occur owing to the ther-
mal movement of localized defects over small energy
barriers; but with longer repeats, as in nylon and
PET, change would involve a major disturbance and
have to pass a very unfavorable energy state. Two
particular illustrations can be given.
Crystal nucleation should be randomly located and
lead to growth of randomly distributed crystallites
with sizes determined by crystal growth rates. How-
ever, with those restrictions, the degree of crys-
tallinity is limited by the problems of packing in such
a random way. In order to get to 50% crystallinity, we
are led into proposing structures in which crystallites
are regularly stacked in fibrillar arrays in a form
approximating to a super-lattice. In classical terms,
 Does QuantumMagic Impinge OR Polymer Physics?
there would seem to be great difficulty in proposing a dered polymer segments trapped between zones of
route from the initial random arrangement to the amorphous entanglement, as illustrated schemati-
h a l more ordered one; but this would be a natural cally in Rg. 1. At low temperatures the chains would
consequence of a quantum mechanism. be packed in a crystalline lattice. At hgh tempera-
Annealing poses similar problems in classicalterms. tures, they would show liquid-like motion between a
How can an assembly of small crystals transform variety of arrangements, but, for short times the or-
itself into an assembly of larger crystals without com- dered set would still be constrained to act as a cluster
plete melting and reorganization? Yet we know that trapped by the entanglements. Over long times, the
this sort of change does take place. relative movement of molecules, by reptation or in
other ways, would allow flow and self-dinusion of the
AN APPLICATION OF “CLASSICAC” total system as a liquid.
QUANTUM THEORY The quantization of energy levels would be similar
Atomic Cfarters to that described by Berry: very few in the crystal
form and very many in the liquid form. Consequently,
The above discussion brings in the difficult p h i b it is possible that there will be a range of temperature
sophical questions of the interpretation of quantum below the observed melting point at which the or-
theory, on which I give a few general comments later. dered sets are flipping between crystalline and liquid
However, another piece of general reading shows the states. In this range, the material as a whole will be
possible relevance of what one might call “classical” solid because it will be held together by the sets that
quantum theory, namely the consequences in statis are crystalline, which will always be present though
tical mechanics of a quantization of energy levels, as their identity will be changing. Other sets, also
introduced by Planck. In an article in ScientiiArnerC changing in identity, will be liquid. If there are stresses
can (5). Berry discusses the behavior of small clus- present, it will be possible for these to be relieved by
ters of atoms, which show a transition from solid to localized movements of segments associated with liq-
liquid not at a sharp melting point, but over a range uid clusters. For example, a chain could move through
of temperature. This is confirmed by computations of the cluster with a segment leaving one end and a
theoretical models and by experiments on collections replacement entering at the other end.
of between about 5 and 100 argon atoms. The above description offers a possible mechanism
The classical argument for melting is as follows. At for the heat-setting of nylon, polyester, and similar
absolute zero temperature, the crystalline solid is a fibers, which has never been adequately explained. It
lower energy state than the disordered state, and is is known that temporary setting is associated with
thus the preferred form.As the temperature rises, the
addition of the (negative) entropy term to the free
energy lowers the value for the disordered state more
than for the crystalline state. Eventually the disor-
dered liquid state has a lower free energy and is
preferred. The melting point is the temperature at
which the free energies of the two forms are equal.
Quantum effects come in because of the difference
in the number of available energy levels in the two
states. The crystal is a deep trough with few energy
levels: the liquid is shallow with many energy levels.
This increases the chances of the cluster being in the
liquid state, even at a hlgher energy level. The results
of Berry’s computations, which are confirmed by ex-
periments with a probe atom present, are that over a
substantial range of temperature the cluster will flip
between one state and the other. For a period, it will
appear as a crystal, then it will change to a period as
a liquid, then back to a crystal, and so on. Below a
certain temperature, the crystal is a stable form:
then, for a range of perhaps 10K at about 25K, the
two forms will coexist; and fmally above a certain
temperature, the liquid will be stable. The effect
depends, of course, on being able to isolate small
clusters of atoms.

A posemillty of Heat-Setting of Polymeric Fibers

(a) (b)
What is the possible relevance of this to polymers? F@. 1 . Schematic illustration of polymer segments trapped
In a rapidly quenched fiber, say of nylon or PET, a between amorphous entanglements. (a) In crystallographic
small “crystallite” could be regarded as a set of or- register. (b)In a less ordered liquid state.

POLYMEF)ENGINEERING AND SCIENCE, FEBRUARY 1994, Vol. 34, No. 4 263

 John W. S . Hearle
the glass transition in amorphous regions at around
100°C. Above this there is a plateau without setting,
until the more permanent setting effects start at
about 180°C in dry nylon 66 and in PET. Industrial
heat-setting can then be carried on up to about 240°C.
when the fibers become so soft that they stick to-
gether. Real melting does not happen until about
265°C. If Berry’s quantum cluster theory applies in
this situation, then the transitory liquidization of
crystallites would allow annealing, which stabilizes or
heat-sets a deformed fiber, to take place.
A BROADER VIEW
Quantum Philosophy
As a physics student in the 1940% I was intro-
duced to quantum theory in different courses, where
it impinged on the particular topic. Subsequently in
my research and teaching career, I assumed that I
was always working in the realm of classical physics,
even when I was considering the behavior of polymer
molecules. In a pragmatic way, I accepted the Copen-
hagen hypothesis, that problems could be treated
either as classical physics or quantum physics,
though at a deeper level I took the (incomect) view
that if one could solve Schrodinger’s wave equation
for a large enough collection of atoms all the observed
results would come out. Later, when I became aware
of molecular modeling I accepted that ab initio quan-
tum calculations would give the potentials between
atoms, which could then be used for classical calcu-
lations of the behavior of collections of atoms.
It was only after reading Penrose’s book that I read
more widely on the philosophical problems of the
interpretation of quantum physics, which had been
discussed extensively from the time of the Bohr/Ein-
stein controversies. I found The Mystery of the @an-
turn World by Squires (6) to be most helpful, though
an article by Bell (7) entitled “Against ‘Measurement’”
was also stimulating. The essence of the difficulty is
that the interference effects in the two-slit experi-
ments typically used in discussions of quantum
physics lead, apparently inescapably, to the conclu-
sion that multiple states are coexisting, and that they
only reduce to one when the particle is observed with
macroscopic apparatus. This is shown to be an in-
evitable consequence of solving the wave equation,
which only deals in a probability density function,
and, accepting the reality of quantum theory, is taken
to apply not only to simple cases of one or a few
particles, but to large systems.
This then leads, for example, to the paradox of
Schrodinger’s cat. The postulate is that, within an
enclosed system, a two-slit experiment is performed.
If the particle passes through one slit, it triggers an
event that kills the cat: if through the other the cat
lives. But, since there is no observer, both states
must coexist and the cat is both alive and dead.
Reduction to a single state of life or death only h a p
pens when the box is opened and the system is
observed.
264 POLYMER ENGINEERING AND SCIENCE, FEBRUARY 1994, Vol. 34, No. 4
Squires summarizes the arguments by presenting
a Table on the interpretation problems of quantum
theory. None of the end-results is satisfactory. If the
wave function is not real, then interference cannot
occur, but it does. If the wave function is real, but
does not reduce, then our observation of one result is
explained either by hidden variables, which are be-
lieved to be impossible, or by the existence of many
worlds, which is implausible to say the least. If the
wave function reduces, then we need to explain how
and why. One explanation has been that it is a conse-
quence of conscious observation, but this also seems
implausible.The final possibility listed by Squires is
that reduction occurs in macroscopic systems. How
this happens has not been explained: it is not a
consequence of an obvious solution of the wave equa-
tion and must involve some other effect. We have
seen above that Penrose thinks it would result from
an amalgamation of general relativity and quantum
theory that has not yet been worked out.
My own view would be that physics has demon-
strated the existence of two realities: the macroscopic
world of classical physics and the microscopic world
of quantum physics. Because our everyday experi-
ence of the macroscopic world has been progressively
explained by going into ever finer detail of the physics,
and this has convinced us of the reality of atomic and
nuclear physics and of fundamental particles, there
has been a tendency to put quantum theory on a
higher level of reality than classical physics. But, if
we had been living in a microscopic quantum world,
the exploration to ever-larger sizes would have re-
solved many problems and classical physics would
seem to be the higher reality. I believe that both
realities are of equal validity and that some form of
the macroscopic reduction hypothesis must link
them. But this raises some neglected issues that
impinge strongly on polymer physics.
The Transition From Quantum to Classical
A weakness in all the discussions of the subject is
that for understandable reasons, both theory and
experiment are treated in terms of systems that are
as simple as possible. For example, a particle, two
slits, and a measuring device are isolated from any-
thing else. In these circumstances, there can be a
clear-cut reduction at the instant of measurement
from the coexisting quantum states to the single
classical state. But this would not be so in the messy
world of real large systems. The boundaries of inter-
action cannot be defined. Quantum effects will be
taking place within large pieces of classical material.
The distinction between quantum and classical can-
not be as sharp as the philosophical discussions
assume.
I believe that this is a subject that should be ad-
dressed by theoretical and experimental physicists.
When dealing with particles, atoms and small
molecules, the separation can be usefully handled in
approximate ways. Localized quantum effects can be
regarded as occurring within a generalized classical
 Does QuantumMagic Impinge on Polymer Physics?
system. For example, individual electrons can be con-
sidered to tunnel through energy barriers established
by the neighboring environment.
But, for polymers, the distinction between micre
scopic and macroscopic is not sharp. Localized inter-
actions between neighboring segments in different
molecules have effects over large distances through
forces along the individual chains. Energy levels will
depend on structural arrangements over large vol-
umes.
If we accept, with Penrose, the orthodox view that
at the quantum level there is an existence of many
worlds of coexisting states, we are forced to define
more particularly what aspects of the system are in
the quantum condition. Presumably, at appropriate
temperatures in poorly annealed samples, the pack-
ing of the molecules must be treated by the quantum
rules, but the chain molecules themselves will be
defined classical entities. This is a complex no man’s
land of unexplored territory. There is no level lying
“comfortably” between the quantum and classical
levels.
CONCLUSION
It seems difficult to avoid the conclusion that we
must consider the possibility that the multiplicity of
energy levels of structural arrangements within crys-
tallizing polymer systems-and perhaps polymers in
other forms-means that quantum effects must be
considered.The difficulty is to know how to do this in
a useful way. A full quantitative solution is impossi-
ble. What approximate treatments or qualitative a p
proaches might help our understanding? The issues
POLYMER €NOfN€€RlNG AND SCI€NCE, FEBRUARY 1994, Vol. 34,No. 4
raised pose both a particular worry and an opportu-
nity.
The worry relates to dynamic molecular modeling,
which is now being used to predict polymer behavior.
This assumes that an assembly of molecules can be
treated as a classical system obeying Newton’s Laws.
Modem computing enables the evolution of such a
many-body system to be followed for limited, but
significant, times in limited amounts of material,
which are adequate for collections of small molecules
though somewhat restricted for polymers. But what
differences would there be if the system followed the
rules of quantum dynamics instead of Newton’s Laws.
The opportunity is that the application would lead
to a more realistic understanding of polymer materi-
als. In turn, this might enable engineers to manipu-
late temperatures, stresses, and other factors to p r e
duce new effects and generate polymer structures
with new and useful properties. This was Linden-
meyer’s vision of what might come from the ideas
that he propagated and which also lie in the science
of complexity.
REFERENCES
1. P. H. Lindenmeyer, TextileRes. J., 50, 395 (1980).
2. R K. Bullough, private communication (1990).
3. J. W. S. Hearle. J. AppL PoZyrn Sct: AppL Polyrn Symp.,
47. l(1991).
4. R Penrose, The Emperor’s New Mind, Oxford Univ. Press,
London (1989).
5. R S. Beny, scientijk American, 263 ( 2 ) (Aug. 1990). 68.
6. E. Squires, The Mystery of the Quantum World, Adam
Hilger, Bristol(1986).
7.J. S. Bell, Physics World, 3 (8) (Aug. 1990). 33.
265