Introduction To The Thermodynamics - Ericksen JL

Applied
Mathematical Sciences Volume 131 Editors J.E. Marsden L. Sirovich

Advisors S. Antman J.K. Hale P. Holmes T. Kambe J. Keller K. Kirchgssner
B.J. Matkowsky C.S. Peskin Springer New York Berlin Heidelberg Barcelona
Budapest Hon Kon London Milan Paris Santa Clara Singapore tokyo
Applied Mathematical Sciences J.L. Ericksen 1. John: Partial Differential

Equations, 4th ed. 2. Sirovich: Techniques of Asymptotic Analysis. 3. Hale:
Theory of Functional Differential Equations, 2rid ed. 4. Percus: Combinatorial
Methods. 5. von Mises/Friedrichs: Fluid Dynamics. 6. Freiberger/Grenander: A
Short Course in Computational Probability and Statistics. 7. Pipkin: Lectures on
Viscoelasticity Theory. 8. Giacoglia: Perturbation Methods in Non-linear
Systems. 9. Friedrichs: Spectral Theory of Operators in Hilbert Space. 10.
Stroud: Numerical Quadrature and Solution of Ordinary Differential Equations.
11. Wolovich: Linear Multivariable Systems. 12. Berkovitz: Optimal Control
Theory. 13. Bluman/Cole: Similarity Methods for Differential Equations. 14.
Yoshizawa: Stability Theory and the Existence of Periodic Solution and Almost
Periodic Solutions. 15. Braun: Differential Equations and Their Applications,
3rd ed. 16. Lefschetz: Applications of Algebraic Topology. 17.
Collatz/Wetterling: Optimization Problems. 18. Grenander: Pattern Synthesis:
Lectures in Pattern Theory, Vol. 1. 19. Marsden/McCracken: Hopf Bifurcation
and Its Applications. 20. Driver: Ordinary and Delay Differential Equations. 21.
Courant/Friedrichs: Supersonic Flow and Shock Waves. 22.
Rouche/Habets/Laloy: Stability Theory by Liapunov's Direct Method. 23.
Lamperti: Stochastic Processes: A Survey of the Mathematical Theory. 24.
Grenander: Pattern Analysis: Lectures in Pattern Theory, Vot. lI. 25. Davies:
Integral Transforms and Their Applications, 2nd ed. 26. Kushner/Clark:
Stochastic Approximation Methods for Constrained and Unconstralned Systems.
27. de Boor: A Practical Guide to Splines. 28. Keilson: Markov Chain Models--
Rarity and Exponentiality. 29. de Veubeke: A Course in Elasticity. 30.
Shiatycki: Geometric Quantization and Quantum Mechanics. 31. Reid: Sturmian
Theory for Ordinary Differential Equations. 32. Meis/Markowitz: Numerical
Solution of Partial Differential Equations. 33. Grenander: Regular Structures:
Lectures in Pattern Theory, Vol. III. 34. Kevorkian/Cole: Perturbation Methods
in Applied Mathematics. 35. Carr: Applications of Centre Manifold Theory. 36.
Bengtsson/Ghil/Kiilldn: Dynamic Meteorology: Data Assimilation Methods. 37.
Saperstone: Semidynamical Systems in Infinite Dimensional Spaces. 38.
Lichtenberg/Lieberman: Regular and Chaotic Dynamics, 2nd ed. 39. ?
iccini/Stampacchia/Vidossich: Ordinary Differential Equations in R". 40.
Naylor/Selh Linear Operator Theory in Engineering and Science. 41. Sparrow:
The Lorenz Equations: Bifurcations, Chaos, and Strange Attractors. 42.
Guckenheimer/Holmes: Nonlinear Oscillations, Dynamical Systems, and
Bifurcations of Vector Fields. 43. Ockendon/Taylor: Inviscid Fluid Flows. 44.
Pazy: Semigroups of Linear Operators and Applications to Partial Differential
Equations. 45. GlashofigGustafson: Linear Operations and Approximation: An
Introduction to the Theoretical Analysis and Numerical Treatment of Semi-
Infinite Programs. 46. Wilcox: Scattering Theory for Diffraction Gratings. 47.
Hale et al: An Introduction to Infinite Dimensional Dynamical Systemseometric
Theory. 48. Murray: Asymptotic Analysis. 49. Ladyensaya: The Boundary-
Value Problems of Mathematical Physics. 50. Wilcox: Sound Propagation in
Stratified Fluids. 51. Golubilsky/Schaeffer: Bifurcation and Groups in
Bifurcation Theory, Vol. I. 52. Chipot: Variational Inequalities and Flow in
Porous Media. 53. Majda: Compressible Fluid Flow and System of Conservation
Laws in Several Space Variables. 54. Wasow: Linear Turning Point Theory. 55.
�osida: Operational Calculus: A Theory of Hyperfunctions. 56. Chang/Howes:
Nonlinear Singular Perturbation Phenomena: Theory and Applications. 57.
Reinhardt: Analysis of Approximation Methods for Differential and Integral
Equations. 58. Dwoyer/Hussaini/Voigt (eds): Theoretical Approaches to
Turbulence. 59. Sanders/Verhulst: Averaging Methods in Nonlinear Dynamical
Systems. 60. Ghil/Childress: Topics in Geophysical Dynamics: Atmospheric
Dynamics, Dynamo Theory and Climate Dynamics. (continued following index)
Introduction to the Thermodynamics of Solids Revised Edition With 25
Illustrations Springer
J.L. Ericksen 5378 Buckskin Bob Drive Florence, OR 97439-8320 USA Editors
J.E. Marsden Control and Dynamical Systems, 116-81 California Institute of
Technology Pasadena, CA 91125 USA L. Sirovich Division of Applied
Mathematics Brown University Providence, RI 02912 USA To my dear wife and
friend, Marion E. Ericksen Mathematics Subject Classification (1991): 73B30,
7301,76A 15, 80A20 Library of Congress Cataloging-in-Publication Data
Ericksen, J. L. (Jerald L.), 1924- Introduction to the thermodynamics of solids /
Jerry L. Ericksen. -- Rev. ed. p. cm. -- (Applied mathematical sciences; 131)
Includes bibliographical references and index. ISBN 0-387-98364-3 (hardcover:
alk. paper) 1. Materials. 2. Thermodynamics. I. Title. II. Series: Applied
mathematical sciences (Springer-Verlag New York Inc.); v. 131. TA403.6.E74
1997 621.402' 1c21 97-37938 Printed on acid-free paper. The fin-st edition of
this book was published by Chapman & Hall, UK, � 1991. � 1998 Springer-
Verlag New York, Inc. All rights reserved. This work may not be translated or
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edition) ISBN0-387-98364-3 Springer-Verlag New York Berlin Heidelberg
SPIN 10647553
Preface Although I have never been actively engaged in research on

thermodynamics, per se, I have had to utilize it while attempting to develop
theories better able to deal with various kinds of nonlinear macroscopic phenom-
ena encountered in materials. In trying to help younger workers to start in
research of this kind, I have been impressed with how little most of them know
about common and elmentary applications of thermodynamics to solids,
although they have taken at least one elementary course in thermodynamics at
some university. Observation of a number of elementary books on
thermodynamics indicates that this is due more to lack of exposure to such ideas
than to some fault of the students. When my department had a service course
become obsolete, I accepted responsibility for developing a replacement course
dealing with such applications. The intended audience consisted of seniors and
beginning graduate students from various engineering and scientific
departments. To make the course accessible to the various groups meant keeping
the prerequisites to a minimum, so I settled on mastery of calculus as the basic
requirement. The first nine chapters of this book represent lecture notes
developed for this purpose. In the actual lectures some constituents of the tenth
chapter are mentioned, but this has not been an integral part of the course.
Additionally, a number of simple demonstration experiments are used to
illustrate, in a rather crude way, the real phenomena that are being analyzed,
but these are not described here. These notes have also been used for self-study
by persons more adept in mathematics and mechanics. For example, I advise
graduate students in these disciplines to save time by doing this instead of taking
the course. In
viii Preface Preface ix this way, the course has helped to fill in the gap in
education mentioned at the beginning. Chapter 10 is part of the package for such
readers. This covers some of the difficulties encountered in trying to apply
thermodynamics to obtain a better understanding of the phenomena
encountered in solids, partly to indicate the need to grasp the basic concepts of
classical thermodynamics. Unfortunately, different experts in thermodynamics
have discordant ideas as to what these basic concepts are. In as elementary a
manner as possible, therefore, I discuss what they are as I understand them.
How- ever, this chapter is not so elementary as it deals with matters which are
unsettled and controversial. In this treatment, classical thermodynamics is
interpreted to exclude an important branch based on molecular theory, that is,
statistical thermodynamics, only because covering this in any reasonable way
would make the notes excessively long. The intent is to provide a small bridge to
newer work in thermodynamics. I have tried to choose a few references which
seem likely to be useful, rather than attempting to include all that may be of
interest. Since the notes have been used by readers from quite varied
backgrounds, references cited range from the very elementary to rather
sophisticated works. Readers will need to pick a subselection. I do not intend
this to be a replacement for other elementary books on thermodynamics and do
assrune that the reader has a little familiarity with the subject. For those who feel
a need for supplementary reading, I note a few of the many possibilities. I do
think it desirable for writers of elementary books to better cover applications to
solids. Historically, the subject first emerged from studies of ancient heat en-
gines, with a corresponding emphasis on dynamic processes. In particular, this
produced early ideas about energy and entropy as they are related to the old laws
of thermodynamics. Much in this spirit, although more modern in style, is the
book by Truesdell and Bharatha [1]. What has become a more conventional view
is that energy and entropy are related more to equilibrium states although one
may be dealing with nonequilibrium processes. For a development of the subject
from this point of view, the reader is referred to the work by Kestin [2], for
example. He is influenced by Gibbs's ideas concerning equilibrium theory,
which will be discussed here. One of the most ardent proponents of the notion
that energy and entropy must be related to equilibrium states is Tisza [3],
although he is very critical of Gibbs's ideas. It is not clear how many really
believe that this view is a "law" of thermodynamics, but most writers of
elementary books abide by it. Included are some who exhibit independence of
thought in considering various other ideas about thermodynamics. In this
category is Pippard, whose book [4] is interesting for its comments and
examples, including some relating to solids. Others, myself included, see no
grounds for accepting the restriction and some reason to consider alternatives. In
the first nine chapters of this book, the theories treated do fit this mold fairly
well, with some caveats mentioned in Chapter 10. However, in Chapter 2, I
introduce ideas which are now being used frequently by those willing to consider
alternatives. This is one way of gaining experience with the Clausius-Duhem
inequality which is accepted and used in studies of irreversible processes by
some who, in practice, do accept the conventional view mentioned above, Kestin
in particular. Many elementary books do not mention this old inequality. Rather
obviously, it is probable that theories of equilibrium will fit the conventional
mold and it would have been easy to include many more examples of this kind.
For example, the basic ideas are made available to take the three-dimensional
linear theory of thermoelasticity and deduce all the useful inequalities satisfied
by moduli using the Clausius Duhem inequality and the thermodynamic theory
of stability. My experience is that this is not a matter of common knowledge
among experts in this area, but applications of this kind are fairly routine and
useful. It is also very easy to find theories of solids that are commonly used,
some quite old, which do not fit the conventional mold, as was mentioned
earlier. It can then be very difficult to know how best to try to apply ideas of
thermodynamics. One who has wrestled hard with problems of this kind is apt to
see the subject in a somewhat different light. In this category is Bridgman [5],
who had a strong interest in applications to plasticity, in particular, although he
had no great success in mastering the difficulties involved. Readers unfamiliar
with elementary continuum mechanics may find helpful the text by Bowen [6].
Particularly in discussions with chemists I have encountered another prejudice.
Roughly, it is that if a material really attains equilibrium, any shear stress must
have relaxed to zero. Perhaps this is why so many authors of works on
thermodynamics consider only problems of solids subject solely to a hydrostatic
pressure, if at all. In this respect most of the examples to be considered illustrate
rather common practices of users which tend to be ignored by authors of texts.
Considering how the various structures we make tend to deteriorate, I do
concede that those chemists have a point. If we grant it, equilibrium theory for
solids should be similar to that for fluids. Then the different theories of
thermoelasticity which appear to be equilibrium theories are not really of this
kind, despite appearances. If I accepted this and Tisza's view, as I interpret it,
thermoelasticity theory is based on improper usage of thermodynamics. I think
that it may well be that there is something deeper to be understood here, which
could well influence and improve our understanding of energy and entropy. In
Chapter 10, I will say a little more about this. However, it often happens that
theories which prove to be successful were arrived at by infirm reasoning and
this alone is no reason to reject them. I subscribe to the view that, if we can
understand more fully why such theories succeed, we will improve our chances
of constructing a still better theory.
x Preface So, almost everything to be discussed is, to some degree, controversial.

I do not enjoy controversy. However, it seems hard to avoid it when, as here, the
various experts seem unable to come to agreement as to what should be
considered to be the basic concepts and laws of the subject. In terms of basic
content, this revised edition differs from the first edition by including lists of
exercises. I have added some comments that did not come to mind when I
prepared the first edition and a few references to provide better coverage of
some topics. Otherwise, there are some minor corrections and numerous changes
in wording. Last, but not least, I wish to thank those who have assisted me in this
en- terprise. Some of these have helped me to clarify my own views in debates
over matters of principle, particularly Bernard Coleman, Joseph Kestin, Ingo
Miiller, Paul Naghdi, Ronald Rivlin, James Serrin and Clifford Trues- dell. Alan
Gent produced very helpful comments concerning my coverage of elastomers
and adhesion. A careful reading of early drafts by Millard Beatty and Antonio
DeSimone enabled me to eliminate numerous misprints and other slips. As a
person who dislikes writing, it is unlikely that I would have brought this to
completion without the encouragement of Gunhard ./E Oravas and Patarasp
Sethna. Finally, I thank Kathryn Kosiak and Lee Reynolds for much help in
preparing the manuscript. J.L. Ericksen Contents Preface 1 vii Constitutive
Theory of Heat Transfer for Bars and Plates 11 2.1 Thermodynamics of Rigid
Bars ............... 11 2.2 Constitutive Theory for Rigid Bars ............. 17 2.3
Constitutive Theory for Thermoelastic Bars ........ 21 2.4 Constitutive Theory for
Shearing of Plates ......... 29 2.5 Thermodynamic Experiments ................ 31 34
2.6 Exercises ............................ Equilibrium Theory of Bars 37 3.1 Equilibrium
of Bars Subjected to Dead Loads ....... 37 3.2 Equilibrium Theory of Bars in
Hard Devices ........ 50 3.3 Exercises ............................ 56 4 Equilibrium Theory
of Plates 57 4.1 Martensitic Transformations ................. 57 4.2 Bifurcation
Diagrams ..................... 62 Generalities 1 1.1 Energy, Heat, and Power
................... 1 1.2 Temperature and Entropy ................... 3 1.3 Thermodynamic
Equilibrium ................. 6
xii Contents 4.3 Exercises ............................ 65 Balloon Problems 67 5.1

Equilibrium of Spherical Balloons at Fixed Pressure � . . 67 5.2 Equilibrium of
Balloons Containing a Fixed Mass of Gas. 72 5.3 Exercises ............................ 76
5 Biaxial Stretch of Rubber Sheets 79 6.1 The Idealized Problem .....................
79 6.2 The Treloar Instability .................... 83 6.3 Exercises ............................ 90
Moving Discontinuities 93 7.1 Shock Waves in Bars ...................... 93 7.2
Breaking Bars ......................... 99 7.3 A Peeling Problem ....................... 100 7.4
Another Peeling Problem ................... 103 7.5 Exercises ............................ 106
Mixture Theory 109 8.1 General Remarks ........................ 109 8.2 Elementary
Theory ...................... 110 8.3 A Solid in an Ideal Gas .................... 118 8.4
Exercises ............................ 122 Equilibrium of Liquid Crystals and Rods 123
9.1 Liquid Crystal Energies .................... 123 9.2 Orientation by Fields and
Walls ............... 128 9.3 Measurement of Moduli .................... 130 9.4 Elastica
Theory ......................... 137 9.5 Exercises ............................ 141 10
Reconsideration of Generalities 143 10.1 Systems, Energy, and Temperature
............. 143 10.2 General Processes ....................... 147 10.3 Static and
Reversible Processes ............... 149 10.4 Cyclic Processes and Cycles .................
156 10.5 States .............................. 158 10.6 Laws of Classical Thermodynamics
............. 167 References Index 181 187 1 Generalities 1.1 Energy, Heat, and
Power Thermodynamic systems are capable of occupying a variety of states
linked by time-dependent processes. Often we think of a process as leaving one
state and arriving at another or passing through a succession of states. To induce
a system to undergo the processes of which it is capable, we generally need to
bring it into contact with, or let it interact with, various other kinds of systems.
The variables needed to describe states properly are different for different
systems and, for a given system, can depend on the range of situations to be
considered. For solids, some measures of strain and temperature are likely to be
included. Such things as loading devices of different kinds, thermostats, and so
on, will be used to induce changes of such states and need to be described. If one
is concerned with, say, liquid crystals, one needs also to introduce appropriate
variables describing orientation and electromagnetic fields, as will be discussed
in Chapter 9. Similar remarks apply to the description of processes. For a
thermodynamic system, the first law asserts that, for any possible process, dE - p
+ Q, (1.1.1) dt where E is the energy of the system, P is the power, that is, the
rate at which work is done on the system, and Q is the rate at which heat is
supplied to the system. Intuitively, other systems do supply the power and
2 1. Generalities 1.2 Temperature and Entropy 3 heat. However, there is some

implication that, in a theory for a system, we should have formats for calculating
P, Q, and E for any possible process. Often, we consider a system to be in
contact with another system that interacts with it in a special way. In terms of
how P may be affected, some of the possibilities of interest include the
following: P = 0 (mechanically isolated system). (1.1.2) This can occur because
no forces are applied or, often, because forces are applied but motions are
restricted by rigid walls, and so on so that the forces do no work. For systems we
think of as power sources, it is reasonable to assume that P _ 0 (mechanically
passive system). (1.1.3) Systems loaded by gravity, springs, and so on, often fit
the description P-- -dx/dt (conservative loading devices). (1.1.4) Here, it is
usually understood that X can be calculated given the relevant state variables.
Various little sources of dissipation in a loading device, or adding damping
mechanisms, can shift (1.1.4) to P _ -dx/dt (dissipative loading device). In terms
of Q, we could have, with suitable insulation, (1.1.5) Q = 0 (thermally isolated
system). Systems designed to give off, but not accept, heat fit (1.1.6) Q _< 0
(thermally passive system). (1.1.7) If a system is not in contact with any other
system, we expect that P = Q = 0 = E = const. (isolated system). (1.1.8) If the
environment is such that either (1.1.6) or (1.1.7) and one of (1.1.2) (1.1.5)
applies, the intuitive expectation is that the system should approach equilibrium.
However, at this stage, it is not easy to assign any reasonably clear meaning to
the statement. A pattern of thought underlies measurements of energies for
thermodynamic systems. Consider any pair of states labelled i and 2, a process
leaving 1 at time tl and arriving at 2 at time t2; then, integrating (1.1.1) gives E2
- El ---- 5W 5Q, (1.1.9) where 5W = Pdt, 5Q = Qdt (1.1.10) represent the total
work done on the system in the process and the total heat supplied, respectively.
There may be many processes connecting the two states giving different values
of 5W and 5Q but, as the first law is commonly interpreted, the value of E2 - E
should be the same for all; it depends only on the end states. For one of the
possibilities, experimental data is required enabling the estimation of 5W and
SQ. Calorimetry provides methods for measuring 5Q, rather routine in some
cases. Measuring 5Q for a solid held in a loading device is not so easy and it
certainly helps to be able to think of I and 2 as being static equilibrium states. To
some degree, estimating work from measurements of forces and displacements is
a familiar problem in mechanics. However, because of the complicated methods
commonly used to grip solids, in practice it can be very hard, perhaps
impossible, to make an accurate estimate of 6W. Consider 1 as a fixed state and
2 as any other state. Then, assuming one can get the requisite experimental
estimates, E can be determined, to within a constant, for each of the possible
states. Physically, only energy differences have significance, so one can fix the
constant in any convenient way. We have discussed two rather different views of
energy. In (1.1.1), it is a function of t, somehow calculable for any possible
process. Then, in the later discussion, it becomes associated with states. To
combine the two, one needs to make an assumption about the relation between
states and processes--basically that, at each point in time, a process uniquely
determines a state. Then, for a process, E(t) is the value of E for the associated
state. 1.2 Temperature and Entropy Entropy and temperature play important
roles in thermodynamics. The reader is assumed to have some familiarity with
the notion of absolute temperature, which we denote by 0, with values satisfying
0 > 0. In terms of this, we can describe another kind of thermal environment, that
of an ideal heat bath, whose temperature 0 = Oz(t) (1.2.1) depends possibly on
time t but not on position. Consistent with this is the idea that putting a system in
contact with the heat bath does not change Os(t), although the temperature in the
system can differ considerably from this value. Think, as Newton did, of a small
hot poker cooling off in a large room. It will be hot to the touch, but Os,
interpreted as room temperature far from the rod, will not change much. In other
systems, we employ cooling devices, and so on, to keep the temperature of at
least part of a system near a definite value, identified as Os. Commonly, changes
in entropy are inferred from measurements in an environment of this kind, with
Os held constant for quite a while, changed a little, then held at a new constant
value.
4 1. Generalities Such determinations of entropy involve an assumption which is

rather restrictive for solids: every pair of states can be connected by at least one
reversible process, or at least by approximating this situation. Physically, this
tends to exclude inherently irreversible phenomena such as are encountered in
sliding friction or plasticity; so we will ignore such exccptions. The idea is that
the entropy $ of a system in contact with a heat bath should satisfy what is often
called the Clausius-Planck inequality d__S > (1.2.2) dt - OB in the processes that
are possible. Here, there are no restrictions as to how power can be supplied to
the system: it is only the thermal environment that is somewhat special. Involved
is the idea that, in (1.2.2), equality holds for reversible processes. As in the
discussion of energy, we think of processes starting at state 1 at time tl and
arriving at state 2 at time t2. Then, integrating (1.2.2) gives, for the entropy
difference, $2 - (Q/OB)dt. (1.2.3) Next, we try to find a reversible process,
reducing (1.2.3) to $2 - $ -- (Q/OB)dt. (1.2.4) Since Q is not easy to measure, the
usual practive is to try to arrange that 0 is constant, so that we have S2 -- S1 :
tQ/OB, (1.2.5) where 5Q is given by (1.1.10). Then, of course, 5Q may be
measured by calorimetric techniques. With 0B also measured, we get
experimental values of the entropy difference between two states. We do this for
as many states as is feasible. In principle, this determines values for $ for such
states to within an unimportant additive constant. From what has been said here,
it is unclear as to what properties entropy may have or how it is to be defined or
measured when the environment does not fit the above "heat bath" prescription.
Common practice involves, at least tacitly, the assumption that from
measurements in such environments one can infer values of $ for states
occurring in more general kinds of processes. One should appreciate that
"common" has a different meaning from "universal." Said differently, an
intelligent person does not accept popular practices thoughtlessly. In a famous
paper on thermodynamic equilibrium, Gibbs [7] began with a quotation from
Clausius: 1.2 Temperature and Entropy 5 Die Energie der Welt ist constant. Die
Entropie der Welt strebt einem Maximum zu. It is hard to be sure exactly what
Clausius meant by "der Welt," but later writers, including Gibbs, interpreted that
as meaning an isolated system. Then, a translation is: The energy of an isolated
system is constant. The entropy of an isolated system tends to a maximum.
Clearly, the first statement agrees with (1.1.8). Related to the second statement
is a widely accepted idea (concerning isolated sytems) that P = Q = 0 dS/dt _ O.
(1.2.6) In fact, it is generally accepted that the restriction to mechanically
isolated systems is not necessary, although that to thermally isolated systems is.
That is, (1.2.6) can be replaced by Q = 0 dS/dr _ O. (1.2.7) It is hard to compare
either of these statements with (1.2.2), since it is not reasonable to think of a
thermally insulated system as being in contact with a heat bath. As to what
energy and entropy meant to Gibbs, we have his rather terse statement: As the
difference of the values of the energy for any two states represents the combined
amount of work and heat received or yielded by the system when it is brought
from one state to the other, and the difference of entropy is the limit of all of the
possible values of the integral f (dQ denoting the element of heat received from
external sources, and t the temperature of the part of the system receiving it), the
varying values of the energy and entropy characterize, in all that is essential, the
effects producible by the system in passing from one state to another. There is a
rather common view that no real process is quite reversible, so reversible
processes may be thought of as limits of processes which are not themselves real
processes. Perhaps Gibbs's use of the phrase "the limit" indicates that he held
this view. Some tend to associate nearly reversible processes with those taking
place very slowly--the "quasi-static" processes. This probably stems, at least in
part, from experience with classical theories of heat conduction, viscosity, and so
on. However, a ball made of silly putty behaves almost reversibly when bounced
rapidly and various other high polymers have similar predilections. So, it seems
prudent to be open-minded in considering what may be reversible processes for
particular systems.
6 1. Generalities It is a blunt fact that the general ideas of entropy and, to some
extent, power, heat, and energy remain somewhat nebulous. Despite this, they
have been used quite successfully in analyzing various kinds of physical
systems. In the first eight chapters of this book the aim is modest. It is to discuss
some of the kinds of thermodynamic ideas commonly used in analyzing the
behavior of solids, illustrating this by relatively simple examples. Chapter 9
serves to provide a broader perspective. After acquiring this experience, we will
reconsider the basic concepts in Chapter 10. 1.3 Thermodynamic Equilibrium Of
considerable importance are general ideas of equilibrium and the related stability
theory. Intuitively, systems can be expected to approach equilibrium only if
they are kept in rather special environments. In particular, we expect a trend to
equilibrium in physically isolated systems. Gibbs took this intuitive idea together
with older thermodynamic ideas discussed in Section 1.2 and used them to
motivate definitions of thermodynamic equilibrium, and criteria for the
stability thereof, for isolated systems. In his words, I. For the equilibrium of any
isolated system, it is necessary and sufficient that in all possible variations of the
state of the system which do not alter its energy, the variation of its entropy shall
either vanish or be negative. He also gave a plausible argument I indicating that
this statement is equivalent to II. For the equilibrium of any isolated system, it
is necessary and sufficient that in all possible variations in the state of the system
which do not alter its entropy, the variation of its energy shall either vanish or be
positive. Discussion following this indicates that one should exercise some good
physical judgement in deciding as to what are the "possible variations." This
kind of difficulty occurs in all forms of stability theory for rather simple reasons.
Nothing, it seems, is indestructible, so it is too much to ask that a system remain
stable with respect to every conceivable kind of disturbance. Some quite
unstable systems, such as a room filled with natural gas, can tolerate some small
vibrations but be set off by a small spark. Basically, It is hard to see how one
could give a general proof of this since the statements are not very precise,
serving more as guidelines. When there is any doubt about equivalence, workers
take as basic the first statement. 1.3 Thermodynamic Equilibrium 7 we want to
know whether a particular system will be stable with respect to those
disturbances that are likely to be encountered but are beyond our contrdl. So,
inevitably, we must exercise some judgement in deciding what these might be.
As was mentioned before, when one encounters phenomena such as sliding
friction or plasticity, entropy is ill-defined so that statements are not applicable.
Curiously, Gibbs did not mention this difficulty but did warn against trying to
use the criteria in such cases. His is a long memoir, discussing many types of
physical problems fitting this mould and including such topics as chemical
reactions in fluids, absorption of fluids by solids, dissolving solids in fluids,
stability of fluids surrounded by solids and vice versa, as in pressure vessels, and
so on. It is not easy to read but the density of ideas is high, and many are now
commonly used by engineers and scientists of various disciplines. Often, the use
of thermostats makes it more natural to think of a system not as thermally
insulated but as in contact with a heat bath at a constant temperature OB. Then,
from (1.1.1), with the system considered as mechanically isolated, we have 2
and, from (1.2.2), so where dE - Q (1.3.1) dt dS Q _< oB dW' dEB -- < 0. (1.3.2)
dt EB = E - OB s. (1.3.3) Physically, one expects an approach to equilibrium in
such systems, with a caveat. There exists the phenomenon of Brownian motion
which is rather easy to observe in fluids. Statistical theory a leads us to expect
such motion to occur in solids, little fluctuations preventing the system from
quite reaching equilibrium. Usually, the motion is so small that errors that result
from neglecting it is of little practical significance and we will ignore it. Then,
with EB decreasing in any process, we expect that EB will be some kind of a
minimum in stable equilbrium. The quantity EB is called the ballistic free
energy. This suggests a third statement which we write, in the style of Gibbs, as
III. For the equilibrium of any mechanically isolated system, in contact with a
heat bath at constant temperature, it is 2In this discussion, we lean rather heavily
on ideas of Duhem [8]. aEarly work on this, performed by Einstein, is collected
in reference [9].
8 1. Generalities necessary and sufficient that in all possible variations of the

system the variation of its ballistic free energy shall either vanish or be positive.
As will become clear, this gets us rather close to the "energy criteria" commonly
used by engineers to analyze stability of various structures. In any of these
situations, the systems could contain fluids of unknown viscosity--various other
kinds of dissipative mechanisms which we might not know how to describe
quantitatively. More often than not this is the situation encountered in practice.
From the statements it is clear that one does need prescriptions for calculating
energies and entropies. Given this, one can use these ideas to find and test the
stability of equilibria. It is not a trivial matter to find good prescriptions. Later
we will discuss some rather common kinds of difficulties that do arise in
practice. Also, we will encounter cases where predictions obtained depend on
the selection of the "possible variations" among choices which seem rather
likely. Common to the three statements is the restriction that the system be
mechanically isolated. By lumping together solid specimens and devices used to
load them one can meet this requirement, in a reasonable way, in various
situations of physical interest. It is common to relax this requirement somewhat
by admitting loading devices that are conservative or dissipative, in the sense
indicated by (1.1.4) or (1.1.5), respectively, then regarding the solid specimen as
the thermodynamic system. For example, we might load a specimen by attaching
a bucket, to which we will add fluid, in the earth's gravitational field, identifying
X with the gravitational potential. In itself the gravitational force is conservative,
but any motion of the fluid could induce viscous dissipation and (1.1.5) can
cover this. By an obvious modification of the reasoning leading to (1.3.2), one
now obtains where d E x _< 0, (1.3.4) E x = E + X - OB$, (1.3.5) which we shall
also call the ballistic free energy of such systems. This serves to motivate a
fourth statement: IV. For the equilibrium of any system in a conservative or dis-
sipative loading device, in contact with a heat bath at constant temperature, it is
necessary and sufficient that in all possible variations of the system the variation
of its ballistic free energy shall either vanish or be positive. In practice, workers
often use III or IV, simplified by the assumption that, throughout the system, the
temperature is 0B, although the "possible variations" generally include other
kinds of temperature distributions. Such 1.3 Thermodynamic Equilibrium 9
criteria are slightly inferior in principle, but the differences tend to be com-
pensated for by other assumptions accepted by such workers, sometimes tacitly.
Later, we will elaborate on this for special cases. The four statements summarize
ideas that have been used with considerable success to analyze stability of
equilibrium for a great variety of physical systems. One could generalize to
cover passive systems, but, for arbitrary thermodynamic systems,
thermodynamic criteria for stability do not exist and there are the
aforementioned difficulties in covering such topics as plasticity or Brownian
motion. So, the thermodynamic theory of stability has its limits. Other
approaches to stability theory are covered, in a rather elementary way, in Pippard
[10], for example.
2 Constitutive Transfer for Theory of Heat Bars and Plates 2.1 Thermodynamics
of Rigid Bars In this section, we consider the one-dimensional theory of heat
transfer in rigid, stationary bars, illustrating how some of the general
thermodynamic ideas are interpreted in this context. Mathematically, the points
on a bar are represented by points in the interval 0 < x < L. (2.1.1) Quantities of
interest, such as temperature, will then, in any process, be functions of x and t.
We require a theory capable of describing the possible temperature distributions.
One rather general idea is that a part of a thermodynamic system can itself be
considered as a thermodynamic system, so, in particular, any part of the bar
qualifies. In Chapter 8, we will note that it is not always feasible to use this idea.
Forces may act on any such part but these will do no work because motion is
excluded. Thus, any such part, or the whole bar, will be mechanically isolated, P:
0. (2.1.2) Another general idea is that energy and entropy are additive. 1 Here,
the traditional way of covering this is to assume that they are representable by
1Generally, thermodynamicists call such quantities extensive variables, refer-
ring to quantities which are not, for example O, as intensive variables.
12 2. Constitutive Theory of Heat Transfer for Bars and Plates integrals E--fedx,
$--frldx , (2.1.3) where thc integral can be over the interval (2.1.1), or a subset.
Physically, heat transfer can take place along the bar by conduction. To describe
this, we introduce a heat flux q. In terms of this Qc, the rate at which heat is
supplied by this mechanism to a subinterval (x,x2) is rcpresented by Qc --
q(x2,t) - q(x,t) = q x2. (2.1.4) With one-dimensional thcory, it is difficult to
describe transfer through the sides of the bar in a similar way, so we introduce
another representation, Qo -- rdx, (2.1.5) sometimes considered as a measure of
radiation, sometimes as a crude approximation to the effects of conduction or
perhaps somc combination of both. Then, for the subinterval, (1.1.1) takes the
form dE d dt - dt e dx = Q = Qc + Q0 (2.1.6) = q(x2, t) - q(xl, t) q- r dx.
Assuming the functions are smooth enough, we can rewrite this as I dx ---- i XX
+ r dx, (2.1.7) and infer from the arbitrariness of x and x that Oe Oq - q- r.
(2.1.8) Ot Ox In this context, the accepted view is that the entropy is involved in
an inequality, the so-called ClausiusDuhern inequality, rldx _> (q/O) + (r/O)dx,
(2.1.9) reducing to the local form, Or> 0 _ xx(q/O ) + r/O. (2.1.10) 2.1
Thermodynamics of Rigid Bars 13 Additional equations are needed, and
physically these should take into account that the thermal response will be
different for different materials. Before considering this, let us consider some of
the different ways of describing the notion that the bar is in contact with a heat
bath at temperature 0B(t), a given function of t. One possibility, envisaging that
the side of the bar is coated with an insulator, is r = 0, O(O,t) = O(L,t) = OB(t).
(2.1.11) Then, applying (2.1.9) to the whole bar, we get dS d fo L dt -- dt rldx >
[q(L,t) - q(O,t)]/O, (2.1.12) agreeing with the Clausius Planck inequality (1.2.2).
Or, we might replace these temperature boundary conditions by boundary
conditions of the radiation type. With Newton's law of cooling, this would give
q(L, t) = a[O - O(L, t)], (2.1.13) q(0, t) = -ct[0 - 0(0, t)] with a a positive
constant. That a should be positive reflects the idea that heat should flow into the
bar if it is cooler than the heat bath, out if it is hotter. Then, it is easy to verify
that q(L, t)/O(L, t) = a[O - O(L, t)]/O > q(L, t)/OB (2.1.14) -q(O, t)/O(O, t) > -
q(O, t)/O. Putting this together with (2.1.4) and (2.1.9), again assuming r = O,
we get dS -- > Q/OB, (2.1.15) dt - also agreeing with (1.2.2). Another commonly
used radiation condition is the Stefan-Boltzmann law, which would give q(L, t)
=/[0 - 04(Z, t)], q(0, t) = -/[0 - 04(0, t)] (2.1.16) with a positive constant, again
leading to (2.1.15) when r = 0. One can consider heat transfer from the sides of
the bar while insulating the ends. Using, for example, Newton's law of cooling,
this gives q(O,t) = q(L,t) = 0, r = a[0 - O(x,t)]. (2.1.17) Again, ct should be
positive, to have heat flow into the bar when it is cooler and out of the bar when
it is hotter. Also, it follows that r(x, t)/O(x, t) _> r(x, t)/Os(t), (2.1.18)
14 2. Constitutive Theory of Heat Transfer for Bars and Plates and that (2.1.15)
again holds, now with Q = Qb- One can replace the insulated end conditions by
radiation boundary conditions, again confirming (2.1.15). So, under various
assumptions of this kind, the Clausius-Duhem inequality implies the Clausius-
Planck inequality. Unlike the latter, it also applies to cases where 02 might be
considered to depend on x, or to cases where 0 might be assigned different
values at the ends, in a bar with insulated sides. For classical studies of
equilibrium, one needs a constitutive equation depending on the material, and
one of the form e = e(V) (2.1.19) would fit Gibbs's preference. Let us consider
this bar in contact with a heat bath at temperature 0s = const. and explore the
consequences of definition III, in Section 1.3. We have L Es = 0 [e(V) - Ov]dx,
(2.1.20) defined for some functions (x). At let one of these should occur a
thermodynamic equilibrium state; call it . As possible variations of it, we
consider a one-parameter family of functions, as is commonly done in the
calculus of variations, where is the parameter and 5 an arbitrary smooth function
of x. A common idea is that any variation of this kind is possible, if it is small
enough, and, given 5, we can make it small by making small. For the moment,
consider 5 v fixed, and consider L E() = [e( + SV) - O,( + SV) ] dx. (2.1.21) For
small, we have, a first approximation, where Es(O) 5Es -- E(O) = (V) - Os 5vdx
(2.1.22) is called the first variation. We interpret the criterion for equilibrium as
meaning that we should have 6Es >_ 0, 2One of the better elementary treatments
of this subject is reference [11]. 2.1 Thermodynamics of Rigid Bars 15 and,
since/ can be chosen to be positive or negative, this requires that 5Es = O, for
arbitrary 5. By a fundamental lemma in the calculus of variations, this holds if
and only if d() = Os (2.1.23) Briefly, if this were not true, the bracketed quantity
in (2.1.22) would be positive or negative in some interval. Choosing 5 positive in
a subinterval of this and zero elsewhere produces a contradiction. So, (2.1.23)
gives an equation for determing (stable or unstable) equilibrium values of . With
other theories, similar reasoning is used in interpreting the criteria for equi-
librium. In equilibrium, one expects 0, the temperature of the bar, to match that
of the heat bath. This fits the common assumption that 0 and are always related
by de 0 = --. (2.1.24) d As a general proposition, it is certainly not safe to assume
that an equation that holds in equilibrium also holds more generally. Here,
there is a consensus of opinion that the assumption has a range of validity which
is not restricted to equilibria but might well not include processes involving large
departures from equilibrium. Now, we can proceed to obtain stability conditions.
As a test for a local minimum, many would use the second derivative test, 52Es
= E(O) > 0 (2.1.25) or f0 2 dx 0 q which, by (2.1.24), leads to d d e . . (7)= k o.
(2.1.26) Briefly, if the second derivative were negative, it would be negative in
some interval by continuity and one could again find 5r/ for which the integral
inequality is violated. Conditions very similar to (2.1.23) and (2.1.26) emerge,
by similar reasoning, in a great variety of theories. They represent what may be
viewed as minimal requirements for stable or metastable equilibrium. If (2.1.24)
gives 0 as a monotonically increasing function of r/, taking on all positive
values, then (2.1.23) holds for exactly one value of and (2.1.26) will be satisfied.
Some workers are happy to consider only constitutive equations
16 2. Constitutive Theory of Heat Transfer for Bars and Plates 2.2 Constitutive
Theory for Rigid Bars 17 having these properties. This excludes some
instabilities that might occur in principle, but I know of no clear evidence that
they occur in practice. According to the criterion, the most stablc equilibria
corrcspond to absolute minima. Clearly, the integral will be smallest if thc
integrand everywhere takes on its minimum value? so the criterion for this is or
with (2.1.23), - oBv_> s(V) - oBv, de e(r/) - s(7) >_ -rr/(7)(r/- 7) D r/, (2.1.27)
where D is to be read as "for all." The aforementioned common assumption
implies that this holds for every choice of r/and 7. Mathematically, e is then a
convex function of r/. Were it not, (2.1.27) would require that (7, s(7)) be a point
of convexity of the graph of e = e(r/); the graph must be above the tangent line at
this point. For simplicity, make the assumption alluded to above, so we can solve
(2.1.24) to obtain r/as a function of 0, either quantity serving as a label for states.
The derivatives will satisfy d dO -- . dO d Note that, if equality holds in (2.1.26),
&l/dO will not be finite. Actually, this can happen at particular values of 0 at
which phase transitions take place, although some more general theory is needed
to describe what then occurs. 4 We will exclude this possibility. Now consider
starting with a bar in equilibrium at some temperature 0. Change this a little, to 0
+ A0z, and allow it to reach equilibrium. This will give a change in energy; by
(2.1.23) and (2.1.24) L AE= A o e(7) dx (2.1.28) LoXO ZXO ---- B ---- LOB B.
Here, the overbar denotes evaluation at the state corresponding to 7. Since no
work is done on the bar, this should also be the total amount of heat supplied to
the bar, which can be measured using a calorimetcr. Clearly L, 0 and A0B can
also be measured, so one can infer values of de/dO and drl/dO. By doing this for
a range of temperatures, one can get s and 3This excludes some commonly
ignored mathematical possibilities, like the function not being bounded below, or
not attaining a minimum. 4See, for example, the discussion of lambda transitions
by Pippard [4]. r/ as functions of 0, at least for some range of temperatures, and
from this, calculate e(r/). A careful worker will at least increase and decrease
temperature to see if thc results thus obtained are consistent. 2.2 Constitutive
Theory for Rigid Bars In the previous discussion, we said rather little about
some items, q in particular, but they play a more important role in the
consideration of heat transfer. The aim is to somehow relate these to
temperature. The classical theory of heat conduction uses Fourier's law q = n
O0/COx, (2.2.1) where n is a constant, or more realistically, a function of
temperature. This suggests that items of interest should depend on 0 and
COO/COx. Equilibrium studies suggest that e and r/ depend only on 0, but they
deal with cases where cOO/cOx could well be small enough to make a negligible
contribution. Thus, a likely assumption may be that we have constitutive
equations of the form s = s(0, CO0/COx), r I = rI(O, COO/COx), q: q(O,
COO/COx), (2.2.2) depending on the material from which the bar is made. The
usual idea is that these do not change when we put the bar in different
environments. In a slightly different category is r, which is not as independent of
the environment from the examples of radiation laws. We do need some
prescription(s) for it, more or less like the examples discussed in Section 2.1.
The basic idea is to convert the energy equation (2.1.8) to a differential equa-
tion for 0 and to arrange that any solutions satisfy the Clausius Duhem inequality
(2.1.10). One way of proceeding is to eliminate r between thc two to obtain corl
x COt COq (2.2.3) O -0 ( q, O ) _> COt COx and to restrict the constitutive
equations (2.2.2), so this holds for essentially arbitrary smooth functions O(x,
t); one can respect obvious conditions such as 0 > 0. This procedure is not as
arbitrary as it may seem. For example, suppose that we accept Newton's law of
cooling together with the prescription for r given in (2.1.17) with the idea that 0
is an assignable constant. Choose the bar temperature function O(x, t) and think
of using (2.2.2) to calculate s(x, t), and so on. Then calculate COt COq f(x, t) --
COt COx' Now choose particular values of (x, t) = (x0, to), say, and solve f (xo,
to) = r(xo, to) = - O(xo, to)]
18 2. Constitutive Theory of Heat Transfer for Bars and Plates for 0B, to satisfy
(2.1.8) at (Xo,to). Clearly, (2.2.3) must then hold at (Xo, to). Actually, it is not
too unrealistic to assume that 0B is an assignable function of x, t. Accept this
and avoid evaluation at particular values of x and t. A weakness in the argument
is that the calculated values of 0 could be negative, and this is not physically
acceptable. Hence, we may sacrifice some generality in accepting the indicated
assumption. We now rearrange (2.2.3) by introducing �=e-0/=� O, , (2.2.4) the
Helmholtz free energy per unit length. By simple calculation, O O OO O 0 - Ot
O00t O(00/Ox) OxOt (2.2.5) O0/0 O0 -< q xx l - rl ' We want to ensure this will
hold for any choice of the function O(x,t), assuming (2.2.2) is used to calculate
q. Consider (x, t) = (Xo, to), any particular point and time. It is easy to
construct temperature functions such that 0(Xo, to) = a, 0--0x (Xo, to) = b, (Xo,
to) = c, (2.2.6) 020 OxOt (x0, to) = d, where a, b, c and d are arbitrary constants,
with a > 0; simple polynomial functions will suffice. Now, use these values in
(2.2.5) evaluated at (x0,t0), to obtain an inequality of the form A + Bc + Cd <
O, where A, B and C are functions of a and b only. Fix a, b, and c. If C > 0, we
could take d negative and large enough to violate this inequality and, if C < 0,
we could similarly violate it. A similar argument applies to B, so we must have
B=C=0, A<0, for all values of a and b, that is, for all values of 0 and O/Ox. This
gives 0 oo -- 0 = � = �(0), (2.2.7) () 2.2 Constitutive Theory for Rigid Bars 19
and 1= dO' (2.2.8) This leaves us with the inequality g 0,xx = qxx >0' (2.2.9)
Now, for 0 fixed, g clearly vanishes when O0/Ox = 0, and, being nonnegative,
it has a minimum there, so Og (0,0) = q(O,O) = 0. (2.2.10) 0 oo Physically, 0 is
constant in equilibrium and the heat flux then vanishes. Fourier's law (2.2.1) then
emerges in a natural way as a first approximation for O0/Ox suitably small.
Equation (2.2.9) reduces to the condition n k 0, which is always sumed in such
theory. With a more nonlinear theow, q must be chosen to satisfy (2.2.9). As w
mentioned in our considerations of equilibrium theory, it is commonly assumed
that is a monotonically increing function of 0, so, by (2.2.8) d d2 - > 0, (2.2.11)
dO dO 2 and (2.2.8) can be inverted, to obtain 0 a function of . Also, from
(2.2.4) and (2.2.8), de de dr I _ o drl dO' involved earlier in (2.1.28), there
deduced from equilibrium theory. With this, the energy equation (2.1.8) becomes
Oe de O0 drl O0 - 0 ot dO Ot dO Ot (2.2.12) _ 0 0rl _ Oq + r. Ot Ox With, say,
Fourier's law and Newton's law of cooling, this gives de O0 0 (n(O) 00 ) dO Ot-
Ox xx + (03 - 0), (2.2.13) as the temperature equation, our discussion in Section
2.1 covering some possible boundary conditions. Linearizing this about 0 = 0a =
const., gives
20 2. Constitutive Theory of Heat Transfer for Bars and Plates a linear equation,
likely to be used in problem solving in cases where the change in temperature is
expected to be small compared to some constant value. The linearized equation
is of the form with 00 020 Co = no x 2 q- a(0, - 0), (2.2.14) de (Os), no = n(Os).
(2.2.15) Co = Equation (2.2.14), with a ---- 0, is known as the diffusion equation
or the heat equation. If (2.2.12) holds, we can calculate that dS dor q (; 00/02 dr-
dr vdx = + + q ox / j dx. (2.2.16) With this and the earlier discussion of heat
baths, it is fairly easy to convince yourself that the sumptions of reversibility
made in calorimetry cannot be quite correct according to this kind of
nonequilibrium theory. Generally, the nonequilibrium theory is considered to be
sounder. This and similar experiences with other nonequilibrium theories serve
to motivate the rather common opinion that reversible processes are not really
physically attainable. There is one ce in which a simple analysis gives an
estimate of the errors involved. Suppose we start with the bar in equilibrium,
with 0=0}=00 fort<0. (2.2.17) Suppose that we insulate the ends, so that q(L, t)
= q(O, t) = O, Dt. (2.2.18) Then, at t = 0, we change the heat bath temperature to
0 = (1 + a)00, (2.2.19) where a is a small number. Then, reonably, we can use
the linearized equation (2.2.14), with boundary conditions 00 a0=0 at x = 0, L,
and we can satisfy this by taking 0 independent of x. This would also be true if
we used nonlinear theory. However, with linear theory, we get a simple
equation, 00 a = - 0), = > 0. 2.3 Constitutive Theory for Thermoelastic Bars 21
Integrating this, and using the initial condition (2.2.17), we get 0s - 0 = (0s - 00)
exp(-/t) (2.2.20) = aOo exp(-3t), so 0 approaches 0s exponentially, as t - cx>.
The total heat supplied to the bar is 5Q=/ / rdtdx=aL (OB--O) dt (2.2.21) = L -
LCoaOo. With (2.2.16) the total change in entropy, according to nonlinear
theory, is AS = dt dx = aL dt. (2.2.22) As estimated by linear theory, we
calculate that Os - 0 a exp(-/t) 0 I + a[1 - exp(-/t)] a exp(-/t) with an error of the
order O(a2). In this approximation, we then obtain Laa 5Q AS -- - 3 0o' or the
approximate reversibility needed to correlate with equilibrium studies such as
are involved in calorimetry. So, one needs/t to be large to get near
thermodynamic equilibrium and the heat bath temperature changes to be small,
as measured by a, to approximate results obtained from equilibrium theory.
This exemplifies a remark made in Chapter 1. The desired reversible processes
do not always exist. Often, we can approximate reversibility as closely as we
like, here by making a small enough. In the limit a = O, we do get a reversible
process, but it requires the bar to remain in equilibrium, at 0 = Os, and, for
calorimetry, we need the temperature to change slightly. 2.3 Constitutive Theory
for Thermoclastic Bars Here we generalize the previous theory, allowing the bar
to stretch. This involves picking a reference configuration of the bar. The usual
practice is to identify this as a rather stable equilibrium configuration, subject to
no
22 2. Constitutive Theory of Heat Transfer for Bars and Plates forces, at a

particular (constant) reference temperature 0n. Here, x will describe positions in
this reference configuration, a fixed interval 0 < x < L, (2.3.1) as before. Such
points can move to other points of the line containing this interval. Motion will
then be described by an equation of the form y = y(x, t), (2.3.2) where y denotes
the coordinate of a material "point," really an average position of a cross section
which was at x in the reference configuration. Two quantities of interest are the
velocity Oy and the stretch s a dimensionless (2.3.3) Oy A = xx > 0, (2.3.4)
measure of changes of length. Generally, we will use a superposed dot to denote
partial differentiation with respect to t, holding x fixed. Often, workers use
instead the strain, e = A - 1, (2.3.5) interpretable as the change of length divided
by the reference length of an infinitesimal part of the bar. As before, we assume
that the physical properties of one cross section are like those of any other.
Physically, the bar should be made of an homogeneous material and be of
cylindrical form. Then An, the area of a cross section in the reference
configuration, is a constant, unaffected by motions of the bar. If one is dealing
with bars of the same material and geometrically similar in shape, it is
commonly assumed that they can be described by essentially the same equations
and this is in reasonably good agreement with experience. Certainly, a fatter bar
has a greater mass, for example. To compensate for such obvious differences, we
consider additive quantities, such as energy, entropy and momentum, as divided
by An. Thus, in applying the first law to parts of a bar, we use E=P+Q, =E/AR,
=P/An, Q=Q/AR. (2.3.6) Since it becomes clumsy to introduce too many
notations we will drop the bars, understanding that E is to be thought of as
energy per unit reference area, and so on. 5The value A 0 reflects the physical
idea that the length of a segment cannot be reduced to zero. 2.3 Constitutive
Theory for Thermoelastic Bars 23 Equations of motion are based on the idea that
the rate of change of momentum equals the force. With one-dimensional theory,
we can only account for forces directed along the line representing the bar.
Detailing this, we introduce the format pdx fdx + (2.3.7) with x and x2
representing any two points in the interval (2.1.1). Here p is the (constant) mass
per unit reference volume, so represents momentum per unit reference area.
Similarly, f represents force per unit reference volume, distributed along the
length of the bar. With er we denote what is commonly called the engineering, or
Piola Kirchhoff stress. It covers the force exerted on the material on one side of a
cross section by the nearby material on the other side. Adopting arguments very
similar to those used to deduce (2.1.8), we obtain from (2.3.7) the partial
differential equation 02y Ocr p = p = f 4- xx' (2.3.8) With the motion, the energy
will consist in part of kinetic energy and it is convenient to recognize this
explicitly. So we write, for the energy (per unit reference area), for a part of the
bar x2 1 .2 Here e is called the internal energy (per unit reference volume).
Similarly, we need to consider the power represented by P = fdx + er = + cry dx.
For Q, we use the same kind of format adopted for rigid bars, fx2 qX, ( 0xq ) Q
= r dx + = r + dx. 1 X 1 1 (2.3.10) (2.3.11) Bear in mind that this represents the
rate at which heat is supplied, per unit reference area, so this q has different
physical dimensions. Then, by arguments which should now seem familiar, we
use the first law, dE -- =p+Q, dt
24 2. Constitutive Theory of Heat Transfer for Bars and Plates to obtain the
differential equation p - + o Oq -- f 9 + xx ( ag ) r xx ' Using (2.3.8), we can
cancel some terms giving O Oq (2.3.12) =o+r+o- , the idea being to use this as
an equation for O(x, t). Again, we use the Clausius Duhem inequality (2.1.9),
dSd x2 x2r dt -- dt 1 dX dX + , (2,3,13) merely reinterpreting S to be entropy per
unit reference area. As before, we then have 1(Oq) 0 r+ -q 02 . (2.3.14) The
usual idea is that, for a given bar, f and r may be specified in different ways,
depending on the systems with which it is to be in contact. So, we require a
theory enabling rather arbitrary specifications of these and we will not formulate
constitutive equations for them. In (2.3.12), f h already been eliminated and,
before, we can eliminate r between (2.3.12) and (2.3.14), to obtain the inequality
o o0 - oo + (q/O) . Also, before, it is convenient to introduce = - On, (2.a.lS) the
Helmholtz flee ener per unit reference volume, satisfying O Va + (q/O) O0 (2..1)
Then, we seek constitutive relations, relating , a, , and q to motion and
temperature, allowing for the fact that different bars can respond differently.
Here, we aim at theories which are, in a sense, very local. Consider any fixed
values of x, t, designated by x0 and t0. For small enough values of x - x0 and t -
t0, we have, approximately Oy y(x, t) y(xo, to) + (x0, to)(x - xo) + (xo, to)(t -
to), (2..x7) o0 O(x, t) O(xo, to) + (x0, t0)(- x0) + O(xo, to)(t- to). 2.3
Constitutive Theory for Thermoelastic Bars 25 Then, roughly, the assumption is
that the behavior of a material point is influenced by the general motion and
temperature. This influence is small except when it occurs very close to the point
in position and time. Using (2.3.17) to estimate this, we are led to the assumption
that b, a, , and q are functions of the following quantities: Oy O0 y, A--0' ' 0, xx' '
(2.3.18) Two arguments are used to restrict these functions. One is the notion
that these should be objective functions, as it is sometimes put, meaning that
their values are unaffected by superposing rigid motions. Suppose, for example,
that we have two motions y(x, t) and (x, t), with (x, t) = y(x, t) + a + with a and b
constant. Here, it would be acceptable to replace a + bt by an arbitrary smooth
function of t, but one gets the same restrictions, either way. Suppose also that the
temperature functions are the same, (x, t) = 0(, t). It is true that a given particle
takes on differcnt positions and the velocity differs by a constant; but,
physically, we do not expect this to affect heat fluxes, entropies, and so on.
Thus, for cxamplc, we should have Oy oo y-a+bt, xx' -b, O, xx' ( Oy oo) = y, , ,
0, , O , for any given motion y(x, t) and any choice of constants a and b. It then
follows that this will be true only if b does not depend on y or . By this kind of
argument, we reduce (2.3.18) to Oy O, 00, . (2.3.19) 0-' and q depend on these
variables, we put this into Assuming q, /, a, (2.3.16) to get 1o (o,)o,.. (2.3.20) O
O (q/O)-. + O(00/Ox) Ox - As before, we want to restrict the constitutive
functions so that the inequality is satisfied for all motions and temperature
distributions. We use
26 2. Constitutive Theory of Heat Transfer for Bars and Plates the fact that, with
the variables (2.3.19) fixed, at x -- x0, t = to, we can still regard as independent
variables higher derivatives such as . This gives the restrictions (2.3.21) 04, 04,
O(Oy/Ox) with the remaining restriction that (q/O) - + vo. Since this expression
vanishes when = OO/Ox = 0, it then takes on its minimum value. Applying the
first derivative test for a minimum to this function then gives = oo/Ox = 0 q = 0,
v = -oz/oo. Usually,. workers sume that q is independent of and that V is
independent of and OO/Ox, and we will follow suit. With the indicated
sumption we have, always, V = -0/0, q , , 0. (2.3.24) Often this is specialized
more, with the sumption that q=k , O 0' k0, (2.3.25) which seems to be adequate
practically. Underlying (2.3.24) is the classical view that entropy is defined
using processes which are, at let approximately, reversible. It would not hurt
for you to think hard about this yourself, but it does at least seem dicult to
reconcile this with the idea that V can depend on and/or OO/Ox. The effect of
this is to sume that, at each particle, the entropy is given by the constitutive
equation applying to equilibria. For various other theories which are, in a similar
sense, local, therm dynamicists often use this sumption with some success. It is
called the pnnciple W local states or the hypothesis W local theodynamic
equilibum and other similar names. Often workers interested in viscoeltic effects
em- plw theories which are not local, in the temporal sense. For example, the
�If you wish to explore this more deeply, you might find it helpful first to study
Chapter 10. 2.3 Constitutive Theory for Thermoelastic Bars 27 stress at any
particular time depends on values of the stretch experienced at all previous
times. Here, such assumptions are commonly rejected. For example, one expert,
Rivlin [12] offers physical arguments to help explain why he considers them to
be unsound for use in connection with such theories. Various other experts
have made clear that they came to a similar conclusion. This will be discussed in
more detail in Chapter 10. It is not reasonable to infer from this that the reasons
that convinced one would be the samc as those that convince another. Obviously,
one needs some alternative, and, concerning this, there are some differences of
opinion. There are still different ideas about entropy, stemming from statistical
molecular theories, for example, which do not require the association with
reversible processes. Such theory also suggests a need for generalizing the
Clausius Duhem incquality. It would take a very lengthy discussion to elaborate
these remarks so we will not pursue it. With the specialization indicated, we
have what is generally regarded as thermoelasticity theory or, more properly, the
one-dimensional version of such theory. Such theory has been used,
successfully, to describe numerous phenomena. With a given by (2.3.21), the
equations of motion (2.3.8) become /) P=xx +f' (2.3.26) it being understood that
some appropriate prescription for f is to be given. In most situations, it is
reasonable to take f = 0. When exceptions are encountered, they are likely to
involve forces exerted by gravitational or electromagnetic fields and, in the
latter case, it is probable that more general kinds of constitutive equations are
needed. To obtain the temperature equation, we use (2.3.12) and note that with
our constitutive equations, oV=-o from which (2.3.27) Superficially, this is the
same as the equation (2.2.12) derived for rigid bars. However, here q depends
not only on 0, but also on A, so (2.3.26) and (2.3.27) are a coupled set of
equations for motion and temperature. Again, r needs to be specified and the
possibilities for this are well-covered by our discussion of rigid bars.
28 2. Constitutive Theory of Heat Transfer for Bars and Plates Sometimes

(2.3.21) is replaced by an alternative. Suppose we can invert (2.3.23) to get 0 =
f(r/, A). Then, express e as a function of A and r/, as indicated by = 0(, O) + Or/(,
O) = 0(A, fir/, A)) + f(r/, A)r/= z(A, r/). Mathematically, e is a Legendre
transform of and such transforms are used in various places in thermodynamics.
Then, by the chain rule, and & x O0 Of Of Oe , O0 o OO O f Of - OA =a. So,
instead of (2.3.21), we can use = (, = , (zs.8) 0 0V Various kinds of wave
propagation are considered to take place almost isentropically ( nearly constant),
and, for such processes, (2.3.28) is a convenient choice. Processes more nearly
isothermal are encountered in slow, quasi-static tests done at constant
temperature and, for these, (2.3.21) is more convenient. It is worth noting that,
while $(l, 0) and e(l, ) are, in the sense indicated, equivalent constitutive
equations, an equation of the form e = e(l, 0) gives a less complete description.
Suppose, for example, that this function is independent of A: e = e(0). (za.9)
This statement does in fact apply rather well to rio kinds of rubber long I is not
extremely large. When (2.3.29) holds, we have, using 2.4 Constitutive Theory
for Shearing of Plates 29 (2.3.24), .(o) dO -- - o�--o (0 + _ oo 0o This implies
that r/is of the form r/=f(O)+g(A),f'=d(O)/O. (2.3.30) Also, & - 0 = (0 + 0r/ = a+
0 00- = + Og'(A). or Also, where Or/ -0g'(X). (2.3.31) a = -0 = 0=h(0) -0g(X),
(2.3.32) h(O) -- (0) - Of(O). Given any function b of the form (2.3.32), we have
o =;b+0r/=;b-0=h-0h', which is a function only of 0. Clearly, we can also obtain
a and r/ from (2.3.32). However, from (2.3.29), there is no way to determine
g(A). Re- sponse of this kind is sometimes called "entropy elasticity" since, from
(2.3.31), a is associated primarily with changes in r/ and this indicates a
characteristic feature: at fixed A, a is proportional to 0. 2.4 Constitutive Theory
for Shearing of Plates By what is essentially a reinterpretation of the foregoing
theory, we can obtain the one-dimensional theory of shearing of plates. Here, we
think similarly of a reference configuration, associated with an interval on a line,
0 < x < L, (2.4.1)
30 2. Constitutive Theory of Heat Transfer for Bars and Plates the line now
being normal to the plate in its reference configuration. Motion involves a
displacement u, in a perpendicular direction, described by an equation of the
form u = u(x, t), (2.4.2) the analogue of the previous y. With it is associated the
velocity, Ou /t = , (2.4.3) and the analogue of the stretch A, the shear strain Ou '
= xx' (2.4.4) with - -- 0 in the reference configuration. There is a difference in
that, physically, A should be positive, while - can be positive or negative. As-
sociated with the shearing motion is a shear stress r analogous to a. The
equations of motion are of the form 0r p5 = xx + f' (2.4.5) f acting in the
direction of the displacement u or its opposite. Then, as analogues of (2.3.21),
(2.3.24), and (2.3.28), we have relations of the form or 0 = 0(v, 0), (2.4.6) oo r/-
00' (2.4.7) ov For a temperature equation, we have the copy of (2.3.27), Oq 0//=
xx + r. (2.4.8) One difference is that here a notion of material symmetry is of
some importance. For plates made of isotropic and some anisotropic materials, it
is reasonable to assume that q5 is an even function of % qS(h,, 0) = qS(-h,, 0).
(2.4.9) 2.5 Thermodynamic Experiments 31 Reversing the sign of 'amounts to
reversing the shear displacement. For, say, isotropic plates, one expects that this
will be associated with forces of the same magnitude but opposite directions (r -
-r and f - -f), keeping O(x, t) the same. So, (2.4.9) summarizes common
experience of this kind. One can encounter cases where it is unreasonable to
assume (2.4.9), in dealing with some kinds of crystal plates, for example. Later,
(2.4.9) will play an important role in discussions of Martensitic transformations,
phenomena which are rather common in crystalline solids. As is rather obvious,
various ideas and results used in analysing bars can be borrowed to analyze
plates and vice versa, and we will not belabor the obvious. 2.5 Thermodynamic
Experiments Clearly, it is important to know the form of the function q5 for
particular bars or plates and there is a rather common strategy for using experi-
ments to try to accomplish this. The same kinds of ideas are used in dealing
with three-dimensional thermoelasticity theory. Later, we will consider some
two- and three-dimensional theories. To be definite, we will discuss the bars. We
would like to induce the bar to be in various configurations in which A and 0
take on a variety of values, independent of position. Physically, we would like to
know that each of the pairs of values can be connected to the reference values (A
= 1, 0 = 0R) by a process which is, at least to a good approximation, reversible.
Theoretically, entropy changes are involved in a rather important way and we
need some assurance that it is physically well-defined. Commonly, workers try
three types of experiments: 1. measurements of thermal expansion; 2.
measurements of specific heat Co(O) in unstressed specimens at various
temperatures; 3. static mechanical experiments performed at constant
temperature, at a variety of temperatures. If all goes smoothly, this combination
can, in principle, suffice and for a first look we will assume that it does. Thermal
expansion refers to the deformation caused by a change of temperature in an
unloaded body. Theoretically, we would derive it by solving for A, oo er = (A,0)
= 0, (2.5.1) to get A = X(0). (2.5.2)
32 2. Constitutive Theory of Heat Transfer for Bars and Plates 2.5

Thermodynamic Experiments 33 By assumption, we have chosen our reference
configuration so that (0R) = 1. (2.5.3) At this stage the function b is unknown,
but we can observe the stretch (0); it should be a uniform stretch, varying
continuously with 0, for things to go smoothly. Also, as a check on reversibility,
we should check that we get the same (0) if we increase or decrease 0. Often,
thermal expansion is a small effect, so one finds some workers omitting this
experiment. However, it is sensible to understand the scheme before considering
such shortcuts. Turning to the measurement of Co(O), we are concerned with
changes in occurring when we keep a = 0 and change 0, hence with V(0) =
V((0), 0). (2.5.4) Conceptually, this is the same as measuring the specific heat
for a rigid bar, with 7(0) as its entropy function. By calorimetry, we can find (07
0Td) (2.5.5) Co(O):O =0 + . It is customary for workers making isothermal
mechanical measurements normally to take as a reference configuration an
unstresscd configuration at the temperature 0E at which the experiment is
performed. Relative to our fixed reference configuration, the material point at x
has moved to the position yE = (OE)x. (2.5.6) Adding loads then takes ye to y =
AEy = A(O)x = Ax, (2.5.7) A being what the experimentalist would term stretch.
What he means by stress is force divided by area in some unstressed
configuration. Suppose that this configuration is ours, that in the fixed reference
configuration. If not, we need to know the relation between the areas in order to
compare results which can involve another aspect of thermal expansion. Then,
with standard simple tension and compression tests, the experimentalist seeks to
determine relations of the form a = frAE, 0), f(1, 0) = 0, (2.5.8) for some range
of Ae and 0. For all to go smoothly, a should vary smoothly with AE and the
same relation should hold whether we are increasing or decreasing a. From this,
we obtain the so-called isothermal strain energy function, given by W(AE, 0B) =
f((, 0E) d, (2.5.9) with the properties that OW o'-- and that is vanishes when Az -
- 1, that is, when (2.5.10) W(1, OE) = O. (2.5.11) Given this, we can calculate
the function representing energy per unit reference length, W(A,O)=W(O), 0)
(0), (2.5.12) where we have used (2.5.7). Then, by the chain rule, OA -- OA OA
-- a. (2.5.13) Also, from (2.5.11) and (2.5.12), we have W(A, O) = O. (2.5.14)
Now, from (2.3.21) and (2.5.13), we should have so ow OA b = W(A, 0) + f(O).
(2.5.15) To determine f(O) we note that, if we set A = (0) and vary 0, W stays
zero and, of course, er = 0. Thus, bearing in mind (2.5.4), we have d(b = f'(O)
dO = -7(0) dO when er = 0. (2.5.16) So, given Co(O), from measurements of the
specific heat at zero stress, we integrate (2.5.5) giving 0 Co(i) d - a (2.5.17) with
a an arbitrary constant. Then, using (2.5.16), we integrate once more, to get f = -
ddv - aO - b, (2.5.18) where b is another integration constant. Physically, it is
unimportant what values we assign to a and b; it is only differences in entropy
and energy which are physically significant.
34 2. Constitutive Theory of Heat Transfer for Bars and Plates Intuitively, it is

clear that the program can fail for various reasons. Spec- imens may break,
buckle, or melt, for example. One can encounter phase transitions where
quantities of interest change in a discontinuous manner, thus causing difficulties.
Later, we will discuss some ideas for coping with them. It is worth bearing in
mind that while the conventional program discussed involves relatively simple
experiments, when they work, the program is not infallible. Particularly when
some mysterious difficulty is encountered, it is worth considering what other
kinds of experiments may be performed to help illumine the situation. Clearly,
similar ideas can be used for the plates. For these, if the material symmetry is
such that (2.4.9) applies, it is somewhat likely that the analoguc of thermal
expansion will not occur because r = 0 forces ' to be zero. As will later become
clear, this is not always the case. When (2.4.9) does not apply, the analogue of
thermal expansion will most likely occur, changes in temperature producing
shear when r = 0. In either case, one may well get changes in volume not
describable by our one-dimensional theory. Ideas similar to those used in this
chapter have been adopted to construct a great variety of three-dimensional
theories of materials too complicated to be discussed here. Often,
experimentalists and others interested in materials science do use one-
dimensional theories; we have simply looked at a few of these to illustrate
common types of thermodynamic reasoning used in formulating them. 2.6
Exercises For rough analyses of rubber bars, workers often use the so-called
Neo- Hookean theory, for which b is of the form ---- aO(A 2 q- 2/A -- 3) -- b[O
ln(O/c) -0 + c], where a, b, and c are positive constants. For Exercises 2.1 2.5,
use this form. 2.1. What does this form predict for thermal expansion? 2,2, 2,3,
What constitutive equation for a is appropriate for isothermal processes (0 =
const)? What constitutivc equation for a is appropriate for isentropic processes
(/= const)? 2.4. For isentropic processes, what is the strain energy function? 2.6
Exercises 35 2,5, From thermodynamic experiments on a material, we find that
the constitutive equation fits fairly well for a choice of the adjustable constants,
but needs some correction. The fit for specific heat is satisfactory. The strain
energy function fits, if we replace A by AE, and curve- fitting measurements of
thermal expansion gives (0) = 1 + k(O - OR) for the temperatures occurring in
the experiments, k being a constant. Work out the corrected constitutive equation
for 6, and determine how this affects 2.6. For bar theories, the quantity 5 - Oil
O(q/O) _ ri o Ot Ox is commonly considered to be a measure of dissipation. For
our theory of rigid bars, with O(q/O) q : k(O) xx ' r : [O(t) - O], k>O, c>O, what
can you say about the possibility of solutions of the temperature equation
(2.2.13) that involve no dissipation (5 = 0)? 2.7. Consider the graph of a smooth
function y -- y(x) and the tangent linc to it at a point (x, y = y()). Show that
points in the x-y plane lie above this line whenever their coordinates (x, y)
satisfy the inequality y - - - > 0, and below it when the opposite inequality holds.
Equilibrium Theory of Bars 3.1 Equilibrium of Bars Subjected to Dead Loads In

commonly used jargon, a dead loading device is one that applies a constant
force to some part of a specimen while leaving the part free to move. For
example, one might load a bar by hanging it, clamping the upper end so it cannot
move, and attaching weights to the lower end. Static experiments of this
general kind have been done for centuries on a great variety of solid materials as
is discussed in a lengthy article by Bell [13]. Typi- cally, the apparatus is
designed so one can add a small weight, allow it to come to equilibrium, then
add a little more weight, to determine experimentally how stress is related to
deformation. This is a rather standard way of approximating the condition of
dead loading on the lower end with tensile loadings. By incorporating levers, for
example, one can also apply compressive loads. So, for bars, this is one way of
attempting to perform isothermal mechanical measurements needed to determine
b(A, 8) experimentally. Naturally, one must exercise some judgment in
deciding whether the observations are compatible with the theory considered, in
this case our one-dimensional bar theory. Actually, such theory can handle some
phenomena which may seem to be outside its range. Thus, it is worthwhile to try
to obtain a better understanding as to what it can do, with an open mind. We now
return to the theory of thermodynamic stability discussed in Chapter 1. Roughly,
our thermodynamic system consists of the bar and the loading device in contact
with a heat bath at a constant temperature
38 3. Equilibrium Theory of Bars For a static analysis we are not concerned with
motions but deformations y = y(x). However, we can allow any which could
occur instantaneously in a motion. A similar remark applies to temperature
functions O(x) or /(x). The condition that the upper end is clamped limits the
possibilities. We represent this as the condition that y(0): 0. (3.1.1) This in turn
means that no work will be done on this end. From a dynamical point of view,
power is supplied to the other end by the fixed force, expressible in the form P =
k(�, t): -x/t (3.1.2) where X = -ky(L, t) + const., (3.1.3) k being a constant
measuring the size of the force. It is convenient to take this as the weight divided
by the reference cross-sectional area of the bar since we divided the bar energy
by this area. From (1.1.4), we have here our first example of a conservative
loading device. For static analysis, the dependence on t is irrelevant. In principle,
the bar's own weight will cause it to stretch a little; very little for the small bars
used in laboratory experiments. So, as is customary, we neglect such effects,
assuming that the body force f -- 0. Of course, it is understood that forces are
applied to the ends of the bar and not to its sides. Then, from the discussion in
Chapter 1, we expect the system to approach equilibrium, our situation being
covered by statement IV, with E here interpreted as the energy of the bar. The
relevant thermodynamic potential is then given by (1.3.5) or E x =E-OsS+x
(3.1.4) L = fo ( - OBI) dx - ky(L) and we are concerned with its variations. We
interpret this in much the same way as we did in the consideration of rigid bars.
For bar theory, we should have some constitutive equation, it being convenient
to use one of the form Oy = (, 1), - Ox' (3.1.5) This has the features noted in
(2.3.28). First, we want to know what conditions y = (x) and /= (x) must satisfy
in order to qualify as equilibrium configurations. All deformations must satisfy
(3.1.1). So, we consider functions of the form y(x) = + (3.1.6) v(x) = + 3.1
Equilibrium of Bars Subjected to Dead Loads 39 where/ is a small parameter and
the pair (Sy, &/) are any smooth functions of x such that 5y(0) = 0. (3.1.7) This
describes variations in the system. As before, we calculate the variation in E x by
regarding 5y and &/to be fixed, so E x reduces to a function of/ only, and taking
5E x = Ex(0 ). (3.1.8) Then, statement IV is interpreted as meaning that we
should have i. tSE x _> O, (3.1.9) for any admissible choice of 5y and 5/.
Assuming that all functions involved are smooth, we can differentiate under the
integral sign to get ( )] 6E x = - -- + - OB 51 dx - k6y(L), (3.1.10) Ox with
overbars denoting evaluation at the putative equilibrium state. From the general
theory, the stress P and temperature in this state are given by c _ c (3.1.11) We
then perform an integration by parts to replace O(Sy)Ox by 5y dx = Sy - xx 5y
dx, a standard procedure in such variational problems. So, using (3.1.7), we have
5E x = ( - O)&l - xx Y] dx 4- ( [= - k) 5y(L) (3.1.12) and interpret the criterion
for equilibrium as the condition/SE x _> 0. Note that, if/SE x were positive for
some choice of (&/, 5y), it would be negative for 5- = -&/, 5- = -Sy, another
allowable choice, so we must in fact have 5E x = 0 for all variations:
equivalently, we could take/ positive or negative. By arguments similar to those
used for rigid bars, we deduce that the equilibrium conditions are that 0 0 ==>
const., (3.1.13) Ox
40 3. Equilibrium Theory of Bars That is, the definition of thermodynamic

equilibrium implies that the temperature of the bar must reduce to that of the
heat bath, plus the conditions which could also be obtained from standard
reasoning in mechanics as conditions for static equilibrium. We have here one of
many examples reinforcing the view that, physically, the general theoretical
ideas of thermodynamic equilibrium are sensible. Also involved is the idea that
such equilibria may or may not be stable. For them to be stable (metastable),
they should correspond to absolute (relative) minimizers of E x. Most workers
are happy to make an assumption that makes such analyses easier and is not in
obvious disagreement with experience; namely that, for any value of A, s is a
strictly convex function of /. That is, for any A, 711 , and /2, e(A, Vl) - e(A, /2) -
(A, /2)(h - /2) _> 0. (3.1.14) The equality holds only if /2 = /1. Assuming this,
suppose that we choose /2 depending on A, so that 0__ (A, /2) = 0B. (3.1.15)
Then, the inequality gives e(/,/]1) -- OBI]I _ (/, 7]2) -- OB?]2 ---- (( , OB ).
(3.1.16) Now, suppose that wc were to find y = )(x) minimizing the potential F =
qS(A, 0) dx - ky(L), (3.1.17) so that L F _> " = b(, 0) dx - k)(L), (3.1.18) perhaps
with the proviso that A be close to . Then, using (3.1.16), we will have for the
same y(x) E x _> F _> " = x- (3.1.19) The last equality follows from the fact that
any minimizer will have 5E x = 0, implying that its temperature must be 0. So,
many workers will use the Helmholtz free ener in place of the ballistic free ener
in applying the stability criterion and it does make the analysis eier. As is rather
obvious and eily verified, (3.1.13) also gives the conditions obtaining from 5F =
0. One test for a relative minimum is the second derivative test, often used in
such contexts. Represent y(x) in (3.1.6) to get F a function of , and calculate ff
5F = F"(0) = 0& ax ] 3.1 Equilibrium of Bars Subjected to Dead Loads 41 1 k M
k m 3. FIGURE 3.1. A simple nonmonotone stress-stretch curve, with horizontal
tangents at Am and Am. where, as before, the overbar denotes evaluation at the
equilibrium state. For a relative minimum this should be nonnegative for any
choice of 5y such that 5y(O) = 0. From this, it follows that we must have
throughout the bar, 52q5 OB) _ O. (3.1.21) Now, there are two possibilities. One
is that the equation of state satisfies 02b/0A 2 > 0 for all A at this temperature, so
a is a monotonically increasing function of A. Then, there is at most one value
of A = X satising a(X, 0) = k, a given constant. Assuming there is one, then for
this value, one gets the homogeneous deformation satisfying (3.1.1). Also, one
can show that it is the one and only minimizer of F. Physically, the theory is
bound to fail for one re,on or another if k gets too large. This calls for some
judgment. The other possibiliW is that the function a(A,0s) is not everywhere a
monotonically increing function of A, a possibility which is seriously
considered. A relatively simple possibility is to have a graph of the kind shown
in Fig. 3.1. With a = 0/0A, it is ey to see that the graph of at 0 = 0 h the form
shown in Fig. 3.2. It h points of inflection at Am and AM and fails to be convex.
Another possibility is a graph of a(A, 0) like that shown in Fig. 3.3, for which &
h a graph at 0 diagrammed in Fig. 3.4, exhibiting a second minimum, which
could be aolute or relative minimum.
42 3. Equilibrium Theory of Bars 3.1 Equilibrium of Bars Subjected to Dead

Loads 43 1 'M Lm ' FIGURE 3.2. The graph of b corresponding to Fig. 3.1, with
points of inflection at X4 and X,. 1 ;% , , FIGURE 3.4. The graph b
corresponding to Fig. 3.3. For either of these situations, one can find the absolute
minimizers of F, the most stable configurations. With (3.1.1), we have so we can
write y(L) = / dx = Adx, (3.1.22) L F: J(o [�(A, 0B) - kA] dx. (3.1.23) Clearly,
the integral will be smallest if the integrand is everywhere smallest which will
occur at A = X such that FIGURE 3.3. A stress-stretch curve similar to that in
Fig. 3.1, but intersecting the a-axis at three places, X = 1, Xo, and Xx. �(A,0B)-
kA �(X, 0) - kX (3.1.24) for all A. Of course, the first derivative test gives a(X,
0) - 0� _ k, (3.1.25) where the overbar is interpreted as before. So, on the graph
of b we locate the points with slope k. Then, the inequality means that the graph
of b must be everywhere above the tangent line drawn through this point; we
went through a mathematically identical consideration before in the con-
siderations of rigid bars. Choose a constant satisfying these conditions, and y -- x
will be an admissible deformation minimizing F. Theoretically, this is the best
that can be done in terms of stability. Somewhat stable (metastable)
configurations are not ruled out by these considerations. In terms of a particular
theory, the distinction between stable and metastable
44 3. Equilibrium Theory of Bars FIGURE 3.5. The common tangent line added
to the graph in Fig. 3.4, kxt denoting its slope, X1 i and X2 M denoting values of
X at the points of tangency. is as clear as the distinction between absolute and
relative minima. How- ever, physically the distinction is more artificial. For
example, it is intuitively clear that compressive loads can cause a bar to buckle
and some of the configurations we here call stable are, no doubt, physically
unstable for this reason. To explore this, we would need a more general theory,
capable of describing the buckled configurations and this is not the only
possibility omitted from our considerations. More accurately, "stable" means the
most stable of the possibilities we choose to consider and one needs to exercise
good judgment in deciding which to consider. Now, for graphs of 0 of the kind
indicated, there is a particular value of k for which two values of X qualify in
that they have a common tangent line below the graph, say at k = kM. Then,
�(X,0B) - b(X, 0B) - kM(X -- X) = 0. (3.1.26) Now, for any value of k we
know what it means for (3.1.24) and (3.1.25) to be satisfied by some value A =
X: the graph of �(A, 0) must lie in the region above the tangent line, at A = X.
Geometrically, it is clear from the graph that this will occur for some X such that
X < X when k < kM, (3.1.27) and X > X when k > k. (3.1.28) Thus except when
k = kM, the most stable configuration is obtained by setting y = Xx, (3.1.29) 3.1
Equilibrium of Bars Subjected to Dead Loads 45 1 "1 "3 '2 ' FIGURE 3.6. The
stress-stretch curve in Fig. 3.1, hatchings indicating two areas associated with a
load line a = k. where X is the (unique) value of X determined by these
considerations. Clearly, this changes in a discontinuous manner as k passes
through the value kx. There is another way of picturing the situation in terms of
the graph of a(X, 0B). We are concerned with values of k such that the line a = k
intersects this graph in three places, as indicated by Fig. 3.6. Let A denote the
hatched area indicated between X and Xa. It is given by Xa A = rrd -- k(X1 --
X3) = gS(X3, OB) -- ((Xl, OB) -- k(Xl -- Similarly, the other hatched area, A2,
is given by -A2 = qb(X2, OB) -- qb(X3, OB) -- k(X2 -- X3). Thus, A1 - A2 =
qb(X2, OB) - (b(X., OB) - k(X2 -- (3.1.30) Comparing this with (3.1.26), we see
that A1 = A2 when k = kM. (3.1.31) This is the so-called equal area rule, first
introduced by Maxwell in a mathematically similar analysis of van der Waals's
fluids. It turns up in various physical problems. For k < kM, one has X ---- A and
A > A2. For k > kM, X=X2 andA2 >Ax. We have presented reasoning that is
very commonly accepted by workers interested in such phenomena. What is not
widely appreciated is that it
46 3. 3.1 Equilibrium of Bars Subjected to Dead Loads 47 Equilibrium Theory

of Bars FIGURE 3.7. Loci of stable configurations, dead-loading device. for the
graph in Fig. 3.1, in a involves a rather subtle tacit assumption, pointed out by
Kahl [14]. By modifying this one can come to different conclusions. We will
ignore this complication, our aim being more to illustrate common practices.
Now, for the moment, suppose that the bar always chooses its most stable
configuration as one increases k by small increments, starting from k = 0. It is
then highly unlikely that one will hit the value k -- kM exactly. However, one
will reach a point where adding a small load moves k through thc critical value
kl, producing a sudden increase in the stretch, something many would regard as
a phase transition. So, one will obtain data points like those shown in Fig. 3.7
and one should obtain essentially the same points when one similarly takes off
weights for the thermoelastic model to apply, as we here interpret it. So, we
simply do not get any equilibrium data points for an interval of values of A.
However, granted thc reversibility, we can use (3.1.26) to estimate the change in
b associated with thc transition which is helpful in the effort to determine this
function experimentally. When the assumptions apply, the sudden jump provides
an example of a process that is reversible but not reasonably considered to be
quasi-static. As a matter of experience, solids are rather prone to remain in
metastable configurations, so the assumption just made may well fail to apply.
Then, motivated to some degree by dynamical considerations discussed in
Chapter 1, we accept one limitation on what can happen in time: RULE: With k
and OB fixed, E x may change to a lower value but it cannot change to a higher
value. From the second derivative test, we have a minimal requirement for sta-
bility: configurations involving values of X such that da/dX < 0 are too 1 'M 'm '
FIGURE 3.8. Loci of metastable configurations, for the graph in Fig. 3.1, in a
dead-loading device. unstable to be observed in the experiments considered.
Indicating these by a broken curve, we have the effect shown in Fig. 3.8.
Following Gibbs, many refer to unstable regimes such as that occurring here
when d/dA 0 as spinoidal regimes. Physically, stretches passing the second
derivative test may or may not be stable enough to be observed. However, in
loading up from k -- 0, one is likely to stay on the left full curve in Fig. 3.9 until
k becomes somewhat larger than kM. Then there is a transition to the right
curve, following this up as k increases, obtaining data points similar to those
discussed before. If one then decreases k, as suggested in Fig. 3.9, the
deformation cannot retrace its path, as this would violate the above rule. One
must stay on the right branch at least until k reaches the value k. It may well stay
here until k reaches a lower value, then shift to the more stable left branch. This
gives rise to the phenomenon of hysteresis, with loading and unloading curves
forming a loop like that shown in Fig. 3.9. Rather commonly, one sees effects of
this kind accompanying phase transition in solids. The values of a at which
transitions occur may or may not be very reproducible; they may be different for
seemingly identical specimens loaded in the same device, for example. One
sees a little more of the graph of a(A, 0B) than previously. On the other hand,
there is no good way to connect values of b on the two branches from such data
alone, since the change of b accompanying a transition only satisfies an
inequality, not an equation. By assumption, the left branch contains a point
where a -- 0. It is possible that the right branch does also. If so, we might start on
the left, load up enough to induce a transition, then unload, obtaining what seems
to be permanent deformation. This particular process is not reversible. To justify
the notion that our theory applies, one should try to find some other
48 3. Equilibrium Theory of Bars FIGURE 3.9. Hysteresis loop encountered

when loads are increased, then decreased, involving metastable configurations.
The arrows indicate where the load is being increased or decreased. process
connecting these two stretches, at 9 -- 9u, which is, at least to a good
approximation, reversible. In this, 9 may well change as long as it begins and
ends at the value 9. In so-called semicrystalline polymers, one can sometimes
obtain such processes by taking the polymer to a higher temperature, stretching
it, and cooling it, holding the stretch fixed, removing the loads, then reversing
this process. For these, heating the more stretched state when unloaded causes a
sudden shift back to the reference configuration. The phenomenon is exploited in
"heat-shrink" insulating material and in sealing up poultry in polymer coverings,
for example. At least qualitatively, one can model such phenomena in the
following way. Assume that, at a sufficiently high temperature, b is a convex
function of A, but at lower temperatures it is more like that pictured in Fig. 3.4,
having two minima, providing two unstressed configurations which are at least
metastable. Behavior roughly like that predicted by such models is observed in
various high polymers and is exploited in various applications. It seems to have
first been exploited in making nylon fibers: inducing nylon to be in a more
stretched state makes the fiber stronger. Some other kinds of models for
describing such phenomena are discussed by different authors in reference [15],
for example. In this discussion we have assumed, rather tacitly, that at each
value of k, A is independent of x. Actually, there are possibilities for having A
take on different values in different parts of the bar. Shortly, we will be forced to
consider this possibility. Here, we have examples of the kinds of difficulties that
can arise in trying to use experiments to determine b(A, 9), associated with the
occurrence of phase transitions. It is worth bearing in mind that it is not
necessary to use 3.1 Equilibrium of Bars Subjected to Dead Loads 49 only the
standard kinds of experiments discussed earlier. An ingenious person knowing
something about the difficulties encountered may find another way to obtain
some valuable information. Now, let us return to (3.1.25) and consider what
happens when we change the ambient temperature 9 a little, assuming that the
bar continues to be in the stable configuration. Generally, the graph of b versus
A will change a little since b depends on . Physically, one will still get a
transition, but --M kM, 1 and 2 will become functions of 9, changing as 9 does.
Bearing this in mind, we can differentiate (3.1.26) with respect to 9, giving 0=
[a(X,0.)- kM] d- [a(2 ,0.)- kM] dO. However, from the way things are defined,
the two values of are both equal to kM, so this simplifies to --M --M &2 - - Now,
write --M --M A/= /(A 2 , 0) - /(A 1 , 0) = Qi/O. (3.1.33) Here QL, called the
latent heat, is the heat supplied to the bar when the --M stretch changes from 7 to
A 2 in a reversible process. It is not easy to measure with the loading device in
the picture. However, if the bar always remains in the most stable configuration
the transition should be close to reversible, if we load in order that it occurs for k
very close to kM. Then, by doing experiments at different temperatures, we can
estimate the functions kM(0B), /(0B) and 2M(0) and calculate QL and At/.
When there is some hysteresis but fairly reproducible transition conditions, one
can get two curves in the or- 0 plane, one indicating where transforms to 2, the
other where 2 transforms to 1. One finds workers using these to make educated
guesses as to the quantities needed here. Of course, we can rewrite (3.1.32) and
(3.1.33) in the form do' Q - (3.1.34) dO OAA' where we have written a in place
of kM and so on, to conform better to convention. This is sometimes called the
Clausius Clapeyron equation, the analogue of an equation with the same name
which has long been used in connection with phase transitions in fluids. It is
useful in connecting the values of in the two phases. Clearly, one can do
essentially the same analysis for the theory of plates mentioned earlier. We will
discuss this later.
50 3. Equilibrium Theory of Bars 3.2 Equilibrium Theory of Bars in Hard

Devices 51 3.2 Equilibrium Theory of Bars in Hard Devices In commonly used
jargon, a hard device is a device sturdy enough to hold parts of a specimen in
fixed positions. Various testing machines are designed to do this, at least to a
good approximation. For our bars, the aim is to fix the end positions so we have,
say, y(o) = o, > 0 (3.2.x) where a is a parameter we can now control. As before,
we assume no body forces act, (f = 0) so, as long as a is fixed, no work is done
on the bar. Therefore, it can be considered as a mechanically isolated system. As
before, we consider it to be in contact with a heat bath at a constant temperature
0B. From the discussion in Chapter 1, the situation is covered by statement III
and we should use as thermodynamic potential the ballistic free energy indicated
by (1.3.3), with E and $ the energy and entropy of the bar, respectively.
However, we follow the common practice of using instead the Helmholtz free
energy, L F = 4,(A, OB)dx. (3.2.2) This and the previous F are defined
differently, but this should cause no confusion. Also, we will simplify notation
by writing 0 in place of 0B. Of course, it is to be understood that all
deformations allowed must satisfy (3.2.1), so A must satisfy L a = y(L) = fo dx.
(3.2.3) To determine the possible equilibria, we proceed as before to get 6 F = dx
= dx 55 k ox } k } L C bydx +by C =-- xx (3.2.4) f0 L = - xx 6ydx = 0, the
overbar denoting evaluation at y = (x), the putative equilibrium state. The
calculation presumes some smoothness of the functions involved, and we will
need to reconsider this later. By reasoning now familiar, we can then conclude
that Ox 0 k const., (3.2.5) but this constant is now not given. Similarly, one can,
as before, use the second derivative test to get the condition 024' > 0 (3.2.6) OA2
- as a minimal requirement for stability. Now, if at the temperature considered 4,
is a convex function of A, (3.2.6) will hold for any choice of A. Then, with a a
monotonically increasing function of A, (3.2.5) cannot hold for two different
values of A, so must be constant throughout the bar. Then, from (3.2.1), we must
have X = a/L, = axiL. (3.2.7) Putting this value into the constitutive equation for
a, we can determine the value of the constant k. Or, if we measure X and k, or
the equivalent, we can use the information on such isothermal mechanical
experiments to help determine the function 4,(A, 0), discussed before. As is clear
from our study relating to dead-load devices, (3.2.5) can be satisfied for more
than one value of A when is not a convex function of A, at least for some values
of k. Consider the possibility that just one value of A occurs in the bar. Then
(3.2.7) must hold and, for some values of a/L, (3.2.6) will fail to hold. Such
configurations cannot even be mettable. So we must consider the possibility that
X is not constant throughout the bar. It is rather obvious that, for constitutive
equations anything like those considered before, X cannot vary smoothly with x
and satisfy (3.2.5). For (x) to be discontinuous would mean that the bar moves
through itself, which is unreonable, or that it breaks, a possibility which we will
try to exclude, if we can. It will be considered later, in Chapter 7. Let us
reconsider 5F, allowing for the possibility that X(x) and OSy/Ox are continuous
except at x = < L, with 5y remaining continuous at x = . Then, we calculate that
d dx + - =-- : - dx - 5y dx - - = 0, where + is the limit approached by x , with x >
, and is the limit approached from the other side. As before, we can argue that
(3.2.5) must hold in each of the two inteals by considering 5y nishing at the end
points, so = k + in one interval, = k- in the other. Putting this back in 5F, we see
that we mt have k + = k-, so (3.2.5) mt hold throughout
52 3. Equilibrium Theory of Bars '1 3,=a/L 2 FIGURE 3.10. With the graph in
Fig. 3.1, indicating quantities of interest when the overall stretch = all falls in an
unstable range. the bar. Similar arguments apply if such discontinuities occur at
more than one place. Also, by rather similar arguments, (3.2.6) must hold where
X is continuous. It is rather obvious that these conditions should hold for the
forces to remain balanced. From this viewpoint, we are checking that the
definitions of thermodynamic equilibrium are consistent with ideas of
mechanical equilibrium. Consider a graph of or(A, 0) as we considered before
and a value all in the range of concern, as shown in Fig. 3.10. Although we do
not know the value of k, we cannot succeed unless the line cr = k gives us two
values of , l, and X2 in the sketch, both satisfying (3.2.6). If it does, we can put
the stretch equal to Xz in some part, X2 in the other, arranging that is
continuous. For example, for some = bL, 0 < b < 1, set y = Xix, 0 < x < bL,
(3.2.8) y=X2(x-bL)+XbL, bL<x<L. Then, (3.2.3) gives from which 12 ---- [Xlb
q- X2(1 - b)]L, (3.2.9) b - (X2 - a/�) (X2 -- Xl) (3.2.10) We want to ascertain
that b lies between 0 and 1, which will be true if _< a/L <_ X2. (3.2.11) From the
figure, this is clearly true if A = all lies in the interval where oq2(/)/oq. 2 < O.
However, such configurations are possible when it does not. 3.2 Equilibrium
Theory of Bars in Hard Devices 53 In the graph of rr they are possible as long as
_< a/L _< , (3.2.12) with A and A denoting places where the horizontal tangents
to the graph again intersect the graph, so this whole range is worth considering.
For those configurations, it is easy to use (3.2.2) to calculate that (3.2.13) Of
course, the most stable of these will be those for which F has the smallest value,
for 0 and all fixed. Here, we have our first example of the possibility of an end-
point minimum. Physically, b and 1 - b cannot take on negative values. Possibly,
a configuration with b = I minimizes F, and we then cannot allow variations
increasing b. Similarly, variations in b cannot decrease b, when b = 0. When the
inequalities in (3.2.12) are strict, it is easy to see that we can get configurations
of the kind considered for values of k in an interval, so we can vary this,
producing variations in , 2, and b. From (3.2.13), we have, for the differential of
F dF: L b 11 dX + �(X, 0) db+ (1 - b) 22 dX2 - �(X2, 0) db. (3.2.14) We
already know that, for some value of k, we must have and, from (3.2.9), we must
have - k, bdX + (1 - b) dX2 = (X2 - Xl)db. Using these, we can simplify
(3.2.14), to get the condition for a minimum dF = L[�(X,0) - �(X2,0) - k(X1 -
X2)] db > O. (3.2.15) There are then three possibilities. For b = 0 to qualify, we
can only have db> 0, so we might have b = 0, qS(X, 0) - 5(X2, 0) - k(X1 - X2) 0.
(3.2.16) Similarly, we might have b = , �(X, 0) - 0(X2, 0) - k(X - X2) 5 0.
(3.2A7) Finally, for other values of b, db can be positive or negative, giving 0 <
6 < , �(X, 0) - 0(X2, 0) - k(X - X2) = 0 (a.2.8)
54 3. Equilibrium Theory of Bars and, from (3.1.24), this puts us on the Maxwell
line, with k = k, X = A 1 , X 2 = A 2 , this being determined by the equal area
rule. In these terms, (3.2.16) trans- lates to b = 0, A < A2, (3.2.19) and (3.2.17)
becomes b = 1, A1 > A2, (3.2.20) with A and A2 the areas discussed in Section
3.1. With these results, it is easy to determine that the most stable configurations
are given by Z --M b=0 when >A2 , (3.2.21) a --M b=l when (A , --M a -- b is
given by (3.2.10) with 1 = 1 , 2 = when . So, again, the Mwell line plws an
important role. The most stable configurations are thus indicated by Fig. 3.5. If
the bar alwws chooses its most stable configurations, it should follow this path
whether a is being increded or decreded, the stretch becoming discontinuous, to
attain the desired overall stretch when necessaw. Again, solids are rather prone
to "hang up" in mettable configurations d we m W well get one to take on a
variety of different mettable configurations depending on what we have done to
it. Changing b slightly only changes F slightly. However, it causes some little
part of the material to change its state quite significantly. If the two states are
separated by a high ener barrier, such interfaces may well not move, leaving us
with configurations that are really rather stable, although the ener would
decrede if the interface would move. For example, we might attain a stable
configuration of the kind in (3.2.21) involving a phe mixture. If we hold a fixed
d change 0 a little, one can see that b should change to adjust to the new Mwell
line, but experience indicates that it might not. Any criterion stronger than
(3.2.6) is likely to exclude such possibilities. Again, there is an accepted rule,
governing what can happen, similar to that discussed in Section 3.1. RULE:
With 0 and a fixed, it is possible that the bar's configuration will change to
another if, and only if, the newer configuration has a smaller value of F. For
example, as we start increasing a from an initially unstressed, homogeneous
configuration, it is not unlikely to continue to deform homoge- neously until all
becomes somewhat larger than X1M. The corresponding 3.2 Equilibrium Theory
of Bars in Hard Devices 55 k c k FIGURE 3.11. As the bar shifts from a
metastable configuration, in a hard device, stress generally jumps, to the
Maxwell line, with a = k4. stress will then get larger than kM. A reasonable
possibility is that, at some point, it will change to the most stable configuration.
When it does, the stress will drop to the value kM and, from the rule, this
process is not reversible. What we then see is a path of the kind shown in Fig.
3.11. Often, one does see a drop in stress more or less like this as the "phase
mixture" first forms. To try to decide whether our theory may continue to apply,
we would like to know whether there is another way of moving from the initial
state to this end state by a reversible process. This could involve intermediate
changes of temperature, and so on. This kind of problem is not routine, so an
experimentalist probing it needs to exercise some inge- nuity. As one increases a
from this point, one might stay on the Maxwell line until all reaches the value
X2 M. However, the rule does not exclude the possibility that a change of a
again puts the bar in another metastable configuration, perhaps followed by
another drop back to the Maxwell line. Said differently, equilibrium theory does
not supply very definite predictions about metastable configurations. Other
kinds of theory, for example, dynamical theory, sometimes do better, but our
ability to make reliable predictions about such phenomena is very limited. In
any event, it is clear that, theoretically, the behavior of bars in hard and soft
devices can be rather different, and this is consistent with experience. Also, we
have learned that there are rather subtle differences between the function er(A, 0)
and the relations between er and A which may be observed in experiment.
Phenomena of this kind do complicate the experimental program discussed in
Section 2.5 but, to some degree, we can cope with them.
56 3. Equilibrium Theory of Bars 3.3 Exercises 3.1. Consider the constitutive

equation for rubber used in Exercise 2.1 2.5. Suppose that we start with the bar
in equilibrium, with X = 1, 0 -- 00, then cause it to deform in an isentropic
process, to get a to be a constant tensile stress. Derive a formula for the
corresponding change in temperature and determine whether the bar becomes
hotter or colder. Roughly, this describes what should happen if the bar is
stretched quite rapidly. Quickly stretch a rubber band and touch it to your lip and
see if you experience what you predicted. 3.2. For the same material, we now
clamp one end and hang a weight on the other, to dead load it, at room
temperature, and let it come to equilibrium. Then we increase the ambient
temperature and let it come to equilibrium at this temperature, without changing
the load. Theoretically, should this heating produce an increase or decrease in
the length of the bar? Try to design and carry out a simple experiment on a
rubber band to check your prediction. 3.3. For a smooth function y(x), defined
for all x, show that the following two conditions are equivalent: (a) Fo ,t x, "(x)
> O. (b) For all choices of x and x2, y(xl)-y(x2)- y(x2)(xx-x2) _ 0. For Exercises
3.4 3.7, suppose that, at a temperature taken as the reference for some bars, the
strain energy functions for this all have the form W(A) - a(A - 1) b(A - 1) c(A-
1) 4 2 + 3 + 4 ' where a, b, and c are constants. To simplify considerations, you
can assume that this applies for -cc < A < cc, although this is physically
unrealistic. 3.4. For what values of the constants is W(A) a convex function? 3.5.
For what values of the constants does W(A) fail to be convex, but have the
property that a -- 0 only when A = 17 3.6. For what values of the constants are
there two values of A for which a = 0, both passing the second derivative test for
stability in a deal- loading device at zero load? 3.7. For what values of the
constants are there two values of A for which a -- 0, both being stable equilibria,
when the bar is considered to be dead-loaded? 4 Equilibrium Theory of Plates
4.1 Martensitic Transformations The previous theory can be adapted, in an
obvious way, to the one- dimensional theory of shear in plates. However, the
latter does better than the former in illustrating some phenomena which are
rather common in crystals, called Martensitic transformations. Here special
kinds of material symmetry are important. With our plates, we can have this
described by �(% 0) = �(-% 0), (4.1.1) as was discussed before. In this
context, two pictures serve as representative. For the first, the graph of � versus
? changes with 0 as indicated in Fig. 4.1. That is, it is convex at higher
temperatures, with a minimum at ? = 0, this being replaced by minima at f = :kf0
when 0 < 0c, the value of f0 depending on 0, and approaching zero as 0 - 0c. Of
course, it is the material symmetry that forces b to have a minimum at -fro if it
has one at fro. For 0 > 0, the minimum at f = 0 is associated with a phase called
Austenitc. The minima at f = :kf0 0 for 0 < 0 are associated with "twin" phases,
called Martensite. In real crystals, Austenitc is, typically, a crystal configuration
with greater symmetry than the Martensite phases. The Martensite phases have
comparable symmetry. For example, one might be a mirror image of the other.
Here, the minimizing values of f depend continuously on 0. If measurements
indicate this and there is no latent heat associated with the transition at 0 = 0,
these are what workers are likely to call second-order phase transitions. The
other picture has the graphs changing as indicated in Fig. 4.2.
58 4. Equilibrium Theory of Plates [,// e > e c 0<0c % 70 FIGURE 4.1. Sketch

showing the shape of the graph of qb vs. f for a typical second-order transition,
at temperatures near the transition temperature 0c, where f!-v = 0 at f = 0. The
line indicates where f: 0. The curves have been displaced om each other
vertically, to make the picture clearer. Again ? = 0 is associated with Austenite,
+70 with Martensite. For 0 near 0c, we have minima corresponding to Austenite
and Martensite, one or the other being a relative minimum depending on the
value of 0. Here, 0c denotes the critical value of 0 at which 6 has three absolute
minima. As before, 70 depends on 0, representing the analogue of thermal
expansion in bars. However, unlike the previous case, we never have % = 0. As
we reduce 0 through the value 0c the absolute minimum changes in a
discontinuous manner, from ? = 0 to ? -- +70 and, typically, there will be some
latent heat associated with this. Here, thermal expansion occurs in a dramatic
way. This is a rather typical picture of what workers would call a first-order
Martensitic transformation. These are more common than those of second- order.
Martensitic transformations can involve various kinds of changes in crystal
symmetry. Workers often use the theory of Landau [16] to estimate whether a
particular kind of symmetry change is likely to occur as a second- order
transition. Originally, such transitions were discovered in steels, associated with
changes of composition. One old way of making steel involves putting some
carbon into iron, a cubic crystal. If the carbon content is low enough, one still
gets cubic crystals, but when the content is sufficiently high, one gets tetragonal
crystals. To analyze this, one needs to introduce additional variables to describe
thc amounts of the different ingredients. After such revision, one again uses the
general ideas of Gibbs to formulate criteria for stability of equilibrium, as will be
discussed later. Now, for the problem at hand, stability of the plate under dead
loading can be formulated by copying the anlysis for bars. Consider one face to
be 4.1 Martensitic Transformations 59 x o = o c -7o 7o FIGURE 4.2. Sketch
analogous to Fig. 4.1, for a typical first-order transition. Here, 0c is the value of
0 at which qb takes on its minimum value at three places. Upon cooling from
higher temperatures, the graph first acquires points of inflection at 0 = 02, then
gets relative minima at f = firfro, which become absolute minima for 0 < 0c. At 0
= 0z, the relative minimum at f = 0 disappears, to become a relative maximum at
lower temperatures. Bear in mind that 9o has different values at different
temperatures, as suggested by the sketch. held fixed, giving the boundary
condition u(0) = 0. (4.1.2) The other face is to be subjected to a constant shear
force per unit area, k denoting its magnitude. As before, we have the
arrangement in contact with a heat bath and, taking the usual short-cut, we
consider this to be the temperature of the plate. Then, from the analogue of
(3.1.17), we have L F = / 6(7, O)dx- ku(L) (4.1.3) as the thermodynamic
potential, whose absolute or relative minima correspond to stable or metastable
equilibria. Recall that the shear stress - and entropy density z/are given by ' = ' /-
00' (4.1.4) We might reconsider one point learned from our study of bars in hard
devices. It may be reasonable to allow for the possibility that ? = Ou/Ox
60 4. Equilibrium Theory of Plates could be discontinuous but, for the same

reasons as before, we want u(x) to be continuous. As before, we get, as a
condition for equilibrium, that - 07 - k. (4.1.5) Here, we have not added overbars
to denote evaluation at the equilibrium state: it should be sufficiently familiar to
make this unnecessary. Similarly, at least where ? is continuous, the second
derivative test for a minimum applies, giving - > O. (4.1.6) Oh '2 Oh' - Also, we
can borrow the previous geometrical considerations of stability relating to the
graph of ;b versus % That is, on this graph, we find the tangent line(s) with slope
k. If, at such a point, the entire graph lies in the half-plane above the line, the
corresponding value(s) of h` generate stable configurations. For metastable
configurations, only points on the graph near the point in question need lie in
this half-plane. At high temperatures, where b is a convex function of % the
equilibria are unique and stable. In terms of the graphs of b, the geometrical
picture of stability is similar to that for the bars. Given k, locate the point(s)
where the tangent line(s) have this slope. For the corresponding values of % we
can divide them into three sets. Unstable equilibria are of no interest. This
includes values of h` for which 02;b/0h' < 0, or some with 02;b/0h' = 0. What is
really relevant is whether any nearby points on the graph lie below the tangent
line. If there are such points arbitrarily close, they correspond to unstable
equilibria. If the whole graph lies above the tangent line, the corresponding value
of h' can occur in a stable configuration. When there is more than one stable
configuration, one can have either the homogeneous configurations with h' equal
to one of these, or a phase mixture when h' takes on the different values in
different parts of the plate. For metastable equilibria, it is still important that
points on the graph lie above the tangent line, but only that part of it which is
associated with values of h' sufficiently close to the value considered.
Observations indicate that phase mixtures involving such metastable values of h'
do occur. For example, for ;b behaving as indicated in Fig. 4.1, the unloaded
configuration has ? = 0 as the only equilbrium configuration for 0 _> 0c and it
is stable. For < c this is unstable but 4-70 both qualify as stable. One can then
construct an infinite number of stable phase mixtures with h` = % in some
subintervals, h` = -% in the remainder. For rather obvious reasons the two phases
are sometimes called twins, the mixture forming twinned Martensite. This can
and should be done in such a way that u(x) 4.1 Martensitic Transformations 61 is
continuous. For example, we could take -h`0x, 0 < x < L, u(x): h`(x -- L1) - h'L1,
L1 < x < L2, -h'(x - L2) -k h'(L2 - 2L1), L < x < L. (4.1.7) where L1 and L2 are
any numbers satisfying O<L<L2<L. Such configurations often occur
spontaneously as one cools Austenite to obtain Martensite. The second sequence
of pictures, in Fig. 4.2, becomes more complicated for near 9c where both
Austenite and Martensite are at least metastable and, at 0 = 9c, both are stable.
Theoretically, one can then construct phase mixtures involving Austenite and
twinned Martensite, which are metastable near = and stable at = 0. In real
crystals, one does see Austenite and twinned Martensite occurring in the same
specimen, as suggested by this. Often, one sees regions where the twins occur
as parallel planes, as suggested by one-dimensional theory. However, the in-
terfaces between Austenite and Martensite generally have quite a different
direction, so it is necessary to use three-dimensional theory to do realistic
analyses of these. There is another matter which is one of some interest. Suppose
that one has twinned Martensite and a shear stress is applied to it as a small dead
load, with k > 0, say. On the graph of ;b, this will give tangent lines with this
slope at values of % one near h`0, the other near -h'0- It is easy to see that, for
the one near -h'0, the graph of q lies partly below the tangent line, so this is now
only roetastable. Similarly, one sees that the one near % remains stable. If one
increases k sufficiently, that closer to -h`0 becomes unstable, so, for some
intermediate value of k, the twinned configuration must shift to the more stable
homogeneous configuration. Me- chanical treatments like this are sometimes
used to eliminate twins which can be undesirable for some applications. This
trick was discovered during World War II. The Allies, needing quartz for
piezoelectric crystals, were forced to use what occurred naturally in France. This
contained so-called Dauphin twins which affected the performance of the
crystals. This is not really quite what experts mean by twinned Martensite, but
the basic idea is similar. With some rather elementary theory, eventually
published by L.A. Thomas and W.A. Wooster [17] they worked out schemes for
loading to maximize the energy differences which were used successfully to
obtain better crystals. Later, similar treatments were, and still are, used on vari-
ous other kinds of twinned crystals. The experience is that it does not work if the
loads are too small, again indicating some tendency for such phase mixtures to
"hang up" in metastable configurations. So, one makes the loads exceed a critical
value, determined empirically. There is no reliable theory for determining this,
as far as I know.
62 4. Equilibrium Theory of Plates Later, various workers became interested in

alloys exhibiting shape memory effects. These contain phase mixtures of
Austenite and Martensite, with a morphology easily changed in a rather
reversible way by the application of loads or temperature changes. Wrap a wire
around your finger and it will seem to deform permanently, as would a soft
copper wire. However, unlike the latter, one can get it to spring back to its
original form by raising the temperature sufficiently. Solid-state engines have
been made which involve alternating the temperature between values above and
below the transition temperature and various other kinds of devices are being
developed by entrepreneurs. The transformations do bear some resemblance to
what occurs in steels, for example, but in the latter, processes changing the
morphology tend to be far from reversible. With the structural metals, the
metallurgist tries to "lock in" morphologies, to attain desired features of strength.
A great deal of information concerning such materials is available in
conference proceedings, [18 19]. Much information on Martensitic
transformations in other materials is presented by Nishiyama [20]. Related three-
dimensional mathematical theory is discussed by James and Kinder- lehrer [21],
for example. Such theory is becoming more sophisticated, a trend that is likely to
continue. 4.2 Bifurcation Diagrams In considering transition phenomena,
workers find useful another kind of picture, sometimes called a bifurcation
diagram. Essentially, it is a picture of equilibria of interest, indicating how they
vary and branch as the variables of interest change. For our Martensitic
transformations, one point of interest is the behavior of unloaded configurations
as we change 0. The possible equilibria are then described by v) = 0, (4.2.1)
which we can picture as curves in the 07 plane. One of these is the trivial
solution, giving us the straight line ? -- 0. For our typical second-order transition,
there are no other points where r -- 0 when 0 > 0c, but we get two more when 0
< 0c, corresponding to 7 2 = 7(0), and 7 is small when 0 is close to 0c. For small
7, we can approximate b by the first few terms in a Taylor expansion, if it is
smooth enough, 1 tActually, experiments on "critical exponents" indicate
thermodynamic potentials are likely to have rather mild singularities at values
of their arguments at which second-order transitions occur, these being
analogous to "critical points" in fluids. Some discussion of these matters is given
by Sengers et al. [22]. 4.2 Bifurcation Diagrams 63
........................................................ (o) FIGURE 4.3. Graph of the curves *- = 0,
for a typical second-order Martensitic transformation, with Oc as indicated in
Fig. 4.1. The dotted line is to remind us that the line = 0 is included. , a(0)+ +
v(0 + 0" b + 3 . At ff = 0, we should have b = 0"/0ff changing kom positive to
negative 0 decre,es and passes through 0. At 0 = Oc, h a minimum at ff = 0,
indicating that c(Oc) 0 and, a general rule, c(O) p 0, so we sume this. Then, by
continuity, c(Oc) O, for 0 suciently close to Oc. Setting = 0, we then get for 0 ( 0
and (Oc - O) small y 0. Also, in first approximation, -'(0)(0- O)/c(O), (4..4)
indicating that this curve resembles a parabola near 0 = 0, crossing the line ff = 0
with infinite slope. The curves = 0 look rather like a pitchfork, illustrated in Fig.
4.3. "Pitch-fork bifurcations" giving pictures like this occur in a riety of physical
situations. Later, we will encounter another associated with biial stretching of
rubber sheets. Physically, for 0 ( 0, the line ff = 0 is too unstable to be observed,
but it is a good idea to record such points in a bifurcation diagram. This can help
to provide a better picture of the connection between branches. With the typical
first-order transition, we get, at some temperatures, five points where w = 0,
three at the lowest temperatures. At lower temperatures there is a temperature 0
at which the local minimum at ff = 0 changes to a local mimum, with 0w/0ff = 0
at 0 ( 0, ff = 0. Vew near this the
64 4. Equilibrium Theory of Plates ' .......... ; ................. (>o) o FIGURE 4.4.

Graph of the curves *- = 0, including the dotted line indicating inclusion of ff =
0, for a typical first-order Martensitic transformation, 01 and 02 being values
indicated in Fig. 4.2. picture looks like that above, with 0c replaced by 01,
except that the double well occurs at higher, instead of lower, temperatures as
one can check by essentially the same analysis. At higher temperatures, r -- 0 = ?
-- 0 for 0 > 02, some value of 0, and we begin to get five points for 0 < 02. On
the right sidc of the graph are two close together, for (02 - 0) positive and small.
As 0 - 02 they come together to give a single point (02,332), with -- 033 -0 at
(02,332), (4.2.5) as one can see from considerations of continuity. Now
differentiating -(33, 0) = 0, we get the differential equation a0 o/o33 d33 0/00'
(4.2.6) giving a differential equation for a curve. Generally, 0-/00 will not vanish
at (02,332), so the right side will be a smooth function of 0 and 33. Solving this
with the initial condition 0 = 02 when 33 -- 332 then gives 0 as a function of 33,
with dO/d33 -- 0 initially. This indicates that our two points at fixed 0, 33 > 0
really lie on the same curve. To make a long story short, one gets the picture
sketched in Fig. 4.4. Pictures like this are also quite commonly encountered in
physical problems and are sometimes said to involve subcritical bifurcations.
Here, if we considered lowering the temperatures from high values and relied on
second derivative tests for stability, we would see no indication of instability as
long as 0 > 01. Yet for any 0 < 0c, 0 > 0, the system is only metastable and can
be expected to transform before 0 reaches 0x. Bifurcation theory includes
techniques for finding crossing branches but it is hard to locate isolated
branches. Here, the branch crossing 33 --- 0 seems at first to be 4.3 Exercises 65
irrelevant. However, follow it and you will be led to the outer parts, which are,
in fact, stable. In dealing with near-transition phenomena, it is rather common to
assume q5 is a polynomial and use available experimental data to estimate the
coefficients. For our second-order transitions, most would assume the quartic
used above, with c a positive constant, b proportional to (0 - 0), with a(O) fit to
available data on specific heats. For first-order phase transitions, 332 can be
fairly small. Particularly in such cases, workers are likely to try assuming B 332
C 334 D q = A + + + - 336, (4.2.7) where the coefficients are simple functions of
0, again using available data to estimate these. With suitable choices of these
functions, one can obtain graphs of q5 which change with 0 in the manner
indicated by the typical pictures. One needs a polynomial of degree six, at least,
to provide five values of-at which - = 0. Basically, it is for this reason that
workers use a sextic, the polynomial of lowest degree which can describe the
phenomena, at least qualitatively. Roughly, a bifurcation diagram is a picture of
the response of a system when a control variable is changed. Commonly, it is
marked to distinguish the unstable from more stable parts. Here, we consider
controlling 0, keeping v = 0. As another example, an isothermal stress-strain
graph, suitably marked, could be viewed as a bifurcation diagram if we were
controlling % keeping 0 fixed. 4.3 Exercises 4.1. Suppose that, for a plate, q5 is
given by a constitutive equation of the form C 4 d33 6 q _ (aO - 0)33 2 4- 4- 4-
f(O), where a, b, c, and d are constants, f(O) being some smooth function. Show
that this is the polynomial of lowest degree in 33 which can describe a first-order
Martensitic transformation. 4.2. For this form of constitutive equation, decide
what are reasonable assumptions concerning algebraic signs of the constants to
describe a first-order Martensitic transformation. Then derive formulae, ex-
pressing the following quantities in terms of these constants: 01 The temperature
at which Austenite changes from metastable to unstable. The upper bound of
temperatures for which Martensite is metastable.
66 4. Equilibrium Theory of Plates Oc o(O) The temperature at which

Martensite and Austenitc are both stable. The shear strain in unstressed
Martensite. 4.3. For this example, decide what should be meant by the strain
energy for the Martensite and give a formula for it. 4.4. For the special cases of
the above constitutive equation with d = 0, which can describe second-order
Martensitic transformations, calculate the corresponding "/0(0). 4.5. For the
same special cases, at some temperature below 0c, consider an unstressed
sample containing a pair of twins with the discontinuity in the middle of the
specimen. Then consider dead-loading the specimen a bit, with r > 0. Suppose
that the discontinuity does not disappear or move. Find a formula for the
difference in strain energies for the two parts as a function of r. If necessary, you
may use approximations appropriate for small -. 4.6. Consider the analog for
shear of the Clausius-Clapeyron equation (3.1.34). dr Q dO 0 A? ' Using results
obtained in Exercise 4.2, calculate dr lim --. o-o dO 5 Balloon Problems 5.1
Equilibrium of Spherical Balloons at Fixed Pressure Here, we will be concerned
with rubber balloons subjected to inflating pressures. For simplicity, we assume
they are spherical and remain so under such loads. It is known that rubber is, to
a very good approximation, incompressible. Also, it can reasonably be
considered to be homogeneous and isotropic. As before, we introduce a
reference configuration, an unloaded, spherical shape, at a reference temperature
which we consider as room temperature. Material points will then lie on spheres
of radius R, with R _< R <_ R2, (5.1.1) where R and R2 are, respectively, the
inner and outer radii of the balloon in the reference configuration. A deformation
then changes R to r = r(R), with /'1 = r(Rx) _ r(R) < r(R2) -- r2. (5.1.2) The
incompressibility assumption means that the volume of that part between R1
and R must be the same as that between rl and r(R) or r(R) a - r a = R a - R.
(5.1.3) For a given balloon, r(R) is thus determined by r = r(R). Also, for typical
balloons, (R2- R)/R1 << 1,
68 5. Balloon Problems 5.1 Equilibrium of Spherical Balloons at Fixed Pressure

69 V//////////////////////////A" l_ FIGURE 5.1. One device for controlling the
pressure in a spherical balloon. they being so thin that we may well think of
them as infinitely thin in considering measurements of radius, which we shall do.
Such thinking mo- tivates us to assume that one number will suffice to describe
the configurations considered. A dimensionless measure of stretch, similar to
that used for bars, is = r/R. (5.1.4) However, calculations become easier if we
use instead a measure based on the volume V enclosed by the balloon V/Vn =
r3R 3 = h a. (5.1.5) Then, a likely assumption is that, for the balloon, the
Helmholtz free energy function is of the form F = F(V/Vn, 0). (5.1.6) Then, we
consider the possibility of using experiments to help determine the form of this
function, in particular the isothermal mechanical experiments involved in a
typical program of this kind. For simplicity, we think of working at a single
temperature, room temperature, ignoring the dependence on 0. We have in
mind that no force will be applied to the exterior of the balloon, so this part will
be mechanically isolated. The volume V will be filled with a gas to supply an
inflating pressure p. Let us first consider a device designed to try to control p. It
involves a cylinder and a piston atop which we can add weights, connected by a
small opening to the balloon, as indicated in Fig. 5.1. Into this, we have put a
measured mass M of gas. If A is the area of the piston, the total volume Va
occupied by the gas is given by Va = Ah + V, (5.1.7) neglecting the small
amount in the connecting tube. For this, we do need some information, namely,
an equation of state. For a gas, the likely models are of the form Fa = M4 (Va,o
(5.1.8) the gas pressure being given by P- OVa' (5.1.9) with Op 02 Fa O'-a - OV
< O. (5.1.10) A likely possibility is to use the ideal gas model with Va p = 0 x
const. = const. (5.1.11) at room temperature. With (5.1.9), this determines Fa to
within a function of 0, which is good enough for our purposes. Except in
consideration of the weight W on top, we ignore the effects of gravity. With it is
associated the potential energy which can be taken as Wh. Then, adding up the
three contributions, we get the thermodynamic potential E = Wh + Fa + F.
(5.1.12) Again, we have taken the usual shortcut, assuming that the temperature
throughout is the ambient temperature. Here, the idea is that h and V can be
varied independently, with the proviso that neither can become negative.
Physically, there is a real possibility of having equilibria with the piston sitting
on the bottom of the cylinder with h = 0. Physically, the possibility of having V
= 0 is unreasonable. Then, possible variations in h cannot decrease it, this being
like the end point minima discussed before. For the moment, let us exclude this
possibility. Then, we obtain, as one equilibrium equation OE OFa (A] O = 0 = W
+ -a' ' (5.1.13) = W -pA, or p = W/A, (5.1.14) the rather obvious balancing of the
weight with the gas pressure. It is in this sense that we control p and, clearly, it
need not hold when h = 0. As the other equilibrium equation, we have, using
(5.1.6), OE OFa OF 1 ov = o = ova + o(v/vn) n -- -- (5.1.15)
70 5. Balloon Problems or OF 1 (5.1.16) P = O(V/VR) VR' Now, given (5.1.11)

or another such equation satisfying (5.1.10), p is a monotonically decreasing
function of VG with M fixed, as it is here. Then we can solve (5.1.14) for VG as
a function of W/A. Note that this also gives FG as a function of W/A. Here,
experienced workers would be likely to take another shortcut. Take it as obvious
from the start that (5.1.14) will hold. Then, for fixed p, we have Wh = pAh =
p(Vc - V) = -pV + const., and FG also becomes a constant, so we can replace
(5.1.12) by the potential E = -pV + F, (5.1.17) (5.1.16) being the condition that
OE/OV = O, -pV being a kind of potential energy associated with work done on
the balloon by the gas. If we use (5.1.16), the second derivative test for a
minimum becomes simply 02 02 F 1 - o(v/v,d >- o, (5.1.18) a test for
metastability, p being now regarded as fixed. Had we not taken the shortcut, we
would be concerned with the second derivative test as it applies to E(h, V), a
function of two variables. For this, one calculates the second differential, and
requires that this be nonnegative, 02 E 2 02 E 02 E dE: b--(dh) + 20gV dhdV +
b- dr2 -> o, (5.1.1o) for all dh and dV. Conditions necessary and sufficient for
this are that 02E Oh _> 0, O2E ov 2 >_ o, (5.1.20) 02E ,2 02 E 02 E O-V ] -< Oh
OV 2' the second derivative test being inconclusive if any of the equalities hold.
Using (5.1.10), one can show that this does, in fact, give the same condition as
(5.1.18). 5.1 Equilibrium of Spherical Balloons at Fixed Pressure 71 It remains
to consider the possibility of equilibria with h = 0. Then, the differential E
should be non-negative for possible dh and dV, OE OE dE = g-g dh + dV _> 0.
(5.1.21) Here, dh can be positive, but not negative, so we get OE -- = W- pA _>
O, Oh or p _< W/A. (5.1.22) Also, since dV is not restricted, (5.1.16) still holds.
Further, if equality holds in (5.1.22), dE -= 0 and one can still use (5.1.19) as a
second derivative test. It is not hard to see that if d2E _> 0 for all dV and all
positive dh, it must also be nonnegative for negative dh so, again, (5.1.20) must
hold. If we use the simpler potential, a simple and now familiar picture gives the
most stable configuration with h > 0. Rewrite (5.1.16) and (5.1.17) as E = F V -
k -, k = pVR -- O(V/VR' (5.1.23) k being a load parameter that is being
controlled. On the graph of F versus V/Vn, locate the tangent lines with slope k,
such that the entire graph lies above them. Any such configuration corresponds
to a most stable configuration with h > 0. For the configurations with h = 0,
(5.1.7) implies that VG = V. The most stable of these are then those that
minimize with M fixed. We will discuss this more later. Such minimizers may
be unstable to variations increasing h, for example, because (5.1.22) is violated,
or because the second derivative test indicates this. In the end, it may be
necessary to do a numerical calculation to determine whether the actual
minimizer of E occurs with h = 0 or h > 0, even when the constitutive equations
are known. Observations of balloons indicate I that, at some values of pressure,
we can have more than one value of V occurring in equilibrium configurations.
If F always satisfies (5.1.18), it would be impossible for (5.1.15) to be satisfied
by two values of V at a given value of p. Thus, it is rather clear that F is not a
convex function of V/Vn. Suppose that we have a situation such as that
previously considered for bars, involving a graph like that in Fig. 5.2. 1Simple
experiments demonstrating this are discussed by Beatty [23] and Kitsche et al.
[24].
72 5. Balloon Problems ,',v aF k = , R =a(R) l FIGURE 5.2. Graph indicating a

reasonable kind of material response for a balloon. For equilibria with h > 0,
we can use (5.1.23), clearly analogous to that used for bars in soft loading
devices. The equal area rule then gives us the Maxwell line. The downward
sloping part of the graph corresponds to unstable equilibria. If we start
increasing pressure in our device by increasing W, we know what we should see.
That is, V should increase smoothly with pressure until we get to the Maxwell
line, or a little higher if it tolerates being in a metastable configuration. Then, at
some pressure, we should see values of V attained in equilbrium change in a
discontinuous manner to find a more stable location on the part of the curve to
the right. What is observed is that the transition occurs smoothly, but most
rapidly, indicating that nonequilibrium theory would be needed to describe this.
It occurs at a value of V/VR close to x/, a value not much affected by the quality
of the rubber, nor by modest departures from spherical shape, such as one gets in
toy balloons which usually are not quite spherical. Of course, the possibility that
we may attain equilibrium with h = 0 complicates the picture. If we ignore this,
experiments of this kind involving measurements of p and V can give us only
part of the curve. Observation of the jump in V would provide some support for
the notion that the graph has a shape more or less similar to that illustrated. 5.2
Equilibrium of Balloons Containing a Fixed Mass of Gas When we blow up a
balloon, we insert some fixed mass M of gas into the balloon, then close off the
opening. It is interesting to find out what we need for stability under these
circumstances and it will help us to understand ii 5.2 Equilibrium of Balloons
Containing a Fixed Mass of Gas 73 the previous situations better when h = 0.
Here, only the balloon and gas are involved, and we will always have Vo = V.
(5.2.1) The relevant potential now is given by (5.1.12), which we write as and
we are interested in the absolute and relative minima of this, corresponding to
stable or metastable equilibria. The first derivative test gives OE OFG OF 1 ov o
+ o(v/vn vn' (5.2.a) or, as before, OF 1 (5.2.4) P- O(V/VR) VR However, the
second derivative test now gives 02 E 02 F 02 F 1 - ov + o(v/vnp >- o. (5.2.5)
From (5.1.10), the first term is positive; so, unlike before, we can have
configurations which are at least metastable, when the second term is negative,
but small enough to be dominated by the first term. Roughly, the pressure is now
free to adjust and it works to help stabilize such configurations. Clearly (5.2.5)
may hold for all or only part of the range where the second term is negative,
depending on the detailed form of the equations. Experiments on balloons
indicate that one can cover all, or at least a good part of the apparently unstable
range with this kind of experiment. So, for determining the function F, this type
of experiment is better than that considered before. Qualitatively, the graph of
OF/O(V/VR) sketched in Fig. 5.2 is like that found in such experiments. As is
discussed by Beatty [23], it is a good idea to break in a balloon before
performing measurements. Blow it up and deflate it once or twice. If one does
not, the graph is likely to be quite a bit higher on the first run than on subsequent
runs. After break-in, the experimental curves come closer to being reproducible
and reversible, features one would like to have. In such respects, cheap toy
balloons will not perform very well as a rule and a careful experimentalist will
want better materials. However, the general phenomena indicated are quite
robust, occurring in balloons from various sources which may or may not be
very close to spherical. It is related to a common experience. As one starts
blowing up a balloon, at first one must blow quite hard to increase the size a
little. Then, rather suddenly, it becomes easier as one goes over the hill in the p-
V diagram.
74 5. Balloon Problems Then, it gets harder again until the balloon decides to
burst. It is hardly reasonable to use the same analysis for long tubular balloons,
although one observes somewhat similar phenomena, along with aneurisms
which develop and grow in length as air is added. To simplify analyses, we
assume that the balloons stay spherical. Insta- bilities could occur, inducing the
balloon to take on some less symmetrical shape. Later, we will discuss some
evidence suggesting that the possibility is real. However, it is a more difficult
problem to analyze this, and, for the experimentalist, it is hard to get balloons
that are very good spheres of uniform thickness, and so on. It is a matter of
experience that, near conditions at which instabilities occur, small differences
of this kind can have a significant effect. Such quirks are discussed by
Thompson and Hunt [25]. To get an idea of the number and character of
equilibria, it helps to consider another picture. First consider the graph of
OF/OV, regarded as a function of V. This differs from that given in Fig. 5.2 only
by a simple change of scale. For simplicity, assume that we use the ideal gas
model, described by (5.1.11) with Vc -- V. With V as abscissa and p as ordinate
add in the p-V curves, in this case hyperbolae, for various values of M. From
(5.2.4), the possible equilibria are given by the points where one of these
intersect the graph for the balloon. From such a sketch, one can see that there is
at least a theoretical possibility that by adjusting M, one might get one, two or
three equilibria? Consider the picture in Fig. 5.3 when there are three, giving V <
V2 < V3 as equilibrium volumes. Now, as we did before in considering the equal
area rule, we can picture energy differences as area differences. Obviously - pdV
- - pdV (5.2.6) with the latter integrals referring to the gas. However, with (5.1.9)
we can replace these by differences in Fc, for example -/v2pdV---F6()-F6(-) �
(5.2.7) 2By adjusting the shape of the rubber curve, as indicated in Fig. 5.3, you
can get a rather similar sketch where the two curves never intersect more than
once. This is a way of constructing cases where (5.2.5) always holds. According
to Alexander [26], this type of behavior is encountered in some neoprene
balloons used for high-altitude measurements. 5.2 Equilibrium of Balloons
Containing a Fixed Mass of Gas orp 75 v. v, v v v FIGURE 5.3. Sketch of the
balloon and gas response curves, for a value of M giving three points of
intersection. Here A and A2 denote the areas of the cross-hatched regions. The
dashed curve indicates another possible graph for the balloon giving only one
point of intersection with the graphs for the gas. Then, with (5.2.2) we have
E(V2, M) - E(Vx, M) -- Az > 0 (5.2.8) E(V2, M) - E(V3, M) = A2 > O. Thus,
the equilibrium at V = V2 is less stable than those at Vz or V3. It is in fact
unstable, as can be seen by doing similar area comparisons, for V near V2. The
stability enhancement indicated by (5.2.5) is associated with the possibility of V
taking values where oq2F/oqV 2 < 0, as it can. Again, area comparisons indicate
that, as long as we have the three equilibria, V and V3 are both at least relative
minima. From (5.2.8) one can read off which is stable: A1 _ A2 V1 stable,
(5.2.9) Az _< A2 = V3 stable. So, we do have an "equal area" rule somewhat
similar to those discussed earlier, although the areas are not defined by
intersecting the basic graph with a straight line (p = const.). With a single
spherical balloon, we do not have a physically reasonable analogue of the phase
mixtures encountered in bars and plates. One begins to obtain something similar
if one considers several balloons, interconnected so gas is free to move from one
to another. Here, since pV is proportional to M for an ideal gas, increasing M
moves the p-V curve outward, in an obvious sense. If M is small enough, it will
intersect the graph just once, to the left. As M increases, it will attain a value
where the p-V curve touches the graph: here V2 and V3 just appear, with V2 =
Va. As M increases further, these split, V2 becoming unstable, Va metastable.
Further increasing M brings us to the equal area configu-
76 5. Balloon Problems ration, where V1 gives way to V3, becoming the

metastable configuration. Increasing M then moves V1 and V2 together: Vx
stays metastable until they coincide. For greater values of M there is again just
one possible equilibrium configuration. Clearly, the stability picture here is
quite different from what it is when pressure is controlled, although it is not hard
to see that we will be left with some values of V too unstable to be observed,
when Fig. 5.3 applies. Of course, this picture also applies to possible equilibria
with h = 0 in the balloon problem first considered. It is somewhat complicated
by the need to account for (5.1.22), a limitation on pressure which depends on
the weight, along with the possibility that the most stable configurations may
occur when h 0. We will not pursue analysis of this: the ideas needed to do so
have been covered. 5.3 Exercises 5.1. To check the mathematical result used in
(5.1.20), consider f(x, y) = ax + 2bxy + cy , where a, b, and c are constants.
Show that, to have f(x, y) _ 0 for all x and y, it is necessary and sufficient that a
_ O, c_ O, b _ ac. 5.2. Show that (5.1.18) and (5.1.20) give the same results
when h 0. Do they when h = 07 5.3. For a spherical balloon at fixed temperature,
the Neo-Hookean theory of rubber yields a total strain energy function of the
form F = a(2A + A -4- 3), A r R' with a a positive constant. Make a sketch of the
corresponding graph of the pressure-volume function. For cases where it is
subject to constant pressure, calculate the value of V/Vo representing a limit of
metastability and say what you can about the possibility of stable equilibria. 5.4.
Another commonly used theory of rubber is the Mooney-Rivtin theory. For a
spherical balloon, F = a[2A 2 d- A -4 -- 3 + (2A -2 d- A 4 -- 3)/K], where a and
K are positive constants. Fitting data on various kinds of rubber generally gives
values of K in the range 4 _< K <_ 8. Make 5.3 Exercises 77 a sketch of the
graph of the pressure-volume function for a realistic value of K. Is there any
important difference between this and the previous graph, and, if so, what is it?
5.5. In terms of three-dimensional theory, the above estimates of F are made
using an approximation which is reasonable when R - R1 More accurately, for
the neo-Hookean theory, F = 4r WR dR, where W, the strain energy per unit
volume, is the function W = C(2A 2 d- A --4 -- 3). Here, C is a positive constant,
depending only on the type of rubber. For a very thin balloon, relate the constant
a in Exercise (5.3) to C and quantities relating to the geometry of the balloon.
Here, volume refers to that of the unstressed material.
6 Biaxial Stretch of Rubber Sheets 6.1 The Idealized Problem We now consider
biaxial stretch experiments performed on rubber, one of the isothermal
mechanical experiments done to obtain information about the relevant strain
energy functions. Again, we choose as a reference a stable unloaded
configuration, say at room temperature. For simplicity, we will only consider
experiments at this temperature. In the reference configuration, the sheet
occupies a region described by -a _ X 1 __ a, --a <_ x2 <_ a, -b _< xa _< b,
(6.1.1) where (X l, X2, X3) are coordinates in a suitable selected rectangular
Carte- sian coordinate system. Generally, b/a is quite small; thin sheets are com-
monly used. The aim is to produce simple kinds of deformations by applying
suitable loads to the edges of the sheet. Briefly, the material point at (Xl, X2,
X3) goes to (y, y, Y3) with yl = ,1Xl, y = A2x2, Y3 = '3X3, (6.1.2) where the
stretches Ai are positive constants. That is, we will only consider deformations
of this kind. Here, the assumption is that the strain energy function W is a
function of Ai, satisfying W(l, 2, 3) = W(2, 1, 3) = W(l, 3, 2) (6.1.3)
80 6. Biaxial Stretch of Rubber Sheets 6.1 The Idealized Problem 81 and

w(1,1,1) = o, (6.1.4) this being interpreted as energy per unit reference volume.
To within an additive constant this is also the Helmholtz free energy function at
the same temperature, the analogue of the relation between such quantities we
had in our earlier discussion of thermodynamic experiments on bars, in Section
2.5. That (6.1.3) should hold is inferred from the fact that rubber is an isotropic
material. Here, as in our considerations of Martensitic transformations,
considerations relating to material symmetry will play an important role. As
noted in our discussion of balloons, it is reasonable to consider rubbers as
incompressible materials, which means that the/i should always satisfy the
equation AiA2A3 = 1. (6.1.5) Using this, we can replace W by a function of two
variables, setting ( U = U(,,i,/2) = W 1,,,2, ,''2 ' (6.1.6) Then (6.1.3) implies that
= u(2, = u � (6.1.7) Ideally, we would like to apply forces on the edges which
are normal to the edges and uniformly distributed, with equal and opposite
forces on opposite edges, leaving the faces :r3 = +b free. On the faces :rl = �a,
we can then represent the resultant forces by FL = 4T, ab, (6.1.8) and F� =
-4Tab, (6.1.9) where T is a number representing force per unit reference area, a
stress. The forces on :r2 = +a are similarly represented by a number We consider
an ideal dead-load device, able to control these forces to keep T and T2 at fixed
values. Consider changing Yi to Yi + Ayi. On the face :r -- a, this will produce
the displacement Ay = (AA)a, so the work done here by F + is F+Ay =
4a2bTAA1. Adding the similar contributions from the other three faces, we get
as the total 8a2b(T,A,Xl + T2A,X2) = 8a2/A(T,,Xl + since Tx and T2 are here
held fixed. This means that the loading device can be considered to be
conservative with the potential energy X -- -8a2b(Tl.'\x Of course, we have in
mind that this system is in contact with a heat bath at room temperature, so we
have a situation fitting statement IV in Chapter 1. However, we will take the
usual shortcut, assuming that the sheet, etc., is at room temperature, using the
Helmholtz free energy in place of the ballistic free energy. For the sheet itself,
we can use the total strain energy 7(2)(2)(2) = After cancelling the numerical
factor 8a2b, this gives the relevant thermodynamic potential as Z = U(i, ,'2) -
TiA1 - T2A2. (6.1.10) As usual, stable or metastable equilibria correspond to
absolute or relative minima of this function of hi and A2 for fixed values of T1
and T2 and, here, physically possible variations include arbitrary small changes
in these variables. Again, there is a possibility that we will miss some
instabilities because we only allow for some very simple kinds of deformation.
Physically, some kinds of loads can easily make a thin sheet undergo more
complicated buckling deformations beyond the scope of our theory. With
(6.1.10), the first derivative test gives the equilibrium equations OU OU T1 -- 0/'
T2 - 0A2' (6.1.11) the idea being to try to solve this for A1 and A2 for given
values of T1 and T2 and to discard those corresponding to unstable equilibria.
As before, we are concerned with a function of two variables and the second
derivative test gives us the conditions analogous to (5.1.20), which are 02U _> o,
02U 0A22 >_ 0, (6.1.12) . For stable equilibrium, we find values 1 and 2
satisfying (6.1.11) such that, for any possible value of A1 and V(.,l, A2) - TIA1 -
T2A2 _ V(/l,/2) - T1X1 - T2X2. (6.1.13)
82 6. Biaxial Stretch of Rubber Sheets 6.2 The Treloar Instability 83 FIGURE

6.1. Sketch of specimen used in biaxial stretch experiments. Associated with this
is a geometrical picture similar to that associated with the one-dimensional
theory of bars, etc., under dead loads. Consider (A1, A2, U) as rectangular
Cartesian coordinates in three-dimensional space. Then U = U(A, A2) is the
equation of a surface. On this is the point (A, A2, U = U(A, A2)). Here, the
tangent plane to the surface has the equation U - - Vl(, 1 - 1) - T2 (,2 - 2) -- 0,
(6.1.14) when and 2 satisfy (6.1.11). Points lying above this plane have coordi-
nates satisfying the inequality u - U - - - T2(.2 - X2) > 0, and those lying below it
have coordinates satisfying the reverse inequality. Thus, (6.1.13) means that
every point on the surface must lie in the half- space above the tangent plane.
For U(A, A2) to be a convex function means that it does lie in this half-space for
the tangent planes at all points on the surface. With the same assumptions
concerning the allowed deformations, the theory of hard devices is trivial. That
is, if we fix the values of Yi on the edges, we will have either an impossible
situation or only one possible deformation. For example, on Xl = a, Yl = Aa, so
fixing y fixes '1, etc. So, we are left with no possible variations, implying that
any possible configuration is stable. Although our formulation is very simplistic,
it is good enough to provide a basis for beginning to understand some interesting
phenomena occurring in rubber. Experimentally, one cannot come very close to
matching the ideal conditions assumed above. Earlier devices were designed to
approximate dead loading. The test specimens had fillets on the edges, a square
grid marked on the interior, as indicated in Fig. 6.1. To the lugs are attached
fairly long strings or wires, the other ends being connected to a square frame in
such a way that one can adjust them to vary the force exerted by them on the
specimen. One makes adjustments to get the grid lines straight and perpendicular
as they should be for the kinds of deformations we have assumed. This is a
tedious matter but, with some experience, one can get what appears to be the
correct kind of deformation in a sizeable part of the sheet and hence estimate
values of A and A2. From measurements of the forces supplied through the
strings, one then estimates the resultant forces applied to edges of this part,
obtaining an estimate of T1 and T2. These are always tensile forces (Ti _ 0). At
least to some degree, this helps to avoid the buckling which is more associated
with compressivc loads. Various modifications in design were tried, the trend
being to make the devices harder to come closer to controlling the edge
displacements. Our crude theory suggests that this may help to extend the range
of values of A1 and A2 which can be observed by suppressing instabilities
which may occur in softer devices, producing deformations of a more
complicated kind. I do not know of clear experimental evidence supporting this
view. Possibly related to this is a curious matter discussed in the next section.
6.2 The Treloar Instability In 1948, Treloar [27] published some data on rubbers
obtained using a biaxial stretch device of the old kind. 1 Although he did not say
much about it, some of the measurements were, in one respect, curious.
Intuitively, one expects that when Tx = T2, we will have A1 = A2. In some
cases, his data for situations where T1 = T2 indicated that A1 A2 and the
difference seems too large to be attributed to the inevitable experimental errors.
This appears to have been overlooked or forgotten by rubber workers until 1986,
when Kearsley [28] discussed it and some theoretical reasons for believing that
this phenomenon is real. Let us consider a slightly different analysis of it,
indicating that it is, in some respects, similar to the Martensitic transformations
discussed before. For this purpose, it is convenient to make a change of
variables. Set 1: + := = (1 + 2)/2 := > ]], (6.2.1) 7 and set = Then, from (6.1.7)
we have, in particular, (6.2.2) v) = (6.2.3) I Included in Treloar's paper is a
photograph of a loaded sample.
84 6. Biaxial Stretch of Rubber Sheets 6.2 The Treloar Instability 85 You may
explore for yourself the other implications. becomes E = V - r5 - r,7, where =
+T2, r=T1-T2, and the equilibrium equations now become Also, (6.1.10) now
(6.2.4) (6.2.5) ov ov r = 0(i' r = 0,7 (6.2.6) With V an even function of ,7 and r
related to it as the derivative with respect to '7, r and ,7 become analogous to the
shear stress and shear strain considered in the theory of Martensitic
transformations. That another variable (i is involved does complicate matters
somewhat. However, its variations may be considered to be similar to the
variations in 0 considered before. In these terms, Treloar's data indicate that, for
some values of (i, r = 0 but ,7 0, giving us an analogue of Martensite. It is not
likely that this is true for all & For example, indications are that there is only one
unloaded state, so r = r = 0 = (i = 1 and ,7 = 0, giving us an analogue of
Austenitc. Indications are that something more or less like a Martensitic
transformation should be encountered in some loading programmes. One might
expect to see something similar to twinning but experimentMists seem not to
have reported this. Theoretically, one can understand this. If one tries to
construct deformations involving jump discontinuities in '7, even allowing them
in (i, one finds that it is impossible to have all three components of displacement
continuous. Thus, in this respect, the analogy with the theory of Martensitic
transformations breaks down. Conversations with some rubber experts indicated
they were unaware of the possibility of such an instability, until Kearsley
revived the issue and his work is not yet widely known. Occasionally, something
small can produce a surprising error in an experiment, so it is important to try
to make an assessment of this situation theoretically. One approach is to take a
form of W which can be analyzed and fits some relevant data, at least roughly.
For rough calculations, workers often use the Mooney-Rivlin form, W
C(A12+A2+A32 3)+C2(12 1 1 ) : - + , with Ct and C2 constants, determined by
curve fitting. What is important for our purposes is their ratio, so we will use the
simpler form I 1 1 W = K(A 2 + A22 + A32 - 3) + A + A + A - 3. (6.2.7) This
gives V=K [2((i 2+,7 2 )+ ((i2 _ '772)2 1 1 + ((i +,7) + ((i - Then a calculation
gives + ((i2 _ '72)2 OV 4'7 0'7 ( (i2 _ '72)3 (6.2.8) = {K[((i2-,72)a+l]+,72+3(i2-
((i2-,72)4}. (6.2.9) One of the conditions for metastability is that 02V/0,72 _> O.
Let ns explore this at '7 = 0, using 02V' = lim _1 o___V_v 0'72 ] =o -o ,7 0,7 =
if6 [( K((i6 + 1) + 3(i 2 - (i s] (6.2.1o) _ 4((i 6 + 1)[K - f(&l, where (i2((i6 _ 3)
(6.2.11) if(i)- (i6+1 ' is rather easy to visualize, from its graph. For a positive
value of K, such as that indicated in Fig. 6.2, there is just one value of (i = for
which f = K, and we have K > f((i) for (i < , K < f((i) for (i > , so we have
instability at ,7 = 0, when (i > , and when (i < the one stability inequality is
satisfied. Curve fitting produces various values of K depending on the particular
rubber and the range of deformation which one selects to fit best. Kearsley
mentions that likely values range from 4 to 8, although one can find estimates
outside this range. Roughly, this puts somewhere between 2 and 3, not
unreasonably large for rubber. Also, this means that for any fixed (i < and '7
close enough to zero, V is a convex function of '7 and this is not true for (i > .
Thus, for fixed (i < , r is a monotonically increasing function of '7, suggesting
that we have an analogy with the second-order Martensitic transformations. To
consider other possible solutions of r = 0, we note that they will occur when
K[((i 2 - ,72) a + 1] + '7 2 + 3(i 2 - ((i2 _ '72)4 = 0.
86 6. Biaxial Stretch of Rubber Sheets 6.2 The Treloar Instability 87 FIGURE

6.2. Graph of the function given in equation (6.2.11). Set and the last equation
can be rewritten in the form 47----- + K - f() = 0. (6.2.12) Bearing in mind that
`52 > ?2, the first term is positive, so the sum of the other two terms must be
negative. From above, this means that we must have Thus, for any fixed `5 < , - -
- 0 implies ? = 0. Consider a fixed `5 > . It is easily checked that the first term in
(6.2.12) is an increasing function of ./2. As ./2 increases, 8 decreases, as does f().
Thus the entire expression increases with ./2. At ? = 0, it is negative and it is
positive when V/_ ./2 _- . So, it must vanish for one value of ./2 between these
values and for no other values of ./2. By a similar argument, the values of satis-
fying (6.2.12) must increase as ./2 increases. This also makes the behaviour with
`5 increasing rather like that which we saw with decreasing 9 in the Martensitic
transformations, when the latter are of second-order. For `5 , drawing a graph of
- versus ? with a negative slope at ? -- 0, with - = 0 at one other value of ./2 gives
a graph at least roughly like that suggested by the analogy, as shown in Fig. 6.3.
By a rather similar argument, one can show that for fixed `5 < , - is a
monotonically increasing function of ?. Of course, it is possible that, for a more
realistic form of the strain energy function, one may get a picture more like that
suggested by the first-order Martensitic transformations or something else.
Other arguments given by Kearsley make it seem very unlikely , FIGURE 6.3.
Graph of vs % for fixed that one will not have some such instability. It is curious
that experimentalists working more recently than Treloar have not noticed, or
at least not reported, something unusual associated with this instability. Possibly,
by employing harder devices, they have eliminated such instabilities. Possibly,
some would have spotted something if they knew what to look for. It is also
possible that some dealt with limited ranges of stretch which happened not to
include these instabilities. For thc model we are exploring we have not
completed checking the inequalities governing stability or metastability. We do
know that the nontrivial solutions of - = 0 give values of ?2 which decrease as
we decrease `5 until they become zero at `5 = . This means that the plot of the
curves - = 0 in the `5- plane then looks much like the pitchfork discussed in
Section 4.2. For stability, it is also important that we have 02V Ox -- - > 0.
(6.2.1a) 0`52 0`5 - A simple calculation shows that the strict inequality holds for
all possible values of `5 and ?. This means that, for fixed ?, V is a convex
function of `5, with r a monotonically increasing function of `5. Thus we can, in
principle, solve OV 71'-- 0`5 ' giving `5 = ?), although it is not easy to do this
explicitly. To check the remaining inequality 02V 0217 > ( 02V 0? 2 0,52 - k,
0`507 (6.2.14) (6.2.15)
88 6. Biaxial Stretch of Rubber Sheets is not so easy. It is simple to check this

when "7 -- 0 since the right side vanishes. Thus (6.2.15) holds, strictly when 6 <
, and it fails when 6 > . By continuity, it will also fail for 6 > , when "7 is
nonzero, but sufficiently small. Now, a straightforward calculation gives, for .7
0, 6 .7 62 "72 ' (6.2.16) which increases with (62 -"72). Consider the outer tine
of the pitchfork with "7 0. On it, as "7 increases so does "72 and, as already
noted after (6.2.12), so also will 6 and (62 - "72). On it, 6 will be a function of
"7, with dr 0r 0r d6 = + 06 d.7 - o. (6.2.17) From Fig. 6.3, it is clear that here &r
02 V > o, (6.2.18) one of the inequalities needed for stability. Another is
02V/062 0, which, we have noted, is always satisfied. Since 6 increases with "7,
(6.2.17) can only be satisfied if Or 02V 06 0"706 We also know that, on this
curve, &r d.7 0"7 < 0. (6.2.19) 02 V 02 V d6 0"706 062 d.7 >0. (6.2.2o) Look at
(6.2.16), bearing in mind that 6 and (62 - "72) increase with "7 on this curve.
Solving for d6/d% and substituting this in (6.2.20) gives 02V 02V 02V / 02V
Multiplying this by the negative quantity 02V/0.706 then gives the third stability
inequality listed in (6.1.12), ( 02V , 2 02 V 02 V 0-] 062 0"72 < 0. (6.2.21) So,
on this branch, we have equilibria which are at least metastable. Actu- ally, they
are stable. A similar argument gives the same conclusion for the 6.2 The Treloar
Instability 89 other outer tine, on which .7 < 0. In between them, somewhere
near .7 = 0, is a region of instability. Qualitatively, the picture is then clear, and
we cannot trust the constitutive equation to give quantitatively correct
estimates of the situation. Assuming the estimate is qualitatively correct, it
suggests a strategy for designing experiments to learn more about the
instabilities. Roughly, we would like to devise loading programs to aim at the
boundary of the unstable region and find out what really happens. It may be
profitable to use a soft device, one of the older designs being better than the
newer. If we start with the unloaded configuration, keep r: 0 and increase r, 6
should increase with .7 staying zero for a while; but, if 6 becomes large enough,
we should hit the instability at 6 = , "7 = 0. The simplest possibility is that we
continue to have the simple kind of deformation assumed, but move along the
curve path r = 0, .7 becoming nonzero. Treloar seems to have hit points on r = 0,
"7 0, accidentally, with deformations fitting our assumptions, so this could well
happen. "Pitchfork bifurcations" more or less like this are encountered in various
physical systems. Now, by making r 0, we can try to head back towards "7 = 0
and should encounter other points on the boundary of the unstable region and see
something unusual happen. Here, by thinking hard about a somewhat shaky
theory, we have been led to the design of an experiment which is likely to
produce useful information. There is a loosely related matter. In considering the
balloon problems, we assumed that they remain spherical. Intuitively, this is
associated with the notion that at any point on the balloon, the material should be
stretched equally in all tangent directions, the amount of stretch being the same
at all points. Roughly, this is similar to assuming homogeneous deformation in
the sheets, with .7 = 0 when r = 0. We now have some reason to question such
assumptions, although the conditions for stability are somewhat different in the
two cases. If one blows up toy balloons of a symmetrical shape, more or less,
sphere-like, one does see the development of curious asymme- tries. One can
argue that such effects stem from variations in thickness, etc. However, one
rubber expert, who had made a strong effort to obtain the best possible spherical
balloons, told me that he is convinced that this is a real effect. Also, Alexander
[26] presents a combination of theoretical and experimental evidence that the
effect is real in some neoprene balloons. The analysis of Haughton and Ogden
[29] suggests that it might not be true for thicker balloons in the case where the
pressure is controlled. Bear in mind that rather thick balloons are what we often
call balls and ask yourself what your experience suggests about the difference
between balls and balloons. The behavior of some biological materials is rather
like rubber. Esti- mates of strain energy functions I have seen for some lung
tissue suggest that a similar instability may occur in these, although this does
involve extrapolating the function to larger stretches than were observed.
90 6. Biaxial Stretch of Rubber Sheets 6.3 Exercises 91 For the experiment at

hand, allowing for more complicated deformations does change the conditions
required for stability to some degree. The best available analyses of this are by
Chen [30, 31]; the latter deals with hard devices and does indicate that the
stability conditions for these are different. One of the best general references on
the physics of rubber is the book by Treloar [32]. 6.3 Exercises 6.1. Determine
whether a strain energy function of the Neo-Hookcan form w: + + - 3), c > 0 is
capable of describing the Treloar instability. 6.2. In practice, our sheet might be
called a bar, if two of its dimensions are small compared to the third; replace
(6.1) by -a _< X 1 __ a, -b _< x2 _< b, -c _< xa < c, with b/a << 1, c/a << 1.
With this, bar theory would identify the stretch A as A1 and assume that forces
are applied only in the xl direction, so take T2 = 0. For the Mooney-Rivlin form
of W, determine the corresponding form of the strain energy function for bar
theory. 6.3. For the bar theory just deduced, is the strain energy function a
convex function for positive values of A and realistic values of K? From your
experience with bars, what would infer about possible instabilities that might be
predicted by such theory? 6.4. In Section 6.1, it was asserted that points lie
above or below the tangent plane given by (5.1.14), depending on whether U - -
T1(1 - I) - T2(2 - 2) is positive or negative. Prove or disprove this. 6.5. In
Section 6.1, after (6.2.12), it was asserted that "the value of satisfying (6.2.12)
must increase as 7 2 increases." Prove or disprove this. 6.6, Take a toy balloon of
spherical shape. What do you think would happen to a great circle drawn on it,
when it is inflated just enough to do this with a marking pen, then inflated more?
Try this experiment, and you might see why some workers have concluded that
the actual deformation is more complicated than was assumed in our balloon
studies, even when the balloon appears to stay close to being a sphere.
Developing better theory is not an elementary exercise, as is often the case in
stability studies.
7 Moving Discontinuities 7.1 Shock Waves in Bars We have encountered

examples of static discontinuities, for example the twins in Martensite or the
"phase mixtures" in bars. Physically, such discontinuities are often better
regarded as thin regions through which the quantities of interest vary smoothly,
but rapidly. However, simpler kinds of equations sometimes permit us to model
them better if we treat them as discontinuities. Such phenomena are likely to
occur dynamically, when one suddenly imposes a load on a solid, by an impact,
or sometimes, by setting off an explosive on its surface. Often, experiments of
this kind along with one-dimensional theory are used to provide information
concerning constitutive equations for solids. It is common to use thermodynamic
considerations. Here, we will discuss commonly used ideas, in the context of
bar theory. In this context a "surface" of discontinuity becomes a point x = �(t),
moving through the material with velocity v = �(t), (7.1.2) which we assume is
positive. This is called the material or referential wave speed, or, more briefly,
the wave speed. Some functions of interest are assumed to have jump
discontinuities at this point. If g = g(x, t) is such a
94 7. Moving Discontinuities function, we can fix t and consider the limit as we

approach the point from the front, the region into which the wave is moving, to
define g+(t)= lim g(x,t). (7.1.3) x+(t) Similarly, we have the limit from the
opposite side and the abbreviated notation for the jump indicated by g-(t): lim
g(x,t), [g]: g+- g-. (7.1.4) x- (t) As in the static case, we assume that y(x, t) is
continuous, excluding possibilities of breaking, etc., so [y] = 0. (7.1.5)
Consider the possibility that the stretch A and velocity 9 have finite discon-
tinuities. Evaluating y(x, t) on the front and back sides and differentiating with
respect to t, we then obtain dy+/dt = A+v + 9 + (7.1.6) dy- / dt = A-v + 9-.
Differentiating (7.1.5) with respect to t then gives d[y]/dt = [A]v + [9] = 0 (7.1.7)
as a kinematic condition, restricting these jumps. With the discontinuities, it is
not sufficient to satisfy the differential equations of motion, etc., where things
are smooth enough to do so, although this should be done. Consider the integral
forms. One is the usual mechanical equation pgdx = fdx+er (7.1.8) with x and x2
chosen so that, at a particular time, Xl < b(t) < x2. Recall that p is a constant. We
assume that, if Xl and x are close enough to b(t), the functions are smooth,
except at x = b(t). Then, on the left, we have d- P9 dx + P9 dx = p dx + pg-v -
pg+v (7.1.9) or d- p dx = p dx - pv [9]. (7.1.10) Putting this back in (7.1.8) and
taking the limit as x --+ b-, x - b +, we obtain -pv[9] = [er], (7.1.11) 7.1 Shock
Waves in Bars 95 as another restriction on jumps. By a similar analysis, the
energy equation e+p9 dx= (fg+r)dx+(ag+q) (7.1.12) gives rise to -v e + py = [r9
+ q]. (7.1.13) These conditions are, in principle, applicable to plastic wave
propagation although in practice, many such waves are not well-idealized as
sharp discontinuities. Finally, in a similar way, the Clausius Duhem inequality
can be applied to cases where entropy is well-defined, which does exclude plas-
ticity: -- 7dx dx + (7.1.14) It yields the inequality om hereon, we sume that our
thermoeltic theory of bars applies. 1 Commonly, this is used one criterion for
deciding whether mathematically possible singular solutions are physically
acceptable. As is eity checked, if all the equations are satisfied and if we
interchange the values (A +, V +) and (A-, V-), the equations are again satisfied
with the same v. If the first choice satisfies (7.1.15), the second will not, unless
the equality holds in (7.1.15). Now, using (7.1.7), we can reduce (7.1.11) to the
form -[] (7..6) []' from which it is clear that, for a given material, the wave speed
depends on the values of A and V (or 0) on the two sides. Also, [a] and [A]
cannot have opposite signs. Now, using (7.1.7) and (7.1.11), we have [] = ++ - --
(+ -- -) + (+ + -) + + - [] -- -- (+ -- -)(+ + -) a + + a- p[] 2 2 1 Formally, this is
analogous to the older one-dimensional theory of shock waves in gases, both
being discussed in more detail by Courant and Priedrichs [33]. An exposition by
Dunn and Fosdick [34] clears up some old misconceptions about thermoelastic
theory of shock waves.
96 7. Moving Discontinuities FIGURE 7.1. Sketch indicating the possibility of

slowly moving shock waves, in bars with nonmonotone stress stretch curves.
With this, (7.1.13) reduces to a + +a- 1 Is] 2 [A] = -;[q]. (7.1.17) Very slowly
moving waves can occur as interfaces between different phases or twin planes.
As we have seen from static studies, they can even come to rest. In considering
cases of this kind, one finds some workers 2 assuming that [0]: 0. (7.1.18) Then,
it is convenient to introduce the Helmholtz free energy at this common
temperature, and put e = b + 07 in (7.1.17) to get a + +a- 1 [b] 2 [A] = -0[7] -; [q]
v (7.1.19) <0, where we have used (7.1.15) and 0 = 0 + = 0-. Then, (7.1.16) and
(7.1.18) have nice interpretations in terms of the graph of a(A, 0), the isothermal
stress-stretch curve at this temperature. It may look like Fig. 7.1. From (7.1.16),
the angle X in the diagram satisfies [a] _ pv2, (7.1.20) tanx- [A] 2Our treatment
is oversimplified. In dealing with moving phase boundaries, it is of some
importance to account for surface, as well as bulk, energies associated with the
interface between phases and workers consider possibilities other than (7.1.18).
Three-dimensional theory of this kind is covered by Gurtin [35]. 7.1 Shock
Waves in Bars 97 so we are considering X to be a rather small angie. in (7.1.19),
[b] is the (signed) area under the stress-strain curve between A + and A-, being
negative in the illustration. Also, the (signed) area between A + and A-,
bounded above by the chord joining (a +, A +) to (a-, A-) is (a + +a-)[A]/2,
which is also negative in the illustration. So, it is a matter of comparing these
areas in deciding as to whether (7.1.19) is satisfied. In the situation pictured, it
will be if A + is close enough to the local maximum for the graph. Impacts, etc.,
are likely to generate waves which travel much faster, being more like shock
waves in air. Here, workers often assume that the effects of heat conduction can
be neglected, using q = 0 (7.1.21) in place of (7.1.18). Then (7.1.17) reduces to
what is often called the Rankine-Hugoniot equation a + [el - 2 [A]. (7.1.22) With
an equation of the form e = e(A,r/), this relates the two states (A+,r/+) in a
manner depending only on the material. Also, (7.1.15) reduces to V- - 7 +-
(7.1.23) If this constitutive equation is known, one can select (A +, 7 +) and,
from (7.1.22) and (7.1.23), find all the thermodynamically admissible states (A-
,V-) which generally lie on a curve in the A- 7 plane, the Rankine- Hugoniot
curve. In a similar way, (7.1.16) generates a set of curves, one for each value of
v, called Rayleigh curves. For a given value of v, the possible states behind
correspond to points where this Rayleigh curve intersects the Rankine-Hugoniot
curve when they satisfied (7.1.23). In this context, it is of interest to consider
weak shocks, where [A], [r/], etc., are suitably small. Think of fixing (A+,r/+)
and solving (7.1.22) for [7] in terms of [A], assuming [7] approaches zero as [A]
does. A first approximation to v can be obtained from (7.1.16) by letting [A] - 0,
7- - 7 + which gives pv = 0a(A+, 7+), (7.1.24) v0 being called the acoustic wave
speed, measured by the slope of the isentropic stretch-strain curve at the values
(A +, 7 +) of interest. To estimate what (7.1.22) gives in this limit, use the linear
approximation ,- = e(x-,v-) Oe + _ Oe + . e(A+,v+) + - A +) + (v - = e + - a + [A]
- 0 +
98 7. Moving Discontinuities so = + 0+ [._l _ + (7.1.25) 2 Letting [A] -- 0 and

er- --+ er +, we get [7]/[A] - 0. So, an expansion of in powers of [A] gives zero
for the linear term, suggesting it looks like [r/] = a[A] 2 + b[A] 3 +... , (7.1.26)
Then, to second order in 1 (Oq2S' - - 0+ 2 + and, on the right side of (7.1.22), we
can use a first-order approximation - 0x - Putting these approximations into
(7.1.22), we get a = O. rther calculation indicates that, in general, b 0 so, in first
approximation [,] = [X] 3, (7.1.27) for [X] small. It then follows that, to first
order in IX], where v0 is the acoustic speed, given by (7.1.24). One is then in the
realm of linear theory and the pulses accurately described by this are often called
acoustic waves or stress waves. To a good approximation equality then holds in
(7.1.15). Accepting this, workers then do not worry about the implications of the
possible inequality. Bear in mind that here we only explored conditions relating
to a discontinuity. Complete analysis of a problem also involves satisfying
equations of the kind discussed in Chapter 2, where solutions are smooth. Also,
we have emphized how thermodynamic reoning is used and other kinds of
reoning are employed. In practice, one encounters situations in which more than
one solution satisfy all the conditions discussed. One of the Mnds of reoning
used to try to decide which is best then involves considering the possibility that
the shock can generate pulses of smaller amplitude. Consider the front side and
suppose that these weaker waves have speeds fter than that of the shock. They
will then tend to move out ahead of it. The notion is that this will tend to make
the shock smooth out, almost instantaneously. So, the shock is more likely to
persist if these weaker waves travel more slowly. Similarly, it is better if weaker
waves on the back side travel more quicMy than the shock. One can use (7.1.24)
a first estimate of the wek wave speed ahead, using the analogous estimate
behind, to be 7.2 Breaking Bars 99 compared with the shock speed, given by
(7.1.16). Notice that this uses the slope of the isentropic stress-stretch curve. If
one uses the slopes of the isothermal stress-stretch curve in Fig. 7.1 to estimate
the weak wave speeds, the situation looks favourable at A-, unfavorable at A +.
One could make it appear more favorable by increasing A + sufficiently to make
the shock chord tangent at A +. It is not difficult to calculate the difference
between the isentropic and isothermal slopes at corresponding values of O and 7,
so you can try this to see if you come to a different conclusion. 7.2 Breaking
Bars As was mentioned in the preceding section, it is sometimes relevant to
consider surface energies associated with discontinuities. Let us consider a
different possibility of this kind. We return to the equilibrium problems
involving bars in hard loading devices, discussed in Section 3.2. Generally, this
loading makes the relevant energy higher than it would be if the bar were
unloaded. There is a way for this energy to be reduced. Let the bar break and this
will certainly cause it to be unstressed, making y(x) itself discontinuous. This is
a possibility we have avoided considering, although we all know that it can
happen. However, the reasoning seems to indicate that the slightest stress should
suffice to break it, which does seem contrary to experience. Here, the reasoning
commonly accepted is that the process of breaking creates new surfaces and with
these is associated an energy proportional to their area. Usually, this is
considered as the area occurring when the sample again becomes unstressed. So,
if our bar breaks cleanly on a plane whose normal is parallel to the long
direction, represented mathematically by our x-interval, this produces an
energy e = 2G AR. with AR our reference area, G being the energy per unit
reference area. The factor of 2 arises because the break obviously creates two
surfaces. Solutions of this kind discussed in Section 3.2 then apply as long as F,
given in (3.2.2), is smaller than e and, when F > e, the bar should break. There is
an intermediate possibility that a crack will be produced, go part of the way
through the specimen and stop. One then needs two- or three- dimensional
theory to analyse the associated adjustment in the Helmholtz free energy. In
some cases it diminishes enough to make it energetically disadvantageous for the
crack surface area to increase. This provides some basis for understanding
whether an expensive structure containing such flaws can be considered safe,
among other things.
100 7. Moving Discontinuities 7.3 A Peeling Problem Somewhat similar to the

previously mentioned crack propagation problems are peeling problems.
Suppose that a very thin and flexible adhesive tape has adhered to a fiat surface
of a stationary rigid body. We consider the possibility of peeling it off, by
applying a tensile force as a dead load at one end. As usual, we assume that the
ambient temperature is fixed. Think of our tape as a rectangular bar, with width
a, thickness b, b/a << ! and assume that it has been applied so that it is
unstressed, although peeling it will change this. Then, for the bar, it is
convenient to use the strain energy per unit volume W(A), at the prevailing
temperature, giving L FB = ab fo W(A) dx, w(1) = o, (7.3.1) as the relevant
energetic contribution for it. If the force peels off part of the tape we will have a
configuration like that pictured in Fig. 7.2. In principle, there is some energy
associated with bending the tape, which we neglect. Where the tape still adheres,
we assume that the bar stays unstretched (A -- 1). In the remainder, there will be
some other stretch A, the distance d in the figure being given by fx L d -- dx.
(7.3.2) o There is the usual potential involved with the dead loading device. For
it, we need the scalar product of the vector force with the vector displacement or,
what is the same, f, multiplied by the component of displacement which is
parallel to the force. Using simple geometry, this gives the potential -fid - (L -
xo) cos g]. (7.3.3) Also, we introduce the idea that there is a surface energy to be
added, proportional to the area occupied by the part of the tape which has come
off, before it was removed. So, it will be of the form e -- Ga(L - xo)a, where Ca
is a positive constant depending on the tape and the material from which the
rigid body is made. It is a matter of experience that a given tape will adhere
better to some materials than to others and it is here that we account for this.
Adding the contributions we get the thermodynamic potential fx L F=ab
W(A)dx- f[d-(L-xo)cosg]d-G,(L-xo)a, o (7.3.4) 7.3 A Peeling Problem 101
FIGURE 7.2. A fixed force of magnitude f, acting at the angle o, peels part of
the tape off the rigid body. The nearly vertical arrow indicates the displacement
at the end. with d given by (7.3.2). We will disregard the possibility that the tape
breaks or that the rigid body gets damaged. We do need to bear in mind that the
configuration pictured can hardly apply if the tape is all peeled off, or if none of
it is. However, for the time being, we will not worry about this. For other values
of x0, we can vary x0 and the bar deformation independently. Varying the latter
gives, as an equilibrium equation, the force balance ,,W' (. ) = ,,, = f . (7.3.5) For
simplicity, we assume that W(A) is convex, so this determines just one value of
A. Putting this back in (7.3.4) gives r = (L - x0)bb[w() - - cos + ago). (7.3.6)
Clearly, this has a minimum at x0 = 0 when ab[W(A) - (A - cos g)er] d- ago 0
(7.3.73) xo = L when ab[W(A) - (A - cos g)cr] + aG, > 0 (7.3.7b) and is
independent of xo when b[W(A) - (A - cos g)er] + Ga = 0. (7.3.8) Now, if no
tape is peeled off, the obvious value of F is F = 0 and (7.3.6) reduces to this
when x0 = L. Then, (7.3.7b) gives a reasonable estimate of what is needed for
such configurations to be stable. Similarly, (7.3.8) gives a critical condition for
the tape to begin to peel off. Once the inequality in (7.3.73) holds, it is better for
x0 to decrease, that is, more of the tape to peel off. Physically, (7.3.73) cannot be
trusted, implying that the tape can still support a stress when the area with which
it contacts the rigid body reduces to zero. Instead, it will in fact lose its ability to
be in equilibrium supporting the force applied at one end. To analyze what then
happens,
102 7. Moving Discontinuities one would need to say more about the mechanism
for applying the force and we will not pursue this. Otherwise, the model is
reasonably consistent with experience. Let us try to obtain a better understanding
of what it predicts. If, as was assumed, W(A) is a convex function of A, a() is a
monotonically increasing function of , with a(1) = 0. Thus the values of
satisfying (7.3.5) will, for positive f, increase with f and be greater than one.
Consider, for any fixed value of g() = b[W(A) - ( - cos )o-1 + a, (7.3.9) we have
and 9(1) = aGa > O, (7.3.10) g'(A) = .b[W'(A) - - (A - cos (7.3.11) = -ab(A - cos
0)cr' < 0. For A > 1 and (A- 1) sufficiently small, g(A) will be positive by
continuity and this will correspond to having f small enough. Then, (7.3.7b)
implies that the whole tape should remain in contact with the other body. As f
increases, (7.3.5) implies that g(A) decreases. Mathematically, it could approach
a positive constant as A becomes large. Physically, something must happen if the
force gets sufficiently large but there is some possibility that this may occur, by
breaking out chunks of the other body, for example. Assuming g does continue
to decrease, it will vanish at some critical value fc of the force. Here, in
principle, any part of the tape could peel off with the rest staying in contact. For
f > fc we will have g < 0, the somewhat shaky (7.3.73) seeming to imply that the
whole tape should come loose. With the inevitable experimental errors, it is
unlikely that we will attain the value of fc exactly. Granted this, one should see
the tape either staying in complete contact, or coming completely free,
depending on the size of the force, in this kind of experiment. This is consistent
with experience on relatively long tapes, for which L/a is relatively large.
Generally, applying a force in the manner indicated either leaves the whole tape
in contact with the other material, or the whole tape comes off. If a force induces
it to come off, a larger force simply makes it peel off more quickly, assuming
that there are no other complications such as having the tape break. Also, from
our considerations, the critical force fc occurs when (7.3.8) holds and this clearly
depends on the angle 0, which should be in the range 0 physically. In this range
and with cr 0, as it must be, it is easy to see that for any fixed value of A ) 1, g
increases with T. Combine this with (7.3.11) and consider the critical values of
A, say Ac(0), obtained by solving g(, V') = 0, (7.a.1.) and you can conclude that
A must decrease as o increases. From this, it follows that fc is a monotonically
decreasing function of o. At least qualitatively, this is also in accord with
experience. 7.4 Another Peeling Problem 103 Another picture can be useful.
Rewrite (7.3.8) as (/k c -- COS (fi)cr(.c) -- W(/kc) ---- Ga/b. (7.a.la) Then,
consider the graph of or(A) in the A-or plane. The first term can be interpreted as
the area of a rectangle with height cr(Ac), base (Ac - cos o), the length of a line
segment on the A axis, running from A = cos o < 1 to A = A 1. From this, we
subtract W(Ac) which we know is the area under the stress stretch curve
between A = 1 and A = Ac. Thus, the left side of (7.3.13) represents the area of
the rectangle which remains after removing the latter part. When this area
matches the number on the right, the equation is satisfied. From our previous
considerations, there cannot be two values of Ac satisfying it if W(A) is convex.
If it is not, then one can get into complications such as are discussed in Chapter
3. 7.4 Another Peeling Problem Here, we consider a procedure permitting us to
peel off only part of the tape, also indicating how we might apply the tape so
that, after it is placed, it will be unstressed. Again, we gloss over some physical
difficulties occurring when only a small part near one end is in contact. Here, the
end x = L is to be moved perpendicular to the rigid body to a height h, then held
at this fixed position. Otherwise, the assumptions are similar to those made
before. Figure 7.3 indicates the configuration to be considered. Here, the angle o
is not given. As before, W(A) is assumed to be a convex function for simplicity
and we again ignore complications associated with damage to the materials. It is
then rather clear from our past experience that, in the part pulled off, the stretch
A will be constant, so we will assume this although it is something that could be
proven. Here, with the end held fixed, no work will be done on it so, in place of
(7.3.4), we now have L F=,o f w(A)cx +G.(�-xo)a o = a[bW() + (7.4.1) where
and note, from Fig. 7.3, that I = L - x0, (7.4.2) d'2 = 12 + h 2 (7.4.3) ____ ,2/2,
104 7. Moving Discontinuities / d � h FIGURE 7.3. Raising the end of the tape
vertically, to a height h, partially peels off the tape. and tan qo = hi1. (7.4.4)
Thus, two of the three variables (A, l, q) can be expressed in terms of the third.
We could take any one as the basic independent variable, it being a matter of
judgment which is best. First, let us try using = l/h 0 _< _< L/h. (7.4.5) Then,
(7.4.3) gives A = X/f+/z -2 > 1, (7.4.6) and (7.4.1) reduces to the form where
F/ah = U(.) + (7.4.7) (7.4.s) If/z is very small, A is very large, approaching
infinity as p -+ 0. Physically, it is then unlikely that we will have an end point
minimum at p -- 0. Also, having p at the other limit really means that all the tape
h peeled off. If we continue to hold one end fixed the remainder will be subject
to no force, so no work will be done on the tape. It should then come to
equilibrium, unstressed, giving F = aLC (7.4.9) a reonable estimate of the energy
it will then have. The remaining possibility is to have equilibrium with not at
either limit. Then, mathematically, analysis of (7.4.7) is essentially the same
that of analyzing bars under dead loads discussed in Section 3.1, or of the
balloons under fixed pressure discussed in Section 5.1. The equilibrium equation
is '() = -C, (7.4.0) 7.4 Another Peeling Problem 105 the second derivative test for
stability giving U"(p) k 0. (7.4.11) Conditions for stable equilibria can be
pictured, as before, in terms of the graph of U(/) or of U'(I). Some points are
worth noting. Suppose (7.4.10) is satisfied by some value of/ -- . This is
acceptable only if it satisfies < L/h, which will be true if we make h small
enough, but not if h is too large. For the range of h for which it is acceptable,
(7.4.4) will give a value of qo = which is independent of h. Ignoring the question
of stability, the implication is that if we increase h a little, more of the tape will
come loose, enough to get back to its original value with no change in the value
of Clearly, it can so adjust only as long as there remains enough tape to be
peeled off, that is for h <_ Ltan. (7.4.12) For such configurations to be more
stable than they would be if the tape pulled off completely, using (7.4.7) and
(7.4.9) gives the condition h[U() + G] < LG. (7.4.13) Now consider (7.4.8). With
(7.4.6), straightforward calculations give b + =b [W(A)-(-a 1) -a(A)] (7.4.14) :
Note first that, from Fig. 7.3, L - x0 I 1 ..... . (7.4.15) cos - d d With this, we see
that (7.4.14) agrees with (7.3.8), which is not surprising. Also (7.4.16) _ + d
Now, kom (7.4.6), dA/d < 0 and A > 1. om our smption that is convex with (1) =
O, it follows that (A) > 0 for A > 1 and (A) k O, kom which U"() > O. (7.4.t7)
106 7. Moving Discontinuities There then can be no more than one equilibrium
value of the kind discussed above. Also there can be at most one value of the
angle , in the range 0 <_ < r. Assume there is one. Then, for h satisfying (7.4.11),
we have equilibrium configurations satisfying all the requirements for stability
except perhaps (7.4.12). With a fixed number, this will also hold if h is
sufficiently small. For the largest possible value of h, given by the equality in
(7.4.11), it is easy to see that (7.4.12) fails to hold. Thus the two energies
become equal at some value hc, given by hc = ' (7.4.1s) So for h < he, the more
stable configuration has the tape partially adhering, enough to conform to the
angle . For h > he, the more stable configuration changes, to have the tape
completely removed. From the analysis, the possibility of the tape adhering
when h > hc giving a metastable configuration does not seem unreasonable in
cases where we are increasing h, to peel off more of the tape. In laying a tape
down, we commonly hold the part near an end in place to get the process started.
Clearly, our analysis does not cover this. Essentially, the theory is designed to
apply to situations such that one can lay down and peel off the tape without
damaging the tape or the other material. To determine W(A) for A 1, most would
try a simple tension experiment. Either of the two peeling experiments could be
used to try to estimate Ga. Here, one could measure the stretch in the stretched
part. Similarly, hc might be measured. Think a little more about the measurables
in the two experiments and you have a design for an experimental programme to
provide a test of the theory in order to see if its predictions agree with the
experimental findings. This is a sample of ideas used in tackling problems
relating to the adhesion of one material to another. Works dealing with this
general topic include the books by Cheng [36] and Wu [37]. 7.5 Exercises For
Exercises 7.1-7.3, adapt the theory of fast shock waves in bars to the theory of
shearing of plates, using the constitutive equation �_ a(1-bO) 2 cIOln(- )_O+d
1 2 ' where a, b, c, and d are positive constants. For various metals, empirical
estimates of b give it the value 1/(202u), where OM is the melting temperature,
so the theory does not apply if 2bO _> 1. If some prediction violates this, note it.
For the exercises indicated, assume that, on one side of a shock, 7 = O, 0 = d,
and on the other, 7 = � > O. 7.5 Exercises 107 7.1. Derive the Rayleigh
equation. 7.2. Derive the Rankine-Hugoniot equation. 7.3. What can you say
about the admissibility of such a wave? 7,4. Consider the kind of peeling
problem discussed in Section 7.2 for a linear elastic tape with the strain energy
function W = E(A - 1)2/2, E being Young's modulus, a positive constant. Let
f(b) denote the lower bound of the force required to peel off the tape, when it is
applied at the angle b. Derive formulae for the ratios f()/f() and f(3_)/f(). 7.5.
Derive an equation relating isothermal and isentropic acoustic wave speeds for
bars, in terms of things either measured or easily calculated from things
measured in the common thermodynamic experiments.
8 Mixture Theory 8.1 General Remarks From a macroscopic point of view, the
composition of matter can change in various ways. It is a familiar fact that
changes in the humidity occur in the air we breathe, causing wood to shrink or
swell. This makes it reasonable to think that the wood absorbs different amounts
of the vapour depending on its environment, producing an effect somewhat like
thermal expansion. Materials like glass are clearly more reluctant to absorb the
water, making it clear that the water vapour is not uniformly distributed in a
room containing various kinds of materials, although it may be uniformly
distributed within a particular substance. Again, it is a matter of experience that
different amounts of a solid can be dissolved in a given amount of a suitable
fluid and that, if we change the temperature, say, some of the dissolved solid can
come out of solution. Sometimes we use this to grow larger crystals from small
ones. Not so different are the procedures used by a metallurgist to make alloys;
that is, melt and mix together different kinds of solids, then cool the mix to
solidify it. With the same ingredients mixed in different proportions he can
obtain different alloys. For example, he might produce a or /3 brass by using
different proportions of copper and zinc. In many situations like this, it is
reasonable to think that the ingredients retain their identity so the total mass of
one remains fixed. We are then concerned with mixtures which are, in a sense,
nonreacting. Chemical reactions can change the mass of particular ingredients
with, for example,
110 8. Mixture Theory hydrogen and oxygen gases reacting to produce some
water. Stoichiome- try provides rules, restricting how the different masses can
change in such reactions. Gibbs' general ideas of thermodynamic equilibrium
and stability can be applied to such phenomena. Indeed, Gibbs was a pioneer in
developing such theory. Here, we will discuss the most elementary format for
nonreacting mixtures, in situations where effects of shear stresses in the solids
can be ignored. To deal with such questions one needs to think of equations
describing parts of a system and this involves some judgment. In the first
example mentioned, most would think of the air and water vapour as one mate-
rial, described by one constitutive equation. A different equation would be used
for the wood and its water vapour. Generally, one idea is to try to arrange that
each constitutive equation can reasonably be considered smooth enough to let us
use common tools of analysis in each part. As we have seen before, smooth
constitutive equations can produce equilibria with discontinuities and we tend
to judge things on the basis of observations of equilibria. Given this, it is
inevitable that we exercise some judgment. In the simplest situations, one can
reasonably decide how to further subdivide so equilibria are also smooth in each
part. 8.2 Elementary Theory We consider a hypothetical example to introduce
some of the ideas. Pic- ture a mixture filling some volume V. Consider it to be
composed of homogeneous parts. That is, within a part, relevant state variables,
such as temperature, etc., can be considered to be independent of position. So the
presumption is that we know how to subdivide so that the equilibria are smooth
in each part. The parts will occupy volumes with =v. (8.2.1) i=1 An identifiable
ingredient, such as our water vapour, may be present in all of these parts and we
allow that this can happen, initially, and that the amount in one part can be
considered to change. Suppose that we have n ingredients, with masses ME, a =
1,..., n. Then, if M (i) is the mass of the ath ingredient in the volume V/, we must
have M (i) = ME, a = 1,..., n, (8.2.2) i=1 8.2 Elementary Theory 111 it being
possible that some of the M (i) vanish. This is a static theory, so we are not
concerned with motion. With the ith part we associate a total energy Ei and
entropy $i and a constitutive equation. That for i = i is assumed to be a smooth
function of the form Z 1 = Ei(Vi,Sl,M?),...,Mn(1)), (8.2.3) with similar
assumptions for E2, etc. It is possible that one constitutive equation applies to
two more parts. The assumptions are fairly reasonable if we have solid parts
separated by fluid parts, so the solids can adjust their shape fairly freely to avoid
shear stresses. The idea is that the partial volumes and masses can vary, subject
to the requirement that (8.2.1) and (8.2.2) be satisfied; we do not want
overlapping volumes, for example. We set OEi (8.2.4) Pi -- 0V/' interpreted as
the pressure in the ith part, (8.2.5) Oi - OSi ' the temperature in this part and OEi
ti, OM(i) , (8.2.6) these being called chemical potentials. Now look at the
differential of Ex. One term, -p dV can reasonably be interpreted as the work
done by the pressure as the volume V1 undergoes an incremental change. An-
other, OdSx, similarly can be identified with heat supplied reversibly. If we
stopped here, things would make reasonable sense in terms of the first law.
However, there is a problem in dealing with the changes in E produced by
changing the masses in V which does not really fit the first law. One could try to
generalize the first law to cover this. What is more often done, sometimes,
tacitly, is to consider that any thermodynamic system deals with a fixed set of
matter. From this viewpoint the energy E is then an energy associated with part
of a thermodynamic system, which is not itself a thermodynamic system. The
usual idea that energies and entropies are additive then gives for the energy E
and entropy $ of the system, m E = y]Ei, i=1 m S = y]Si. i=1 (8.2.7)
112 8. Mixture Theory Physically, we can reasonably think of this as a

mechanically isolated system if we think of V as the volume of a fixed region
so that forces acting on its boundary do no work. Further, it should prevent any
matter from leaving or entering, so that Me become fixed constants. Thermally,
a likely assumption is that the system is in contact with a heat bath at the con-
stant temperature 0B. Then, the appropriate thermodynamic potential is the
ballistic free energy, EB = E - OS. (8.2.8) In considering possible variations, one
needs to consider the possibility that some of the masses M (i) or some of the
volumes may vanish. 1 This reflects the experience that, in the first case, some
materials are very reluctant to absorb others. In the second case, we know that
a solid lump is sometimes completely dissolved in a fluid. The fluid might well
be capable of dissolving more if it were supplied. Clearly, we cannot allow
variations making masses or volumes negative. One can modify the scheme a
little. For example, if one is convinced that it is quite impossible for one sub-
stance to penetrate another, one can impose the constraint that one of the M (i)
always vanishes. Materials like this are certainly of some importance, as
containers for other materials, the thin films which serve as barriers to water but
not air, etc. However, we will not consider this kind of possibility. It is assumed
that V =OE =0. As usual, we proceed to use the first derivative test, to obtain
equations of equilibrium. That is, we want the differential condition dE3 = dE -
03 dS = (dEi - 03 dSi) > 0, i=1 (8.2.9) for all possible variations in the
independent variables involved. There are the constraints, i=1 m dV = = O, i=l
(8.2.10) In the case where the volume occupied by an ingredient approaches
zero, it can be tricky to try to take limits of this kind. Usually, one can explore
equilibria with or without complete dissolving, then determine which is most
stable by an energy comparison. Think back to what we did for the balloon with
pressure controlled. 8.2 Elementary Theory 113 at least. First consider varying
only the entropies $i. With (8.2.5), this gives, assuming no V/= 0, ra :0. i=1 With
the usual assumption that entropies can be varied arbitrarily, this gives OEi Oi -
OSi - 0. (8.2.11) If some V/= 0, one simply does not get the corresponding
equation. Phys- ically, in equilibrium the temperature throughout the system
must reduce to that of the heat bath. As in other cases discussed before, most
workers are willing to assume this and that (8.2.5) can be solved for Si as a
function of Oi and the other variables. Then, one can replace Ei by the
Helmholtz energy F : F(�, 0, M (0) : E - OBSi. (8.2.12) By an exercise in
calculus, one can then show that OF OF OF $i -- Pie -- -- (8.2.13) Pi -- OVi '
OOB ' OMa (i) ' Similarly, (8.2.9) can be replaced by ra dF = dFi _> O. (8.2.14)
i=1 So, let us use this formulation. First, consider possible equilibria for which
none of the masses or volumes vanish, assuming that all the differentials
satisfying (8.2.10) are permissible. With our assumption it is easy to see that, in
(8.2.14), it is not possible for the inequality to hold. In part, we then get the
conditions m OFi i=l or, with (8.2.13) m Zpi dV/ = O, (8.2.15) i=1 for all dV/
satisfying (8.2.10). Clearly, we can assign arbitrary values to dV2,..., dVm and
solve (8.2.10) for dV. If we multiply the sum in (8.2.10) by pi and subtract this
from (8.2.15), we get m '(Pi - P) dV/= 0,
114 8. Mixture Theory where the dV/ occurring here are arbitrary, so we must
have Pl P2 ..... Pm, (8.2.16) the equality of pressures which we might also infer,
mechanically, as a balance of forces. Similar consideration of variations of
masses gives, with (8.2.13), the equality of chemical potentials given by Pa =
P2a ..... Pm, a = 1,...,n. (8.2.17) So, (8.2.16) and (8.2.17) give the equations of
equilibrium. Of course, we also must satisfy (8.2.1) and (8.2.2). With Ms and V
here considered as given, the number of equations is then the same as the
number of unknowns (V/ and M(i)). While we shall not discuss in detail the
equilibrium conditions which apply when some of the volumes and/or masses
vanish, there is another assumption concerning constitutivc equations which
deserves to be mentioned. Briefly, it is that, if we multiply all masses and
volumes by a common factor, we can get the new energy by multiplying the
old value by the same factor. Roughly, it is the proportions which matter, not the
absolute amounts. For example, for the function F, we assume that for any
positive number k, and any possible values of the arguments, we have a (kV, 0,
kM?) -- 1 (V, 0, M?). (S.2.18) as a restriction on the form of this function. If we
differentiate this relation with respect to k, then set k = 1, we obtain the identity
n -pig1 q- Z I/laMa(I) -- Fl' (8.2.19) There are various ways of taking care of this
restriction. For example, taking k = l/V1 in (8.2.18) and setting Fl(X,O,p(a 1)) :
(1(0, p(al)), p(a 1) : MI)Iv1, we have Fx = Vq (O, p?), (8.2.20) are interpretable
as mass densities, qb as the Helmholtz free where p(l) energy per unit volume.
As is easy to check, if we take any function (/)1 of the indicated arguments and
use (8.2.20) to define F, it will satisfy (8.2.18) and (8.2.19). This opens the door
for dealing with problems in which the mass densities p(l) might vary with
position, as they will in a gravitational field. This can be important for
estimating water content in soil near a deep lake, for example. Then, the total
Helmholtz free energy F in a region occupied by this component could be taken
as F ---/�1(0, p(2 )) aV, (8.2.21) 8.2 Elementary Theory 115 giving (8.2.20)
when the integrand is constant and the volume of the region is V. Clearly, much
the same considerations apply to the other Fi and to the El, with the
understanding that entropies are to be replaced by entropies per unit volume.
With (8.2.20), one can verify that (8.2.19) reduces to -p + /aP ) = (/)1' (8.2.22) A
slightly different formulation can be obtained by introducing m (1): Ma (1),
(8.2.23) the total mass in V and the concentrations (mass fractions) c( 1) =
M()/m 0), (8.2.24) numbers lying between zero and one, satisfying n c( 1) = 1.
(8.2.25) ot=l Then, one can introduce the specific volume v = V1/m O) 1 = --,
(8.2.26 Pl where/91 is the total mass density in Vx. Then, taking k = l/m0), we
see that we can also write F in the form F 1 : TY/(1)()l, 0, c 1)) : Vlpl,()l, 0, cl)),
(8.2.27) and we can, if we like, use (8.2.25) to eliminate one of the c(a 1).
Originally, Gibbs introduced this kind of theory as a theory of fluid mixtures but
later workers, like those interested in alloys, have applied it to cases where some
of the parts are solid. Confining solids to a fixed region can easily induce shear
stresses, so it is a little more natural to think of V as the volume of a region
partly occupied by solids which are surrounded by a fluid at a fixed pressure p,
where the shape and volume V of the region can change, to help avoid such
complications. Then, the surrounding fluid serves as a loading device which can
do work on the solids. This changes the relevant thermodynamic potential from
F to G = F + pV, (8.2.28) sometimes called the Gibbs' function. Involved, tacitly,
is the assumption that the solids will stay in V, and not diffuse into the
surrounding fluid,
116 8. Mixture Theory 8.2 Elementary Theory 117 an assumption which can be
quite good, or very bad, depending on the materials involved. It is a poor
assumption for dry ice in air at room temperature, for example. Here, the
subvolumes are still considered to add up to V, as indicated by (8.2.1), but V can
vary. Also, (8.2.2) should hold with ME fixed. Again assuming non-zero
volumes and masses, we get, as equilibrium equations, Pl ..... Pm ---- P, (8.2.29)
as a replacement for (8.2.16) and, as before, (8.2.17), the equality of chemical
potentials. Here, V is not known but p is regarded as a given constant. Often,
workers will go a step further. Suppose p is a monotonically decreasing
function of V1 when the other variables are held fixed (Opl/OV1 = -02F1/OV12
< 0). Then, we can solve p -- p for Vx = f(p,O, Me()), and express G = F + pV1
(8.2.30) as a function of these variables. Then, an exercise in calculus gives 0- --
Sl, Op -- V1, 0Me(1) - 13. (8.2.31) With similar assumptions, we can do the
same for the other ingredients and get m m G-- y.Gi-- y.(Fid-pVi) = F+pV, i= i=
(8.2.32) = G(O,p, Me(i)). Breakdowns in the assumed invcrtibility associated
with phase transitions sometimes occur. Attempts to perform the inversion can
then lead to Gibbs' functions which are multivalued and/or exhibit singularities
when the corresponding Hclmholtz free energy function is well-behaved. This
is not to say that the latter cannot be ill-behaved, but the situation described is
rather common. Commonly, phase diagrams are drawn to indicate under what
conditions phase transformations take place. Typical diagrams for alloys are
discussed by Ricci [38]. After taking care of satisfying the equilibrium equations
one would like to test for stability and a common procedure is to try to use the
second derivative test. If, say, one is using (8.2.9) and is not concerned with the
possibility of zero masses or volumes, one would calculate the second dif-
ferential of EB, a quadratic in the differentials of Me (i) , Vi and $i. Some of the
differentials can be eliminated, expressed as linear combinations of others, to get
a quadratic form involving differentials which can be varied arbitrarily. For
metastability one would like this to be positive or maybe zero, for all choices of
the differentials. Schematically, one has a quadratic condition like Q = aijxixj _
0 (i,j=l) for all choices of xi, and we can assume that (8.2.33) aij - aji. If this is
not true, we can replace the cocffcients aij by (aij d- aji)/2, which does not affect
Q. One way of proceeding is to determine all of the cigcnvalucs of the matrix ]]
aij ]]; they must be nonnegative. In most cases it is easier to use another test.
Suppose first that the inequality is to be satisfied in the strict sense, Q = 0 only
when all xi = 0. Then, in the matrix ]] aij [[, go down the main diagonal,
blocking out i x 1, 2 x 2,..., matrices as indicated by the diagram [i, a13 a32 a33 [
aln aln a2n a3n ann Then, we will have Q > 0 if, and only if, the determinants of
all these matrices are positive? This gives a string of inequalities such as all > O,
alla22 -- a122 > 0,... , (8.2.34) not so difficult to check. If (8.2.33) does not hold
in the strict sense, there will be some nonzero xi for which Q -- 0 and, with Q _
0, these will satisfy the first derivative test for a minimum, aijxj ----- O, (8.2.35)
j=l linear equations which are fairly easy to solve. One can then make a change
of variables to get a quadratic form in fewer variables, which is strictly positive,
then use the above criterion for it. This covers some of the basic ideas used in
formulating elementary problems involving mixtures, enough to indicate that
they are similar to ideas we have used before. As might be expected from our
discussion, analysis of physical problems of this kind tends to be rather
complicated but involves ideas much like those used before. 2A proof is given in
Frazer et al. [39].
118 8. Mixture Theory In part, we introduced this to cover stability problems

which can involve a large number of variables. One can encounter these in
various other situations. Even with our simple balloon problems, one
encounters the need to take several variables into account if one considers many
balloons, connected by pipes so air can move from one to the others. In part,
we have also introduced this to indicate that, while deformations and
temperatures generally have some relevance to the description of the states of
solids, other quite different variables may also be needed. Amongst other things,
this indicates that the "typical" thermodynamic experiments discussed in Section
2.5 need to be revised to provide relevant information concerning the other
variables. Finally, mixture theory is being used, increasingly, to help us
understand a variety of phenomena, so it seerns worthwhile to discuss it a little.
8.3 A Solid in an Ideal Gas Here, we will consider one of the simplest situations
employing two volumes, involving a solid surrounded by an ideal gas. The
assumptions are as before, except that we assume that the solid remains intact,
no part of it entering the surrounding gas. However, gas can move into the solid.
The problem is to design the analogue of the thermodynamic experiments for
bars discussed in Section 2.5, to determine F. If the index 1 refers to the solid, so
it occupies the volume V etc., our assumption is that = 0 M?) = (8.a.1) a fixed
constant for a given sample of the solid. For the solid, the Helmholtz free energy
function is an unknown function of the form Fx(V, M1, M x), 0), (8.a.2) and we
are concerned with this at a fixed values of 0, in considering isothermal
mechanical experiments. This leaves V and M2 O) as two variables which we
want to vary independently. For the surrounding gas, (8.3.1) per- mits us to
continue to model this as an ideal gas, so we will have ROM2 (2) P2- (8.3.3)
Also, the usual assumption is that Cv, the specific heat at constant volume, is
constant. With this, the corresponding Helmholtz free energy function is of the
form V2 b] F2 = M2 (2) -RO In 2(2 ) - Cv 0 In 0 + aO + , (8.3.4) 8.3 A Solid in
an Ideal Gas 119 where a and b are constants. This fits the format indicated by
(5.1.7) in our discussion of balloons. In such cases, where the mass of gas is held
fixed, the values we assign to a and b are unimportant. Here, their values will
affect values of chemical potentials, so it seems safer to avoid assigning values
to them to see what happens. To simplify notation, we write M 2 : M, M2 (1)
=/T : M2 (2) = M- IT. (8.3.5) It is a reasonable guess that, to vary V1 and m
independently, we will need to use two control parameters. For one of these, let
us try using the total volume V, with V: Vl q- V2, (8.3.6) Physically, this could
be done using a sturdy pressure chamber involving a movable piston as a wall.
As the other, we consider using the amount of gas put into it, as measured by M.
Physically, one wants to keep the walls from enough contact with the solid to
induce shear stress, etc., so cases where V2 = 0 are not of all interest. Said
differently, we can vary V2 sufficiently to get equality of pressures 0F2 (8.a.7)
P2: Pl -- OVI ' Otherwise, equilibria of the endpoint type could occur, with m =
M or m - 0 but, for the moment, we will exclude these cases. Then, we should
have the equality of chemical potentials indicated by (8.2.13) and (8.2.17). With
(8.3.4) and (8.3.5), we thus get OFx [1-1n .- j ] - CvO -no In 0 + aO + b. (8.3.8)
Similarly, (8.3.3) and (8.3.5) give OF { M_-_m (8.3.9) - n� k v- ] ' So, for
various values of O, we should vary M and V as much as is feasible, performing
the measurements required to obtain corresponding values of m and V1. If all
goes well, we then get empirical relations of the form m = re(M, V, 0), Vl = V
(M, V, 0), invertible to give relations of the form M = M(m,V,O), V =
V(m,V,O). (8.3.10) Realistically, one might encounter complications more or
less like those we have encountered in other situations, but we will ignore this.
120 8. Mixture Theory Now consider what happens if we let M approach zero,
which will also force m to approach zero. Since we are dealing with a solid, V is
not likely to approach V if we make V large enough, so the pressure should
approach zero. Under these conditions, if we vary 0, the pressure will remain
zero and the volume V1 can be expected to change. This is the analogue of the
thermal expansion discussed in Section 2.5. This gives a function which can be
measured V: v(O), when M = m = O, (8.3.11) such that the derivative in (8.3.8)
vanishes. With this, and (8.2.13), we then have dF1 = -1 dO, (8.3.12) where = S
[ = (O) (8.3.13) v =v(0) is the entropy function for the special processes
considered. To determine it, one needs measurements of the specific heat at zero
stress, the analogue of the Co(O) mentioned in Section 2.5. This will determine
to within an unimportant additive constant. Now, we can introduce a kind of
analogue of the strain energy function introduced in Section 2.5. Bear in mind
that M is considered as a fixed constant, so the empirical functions could depend
on M were we to consider other values. Here, we introduce a function such that
W = W(V, m, 0), (8.3.14) w(v(o), o, o) = o, (8.3.15) OW OF1 OW OF1 OV1
OVi' (8.3.16) where the right sides of (8.3.16) are expressed as functions of Vx,
m and 0 using (8.3.7), (8.3.8) and (8.3.9). The idea is to integrate these
equations, subject to (8.3.15), to obtain W. Given suitable isothermal mechanical
data, this is enough to determine W uniquely. By arguments similar to those
used in Section 2.5, it then follows from above that (8.3.17) F 1 = W-/l(O)dO.
We will not elaborate on these matters. However, some things are worth noting.
There are the constants a and b which must be regarded as rather arbitrary,
physically. As is clear from (8.3.7), they do affect the values of 8.3 A Solid in an
Ideal Gas 121 chemical potentials, so these are not really so uniquely defined for
a given pair of materials. In turn, this affects F and, through it, the dependence of
the entropy $1 on m. For common kinds of stability analyses, such ambi- guities
seem not to matter. In other kinds of thermodynamic systems, am- biguities of
this kind become, in some sense, greater. As a second point, we note that, given
sufficiently smooth data, we could calculate 02F1/OmOV2 in two different
ways, either by differentiating (8.3.8) with respect to V, or by differentiating
(8.3.9) with respect to m. Equating the two gives o ( v- o (8.a.18) 0--11 In .' L ] =
mm . V - V ]' Sometimes, relations of this kind are used as a crutch, to try to get
the best estimates of the empirical functions from data which might be too sparse
or inaccurate to make a very reliable direct determination. Of course, one cannot
exclude the possibility that any theory may be overturned by contradictory
experimental results, but with rather old, generally accepted theories such as we
are considering, I think workers would be more likely to believe that it is the
experiment which is in error. Some interesting observations are reported by Gent
and Tompkins [40]. Briefly, a piece of rubber is placed in a pressure chamber
which is then filled with a gas. One then waits for some time to let the system
come to equilibrium, or at least very dose to this. Then the chamber is vented to
permit quick escape of the gas. If the pressure was high enough, the whole block
explodes, becoming a collection of small fragments. The explanation they
propose is as follows. Inevitably, a piece of rubber contains tiny holes. In the
first phase, the gas moves rather slowly into the rubber, hence into the holes.
Generally, diffusive motions like this are not very fast. As suggested by the
above analysis, the holes then fill with gas, at a pressure comparable to that in
the gas external to the sample. When the exterior gas is vented, that in the holes
cannot move out so quickly, so one still has the high pressure there. Relatively,
this is like imposing a high tension on the solid and, intuitively, this could pull
it apart. Using this idea, combined with some rough calculations involving
rubber elasticity theory, they get an order of magnitude estimate of the value of
the pressure which must be exceeded to produce this kind of failure and it is
compatible with the observed values. As far as I know, no one else has proposed
a better analysis of the phenomenon. Phenomena somewhat like this are
sometimes explained in a very different way. If one ignores the possibility that
the gas enters the solid, one could argue that the sudden release of the exterior
pressure initiates something similar to a tensile shock or stress wave moving
into the solid. Generally, such analyses use linear theory, with some ad hoc
estimate of how large the tension must be to produce breakage, and, usually, this
kind of argument predicts breakage at particular places, producing spalling of
plates, etc. It is not inconceivable that one could use some analysis of this
general kind to explain the phenomenon. Generally,
122 8. Mixture Theory one can encounter cases where two quite different
theories seem to explain the same phenomenon. Then, one tries to decide which
is best. Decisions of this kind are made, occasionally, but no simple rule book
describes how they are made. However, arguments about such matters can result
in the design of interesting experiments in order to test the merits of different
proposals. 8.4 8,2, Exercises For the thermodynamic experiments discussed in
Section 8.3, one assumption is inappropriate for a solid like dry ice, which
readily transfers some of its mass to air. Revise the analysis to apply such solids.
To simplify considerations, assume that air does not transfer any of its mass to
the solid. You may introduce one other simplifying assumption which seems
physically reasonable to you, based on your experience with such solids, after
clearly stating what it is. Discuss how the kinds of measurements needed differ
from those discussed before. In the three-dimensional theory of linear elasticity,
W, the strain energy (per unit volume) function, is assumed to be an
homogeneous quadratic function of six measures of strain, and that it is positive
definite. For a transversely isotropic material, symmetry considerations reduce
this to the form W = Cl(x I -]- x2) 2 - C2x - C3(x I - x2)x3 - C4(x _]_ x5 2) '-
C5(x6 2 - XlX2) , where the C's are material constants and the x's label the
strains. What inequalities must the constants satisfy, for the quadratic to be
positive, in the strict sense? 9 Equilibrium of Liquid Crystals and Rods 9.1
Liquid Crystal Energies Although they are liquids, nematic liquid crystals
commonly used in display devices involve equilibrium problems which are more
like some encountered in solids. Thus, for example, one finds a chapter on them
in a volume on elasticity theory in the Landau-Lifshitz series on theoretical
physics [41]. At the same time, consideration of them will involve issues which
are different from those encountered before. Here, orientation replaces
deformation as an important quantity. For equilibrium situations, forces can be
involved, but they are generally not of sufficient interest to induce workers to try
to measure them and, more often than not, workers solve problems without
considering them explicitly. Also, for the first time, we will need to consider
effects associated with electromagnetic fields. Additionally, in the design of
devices and in measurement of material moduli, transitions play an important
role. These are liquids which are optically anisotropic when they are at rest,
being of what is often called the uniaxial kind, as are some crystals like Iceland
Spar. Roughly, such materials have one preferred direction, any direction
perpendicular to this being physically indistinguishable from any other. Suffice
it to say that one can use optical observations to determine the preferred
direction. We represent it by a unit vector n, n-n = 1, (9.1.1)
124 9. Equilibrium of LiquidCrystals and Rods commonly called the director.

Actually, the observations do not distinguish between n and -n, so n and -n are
physically equivalent. (9.1.2) Commonly, observations indicate that in a sample,
n is not constant but varies with position. Just how it varies is influenced by the
nature and sometimes, prior treatment of other materials brought into contact
with it, or by placing it in electric or magnetic fields, among other things. The
director vector field then defines a kind or orientation pattern and, in turn, what
it is affects light passing through the material. By learning how to analyse and
control such phenomena workers have been able to design and improve the now
familiar practical devices. From a thermodynamic point of view, we need a
constitutivc equation for, say, the Hclmholtz energy per unit volume. For most
fluids, we would think of this as a function of O, and p the mass density. Here,
we are dealing with liquids and, as is usually the case for these, it is reasonable
to assume that they can be idealized as incompressible materials. Said
differently, we can neglect variations in p. For the moment, assume that
electromagnetic fields are absent. Then, observations indicate that one can have
various orientation patterns induced by contact with other materials, etc.
Reasonably, different energies are associated with these. As a first guess,
workers are likely to try a local theory, using ideas similar to those discussed in
Chapter 2 and theory of this kind has performed well. I will sketch the ideas used
but omit some derivations. If we introduce rectangular Cartesian coordinates, n
has three components. First partial derivatives of these with respect to the three
coordinates can then be represented by a 3 by 3 matrix, denoted by Vn. The
basic assumption is that o, the Helmholtz free energy per unit volume, is of the
form o -- o(n, Vn, O). (9.1.3) Physical considerations impose some restrictions
on the function. From (9.1.2), we should have o(n, Vn, 0) = o(-n, -Vn, 0). (9.1.4)
Also, there is the notion of objectivity, used a little in Chapter 2. Here, the idea is
that merely rotating a liquid crystal should not change o. Any such rotation can
be described by a matrix R, satisfying R'R = 1, detR= 1. (9.1.5) The requirement
is then that, for any such rotation, we should have o(n, Vn, 0) = o(Rn, RX7nR ',
O). (9.1.6) 9.1 Liquid Crystal Energies 125 Roughly, there are two kinds of
liquid crystals covered by the description and some others which are not. Typical
display devices used in watches, personal computer screens, etc. employ nematic
liquid crystals. For these o is also invariant under reflections. This gives rise to
one more condition, o(n, Vn, O) = o(-n, Vn, O), (9.1.7) obtained by using
(9.1.6), with R describing a central inversion (R = -1). The second kind,
cholesteric liquid crystals, are used in different sorts of devices, for example
those serving as thermometers, by changing color as the temperature changes.
For these, o is not invariant under reflections. Typically, liquid crystal molecules
are rather rigid, with one direction large compared to others. In this sense they
are rather like the bars we have discussed. Depending on the material, these
molecules may or may not display some symmetry with respect to reflections
and, usually, it is this which decides whether they are to be regarded as nematics
or cholesterics. Here, we will only consider nematics, so (9.1.7) applies. Another
kind of simplification is based on observations. They suggest that, left to
themselves, nematic liquid crystals would prefer to have uniform orientation, n
= const. This suggests that such configurations minimize o o(n, Vn, O) _> o(n,
0, O). (9.1.8) Granted this, we have, as an analoguc of the strain energy
functions used before, W(n, Vn, O) = o(n, Vn, O) - o(n, 0, O) _> 0, (9.1.9) with
the property that W(n, 0, O) = 0. (9.1.10) For cases where n does not vary too
rapidly with position, it is reasonable to assume that W can be approximated
sufficiently well by its expansion up to terms quadratic in Vn about Vn = 0.
Imposing all the conditions noted above, one can use rather elementary
arguments, discussed by Frank [42], to determine the possible forms of W. This
gives, with notation now used by many workers, 2W = K(V. n) 2 4- K2(n. curl
n) 2 4- K3i[nxcurl nil 2 (9.1.11) 4- (K2 4- K4)[tr(Vn) 2 - (V' n)], where the K's
are material moduli, functions of 0 depending on the material. To have the
inequality indicated in (9.1.9) satisfied, these should satisfy K >_ 0, K2 _ ]K4[,
K3 _> 0, 2K1 _ K2 4- K4. (9.1.12) 1In this respect, the cholesterics are different,
preferring a kind of twisted configuration, like some to be described later.
126 9. Equilibrium of LiquidCrystals and Rods This is the so-called Oseen-

Zocher-Frank theory, an old workhorse which has satisfactorily described
numerous observations and has been part of the basis for designing experiments
and devices, etc. It provides a description of what is reasonably regarded as
mechanical energy. Also needed is some way of accounting for energies
associated with electromagnetic fields and crude estimates do well enough for
our purposes. One way to think of it is to consider the liquid crystal as a
thermodynamic system, acted upon by fields which are produced externally. The
problem is then to estimate the power they supply to the liquid crystal or, what is
more pertinent for equilibrium theory, the work they do on the liquid crystal.
This is subtle, so it seems worthwhile to consider a simple model to help
motivate what is done. Suppose the liquid crystal is placed on a constant electric
field. The force exerted by it on any charge is then obtained by multiplying the
(constant) electric vector E by the charge. We are dealing with dielectrics, their
electric response being like the insulating coatings applied to conducting wires,
for example. This means that charges able to move very freely are absent. A
molecule will, of course, contain the charged electrons and protons, but they
remain bound to it, the net charge for the molecule being zero. Thus, the
resultant force on the molecule exerted by the constant field is zero. One may
conclude from this that the field does no work on the liquid crystal, but this is
wrong. Consider the simple case of a dipole, consisting of two point charges, a
positive charge q with position vector r +, a charge -q at r-. By convention, we
associate with them a polarization vector p, given by p = q(r + - r-). (9.1.13)
Generally, they will exert forces on each other and be subject to forces exerted
by their neighbors, but our concern is more with the influence of E. If, in its
presence, the position vectors change a little to r + 4- Ar + and r- 4- At-, and if
AW denotes the work done by E, we then have AW = qE. Ar + + (-q)E � Ar- =
E. Ap, (9.1.14) which is generally nonzero. Here, the force averages to zero but
it still does ' some work. In, say, the biaxial stretch of rubber sheets, it is
obvious, physically, that the forces are not uniformly distributed along the edges.
The work done by them is not likely to be the same as it would be if they were
uniformly distributed, when the resultant forces match. Similar remarks apply
to loading the bars, etc. Were there some accepted way of correcting for such
errors, we would have commented on it in discussing such problems. Here, we
do at least have an example of one correction of this kind which is in common
usage. Commonly, liquid crystal molecules do have a dipole moment, a po-
larization vector of which one can think as attached to them. If they were all
aligned the same way, we could simply multiply (9.1.14) by the number per
unit volume to estimate the work done per unit volume. However, 9.1 Liquid
Crystal Energies 127 they are far from being so aligned. One can represent the
net effect macro- scopically by a vector P, a kind of statistical average of the
individuals in a unit volume. In the absence of an external field, the molecules
tend to be randomly aligned, which gives P = 0. Applying a field changes this a
little, causing some partial alignment, making P 0. For liquid crystals, the effect
is described sufficiently well by a linear equation of the form, P = aE+ b(E. n)n,
(9.1.15) where a and b are functions of O, invertible to give E = cP + d(P. n)n,
(9.1.16) with c = l/a, d = -b/[(a + b)a]. (9.1.17) For any fixed value of n, one can
use the obvious analogue of (9.1.13), which can be integrated to get WE, the
electric field energy per unit volume. wE = P = [cP. P + n) 2 OWE E- oP
(9.1.18) This is then a kind of potential energy, describing the work done on the
liquid crystal by the field in changing P from zero to the value of interest.
Physically, we expect this to be positive, conditions for this being that c
>O,c+d>O=,a>O,a+b >O. (9.1.19) What is neglected here is the induced field.
Briefly, a dipole itself produces a field which depends on its polarization. When
they are randomly aligned, these fields cancel each other, but there is some net
effect when they begin to be aligned by an external field, producing an addition
to E, an induced field. This is a relatively small effect, often, but not always,
neglected by workers: we will ignore it. In our argument, we assumed E is
constant for simplicity. However, the end result also applies to cases where it
varies with position. It should satisfy the equations for a static field, in vacuum,
or, more realistically, in air, which are V. E = curl E = 0. (9.1.20) A very similar
estimate covers the work done by magnetic fields. In place of E we have the
vector H describing the imposed magnetic field. It satisfies (9.1.20), with E
replaced by H. In liquid crystals it produces an analogue to P, magnetization
described by a vector M. The assumption is that M
128 9. Equilibrium of LiquidCrystals and Rods and H are linearly related, by

equations entirely similar to (9.1.15) and (9.1.16). The field energy is then the
analogue of (9.1.18), W, = 1/2M-H, (9.1.21) and, again, this should be positive.
Again, this neglects an induced field, an effect so small that, as far as I know, no
one tries to correct for it. Often, workers replace WE by a different expression --
1 WE = - D. E, where D = e0E + 4r P is the so-called electric displacement
vector, e0 being the dielectric constant for vacuum. One then has - WE - WE =
0E � E. This has some merit if one starts to correct for induced fields.
Otherwise, one generally considers E as a given field, WE and WE then giving
the same energy differences, so it does not matter which of these we use.
Bearing in mind that WE and Wn represent work done on the liquid crystal, we
then subtract these from W to obtain WT = W - WE - Wn, (9.1.22) as the total of
the mechanical and field energies per unit volume. For most cases of interest,
this covers the energies for which we need to account. 9.2 Orientation by Fields
and Walls First, let us think about what a liquid crystal would prefer to do if it
were under the influence of a constant electric field but otherwise were free to do
as it wished. Reasonably, it should try to minimize WT, given by (9.1.22). From
our discussion of W, its smallest value is zero, obtained when n is any constant
vector. As to WE, we can use (9.1.15) to express this in terms of E and n, the
rest of the energy being -WE=-E.P--- [aE.E+b(E.n)2]. (9.2.1) The problem is
then one of determining the unit vector(s) n for which this has the smallest
possible value, E being given. It makes a difference whether b is positive or
negative. The minimizing configurations are easily determined to be of the form
b>0=:n [I E, (9.2.2) 9.2 Orientation by Fields and Walls 129 or b<0n _ E. (9.2.3)
Liquid crystals fitting either case are available. With b > 0, one can use E to
induce n to take a definite direction. This is exploited in modern display devices,
for example. Some older devices used materials with b < 0, leaving n free to take
any direction in a plane. They did not perform as well and exhibited complex
behavior which is hard to analyze. It is instructive to look at the other equilibria.
Taking the differential of (9.2.1), we get the condition -b(E-n)(E. dn) _ 0, (9.2.4)
for possible dn. These are restricted by the condition that n be a unit vector, d(n.
n) = 2n. dn = 0, (9.2.5) being otherwise arbitrary. It is not very hard to show that,
for (9.2.4) to hold for all dn satisfying (9.2.5), n must be either parallel or
perpendicular to E. So, if b > 0, one has the stable equilibrium configuration
with n [[ E and unstable equilibrium with n _L E. Other influences can stabilize
the latter and this is used in various ways to produce interesting and useful
phenomena. We will return to this later. There is a different, more mechanical
way of understanding these equilibria. By calculating the resultant moment on
a dipole, one can motivate the idea that E produces a couple LE per unit volume,
given by LE = P x E = [aE+ b(E. n)n] x E = b(E. n)n x E, (9.2.6) so the above
equilibrium conditions coincide with the condition that LE ---- 0. As was
suggested before, the constant field gives a zero body force so, with LE = 0, we
have taken care of conditions which may be inferred from ideas of mechanical
equilibrium. Again, the corresponding situation for nagnetic fields copies this,
replacing E by H, etc., giving the body couple Ln = M x H. (9.2.7) In
mechanical terms, the most important effect of the fields is to produce these
couples. Roughly, they serve as wrenches which we can use to adjust the
orientation, represented by n. At an interface where a liquid crystal contacts
another material, there is a curious effect, long known, but still not very well
understood from the view of basic science. Often, the director assumes some
definite direction, this being called strong anchoring. If not, the experience is
that it will make a constant angle with the normal vector to the interface, being
free to swing around, subject to this condition, producing what are called conical
130 9. Equilibrium of LiquidCrystals and Rods boundary conditions. In detail,

what happens depends on the two materials, and, often, on the prior treatment of
the other material. For at least some of the more commonly used liquid crystals
in contact with an untreated glass plate, n is tangent to the plate, favoring no
particular tangent direction. One could easily induce it to choose one, by using a
magnetic field acting tangentially, for example. However, it would still remain
tangent if one applied the field in another direction, at least if the field is not
excessively strong. However, it will influence the direction assumed in the
interior. Now, consider the glass to be treated, by rubbing it in one direction a
number of times. Then n will align tangentially, 2 in the direction of rubbing. So,
this converts it from a conical case to strong anchoring. Instead of rubbing, one
can wash the plate with certain acids or detergents, or use certain coatings, to get
n to be normal to the plate, another kind of strong anchoring. Other tricks are
known for getting strong anchoring, with n making other angles with the
interface. Suffice it to say that there is a well- developed art of making n satisfy
one of a variety of boundary conditions at such interfaces. This covers the
general ideas commonly used in designing devices and experiments. 9.3
Measurement of Moduli That W has the form given by (9.1.11) was arrived at by
using theoretical ideas to mathematically formulated hunches based on rough
observation and not really by curve-fitting any quantitative measurement.
Certain kinds of experiments for measuring K, K2 and K3 have long been used
and are not too difficult to analyze, at least roughly. They employ very similar
ideas with only slight differences in the set-ups, so we will consider only one in
detail, the measurement of K2. This, like the others, involves a liquid crystal
sandwiched between fixed parallel plates. In this case, these samples are
prepared to make n take up a fixed tangential direction, the same on both plates;
one could apply the rubbing technique for glass plates, discussed before. The
arrangement is such that the distance between the plates is very small compared
to the lateral dimensions of the sample, so it should not matter much what goes
on at the edges of the sample. The aim is to get n = const., matching the
boundary conditions on the plates, and the experience is that one can get a good
approximation to this. We will consider only the liquid crystals for which (9.2.2)
applies, so an electric field will try to induce n to align parallel to it. Actually,
workers often use magnetic fields which do have such an aligning effect. As
should be clear from the previous discussion, the theory of these two cases 2One
expert informs me that it is not quite tangential, but tilted off by a very small
angle. 9.3 Measurement of Moduli 131 is essentially the same. To measure K2,
the idea is to apply a constant field, with E perpendicular to the constant n
described above and in a direction tangent to the plates. Then, in this
configuration, the body couple given by (9.2.6) is zero, so this is an equilibrium
configuration. Although it does not satisfy (9.2.2), the wall has some stabilizing
effect on it. To analyze this, we introduce rectangular Cartesian coordinates,
with the positive x-axis in the direction of the constant vector n described above,
the positive y-axis in the direction of the applied field and the z-axis then being
normal to the plates. Think of the region occupied by the liquid crystal as
extending to infinity in the x and y directions and in the interval 0 _ z _ L, in the
third direction. For the configurations considered, the assumption is that they
vary only with z, n remaining parallel to the x-y plane. Bearing in mind that n
must be a unit vector, we can represent it in terms of the angle q it makes with
the x-axis, n = (cos q,sin q, 0), q = q(z). (9.3.1) We assume qz(z) is a smooth
function which is consistent with the observations. The strong anchoring
conditions at the plates give the boundary conditions � (0) = (L) = 0. (9.3.2) As
usual, we assume 0 = const. With (9.1.11), a calculation gives, for the
mechanical energy, 2W = K2(q') 2. (9.3.3) With our choice of coordinates, E =
e(0, 1, 0), (9.3.4) e being the magnitude of the field. Then, (9.2.1) gives 2WE = e
[a + b sin = be sin 2 q + const. For the infinite sample, the total energy will be
infinite, energy per unit plate area, � = (W - WE) dz. (9.3.6) Dropping the
unimportant constant in (9.3.5), we get 2� = f(q, a;') dz, (9.3.7) with f(q, q?) =
K(q?) 2 - be sin q. (9.3.8) (9.3.5) so we look at the
132 9. Equilibrium of LiquidCrystals and Rods 9.3 Measurement of Moduli 133

Of course, any variations of � considered should conform to (9.3.2), and we
will want to consider these in much that same way as we did in deriving
equilibrium equations for bars, etc. A trick is commonly used in variational
equations of this general kind so, for the moment, we ignore (9.3.8). To get
equilibrium equations, we proceed, as we have done before to calculate 5�,
getting 25� = -G 5 + 5 dz (9.3.9) : 56- b-G From arguments such as those used
before, the equilibrium equations obtained by setting 6� = 0 are then = o.
(9.3.10) Here, the last term vanishes because 5 = 0 at the end points, but the trick
works for other kinds of problems. Now, by calculation, ( os os os _ los' I- = +
Conversely, if (9.3.11) holds, (9.3.10) will be satisfied, except perhaps when �
is constant. So, one chec (9.3.10) for the possible constant solutions and uses
(9.3.11) for the less trivial possibilities. Here, (9.3.10) gives, with (9.3.8) K2" +
be sin cos � = 0 (9.3.12) and there is the constant solution � = 0, the only one
satisfying the boundary conditions. We anticipated it from the consideration
involving L. For possible nontrivial solutions, we can use (9.3.11) to replace
(9.3.12) by K2 + be sin 2 � = const. (9.3.13) Before considering these, let us
consider the stability of = 0. For this, it is convenient to use PoincarPs
inequality, satisfied by any smooth function which vanishes at the ends of the
interval, 2 dz 2 dz. (9.3.14) The equality holds when � is a constant times
sinGrz/L ). To see where this comes from, one can proceed as follows. Consider
the ratio n- foC 2 dz ' for smooth nonzero functions , vanishing at the end points
of the interval. This is sometimes called a Rayleigh quotient. Now try to find the
smooth function(s) which minimize it. 3 As we have done before with such
integrals, we can find extremals by considering � as one, writing = +p6, where /
is a small parameter, etc. This gives which should vnish for = . Let be the value
of for � and the condition reduces to from which it follows that � should
satisfy the equation A general integral of this is a linear combination of cos()/z
and sin()/z. Impose the condition that such a function vanishes at the end points
and you find that the coeMcients of cos()/z must vanish and that Clearly, the
smallest such value occurs for n = 1, and this gives (9.3.14). Also, it is ey to
verify that Thus, from (9.3.7) and (9.3.8), jo L 2�: [K2(') 2 - be 2 sin 2 ] dz >
(K2r2-be2) fo2dz. - (9.3.16) 3For a complete and rigorous treatment, one needs
to show that the minimum is attained by some such function. A proof of this is
given on p. 122 of Courant and Hilbert [43]. One can use simple functions, for
example, the trigonometric functions mentioned below, to show that 77 can be
arbitrarily large, so 77 does not take on a maximum value for any smooth
function.
134 9. Equilibrium of LiquidCrystals and Rods Obviously � = 0 when = 0 so =

0 will minimize � whenever the last expression is nonnegative. That is be2L 2 _
K2r 2 := � = 0 is stable. (9.3.17) To explore this when the inequality fails, we
can use the second derivative test. For this, we proceed as usual. This amounts to
taking =/zS, where /z is a small parameter, and approximating � to quadratic
terms in/z. This gives L 2� - IZ262� = I z2 / [K2(5t) 2 - be2(6) 2] dz (9.a.18)
with (9.3.14) being used again, now applied to 5q. Also, the equality will hold
for 5q = sinOrz/L ). If 2 ( 0 for any admissible choice of 5q, q = 0 is unstable so
be2L 2 > K2r 2 = � = 0 is unstable (9.3.19) and the liquid crystal must then
adopt some other configuration to be in stable or metastable equilibrium. The
borderline defined by the change in stability of = 0 gives a critical value ec of the
field strength e, given by be2c L2 = K2r 2. (9.3.20) The idea of the experiment is
to determine ec. That is, one adjusts e to find the value at which the uniformly
oriented configuration = 0 shifts to another kind. One can use optical methods to
detect this, although workers have found other methods to be more accurate. Of
course, L can be measured. With (9.3.20) this gives an experimental estimate
of K2/b. Another kind of experiment is used to determine b, but we will not
discuss it. With the two, one also gets an estimate of K2 at the prevailing
temperature. This modulus has force as its physical dimension. Of course, it
varies with the material and, for a given material, with temperature. Typically, it
is of the order of 10 -6 dynes, which is an exceedingly small force by normal
standards. Roughly, it is this which lets the devices operate with a very small
supply of power. It is worth noting that, according to elementary electromagnetic
theory, V = eL has the physical dimensions of the electrostatic potential,
commonly meausured in volts, so (9.3.20) could be written in terms of a critical
"voltage" Vc bv:/C2r 2. (9.a.21) In this arrangement Vc has no very clear
physical significance. Devices and other experiments commonly employ fields
directed normal to such plates and involve similar bifurcations. Then the
analogous critical voltage 9.3 Measurement of Moduli 135 space is the voltage
across the plates. Typically it is a few volts. In this form it is independent of L, a
prediction which agrees with experience. One can proceed to analyze the
nontrivial equilibria. It turns out that as one increases e, one passes through
critical values, marking places where the number of solutions of the equilibrium
equations jumps to a higher value. One can analyze these to determine which are
the energy minimizers, but I will not try to discuss this. Actually, the minimizer
has the properties one might expect intuitively. As soon as e gets larger than ec,
one gets a compromise between the wall and field effects. At the wall, the wall
has its way, maintaining the boundary conditions. Away from the wall, the
director rotates a little, a small step towards becoming parallel to the field. As
one moves away from the walls it rotates more, reaching a maximum at the mid-
plane z = L/2. It is easy to see that if (z) is a solution, so is -(z), or, said
differently, it could rotate either to the left or the right, a prediction not
contradicted by experience. The behavior is somewhat similar to that which we
have encountered before, in the "pitchfork" bifurcations, and some workers use
the name for them. For one of the two solutions we will have � increasing with
z, from zero at z = 0, to some maximum value 0 < r/2 at z = L/2. Since it is a
maximum, we will have o = (L/2), '(L/2): 0. (9.3.22) Then, (9.3.13) takes the
form K2(') 2 + be 2 sin 2 � = be 2 sin 2 0, from which it is clear that sin 2 � <
sin 2 0. (9.3.23) (9.3.24) We now do some juggling. Let k = eV/--/K2. (9.3.2S) It
is a number with the reciprocal of length as its physical dimension. With
(9.3.24), we can introduce an angle X satisfying sin X = sin /sin 0, (9.3.26)
varying from zero to r/2 as � varies from zero to 0- In terms of these quantities,
a routine calculation gives, as a replacement of (9.3.23), (X') 2 = k211 -- sin 2 0
sin2 X], (9.3.27) the conditions on X being x(0) = x(L) = 0, x = (9.a.28)
136 9. Equilibrium of LiquidCrystals and Rods Consider the solution for 0 _< z
_< L/2 where X > 0. Then (9.3.27) and (9.3.28) become d�> (9.3.29) kz = X/1 -
sin 2 0 sin 2 99 and kL (93.30) 2 J0 V/1 -- sin2 0 sin 2 qo Given k and L, the
idea is to solve (9.3.30) for 0. Sutituting this in (9.3.29) gives z a function of X,
the inverse of the function X(z) for 0 < z < L/2. To obtain the solution in the
upper half, put X(z) = x(L- z), L/2 < z < L, (9.3.31) it being a simple matter to
verify that this gives a solution of (9.3.27) satisfying (9.3.28). Concerning h(0),
given by (9.3.30) for 0 0 < /2, one can show that (a) h(0) is a monotonically
increasing, continuous function of 0; (b) lim h(o) = orr/2 (c) h(0) = This means
that kL determines a unique value of 0 in the range of interest provided kL eL : >
r. (9.3.32) From (9.3.19), this means that these solutions occur whenever
conditions are such that = 0 is unstable. For these nontrivial solutions, it follows
from (a) and (c) that as kL approaches the critical condition indicated by
(9.3.20), 0 approaches zero, so near this, it and hence sin 2 0, will be small. Then
(9.3.13) implies that will be small, close to zero. So, the distortion develops
rather smoothly as one increases e, passing through ec, again like the pitchfork
bifurcations we studied before. Actually, this makes it a little difficult to observe
exactly when the transition occurs: other methods can detect it, before it is
optically discernible. As one increases e, or, if you like, the somewhat fictional
voltage eL, kL increases so, from (a), 0 increases, n becoming more nearly
parallel to E near the mid-plane. The experience is that it only takes a few volts
to get n fairly close to the direction of E in a large fraction of the gap. In the
small parts near the walls, n then varies rapidly with position to adjust to the wall
orientation. Transitions somewhat similar to this occur in various other situations
of physical interest. To recall what we did, we recognized that, with an electric
9.4 Elastica Theory 137 (or magnetic) field, we could have unstable equilibria,
with n perpendicular to the field. We then introduced something else, the wall
effects, to help stabilize this. As we have seen, this can be successful if the field
is not too strong. If it is strong enough it gives a transition. Workers refer to the
transitions of this kind as FriedeWcsz transitions in honor of a Russian scientist
who discovered them experimentally using magnetic fields. The classical
methods for measuring K and Ka employ rather similar set-ups and transitions.
For K1, we start with the sample oriented as before, but apply a field in the
direction normal to the plates, one case where the voltage across the plates is the
product of the field strength and the gap width. For Ka, the plates are treated to
make n align normal to them. The field is then applied perpendicular to this
direction. The corresponding calculations are discussed by various writers. For
example, they are included in three of the best general reference works on liquid
crystals, the books by Chandrasekhar [44], de Gennes [45], and Virga [46].
Display devices exploit Frederlcsz transitions, using fields strong enough to
induce n to become nearly parallel to the field except very near the walls.
Chandrasekhar dis- cusses the twisted nematic cell, which is used in many such
devices. The mathematical theory of nematic liquid crystals has undergone a
period of rapid development, as is discussed by Virga [46]. There is a point
worth bearing in mind. We considered only some very special types of
configurations. Those regarded as stable may turn out to be unstable with respect
to more general variations. Cohen [47] explored this theoretically for the set-up
used to measure K. He finds that, for many values of the moduli, there is an
instability which sets in at a field strength lower than that given by one-
dimensional theory, causing n to be nonuniform in a periodic manner.
Conversation with experimentalists indicates that some had noticed a little
undulation which could be associated with this, not so small in recently
discovered liquid crystals where K is relatively large, so there is some reason to
be concerned about this. So far at least, it has not been feasible to analyze the
sample of finite size which must be used in the experiments. So, as is typical,
one gets into more sophisticated problems as one tries to take care of the
inevitable loose ends, in order to understand nature a little better. 9.4 Elastica
Theory It is a matter of common experience that the straight long thin bodies we
call rods, bars, beams and wires tend to depart from their straight shape, to
buckle when we apply compressive loads of moderate size at their ends.
Obviously, the bar theory discussed earlier cannot cope with this. One can use
somewhat similar one-dimensional theory, but it must let the line segments
become curves. The simplest possibility is that the curve is contained in some
plane, and, for a number of physically interesting
138 9. Equilibrium of LiquidCrystals and Rods situations, this is the case. The
simplest theory of this kind is Euler's theory of the Elastica, created by this
famous scientist in the eighteenth century. It has proved to be very good, so it is
still used by those concerned with designing safe structures. It may seem strange
to group these rods with liquid crystals. The reason is that, mathematically, the
more elementary analyses of Frederlcsz transitions are almost the same as the
Euler buckling problems. For this reason, functions like the h(q0) occurring in
(9.3.30), one of the so-called elliptic integrals is, much like the trigonometric
functions, long considered to be important enough to have their values listed in
tables of functions, now readily calculated by computer. The notion of a
reference configuration can be carried over unchanged from bars: the stable
unstressed configurations are considered as straight, either way. However, we
prefer to use different notation. Instead of x, we will write $, with 0 < $ < �
(9.4.1) describing the reference. A deformation will take this to some plane
curve, so we introduce rectangular Cartesian coordinates (x, y) in the plane. The
plane curve can then be represented parametrically by equations of the form x =
x(S), y -- y(S). (9.4.2) We can also introduce an analogue of the y(x) used in rod
theory; it is the arc length s, the distance measured along the curve, given by 4 s
= V/(x,)2 + (y,)2 dS = s(S). (9.4.3) In terms of this, we can introduce the stretch
A = s , (9.4.4) describing changes in length in the same way it did in bar theory.
In buckling phenomena, the bending deformations are generally large enough
to be perceived by the eye, but the changes of length tend to be relatively small.
The classical theory introduces an approximation associated with this which
does simplify the theory. It is that the rod is considered to be incxtcnsible,
incapable of changing its length, so, always, s = S, A = 1 = x 2 -t- y2 = 1. (9.4.5)
This makes the vector (x , y), tangent to the curve, a unit vector, representable
in the form x' = cos u, y' = sin u, (9.4.6) 4Readers not familiar with this can find
a discussion of it, curvature, etc., in any elementary book on differential
geometry. 9.4 Elastica Theory 139 u being the angle it makes with the x-axis. To
cover the fact that a rod offers some resistance to bending, a bending energy per
unit length W is introduced, a kind of strain energy function. For the ancient
theory, the assumption is that it is of the form 1 K(u,)2 ' w = w(o, = (9.4.7)
where K is a positive function of O called the flexural rigidity. From differen-
tial geometry y is the curvature of the curve. Different kinds of boundary
conditions, etc., are used to model different kinds of physical problems. Often,
but not always, they are such that the thermodynamic ideas of equilibrium are
applicable. We will consider one case where they are, as an illustrative example.
Suppose a rod is set into concrete, forming part of a floor, with the rod normal to
the floor. Choose axes so that the floor is the plane x -- 0, the rod's reference
configuration being on the x-axis. We will regard one end of the rod as being at
the origin, ignoring the piece buried in the concrete except for estimating the
boundary conditions. Physically, setting it in will fix the end position and also
fix the tangent vector at this end, say $ = 0, giving the boundary conditions x(0)
= y(0) = .(0) = 0. (9.4.8) Physically, no work will be done on this end. The sides
are to be left free so no work will be done here. As the words suggest, we
consider the system to be in the earth's gravitational field, giving a gravitational
force acting in the direction of the negative x-axis. We ignore the effect of this
on the rod itself. However, we will use it to dead-load the end $ = �. That is, we
will here firmly attach a rigid body with weight w. Associated with this is a
potential energy which can be taken as wxc, (9.4.9) where xc is the x-coordinate
of the centre of mass of this body. For simplicity, we assume it attached so that
this point is also the end of the rod, so xc = x(�). (9.4.10) So, overall, the
loading is conservative and, as usual, we assume 0 = const., one of the standard
situations covered by equilibrium theory. The applicable thermodynamic
potential can be taken as = K(u') dS + wx(�). (9.4.11) Here, there is a
possibility of having end-point minima, with the weight and perhaps part of the
rod, coming into contact with the floor. Clearly, this
140 9. Equilibrium of LiquidCrystals and Rods depends on the size and shape of
the weight. We will ignore this constraint and, for this reason, our analysis will
be incomplete. In part, the boundary conditions (9.4.8) can be taken care of, by
using (9.4.6) to write x(S) = cosydS, y(S) = sin vdS. (9.4.12) With this, we can
rewrite (9.4.11) in the form = /oe I K ( v')2 -k w cos vl dS, (9.4.13) with v still
subject to the boundary condition v(0) = 0. To determine the conditions needed
for equilibrium, we can, as usual, calculate 5 and equate it to zero. In the interior
of the interval, we get the equation which one would expect from (9.3.10), Kv" +
w sin u = 0, and the first integral suggested by (9.3.11). In addition, the analogue
of the last term in (9.3.9) produces another boundary condition: we should have
v(0) = v'(�) = 0. (9.4.14) Essentially, this is the liquid crystal problem we
analysed earlier. To see this, put v = = �/2, (9.4.15) so we have � (0) = o, = o,
(9.4.16) fitting conditions listed in (9.3.2) and (9.3.22). Also, (9.4.13) becomes
L/2 = [2K(') 2 + w(1 - 2 sin 2 r)] dS J0 (9.4.17) z,/2 = 2 [K(t) 2 - w sin 2 ] dS +
const., J0 the integrand being of the same form as in (9.3.16) with the constants
labeled in a different way. The upper limits look different so, in effect, we are
looking at the liquid crystal energy for the lower half of the sample. However,
from symmetry, it is easy to see that the upper half has the same energy, so one
can replace the upper limit in (9.3.16) by L/2 and multiply the new integral by 2.
Thus, with some bookkeeping, one can use the whole analysis for these two
problems, which are physically quite different. The critical condition
corresponding to (9.3.20) works out to be wc� 2 = Kr 2. (9.4.18) 9.5 Exercises
141 Thus, for w < wc the rod stays as is in its reference configuration. For w a
little larger than Wc, it will start to bend over a little. As the load increases,
v(�) will get closer to w, the rod bending nearly double. Realistically, some-
where along the line it will bend enough to let the weight contact the floor.
Consideration of this would, of course, make the two problems different. In this
case, it is not customary to try to use (9.4.18) to obtain an experimental value
for K, partly because small misalignments etc. introduce noticeable errors in
such measurements. A classical estimate which seems good gives K -- El, where
E is Young's modulus, obtainable from a simple tension test and I is a
geometrical factor, a certain moment of inertia. One can get it directly using a
simple bending experiment, for example. These and some other aspects of
classical rod theory are discussed in more detail by Love [48], for example. In
previous studies we have concentrated more on issues relating to attempts to
find equations to describe response of materials. Here, this issue is fairly well
settled and we move into the province of the engineer who needs to resolve
stability questions in order to design safe structures. Such workers use various
ideas which have not been mentioned in our discussions, as can be seen from
the books of Leipholz [49] or Thompson and Hunt [25], for example. Numerous
other kinds of workers are interested in aspects of stability, producing a literature
so large as to be indigestible for one person. 9.5 9.2, Exercises An unusual
stability problem arises in liquid crystals, associated with what is called the
"plage tordue." The sample is prepared like that discussed in Section 9.3 except
that no field is applied. Instead, one plate is simply rotated relative to the other,
keeping them parallel, so the orientation at the two plates becomes different. To
analyze this, use (9.3.3) to calculate the energy. Then determine the equilib-
rium equation and boundary conditions, and find the solutions. You should get
two solutions for each angle of rotation, if you read Section 9.1 carefully.
Determine which of these is most stable and how this changes as the angle of
rotation increases. An experiment long used to determine values of K in (9.1.11)
em- ploys a sample of the kind described in Section 9.1, except that the field is
here normal to the plates. Instead of (9.3.3), assume that n = (cos X, sin X), X =
X(z). Substituting this in (9.3.3) gives 2W = (K1 cos 2 X + K3 sin 2 X)(X) 2, X
= X(z),
142 9. Equilibrium of LiquidCrystals and Rods an assertion you should check.

Calculate the function describing the field energy, then derive the equilibrium
equation and boundary conditions. If you have trouble getting this equation,
review Section 3.1. 9.3. For the situation just described, determine whether the
equilibrium equation has any trivial solutions satisfying the boundary conditions,
then find an integral of the equation. How does what it implies about trivial
solutions compare with your findings? 9.4. Can you find a physical problem for
the Elastica which is essentially the same, mathematically, as that discussed in
Exercise 9.3, perhaps for special values of the constants K and K37 l0
Reconsideration of Generalities 10.1 Systems, Energy, and Temperature Some
general ideas about classical thermodynamics were mentioned briefly in Chapter
1, later chapters providing some examples of how they are used in practice. One
needs to obtain a better grasp of them to avoid misuse and to begin to understand
some of the real difficulties involved in their application to some phenomena
encountered, particularly in solids. Firstly, not every physical system can be
properly regarded as a thermodynamic system fitting the ideas of classical
thermodynamics. It is generally agreed that this is a macroscopic theory, not
applicable to an electron, for example. However, various kinds of macroscopic
systems are also excluded. In particular, the first law should be applicable and it
involves two ideas. One is the equation relating changes in energy to power and
heating. The other is a relation of energy to states. In this section, we will
consider the first. Our study of mixtures suggested one limitation based on
consideration of this, that a thermodynamic system should contain a fixed set of
matter. Occasionally, workers do consider systems which do not contain fixed
sets of matter, but it is somewhat tricky to deal with these in a physically sound
manner. In our study of liquid crystals, we encountered those electric and mag-
netic fields which do not vanish in parts of space where there is no matter, that is
"vacuum fields." More generally, this includes time-dependent electromagnetic
fields describing radiation, for example. According to electromagnetic theory
there is an energy associated with such fields. For, say, a
144 10. Reconsideration of Generalities fixed region of space, the time

derivative of this energy is related to the flux of energy through the boundary.
However, in general, there is no reasonable way to consider this flux as
representing power or heating. If you recall, in the liquid crystal study we did not
try to treat the vacuum fields as thermodynamic systems. They did interact with
the important part of the thermodynamic system there considered, the liquid
crystal. There, we were able to account for the interaction in a way which makes
sense in terms of the first law, as it applies to the liquid crystal. From this, we
see that sometimes, something which is not properly regarded as a
thermodynamic system can be considered to interact with a thermodynamic
system. Now, if one tries to construct a general, systematic theory of
thermodynamics, it makes life much easier to assume that a thermodynamic
system can only interact with other systems of this kind, so the first law, etc., can
be applied to one, or any combination of these. So we bent this rule to make
possible the analysis of a situation of interest. Appreciate that one is taking a risk
in bending or breaking this rule. The rule has been broken in a different way
with good results in the application of thermodynamics to black-body radiation.
This involves radiation in a cavity with rigid walls, maintained at constant
temperature and also opaque to radiation. This means that, at the walls, the flux
of electromagnetic energy is to vanish. In his discussion of this, Pippard writes
(in Chapter 6 of [4]) that, It is not at all obvious that we are justified in applying
thermodynamics to such a problem, since the formulation of the laws of
thermodynamics was based on experience of material bodies, and we need feel
no a priori confidence that they are of suciently wide validity to embrace
mechanical processes in which radiation provides the motive force. Read what
else he said and you will see that he is not expressing doubts about the end
results. As I see it, there is here the implication that something is wrong with
the old laws. If the first law really applied, why should it be necessary to make
the walls opaque? Actually, with our liquid crystal studies, we would have
encountered more serious ditficulties had we tried to introduce corrections for
induced fields. In various crystals, application of stress induces electric fields.
Classical thermodynamics cannot deal satisfactorily with such phenomena and,
in particular, one needs to consider modifications of the first law. Relevant
theory of this kind is discussed by Grindlay [50] and Brown [51], for example.
There is some consensus of opinion that the energy equation for bars con-
sidered in Chapter 2 remains applicable when the phenomena of plasticity and/or
viscoelasticity occur. However, other ditficulties arise in trying to apply ideas of
classical thermodynamics to such situations. Later, we will elaborate on this and
discuss some of the ideas which remain applicable. 10.1 Systems, Energy, and
Temperature 145 In dealing with behavior near phase transitions, workers rather
frequently introduce a modification of theory which goes under various names,
being called Cahn-Hilliard theory, Landau-Ginzberg theory, Korteweg theory,
or Van der Waal's theory. About a century ago, van der Waals [52] first
considered theory like this for fluids, deduced from consideration of molecular
theory. Roughly, it involves taking the commonly used formula for the
Helmholtz free energy density and adding quadratic terms in higher derivatives.
The intuitive idea is that these will be small terms, not af- fecting predictions
much, except when the usual form suffers the loss of convexity associated with
spinoidal regimes. Then, the experience is that it does produce some significant
and interesting modifications in predictions. For our thermoelastic theory of
bars, the usual function p(A, 0) would be replaced by � = o) + a kOx/ ' (lO.1.1)
where a is a positive constant. Internally consistent three-dimensional theory of
this kind is discussed by Dunn and Serrin [53]. To obtain this consistency, one
needs to modify the format used before. The usual equation of motion (2.3.8)
still applies but the constitutive equation for the stress a changes. The effect is to
replace an equation which was of second order in y(x, t) by an equation of fourth
order. Mathematically, one then expects to need an additional boundary
condition. It is not entirely clear how best to select boundary conditions to model
particular physical situations. Some try to avoid dealing with this by considering
bars of infinite length. Others make some definite choice which seems
reasonable to them, but there is a lack of hard evidence bearing on the
correctness of such choices. So, in this respect, this kind of theory is somewhat
shaky, although it is an old theory which has generated a sizeable literature. In
terms of thermodynamics, a ditficulty arises in considering the energy equations
discussed in Section 2.3; one finds that it needs to be modified. If one tries to
match this to the first law, the expression for power should now take the form ( P
= + xx]10 + fgdx, (10.1.2) where is given by a certain constitutive equation. In
terms of intuitive ideas about power, it is at least ditficult to motivate inclusion
of the additional term. If we accept it, we have other complications. For
example, if we set f = 0 and clamp the ends so that (0, t) = (L, t) = 0, this is not
sutficient to attain mechanical isolation (P = 0). Mathematically, it would be
quite acceptable to obtain P = 0 by adding boundary conditions making O/Ox --
0 at the ends. However, physically it is not clear as to what we should do to
realize this. So, for example, it is at least tricky to analyse possible equilibria
using theories of this kind and the ditficulties are associated, in part, with trying
to make good sense of the first law. Actually, one
146 10. Reconsideration of Generalities needs a modification similar to (10.1.2)

for a reasonable thermodynamic treatment of the older theory of the Elastica,
mentioned in Chapter 9, but for it, the problem of realizing analogous conditions
at the ends are better understood. Somewhat similar quirks occur in other
theories of rods, plates and shells. In liquid crystal theory, power is considered to
include the possibility that one can do work by causing the director to change, as
well as by causing samples to move, as is discussed in references cited in
Chapter 9. One needs to bear this in mind in interpreting what it means for such
a system to be mechanically isolated, for example. In later discussion of the laws
of classical thermodynamics, remember that workers can and do use such
rcinterprctations to try to extend their range of applicability. It does seem
difficult to justify such practices on an a priori basis, but some good theory
would not exist if such practices had not been used. As a general rule, writers of
elementary texts on thermodynamics focus on theories fitting a certain pattern, to
be discussed more later. In previous chapters, we used theories which do fit this
mould fairly comfortable. As is suggested by the remarks made above, in various
situations which are commonly encountered, one meets theories which do not fit
the mould so well. The better one understands the general ideas, the better are
one's chances of adapting these to apply classical thermodynamics to theories
which are, in one way or another, awkward. As a matter of common experience,
you know that if you take a mercury thermometer from a warm room and plunge
it into cold water, it takes some time before the thermometer reads what you can
believe to be the temperature of the water. If, for some reason, the water
temperature were changing rapidly with time, such a thermometer could be put
into it and read, but the readings would be rather meaningless, physically. A
different kind of thermometer may adjust more quickly and provide meaningful
measurements of temperature. A situation of this kind does occur in turbu- lent
flows. In air, workers have used hot-wire anemometers to get what are regarded
as meaningful measurements of temperature, for example. Said differently, we
want the thermometer to adjust quickly enough to be in equilibrium, or very
close to it, at each time, although the system may be quite far from equilibrium.
Similarly, if the temperature in the system varies rapidly with a position, a large
thermometer can at best provide some average of the temperature in the system.
So if a smaller thermometer is used, one would expect to get a different
reading. If it can be made small enough to provide a reading which we can
believe, the thermometer is acceptable, as a practical matter. Again, the demand
is that the thermometer be in equilibrium, or at least very close to this, although
the system is not. Essentially, classical thermodynamics presumes that it is
possible to find thermometers able to provide meaningful measurements: the
classical theory of thermometers is an equilibrium theory. One implication is
that absolute temperature is here considered to be a meaningful concept 10.2
General Processes 147 in a system undergoing nonequilibrium processes. At
least, this is my view of classical thermodynamics. If you converse with
thermodynamicists, you may well find some contradictory opinions and for a
more basic treatment, one really should start with a more primitive idea of
empirical temperature. Certainly, I concede that this classical idea has its limits.
My view is that, when one exceeds these, one may well need to think about
temperature in quite a different way, if at allJ In molecular theory, one
encounters a different notion of temperature, related to kinetic energy of
molecular motions. It then becomes a tenable notion that different species in a
mixture can have different temperatures, at what is, from a macroscopic view,
the same point, for example. Classical thermodynamics does have its faults and
virtues, but one cannot make one's own judgment about these, if one does not
understand the subject. Suffice it to say that there are other, rather different kinds
of thermodynamics beyond the scope of this work. Briefly, we will, as before,
use absolute temperature freely. Bear in mind that different workers can have
somewhat different views of exactly what should be meant by classical
thermodynamics. For this reason, I am trying to make my own view reasonably
clear. 10.2 General Processes For various reasons, one needs some picture of all
of the processes which can occur in a thermodynamic system. Ideally, we would
like to know everything to be known about them. If we attain this goal for a
system, we have mastered the problems which may be involved in trying to
apply thermodynamics. Thus, in practice, we will start with a picture which is
incomplete and possibly incorrect, to be rectified as our understanding improves.
Realistically, we impose some limits on what can be done to the system to
develop manageable theory. For, say, a wooden beam of good quality, we could
use our theory of thermoelastic bars for some purposes. Or, if we were
concerned with buckling we could try Euler's theory of the Elastica. With the
theory of mixtures, we open the door to exploring effects in the beam produced
by changes in humidity. Obviously, it would take a much more complicated
theory to deal with all these effects and we would still exclude some possibilities
such as setting the beam on fire. So, what is to be considered as the set of
possible processes in the beam depends on the judgment and concerns of the
worker who may be interested in it and these may change as the worker learns
more from studies based on the picture adopted at the start. We saw this in the
equilibrium theory, when some considerations induced us to abandon the notion
that equilibria be free of 1 Obviously, there are conceptual difficulties involved
in trying to associate a temperature with those vacuum fields, for example.
148 10. Reconsideration of Generalities discontinuities. In this, we did not

explore as to whether our nonequilibrium theory is capable of describing such
topics as the evolution of our "phase mixtures" from initially smooth
configurations by time-dependent processes and, if so, whether this involves
initiation of shock waves, for ex~ ample. If it cannot cope with such phenomena,
this theory is in difficulty. In pondering such possibilities, it is a good idea to
bear in mind that a variety of different nonequilibrium theories can become
indistinguishable for typical equilibrium analyses. For the case at hand, various
versions of viscoelasticity theory would, in this sense, agree with our
thcrmoelasticity theory. So, if a worker encounters some obstacle of the kind
indicated, he may well try some other nonequilibrium theory in order to find a
way of eliminating the difficulty. We have just introduced a notion which, in
effect, says that we can change the set of possible processes by making some
change in the constitutivc equations. If you accept this, you may have some
qualms about arguments made in Chapter 2 in deducing restrictions on
constitutive equations. When we considered those processes, we assumed that
those "sources" f and r could be prescribed arbitrarily. One finds some workers
proceeding in a way which I interpret as meaning that they tacitly accept
assumptions of this kind. Some, for example Coleman and Noll [54], do make
such assumptions explicit. This has the effect of eliminating, or at least
diminishing, the influence of the form of the constitutive equations on the set of
possible processes. There is another school of thought, illustrated by the work of
Miiller [55], for example, which I do find attractive. According to this, such
'source terms' are to be assigned only in ways which are physically realistic. Of
course, this involves some exercise of judgment. For the bar theory, one person
might decide that it is only reasonable to have f -- 0 and either r = 0, or that r be
given by Newton's law of cooling, for example. This has the effect of making the
set of possible processes smaller in what is essentially the same theory. With the
latter approach, one has to work harder to get the implied restrictions on
constitutivc equations and one may or may not obtain the same restrictions for a
given kind of theory. What we should do is to rederive the restrictions, using the
different assumptions, to see if we do arrive at the same or different conclusions.
I will leave it to the interested reader to try this for himself. It may be helpful to
examine how Miiller does this, using a "Lagrange multiplier" theorem due to Liu
[56]. I will not belabor this. However, it is my view that the general scheme
should be sufficiently flexible to leave the decision of how best to define the set
of possible processes to the individual. Different workers could come to
contradictory conclusions about the same system. Then is the time to examine
the differences carefully and objectively in an attempt to decide which view is
better. 10.3 Static and Reversible Processes 149 10.3 Static and Reversible
Processes Of course, a process can be independent of time, being then what I
will call a static process. These are the only processes which we considered in
our various equilibrium studies and, at least partly because of this, some ther-
modynamicists like to call these "equilibrium states." I dislike the name for two
reasons. Consider a spacecraft not using its mean of propulsion in outer space, so
it can be regarded as being subject to no forces. From commonly used ideas in
mechanics, its total linear momentum and moment of momentum should be
constant, so it cannot come to rest if these do not vanish. Consider it to be
thermally insulated, making it an isolated system. Then, it is perfectly reasonable
to think that it will come to equilibrium according to the definition we have used
for this, mentioned in Chapter 1. One has to take into account the
aforementioned conditions in deciding what are the "possible variations," but
one always needs to worry about this. There are also good precedents in the old
theories of planets. Some discussion of how examples of this kind fit into the
thermodynamic scheme is given by C. S. Man [57]. Older literature on this
includes a massive and famous work by Poincar [58] which he clearly labels as a
study of the equilibrium of rotating fluid masses, following still older practice. It
is then misleading and somewhat blinding to think that only static processes can
qualify as equilibria. As a second point, in my opinion some static processes
should not be regarded as equilibria. At least the studies we have made all
suggest that, in equilibrium, the temperature should be independent of position.
With our rigid bars, we may obtain steady state heat conduction by insulating the
sides and keeping the ends at different constant temperature. To me, this is not
equilibrium although it is a static process. Rather commonly, thermodynamicists
seem to prefer to regard "equilibrium" as a primitive concept, providing some
verbal description of what they mean by this. Those I have examined conform to
my understanding of a static process, I think. There seems to be a common
prejudice that time-dependent reversible processes are not really attainable, but
"equilibrium states" are. I do accept, as mentioned in Chapter 1, that fluctuations
can also prevent equilibrium states from being realized, physically, so I disagree
with this notion. My own view is that, in most cases, equilibria are special kinds
of reversible processes 2 and that static processes are not all reversible, which
is 2A curious situation occurs in considerations of equilibrium theory used to
describe observations of piezo-electric and piezo-magnetic effects, as is noted by
Ericksen [59]. There is agreement that these are nondissipative processes. How-
ever, there axe in the literature two contradictory rules for transforming electro-
magnetic variables. Depending on which one ccepts, one of these kinds of
effects is not reversible, but the other one is. So, either way, we have an
exception to the usual idea that nondissipative processes are the same as
reversible processes,
150 10. Reconsideration of Generalities subtle. From Chapter 1, reversible

processes are of some importance in the determination of entropy changes, so it
is important to know about sub- tleties pertaining to them. Even if one thinks
that they represent limits of processes which cannot be realized, it cannot hurt to
know something about what is being approximated. Also, there are theories
which treat all possible processes as reversible. Ideas involved are also useful
for understanding some other parts of thermodynamics so this deserves some
discussion. How- ever, before turning to this, I will make some comments about
equilibria which are a little unconventional but are, I think, sound. In the
nineteenth century, it was the view that, in a mechanically isolated system,
which may be thermally isolated or in contact with a heat bath at a fixed
temperature, equilibrium would be eventually attained and maintained.
Expressed one way, some equilibrium configuration would serve as an attractor,
other processes approaching it as time increased. Equilibrium theory evolved as
a technique for locating such attractors and has proved to be rather successful for
this purpose. With the development of the theory of Brownian motion, now
called fluctuation theory, it became clear to at least some that this old picture is
in error. The fluctuations occur in a somewhat random fashion, keeping the
system from attaining equilibrium. Statistically, there is no real limit to the size
of the fluctuations possible although, loosely speaking, the probability of
occurrence decreases rapidly with size. Still, the attractors determined by the old
methods maintain their status as attractors, at least for what seems to us to be
long periods in terms of human experience, and it is for this reason that we still
take them seriously. Now, experience also indicates that some nonequilibrium
processes, for example steady state oscillations, can play a similar role as
attractors. However, attempts to devise general thermodynamic techniques for
locating such attractors have not been very successful. For special kinds of
theories and problems, it may be provablc that some measure of dissipation is
minimized or maximized by attractors. Understandably, workers have tried to
extrapolate such criteria to other kinds of systems with results which may be
good or bad, depending on the system. So, ! do not feel comfortable in
recommending any such criterion. As was mentioned in Chapter 1, there are
various other approaches to stability theory, techniques for locating attractors
which are not based on thermodynamics. As I see it, if the thermodynamic
theory of equilibrium seems to be notice- ably different from nonequilibrium
theory, it is at least partly because it includes a rather successful stability theory.
Otherwise, equilibrium theory deals with a relatively simple subset of processes,
and, certainly, it is easier to find constitutivc equations, etc., which are capable
of dealing with this as I interpret this. Obviously, it would be desirable for
physicists to make better sense of this, but as far as I know, no one has. 10.3
Static and Reversible Processes 151 subset. I think that it is clear from our
studies that it is not always so easy to deal with equilibria. Now, returning to
reversible processes, the first step is to consider the variables involved in
describing the system of interest and to decide how each of these should be
transformed under time reversals. Although not to be discussed here, the
Onsager-Casimer relations do have a prominent place in some of the literature
on irreversible processes. As is emphasized by Meixner [60], the time reversal
transformations play an important role in these. As we commonly understand
time, there is no way to cause it to run backwards. However, workers use various
ideas to decide what is best. Generally, it is a matter of deciding whether one
should or should not reverse the sign of the variable in question. For, say, mass,
this is something we always regard as positive, so it is natural to assume that its
sign should not be reversed. It is a common notion that what we regard as the
more basic equations should transform to equations of the same form. For our
theory of bars, this would include the equation of motion (2.3.8), in particular.
Let overbars denote the transforms, and assume, as is customary, that position
coordinates are unchanged under transformation. Then, for the bars, we
obviously have = x, = y, = -, = ), etc. (10.3.1) In order that (2.3.8) should
transform as an equation of the same form, it is then clear that we should take --
f, -- a. (10.3.2) Where forces are encountered in other contexts, they are to be
transformed in a similar way. Generally, the equation representing the first law
should retain its form. Power should transform as force multiplied by velocity,
i.e. have its sign reversed, from which it is clear that we should take = E, = -P, Q
= -Q. (10.3.3) For our bar theory, this implies that Y = -r, = -q, (10.3.4) and, by
general consent, =0, (10.3.5) For our theory of bars, this is enough to cover all
variables of interest. For another theory, involving different variables, you may
need to consult a more experienced worker to determine what are the accepted
rules. The next step is to define the reverse of a process, which may or may not
be in the set of possible processes. A process may be reversible for some
152 10. Reconsideration of Generalities 10.3 Static and Reversible Processes

153 periods of time and not for others, so it is convenient to define the reverse
for any interval of time for which the process is defined. Schematically, let ct(t)
denote a process which is defined for to _< t _< tl at least, along with all the
responses such as energy, stress, heat flux, etc., which are involved in the theory
under consideration. I will call this collection a superprocess. Define the
reversed time variable by = to +t - t to _< _< t. (10.3.6) Making this change of
variable, we then obtain the quantity &() = or(to + t - ). (10.3.7) Now, apply the
time reversal transformations to the variables represented by a, to give oR(i) ----
G(t0 + tl -- ). (10.3.8) Now, consider i to be the usual time, running forward
from to to t. With this interpretation, it makes sense to ask whether aR(i) is in the
set of possible processes. When it is, we say that the process r(t) involved is a
reversible process during the time interval considered. Summarizing this, we
have process r(t) reversible , (10.3.9) describes a possible superprocess, it being
understood that this refers to a time interval of the kind described above. As is
perhaps obvious, a process which is not reversible for some time interval is
called irreversible for this interval. If no time interval is mentioned, a "reversible
process" is a process which is reversible for all times for which it is defined. For,
say, the theory of rigid bars discussed in Chapter 3, a number of variables were
introduced. For present purposes, it is better to include too many in than not
enough, to cover all relevant transformations. A reasonable choice is c = (0, 0, /,
q, r). (10.3.10) It would do no harm to include e, but its transformations, etc., are
implied by variables already included. Similarly, one could add x. It is
understood that constitutive equations of the kind discussed in Chapter 2 apply
so that, given a function O(x, t), suitably defined for 0 _< x _< L and a time
interval to _< t _< tl, we can calculate 0, /, and q as functions of x and t. As was
mentioned in Section 10.2, there can be differences of opinion as to what is to be
assumed about the 'source term' r, in deciding the set of possible processes. To
be definite, we will allow it to be assigned arbitrarily, and consider the processes
to be smooth, taking the same view of processes that we did in Chapter 2. Thus,
the problem of satisfying (2.1.8) is made trivial; we take r(x, t) to be the function
given by r = Oq Oq Ox -- Oil Ox' (10.3.11) Altogether, this gives the procedure
for determining the processes r(t). Now, using (10.3.8) and the transformation
rules, we calculate the reverse of a process r(t), which gives 0R(x,) = O(x, to + -
0R(x,) = vR(x, = 00R qR(X, ) = -k(OR) 'Ox ' (10.3.12) rR(x, = 0R -- Ot Ox ' For
simplicity, we have used Fourier's law for q, although it is not hard to deal with
the general case. Now, for the reverse to be a process, qR should also be what
we calculate using the accepted constitutive equation for heat flux qR =
k(OR)'Ox ' which disagrees with (10.3.12) unless either k = 0 or 0R is
independent of x or, equivalently, k = 0 or 0 = O(t). (10.3.13) If (10.3.13) holds,
then rR, given by (10.3.12) also satisfies (10.3.11) and such processes are
reversible processes. You may be convinced that you can safely neglect the
effects of heat conduction in particular ces of interest, accepting k = 0 and the
ide concerning r, etc. Then, for you, every possible process is reversible. On the
whole, it seems more realistic to regard such processes irreversible if 0 depends
on x. Static processes then become irreversible unless 0 is constant. Of course,
we can choose interesting subsets of processes by making r alistic sumptions
about r, (10.3.11) thus becoming a nontrivial equation. Workers who prefer this
view will then infer that rather different conditions are needed for processes to
be considered reversible. For example, if we insulate the sides to make r = 0
and sume k > 0, then it is ey to check that these processes are reversible only
when 0 is constant. If, instead, you sume r to be given by Newton's law of
cooling (2.1.17), then, of course, O(x, t) must satisfy (10.3.11) for this choice of
r and whatever you wish to sume for the heat bath temperature 0(t). In this ce, a
calculation gives R (, ) = -- [OB (to + t i -- ) -- OR (, )]' (10.3.14) om the most
obvio way of looking at it, the sign reversal implies that r is not given by Neon's
law of cooling unless rn = 0, implying that
154 10. Reconsideration of Generalities O(x,t) = On(t) = q = 0. Then, (10.3.11)

will not be satisfied unless t/ is independent of t, which case will be true only if 0
-- 0B = const. So, except in these trivial cases, the processes considered are
judged to be irreversible. This is a common view. However, one could modify
this argument to allow some such processes to be considered reversible. Suppose
that 0 depends only on time. Take the view that, in defining the set of possible
processes, 0B (t)_ can be considered as any reasonable smooth, positive function
of time. Let O(t) denote that associated with the particular process considered,
with bar temperature O(t) independent of x. Suppose that, for the times
considered, 20(t) > (t) > 0. (10.3.15) Then, another possible choice of a function
OB(t) is given by 0n(i) = 20R() - O.(t0 + - (10.3.16) and, with it, we have rR([) =
a[n([) - 0nt-]. (10.3.17) This fits Newton's law, enabling us to regard the reversal
as a possible process which is then reversible. In Section 2.2 we considered an
example of such a process, there taking a rather conventional view of how it
relates to some common thermodynamic experiments. While these ideas of
reversibility are not equivalent, they do have something in common which
seems to me to be of some importance, conceptually. It is at least a common
intuitive prejudice that irreversibility is associated with dissipation. When the
Clausius-Duhem inequality applies, it is commonly accepted that the
combination of terms involved provides a measure of dissipation: call it A. For
our bar theory, this is given by df0L f0 Lr q A = ldx- dx- (10.3.18) and, as will
be discussed later, a rather simple expression is used for three- dimensional
theories. The usual assumption is that A _ 0 for all processes. For any one-
dimensional theory to which this assumption applies, one can use the basic
definition of reversible processes to show that A -- 0 for all reversible processes.
(10.3.19) Then, the inequality reduces to an equation enabling us to relate
changes in entropy to the other terms involved. This provides a basis for exper-
imental determinations of entropy changes whenever we can obtain data
enabling us to estimate the other terms. Now reconsider the situation discussed
in Section 2.2. If we are willing to assume that Newton's law applies and accept
the notion of reversibility indicated by (10.3.15), (10.3.16) and 10.3 Static and
Reversible Processes 155 (10.3.17), we have a reasonable basis for determining
changes in entropy from measurements of the bar temperature O(t) and heat bath
temperature On(t). For this, it is not necessary that the difference between these
temperatures be very small, or that they vary extremely slowly with time. From
this view, in Section 2.2, we relied on an old idea mentioned in Sec- tion 1.2,
that the Clausius Planck inequality should reduce to equality for reversible
processes. Actually, when it applies it defines a different measure of dissipation,
A' dS Q (10.3.20) = - with A >_ A, typically. What we are discussing are cases
where A > A = 0. Commonly, thermodyamicists interested in irreversible
processes use A as a good measure of dissipation. From this, I infer that what is
faulty is the notion that the Clausius-Planck inequality should reduce to equality
for reversible processes. It did evolve at a time when it was habitual to assume
that the temperature in a system matched that in the heat bath and, of course, this
is not true in the example considered. When the Clausius Duhem inequality
applies, any processes for which A = 0 may reasonably be considered in
designing experiments to measure entropy changes. There seems to be some
prejudice that only reversible processes have this property. I do not see how to
make a compelling and general argument for this and the footnote on page 149
seems to imply that there are exceptions. There is another matter. When we first
studied some equilibria, we considered the possible static processes in
calculating relevant thermodynamic potentials. Later, we took shortcuts,
assuming that the system temperature was a constant matching that of the heat
bath. What we were then doing was restricting our attention to reversible
processes of a static kind. Had we done this from the start, we would have
missed something, namely inequalities involving specific heats. However, the
simplified theory is in more common usage and performs fairly well. With it, the
theory neatly fits in as a chapter in the thermodynamics of reversible processes,
which also includes old theories of heat engines. Conceptually, this is a clearer
way of understanding the strategy, I think. That is, find a way to calculate the
relevant thermodynamic potential for reversible processes and determine which
of these qualify as equilibria. From this view, we really should have added in
any possible time dependent reversible processes in the problems considered,
and I have noted examples of problems where it would be necessary to do so. I
will leave it to the reader to consider the possibility that this may have some
effect on any conclusions we have drawn and what difference it would make if
the word "reversible" were replaced by "nondissipative." Of course, there is no
obvious reason to exclude irreversible processes, for which we can calculate
the relevant potential, and our experience indicates that we may then deduce
some additional conditions. From this view, what seems to me to be poorly
motivated is the
156 10. Reconsideration of Generalities practice of allowing static reversible

processes and nothing else. In this, we are following in the footsteps of Gibbs. I
have great admiration for him and his work but do not think it wise to follow
anyone blindly. 10.4 Cyclic Processes and Cycles Early ideas about
thermodynamics developed from thinking about ancient engines which operate
in a cyclic fashion, so it is understandable that cyclic processes do play an
important role in the subject. What would seem to me to be the most obvious
definition of a cyclic process is one for which the associated superprocess c(t) is
defined for all time and is periodic with some period T > 0 so that c(t q- T) --
c(t). (10.4.1) Assuming this, one could define a cycle as the part of a process
occurring during any time of duration equal to the period, say c(t), to _< t < to q-
T c(t0 q- T) -- c(t0). (10.4.2) One can object to this on the grounds that no real
process continues for all time. At least according to some cosmological theories,
even our universe has not been in existence for all time. Otherwise, I see no
objection to regarding such as examples of cycles. However, in practice, this
does not often well describe what is meant by a cycle. Often, as above, a cycle C
is considered to be only part of a process r(t), defined over some time interval
[to, to q- T]. Roughly, the idea is that r(t), to _< t _< to q- T is a cycle r(t0) -' r(t0
q- T), (10.4.3) where -' is to be read "is physically equivalent to." One might
stretch the notion of cyclic processes in a similar way, but it is the cycles which
are really used in most of the theory. For example, consider one of our
thermoelastic bars at rest under no loads, in equilibrium. This could be viewed as
a static process, satisfying (10.4.1) for any choice of T. With usual ideas of
Galilean invariance, it could instead be travelling with a constant velocity, with
the same stretch and temperature. Then, its position y(x, t) would not satisfy
(10.4.1). However, if we restrict the process to some interval, we may well
regard this as a cycle. In this, there is the implication that, at the beginning and
end of a cycle, the related superprocess should have values consistent with the
notion of equivalence. In discussions relating to existence of energy and entropy,
arguments employing cycles are used. Logically, one cannot include things not
known to exist in the associated superprocess. So, one considers the related
superprocess as consisting of the remaining quantities and makes the judgment
10.4 Cyclic Processes and Cycles 157 about equivalence based on ideas about
these only. With this understood, we describe the equivalence by saying that, at
the end of a cycle, the system has returned to its original state. When entropy
and energy are well-defined, it is understood that their values should be the same
at the beginning and end of a cycle. Necessarily, I think, the notion of a cycle
has no precise mathematical meaning. For this, it would be neater to use
something similar to (10.4.2). However, the experience is that it is better to have
a more flexible concept to deal with a variety of quite different physical
situations. In part, thermodynamicists deal with this by trying to forrealize the
intuitive notion of "state," as is to be discussed shortly. There is some interest in
the design of solid state engines which employ shape memory alloys, involving
cycles during which the solid occurs at some times as Austenite, at other times
as Martensite. Since engines should do some useful work, the interest is in
cycles such that to+T 6W = P dt < 0, (10.4.4) d to wherein to and T have the
meaning indicated above. The efficiency of such engines, sometimes called the
motive efficiency of such cycles, is of interest. To define this, one introduces 6Q
+, the total heat absorbed by the system in a cycle. For this, one integrates Q
over the set of times for which Q is positive to get a quantity 6Q + or,
equivalently, I fto+T = (IQI + Q) dt. (10.4.5) Then, the traditional formula for
the efficiency e is 5W e - (10.4.6) 5Q+ ' Some engines built employ wire loops
which, during a cycle, undergo changes in bending, probably along with changes
in stretch. Any mathematical model capable of describing such phenomena and
the relevant phase transformations is certainly more complicated than any we
have studied. Some possible engines are sufficiently simple to be modelled as
thermoelastic bars. Such an analysis is offered by Wollants et al. [60]. Of those
I have inspected, this is one of the better treatments of this kind. 3 If one
considers cycles wherein heat is absorbed at just one temperature and is 3Bad
notation and terminology used by these authors may be confusing. For example,
the last term in their equation [1] does not make sense because AV is defined
only on a curve: put the A outside the parentheses. Bad terminology is used in
referring to adiabatic cycles, for example, which does not mean cycles for which
6Q + = 6Q = O.
158 10. Reconsideration of Generalities emitted at one other, it is generally

believed that Carnot cycles are most efficient. 4 They concur with this but
consider other possibilities. Concerning the basic definition of efficiency,
engineers do sometimes modify it. For example, if one is making some good use
of what might otherwise be waste heat, one is, by a reasonable interpretation of
the word, increasing efficiency. So, it is reasonable to modify the definition to
take some account of this. It is worth bearing in mind that, in the latent heats
associated with phase transitions, we have what might be regarded as heat
sources of this kind and the above authors do consider this. 10.5 States As was
mentioned before, there is general agreement that some notion of states is
important in considerations of cycles, energy and entropy, at least. With this is
associated the idea that a nonequilibrium process determines states but various
different processes can, occasionally, determine the same states. To some
degree, concepts of this kind are inherent in classical ideas of causality. That is,
to calculate anything physically relevant at one particular time it should not be
necessary to know anything about the nature of the process at any later time.
More often than not, when workers speak of states they have in mind what I
have called static processes, or something very much like it. It is a reasonable
enough idea that one can evaluate a process at a particular instant, to obtain
some function which would fit such a description. So, for our thermoelasticity
theory of bars, we get the pair [y(x), {)(x)] from a process [y(x, t), tI(x, t)], by
taking instantaneous values of the latter. Since adding a constant to y is
commonly regarded as a trivial change, most would instead use the pair (OylOx ,
tt) as a description of state. From what we ended up with as constitutive
equations, it is easy to check that, given a state, we can calculate the entropy and
associate it with a process, as we did previously. According to the first law, we
should also be able to calculate the energy but this is more difficult. That is,
given our state, we can calculate the total internal energy but not the kinetic
energy. As I see it, the best way to fix this is to admit that the notion of state
should be generalized to include instantaneous values of the velocity, but I
concede that this is not such a popular idea. One trick I have encountered is to
consider the "energy" in the first law to mean "internal energy," and to consider
power 4Carnot cycles are discussed in some detail and carefully by Truesdell
and Bharatha [1]. From their treatment, it is clear that the 'general belief' tacitly
accepts some assumptions. Problems involving phase transitions involve various
quirks, so it is wise to think carefully about the possibility and nature of associ-
ated Carnot cycles before hastily accepting the belief. Also, these writers include
a collection of inequalities useful for analyses of efficiency. 10.5 States 159 as
including the negative time derivative of kinetic energy. This will give an
equivalent equation for the theory considered, but, physically, one then needs to
revise statements accepted about mechanically isolated systems, for example. As
one investigates more sophisticated theories, those of plates for example, one
also encounters rotational kinetic energies. If we adopt the indicated viewpoint,
these too should be shifted over to give contributions to power. It is reasonable
to think that some part of the energy could always be calculated by a formula
used for statics. Shift any remainder into power and you have taken care of the
first law formally. I do not think that many would be content with this way of
interpreg the first law. Other workers do acknowledge that the energy is to
include kinetic energy, put in explicitly, but insist that internal energy is to be
determined by those static states. As far as our thermoelastic theory is
concerned, this is the case. By playing with the theory of thermoelastic bars,
regarding f and r as functions which can be assigned arbitrarily, one can
construct processes which are, I think, worth bearing in mind. Consider an
unloaded bar, moving with constant velocity in an equilibrium configuration
for some constant values of A and 0, with t < 0. For t >_ t > 0, it again has these
values of A and 0 but it is now at rest. I will not expend the ink to prove it, but it
is not hard to show that one can find various processes meeting these condi-
tions, adjusting from one to the other fairly smoothly in the interval [0, tl]. As
determined by the pair (Oy/Ox, O), the equilibrium state does return to its
original value at time t. As I interpret what some writers say that they mean by a
cycle, this is one. However, although the internal energy returns to its original
value, the energy does not because of the difference in kinetic energy. By our
interpretation this process violates the first law which will be discussed later.
According to this law the process should then be considered to be impossible. If
I thought this were what it really implies I would reject this law. There are
various ways of fixing the flaw. One is to interpret energy as meaning internal
energy. I have made clear that I do not like this approach. Another is to insist
that the "state" is to include velocity which is my wont. A third is to
acknowledge that kinetic energy is to be accounted for in an explicit way and as
this is the only place where velocity occurs, one need not account for it explicitly
in a description of "state." If there is some real difference between this and
acknowledging that velocity is to be included in the description of state, it is not
apparent to me. It is true that in the old theories of heat engines such questions
did not arise because in them no attempt was made to account for kinetic energy.
This is the case for various other theories including, of course, Gibbs' theory of
static equilibrium which we have used. A pattern of thinking about states
developed from consideration of such examples and habits of thought tend to
persist.
160 10. Reconsideration of Generalities Often, one finds writers discussing

states with the presumption that they can always be described by a finite list of
parameters. There is no reasonable possibility for describing a function, such as
O(x), by a finite number of parameters. However, for theories which are very
local, in a sense more or less like that described in Section 2.2, one can introduce
local versions of processes or states. For states, it is a matter of considering what
information should be needed to calculate energy and entropy densities at a
given position and time. For example, for our bar theory, we need Oy 0' )' 0
(10.5.1) and we argued that b and r/cannot depend on . What Gibbs [7] discussed
were various kinds of local theories, so you can look to see what he assumed
about constitutive equations for internal energy and entropy densities and we
have covered a few examples. If he covered the case of interest to you, copy it. If
not, estimate what it is that he would be likely to have done had he considered it.
I think it a fair statement that, from this view, one may have in the local state
some functions, and sometimes values of their gradients but not higher
derivatives, and temperature or entropy gradients are not included. Assume that
these same constitutive equations apply to nonequilibrium processes and you
have my interpretation of what is meant by the "hypothesis of local equilibrium"
or the 'principle of local states' in the literature on irreversible thermodynamics.
Various theories of fluids fit this mould, as does thermoelasticity theory. By this
literature, I refer to ideas such as are covered in texts by Kestin [2] or De Groot
and Mazur [62], for example. In this respect, theories such as are indicated by
(10.1.1) are not local enough, it seems. From remarks made early in the paper by
Gibbs [7], I think it clear that he deliberately excluded the consideration of
sliding friction and plasticity. So do the aforementioned texts. Unfortunately,
phenomena of this kind are common and important in solids. With the concept of
state used by Gibbs and in the aforementioned tests it is at least tacitly
understood that if a state can be attained once, it can be attained again and again
and that, once it is attained, whatever happens thereafter does not depend on how
many times it has been attained in the past. Also understood is that one can find
many cyclic processes containing any given pair of states, which can also be
joined by processes which are reversible or at least processes well approximating
this. I appreciate that these are loose statements, but, at least, hopefully, it is
enough to provide some intuitive understanding. Take a paper clip and bend part
of it sufficiently to induce what seems to be permanent deformation. Now try to
unbend it, to return it to the original "state." You are likely to find that this is at
least difficult but you may think that you have succeeded. If so, try to repeat the
process. If the wire breaks, or you see some other discernible difference, you
have not attained the goal. It is hard to exclude the possibility that someone may
succeed by making 10.5 States 161 some clever use of heat treatments, for
example. We might agree that we could succeed by melting and re-forming the
wire. This is acceptable, if you are willing to construct a theory general enough
to include such processes. What seems clear is that, if we want "states" to have
such conventional properties, it can be difficult to find many cycles beginning
and ending at a particular state. Whether there are any which also pass through
another given state is not always so obvious. If anything, finding reversible
processes connecting a given pair of states, or good approximations of these, is
harder. I will not try to discuss in detail the numerous theories of plasticity
which try to deal with thermal effects. For bars, typical theories would use the
equation of motion (2.3.8) and energy equation (2.3.12) which we used for
thermoelasticity theory, together with a constitutive equation for e. As before,
the idea is to use the energy equation as an equation for 0. Because of difficulties
such as are mentioned above, it is not clear how to make good sense of entropy
or states and these concepts seem not to have been very useful. Replacing one
constitutive equation for stress is a more complicated strategy for relating
changes in stress, deformation, and temperature. It involves two sets of equations
with a criterion to determine which applies, which depends on the process.
Given the situation, it is not always clear what is to be meant by a cycle, but I do
not think that anyone working in this field would object to the notion that there
are numerous cycles. This is enough to make it possible to make use of laws of
thermodynamics to be discussed later. Perhaps there is some better way to make
use of thermodynamics in such situations and different workers do explore
different approaches. Not being expert in this, I do not feel comfortable in
trying to say more. In any event, plasticity is a very common phenomenon in
metals, in particular, and it is at least awkward to fit it into a general scheme of
thermodynamics. Rather general theories of ther- tooplasticity are proposed by
Green and Naghdi [63]. Somewhat similar difficulties are encountered in
theories of damage such as are covered in the review by Chaboche [64], for
example. Rather different difficulties are encountered in other common kinds of
solid materials, for example, in the elastomers, the various kinds of rubber. Here,
equilibrium theory such as we used for balloons and sheets can be combined and
considered as different ways of using three-dimensional ther- tooelasticity
theory. This does have a rather wide range of applicability and it has been used
quite successfully to master numerous phenomena. However, for more time-
dependent processes, viscoelastic effects are important and these do not fit
comfortably into the pattern treated in texts on irreversible thermodynamics.
Actually, if you look into the literature on observations of those equilibria, you
will find some workers acknowledging that what has been seen is not really
static but is changing very slowly with time. How slowly depends on the nature
of the experiment and the type of rubber. So, there are possibilities for
minimizing such effects, perhaps getting them sufficiently small to be hidden
by experimental errors
162 10. Reconsideration of Generalities for the time scales involved in the
observations. Still, it is hard to avoid the impression that equilibrium theory is
being misused but with some success. Some workers like to think in terms of a
"rubber plateau," involving time scales neither too short nor too long, over which
relaxation processes slow down enough to obtain something that looks much like
equilibrium, in an experiment designed to produce a static response. For
example, one view is that if one clamped the edges of a sheet to produce unequal
stretches, one could produce results similar to those discussed in Chapter 6,
involving some shear stresses, for a time which may seem very long. However,
the notion is that those shear stresses will eventually relax to zero. To see this,
one might need to observe them for times better measured in months or years.
Think of silly putty and you see behavior something like this but speeded up
considerably. I do not regard this as an unreasonable point of view. It does
suggest that true equilibrium theory might be that appropriate for a fluid and we
are using something quite different from this for the nonequilibrium processes
occurring on the plateau. Intuitively, we are then not close to real equilibrium.
Put one way, we seem able to use Gibbs' ideas to find some processes which, for
a limited time only, serve as attractors. Given this, there is some reason to
believe that it should be feasible to use more accurate viscoelasticity theory to
account for the slow changes and to associate with this a means of calculating
energy and entropy. Reasonably, this should not differ much from what we use
for rubber elasticity on the somewhat vaguely defined rubber plateau. There are
others who prefer to believe that, instead of reaching such a plateau, we are
getting close to real equilibrium, better described by theory more like the rubber
elasticity we have used. Also, there is a range of opinions about whether it is
feasible to make sense of entropy as it pertains to viscoelasticity theory and, if
so, how it should be done. The situation is not so clear that reasonable persons
cannot disagree about such matters, as I see it. What is involved is a kind of
theory too complicated to cover in an elementary way. However, I will try to
give some indication as to why such theories involve some unusual difficulties.
More often than not, nonlinear theory is needed to describe phenomena of
interest. However, linear one-dimensional theory is much simpler and is useful
for describing some phenomena, for example, small vibrations. Even here, the
basic difficulty appears. Often, the interest is in behavior in shear, so we will
consider the interpretation in terms of the shearing of plates. The difficulties are
more associated with the mechanics and there is some question concerning the
thermodynamics, so I will consider purely mechanical theory. When I first came
into contact with such work, it was common for workers to draw pictures of
springs and dashpots linked together in some fashion, using this to motivate
considering equations of the form M 0rat N y. am Ot m ---- y. bn On (10.5.2)
0tn, m=0 10.5 States 163 as a substitute for a constitutivc equation for r. Here, as
before, r and 3' are, respectively, the shear stress and strain. This is to be used in
conjunction with the equation of motion (2.4.5). The a's and b's are constant,
related to spring constants and dashpot viscosities in the picture, from which you
can infer their algebraic signs. Typically, M and N differ by one at most. If one
tries to match data on small vibrations, the experience is that, if you try to get by
with small values of M and N, you can only cover a very small range of
frequencies with resonable accuracy. As you try to increase the range of
frequencies covered, you need to increase M and N and there seems to be no
upper limit to this. In this respect, such models are not very satisfactory.
However, workers do still use them or nonlinear generalizations of them, to
analyze some kinds of phenomena. Setting all derivatives equal to zero, one gets
r proportional to 3'- This gives for the static elastic shear modulus, the value
bo/ao. If you conceive the material to be a fluid, set b0 = 0. Otherwise, any
difference between fluids and solids is more quantitative, more associated with
values of the constants estimated from experiment. In another respect, such
models are at least awkward. Typical relaxation experiments involve suddenly
imposing a deformation or force and holding it. So the time derivatives involved
are, initially, very large, perhaps infinite. With such experiences, workers were
encouraged to consider a different model proposed in 1874 by Boltzmann [65].
It replaces (10.5.2) by an equation of the form t): t) + n(t - t) -- (2O (10.5.3)
where /z is the equilibrium shear modulus and h(t - a) is a function depending on
the material. It is considered to decrease quite rapidly as cr -* -cx. In the sense
indicated, the material remembers all deformations occurring in the past but not
as well those that occurred a long time ago. Philosophically, it is not so pleasant
to think that one must know these ancient deformations but many workers find
ways to live with the idea. Also, there are the obvious practical difficulties in
knowing what to assume about this. If you prefer, you can think of starting with
having the plate undeformed ('7 = 0) up to a certain time, which alleviates the
problem but does not completely eliminate it. Some relevant experimentation is
covered by Ferry [66]. Three-dimensional linear theory is discussed by Leitman
and Fisher [67], for example. A stress relaxation experiment involves starting
with a sample which seems to be in equilibrium, with 3' = 0 for t < 0, suddenly
imposing a constant shear strain % and holding it, then measuring r as a function
of time. The aim is to obtain an experimental determination of I(t) = r(t)/7o.
(10.5.4)
164 10. Reconsideration of Generalities FIGURE 10.1. Hypothetical form of

response in stress-relaxation, for an elas- tomer, with the idea that, eventually,
the shear stress relaxes to zero. Usually, no attempt is made to measure the
temperature of the sample or the heat transferred. For such reasons, these have
no clear status as thermodynamic experiments. Because of inertial effects, the
initial jolt produces waves more or less like the shock or stress waves treated in
Section 7.1, so one cannot really attain the constant value of % immediately.
However, these effects seem to disappear rather quickly so one can begin to get
meaningful measurements of/(t) after a short lapse of time. At long times, one
is limited more by the patience of the observer. By a simple calculation, ignoring
inertial effects, we should have u(t): + n(t - With the change of variables z = t - a,
this becomes = + n(z) dz. Granted that h - 0 fast enough as z - x, we will have
(10.5.5) (10.5.6) / = lim /(t), (10.5.7) and u'(t) -- -h(t), (10.5.8) which gives a
simple physical interpretation of the function h and a way of determining it for a
range of values of the argument. A worker who likes to think of elastomers as
fluids would want to have/ -- 0 and may picture /(t) as indicated in Fig. 10.1 for
such "solids." It should have a long, almost fiat part representing the rubber
plateau, with/ --. 0 as t - x. A worker who watches only long enough to
encounter the plateau might reasonably extrapolate to obtain some nonzero value
of /0 and dislike the notion that it is to be viewed as a fluid. It may be valuable
for someone to collect all the evidence bearing on this and perform a careful
critique of it but, as far as ! know, this has not happened. 10.5 States 165 So, this
gives a crude picture of the theories of concern. The first version is in a sense
local, but hardly local enough to fit the pattern of very local theories commonly
treated in texts on irreversible thermodynamics. The pictures of springs and
dashpots cannot be taken too seriously. However, in it, there is the suggestion
that, at least temporarily, it is possible to store some energy in the springs, even
if we are dealing with a fluid and this is at least intuitively consistent with the
"elasticity" which they exhibit. Certainly the second version is far from local, in
the temporal sense. Now, if we ignore the inertial effects, we can calculate the
initial elastic modulus as i(O) = io + h(z) dz. (10.5.9) In this quick stretch, the
body is behaving like a linear elastic body and we can use this idea to make an
estimate of the work done per unit volume, 5W, 5W =/(0)%2/2. (10.5.10) In
cases like this, it is rather commonly accepted that there is too little time for
appreciable heat transfer to take place, particularly in the elastomers which are
not good conductors of heat. So, by the first law, this also gives an estimate of
the energy density, really the internal energy density since we are neglecting
inertial effects. With elastomers and various other high polymers, like silly putty,
which are more obviously fluids, the initial jolt should be close to a reversible
process, intuitively. Thus, it makes some sense to regard this as an isentropic
process and assign to this initially stretched configuration the value of the
entropy occurring before stretching. As a personal matter, I do not think that
these ideas are far wrong, and, as far as I am concerned, they make unreasonable
the idea that you can use the hypothesis of local equilibrium. To avoid some
arguments, consider something like silly putty which is obviously better
regarded as a liquid. Such liquids are reasonably considered as incompressible
and besides, the shearing motions do not produce volume changes according to
linear theory. For equilibrium, the internal energy should then not depend on
anything but entropy. If the entropy is fixed, so is the internal energy. There is
then no way to explain the change in internal energy inferred from (10.5.10) for
such liquids. If you accept the idea indicated in Fig. 10.1, the same argument
applies to elastomers. If you do not, then the problem is to explain why the
hypothesis should work for viscoelastic solids but not viscoelastic fluids. I
consider this to be hopeless, so I reject the hypothesis. Various workers have
come to this conclusion, quite possibly for different reasons. If you agree and
also accept the viewpoint of Tisza, among others, mentioned in the Preface, then
the problem of defining energy and entropy is easy. It is impossible, so forget it.
Of those I know in this business, no one seems completely happy with this
resolution. Some may well be prepared to believe that this
166 10. Reconsideration of Generalities is a possible conclusion but they would

need to see some more compelling argument to accept it. For the clastomers, as
we get well into the plateau or, by the other view, close to equilibrium, the
temperature is likely to be again at least close to the ambient. Either way, we are
in a regime where, by common consent, thermoelasticity theory applies, at least
to a fairly good approximation. Said differently, the notion that energy and
entropy have meaning in this regime seems to be generally accepted. At least
approximately, we can here use thermoelasticity theory to calculate them. For
the situation considered, this leaves us without an obvious way of calculating
these quantities in the regimes where (t) is changing more rapidly with time.
This is one example of a regime for which experts seem not to have come to a
very good agreement concerning how best to deal with these quantities. There
are several reasons for this. As was mentioned earlier, some might hold to the
view that one can only use those equilibrium states excluding the possibility of
defining entropy, etc. Also, as was mentioned, the basic ideas of such theory do
involve some philosophical and practical difficulties and workers can have rather
different ideas about how best to deal with them. For example, we mentioned the
possibility of considering just one standardized initial history for a material, or
allowing for more, and I have encountered some differences of opinion about
this. Also, nonlinear theory of this kind is very complex, making it rather easy
for workers to disagree about how reasonable it is to make rather technical
assumptions which seem to be needed to perform mathematical analyses relating
to general theories of this kind. For such reasons, it is understandable that an
argument which seems convincing to one expert can be considered to be
unconvincing to another. As best as I can assess the situation, Coleman and
Owen [68] seem to have come closest to giving a satisfactory treatment of
energy and entropy for such theories. In this, the distinction between states and
processes gets blurred, with states becoming histories of deformation, etc. The
idea of cycles is modified by introduction of a concept of approximate cycles.
With this, the conclusion is that energy and entropy, like stress, do depend on
those histories. As might be expected from the fact that this is a complex theory,
their treatment is hardly in the elementary category. For theory of this kind, one
can find some things which do fit the description of cycles. For the purely
mechanical theory given by (10.5.3), one can use the idea represented by
(10.4.1) and (10.4.2) to generate some cyclic processes. That is, it is not hard to
show that u(x,t+T) =u(x,t) t=-(x,t+T) -- -(x,t). (10.5.11) It is not immediately
obvious that this is implied by the other version (10.5.2) but, in practice, workers
accept this. Also, the corresponding result holds for at least most nonlinear
theories of viscoelasticity of the "memory" kind encountered in practice,
including three-dimensional theories. For the mechanical theory, this is enough
to justify regarding such processes as 10.6 Laws of Classical Thermodynamics
167 cyclic, generating some cycles. Intuitively, I would not be happy with a
definition of cycles or cyclic processes which let the stress have different values
at the beginning and end of a cycle. Here, it seems difficult to find any very
different kinds of cycles which have this property; one could generalize that
used slightly, requiring only that if(x, t) be periodic in time. Of course, the
mechanical theory should be generalized to include equations governing
temperature variations if we are to seriously consider applying thermodynamic
ideas to such theories. These periodic processes are not the only processes of
interest and one would like to have a much greater variety of cycles to make
better use of the laws of thermodynamics. As in the plasticity case, the
consensus of opinion seems to be that there is no need to modify conventional
equations of motion or energy equations. Simply, it is not a matter of routine to
apply thermodynamics when, as here, one is dealing with theories not of the very
local kind. To some degree, this explains why Coleman and Owen [67] were
motivated to modify the notion of cycles, to obtain more things which could
play a similar role. Once one gets away from the equilibrium problems for
elastomers, one is into issues too complex to be covered in an elementary
treatment of relevant thermodynamics. These are not the only difficulties
encountered in trying to apply thermodynamics to improve our understanding
of solid behavior, in particular. What we have available to overcome them are
the basic laws of thermodynamics. I thought that it may help to have some
inkling of those difficulties encountered in practice before proceeding, since
thermodynamicists rarely mention these. 10.6 Laws of Classical
Thermodynamics To some degree, it is a subjective decision as to what should
be considered as classical thermodynamics. I and some others prefer to
interpret it rather broadly, to at least leave open the possibility of applying the
ideas to troublesome cases, such as were mentioned in Section 10.5. Others pre-
fer to limit it to the cases which are much more routine, covered by the
hypothesis of local equilbrium, etc. A rather common classical view as I
interpret it is that heat, power and temperature are the most basic entities, in the
sense of being most closely related to ordinary experience. More abstract are
concepts of energy and entropy. If these are to be meaningful, they, and
whatever properties they might have, should be inferred from ideas dealing more
with the basic concepts. I believe that it helps to understand what is done if you
accept this view, at least for the sake of argument. Basically, the laws declare
some things to be physically impossible. At least to some degree, they grew out
of experience with ancient engines, so it is not surprising that cycles play an
important role in them. Involved are verbal statements which are subject
168 10. Reconsideration of Generalities 10.6 Laws of Classical

Thermodynamics 169 to interpretation, although there is not very much
disagreement about this. I will make some comments about this along the way.
The first has some implications for any thermodynamic system capable of
undergoing at least one cycle. It reads For any cycle, beginning at time to and
ending at time t, 5W = P dt = -6Q = - Q dt. (10.6.1) By general consent, one
implication of the first law is that, for a loading device to be considered to be
conservative, 5W should vanish for every possible cycle. This does exclude
some things which may be considered to be dead loading devices. For example,
if one maintains a constant torque on a stir rod inserted in a viscous fluid, one
could view this as dead loading but, in likely cycles, 5W is positive, so this is not
a conservative device. Numerous elementary texts discuss how one can use this
law to infer the existence of an energy depending on states for sufficiently
simple theories of systems. ! will not expend the ink to give one more discussion
of this kind. However, I will note that, with our theory of thermoelastic bars, this
statement would fail if we regard as cycles those in the example mentioned in
Section 10.5, where the kinetic energy does not return to its original value.
Obviously, the discussion of the first law given in Chapter i makes a
presumption about existence of energy. Here, this is to be viewed as something
to be proven starting from (10.6.1). With the troublesome theories mentioned in
Section 10.5, this is one of the nontrivial problems. Various implications of
impossibility can be read from (10.6.1). For example, if you wish to obtain some
useful work from a system (SW < 0), you cannot also get the system to emit
more heat than it absorbs, (i.e. having 5Q < 0). It is easy to see that, for the
efficiency e defined by (10.4.6), the first law implies when 5Q + 0, 0 < e < 1.
(10.6.2) With the second law, the situation is more complicated. Different state-
ments were made by older writers and one finds these restated in different ways
in different texts. Some are convinced that these are equivalent and others are
not. Serrin's description [69] of the original statements is accurate. His paper
begins with a quotation of a statement by Bridgman, a noted physicist: It does
seem obvious that not all formulations of the second law can be exactly
equivalent. I think it pertinent to add that his experimental work 5 turned up
numerous interesting facts relating to phase transitions and plasticity
phenomena 5This is covered in Bell's review [13]. in solids. Along with this, he
was a serious student of thermodynamics with a strong interest in trying to apply
it to plasticity phenomena, in particular. He did appreciate at least some of the
difficulties which this involves. Commonly mentioned in texts is a version of the
second law attributed to Clausius. As is discussed by Serrin [68], Clausius
proposed two versions. To this, I would add a third. As noted in Section 1.2,
Gibbs took a statement by Clausius as a basis, or at least a motivation for his
work. Some take it as a motivation for considering (1.2.7) as a statement of the
second law, one version not mentioned by Serrin. To take this as basic, it seems
to be necessary to believe that for any thermodynamic system covered by clas-
sical thermodynamics, entropy can somehow be defined. Presumably, the later
of the other two versions mentioned by Serrin is the best formulated. It reads as
follows: (Clausius) A passage of heat from a colder to a hotter (10.6.3) body
cannot take place without compensation. Clearly, this recognizes that the
intuitive idea that heat flows from hotter to colder bodies is not always true: if it
were, it would not be possible to make refrigerators. Some notion of temperature
is involved to discern which is hotter. As noted in Section 10.1, I have accepted
the assumption that we can always consider temperature to be absolute
temperature. Nominally, the first law contains no reference to temperature.
However, for the first law to make sense, one needs to be able to assign some
numerical value to heat in any particular situation, which means using some
physical units of heat. If one looks at the definition of such a unit, say a calorie,
one finds that it involves a definite unit of temperature, a degree on the
centigrade scale. The other point is, that to compare work with heat, we must use
the same units for both. Converting heat data to these is performed by
multiplying by a universal constant, which does of course depend on which units
are selected. So, in practice, we do accept a universal temperature scale in
interpreting the first law. As at least some interpret (10.6.3), the colder and
hotter bodies are to be described as two heat baths at fixed temperatures O and
02 ) 01. Some thermodynamic system, allowed to undergo a cycle, is somehow
to be in contact with these at some times during the cycle. Any heat transfer is to
be between the system and the heat baths. Thus, for example, when the system is
in contact with one, any heat absorbed (emitted) by the system is emitted
(absorbed) by this heat bath. When the system is in contact with neither, the
process must be adiabatic (Q -- 0), etc. The phrase "without compensation" is
taken by some to mean that the net work done on the system during a cycle must
vanish (SW = 0). Then, from (10.6.1), we should also have 5Q -- 0. I think it
reasonable to relax the restriction as Serrin does [68], for example, using the
interpretation that "without compensation" means 5W _ 0 5Q _ 0, (10.6.4)
170 10. Reconsideration of Generalities where I have used the first law. To
decide for yourself whether such a statement makes sense, a first step is to check
whether it does hold for systems familiar to you. If so, you can try to design and
build a system which violates it. If you cannot, you acquire some faith that the
law is sound, but there is no way to prove this. Let us try one check using the
thermoelastic theory of bars discussed in Chapter 2. For a bar, consider a cycle
beginning at t -- 0, ending at t = T, conform- ing to (10.6.4), so that 5Q = Qdt = -
Pdt = -AW _ 0. (10.6.5) To bring in the contact with the heat baths, we consider
the ends to be insulated, so q(L, t) -- q(0, t) = 0 D t, (10.6.6) and use Newton's
law of cooling, with the assumptions that, for 0 < x < L, r = c[O -- g(x,t)], 0 _ t <
tl, r = 0, tl _ t < r: 0[02 -- O(x, t)], t2 < t < ta, r = 0, ta < t < T, (10.6.7) with c
some positive constant, 0(x, t) being the temperature of the bar. It is not
immediately obvious that any such cycles exist, since some equations must be
satisfied, and I will not deal with this question. The question is more to check
whether any that may exist do conform to this version of the second law. To be
definite, by a cycle, we mean a process defined for times in the interval [0, T],
with y(x,T) = y(x,O) A(x,T) = A(x,O),O(x,T) : 0(x,0) (10.6.8) satisfying the
equation of motion (2.3.8) with f = 0 and the heat equation (2.3.27) with r as
prescribed in (10.6.7). One can allow for such things as the shock waves
discussed in Section 7.1 but I will leave it to you to determine whether this
affects the conclusions we will make. Now, with (10.6.8) we will have, in
particular L O) dx $(T) - $(0) = / q(A, = 0. (10.6.9) Then, from the global form
of the Clausius Duhem inequality (2.3.13), with Xl = 0, x2 = L, we obtain i T
foL(r/O) dxdt < O, (10.6.10) 10.6 Laws of Classical Thermodynamics 171 where
we have used (10.6.6). With (10.6.7), this gives ct [(0 - 0)/0] dt + [(02 - 0)/0] dt
dx <_ O. (10.6.11) From (10.6.4), we must also have a (0 - O) dt + (02 - 0) dt dx
> O. (10.6.12) Here the factor c, being positive, can be canceled. Now, with our
interpretation of this version of the second law, it should be impossible for heat
to be transferred from the colder to the hotter bath under the conditions assumed.
That is, briefly, Clausius : (02 O) dtdx > 0. (10.6.13) Odo Jr2 The question is
whether this really does follow from (10.6.10) and (10.6.12), perhaps by using
something else deducible from the bar theory considered. For this, it is helpful to
note that, for any possible values of 01 and 0, (01 - 0)(0 1 - 0 -1) 0 =: (01 - 0)/01
_ (01 - 0)/0. (10.6.14) Of course, one can here replace 01 by 02. Thus, using
(10.6.11), we have { [(o1- o) /o1] ctt + f i3[(o2 - o)/o2] ctt } ctx (10.6.15) <_
[(01 - 0)/0] at + [(02 - 0)/0] at ax _< 0. Now, use (10.6.12) to eliminate the first
term on the left to give - oi (02- o)ax at _< o, (10.6.16) and, with 02 > 0, this
does give the inequality alleged to hold in (10.6.13). So, as interpreted here, we
have verified that (10.6.3) does hold in the cases considered. It is not hard to
check that we would have encountered a violation had we considered ct to be
negative. Said differently, we have come close to proving that a ) 0 follows from
(10.6.3). To complete the proof, one would need to show that there is at least one
cycle of the kind considered. If you are willing to assume this, you have another
reason to think that (10.6.3) makes sense as interpreted here. Suffice it to say
that this old law is still accepted because it has been tested in numerous ways
and found to be trustworthy.
172 10. Reconsideration of Generalities As is also commonly discussed in texts,

one can use this version of the second law to deduce a useful inequality, even if
one insists on having equality hold in (10.6.4). Consider any system in contact
with a heat bath with temperature 0B (t). Suppose that the system is capable of
undergoing a cycle beginning at time to and ending at time t. For the cycle, we
then have tl [Q/OB(t)] dt _ 0, (10.6.17) this being called the Clausius inequality.
In various simpler theories, it is automatic that 0B is also the temperature of the
system and some writers do not make a clear distinction between these two
temperatures. Also commonly discussed in texts is the fact that, for relatively
simple systems, one can use (10.6.17) to deduce the existence of entropy,
depending on suitably defined states satisfying the Clausius-Planck inequality
(1.2.2). Also for such theories, it is generally easy to show that (1.2.2) implies
(10.6.17). In any event, (10.6.17) represents Clausius' contribution to the
Clausius- Duhem inequality which we will discuss a little more later. For our
bars, another possibility is to have the two heat baths in contact with the bar at
the same time. For example, we could insulate the sides so r = 0 and put each
end in contact with different heat baths, each at fixed temperature. With a
suitable control of mechanical conditions, one may attain a static process which
is, of course, cyclic. It is hard to see how (10.6.17) could yield any information
about this. From such reasoning, it seems clear that the Clausius inequality
should not be regarded as the same as the second law, as interpreted above.
Another commonly mentioned version of the second law is Planck's re-
statement of Kelvin's idea: (Kelvin Planck) It is impossible to construct a
machine which operates cyclically and which does nothing but raise a weight
and cause a corresponding cooling of a heat reservoir. (10.6.18) Most regard this
as equivalent to Clausius' version. Serrin [68] does discuss assumptions which, it
seems, need to be accepted, at least tacitly, in estab- lishing equivalence, at least
as he interprets the statements. I have nothing worthwhile to add to such
discussions, so will leave it at this. In these versions of the laws, the basis is a
relatively simple intuitive idea, structured by conventions which have been
established from long experience in using them. In the basic statements, as
interpreted here, there is no explicit mention of states. By convention, notions of
states have come to be associated with the statements, at least largely because
this is a convenient way of describing the energies and entropies which can be
deduced using these laws, when we know how to do this. However, there is no
implication that such energies and entropies exist for all kinds of thermodynamic
systems and I do not believe that they do. The laws have some implications
10.6 Laws of Classical Thermodynamics 173 for any system which can undergo
at least one cycle. If, by any mode of reasoning, one can decide what are cycles,
one can explore this without also having any preconveived notions about states.
With various theories of plasticity and viscoelasticity, it is rather clear that one
has some variety of cycles and the above versions do have some implications
about these. In such cases, the implications may well be less than what would be
needed to deduce well-defined cntropies at least, but it is not a classical law that
this should always be possible. It would not necessarily violate the laws if one
assumed that they are well-defined and gave some prescription for calculating
them. If you try this, you may well have trouble in convincing others that your
ideas are sound. Also commonly mentioned is a third version, quite different in
character, due to Carathory. First, recall the statements made at the beginning of
our discussion of the second law, by Bridgman, and accept that he was familiar
with the three. Another good physicist, Pippard [4], takes a rather contradictory
view, so I think it worthwhile to explore this. He states what he consideres to be
this version, (Carathdodory-Pippard) In the neighbourhood of any equilibrium
state of a system, there are states which are inaccessible by an adiathermal
process. (10.6.19) It is clear from his discussion that, where I have used the word
"adiabatic," he means "adiathermal." He notes that he likes this least, because
...it is neither intuitively obvious nor supported by a mass of experimental
evidence. However, as he puts it, ...it leads to the same conclusions as the others
.... Clearly, this view is not easy to reconcile with that of Bridgman. Physi- cists
tend to skip little points of mathematical rigor, so one might reasonably explore
what mathematicians have to say about this version, one possibility being the
previously mentioned paper by Serrin [68]. Here, we find a rather different
statement, viz. (Carathorody) Consider a system $ whose behaviour can be
described by a finite number of state variables whose domain is an open set of R
, k _ 2 (with the usual topology). Let ao be a state of the system (a point in ) and
let N be any neighbourhood of o in . Then there must exist in N a point with the
property that no adiabatic process open to q can start at o and end at , (i.e., is
inaccessible from o). (10.6.20)
174 10. Reconsideration of Generalities Read on, and you will see that Serrin
regards this as a very different version, not equivalent to the previous two. Two
things are worth noting. It is more than glossing over points of rigor to fail to
mention that those states should be describable by a finite number of parameters,
as Pippard does. Also, what is a state a0 in (10.6.20) is, in Pippard's version, an
"equilibrium state." So, accept that the world of classical thermodynamics is
limited to the cases which can be described in terms of states which are, in turn,
describable by a finite list of parameters. Further, such states are to fit the
description of equilibrium states discussed earlier. From what else he does, this
is what I infer to be Pippard's view of what is classical thermodynamics and, in
this respect, he has lots of company. Workers who accept this view generally
accept the idea that energy and entropy are well-defined as functions of such
states. This view is too limited for some, Bridgman for one, and I have declared
myself to be with him in this. I have said enough about the problems met in
deciding what should be meant by states to indicate that, sometimes, I do not see
how to use the third version in cases where the other two can be applied. If I had
some conjecture about this, I would return to the previous versions to try to
decide whether it made sense. In this respect, those versions are certainly not
replaceable by the third version for my purposes. The third version has some
merit in providing a basis for simple equilibrium studies such as we have
performed, when one does not want or know how to place these in the context of
some nonequilibrium theory. However, even here, it is hard to see how one
could use this to motivate or justify what we took to b.e basic definitions of
equilibrium. Neither does it seem to warn us against trying to use them for
problems involving sliding friction, for example. As I see it, the view adds little
to what Gibbs said about equilibrium. For such reasons, I do not find the third
version very useful, but you might. Easier to use, when it applies, is the Clausius
Duhcm inequality, which really comes in two versions. We have already
discussed this in relation to one-dimensional theories. For three-dimensional
continuum theories, the more traditional version goes as follows. Some fixed set
of material is considered to be the thermodynamic system. Here, entropy is
introduced from the start. Introduce a reference configuration, some possible
configuration as a three-dimensional analogue of what we have used for bars and
plates. Let denote the region it occupies. With $ denoting the entropy, the
entropy per unit reference volume, we have, by assumption S = f rldv, (10.6.21)
dv being the volume element. Here, to describe Q, we introduce a heat flux
vector q and set Q = fo q' da, (10.6.22) 10.6 Laws of Classical Thermodynamics
175 where 0 denotes the boundary of , da the element of area and qn the
projection of q on the outward normal to the surface. Then, the Clausins- Duhem
inequality is dS/dt > fo (q,/O) da, (10.6.23) where, as usual, 0 is the temperature
of the material which, in general, varies with position and time. By using the
divergence theorem, etc., one can obtain a corresponding inequality which holds
pointwise, but I will not belabor this. If you return to Chapter 1 and read the
quotation from Gibbs, you will find that rather puzzling integral, in which t
denotes ...the temperature of the part of the system receiving it .... It is not clear
what he had in mind but it seems not to be quite the integral occurring in the
Clausins inequality (10.6.17); something more like that occurring in (10.6.23)
seems to be the case. With the assumption that the quantity on the left vanishes
when integrated over a cycle, one gets an inequality somewhat like the Clausius
inequality, fti fO (q,/O)dadt < O. (10.6.24) In the above discussion of bars we
mentioned the possibility of putting different heat baths in contact with the ends
of a bar. Kestin [70] uses a similar idea to conclude that (10.6.23) is deducible
from our (1.2.7) when entropy is defined using the hypothesis of local
equilibrium. Possibly, one could use a similar argument to deduce that (10.6.24)
follows more generally from, say, Clausius' version of the second law. This
could be useful in trying to justify the assumed existence of entropy for more
general systems by this route, but I am not sure of this. The other version of this
inequality has been frequently used since it was suggested by Truesdell and
Toupin (p. 258 of [71]). For bars the quantity r may be thought of as being
defined within the bar. The proposal is to modify (10.6.22) in that analogous
way, writing Q=foq,da+frdv, (10.6.25) replacing (10.6.23) by dS/dr >_
fo(q,/O)da + fob(r/O)dv. (10.6.26) Then, (10.6.24) is modified in the obvious
way to ii [fo(q/O)da + /n(r/O)dv] dt < O. (10.6.27)
176 10. Reconsideration of Generalities It seems less likely that one could
produce a satisfactory derivation of this from any of the other three versions of
the second law. For such reasons, it is at least awkward to tackle problems
related to the existence of entropy with suitable properties, for some systems of
this kind, in particular theories of viscoelasticity. Motivated by such
considerations, Serrin [69] proposed a different version of the second law which
does seem to deliver useful results more easily. In spirit, it is not so different
from the first two versions and, for simpler kinds of theories, it leads to the same
conclusions. Like them, it deals with cycles. Consider any thermodynamic
system, letting C denote any cycle associated with it. Associate with this a
function depending on a parameter O, A(C, O) called the accumulation function,
with the interpretation that A(C, O) = heat received by the system during the
cycle, at temperatures 0 _ O. (10.6.28) Thus, for 5Q interpreted as in (10.6.1),
we have 5Q = A(C, ). (10.6.29) In words, his version is The accumulation
function of a nonadiabatic cycle process cannot be nonnegative. (10.6.30) He
explains how this relates to the Clausius and Kelvin Planck versions, as he
interprets them and, for this, I refer the reader to his paper. He shows that this
statement implies that O-2A(C, 6}) dO < 0. (10.6.31) Under assumptions which
are not very restrictive, one can put this in a form which looks more like the
Clausius inequality. Suppose that, for C fixed, A is a sufficiently smooth
function of O to enable us to integrate by parts. Suppose also that lim A/O = lim
A/O = 0. (10.6.32) From (10.6.29), the first condition will certainly be satisfied
if 5Q < , the second if no heat is received at temperatures near absolute zero and
even less restrictive assumptions would suffice. With these assumptions,
integration by parts gives, for any cycle, o 0 - dA < O. (10.6.33) Roughly, dA
represents the heat received by the system between the temperatures O and
O+dO, making this somewhat like the Clausius inequality. 10.6 Laws of
Classical Thermodynamics 177 Unlike the latter, there is no stipulation on how
heat baths, etc., are to be used to effect heat transfer. This also resembles the
rather mysterious integral mentioned by Gibbs, providing one interpretation
which is meaningful. Let us try evaluating (10.6.33) for a thermoelastic bar. For
simplicity we will ignore heat conduction, so that L Q = fo rdx. (10.6.34)
Consider a cycle beginning at t = 0 and ending at t = T > 0, described by
functions y(x, t) and O(x, t), which should, of course, be defined for the whole
bar, 0 _ x _ L. The relevant points (x,t) in the x-t plane then form a rectangle R.
For r, one can use Newton's law of cooling, the Stefan Boltzmann law, or simply
the function which satisfies (2.3.12) when some inputs are used to calculate the
remaining terms. For simplicity, we assume that r(x,t) and O(x,t) are continuous
functions on the rectangle, which implies that they are bounded. Also, we
assume that O(x,t) is bounded away from zero, so, for some positive constants a
and b, we have 0 < a < O(x, t) _ b < cx:. (10.6.35) For convenience, we have
picked a to be smaller than the minimum value of O(x, t). Now divide up the
temperature interval into N equal parts, n = 1,..., N, giving intervals as indicated
by In : On < 0 <_ On+, O = a, ON+i = b, (10.6.36) On+ - On = (b- a)/N. Now,
we define subsets an of the rectangle R by the condition that (x, t) E an = O(x, t)
In. (10.6.37) No point has two temperatures associated with it, so one point
cannot belong to two such sets. Also, every point in R has a temperature
associated with it, so the union of these disjoint sets is R, N U an: R. (10.6.38)
Now, from (10.6.28) and (10.6.36), for the cycle C considered, A(C,O)=0 ifO<a,
(10.6.39) A(C,O)= rdxdt = rdxdt, ifO_b, which is consistent with (10.6.32). It is
then clear that dA = 0, except when O is in the interval a ( O _ b, so the left side
of (10.6.33) takes the form O 0 --1 dA. (10.6.40)
178 10. Reconsideration of Generalities Now, from at least one definition of the
integral we can approximate it as closely as we like in the manner indicated by N
jab) -1 dA - )i[A(C, )n+l) -- A(C, )n)]. (10.6.41) Now, the difference in the
square brackets is, from the definition of A, the heat supplied at temperature O in
the range On < O _< On+, (10.6.42) that supplied at 0 = On being counted in
both A's. From the definition of an, this is given by r dx dt. Thus, the above sum
can be written as n+ rdxdt. (10.6.43) Now, using (10.6.38), we also have N
/R(r/O)dxdt-- (r/O)dxdt, (10.6.44) and, with this, we can add and subtract this
term, to put (10.6.41) in the form N Note that, if N is large, 0 is nearly equal to
On+ in an. By a more detailed analysis, which I will omit, this sum can be made
arbitrarily small by taking N large enough. In the limit as N - x, we obtain 0 --1
dA = 0 - dA = r/O) dx dt < 0, (10.6.46) which is what we would get by applying
the Clausius Duhem inequality to a cycle when heat conduction is neglected (q --
0). With a similar, but more tedious analysis, one can account for heat
conduction which modifies (10.6.46) in the manner expected from analogous
calculations based on the Clausius-Duhem inequality. Ignored here is the
possibility that the sets an may be so complicated that integrals over them are not
well-defined. For a rigorous treatment, one needs analysis too complex to be
used here, 10.6 Laws of Classical Thermodynamics 179 involving the theory of
Lebesgue integration, but it is possible. In the three- dimensional case, when Q is
given by (10.6.25), one can use similar arguments to show that, formally,
(10.6.27) is equivalent to (10.6.33). For various kinds of theories of solids and
fluids, the Clausius-Duhem inequality applies and gives sensible results. So this
really provides numerous checks on the soundness of this version of the second
law. With, say, plasticity theories, where one has doubts about the existence of
entropy, it would be unsafe to assume that the Clausius-Duhem inequality
applies. However, if you accept that (10.6.25) applies, you can use (10.6.27) as a
mathematical representation of the second law, if you also accept this version. At
least from my point of view, this version fits comfortably as part of the subject
of classical thermodynamics, although it is relatively new. I prefer it to any of
the three versions mentioned before. There are also some different versions of
the third law which deals with the unattainability of absolute zero (8 = 0). As
stated by Pippard [4], two of these are By no finite series of processes is the
absolute zero attainable, (10.6.47) and, what is perhaps better regarded as an
addendum, As the absolute temperature tends to zero, the magnitude of (10.6.48)
the entropy change in any reversible process tends to zero. This provides support
for the view that the second equality of (10.6.32) is not a very restrictive
assumption, among other things. Various writers discuss this law and I will leave
it to the interested reader to pursue this on his own. Finally, some slightly
different versions of another law, the zeroth law, are mentioned by various
authors. As I interpret this, it is more concerned with the theory of temperature
which I have not tried to discuss. In their treatment of this, Fosdick and
Rajagopal [72] take as basic a version due to Maxwell, (Maxwell) Bodies whose
temperatures are equal to that of (10.6.49) the same body have themselves equal
temperatures. In statements used by some others, the notion of equality of
temperature is replaced by a statement that, pairwise, the bodies are in
equilibrium with each other, a notion that I find misleading and confusing.
Newer than the theory of the old engines but certainly old enough to be regarded
as classical, is another branch of thermodynamics, more related to statistical
molecular theory. In this, Gibbs was also a pioneer. This involves quite different
ideas about concepts of temperature, energy and entropy, more related to
statistical averages. That these names are used here reflects the fact that some
situations can be analysed with this and the older theory, with compatible results,
if one agrees to use these names
180 10. Reconsideration of Generalities to make comparisons feasible. However,

it does add confusion conceptually. It would take a very lengthy discussion to
introduce these ideas and to compare them with those discussed above and I will
not attempt this. Briefly, my experience is that each branch has its own virtues
and faults. Pragmatically, I have found that one can be more successful than the
other in dealing with a particular situation, so it helps to be familiar with both.
For dealing with solids, one weak spot in this branch involves guesses which
seem to need to be made to relate macroscopic deformation or motion to atomic
or molecular motion. For crystals, Zanzotto [73] collects evidence that the
commonly used hypothesis sometimes agrees and sometimes fails to agree with
experiment. When it fails, we seem not to have a viable alternative. Workers
interested in elastomers often use one hypothesis, although alternatives have
been considered, to try to obtain some better agreement between molecular
theory and macroscopic observations. At best, this is an indirect way of
assessing the validity of the assumed relation. Suffice it to say there seems to be
no panacea for problems of this kind. I have mentioned only some of the
difficulties encountered in trying to apply ideas of classical thermodynamics to
solids. Of course, it is the difficulties which encourage intelligent workers to
try to modify the old ideas in order to find better ways of treating the
troublesome situations. I do not feel comfortable about giving general advice
about how best to begin learning about such developments. Were I in this
position, I would choose some questions of particular interest to me and ask
experts for the best references relevant to these. However, it is my experience
that many workers are uneasy about some important concepts, particularly that
of entropy. While it is not a panacea, . I believe that it helps to understand how
such concepts evolved, historically. Readers unfamiliar with this might find
helpful the book by Truesdell [74], particularly his Historical Introit. Readers
with much more mathematical ability than is required for my book might consult
that by ilhavy [75], which covers some topics touched upon here in greater
depth, along with some omitted here. References [1] Truesdell, C., and Bharatha,
S. (1977), Classical Thermodynamics as a Theory of Heat Engines, Springer-
Verlag, Berlin. [2] Kestin, J. (1966), A Course in Thermodynamics, Blaisdell,
Waltham, MA. [3] Tisza, L. (1966), Generalized Thermodynamics, M.I.T. Press,
Cam- bridge, MA. [4] Pippard, A.B. (1964), The Elements of Classical
Thermodynamics, Cambridge University Press, Cambridge,. [5] Bridgman, P.W.
(1941), The Nature of Thermodynamics, Harvard University Press, Cambridge,
MA. [6] Bowen, R.M. (1989), Introduction to Continuum Mechanics for En-
gineers, Plenum Press, New York. [7] Gibbs, G.W. (1875), On the equilibrium
of heterogeneous substances. Trans. Conn. Acad., 111, 108-248; Gibbs, G.W.
(1877 78), On the equilibrium of heterogeneous substances. Trans. Conn. Acad.,
111, 343 524. [8] Duhcm, P. (1911), Trait d'enrgtique ou thermodynamique
gnrale (two volumns), Gauthicr-Villars, Paris. [9] Einstein, A. (1956),
Investigations on the Theory of the Brownian Movement (ed. R. Fiirth; trans.
A.D. Cowper), Dover Publications, New York.
182 [lO] [11] [12] [13] [14] [15] [16] [17] [18] [19] References Pippard, A.B.
(1985), Response and Stability, Cambridge University Press, Cambridge.
Gelland, I.M., and Fomin, S.V. (1963), Calculus of Variations (trans. R.
Silverman), Prentice-Hall, Englewood Cliffs, NJ. Rivlin, R.S. (1975), The
thermomechanics of materials with fading memory, in Theoretical Rheology,
Applied Science Publishers Ltd, London. Bell, J.F. (1973), The experimental
foundations of solid mechanics. Handbuch der Physik, vol. Via/l, Springer-
Verlag, Berlin. Kahl, G.D. (1967), Generalization of the Maxwell criterion for
van der Waals' equation. Phys. Rev., 155, 78-80. Ericksen, J.L. (ed.) (1984),
Proceedings of Workshop on Orienting Polymers, Minneapolis 1983. In Lecture
Notes in Mathematics, vol. 1063, Springer-Verlag, Berlin. Landau, L.D. (1965),
On the theory of phase transitions, in Collected Papers of L.D. Landau (ed. D.
Ter Haar), Gordon and Breach and Pergamon Press, New York. Thomas, L.A.,
and Wooster, W.A. (1951), Piezocrescence: The growth of Dauphin twinning in
quartz under stress. Proc. Roy. Soc. London, A205, 43-62. Perkins, J. (ed.)
(1975), Shape Memory Effects in Alloys, Plenum Press, New York. Delay, L.,
and Chandrasekaran, L. (eds.) (1982), Proc. Int. Conf. on Martcnsitic
Transformations. J. Physique, 43. [20] Nishiyama, Z. (1978), Martensitic
Transformations, Academic Press, New York. [21] [22] [23] James, R.D., and
Kinderlehrer, D. (1989), Theory of diffusionless phase transitions, in Partial
Differential Equations and Continuum Models of Phase Transitions (eds. M.
Rascle, D. Serre, and M. Slem- rod), Lecture Notes in Physics, vol. 344,
Springer-Verlag, New York. Sengers, A.L., Hocken, R., and Sengers, J.V.
(1977), Critical point universality and fluids. Phys. Today, 30, 42-51. Beatty,
M.F. (1987), Topics of finite elasticity: hyperelasticity of rubber, elastomers,
and biological tissues. Appl. Mech. Rev., 40, 1699- 1734. References 183 [24]
Kitsche, W., Miiller, I., and Strehlow, P. (1987), Simulation of pseu- doelastic
behavior in a system of balloons, in Metastability and In- completely Posed
Problems (cds. S. Antman, J.L. Ericksen, D. Kinder- lehrer and I. Miillcr), IMA
Volumes in Mathematics and Its Applica- tions, vol. 3, Springer-Verlag, New
York. [25] Thompson, J.M.T., and Hunt, G.W. (1973), A General Theory of
Elastic Stability, John Wiley and Sons, New York. [26] Alexander, H. (1971),
Tensile instability of initially spherical balloons. Int. J. Eng. Sci., 9, 151-162.
[27] Trcloar, L.R.G. (1948), Stresses and birefringence in rubber subjected to
general homogeneous strain. Proc. Phys. Soc., 60, 135-144. [28] Kearsley, E.A.
(1986), Asymmetric stretching of a symmetrically loaded elastic sheet. Int. J.
Solids Structures, 22, 111-119. [29] Haughton, D.M., and Ogden, R.W. (1978),
On the incremental equations in non-linear elasticity - II. Bifurcation of
pressurized spherical shells. J. Mech. Phys. Solids, 26, 111-138. [30] Chen, Y.-
C. (1987), Stability of homogeneous deformations of an incompressible elastic
body under dead-load surface tractions. J. Elas- ticity, 17, 223-248. [31] Chen,
Y.-C. (1988), Stability of pure homogeneous deformations of an elastic plate
with fixed edges, Q. J. Mech. Appl. Math., 41, 249-264. [32] Treloar, L.R.G.
(1949), The Physics of Rubber Elasticity, Clarendon Press, Oxford. [33]
Courant, R., and Friedrichs, K.O. (1948), Supersonic Flow and Shock Waves,
Interscience, New York. [34] Dunn, J.E., and Fosdick, R.L. (1988), Steady,
structured shock waves. Part 1: Thermoelastic materials. Arch. Ration. Mech.
Anal., 104, 295 365. [35] Gurtin, M.E. (1988), Toward a nonequilibrium
thermodynamics of two-phase materials, Arch. Ration. Mech. Anal., 100, 275
312. [36] Cheng, B.W. (1981), Polymer Surfaces, Cambridge University Press,
Cambridge. [37] Wu, S. (1982), Polymer Interface and Adhesion, Dckker, New
York. [38] Ricci, J.E. (1966), The Phase Rule and Heterogeneous Equilibrium,
Dover, New York.
184 [39] References Frazcr, R.A., Duncan, W.J., and Collar, A.R. (1938),
Elementary Matrices, Cambridge University Press, Cambridge. [40] Gent, A.N.,
and Tompkins, D.A. (1969), Nucleation and growth of gas bubbles in
elastomers. J. Appl. Phys. 40, 2520-2525. [41] Landau, L.D., Lifshitz, E.M.,
Kosevitch, A.M., and Pitaevskii, L.P. (1986), Theory of Elasticity, (3rd ed.)
(trans. J.B. Sykes and W.H. Reid), Pergamon Press, Oxford. [42] Frank, F.C.
(1958), On the theory of liquid crystals, Disc. Faraday $oc., 23, 19 28. [43]
Courant, R., and Hilbert, D. (1953), Methods of Mathematical Physics, vol. 1,
Interscience, New York. [44] Chandrasekhar, S. (1977), Liquid Crystals,
Cambridge University Press, Cambridge. [45] de Gennes, P.G. (1974), The
Physics of Liquid Crystals, Clarendon Press, Oxford. [46] Virga, E.G. (1994),
Variational Theories of Liquid Crystals, Chap- man & Hall, London. [47]
Cohen, R.A. (1988), Fractional step methods for liquid crystal problems, Ph.D.
Thesis, University of Minnesota, MN. [48] Love, A.E.H. (1944), A Treatise on
the Mathematical Theory of Elas- ticity, 4th ed., Dover, New York. [49]
Leipholz, H. (1970), Stability Theory, Academic Press, New York. [50]
Grindlay, J. (1970), An Introduction to the Phenomenological Theory of
Ferroelectricity, Pergamon Press, Oxford. [51] Brown, W.F., Jr. (1966),
Magnetoelastic interactions, in Springer Tracts in Natural Philosophy, vol. 9 (ed.
C. Truesdell), Springer- Verlag, New York. [52] van der Waals, J.D. (1895),
Th5orie thermodynamique de la cap- illaritd dans l'hypothse d'unc variation
continual de densitd. Arch. Neefl. $ci. Exactes Nat., 28, 121 209. [53] Dunn,
J.E., and Scrrin, J. (1985), On the thcrmomechanics of inter- stitial working.
Arch. Ration. Mech. Anal., $$, 95 133. [54] Coleman, B.D., and Noll, W.
(1963), The thermodynamics of elastic materials with heat conduction and
viscosity. Arch. Ration. Mech. Anal., 13, 16178. References 185 [55] Miiller, I.
(1973), Thermodynamik, Die Grundlagen der Material The- or/e, Bertelmann
Universit/tsverlag, Diisseldorf. [56] Liu, I.-S. (1972), Method for exploitation of
the entropy principle. Arch. Ration. Mech. Anal., 46, 131-148. [57] Man, C.-S.
(1985), Dynamic admissible states, negative absolute temperature and the
entropy maximum principle. Arch. Ration. Mech. Anal., 9, 263-289. [58]
Poincard, H. (1885), Sur l'dquilibre d'une masse fiuide anime d'un mouvement
de rotation. Acta Math., 7, 259 380. [59] Ericksen, J.L. (1992), Reversible and
nondissipative processes. Q. Jl. Mech. Appl. Math., 45, 545-554. [60] Meixner,
J. (1973), Consistency of the Onsager-Casimir reciprocal relations. Advance
Mol. Relaxation Processes, 5, 319 331. [61] Wollants, P., Roos, J.R., and
Delaey, L. (1980), On the stress- dependence of the latent heat of
transformations as related to the efficiency of a work performing cycle of a
memory engine. $cripta Met., 14, 1217-1223. [62] De Groot, S., and Mazur, P.
(1962), Nonequilibrium Thermodynam- ics, North-Holland, Amsterdam. [63]
Green, A.E., and Naghdi, P.M. (1955), A general theory of an elastic- plastic
continuum. Arch. Ration. Mech. Anal., 18, 251-281. [64] Chaboche, J.L. (1988),
Continuum damage mechanics. Parts I and II. J. Appl. Mech., 55, 59-72. [65]
Boltzmann, L. (1874), Zur Theorie der elastischen Nachwirkung, Sitzber.
Kaiserl. Akad. Wiss. Wien Math.-Naturw. Kl., ?0(II), 275- 306. [66] Ferry, J.D.
(1970), Viscoelastic Properties of Polymers (2nd ed.), Wiley-Interscience, New
York. [67] Leitman, M.J., and Fisher, G.M.C. (1973), The linear theory of vis-
coelasticity, in Handbuch der Physik, vol. Via/3 (ed. C. Truesdell), Springer-
Verlag, New York, pp. 1-123. [68] Coleman, B.D., and Owen, D.R. (1974), A
mathematical foundation for thermodynamics. Arch. Ration. Mech. Anal., 54, 1-
104. [69] Serrin, J. (1979), Conceptual analyses of the classical laws of thermo-
dynamics. Arch. Ration. Mech. Anal., 70, 355-371.
186 [70] References Kestin, J. (1990), A note on the relation between the
hypothesis of local equilibrium and the Clausius Duhem inequality. J. Non-
Equilibrium Thermodynamics, 15, 193 212. [71] Truesdell, C., and Toupin, R.A.
(1960), The classical field theories, in Handbuch der Physik, vol. III/3. (ed. S.
Flfigge), 226-793, Springer- Verlag, New York. [72] Fosdick, R.L., and
Rajagopal, K.R. (1983), On the existence of a manifold for temperature. Arch.
Ration. Mech. Anal., 81,317-332. [73] Zanzotto, G. (1988), Twinning in
minerals and metals: remarks on the comparison of a thermoelastic theory, with
some available experimental results, notes I and II. Atti. Ace. Lincei Rend. Fis.,
82, 723-741 and 743 756. [74] Truesdell, C. (1984), Rational Thermodynamics
(2nd ed.), Springer- Verlag, New York. [75] ilhavy, M. (1997), The Mechanics
and Thermodynamics of Contin- uous Media, Springer-Verlag, New York. Index
Accumulation function, 176 Austenite, 57 Ballistic free energy, 7-8, 14, 38, 40,
112 Biaxial stretch, 79-83 see also Treloar instability Bifurcation diagrams, 62-
65 pitchfork, 63, 87-89, 134-135 sub-critical, 64 Black-body radiation, 144 Body
couples electric, 129 magnetic, 129 Breaking bars, see Discontinuities Brownian
motion, 7, 150 Buckling bar, 13141 see also Euler's elastica Carath6orodory's
second law, 173-174 Chemical potentials, 111, 114 Clausius-Clapeyron
equation, 49, 66 Clausius-Duhem inequality one-dimensional form, 12, 14, 17,
25, 93, 154 three-dimensional form, 174 175 Clausius' inequality, 172 Clausius-
Planck inequality, 4, 13 14, 155 Clausius' second law, 169-171 Concentrations,
115 Conical boundary conditions, 129-130 Convex functions, 16, 60, 82 Cycles,
156-157, 166-167, 168, 170, 176 Cyclic processes, see Processes, cyclic
Difficulties in applying thermodynamics, 7, 26, 34, 143-146, 161-166
Discontinuities in bars breaking, 99 in equilibria, 50, 52-54 shock waves, 93-99
in plates, 61-62 peeling, 100-106
188 Index Discontinuities (continued) see also Clausius-Clapeyron equation,

Mixtures, Waves Dissipation, 154-155 see also Clausius-Duhem inequality
Efficiency of engines, 157-158, 168 Endpoint minima, 53, 69, 140 Energy
general concepts, 1-3, 11, 151, 166, 168 mathematical representations, 11-12,
23, 109-110 see also Ballistic free energy, Field energy, Helmholtz free energy,
Internal energy, Laws of thermodynamics (first), Strain energy, Surface energies
Entropy experimental determination, 16 general concepts, 3-6, 11, 149, 152-153,
154, 165, 166, 170 mathematical representations, 11, 99, 111-112, 124-125, 127-
128 see also Clausius-Duhem inequality, Clausius-Planck inequality,
Dissipation, Ideal heat baths, Law of thermodynamics (second) Equal area rules,
45, 55, 72, 75 Equilibrium concepts, 6-9, 149 Euler's elastica, 138-141, 142
Field energies electromagnetic, 127-128, 143 gravitational, 69, 139-140 Flexural
rigidity, 139 Fourier's law, 17 Fr6edericsz transition, 137 Gibbs' definitions of
equilibrium, see Equilibrium concepts Gibbs' function, 116 Heat flux, 12, 23,
153, 174 see also Clausius-Duhem inequality, Heat transfer Heat transfer
conduction, 12, 17-21, 24-27, 153 general concepts, 1-4, 12, 23, 153, 154, 169-
179 radiation, 12-14, 153 see also Ideal heat bath Helmholtz free energy
balloons, 68 bars, 18, 24, 40, 50, 96, 145 liquid crystals, 124-125 mixtures, 113-
115 plates, 30, 58-59 rubber sheets, 81 see also Thermodynamic experiments
Hypothesis of local thermodynamic equilibrium, 26, 160, 165 Hysteresis, 47-48
Ideal heat baths, 3-4, 13-14, 172 see also Heat transfer Kelvin-Planck's second
law, 172 Latent heat, 49, 158 Laws of thermodynamics zero'th, 179 first, 1-3,
168 second, see Carathodory's second law, Clausius' second law, Kelvin-
Planck's second law, Serriu's second law third, 179 Loading devices
conservative, 2, 38, 69, 127, 128, 140 dead loads, 37-48, 59-62 dissipative, 2
fluid pressures, 69-77, 111-122 hard, 50-55 passive, 2 Martensite, 57 Martensitic
transformations, 57-62, 84 Material symmetry, 30, 79-80, 124-125 Maxwell line,
53, 55, 72 Metastable configurations, 46-48, 54-55, 60-62, 75-76 Mixtures phase
mixtures, 61, 145 theory of fluid-solid mixtures, 109-122 Newton's law of
cooling, 13 Nonequilibrium constitutive theory heat transfer in rigid bars, 17 20
thermoelastic bars, 24 26 Objectivity, 25, 124 Orientation of liquid crystals, 123-
130 Poincard's inequality, 133 Point of convexity, 16 Power, 1-2, 23, 38, 144,
151 Principle of local states, 26, 160 see also Hypothesis of local
thermodynamic equilibrium Processes cyclic, 156, 166-167 general 1, 147-148
irreversible, 152, 154 quasi-static, 5 reversible, 4, 5, 20-21, 26, 149-155 static,
149 superprocesses, 151, 156 Rankine-Hugoniot curve, 97 RankinHugoniot
equation, 97 Rayleigh curve, 97 Rayleigh quotient, 133 Reference
configurations, 21, 29, 67, 79, 138 Rubber plateau, 162, 164 Index 189 Second
derivative tests, 15, 40, 52, 60, 70-71, 73, 85-89, 105-106, 117, 134 Serrin's
second law, 176 Specific heat, 31-33, 120, 154-155 Spinoidal regimes, 47, 143
States, 1, 158-166 Stefan-Boltzmann radiation law, 13 Strain and stretch, 22, 30,
67-68, 79, 139 Strain energy 32, 79, 100, 120, 125, 139 Stress, 23, 30, 80 Stress
relaxation, 163 Strong anchoring, 129 Surface energies, 96, 99, 100, 101
Temperature 3, 19, 27, 146-147, 169, 179-180 Thermal expansion, 31-32, 34,
58, 120 Thermodynamic experiments, 31-34, 118-122 Thermodynamic systems,
1, 144 Time reversals, 150-154 Treloar instability, 83-84 Twins and twinning,
57, 61 Variations, 6-9, 14-15, 38-40, 51-53, 112-114, 132-134, 147 Viscoelastic
effects, 26, 161-167 Waves acoustic wave speed, 97 fast shock waves, 97 jump
conditions, 94-98 referential wave speed, 93 slow shock waves, 96 stress waves,
98

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Applied

Mathematical Sciences Volume 131 Editors J.E. Marsden L. Sirovich

Applied Mathematical Sciences J.L. Ericksen 1. John: Partial Differential

Preface Although I have never been actively engaged in research on

x Preface So, almost everything to be discussed is, to some degree, controversial.

xii Contents 4.3 Exercises ............................ 65 Balloon Problems 67 5.1

2 1. Generalities 1.2 Temperature and Entropy 3 heat. However, there is some

4 1. Generalities Such determinations of entropy involve an assumption which is

8 1. Generalities necessary and sufficient that in all possible variations of the

22 2. Constitutive Theory of Heat Transfer for Bars and Plates forces, at a

28 2. Constitutive Theory of Heat Transfer for Bars and Plates Sometimes

32 2. Constitutive Theory of Heat Transfer for Bars and Plates 2.5

34 2. Constitutive Theory of Heat Transfer for Bars and Plates Intuitively, it is

Equilibrium Theory of Bars 3.1 Equilibrium of Bars Subjected to Dead Loads In

40 3. Equilibrium Theory of Bars That is, the definition of thermodynamic

42 3. Equilibrium Theory of Bars 3.1 Equilibrium of Bars Subjected to Dead

46 3. 3.1 Equilibrium of Bars Subjected to Dead Loads 47 Equilibrium Theory

48 3. Equilibrium Theory of Bars FIGURE 3.9. Hysteresis loop encountered

50 3. Equilibrium Theory of Bars 3.2 Equilibrium Theory of Bars in Hard

56 3. Equilibrium Theory of Bars 3.3 Exercises 3.1. Consider the constitutive

58 4. Equilibrium Theory of Plates [,// e > e c 0<0c % 70 FIGURE 4.1. Sketch

60 4. Equilibrium Theory of Plates could be discontinuous but, for the same

62 4. Equilibrium Theory of Plates Later, various workers became interested in

64 4. Equilibrium Theory of Plates ' .......... ; ................. (>o) o FIGURE 4.4.

66 4. Equilibrium Theory of Plates Oc o(O) The temperature at which

68 5. Balloon Problems 5.1 Equilibrium of Spherical Balloons at Fixed Pressure

70 5. Balloon Problems or OF 1 (5.1.16) P = O(V/VR) VR' Now, given (5.1.11)

72 5. Balloon Problems ,',v aF k = , R =a(R) l FIGURE 5.2. Graph indicating a

76 5. Balloon Problems ration, where V1 gives way to V3, becoming the

80 6. Biaxial Stretch of Rubber Sheets 6.1 The Idealized Problem 81 and

82 6. Biaxial Stretch of Rubber Sheets 6.2 The Treloar Instability 83 FIGURE

86 6. Biaxial Stretch of Rubber Sheets 6.2 The Treloar Instability 87 FIGURE

88 6. Biaxial Stretch of Rubber Sheets is not so easy. It is simple to check this

90 6. Biaxial Stretch of Rubber Sheets 6.3 Exercises 91 For the experiment at

7 Moving Discontinuities 7.1 Shock Waves in Bars We have encountered

94 7. Moving Discontinuities function, we can fix t and consider the limit as we

96 7. Moving Discontinuities FIGURE 7.1. Sketch indicating the possibility of

98 7. Moving Discontinuities so = + 0+ [._l _ + (7.1.25) 2 Letting [A] -- 0 and

100 7. Moving Discontinuities 7.3 A Peeling Problem Somewhat similar to the

112 8. Mixture Theory Physically, we can reasonably think of this as a

118 8. Mixture Theory In part, we introduced this to cover stability problems

124 9. Equilibrium of LiquidCrystals and Rods commonly called the director.

126 9. Equilibrium of LiquidCrystals and Rods This is the so-called Oseen-

128 9. Equilibrium of LiquidCrystals and Rods and H are linearly related, by

130 9. Equilibrium of LiquidCrystals and Rods boundary conditions. In detail,

132 9. Equilibrium of LiquidCrystals and Rods 9.3 Measurement of Moduli 133

134 9. Equilibrium of LiquidCrystals and Rods Obviously � = 0 when = 0 so =

142 9. Equilibrium of LiquidCrystals and Rods an assertion you should check.

144 10. Reconsideration of Generalities fixed region of space, the time

146 10. Reconsideration of Generalities needs a modification similar to (10.1.2)

148 10. Reconsideration of Generalities discontinuities. In this, we did not

150 10. Reconsideration of Generalities subtle. From Chapter 1, reversible

152 10. Reconsideration of Generalities 10.3 Static and Reversible Processes

154 10. Reconsideration of Generalities O(x,t) = On(t) = q = 0. Then, (10.3.11)