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Citation: The Journal of Chemical Physics 47, 597 (1967); doi: 10.1063/1.1711937
View online: http://dx.doi.org/10.1063/1.1711937
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CRYSTAL STRrCTURE OF ALPHA-OXYGEN 597
This is a study of the thermodynamics of nonlinear materials with internal state variables whose temporal
evolution is governed by ordinary differential equations. After employing a method developed by Coleman
and Noll to find the general restrictions which the Clausius-Duhem inequality places on response functions,
we analyze various types of dynamical stability that can be exhibited by solutions of the internal evolution
equations. We also discuss integral dissipation inequalities, conditions under which temperatures can
be associated with internal states, and the forms taken by response functions when the material is a fluid.
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598 B. D. COLEMAN AND M. E. GURTIN
viscosity, but rather by assuming that the ideal-gas of this type by the second law, in the form of the
law pv=RO holds, with the translational (or "active-
mode") temperature, while accounting, in the consti-
Clausius-Duhem inequality. We then give conditions,
in terms of the thermodynamical functions, for dynami-
tutive equations governing the heat capacity, for the cal stability of equilibrium solutions of the evolution
time required for the transfer of molecular motion equations (1.1). After finding logical relations between
from the translational mode, to one, two, or several the various types of stability which can occur, we
internal modes. This is a classical example of a theory discuss special aspects of the theory, such as integral
of dissipation involving a finite number of internal dissipation inequalities, the assignment of tempera-
state variables; the internal variables being the amounts tures to internal states, and the requirements of in-
of energy associated with the various modes of molec- variance. We conclude our study by illustrating the
ular motion. At elevated temperatures the ideal-gas general theory with its simplest nontrivial special case:
law may fail due to chemical dissociation or ionization; ideal gases with a single internal mode of molecular
the finite rates of the reactions of decomposition and motion.
reassociation can then also give rise to pressure-volume
relaxation phenomena. 12 2. THERMODYNAMIC PROCESSES
Recent experience in high-polymer physics shows We consider a body CB with material points X and
that the mechanical behavior of many materials, in- assume that the mechanical forces acting on CB can
cluding polymer melts and solutions, is more easily always be resolved into a body force field and a sym-
described within the general theory of materials with metric stress field. In particular, body couples, couple
fading memory than by theories of the viscous-stress stresses, and multipolar interactions of higher order
type, which do not account at all for gradual stress are assumed absent. We also assume there is no dif-
relaxation, or by theories which rest on a finite number fusion of mass in CB, but CB may deform and conduct
of internal state variables and which, therefore, give heat. Thus, a thermodynamic process for CB is described
rise to discrete relaxation spectra when linearized. by nine functions, of X and the time t, whose values
Using an approach to the thermodynamics of con- have the following physical interpretations:
tinua proposed by Coleman and Noll,1a Coleman and
Mizel14 have found the restrictions the second law (1) The spatial position X= 2C(X, t) in the motion 2C.
places on a class of theories of the viscous-stress type. (2) The symmetric Cauchy stress tensor T=T(X, t).
Later, Coleman15 developed a general theory of the (3) The specific body Jorce b= b(X, t) per unit mass
thermodynamics of materials with fading memory. Here (exerted on CB at X by the external world, i.e., by other
we discuss phenomenological theories of dissipation bodies which do not intersect CB).
which rest upon evolution equations for internal state (4) The specific internal energy E=E(X, t) per unit
variables; we attempt to unify such theories by using mass.
the methods developed in Refs. 13 and 14 together (5) The heatflux vector q=q(X, t).
with techniques from the stability theory of nonlinear (6) The heat supply r=r(X, t) per unit mass and
differential equations. We consider materials for which unit time (absorbed by CB at X and furnished by
the basic local mechanical and thermal variables, such radiation from the external world).
as the stress tensor T, the heat flux vector q, the (7) The specific entropy 7]=7](X, t) per unit mass.
specific Helmholtz free energy 1/;, and the specific en- (8) The absolute temperature O=O(X, t) >0.
tropy 7], are determined through constitutive equations (9) The internal state vector 0:= o:(X, t) = (aI, a2, "',
when the following "state variables" are known: The aN); the numbers a,=a,(X, t) are the internal state
temperature 0, the deformation gradient F (or the variables ,16
"strain"), the temperature gradient gradO, and a set Such a set of nine functions, defined for all X in CB
of N internal or "hidden" state variables (aI, "', aN)' and all t, is called here a thermodynamic process in
We allow the rate of change of each of the ai to be CB if and only if it is compatible with the law of balance
governed by a (generally nonlinear) function Ji of 0, oj linear momentum and the law of balance oj energy.
F, gradO, and the complete internal state (aI, "., aN) : Under sufficient smoothness assumptions, the familiar
ix, =Ji(O, F, gradO, aI, ... , aN), i= 1, .. , N. (1.1) integral forms of these laws are equivalent to the field
equations
We first seek the general restrictions placed on theories px-divT=pb (2.1)
12 See, for example, the discussion of M. J. Lighthill, J. Fluid
and
Mech. 2, 1 (1957). Apparently, the first paper expressing this pe-TL+divq=pr. (2.2)
idea is that of A. Einstein, Sitzber. Akad. Wiss. Berlin Math.
Phys. Kl. 380 (1920). Here p is the mass density, L= grad! is the velocity
13 B. D. Coleman and W. Noll, Arch. Rational Mech. Analysis
13, 167 (1963). 16 Our present pair (F, .. ) forms a vector which Truesdell and
14 B. D. Coleman and V. J. Mizel, J. Chern. Phys. 40, 1116 Toupin,'7 pp. 615-647, call the thermodynamic substate.
(1964). 17 C. Truesdell and R. A. Toupin, "The Classical Field Theo-
lliB. D. Coleman, Arch. Rational Mech. Analysis 17, 1, 230 ries," in Encyclopedia of Physics, S. Fhigge, Ed. (Springer-Verlag,
(1964). Berlin, 1960), Vol. 3, Pt. 1.
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THE R MOD Y N A M I C S WIT H I N T ERN A L S TAT E VAR I ABL E S 599
gradient, and TL is the inner product of T and L; off the following implications of the Clausius-Duhem
i.e., TL=Tr TLT with LT the transpose of L. Since inequality:
grad and div are the gradient and divergence with
respect to x keeping t fixed, these operators refer to
7j~0 whenever F=O, i=O, and g=O, (3.4)
spatial derivatives. A superposed dot denotes the ma- i~O whenever F=O, 7j=0, and g=O. (3.5)
terial time derivative, i.e., the derivative with respect
to t computed keeping X fixed. The specific free energy I/; (also called the "Helm-
To specify a thermodynamic process it suffices to holtz free energy per unit mass") is defined by
prescribe the seven functions ~, T, , q, 7], 0, and a. (3.6)
The remaining functions band r are then determined Since
by (2.1) and (2.2).
In continuum physics one usually identifies each
material point X with its position X in a fixed reference (3.3) can be written
configuration ffi and writes x = X (X, t). The gradient 0"1= -~-1]O+SF_(p8)-lq.g, (3.8)
F of 2C(X, t) with respect to X,
and hence (3.2) yields also
F=F(X, t) = GRAD2C(X, t), (2.3)
~~O whenever F=O, 0=0, and g=O. (3.9)
is called the deformation gradient at X (or at X)
relative to the configuration ffi. We consistently use 4. CONSTITUTIVE ASSUMPTIONS
the notation GRAD for the gradient in ffi, i.e., the
gradient with respect to X. For a scalar field over (lS, In the present theory the material at the point ~X is
such as 0, an elementary chain rule yields characterized by five response functions, if;, ii, S, q,
and f, which give 1/;, 'T}, S, q, and Ii at X when F, 0, g,
GRADO=FT gradO. (2.4) and a are known at X:
Since gradO occurs frequently in thermodynamics it is 1/;=if;(F, 0, g, a), ( 4.1)
convenient to have a single symbol for this vector.
We use the abbreviation 1]=fJ(F, 0, g, a), (4.2)
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600 B. D. COLEMAN AND M. E. GURTIN
proach of Coleman and MizeI14 20 who regarded the solution a= a(X, t) of (4.S) for all t in some interval
Clausius-Duhen inequality as included among the laws [to, to+rJ with a(X, to) = ao(X). Then, using the con-
of physics which can cause a separation of effects, stitutive equations (4.1) -( 4.S) we can compute 1/;, 'T/,
i.e., which can be used to show that certain response f=1/;+e'l], S, and q at each X for all t in [to, to+r]'
functions must be independent of certain variables. Thus to each sufficiently smooth choice of ao, 2C, and e
In fact, we shall show that the derivatives of f, ~, there corresponds a unique admissible thermodynamic
and S with respect to g must be zero. 21 process in ill for some time interval [to, to+r].
Now, let (Fo, eo, go, ao) be an arbitrary point in
5. CONSEQUENCES OF THE SECOND LAW the domain of the response functions f, n, S, q, and f
Within our present framework the second law of for that material point X' of ill which occupies the
thermodynamics is given a precise mathematical mean- place X' in CR. Choosing arbitrarily a time to, a tensor A,
ing by the following postulate of positive production of a vector a, and a scalar a, we consider the motion 2C,
entropy22: and the time-dependent temperature distribution e de-
Every admissible thermodynamic process in ill must fined by
obey the inequality (3.2) at each time t and for all ma- 2C(X, t) = X'+[Fo+(t-to) AJ[X-X'J,
terial points X in ill.
We now seek the restrictions this postulate places e(X, t) =eo+(t-to)a+[go+(t-to)a}Fo[X-X'J,
on the response functions in our basic constitutive (S.7)
equations (4.1)-(4.5).
It follows from (4.1) that in each admissible process for all X in CR and all f?:. to sufficiently close to to. It
follows from the observation made in the previous
f= (OFf) .F+(oef)()+(ogf) .g+(oaf) a, (5.1) paragraph that the fields shown in (S.7) and the
where initial condition a(X, to) = ao determine an admissible
thermodynamic process in ill for t in some time interval
oe.j;(F, e, g, a) = (oloe).j;(F, e, g, a); (5.2) [to, to+r]. Furthermore, this process has the following
the components of ogf and OFf, relative to an ortho- properties:
normal basis el, e2, e3, are given by F(X', to) =Fo, e(X', to) =eo,
[Ogf(F, e, g, a)];= (oldg.)f(F, e, g, a), g(X', to) = go, a(X', to) = ao, (S.8)
i=1,2,3, and
[oFf(F, e, g, a) ];j= (dloFij)f(F, e, g, a), F(X', to) =A, ()(X', to) =a, g(X ' , to) =a. (5.9)
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THE R 1\1 0 D Y N A 1\1 I C S WIT H I N T ERN A L S TAT E VAR I AB L E S 601
have the following four consequences of our postulate holding for nonzero 0.. Such a resolution is valid,
of positive entropy production22a : however, when the following conditions are met: that
f(F, (J, g, a) be independent of g and q(F, (J, g, a)
(i) The response functions -i-, n, and Sare independent
be independent of a. These conditions do not follow
of g; i.e.,1/;, T/, and S are given by functions of F, e, and
from our general assumptions. Yet, the first condition
a alone,
does often follow from special assumptions of linearity
T/=n(F,fl, a), and material symmetry; therefore, it is worth noting
that
(5.15)
agf(F, (J, g, a) =0 => u(F, (J, g, a) ~O
(ii) -i- determines nthrough the entropy relation (5.12) ;
i.e., for all F, (J, g, and a. (5.25)
(5.16)
It is observed that the role played by u in our present
(iii) -i- determines S through the stress relation (5.11); theory is nearly identical to that played by the quantity
i.e., which Coleman in his articles on materials with fading
(5.17) memoryI5 also denotes by u and calls the internal dis-
sipation. For example, our Eqs. (5.21) and (5.15)-
(iv) -i-, f, and q obey the general dissipation inequality (5.17) here yield the equation
(5.14) .
Jj;=S.F-T/8-(Ju, (5.26)
Conversely, using (5.6) it is easily verified that when
the conditions (i)-(iv) hold every admissible process which has the same form as Eq. (8.1) on p. 22 of
in ffi obeys (3.2). Ref. 15. However, in our present theory, if agf is not
It follows from (2.7) and (5.17) that the symmetric identically zero, u may be negative for certain values
Cauchy stress tensor T is given by the equation of g, albeit (5.22) tells us that u~O whenever g=O.
Using (3.6) we can write (5.26) in the form
(5.18)
(5.27)
and hence is a function of F, e, and a. therefore,
The general dissipation inequality (5.14) implies that
when g=O the internal dissipation inequality, u= -e/(J whenever F=O and ~=O, (5.28)
and
aa$(F, e, a) f(F, e, 0, a) ~O, (5.19)
u=~ whenever F=O and e=O. (5.29)
holds, and when aa1/;f=O the heat-conduction inequality,
Since (2.8) and (5.27) imply
q(F, fl, g, a) g~O, (5.20)
u=~-e-l(r-p-l divq) , (5.30)
holds.
If we define the internal dissipation u by
we also have
u=~ whenever pr-divq =0. (5.31)
u=u(F, e, g, a)
= -e-1aa-i-(F, e, a) f(F, fl, g, a), (5.21) Thus, we can assert that in general u measures the
rate ~ at which the entropy of a material point would
we can write the internal-dissipation inequality (5.19; change if the total rate pr-divq of addition of heat were
in the form set equal to zero. In particular, u=~ whenet'er the strain
u(F, e, 0, a) ~O. (5.22) and energy are held constant momentarily.
Further, we may conclude from (4.5), (5.1), and (5.13) 6. STABILITY OF EQUILmRIUM STATES
that
Throughout this section we focus our attention on one
u= -e-1Jj; whenever F=O and 8=0, (5.23) arbitrary material point X in ffi. A triplet (F*, (J*, a*)
and this result when combined with (3.8) yields with
f(F*, (J*, 0, a*) =0 (6.1)
U='Y whenever F=O, 8=0, and g=O. (5.24)
is called an equilibrium state for the material at X.
One cannot generally resolve the inequality 'Y ~ 0 into The domain of attraction at constant strain and tem-
an internal dissipation inequality aa-i- o.~O holding for perature of an equilibrium state (F*, (J*, a*) is the
nonzero g and a heat-conduction inequality qg~O set D(F*, e*, a*) of all ao such that the solution
22. Note added in proof: We have recently seen a report by K. C. a= aCt) of the initial value problem,
Valanis [Iowa State University Bulletin No. 52J giving a theorem
analogous to this. See also the article by E. T. Onat which will a=f(F*, 8*, 0, a) ( 6.2)
appear in the Proceedings of the JUT AM Symposium on Irre-
versible Aspects of Continuum Mechanics, Vienna, June 1966 (to with
be published). . a(O) = It'Q, ( 6.3)
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602 B. D. COLEMAN AND M. E. GURTIN
exists for all t~O and tends to a*, Donder's form of the equation of chemical equilibrium
for that reaction. 24 .25
a(t)-a* as l_oo. (6.4)
We say that an equilibrium state (F*, 0*, a*) is
An equilibrium state (F*, 0*, a*) is said to be (locally) Lyapunov stable at constant strain and temperature if for
asymptotically stable at constant strain and temperature each e> 0 there exists a 5,> 0 such that every solution
if D(F*, 0*, a*) contains a neighborhood of a*, i.e., aCt) of the differential equation (6.2) with
if there exists a r>O such that every internal state I a(O) - a* I <5, (6.11)
vector ao with I ao- a* I <r is in D(F*, 0*, a*).
Let (F*, 0*, a*) be an equilibrium state for the has the property that
material at X, and let ao be in D(F*, 0*, a*). It follows I aCt) - a* I <e ( 6.12)
from the argument containing Eqs. (5.7) that there for all t~O.
exists at least one admissible thermodynamic process Roughly speaking, (F*, 0*, a*) is Lyapunov stable
with the property that at X at constant strain and temperature if holding F and 0
a(O) = ao, while for all t~O, F(t) =F*, fixed for all t and initially setting the internal state
vector a sufficiently near to a* guarantees that a will
OCt) =0*, and get) =0. (6.5) remain near to a* for all t.
It follows from (3.9) that for this process I{;(t) ~I{;(O), Since it follows from (5.19) that for all a
or, by (5.15h, aa~(F*, 0*, a) f(F*, 0*, 0, a) ~O, ( 6.13)
~(F*, 0*, aCt) )~~(F*, 0*, ao). (6.6) ~(F*, 0*, a), as a function of a, can serve as a Lyapunov
function 26 for the equation (6.2), and familiar results
But, since ao is assumed to be in D(F*, 0*, a*), it
follows from (6.4) and the continuity of ~ that in the theory of ordinary differential equations27 yield
the following theorem: Let (F*, 0*, a*) be an equilibrium
lim~(F*, 0*, a( t) ) =~(F*, 0*, a*). (6.7) state and suppose that, in some neighborhood of a*, the
1-+00
following strengthened form of (6.9) holds:
Combining (6.6) and (6.7) we obtain ~(F*, 0*, a) >~(F*, 0*, a*) if a~ a*. (6.14)
~(F*, 0*, a*) ~~(F*, 0*, ao). (6.8) Then (F*, 0*, a*) is Lyapunov stable at constant strain
In words: If the internal state vector a is in the domain and temperature.
of attraction of the equilibrium state (F*, 0*, a*) at If
constant strain and temperature, then the free energy 'Y>O whenever F=O, 8=0, g=O, but ci~O, (6.15)
corresponding to (F*, 0*, a) cannot be less than that
corresponding to (F*, 0*, a*).
then we say that the material under consideration
The following theorem follows at once from (6.8) is strictly dissipative. It is not difficult to show that
(4.5), (5.21), and (5.24) imply the following proposi-
and the definition of asymptotic stability: If (F*, 0*, a*)
is an equilibrium state that is asymptotically stable at
tion: A material is strictly dissipative if and only if the
internal dissipation inequality (5.19) is strict in the sense
constant strain and temperature, then
that
~(F*, 0*, a) ~~(F*, 0*, a*) (6.9) aa~(F*, 0*, a) f(F*, 0*, 0, a) <0 (6.16)
for aU internal state vectors a in some neighborhood of a*, for every triplet (F*, 0*, a) that is not an equilibrium
and, consequently, state.
Suppose that (F*, 0*, a*) is an equilibrium state
aa~(F*, 0*, a) la~a.=O. (6.10) and that (6.16) holds for all a~ a* in some neighbor-
The equation (6.10) may be called the equation of hood m: (a*) of a*; if (F*, 0*, a*) is asymptotically
internal equilibrium. In deriving this equation we have, stable at constant strain and temperature then the
of course, assumed that the variables aI, , aN have argument which gave us (6.8) also gives us the stronger
been chosen so as to be free from constraints of the 24 Th. De Donder, Bull. Classe Sci. Acad. Roy. Belg. 5, 7, 197,
type h( a) =0. Thus, when changes in the internal
state are due to chemical reactions, a.
is not a con-
centration but rather the degree of advancement of the
205 (1922).
25 See, for example, 1. Prigogine and R. Defay, Chemical Ther-
modynamics, Translated by D. H. Everett (Longmans Green and
Co., Ltd., London, 1954), Chaps. 1-4, particularly Eq. (3.29)
ith reaction, in the sense in which the term is used by on p. 40 and Eq. (4.29) on p. 52.
De Donder.23 In this case -aa,I{; is the affinity of the 26 J. Wei, J. Chern. Phys. 36, 1578 (1962), has pointed out that
thermodynamic quantities, such as the free energy, can yield
ith reaction, and the relation aa,I{;=O is just De Lyapunov functions for investigations of stability properties of
chemical reactions.
23 Th. De Donder, Le~ons de Thermodynamique et de Chimie 27 See, for example, P. Hartman, Ordinary Differential Equations
Physique (F. H. van den Dungen and G. van Lerberghe, (John Wiley & Sons, Inc., New York, 1964), pp. 37-40, particu-
Paris, 1920), p. 117. larly Theorem 8.1.
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THERMODYNAMICS WITH INTERNAL STATE VARIABLES 603
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604 n. D. COLEMAN AND M. E. GURTIN
c=ae(F,8, a), (7.1) It follows from (7.11)s and (7.9)3.4 that the general
dissipation inequality (5.14) may be written in the form
where is the response function for the internal energy:
po(F, 'f/, a)aaE(F, 'f/, a) f(F, 'f/, g, a)
(F,8, a) =f(F, 8, a) +8~(F, 8, a). (7.2)
+q(F, 'f/, g, a) g::;O, (7.14)
It follows from the entropy relation (5.16) that
and, in particular,
(7.3)
q=O::::}oaE(F, 'f/, ex)l(F, 'f/, g, a)::;O (7.15)
Henceforth we assume that c is >0 for all (F, 8, a).
Since 8 is >0, this implies that ~(F, fJ, a) is smoothly which is useful for materials which do not conduct
invertible in 8 for each choice of F and a, and we may heat. Of course we also have the following counterpart
rewrite our basic constitutive equations (4.1)-(4.5) in of (5.19) :
the forms oaE(F, 'f/, a) f(F, 'f/, 0, a) ::;0. (7.16)
e= E(F, 'f/, a), (7.4)
According to the definition laid down in Sec. 6, a
8= O(F, 'f/, a), (7.5) triplet (F*, 8*, a*) is called an equilibrium state of
S=S(F, 'f/, a), (7.6) the material at X if and only if it obeys (6.1) at X.
It follows, however, from (7.9)4 that this definition
q=q(F, 'f/, g, a), (7.7) is equivalent to asserting that the triplet (F*, 'f/*, a*)
a=f(F, 'f/, g, a). (7.8) with
'f/*=~(F*,8*, a*), 8*=O(F*, 'f/*, a*), (7.17)
ThefunctionO(F,., a) in (7.5) is just the inverse of
the functi,sm ~(F, ., a) in (5.15)2; the functions E, characterizes an equilibrium state if and only if
S, q, and f are given by
f(F*, 'f/*, 0, a*) =0. (7.18)
E(F, 'f/, a) = (F, O(F, 'f/, a), a}
When (7.18) holds we define the domain of attraction of
=f(F, O(F, 'f/, a), a}+'f/O(F, 'f/, a), (F*, 'f/*, a*) at constant strain and entropy to be the
set D(F*, 'f/*, a*) of internal state vectors ao such that
S(F, 'f/, a) = S(F, Ii(F, 'f/, a), },
the solution a= aCt) of the initial value problem
q(F, 'f/, a) =q(F, O(F, 'f/, a), a),
a=f(F*, 'f/*, 0, a), a(O) = ao, (7.19)
f(F, 'f/, g, a) =f(F, O(F, 'f/, ), g, ex}. (7.9)
exists for all t?,O and approaches a* as t-H/J. We say
It follows from (7.9)1 and familiar chain rules that that (F*, 'f/*, a*) is asymptotically stable at constant
aqE= (aef) (aqO) +o+'f/a~O, strain and entropy if D(F*, 'f/*, a*) contains a neighbor-
hood of a*.
aFE=aFf+(aef) (aFO) +'f/aFO, Since it follows from (7.16) that E(F*, 'f/*, a(t)} is
aa E= (aef) (aaO) +aaf+'f/aaO. (7.10) a decreasing function of t along all solutions of (7.19),
the argument which gave us (6.8) here tells us that
Hence, the entropy relation (5.16) implies that for each a in D(F*, 'f/*, a*)
a~E(F, 'f/, ) = O(F, 'f/, ), E(F*, 'f/*, a)?, E(F*, 'f/*, a*). (7.20)
aFE(F, 'f/, a) =aFf(F, 8, a),
In particular, if (F*, 'f/*, a*) characterizes an equilib-
a"E(F, 'f/, a) =a",f(F, 0, a). (7.11) rium state that is asymptotically stable at constant strain
and entropy, then (7.20) holds for all a in some neighbor-
Of cours~ the number 8 in (7.11h,s is just the tem- hood of a*, and
perature 8(F, 'f/, a) corresponding to F, 'f/, and a.
Equation (7.11h is the expected temperature relation (7.21)
8=avE(F, 'f/, a), (7.12) It of course follows from (7.11)s that (7.21) and
(6.10) are equivalent, i.e., are just different forms of
while (7.11h may be combined with (5.17) to obtain the same equation for a*. This does not, however,
imply that the concepts of stability at constant strain
32 Since both F and IX are held fixed in computing the derivative
m (7.1), the number c may also be called the instantaneous specific
and temperature and stability at constant strain and
!zeat at constant strain (and per unit mass). entropy are logically equivalent: The equation (7.21)
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THE R MOD Y N A M I C S WIT H I N T ERN A L S TAT E V A R I A B L E S 605
or (6.10) is a necessary, but not a sufficient, condition It follows from the first two of these relations that
for these two types of stability. (7.12) and (7.13) can be written in the forms
We say that a triplet (F*, T/*, a*) obeying (7.18)
8=[a,ii(F, , a)]-I, (8.8)
characterizes a state that is Lyapunov stable at constant
strain and entropy if for each >O there exists a 0,>0 s= -aFii(F, , a)/a,ii(F, , a) = -8a Fii(F, , a). (8.9)
such that every solution a= aCt) of (7.19h having
[ a(O) - a* I <li, also has I aCt) - a* I < for all t';?O. From (8.7)3, (8.9), and (7.11h we obtain
The following proposition is an immediate consequence a"ij(F, , a) = -t11a",E(F, T/, a)
of (7.16) and the theory27 of Lyapunov functions: If
(F*, T/*, a*) obeys (7.18) and has the property that for = -t11a",-f(F, 8, a), ( 8.10)
all a in some neighborhood of a* and hence (7.16) becomes
E(F*,T/*, aE(F*,T/*, a*) whenever arfa*, (7.22) a",ii(F, , a)f(F, , 0, a)';?O. (8.11 )
then (F*, T/*, a*) characterizes a state that is Lyapunov
It follows from (8.2)4 that a triplet (F*, T/*, a*)
stable at constant strain and entropy.
characterizes an equilibrium state, i.e., obeys (7.18)
It follows from (7.11)3, (7.9)4, and the proposition
if and only if the triplet (F*, *, a*) with
containing (6.16) that a material is strictly dissipative
if and only if *=i:(F*, T/*, a*), T/*=ij(F*, *, a*), (8.12)
a"E(F*, T/*, a) 'f(F*, T/*, 0, a) <0 (7.23) obeys the relation
whenever (F*, T/*, a) does not characterize an equilibrium f(F*, *, 0, a*) =0. (8.13)
state.
The last proposition of this section follows from When such is the case, the domain of attraction of
arguments completely analogous to arguments used (F*, *, a*) at constant strain and energy is the set
in Sec. 6: If (F*, T/*, a*) obeys (7.18) and if (7.23) D(F*, *, a*) of all internal-state vectors ao with
holds for all arf a* in some neighborhood of a*, then the property that the solution a= aCt) of the initial
the inequality (7.22) is a necessary and sufficient con- value problem
dition for the state characterized by (F*, T/*, a*) to be n=f(F*, *, 0, a), ( 8.14)
aCO) = ao,
asymptotically stable at constant strain and entropy.
exists for all t';?O and converges to a* as t-HJJ. We
8. INTERNAL ENERGY AS AN INDEPENDENT say (F*, *, a*) is asymptotically stable at constant
VARIABLE strain and energy if D(F*, *, a*) contains a neighbor-
The temperature relation (7.12) and our assumption hood of a*. If for each >O there exists a 0,>0 such that
that 8 is strictly positive imply that the function i: in I a(O) - a* I <li, implies I aCt) - a* I < for all t';?O,
(7.4) is smoothly invertible in its second variable T/. then we say that (F*, t*, a*) is Lyapunov stable at
Hence there exists a function ij such that constant strain and energy.
The next two theorems follow from (8.11).
T/=ij(F, , a), (8.1) If a is in the domain of attraction of (F*, *, a*)
and putting then
O(F, , a) = (j(F, ij(F, , a), a), ij(F*, *, a)::; ij(F*, t*, a*), (8.15)
S(F, , a) =S(F, ii(F, , a), a), Hence, if (F*, *, a*) is asymptotically stable at con-
q(F, , a) =q(F, ii(F, , a), a), stant strain and energy, (8.15) must hold throughout
some neighborhood of a* and
f(F, , a) =f(F, ii(F, , a), a), (8.2)
(8.16)
we can write the constitutive equations (7.5)-(7.8)
as follows: [It follows from (8.10) that the equations (6.10),
O=O(F, , a), (8.3) (7.21), and (8.16), giving necessary conditions for
S= S(F, , a), (8.4) three distinct types of stability that an equilibrium
state may manifest, are equivalent.]
q=q(F, , g, a), (8.5) If (F*, *, a*) obeys (8.13) and if for all a in some
n=f(F, , g, a). (8.6) neighborhood of a*
The equations (7.4) and (8.1) imply that ii(F*, *, a) <ii(F*, *, a*) whenever arf a*, (8.17)
a,ij= (a~E)-I,
then (F*, *, a) is Lyapunov stable at constant strain
aFij+ (a,ii) (aFE) =0, and energy.
(a,ij) (a",E) +a",ij=o. (8.7) We may conclude from (8.10), (8.2)4, and the re-
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606 B. D. COLEMAN AND M. E. CtJRTIN
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THE R MOD Y N A M I C S WIT H I N T ERN A L S TAT E V A R I A B L E S 607
constant strain and entropy if and only if it is asymp- be a solution of (6.2), and, by our stability postulate,
totically stable at constant strain and energy. we would have a(t)~a*, which is impossible since
aCt) =const~ a*. Conclusion (ii) is an immediate con-
10. INTEGRAL DISSIPATION INEQUALITIES sequence of (9.7), (9.13), and the sentence following
In a body undergoing an arbitrary thermodynamic (6.8) .
process, we may consider, at a given material point, The stability postulate is not a consequence of the
the following general dissipation integrals,33 defined for Clausius-Duhem inequality but is rather an inde-
any two times to<h: pendent hypothesis expected to hold for some materials
but not all. Under this new postulate a single-valued
function a* relates (F*, 0*) to a*, as in (6.17), and
(10.1)
equilibrium response functions ~*, ~*, etc., may be
defined as in (6.18). Of course (6.20)-(6.27) hold,
and the remark following (6.8) here yields
(10.2)
~(F, 0, a) ~~*(F, 0) (10.5)
for all a.
t1
X(tl, to) =
1 to
tr1 {SF-E-(pO)-lqgldt. ( 10.3) Consider now a material point X and a time to,
and suppose that at X the triplet (F, 0, g) has the
following sort of time dependence:
It follows immediately from the law (3.2) of positive
production of entropy and the expressions (3.3) and (F (t), 0(t), g (t) ) = arbitrary values for t < to,
(3.8) for'Y that
= (Fo, 00, 0) for t~to. (10.6)
d (tl, to) ~1J-(tl) -1J-(to) ,
At the time to, the internal state vector a will have a
~(tl, to) ~E(h) -E(to), value ao, determined, through the differential equation
(4.5), by the histories of F, 0, and g up to time to and
X(tl, to) ~'I/(to) -'l/(h). (lOA)
some initial data for a. Although we may not know
The theory we have been developing here can be the value of ao, we do know that for t>to, aCt) will
brought closer to the theory of materials with fading be the solution of (6.2) corresponding to the initial
memory2-4,15 by adding assumptions about the sta- condition aCto) = ao. Since, by our present stability
bility of solutions of the differential equation governing hypothesis, all solutions of (6.2) must approach a* =
the evolution of the internal state vector a. For the a*(Fo, ( 0) we have
remainder of this section we assume the following
lima(t) = a*(Fo, ( 0 ), (10.7)
stability postulate: t_co
Corresponding to each pair (F*, 0*) there is an internal Therefore, it follows from the (tacitly assumed) con-
state vector a* which makes (F*, 0*, a*) an equilibrium tinuity of ~, ~, T, q, and the equations (6.18) and
state that is asymptotically stable in the large at constant (6.25), that at the point X
strain and temperature.
lim1J-(t) =lim~(Fo, 00 , a(t) )=~*(Fo, ( 0 ),
In other words, we assume that given (F*, 0*) there t-ro t-.m
exists at least one a* such that (F*, 0*, a*) obeys lim'l/(t) =lim71(Fo, 00, aCt) )=~*(Fo, ( 0),
(6.1) and also such that every solution of (6.2) obeys
(6.4).
limT(t) =limT(Fo, 00 , aCt) )=T*(Fo, ( 0 ),
This postulate has the following consequences. t-m t-co
(i) Corresponding to each pair (F*, 0*) there is exactly limq(t) =limq(Fo, 00 , 0, aCt) )=0. (10.8)
one equilibrium state (F*, 0*, a*). t-co t-co
(ii) At each equilibrium state (F*, 0*, a*), the in- When a history up to some time to is extended beyond
equalities (6.9), (7.20), and (8.15) hold for all a with to in the manner illustrated in (10.6), we call the result-
'1/* and E* given by (9.1) and (9.2). ing extended history the isothermal static continuation
To demonstrate Conclusion (i) we need merely note of the original history. Equation (10.8) shows, in
that if to a given pair (F*, 0*) there corresponded two effect, that in any isothermal static continuation of an
equilibrium states (F*, 0*, a*) and (F*, 0*, at), arbitrary history, the free energy, entropy, stress, and
both obeying (6.1) with a*~at, then a(t)=a t would heat flux all approach their equilibrium values as t
increases without limit. Moreover, the first of these limits
33 Our present X, d, and .g differ only in the terms containing q
is approached monotonically, for (3.9) here yields
from the functionals which Coleman (on pp. 27, 35, and 39 of
Ref. 15) calls "dissipation integrals." fCt) =:; 0, for all t> to. (10.9)
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608 B. D. COLEMAN AND M. E. GURTIN
The relations (10.5) and (10.8h tell us that the following implications holds for processes which start at
theorem on minimum free energy, originally proven for to from an equilibrium state of the type (10.10), but which
materials with memory,34 has the following form in are otherwise arbitrary:
the present theory, provided we assume that equilib-
rium solutions of (6.2) are stable in the large: Of all F(lt) =F(to), e(to) =e(tr)~t1(tl, to) '2 0,
histories ending with given values of F and 0, the constant F(tl) =F(to) , 1/(to) =1/(tl) =} ~(tl, to)'20,
history with g held fixed at zero and F and 0 held fixed
at the given values gives rise to the least free energy. F(tl) =F(to), f(t O) = f(tl) =}X(tl, to)'20. (10.20)
Thus, our new stability postulate gives the present We call a process isothermal at X if 8=0 at X,
theory many, but not all, the qualitative properties of isentropic if 1]==0 at X, and isoenergetic if f==O at X.
Coleman'sl5 theory of materials with memory. It is clear from (10.1)-(10.3), that the theorem just
Let us now return to the dissipation integrals defined proven has the following corollary yielding inequalities
in (10.1)-(10.3) and consider processes which start for integrals of the stress power in special cyclic
from an equilibrium state, i.e., processes for which we processes36 : Consider a process starting from an equilib-
have at X, rium state of the type (10.10) and for which the tempera-
F(to) =F*, O(to) =e*, ture gradient g is zero for to 5, ts. tl . If the process is
o:(to) = 0:*= a*(F*, 0*), ( 10.10) either isothermal or isentropic, then
tl
but for which F, 0, and g at X are given by arbitrary
functions F(t), O(t), g(t) for t>to. For each such
process, at X
Ft(I)=F(to)=}
I to
SFdt'20. (10.21)
Combining (10.13), (10.18), and (10.19) with the temperature (or the temperature of the active mode) and
inequalities (lOA), we obtain the following theorem to ei as the temperature of the ith mode. We may observe
on dissipation integralSl5 : that the "temperature of the ith mode" need not be
positive. In fact, as there is at this point no reason to
Under the stability postulate stated above each of the suppose that a".1/#7"'O, we must not rule out the pos-
34 Reference 15, Theorem 3, p. 26.
sibility of ei being infinite.
36 For the corresponding theorem for materials with fading
memory see Remarks 17, 24, and 32 on pp. 27,36, and 39 of 36 For materials with fading memory, analogous results are
Rl;f.1.5, ~iven in Theorem 4/ Remark 2.5, and Remark 3,3 of Ref. 15.
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THERMODYNAMICS WITH J~TERNAL STATE VARIABLES 609
;=1
~ ~O whenever i=O,
8;
g=O, and ~=O.
cpi*(F, &;*(F, 0) )=0 (11.17)
(11.11) for all 0>0. When this condition is fulfilled the func-
The inequality (11.11) appears to be in accord with tion CPi* is uniquely determined by the function &i*
intuitive prejudices about properties to be expected and hence by the function f on the right side of the
of temperatures associated with internal modes. constitutive equation (4.5). We call the value
Suppose now that the function '1/* defined in (11.3) (11.18)
has the special form
M of CPi* at an arbitrary pair (F, ai) the temperature of
'I/*(F, tA, aI, "', aM, ~) ='l/A(F, tA, ~) + L
1'=1
'l/i(F, ai). the ith mode corresponding to (F, ai). We continue
to refer to the number entering the constitutive equa-
(11.12) tions (5.15), (4.4), and (4.5) as the translational tem-
perature. As an immediate consequence of (11.17) we
Then 8=8A is given by a function 0* of (F, tA, ~),
have the following proposition: Each CPi shares with Oi
while each Oi is given by a function Oi* of only (F, ai) ;
for (11.4), (11.5), and (11.12) yield
the property of being equal to the translational temperature
oin states of stable equilibrium.
= [O'A'l/A(F, EA, ~)]-\
O=O*(F, EA, ~) (11.13) Unfortunately, the function CPi* is not, in general,
identical to the function (0",'1/*)-1: Although Oi=CPi=O
Oi=Oi*(F, a,) = [o",'l/i(F, ai) J-I. (11.14) at equilibrium, we can expect to have O'i~CPi away
from equilibrium, except, of course, when '1/* has the
Let us assume, in addition, that there exists a function
special form (11.12). As a matter of fact, if CPI* were
a* which assigns to each pair (F*, 0*) an (*, as in (6.17),
equal to [0"1'1/*]-\ then we could conclude from (11.18)
such that the triplet (F*, 0*, 0:*) constitutes an equi-
that 0"1'1/* must be independent of tA and 012,' " a.v,
librium state for the material point under considera-
and hence that
tion. As we saw in the conclusion (i) of the first theorem
of Sec. 10, this assumption is a consequence of the 'I/*(F, EA, aI, "', OIN) ='1/1 (F, Oil) +'l/2(F, EA, 012, " OIN).
stability hypothesis of Sec. 10. If we write (6.17) in
(11.19)
37 This result should be compared with Truesdell's theorem Thus we have the following result: A necessary condition
about the compatibility of total with partial caloric equations of
state for mixtures: C. Truesdell, Rend. Lined 22,33, 158 (1957), that
Theorem IV. (11.20)
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610 B. D. COLEMAN AND M. E. GURTIN
is that the function 7]* have the special form (11.19). tensor Q, the following identities in F, 0, a, and g:
A similar result holds for a2, a3, etc.
In view of the fact that temperatures of internal l/-(F,O, a) =l/-(QF, 0, a),
states are often regarded as definable only in terms of n(F,O, a)=n(QF,O, a),
statistical concepts, we think it worthwhile to make the
following observation. The results of this section sug- QT(F,O, a)QT=T(QF, 0, a),
gest that if we accept the general assumptions made Qq(F, 0, g, a) =q(QF, 0, Qg, a),
here and in Secs. 4 and 5, then the question of whether
we can associate a temperature Oi with a particular f(F, 0, g, a) =f(QF, 0, Qg, a). (12.3)
internal state variable ai becomes one that can be These identities can be used to derive the following
settled on purely phenomenological grounds, namely by reduced forms of our constitutive equations:
inspection of the caloric equation of state and the
equation governing the evolution of ai in a thermo- if;=if;t(C, O, 0:),
dynamic process. 7J=7]t(C,O, a),
12. OBJECTIVITY T=FTt(C,O, a)FT,
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THERMODYNAMICS WITH INTERNAL STATE VARIABLES 611
13. MATERIAL SYMMETRY, FLUIDS gases with internal molecular relaxation forms an im-
portant special case of our present theory, we give the
The symmetry group S of a material is the set of all reduced forms taken by our general constitutive equa-
nonsingular changes of local reference configuration tions when the material under consideration is a fluid.
that leave the response functions of the material un- We say that a material is a fluid if its symmetry
altered.39
If we assume that the internal state variables are
quantities unaffected by the choice of reference con-
a. group S is the group 'U of all unimodular tensors. The
property of being a fluid is intrinsic to the material
in the sense that S='U for one reference configuration
figuration, then in our present theory the symmetry only if S='U for all reference configurations. Assuming
group S may be identified with the group of all m- that the internal state variables a, obey the "scalar
vertible tensors H for which the identities transformation rule" (12.2) under changes of frame,
$(F, 8, a) =$(FH, 8, a), and using arguments now familiar in continuum
mechanics, one can easily show that for a fluid the
n(F, 8, a) =~(FH, 8, a), following representation formulas must hold for the re-
T(F,8, a) =T(FH, 8, a), sponse functions occurring in the identities (12.3) and
(13.1) :
q(F, 8, g, a) =q(FH, 8, g, a),
(13.3)
f(F, 8, g, a) =f(FH, 8, g, a), (13.1)
(13.4)
hold for all F, 8, a, and g. This group S depends on
the choice of reference configuration, but the sym- T=-pl, p=p(u,8, a), ( 13.5)
metry group corresponding to two different reference q=-Kg, K=R(u,8,g, a), ( 13.6)
configurations of the same material are conjugate and
hence isomorphic. A theorem of Gurtin and Williams40 ci=f(v, 0, g, a). (13.7)
tells us that the postulate of positive production of
entropy requires that S must be a subgroup of the uni- Here u = 1/p is the specific volume; g= (g. g) 1/2 is the
modular group; i.e., that each H in S must have magnitude of gradO; $, n, p, R, and the components
I detH 1=1. ji of f are all scalar-valued response functions; p
The similarity between the equations (13.1) and the and K are called, respectively, the pressure and the
identities used to define the symmetry group of an thermal conductivity. It follows from (13.3)-(13.5) that
elastic material with heat conduction is striking,41 and for fluids the entropy relation (5.16) and the stress
one can immediately apply here many results originally relation (5.17) become
obtained within the framework of the theory of elastic
TI=-a8~(V, 0, a),
materials. For example, using an argument given by
Coleman and Nollia one can easily show that if the (13.8)
inversion transformation -1 is in S then
When it is more convenient to take the specific entropy
q(F, 8, 0, a) =0 (13.2) of the fluid, rather than the temperature, as an inde-
for all F, 8, and a. Thus, even if (F, 8, a) is not an pendent variable, we have
equilibrium state, the presence of -1 in S implies =E(V, TI, a),
that the heat flux q vanishes when grad8 vanishes.
We do not discuss here the symmetry groups ap- O=O(u, TI, a) =a~E(U, TI, a),
propriate to the various types of solids. The interested
reader will have little difficulty in extending to our p=p(u, TI, a) = -avE(U, TI, a), (13.9)
present subject the known theory of symmetry in finite
and when the specific internal energy is the preferred
elastic deformations.42 However, since the theory of
independent variable
39 This is essentially a definition due to Noll3s who defined the
local isotropy group 9 of a material to be the set of density-pre- TI=71(u, , a),
serving changes of local reference configuration which leave the
response unaltered. It has recently been shown40 that our present 8= B( u, , a) = [a.71 ( u, , a)]-I,
S must reduce to Noll's g.
40 M. E. Gurtin and W. O. Williams, Arch. Rational Mech. p=p(v, , a) =oav71(v, , a). (13.10)
Analysis 23, 163 (1966).
41 See, for example, Ref. 13, Eq. (3.7). It is clear that for fluids all the remarks we made
42 For some pertinent results in that theory see the articles of
Smith and Rivlin43 and Coleman and Noll.44 about stability in Secs. 6-10, remain valid if the modi-
43 G. F. Smith and R. S. Rivlin, Trans. Am. Math. Soc. 88, fier "at constant strain" is replaced by "at constant
175 (1958). volume"; i.e., if the condition that F be constant is
4' B. D. Coleman and W. Noll, Arch. Rational Mech. Analysis
15, 87 (1964). replaced by the weaker condition that u be constant.
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612 R. D. COLEMAN AND M. E. GURTIX
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THE R MOD Y N A M I C S WIT H I K T E R K AL S TAT E V A R I "\ B L E S 613
we see that iiA must have the special form Let us now assume that for each a and v we can
find a 0 such that a=/(v, 0). It is then a direct conse-
1]A =R Inv+h(EA). (14.10) quence of the theorem following (11.16) that for each
Assuming that h is smoothly invertible, we can write fixed v the function Ov defined in (14.5) is the inverse
(14.10) in the form of the function I( v, .). Hence I( v, 0) must be inde-
pendent of v,
EA=WA(V exp( -1]A/R)
I( v, 0) = 1(0), ( 14.16)
=WA(V exp{[iiv(a) -1]J/R}) and
(14.17)
=~(v, 1], a) -a. (14.11)
with the function 1-1 the inverse of I.
It follows from (13.9h and (14.11) that Equations (14.3), (14.13), (14.15), and (14.16)
0= -R-1WA ' (v exp( -1]A/R)v exp( -1]A/R) (14.12) imply that the value E* of the specific internal energy
of the gas when it is in equilibrium with temperature
with the prime indicating the derivative; hence 0 is a 0* and specific volume v* is independent of v*; in fact,
function of only vexp( -1]A/R). Assuming that this
function is invertible, we may solve (14.12) for e* = fA (0*) +/(0*). (14.18)54
v exp( -1]A/R) in terms of 0 and write (14.11) in the In view of (14.16), we can write (14.14) in the form
form
( 14.13) a=k(v, 0)[/(0)-0'], (14.19)
where
Thus, the active-mode energy is here a function of the k(v, 0) >0, 1(00. (14.20)
translational temperature alone.
We now add the natural assumptions that a is ACKNOWLEDGMENTS
always positive and that the differential equation (14.6)
obeys the stability postulate discussed in Sec. 10. We thank J. Kestin, J. Meixner, and B. H. S. Rarity
These assumptions imply that (14.6) can be written for stimulating discussions about thermodynamical
in the form systems with internal degrees of freedom. This re-
( 14.14) search was supported in part by the U. S. Air Force
a=k(v, 0) (/(v, 0) -a),
Office of Scientific Research under Grant AF-AFOSR
with the functions k and I positive. Furthermore, the 728-66 and by the Office of Naval Research under
function I in (14.14) here plays the role of the equilib- Contract Nonr-51031.
rium response function a* in (6.17): For each pair 54 Since the equilibrium pressure p* is just R()* /v*, to prove
(v*, 0*) the vibrational energy 0'* given by .*
that is a function of ()* alone we could have used an argument
similar to that giving us (14.13). In this instance the proof would
( 14.15) proceed exactly as it does for an ideal gas without relaxation
a*=/(v*, 0*) effects, in which context the proof is spelled out in detail by R.
Courant and K. O. Friedrichs, Supersonic Flow and Shock Waves
makes (v*, 0*, 0'*) an equilibrium state. (Interscience Publishers, Inc., New York, 1948), pp. 8, 9.
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