6

On thermodynamic potentials in linear thermoelasticity
V.A. Lubarda
*
Department of Mechanical and Aerospace Engineering, University of California, San Diego, La Jolla, CA 92093-0411, USA
Received 13 March 2004; received in revised form 28 May 2004
Available online 13 August 2004
Abstract
The four thermodynamic potentials, the internal energy u u
ij
; s, the Helmholtz free energy f f
ij
; T, the
Gibbs energy g gr
ij
; T and the enthalpy h hr
ij
; s are derived, independently of each other, by using the Duh-
amelNeumann extension of Hookes law and an assumed linear dependence of the specic heat on temperature. A
systematic procedure is then presented to express all thermodynamic potentials in terms of four possible pairs of
independent state variables. This procedure circumvents a tedious transition from one potential to another, based on
the formal change of variables, and inversions of the stressstrain and entropytemperature relations. The general
results are applied to uniaxial loading paths under isothermal, adiabatic, constant stress, and constant strain conditions.
An interplay of adiabatic and isothermal elastic constants in the expressions for exchanged heat along certain ther-
modynamic paths is indicated.
2004 Elsevier Ltd. All rights reserved.
Keywords: Thermoelasticity; Thermodynamic potentials; Internal energy; Helmholtz free energy; Gibbs energy; Enthalpy; Entropy;
Specic heats
1. Introduction
The structure of the constitutive equations relating the stress, strain, entropy, and temperature in linear
thermoelasticity is well-known (e.g., Boley and Weiner, 1960; Sneddon, 1974). Most commonly, the deri-
vation of these equations proceeds by assuming a quadratic representation of the Helmholtz free energy in
terms of strain and temperature, with the coecients specied in accord with the observed isothermal
elastic behavior, the coecient of thermal expansion, and the specic heat. This yields (e.g., Kovalenko,
1969)
f
ij
; T
1
2
k
T
2
kk
l
ij
ij
j
T
a
0
T T
0
kk
c
0
V
2T
0
T T
0
2
s
0
T T
0
f
0
; 1
*
Tel.: +1-858-534-3169; fax: +1-858-534-5698.
E-mail address: vlubarda@ucsd.edu (V.A. Lubarda).
0020-7683/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijsolstr.2004.05.070
International Journal of Solids and Structures 41 (2004) 73777398
www.elsevier.com/locate/ijsolstr
where k
T
and l are the isothermal Lame elastic constants, j
T
k
T
2l=3 is the isothermal bulk modulus,
and a
0
, c
0
V
, and s
0
are, respectively, the coecient of volumetric thermal expansion, the specic heat at
constant strain, and the specic entropy, all in the reference state with temperature T
0
. The corresponding
free energy (per unit reference volume) is f 0; T
0
f
0
. The stress and entropy in the deformed state are the
gradients of f with respect to strain and temperature. The specic heat at constant strain, associated with
Eq. (1) is
c
V
T
os
oT
_ _
T
o
2
f
oT
2
_ _
c
0
V
T
T
0
: 2
Once the Helmholtz free energy is specied as a function of strain and temperature, the internal energy
u f Ts can be expressed in terms of the same independent variables by simple substitution of Eq. (1)
and the corresponding expression for the entropy. This yields (e.g., Ziegler, 1977)
u
ij
; T
1
2
k
T
2
kk
l
ij
ij
j
T
a
0
T
0
kk
c
0
V
2T
0
T
2
T
2
0
u
0
: 3
In the sequel, it will be assumed that the internal energy vanishes in the reference state, so that
u
0
0; f
0
T
0
s
0
: 4
However, the internal energy is a thermodynamic potential whose natural independent state variables
are strain and entropy, rather than strain and temperature, since the energy equation species the increment
of internal energy as
du r
ij
d
ij
T ds: 5
The desired representation u u
ij
; s can be obtained from u f Ts by eliminating the temperature
in terms of strain and entropy via Eq. (1). The end result is
u
ij
; s
1
2
k
S
2
kk
l
ij
ij
j
T
a
0
T
0
c
0
V
s s
0
kk
T
0
2c
0
V
s s
0
2
T
0
s s
0
: 6
The adiabatic (isentropic) Lame constant k
S
is related to its isothermal counterpart k
T
by
k
S
k
T

a
2
0
T
0
c
0
V
j
2
T
: 7
The purely algebraic transition from Eqs. (3)(6) is simple, but little indicative of the underlying ther-
modynamics connecting Eqs. (5) and (6). An independent derivation of (6), starting from the energy
equation (5), and utilizing the experimental data embedded in the DuhamelNeumann extension of
Hookes law, and the assumed specic heat behavior, is therefore desirable. The systematic procedure to
achieve this, and to derive the expressions for other thermodynamic potentials, the Helmholtz free energy
f f
ij
; T, the Gibbs energy g gr
ij
; T, and the enthalpy h hr
ij
; s, is presented. The four ther-
modynamic potentials are then expressed in terms of four possible pairs of independent state variables:
ij
; T,
ij
; s, r
ij
; T, and r
ij
; s. This furnishes a set of 16 alternative expressions, four for each ther-
modynamic potential. Analogous results in the scalar setting, using pressure and volume as pertinent
variables, is commonly utilized in materials science thermodynamics (Swalin, 1972; DeHo, 1993; Ragone,
1995). The obtained general results are applied to uniaxial and spherical stress and strain states, which are
of importance in high-pressure material testing (e.g., Lubarda, 1986; Lubarda et al., 2004). Particular
attention is given to uniaxial loading under isothermal, adiabatic, constant stress, and constant strain
condition. A simple interplay of adiabatic and isothermal elastic constants in the expressions for exchanged
heat along certain thermodynamic paths is obtained.
7378 V.A. Lubarda / International Journal of Solids and Structures 41 (2004) 73777398
2. Thermodynamics potentials in terms of their natural independent state variables
The four thermodynamic potentials are derived in this section in terms of their natural independent state
variables. The derivation is in each case based only on the DuhamelNeumann extension of Hookes law,
and an assumed linear dependence of the specic heat on temperature.
2.1. Internal energy u u(
ij
; s)
The increment of internal energy is expressed in terms of the increments of strain and entropy by the
energy equation (5). Since u is a state function, du is a perfect dierential, and the Maxwell relation holds
or
ij
os
_ _
oT
o
ij
_ _
s
: 8
The thermodynamic potential u u
ij
; s is sought corresponding to the DuhamelNeumann expression
r
ij
k
T
kk
d
ij
2l
ij
j
T
a
0
T T
0
d
ij
; 9
and an assumed linear dependence of the specic heat on temperature
c
V
c
0
V
T
T
0
: 10
The Kronecker delta is denoted by d
ij
. By partial dierentiation from Eq. (9) it follows that
or
ij
os
_ _
or
ij
oT
_ _
oT
os
_ _
j
T
a
0
oT
os
_ _
d
ij
; 11
so that the Maxwell relation (8) gives
oT
o
ij
_ _
s
j
T
a
0
oT
os
_ _
d
ij
: 12
The thermodynamic denition of the specic heat at constant strain is
c
V
T
os
oT
_ _
; 13
which, in conjunction with Eq. (10), species the temperature gradient
oT
os
_ _
T
0
c
0
V
: 14
The substitution into Eq. (12) yields
oT
o
ij
_ _
s

j
T
a
0
T
0
c
0
V
d
ij
: 15
The joint integration of Eqs. (14) and (15) provides
T
j
T
a
0
T
0
c
0
V
kk
T
0
c
0
V
s s
0
T
0
: 16
When this is inserted into Eq. (9), we obtain an expression for stress in terms of strain and entropy
r
ij
k
S
kk
d
ij
2l
ij
j
T
a
0
T
0
c
0
V
s s
0
d
ij
: 17
V.A. Lubarda / International Journal of Solids and Structures 41 (2004) 73777398 7379
The adiabatic Lame constant k
S
is related to its isothermal counterpart k
T
by Eq. (7).
By using Eqs. (16) and (17), the joint integration of
r
ij

ou
o
ij
_ _
s
; T
ou
os
_ _
; 18
yields a desired expression for the internal energy in terms of its natural independent variables
ij
and s. This
is
u
ij
; s
1
2
k
S
2
kk
l
ij
ij
j
T
a
0
T
0
c
0
V
s s
0
kk
T
0
2c
0
V
s s
0
2
T
0
s s
0
: 19
2.2. Helmholtz free energy f f (
ij
; T)
An independent derivation of the Helmholtz free energy function f f
ij
; T again begins with the pair
of expressions (9) and (10). The increment of f is
df r
ij
d
ij
s dT; 20
with the Maxwell relation
or
ij
oT
_ _

os
o
ij
_ _
T
: 21
By evaluating the temperature gradient of stress from Eq. (9), and by substituting the result into Eq. (21),
we nd
os
o
ij
_ _
T
j
T
a
0
d
ij
: 22
The integration of above, in conjunction with
os
oT
_ _
c
0
V
T
0
; 23
provides the entropy expression
s j
T
a
0
kk
c
0
V
T
0
T T
0
s
0
: 24
By using Eqs. (9) and (24), the joint integration of
r
ij

of
o
ij
_ _
T
; s
of
oT
_ _
; 25
yields a desired expression for the Helmholtz free energy in terms of its natural independent variables
ij
and T. This is
f
ij
; T
1
2
k
T
2
kk
l
ij
ij
j
T
a
0
T T
0
kk
c
0
V
2T
0
T T
0
2
s
0
T: 26
2.3. Gibbs energy g g(r
ij
; T)
The increment of the Gibbs energy is
dg
ij
dr
ij
s dT; 27
o
ij
oT
_ _
r
os
or
ij
_ _
T
: 28
To derive the function gr
ij
; T, independently of the connection g f r
ij
ij
and without tedious
change of variables, we begin with the thermoelastic stressstrain relation and an expression for the specic
heat, i.e.,
ij

1
2l
r
ij
_

m
T
1 m
T
r
kk
d
ij
_
a
0
3
T T
0
d
ij
; 29
c
P
T c
0
P
T
T
0
: 30
The rst one is a simple extension of Hookes law to include thermal strain, and the second one is the
assumed linear dependence of the specic heat at constant stress on temperature. The thermodynamic
denition of the specic heat c
P
is
c
P
T
os
oT
_ _
r
: 31
By dierentiating Eq. (29) to evaluate the temperature gradient of strain, and by substituting the result into
the Maxwell relation (28), we nd
os
or
ij
_ _
T
a
0
3
d
ij
: 32
The integration of this, in conjunction with
os
oT
_ _
r
c
0
P
T
0
; 33
provides the entropy expression
s
a
0
3
r
kk
c
0
P
T
0
T T
0
s
0
: 34
Using Eqs. (29) and (34), the joint integration of
ij

og
or
ij
_ _
T
; s
og
oT
_ _
r
; 35
yields a desired expression for the Gibbs energy in terms of its natural independent variables r
ij
and T (e.g.,
Fung, 1965; Kovalenko, 1969). This is
gr
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
a
0
3
T T
0
r
kk
c
0
P
2T
0
T T
0
2
s
0
T: 36
The relationship between the specic heats c
0
P
and c
0
V
can be obtained in various ways. For example, by
reconciling the entropy expressions (24) and (34), and by using the relationship
kk

1
3j
T
r
kk
a
0
T T
0
; 37
following from (27), it is found that
c
0
P
c
0
V
j
T
a
2
0
T
0
: 38
2.4. Enthalpy function h h(r
ij
; s)
The increment of enthalpy is
dh
ij
dr
ij
T ds; 39
o
ij
os
_ _
r

oT
or
ij
_ _
s
: 40
To derive the function hr
ij
; s, we shall again begin with the expressions (29) and (30). By partial dif-
ferentiation from Eq. (29) it follows that
o
ij
os
_ _
r
o
ij
oT
_ _
r
oT
os
_ _
r
a
0
3
oT
os
_ _
r
d
ij
: 41
The substitution into the Maxwell relation (40) gives
oT
or
ij
_ _
s

a
0
3
oT
os
_ _
r
d
ij

a
0
T
0
3c
0
P
d
ij
: 42
The denition (31), in conjunction with (30), was used in the last step. The joint integration of Eq. (42)
and
oT
os
_ _
r
T
0
c
0
P
; 43
provides the temperature expression
T
a
0
T
0
3c
0
P
r
kk
T
0
c
0
P
s s
0
T
0
: 44
When this is substituted into Eq. (29), there follows
ij

1
2l
r
ij
_

m
S
1 m
S
r
kk
d
ij
_
a
0
T
0
3c
0
P
s s
0
d
ij
: 45
The adiabatic Poissons ratio m
S
is related to its isothermal counterpart m
T
by
m
S

m
T
2l1 m
T
a
1 2l1 m
T
a
; m
T

m
S
2l1 m
S
a
1 2l1 m
S
a
; a
a
2
0
T
0
9c
0
P
: 46
Note that the adiabatic and isothermal Youngs moduli are related by
1
E
T
1
E
S
a
2
0
T
0
9c
0
P
; 47
in variance with an expression given by Fung (1965, p. 389), where the specic heat at constant strain
appears in the denominator on the right-hand side. A simple relationship is also recorded (e.g., Chadwick,
1960)
c
0
P
c
0
V
j
S
j
T
: 48
This easily follows by noting, from Eqs. (16) and (44), that for adiabatic loading
T
0
T
j
T
a
0
T
0
c
0
V
kk

a
0
T
0
3c
0
P
r
kk
: 49
Since for adiabatic loading r
kk
3j
S
kk
, the substitution into (49) yields (48).
Returning to the enthalpy function, by using Eqs. (44) and (45), the joint integration of
ij

oh
or
ij
_ _
s
; T
oh
os
_ _
r
; 50
yields the expression for the enthalpy in terms of its natural independent variables r
ij
and s. This is
hr
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
a
0
T
0
3c
0
P
s s
0
r
kk
T
0
2c
0
P
s s
0
2
T
0
s s
0
: 51
2.5. List of thermodynamic potentials in terms of their natural independent state variables
u
ij
; s
1
2
k
S
2
kk
l
ij
ij
j
T
a
0
T
0
c
0
V
s s
0
kk
T
0
2c
0
V
s s
0
2
T
0
s s
0
52
f
ij
; T
1
2
k
T
2
kk
l
ij
ij
j
T
a
0
T T
0
kk
c
0
V
2T
0
T T
0
2
s
0
T 53
gr
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
a
0
3
T T
0
r
kk
c
0
P
2T
0
T T
0
2
s
0
T 54
hr
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
a
0
T
0
3c
0
P
s s
0
r
kk
T
0
2c
0
P
s s
0
2
T
0
s s
0
55
3. Internal energy in terms of four pairs of independent state variables
The internal energy was expressed in Section 2.1 in terms of its natural independent state variables as
u u
ij
; s. We now derive its representation in terms of other three pairs of independent state variables.
3.1. Function u u(
ij
; T)
We start with the relationship
u
ij
; T f
ij
; T Ts: 56
The partial derivative with respect to strain at constant temperature is
ou
o
ij
_ _
T
of
o
ij
_ _
T
T
os
o
ij
_ _
T
: 57
Since
r
ij

of
o
ij
_ _
T
;
os
o
ij
_ _
T

or
ij
oT
_ _
; 58
we obtain
ou
o
ij
_ _
T
r
ij
T
or
ij
oT
_ _
: 59
By using the DuhamelNeumann expression (9), this gives
ou
o
ij
_ _
T
k
T
kk
d
ij
2l
ij
j
T
a
0
T
0
d
ij
: 60
On the other hand, by taking a partial derivative of Eq. (56) with respect to temperature at constant
strain, there follows
ou
oT
_ _
T
os
oT
_ _
c
0
V
T
T
0
; 61
having regard to s of =oT
. Therefore, upon joint integration of Eqs. (60) and (61), there follows
u
ij
; T
1
2
k
T
2
kk
l
ij
ij
j
T
a
0
T
0
kk
c
0
V
2T
0
T
2
T
2
0
: 62
This could have been also obtained directly from the relationship u f
ij
; T Ts, by using (24) and
(26) (e.g., Ziegler, 1977, p. 118; Haddow and Ogden, 1990, p. 165, 167). The corresponding expression for
internal energy in the case when it is assumed that c
V
c
0
V
can be found in Chadwick (1960, p. 275), or
Noda et al. (2003, p. 445).
3.2. Function u u(r
ij
; s)
We conveniently start with the relationship
ur
ij
; s hr
ij
; s r
ij
ij
: 63
The partial dierentiation with respect to stress at constant entropy is
ou
or
ij
_ _
s
r
kl
o
kl
or
ij
_ _
s
; 64
since
ij
oh=or
ij
s
. Incorporating Eq. (45), the above becomes
ou
or
ij
_ _
s
1
2l
r
ij
_

m
S
1 m
S
r
kk
d
ij
_
: 65
On the other hand, by taking a partial derivative of Eq. (63) with respect to entropy at constant stress,
there follows
ou
os
_ _
r
oh
os
_ _
r
r
ij
o
ij
os
_ _
r
T
a
0
T
0
3c
0
P
r
kk
; 66
having regard to T oh=os
r
. Since T is given by Eq. (44), this reduces to
ou
os
_ _
r
T
0
T
0
c
0
P
s s
0
: 67
The joint integration of Eqs. (65) and (67) gives
ur
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
T
0
2c
0
P
s s
0
2
T
0
s s
0
: 68
3.3. Function u u(r
ij
; T)
The derivation in this case proceeds by starting with the relationship
ur
ij
; T gr
ij
; T r
ij
ij
Ts: 69
The partial dierentiation with respect to stress at constant temperature is
ou
or
ij
_ _
T
r
kl
o
kl
or
ij
_ _
T
T
o
ij
oT
_ _
r
: 70
The connections were used
ij

og
or
ij
_ _
T
;
os
or
ij
_ _
T
o
ij
oT
_ _
r
: 71
Incorporating Eq. (29) into (70) yields
ou
or
ij
_ _
T
1
2l
r
ij
_

m
T
1 m
T
r
kk
d
ij
_
a
0
3
Td
ij
: 72
On the other hand, the partial derivative of Eq. (69) with respect to temperature at constant stress is
ou
oT
_ _
r
r
ij
o
ij
oT
_ _
r
T
os
oT
_ _
r
a
0
3
r
kk
c
0
P
T
T
0
; 73
having regard to s og=oT
r
. The joint integration of Eqs. (72) and (73) yields a desired expression
ur
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
a
0
3
Tr
kk
c
0
P
2T
0
T
2
T
2
0
: 74
3.4. List of internal energy functions in terms of four pairs of independent state variables
u
ij
; s
1
2
k
S
2
kk
l
ij
ij
j
T
a
0
T
0
c
0
V
s s
0
kk
T
0
2c
0
V
s s
0
2
T
0
s s
0
75
u
ij
; T
1
2
k
T
2
kk
l
ij
ij
j
T
a
0
T
0
kk
c
0
V
2T
0
T
2
T
2
0
76
ur
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
T
0
2c
0
P
s s
0
2
T
0
s s
0
77
ur
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
a
0
3
Tr
kk
c
0
P
2T
0
T
2
T
2
0
78
4. Helmholtz free energy in terms of four pairs of independent state variables
The Helmholtz free energy was expressed in Section 2.2 in terms of its natural independent state vari-
ables as f f
ij
; T. We now derive its representation in terms of other three pairs of independent state
variables. The derivation is in many aspects analogous to that presented for the internal energy in Section 3.
We accordingly record only its essential steps.
4.1. Function f f (
ij
; s)
f
ij
; s u
ij
; s Ts; 79
to obtain
of
o
ij
_ _
s
r
ij
s
or
ij
os
_ _
; 80
and
of
o
ij
_ _
s
k
S
kk
d
ij
2l
ij
j
T
a
0
T
0
c
0
V
s
0
d
ij
: 81
On the other hand,
of
os
_ _
s
oT
os
_ _

T
0
c
0
V
s: 82
f
ij
; s
1
2
k
S
2
kk
l
ij
ij
j
T
a
0
T
0
c
0
V
s
0
kk
T
0
2c
0
V
s
2
s
2
0
T
0
s
0
: 83
4.2. Function f f (r
ij
; T)
f r
ij
; T gr
ij
; T r
ij
ij
; 84
to obtain
of
or
ij
_ _
T
r
kl
o
kl
or
ij
_ _
T
; 85
and
of
or
ij
_ _
T
1
2l
r
ij
_

m
T
1 m
T
r
kk
d
ij
_
: 86
On the other hand,
of
oT
_ _
r
s
a
0
3
r
kk

c
0
P
T
0
T T
0
s
0
: 87
f r
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
c
0
P
2T
0
T T
0
2
s
0
T: 88
4.3. Function f f (r
ij
; s)
f r
ij
; s hr
ij
; s r
ij
ij
Ts; 89
to obtain
of
or
ij
_ _
s
r
kl
o
kl
or
ij
_ _
s
s
o
ij
os
_ _
r
; 90
and
of
or
ij
_ _
s
1
2l
r
ij
_

m
S
1 m
S
r
kk
d
ij
_
a
0
T
0
3c
0
P
sd
ij
: 91
On the other hand,
of
os
_ _
r
r
ij
o
ij
os
_ _
r
s
oT
os
_ _
r
T
0
c
0
P
a
0
3
r
kk
_
s
_
: 92
f r
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
a
0
T
0
3c
0
P
sr
kk
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
: 93
4.4. List of Helmholtz free energy functions in terms of four pairs of independent state variables
f
ij
; T
1
2
k
T
2
kk
l
ij
ij
j
T
a
0
T T
0
kk
c
0
V
2T
0
T T
0
2
s
0
T 94
f
ij
; s
1
2
k
S
2
kk
l
ij
ij
j
T
a
0
T
0
c
0
V
s
0
kk
T
0
2c
0
V
s
2
s
2
0
T
0
s
0
95
f r
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
c
0
P
2T
0
T T
0
2
s
0
T 96
f r
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
a
0
T
0
3c
0
P
sr
kk
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
97
5. Gibbs energy in terms of four pairs of independent state variables
The Gibbs energy was expressed in Section 2.3 in terms of its natural independent state variables
g gr
ij
; T. We now derive its representation in terms of other three pairs of independent state variables,
recording only essential steps.
5.1. Function g g(r
ij
; s)
gr
ij
; s hr
ij
; s Ts; 98
to obtain
og
or
ij
_ _
s

ij
s
o
ij
os
_ _
r
; 99
and
og
or
ij
_ _
s

1
2l
r
ij
_

m
S
1 m
S
r
kk
d
ij
_
a
0
T
0
3c
0
P
s
0
d
ij
: 100
On the other hand,
og
os
_ _
r
s
oT
os
_ _
r

T
0
c
0
P
s: 101
gr
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
a
0
T
0
3c
0
P
s
0
r
kk
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
: 102
5.2. Function g g(
ij
; T)
g
ij
; T f
ij
; T r
ij
ij
; 103
to obtain
og
or
ij
_ _
T

kl
or
kl
o
ij
_ _
T
; 104
and
og
o
ij
_ _
T
k
T
kk
d
ij
2l
ij
: 105
On the other hand,
og
oT
_ _
s
ij
or
ij
oT
_ _
s j
T
a
0
kk

c
0
V
T
0
T T
0
s
0
: 106
g
ij
; T
1
2
k
T
2
kk
_
l
ij
ij
_
c
0
V
2T
0
T T
0
2
s
0
T: 107
5.3. Function g g(
ij
; s)
g
ij
; s u
ij
; s r
ij
ij
Ts; 108
to obtain
og
o
ij
_ _
s

kl
or
kl
o
ij
_ _
s
s
or
ij
os
_ _
; 109
and
og
o
ij
_ _
s
k
S
kk
d
ij
2l
ij

j
T
a
0
T
0
c
0
V
sd
ij
: 110
On the other hand,
og
os
_ _

ij
or
ij
os
_ _
s
oT
os
_ _
T
0
c
0
V
j
T
a
0
kk
s: 111
g
ij
; s
1
2
k
S
2
kk
_
l
ij
ij
_
j
T
a
0
T
0
c
0
V
s
kk
T
0
2c
0
V
s
2
s
2
0
T
0
s
0
: 112
5.4. List of Gibbs energy functions in terms of four pairs of independent state variables
gr
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
a
0
3
T T
0
r
kk
c
0
P
2T
0
T T
0
2
s
0
T 113
gr
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
a
0
T
0
3c
0
P
s
0
r
kk
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
114
g
ij
; T
1
2
k
T
2
kk
_
l
ij
ij
_
c
0
V
2T
0
T T
0
2
s
0
T 115
g
ij
; s
1
2
k
S
2
kk
_
l
ij
ij
_
j
T
a
0
T
0
c
0
V
s
kk
T
0
2c
0
V
s
2
s
2
0
T
0
s
0
116
6. Enthalpy in terms of four pairs of independent state variables
The enthalpy was expressed in Section 2.4 in terms of its natural independent variables h hr
ij
; s. We
now derive its representation in terms of other three pairs of independent variables.
6.1. Function h h(r
ij
; T)
hr
ij
; T gr
ij
; T Ts; 117
to obtain
oh
or
ij
_ _
T

ij
T
o
ij
oT
_ _
r
; 118
and
oh
or
ij
_ _
T

1
2l
r
ij
_

m
T
1 m
T
r
kk
d
ij
_
a
0
3
T
0
d
ij
: 119
On the other hand,
oh
oT
_ _
r
T
os
oT
_ _
r
c
0
P
T
0
T: 120
hr
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
a
0
3
T
0
r
kk
c
0
P
2T
0
T
2
T
2
0
: 121
6.2. Function h h(
ij
; s)
h
ij
; s u
ij
; s r
ij
ij
; 122
to obtain
oh
o
ij
_ _
s

kl
or
kl
o
ij
_ _
s
; 123
and
oh
o
ij
_ _
s
k
S
kk
d
ij
2l
ij
: 124
On the other hand,
oh
os
_ _
T
ij
or
ij
os
_ _
T
j
T
a
0
T
0
c
0
V
kk

T
0
c
0
V
s s
0
T
0
: 125
h
ij
; s
1
2
k
S
2
kk
_
l
ij
ij
_
T
0
2c
0
V
s s
0
2
T
0
s s
0
: 126
6.3. Function h h(
ij
; T)
h
ij
; T f
ij
; T r
ij
ij
Ts; 127
to obtain
oh
o
ij
_ _
T

kl
or
kl
o
ij
_ _
T
T
or
ij
oT
_ _
; 128
and
oh
o
ij
_ _
T
k
T
kk
d
ij
2l
ij
j
T
a
0
Td
ij
: 129
On the other hand,
oh
oT
_ _

ij
or
ij
oT
_ _
T
os
oT
_ _
j
T
a
0
kk
c
0
V
T
0
T: 130
h
ij
; T
1
2
k
T
2
kk
_
l
ij
ij
_
j
T
a
0
T
kk
c
0
V
2T
0
T
2
T
2
0
: 131
6.4. List of enthalpy functions in terms of four pairs of independent variables
hr
ij
; s
1
4l
r
ij
r
ij
_

m
S
1 m
S
r
2
kk
_
a
0
T
0
3c
0
P
s s
0
r
kk
T
0
2c
0
P
s s
0
2
T
0
s s
0
132
hr
ij
; T
1
4l
r
ij
r
ij
_

m
T
1 m
T
r
2
kk
_
a
0
3
T
0
r
kk
c
0
P
2T
0
T
2
T
2
0
133
h
ij
; s
1
2
k
S
2
kk
_
l
ij
ij
_
T
0
2c
0
V
s s
0
2
T
0
s s
0
134
h
ij
; T
1
2
k
T
2
kk
_
l
ij
ij
_
j
T
a
0
T
kk
c
0
V
2T
0
T
2
T
2
0
135
7. Uniaxial loading and thermoelastic eect
The derived representations of thermodynamic potentials for arbitrary three-dimensional states of stress
and strain are greatly simplied in the case of uniaxial and spherical states of stress and strain. The cor-
responding results are listed in Appendices AD. To illustrate the use of some of the derived formulas,
consider uniaxial loading paths shown in Fig. 1. The path OAB is an adiabatic (fast loading) path, the path
OC is an isothermal (slow loading) path, the path AC is a constant stress path, and the path BC is a
constant longitudinal strain path. Along the adiabatic path OAB (see the expression for ur; s from
Appendix A)
u h
1
2E
S
r
2
; 136
while along the isothermal path OC (see the expressions for f r; T and gr; T from Appendix A)
f f
0
g
0
g
1
2E
T
r
2
; f
0
g
0
T
0
s
0
: 137
The temperature drop along the adiabatic path is
T T
0

a
0
T
0
3c
0
P
r; 138
in accord with Kelvins formula describing Joules thermoelastic eect (Fung, 1965, p. 388). The entropy
increase along the isothermal path is
s s
0

a
0
3
r; 139
with the corresponding absorbed heat given by T
0
s s
0
.
The heat absorbed along the constant stress path AC is equal to the enthalpy change
h
C
h
A

a
0
T
0
3
r
A
a
2
0
T
0
18c
0
P
r
2
A
: 140
Fig. 1. Uniaxial loading along isothermal path OC, and along adiabatic path OAB. The paths AC and BC are the constants stress and
constant longitudinal strain paths, respectively.
This is in agreement with the result following from
_
T
C
T
A
c
P
T dT
c
0
P
2T
0
T
2
0
T
2
A
: 141
The heat absorbed along the constant longitudinal strain path BC is
u
C
u
B

1
2E
T
r
2
C
_

a
0
T
0
3
r
C
_
1
2E
S
r
2
B
; 142
which gives
u
C
u
B

a
0
T
0
3
r
A
E
S
E
T
a
2
0
T
0
18c
0
P
r
2
A
: 143
This can be conrmed by integrating
_
s
C
s
B
T ds
_
s
C
s
B
T
0
_

T
0
c
0
P
s
_
s
0
a
0
3
r
_
_
ds; 144
with the stress variation, along the path BC, given by
r
E
S
E
T
r
A
a
0
T
0
3c
0
P
E
S
s s
0
: 145
For metals, the second term on the right-hand side of Eq. (143) is much smaller than the rst term, being
associated with small departures of c
P
and c
V
from their reference values c
0
P
and c
0
V
, inherent in linear
approximations c
P
c
0
P
T=T
0
and c
V
c
0
V
T=T
0
, which are valid for suciently small temperature dierences
T T
0
.
An alternative derivation of (143) proceeds by noting that dr E
T
a
0
dT=3 along the path BC
(because the longitudinal component of strain is xed along that path). The corresponding increment of
entropy is
ds
a
0
3
dr
c
0
P
T
0
dT
c
0
P
T
0
E
T
E
S
dT; 146
recalling the relationship (47) between isothermal and adiabatic Youngs moduli. Therefore,
_
T
C
T
B
T ds
c
0
P
2T
0
E
T
E
S
T
2
0
_
T
2
B
_
: 147
The incorporation of Eq. (138) reproduces Eq. (143).
Yet another derivation is possible by starting from an expression for the heat increment in terms of the
latent and specic heats, i.e.,
T ds l
ij
d
ij
c
V
dT: 148
The components of the latent heat tensor at constant strain are dened by
l
ij
T
os
o
ij
_ _
T
j
T
a
0
Td
ij
; 149
which gives
T ds j
T
a
0
T d
kk
c
V
dT; 150
Since, along the path BC,
d
kk

2
3
1 m
T
a
0
dT; 151
the substitution into Eq. (150), and integration from T
B
to T
C
T
0
, gives Eq. (143). This derivation is
facilitated by noting that, in view of Eq. (46),
1 m
T
a
2
0
T
0
9c
0
P
m
S
m
T
E
S
: 152
The individual contributions of the latent and specic heat to total heat absorbed along the path BC are
_
C
B
c
V
dT
1 2m
S
1 2m
T
u
C
u
B
; 153
_
C
B
l
ij
d
ij
2
m
S
m
T
1 2m
T
u
C
u
B
: 154
The contribution given by (153) is smaller than u
C
u
B
, because m
S
> m
T
. Since the lateral strain is not
held constant along the path BC, there is a small but positive contribution to absorbed heat from the latent
heat, and this is represented by Eq. (154). Both, Eqs. (143) and (153) display in their structure a simple
combination of adiabatic and isothermal elastic constants, via the ratio terms E
S
=E
T
and
c
0
V
c
0
P
E
S
E
T
1 2m
S
1 2m
T
: 155
8. Conclusions
The thermodynamic analysis is presented which yields the expressions for all thermodynamic potentials
(internal energy, Helmholtz free energy, Gibbs energy, and enthalpy) in terms of four possible pairs of
independent state variables from the set of stress, strain, temperature, and entropy. The derived results for
some of the considered potentials, and for the particular pairs of independent state variables, are well-
known from linear thermoelasticity, but are presented here in conjunction with other results for the
completeness of general formulation. The presented analysis is, in essence, an extension of the classical
thermodynamics analysis, which is cast within the scalar setting (involving pressure and volume), to the
three-dimensional tensorial setting (involving stress and strain tensors). When the stress is an independent
variable, the thermodynamic potentials involve in their structure the specic heat c
P
. With the strain as an
independent variable, the specic heat c
V
appears in the representation of the thermodynamic potentials. If
the temperature is used as an independent variable, the thermodynamic potentials are expressed in terms of
the isothermal elastic constants (k
T
, m
T
, j
T
). With the entropy as an independent variable, the adiabatic
counterparts (k
S
, m
S
, j
S
) appear in the representation of the thermodynamic potentials. If a thermodynamic
potential contains a mixed strainentropy term, such as
kk
s, either the ratio j
T
=c
0
V
or j
S
=c
0
P
multiplies that
term. The presented thermodynamic analysis also delivers the relationships between dierent types of in-
volved elastic and thermodynamic constants. The general results are applied to uniaxial and spherical states
of stress and strain, with a particular attention given to uniaxial loading under isothermal, adiabatic,
constant stress, and constant strain conditions. A simple combination of adiabatic and isothermal elastic
constants appears in the expression for the exchanged heat along the constant strain path.
Acknowledgement
Research support from the NSF Grant No. 0243695 is kindly acknowledged.
Appendix A. Thermodynamic potentials for uniaxial stress
For the uniaxial state of stress
r
ij
rd
i1
d
j
1
; r
ij
r
ij
r
2
; r
kk
r:
The corresponding thermodynamic potentials are
ur; s
1
2E
S
r
2
T
0
2c
0
P
s s
0
2
T
0
s s
0
;
ur; T
1
2E
T
r
2
a
0
3
Tr
c
0
P
2T
0
T
2
T
2
0
;
f r; s
1
2E
S
r
2
a
0
T
0
3c
0
P
sr
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
;
f r; T
1
2E
T
r
2
c
0
P
2T
0
T T
0
2
s
0
T;
gr; s
1
2E
S
r
2
a
0
T
0
3c
0
P
s
0
r
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
;
gr; T
1
2E
T
r
2
a
0
3
T T
0
r
c
0
P
2T
0
T T
0
2
s
0
T;
hr; s
1
2E
S
r
2
a
0
T
0
3c
0
P
s s
0
r
T
0
2c
0
P
s s
0
2
T
0
s s
0
;
hr; T
1
2E
T
r
2
a
0
3
T
0
r
c
0
P
2T
0
T
2
T
2
0
:
The constitutive equations are
ij

r
2l
d
i1
d
j1
_

m
T
1 m
T
d
ij
_
a
0
3
T T
0
d
ij
;
or
ij

r
2l
d
i1
d
j1
_

m
S
1 m
S
d
ij
_
a
0
T
0
3c
0
P
s s
0
d
ij
;
and
s s
0

a
0
3
r
c
0
P
T
0
T T
0
:
Appendix B. Thermodynamic potentials for uniaxial strain
For the uniaxial state of strain
ij
d
i1
d
j
1
;
ij
ij

2
;
kk
:
u; s
1
2
k
S
2l
2
j
T
a
0
T
0
c
0
V
s s
0

T
0
2c
0
V
s s
0
2
T
0
s s
0
;
u; T
1
2
k
T
2l
2
j
T
a
0
T
0

c
0
V
2T
0
T
2
T
2
0
;
f ; s
1
2
k
S
2l
2
j
T
a
0
T
0
c
0
V
s
0

T
0
2c
0
V
s
2
s
2
0
T
0
s
0
;
f ; T
1
2
k
T
2l
2
j
T
a
0
T T
0

c
0
V
2T
0
T T
0
2
s
0
T;
g; s
1
2
k
S
2l
2
j
T
a
0
T
0
c
0
V
s
T
0
2c
0
V
s
2
s
2
0
T
0
s
0
;
g; T
1
2
k
T
2l
2
c
0
V
2T
0
T T
0
2
s
0
T;
h; s
1
2
k
S
2l
2
T
0
2c
0
V
s s
0
2
T
0
s s
0
;
h; T
1
2
k
T
2l
2
j
T
a
0
T
c
0
V
2T
0
T
2
T
2
0
:
r
ij
k
T
d
ij
2ld
i1
d
j1
j
T
a
0
T T
0
d
ij
;
or
r
ij
k
S
d
ij
2ld
i1
d
j1

j
S
a
0
T
0
c
0
P
s s
0
d
ij
;
and
s s
0
j
T
a
0

c
0
V
T
0
T T
0
:
Appendix C. Thermodynamic potentials for spherical stress
For the spherical state of stress
r
ij
rd
ij
; r
ij
r
ij
3r
2
; r
kk
3r:
ur; s
1
2j
S
r
2
T
0
2c
0
P
s s
0
2
T
0
s s
0
;
ur; T
1
2j
T
r
2
a
0
Tr
c
0
P
2T
0
T
2
T
2
0
;
f r; s
1
2j
S
r
2
a
0
T
0
c
0
P
sr
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
;
f r; T
1
2j
T
r
2
c
0
P
2T
0
T T
0
2
s
0
T;
gr; s
1
2j
S
r
2
a
0
T
0
c
0
P
s
0
r
T
0
2c
0
P
s
2
s
2
0
T
0
s
0
;
gr; T
1
2j
T
r
2
a
0
T T
0
r
c
0
P
2T
0
T T
0
2
s
0
T;
hr; s
1
2j
S
r
2
a
0
T
0
c
0
P
s s
0
r
T
0
2c
0
P
s s
0
2
T
0
s s
0
;
hr; T
1
2j
T
r
2
a
0
T
0
r
c
0
P
2T
0
T
2
T
2
0
:

r
3j
T
a
0
3
T T
0
;
or

r
3j
S
a
0
T
0
3c
0
P
s s
0
;
and
s s
0
a
0
r
c
0
P
T
0
T T
0
:
Appendix D. Thermodynamic potentials for spherical strain
For the spherical strain
ij
d
ij
;
ij
ij
3
2
;
kk
3:
u; s
9
2
j
S
3j
T
a
0
T
0
c
0
V
s s
0

T
0
2c
0
V
s s
0
2
T
0
s s
0
;
u; T
9
2
j
T
2
3j
T
a
0
T
0

c
0
V
2T
0
T
2
T
2
0
;
f ; s
9
2
j
S
3j
T
a
0
T
0
c
0
V
s
0

T
0
2c
0
V
s
2
s
2
0
T
0
s
0
;
f ; T
9
2
j
T
2
3j
T
a
0
T T
0

c
0
V
2T
0
T T
0
2
s
0
T;
g; s
9
2
j
S
3j
T
a
0
T
0
c
0
V
s
T
0
2c
0
V
s
2
s
2
0
T
0
s
0
;
g; T
9
2
j
T
c
0
V
2T
0
T T
0
2
s
0
T;
h; s
9
2
j
S
T
0
2c
0
V
s s
0
2
T
0
s s
0
;
h; T
9
2
j
T
2
3j
T
a
0
T
c
0
V
2T
0
T
2
T
2
0
:
r 3j
T
j
T
a
0
T T
0
;
or
r 3j
S

j
S
a
0
T
0
c
0
P
s s
0
;
and
s s
0
3j
T
a
0

c
0
V
T
0
T T
0
:
References
Boley, B.A., Weiner, J.H., 1960. Theory of Thermal Stresses. John Wiley, New York.
Chadwick, P., 1960. Thermoelasticity. The dynamical theory. In: Sneddon, I.N., Hill, R. (Eds.), Progress in Solid Mechanics, vol. I.
North-Holland, Amsterdam, pp. 263328.
DeHo, R.T., 1993. Thermodynamics in Materials Science. McGraw-Hill, New York.
Fung, Y.C., 1965. Foundations of Solid Mechanics. Prentice-Hall, Englewood Clis, New Jersey.
Haddow, J.B., Ogden, R.W., 1990. Thermoelasticity of rubber-like solids at small strain. In: Eason, G., Ogden, R.W. (Eds.),
ElasticityMathematical Methods and Applications. Ellis Horwood, Chichester, pp. 165179.
Kovalenko, A.D., 1969. Thermoelasticity. Wolters-Noordho, Groningen, The Netherlands.
Lubarda, V.A., 1986. Finite compression of solidssecond order thermoelastic analysis. Int. J. Solids Struct. 22, 15171524.
Lubarda, V.A., Schneider, M.S., Kalantar, D.H., Remington, B.A., Meyers, M.A., 2004. Void growth by dislocation emission. Acta
Mater. 52, 13971408.
Noda, N., Hetnarski, R.B., Tanigawa, Y., 2003. Thermal Stresses. Taylor & Francis, New York.
Ragone, D.V., 1995. Thermodynamics of Materials. John Wiley, New York.
Sneddon, I.N., 1974. The Linear Theory of Thermoelasticity. CISM Udine, Springer-Verlag, Wien.
Swalin, R.A., 1972. Thermodynamics of Solids. John Wiley, New York.
Ziegler, H., 1977. An Introduction to Thermomechanics. North-Holland, New York.

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On thermodynamic potentials in linear thermoelasticity

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