Modeling the nonlinear large deformation kinetics of volume phase transition for the

neutral thermosensitive hydrogels

Xiaogui Wang

Citation: The Journal of Chemical Physics 127, 174705 (2007); doi: 10.1063/1.2779029
View online: http://dx.doi.org/10.1063/1.2779029
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 THE JOURNAL OF CHEMICAL PHYSICS 127, 174705 共2007兲

Modeling the nonlinear large deformation kinetics of volume phase

transition for the neutral thermosensitive hydrogels
Xiaogui Wanga兲
College of Mechanical Engineering, Zhejiang University of Technology, Hangzhou 310032,
People’s Republic of China
共Received 5 September 2006; accepted 9 August 2007; published online 5 November 2007兲

By regarding the neutral thermosensitive hydrogel as a biphasic mixture media, an incompressible

deformable porous solid skeleton, and an incompressible interstitial fluid phase saturating the
interconnected space, a novel biphasic mixture theory for modeling the nonlinear large deformation
kinetics of the volume phase transition was developed from the first law of thermodynamics and the
continuum mixture theory. The governing equations consist of the saturated continuity equation, the
momentum equations of the fluid, and the momentum equations of the bulk hydrogel. The explicit
expressions of the constitutive relationships, which are capable of characterizing the nonlinear large
deformation kinetics of the volume phase transition of the N-isopropylacrylamide thermosensitive
hydrogels, were derived from the Helmholtz free energy formed by the elastic and mixing
contributions. Both the governing equations and the constitutive relationships are in the Lagrangian
framework, and special attention was paid to the deformable porous solid skeleton. © 2007
American Institute of Physics. 关DOI: 10.1063/1.2779029兴

I. INTRODUCTION makes the minimal of shear energy to be automatically sat-

It is well known that temperature is probably the most
widely used triggering signal for the regulable intelligent
systems. The thermosensitive hydrogels can sense the tem-
perature change stimulus as an input signal and elicit confor-
mational rearrangements accordingly by themselves through
imbibing the fluid from the bathing solution or expelling the
interstitial water to the surroundings. Considerable re-
searches indicated that the thermosensitive hydrogels have
the nearly critical continuous or discontinuous volume phase
transition in responsive to the temperature change stimulus
around the lower or higher critical solution temperature.1–4
The specific properties of the volume phase transition as well
as the dual functions of a sensor and an actuator make the
thermosensitive hydrogel to be a fantastic self-regulated in-
telligent material, having enormous potential applications as
the functional materials in the biomedical engineering, sen-
sors, actuators, drug delivery systems, etc.5–7
The complicated swelling or shrinking kinetics of the
volume phase transition of the N-isopropylacrylamide
共PNIPA兲 thermosensitive hydrogels have been extensively
investigated theoretically and experimentally. An original
collective diffusion theory modeling the deformation kinetics
of the spherical gels was first derived from the theory of
linear elasticity with neglecting the solvent motion and the
shear energy.8,9 However, the experimental results showed
that the swelling or shrinking process of hydrogels was not
pure diffusive and the shear energy was involved to maintain
the shape of hydrogels. This original collective diffusive
model is only capable of describing the deformation kinetics
of spherical gels since the spherical symmetry condition
a兲
Author to whom correspondence should be addressed. Tel.: 86-571-
88320294. Electronic mail: mcwangxg@yahoo.com
isfied by the diffusive process. Therefore, a modified collec-
tive diffusion theory was proposed to solve the deformation
kinetics of hydrogels with arbitrary shape 共such as long cyl-
inders and large disks兲, in which the effects of the shear
energy and solvent motion were taken into account by de-
composing imaginarily the kinetic deformation process into
two consecutive steps, i.e., the pure diffusion process of
polymer network with quiescent solvent and the shear relax-
ation process with the solvent moving together with polymer
network.10 Recently, another extended collective diffusive
model for the analysis of the deformation kinetics and sol-
vent motion was developed by solving directly the coupled
motion equations of the polymer network and solvent.11 Nev-
ertheless, none of the preceding collective diffusive models
can reproduce the experimental results of the anisotropic
swelling kinetics of thin-plate thermosensitive hydrogels
with the chemically clamped top and bottom surfaces.12
Hence a stress-diffusion coupling model, which consists of
Darcy’s law representing the relative motion between the
solvent and the polymer network, and the motion equilibrium
equation describing the mechanical coupling between the
solvent diffusion and the polymer network stress, was devel-
oped for the anisotropic deformation kinetics of gels.13,14 Al-
though the diffusion models based on the linear elasticity
assumption and the diffusion conception can well reproduce
the experimental results of the swelling or shrinking kinetics
of small-deformed gels, none of them can quantitatively
simulate the deformation kinetics of the discontinuous vol-
ume phase transition such as that of spherical PNIPA ther-
mosensitive hydrogels immersed in the bathing solution.1
The multiphasic mixture theory is another powerful tool
for modeling the deformation kinetics of the thermosensitive
hydrogels, since the neutral hydrogel can be considered as a

0021-9606/2007/127共17兲/174705/8/$23.00 127, 174705-1 © 2007 American Institute of Physics

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 174705-2 Xiaogui Wang
biphasic mixture media: a porous deformable solid skeleton
formed by the cross-linked polymer network and an intersti-
tial fluid phase saturating the interconnected space. On the
basis of the mixture theory,15 a triphasic mechanoelectro-
chemical theory was formulated for the charged hydrated
biological soft tissue which was modeled as a triphasic mix-
ture consisting of an incompressible porous charged solid
phase, an interstitial fluid phase, and an ion phase.16 It is
obvious that the neutral hydrogels have the similar composi-
tions as the hydrated biological soft tissues. Based on this
triphasic mixture model, a new set of governing equations in
Eulerian forms was derived by using the generalized first law
of thermodynamics for the hydrated biological soft tissue
which was considered to be an irreversible thermodynamical
system.17 This new model was then utilized to simulate the
deformation response of a hydrogel strip immersed into an
acidic solution in responsive to an external electric field.18
By separating the single ion phase into double phases 共an
anion phase and a cation phase兲, a quadriphasic mixture
theory was also developed for the quasistatic finite deforma-
tion of swelling incompressible saturated charged porous
media, and a Lagrangian form of the second law of thermo-
dynamics was used to derive the constitutive
relationship.19,20 Relative to the diffusion models, an advan-
tage of the multiphasic mixture theory is that it has the abil-
ity to deal with the finite deformation problem such as the
discontinuous volume phase transition of thermosensitive
hydrogels. However, the difficulties to give the explicit ex-
pressions of the constitutive relationships for the thermosen-
sitive hydrogels greatly restricted the application of the mul-
tiphasic mixture theory in the simulation of the deformation
kinetics of the volume phase transition.
It is clear from the foregoing arguments that neither the
collective diffusion model nor the multiphasic mixture
theory can deal with the complicated swelling or shrinking
kinetics of the volume phase transition of the thermosensi-
tive hydrogels. The purpose of the present paper is therefore
to develop a new set of governing equations and to present
the explicit expressions of the constitutive relationships for
the simulation of the nonlinear deformation kinetics of the
continuous or discontinuous volume phase transition of the
neutral thermosensitive hydrogels.
II. PRELIMINARIES
The fully saturated thermosensitive hydrogel in the
swelling equilibrium state can be considered as a porous hy-
perelastic biphasic mixture media formed by a deformable
porous solid skeleton and an interstitial fluid saturating the
interconnected space. In the framework of the continuum
mixture theory, the biphasic mixture media are treated as the
simple superposition of the porous solid skeleton continuum
and the interstitial fluid continuum in the same three-
dimensional space. This means that the same spatial position
is simultaneously occupied by two material particles belong-
ing to different constitutes. The apparent or macroscopic spa-
tial configuration of the hydrogel is identified by the material
points of the porous solid skeleton located at the outside
surface of the hydrogel. When subject to the temperature
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J. Chem. Phys. 127, 174705 共2007兲
stimulus across the critical value, the hydrogel can lose al-
most all the pore-filled fluid and eventually lead to a dra-
matic volume change due to the collapse of the porous solid
skeleton. It can be explained that the porous solid skeleton is
so soft that it has no ability to preserve the spatial configu-
ration of the hydrogel by itself without the supporting of the
pore-filled fluid. This property is different from the tradi-
tional multiphasic porous media such as the saturated soil.
The dramatic volume change with respect to the initial and
target temperatures may be continuous or discontinuous,
which is well known as the famous volume phase transition.
If an inverse temperature change is applied to the collapsed
hydrogels, a reverse volume phase transition will be trig-
gered, whose swelling process and mechanism are similar to
those of inflating a balloon.
If the temperature is changed from an initial value T0 to
another value T, the thermosensitive hydrogel will be trans-
formed accordingly from the initial swelling equilibrium
state ␰0 to another updated swelling equilibrium state ␰ un-
dergoing a dynamic evolution process. The initial swelling
equilibrium state is respect to the temperature T0 at time t0,
and the updated swelling equilibrium state is associated with
the target temperature T at time t0 + ⌬t. It is convenient to
regard the spatial configuration of the porous solid skeleton
with respect to the state ␰0 as the reference configuration for
Lagrangian description, and the spatial configuration of the
porous solid skeleton with respect to the target temperature T
at any instant of time t 苸 关t0 , t0 + ⌬t兴 as the current configu-
ration for Eulerian description. Here we have assumed that
the thermal equilibrium can be reached more rapidly than the
mechanical swelling equilibrium. Let the Lagrangian coordi-
nate X indicate the initial spatial position of a material par-
ticle of the porous solid skeleton in the reference configura-
tion. The mapping spatial position of the same material
particle in the current configuration is denoted by the Eule-
rian coordinate x. Here and in what follows a boldface letter
is used to denote a vector or tensor. The transform conven-
tions between the elemental vectors dX and dx are
dx = F · dX, ˜ x = ⳵x/⳵X
F=ⵜ 共1兲
and
dX = F−1 · dx, F−1 = ⵜX = ⳵X/⳵x, 共2兲
where F is the deformation gradient tensor and F−1 is the
˜ = ⳵ / ⳵X stands for the Lagrangian gradient operator
inverse, ⵜ
with respect to the reference configuration, and ⵜ = ⳵ / ⳵x de-
notes the Eulerian gradient operator with respect to the cur-
rent configuration. The necessary and sufficient condition for
the existence of Eq. 共2兲 is that the Jacobian of deformation is
nonsingular, which can be expressed by three principal La-
grangian Green strains E j as
J = 冑共1 + 2E1兲共1 + 2E2兲共1 − 2E3兲. 共3兲
The Jacobian will be used to characterize the nonlinear large
deformation of the thermosensitive hydrogels intrigued by
the temperature stimulus.
 174705-3 Phase transition for neutral thermosensitive hydrogels J. Chem. Phys. 127, 174705 共2007兲

III. CONTINUITY EQUATION ⳵␸␣

+ ⵜ · 共␸␣v␣兲 = 0, 共12兲
We assume that both the porous solid skeleton and the ⳵t
fluid are intrinsically incompressible. The total volume of the or in the Lagrangian form
biphasic mixture media can be considered as the simple ad-
dition of both constitutes for the fully saturated bulk hydro- ␾˙ s = 0, ␾˙ f + ␾ f ⵜ · ␻ + J␻ · ⵜ␸ f = 0, 共13兲
gels. Let d⍀ = dx1 · 共dx2 ⫻ dx3兲 denote the Eulerian volume of where ␻ = 共v f − vs兲 indicates the flux vector of the fluid rela-
an infinitesimal element with respect to the current configu- tive to the moving porous solid skeleton with a velocity vs
ration and let d⍀␣ indicate the volume of the ␣ constitute and the dot above the Lagrangian variables denotes the stan-
contained in d⍀. We then have dard material time derivative with respect to the material
d⍀ = d⍀s + d⍀ f , 共4兲 particle of the porous solid skeleton in the reference configu-
ration, i.e., the operator ds / dt ⬅ d / dt. Differentiating the
where the superscript ␣ = s stands for the porous solid skel- saturated condition Eq. 共8兲 and using Eqs. 共12兲 and 共13兲, we
eton and ␣ = f stands for the fluid. The true mass density ␳T␣ get the Eulerian saturated continuity equation,
of the ␣ constitute is defined by
ⵜ · vs + ␸ f ⵜ · ␻ + ␻ · ⵜ␸ f = 0, 共14兲
␳T␣ = ␣
dm /d⍀ , ␣
共5兲
and the Lagrangian saturated continuity equation,
in which dm␣ is the mass of the ␣ constitute contained in the ˜ · 关F−1 · 共␾ f v f + ␾svs兲兴 = 0.
volume d⍀. The Eulerian volume fractions ␸␣ and Lagrang- ⵜ 共15兲
ian volume fractions ␾␣ are
␸␣ = d⍀␣/d⍀, ␾␣ = d⍀␣/d⍀0 . 共6兲
IV. ENERGY CONSERVATION
Applying the mapping relationship d⍀ = Jd⍀0 between the
Lagrangian volume d⍀0 and the Eulerian volume d⍀ to Eq. For the porous solid skeleton and the interstitial fluid
共6兲, we get contained in the arbitrary Eulerian control volume ⍀, which
was taken from the bulk hydrogel in current configuration,
␾␣ = J␸␣ . 共7兲 the respective kinetic energy is
For the fully saturated hydrogels, the volume fractions of the
porous solid skeleton and the fluid should satisfy the follow-
K␣ = 1
2 冕⍀
␳T␣␸␣v␣ · v␣d⍀. 共16兲
ing saturated condition:
The time rate of the kinetic energy is readily given by taking
␸s + ␸ f = 1, ␾s + ␾ f = J. 共8兲 respective material time derivative and using the mass bal-
If no phase transition between the porous solid skeleton and ance equation 关Eq. 共9兲兴,
the fluid occurs, the mass balance of each constitute should
take the form
d ␣K ␣
dt
= 冕 ⍀
␳T␣␸␣a␣ · v␣d⍀, 共17兲

d␣
dt
冕 ⍀
␳T␣␸␣d⍀ =
d␣
dt
冕
⍀0
␳T␣␾␣d⍀0 = 0, 共9兲 where a␣ ⬅ d␣v␣ / dt represents the acceleration. Due to the
relative motion between the fluid and solid skeleton, there is
a diffusive drag force g␣ between two phases, also known as
where the material time derivative d␣ / dt = ⳵ / ⳵t + v␣ · ⵜ repre-
the frictional resistance force, which can be formulated to be
sents the time change rate as seen by an observer stationed at
proportional to the time rate of the relative flux vector as
a moving material particle with a velocity.21 Applying the
material time derivative to the integrand of Eq. 共9兲 and bear- gs = ␨␻
˙, g f = − ␨␻
˙, 共18兲
ing the arbitrary choice of the Eulerian volume d⍀ in mind,
where ␨ is the diffusive drag coefficient or frictional coeffi-
the equivalent local differential form of the mass balance can
cient with the dimension of mass density, which is identical
be readily obtained,
to the mass coupling parameter between the fluid and solid
d␣ ␣ ␣ phases presented by Biot.22 It is clear that the sum of the
共␳ ␸ 兲 + ␳T␣␸␣ ⵜ · v␣ = 0, 共10兲 drag forces gs and g f is equal to zero, i.e., gs + g f = 0. The time
dt T
rate of energy dissipation ⌰␣ relates to the diffusive drag
in which the material time derivative of the Eulerian volume force g␣ and the velocity v␣ by

冕
d⍀,
d ␣⌰ ␣
␣ = g␣ · v␣d⍀. 共19兲
d 共d⍀兲 dt
= 共ⵜ · v␣兲d⍀, 共11兲 ⍀
dt
It is obvious that the summation of Eqs. 共17兲 and 共19兲 is
has been used. Since ␳T␣ is constant based on the incompress- equivalent to the time rate of kinetic energy given by Biot.22
ibility assumption for each constitute, the mass balance can The time rate of work done by the external forces to the
therefore be expressed by the volume fractions not mass den- porous solid skeleton and the fluid contained in the Eulerian
sities as the continuity equation in the Eulerian form control volume ⍀ is
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 174705-4 Xiaogui Wang J. Chem. Phys. 127, 174705 共2007兲

d ␣W ␣
dt
= 冕 ⍀
␳T␣␸␣f · v␣d⍀ + 冕
⳵⍀
t␣ · v␣da, 共20兲 兺␣ 冕 ⍀
␸␣
d ␣e ␣
dt
d⍀ − 冕 ⍀
␴:ⵜvsd⍀ − 冕⍀
␴ f :ⵜ␻d⍀

where f is the body force per unit mass of the solid skeleton
or the fluid and t␣ is the surface traction which relates to the
−兺
␣
冕 ⍀
关共ⵜ · ␴␣兲 + ␳T␣␸␣共f − a␣兲 − g␣兴 · v␣d⍀

兺冕
partial Cauchy stress tensor ␴␣ by t␣ = ␴␣ · n. The vector n
denotes the unit external normal vector to the surface ⳵⍀. + 关ⵜ · 共␸␣q␣兲 − ␸␣␥␣兴d⍀ = 0, 共26兲
␣ ⍀
The first term in Eq. 共20兲 indicates the work per unit time
done by the body forces, and the second term denotes the
work per unit time done by the surface tractions. Applying where ␴ = ␴s + ␴ f is the total partial Cauchy stress tensor.
the divergence theorem to the second term, we get Introducing the differential form of the Eulerian saturated
continuity condition 关Eq. 共14兲兴 into Eq. 共26兲 by the Lagrange
d ␣W ␣
dt
= 冕 ⍀
共␳T␣␸␣f + ⵜ · ␴␣兲 · v␣d⍀ + 冕⍀
␴␣:ⵜv␣d⍀.
multiplier p, which can be interpreted as the fluid pressure,
we get

冕 冕 冕
共21兲
d ␣e ␣
兺␣ ⍀
␸␣
dt
d⍀ −
⍀
␴eff:ⵜvsd⍀ −
⍀
共␴ f + ␸ f pI兲:ⵜ␻d⍀
The internal energy of the porous solid skeleton and the fluid
currently contained in the Eulerian control volume ⍀ is
− 冕 关共ⵜ · ␴s兲 + ␳Ts␸s共f − as兲 − gs − p ⵜ ␸ f 兴 · vsd⍀

冕
⍀

E␣ =
⍀
␳T␣␸␣ê␣d⍀, 共22兲
− 冕⍀
关共ⵜ · ␴ f 兲 + ␳Tf␸ f 共f − a f 兲 − g f + p ⵜ ␸ f 兴 · v f d⍀

冕
␣
where ê is the internal energy per unit mass of the ␣ con-
stitute. With the help of the mass balance equation 关Eq. 共9兲兴 +兺 关ⵜ · 共␸␣q␣兲 − ␸␣␥␣兴d⍀ = 0, 共27兲
␣ ⍀
and the incompressibility condition, the material time deriva-
tive of the internal energy is obtained,
where the Eulerian effective stress tensor ␴eff is defined as
d ␣E ␣
dt
= 冕 ⍀
␳T␣␸␣
d␣ê␣
dt
d⍀ = 冕
⍀
␸␣
d ␣e ␣
dt
d⍀, 共23兲
␴eff = ␴ + pI. 共28兲
Let h␣ denote the true volume density of the Helmholtz
where e ␣
= ␳T␣ê␣
denotes the internal energy density which is free energy,
defined as the total internal energy of the ␣ constitute con-
tained in the Eulerian control volume ⍀ divided by the vol-
ume ⍀␣. The density defined in such a way will be refer- h␣ = e␣ − T␩␣ , 共29兲
enced as the true volume density. The rate of heat supply to
both constitutes contained in the Eulerian control volume ⍀ where T is the absolute temperature and ␩␣ represents the
is given by true volume density of entropy. With the definition of the
true volume density of the Helmholtz free energy and the
d ␣Q ␣
dt
= 冕⍀
␸␣␥␣d⍀ − 冕 ⍀
ⵜ · 共␸␣q␣兲d⍀, 共24兲
Lagrangian continuity equation 关Eq. 共13兲兴, the first term of
Eq. 共27兲 is rewritten in the form

where ␥␣ is the time rate of the true volume density of heat

generation and q␣ denotes the heat flux vector per unit sur-
兺␣ 冕 ⍀
␸␣
d ␣e ␣
dt
d⍀ = 兺
␣
冕 ⍀
␸␣
d␣ ␣
dt
共h + T␩␣兲d⍀

冕
face of the Eulerian control volume ⍀.
The first law of thermodynamics of the biphasic mixture = 共Ḣ + T␩˙ 0 + ␩0Ṫ兲d⍀0
media states that ⍀0

兺␣ 冉 d ␣K ␣ d ␣⌰ ␣ d ␣E ␣
+ + =兺 冊 冉
⳵ ␣W ␣ d ␣Q ␣
+ . 冊 +冕 ⍀
ⵜ · 共␸ f e f ␻兲d⍀, 共30兲
dt dt dt ␣ dt dt
共25兲 where H = ␾shs + ␾ f h f and ␩0 = ␾s␩s + ␾ f ␩ f are termed as the
Lagrangian true volume densities of the Helmholtz free en-
Substitution of Eqs. 共17兲, 共19兲, 共21兲, 共23兲, and 共24兲 into Eq. ergy and entropy of the biphasic mixture media, respectively.
共25兲, yields Substituting Eq. 共30兲 into Eq. 共27兲 yields
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 174705-5 Phase transition for neutral thermosensitive hydrogels J. Chem. Phys. 127, 174705 共2007兲

冕 ⍀0
共Ḣ + ␩0Ṫ + T␩˙ 0兲d⍀0 − 冕 ⍀
␴eff:ⵜvsd⍀ − 冕 ⍀
共␴ f + ␸ f pI − ␸ f e f I兲:ⵜ␻d⍀ − 冕
⍀
关共ⵜ · ␴s兲 + ␳Ts␸s共f − as兲 + ⌶ f 兴 · vsd⍀

where
− 冕 ⍀
关共ⵜ · ␴ f 兲 + ␳Tf␸ f 共f − a f 兲 − ⌶ f 兴 · v f d⍀ + 兺
␣
冕⍀
关ⵜ · 共␸␣q␣兲 − ␸␣␥␣兴d⍀ = 0, 共31兲

⌶ f = g f − p ⵜ ␸ f + ⵜ共␸ f e f 兲. 共32兲
␣
The Eulerian gradient of velocity can be expressed by the symmetric Eulerian deformation rate tensor d and antisymmetric
Eulerian rotation rate tensor w␣ as
ⵜv␣ = d␣ + w␣ . 共33兲
Applying Eq. 共33兲 to Eq. 共31兲 yields

冕 ⍀0
共Ḣ + ␩0Ṫ + T␩˙ 0兲d⍀0 − 冕 ⍀
␴eff:dsd⍀ − 冕 ⍀
共␴ f + ␸ f pI − ␸ f e f I兲:共d f − ds兲d⍀ − 冕⍀
关共ⵜ · ␴s兲 + ␳Ts␸s共f − as兲 + ⌶ f 兴 · vsd⍀

− 冕 ⍀
关共ⵜ · ␴ f 兲 + ␳Tf␸ f 共f − a f 兲 − ⌶ f 兴 · v f d⍀ + 兺
␣
冕⍀
关ⵜ · 共␸␣q␣兲 − ␸␣␥␣兴d⍀ = 0, 共34兲

in which the quantity ␺ : w␣ ⬅ 0 associated with a symmetric tensor ␺ has been used to the second and third terms.
In what follows we will transform Eq. 共34兲 into the equivalent Lagrangian form. In terms of the transport formula,

d␣ = F−T · Ė␣ · F−1 , 共35兲

between the Eulerian deformation rate tensor d␣ and the Langrangian Green strain rate tensor Ė␣, and
˜ · 共JF−1 · ␺兲兴d⍀ ,
共ⵜ · ␺兲d⍀ = 关ⵜ 共36兲
0

between the Eulerian and Lagrangian divergences of an arbitrary tensor ␺, the Lagrangian form of Eq. 共34兲 is easily obtained,

冕 ⍀0
共Ḣ + ␩0Ṫ + T␩˙ 0兲d⍀0 − 冕 ⍀0
␲eff:Ėsd⍀0 − 冕 ⍀0
关␲ f + ␾ f 共p − e f 兲F−1 · F−T兴:共Ė f − Ės兲d⍀0 − 冕 ⍀0
˜ · ␶s + ␳s ␾s共f − as兲
关ⵜ T

+ ⌶̃ f 兴 · vsd⍀0 − 冕 ⍀0
˜ · ␶ f + ␳ f ␾ f 共f − a f 兲 − ⌶̃ f 兴 · v f d⍀ + 兺
关ⵜ T 0
␣
冕⍀0
˜ · 共␾␣F−1 · q␣兲 − ␾␣␥␣兴d⍀ = 0,
关ⵜ 0 共37兲

with V. GOVERNING EQUATIONS

In the framework of thermodynamics, both the internal

f ˜ · 共␾ f F−1兲 + ⵜ
⌶̃ = Jg − pⵜ
f ˜ · 共␾ f e f F−1兲, 共38兲 energy and the Helmholtz free energy are the state functions
with the necessary and sufficient independent state variables.
In this paper, the Lagrangian Green strain tensor of the de-
where ␲ f is the second Piola-Kirchhoff stress tensor of the
formable porous solid skeleton Es, the absolute temperature
fluid, ␶␣ is the first Piola-Kirchhoff stress tensor, and ␲eff is
T, and the Lagrangian volume fraction of fluid ␾ f form a set
the Lagrangian effective stress tensor, and they are, respec-
of independent state variables. They are, respectively, asso-
tively, defined by
ciated with the mechanical, thermal, and chemical potential
effects on the deformation kinetics of the volume phase tran-
␲ f = JF−1 · ␴ f · F−T, ␶␣ = JF−1 · ␴␣ , sition of the thermosensitive hydrogels. The Lagrangian true
共39兲 volume density of the Helmholtz free energy H can then be
␲eff = JF−1 · ␴eff · F−T . expressed as a function of these three independent state vari-
ables as H共Es , T , ␾ f 兲. By using the chain rule of partial dif-
ferentiation, we have
The Lagrangian effective stress tensor ␲eff can also be ex-
pressed by the fluid pressure p and the second Piola- Ḣ共Es,T, ␾ f 兲d⍀0 = 关共⳵H/⳵Es兲:Ės + 共⳵H/⳵T兲Ṫ
Kirchhoff stress tensor ␲ = JF−1 · ␴ · F−T of the biphasic mix-
ture media as + 共⳵H/⳵␾ f 兲␾
˙ f 兴d⍀0 . 共41兲
From the Lagrangian continuity equation 关Eq. 共13兲兴, the ma-
␲eff = ␲ + JpF−1 · F−T . 共40兲 terial time derivative of ␾ f is obtained,
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 174705-6 Xiaogui Wang J. Chem. Phys. 127, 174705 共2007兲

␾˙ f = − ␾ f ⵜ · ␻ − J␻ · ⵜ␸ f . 共42兲 ˜ · 共␾ f F−1兲兴
− 兵␻ · 关ⵜ
Substitution of ␾
˙ f into the last term of Eq. 共41兲, we get + ␾ f 共F−1 · F−T兲:共Ė f − Ės兲其⳵H/⳵␾ f d⍀0 . 共44兲
− 共␾ ⵜ · ␻ + J␻ · ⵜ␸ 兲⳵H/⳵␾ d⍀0 ,
f f f
共43兲
whose equivalent Lagrangian form is Combination of Eqs. 共37兲, 共41兲, and 共44兲 yields

冕 ⍀0
共⳵H/⳵Es − ␲eff兲:Ėsd⍀0 + 冕 ⍀0
共⳵H/⳵T + ␩0兲Ṫd⍀0 − 冕 ⍀0
关␲ f + ␾ f 共␮ f − e f 兲F−1 · F−T兴:共Ė f − Ės兲d⍀0

− 冕
⍀0
˜ · ␶s + ␳s ␾s共f − as兲 + ⌸ f 兴 · vsd⍀ −
关ⵜ T 0 冕 ⍀0
˜ · ␶ f + ␳ f ␾ f 共f − a f 兲 − ⌸ f 兴 · v f d⍀
关ⵜ T 0

+兺
␣
冕⍀0
˜ · 共␾␣F−1 · q␣兲 + T␩˙ − ␾␣␥␣兴d⍀ = 0,
关ⵜ 0 0 共45兲

where ˜ · 共␲eff · FT兲 − ⵜ

ⵜ ˜ · 共JpF−1兲 + ␳s ␾s共f − as兲 + ␳ f ␾ f 共f − a f 兲
T T
␮ f = p + ⳵H/⳵␾ f = p + ␮* 共46兲 = 0. 共52兲
is the chemical potential of the fluid and Substitution of Eqs. 共18兲, 共46兲, 共47兲, and 共49兲 into Eq. 共51兲
yields
˜ · 共␾ f F−1兲 + ⵜ
⌸ f = Jg f − ␮ f ⵜ ˜ · 共␾ f e f F−1兲 共47兲
␻ ˜ ␮ f − ␳ f 共f − a f 兲兴,
˙ = ␨−1␸ f 关F−1 · ⵜ 共53兲
T
is the force related only to the fluid. Since the Lagrangian
Green strain rate tensor of the porous solid skeleton Ės, the which has the similar form as Darcy’s law. Likewise the
rate of absolute temperature Ṫ, the relative Lagrangian Green conjugated term with Ṫ should be equal to zero. We then
have the definition of the Lagrangian true volume density of
strain rate tensor 共Ė f − Ės兲, and the velocity v␣ change inde- the entropy,
pendently, all of their conjugated terms should be equal to
zero. Based on this argument, the constitutive equations for ␩0 = − ⳵H/⳵T. 共54兲
the biphasic mixture media and the fluid are obtained by In addition, the Lagrangian heat transfer equation are also
equating the terms conjugated with Ės and 共Ė f − Ės兲 to zero, derived,
␲eff = ⳵H/⳵Es = ␲ + JpF−1 · F−T 共48兲 ˜ · 共␾␣F−1 · q␣兲 + T␩˙ − ␾␣␥␣ = 0.
ⵜ 共55兲
0

and The matric potential ␮* = ⳵H / ⳵␾ f , the effective stress tensor

␲eff = ⳵H / ⳵Es, and the Lagrangian true volume density of the
␲ f = ␾ f 共e f − ␮ f 兲F−1 · F−T
entropy ␩0 = −⳵H / ⳵T will be given in the next section by
or introducing the explicit form of the Helmholtz free energy of
the neutral thermosensitive hydrogel PNIPA.
␶ f = ␾ f 共e f − ␮ f 兲F−1 . 共49兲

Letting the conjugated terms of vs and v f to be zero, the VI. CONSTITUTIVE RELATIONSHIP OF PNIPA
Lagrangian momentum equations for the porous solid skel- HYDROGELS
eton and the fluid with respect to the reference configuration In the Flory mean field theory of the neutral hydrogels,
are then derived, the change of the Helmholtz free energy is considered to be
the sum of the mixing free energy and elastic free energy.23
˜ · ␶s + ␳s ␾s共f − as兲 + ⌸ f = 0
ⵜ 共50兲
T Based on the Flory-Huggins lattice theory, the change of the
and mixing free energy contained-in the Eulerian volume d⍀ in-
duced by changing the solvent-solvent or polymer-polymer
˜ · ␶ f + ␳ f ␾ f 共f − a f 兲 − ⌸ f = 0.
ⵜ 共51兲 contact into the solvent-polymer contact may be expressed as
T
hmd⍀ = Hmd⍀0 = kBTN f 关ln共1 − ␸兲 + ␹␸兴, 共56兲
Taking the summation of Eqs. 共50兲 and 共51兲, the Lagrangian
momentum equation for the biphasic mixture media, i.e., the where Hm is the Lagrangian true volume density of the mix-
bulk hydrogels, can be obtained, ing free energy, kB is the Boltzmann constant, N f is the total
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 174705-7 Phase transition for neutral thermosensitive hydrogels J. Chem. Phys. 127, 174705 共2007兲

molar number of solvent molecule contained in the Eulerian kBTv0e

volume d⍀, and ␸ ⬅ ␸s is the Eulerian volume fraction of He = 关␣21 + ␣22 + ␣33 − 3 − ln共␣1␣2␣3兲兴. 共64兲
2␣01␣02␣03
cross-linked polymer network 共the porous solid skeleton兲.
The polymer-solvent interaction parameter ␹ dependent on The coefficient kBT␯0e / 共2␣01␣02␣03兲 relates only to the initial
both the absolute temperature and the polymer-network vol- equilibrium swelling state when the hydrogel was just
ume fraction has the following form: formed. Taking partial differentiation of H = Hm + He with re-
spect to the absolute temperature, the Lagrangian true vol-
␹ = 共␦h − T␦s兲/共kBT兲 + ␹2␸ , 共57兲
ume density of the entropy of the biphasic mixture media is
where ␹2 is an experiment-based adjustable parameter, ␦s therefore derived,
and ␦h are the changes of the entropy and enthalpy per mo-
kBv0e
nomeric unit of the network, and the values of them are ␩0 = − 关␣21 + ␣22 + ␣23 − 3 − ln共␣1␣2␣3兲兴
0.518, −1.246⫻ 10−20 J, and −4.717⫻ 10−23 J / K, respec- 2␣01␣02␣03
tively, for the neutral thermosensitive hydrogel PNIPA.24,25 k B␾ f
The Lagrangian molar number density of solvent molecule − 关ln共1 − ␸兲 + ␹␾兴. 共65兲
␷
with respect to the Lagrangian volume d⍀0 is defined by
Applying H to the definition expression 关Eq. 共46兲兴 of the
n f = N f /d⍀0 = ␾ f /␷ , 共58兲
chemical potential of liquid phase ␮ f and the expression 关Eq.
where ␷ is the molar volume of the solvent molecule. For the 共48兲兴 of the effective stress tensor ␲eff, we then have
neutral thermosensitive hydrogel PNIPA, the Eulerian vol-
ume fractions of the solute 共cross-linked polymer network兲
and solvent 共interstitial water兲 contained in the Eulerian vol-
␮ f = p + k BT 再 1
␷
关ln共1 − ␸兲 + ␸ + ␹␸2兴

冋 兺冉 冊 册冎
ume d⍀ can be defined, 3
v 0␸ ⳵␣ j 1
␸ = ␰ns/共n f + ␰ns兲, ␸ = n f /共n f + ␰ns兲,
f
共59兲 + e0 J ␣j f − 共66兲
␸ j=1 ⳵␾ 2
where ns is the Lagrangian molar number density of the sol-
ute and ␰ Ⰷ 1 is the ratio of the molar volumes of the solute and
and solvent. Applying Eq. 共58兲 to Eq. 共56兲, the Lagrangian
true volume density of the mixing free energy is then ob- ␲eff
j = k BT 再 1
␷
关ln共1 − ␸兲 + ␸ + ␹␸2兴

冎
tained,
v0e ␸ 2 J
Hm = kBTn f 关ln共1 − ␸兲 + ␹␸兴 = kBT␷−1␾ f 关ln共1 − ␸兲 + ␹␸兴. + 共␣ − 1/2兲 , 共67兲
␸0 j 1 + 2E j
共60兲
where ␲effj represents the jth principal component of the ef-
From the affine network model, the change of the elastic free fective stress tensor. It should be noted that the repeated
energy contained in the Eulerian volume d⍀ for the aniso- subscripts j in Eq. 共67兲 do not mean summation.
tropically swollen hydrogels is For the special case of isotropic swelling or shrinking for
kBTv0e the neutral thermosensitive hydrogels, the three principal
hed⍀ = Hed⍀0 = 关␣2 + ␣22 + ␣23 − 3 components of the Green strain tensor are equal to each
2 ␣ 1␣ 2␣ 3 1
other. The chemical potential and the effective stress compo-
− ln共␣1␣2␣3兲兴d⍀, 共61兲 nent can then be simplified into
where ␯0e is the initial effective cross-link number density
and ␣ j 共j = 1 , 2 , 3兲 are the equilibrium swelling ratios along ␮ f = p + k BT 再 1
␷
关ln共1 − ␸兲 + ␸ + ␹␸2兴

冋冉 冊 册冎
the three principal axes of deformation which are defined by
␸ 1/3
␸
␸ 0
d⍀ d⍀ d⍀0 + v0e − 共68兲
␣ 1␣ 2␣ 3 = = = = J␣01␣02␣03 , 共62兲 ␸0 2␸0
␸ dV0 d⍀0 dV0
and

冉 冊 再
in which the quantities with superscript 0 refer to the initial
equilibrium swelling state when the hydrogels were just k BT ␸ 0 2/3
1
␲eff = 关ln共1 − ␸兲 + ␸ + ␹␸2兴
formed, ␣0j represents the equilibrium swelling ratio along 共 ␣ 0兲 2 ␸ ␷
the jth principal axis of deformation, dV0 is the initial vol-
ume of hydrogel, and ␸0 is the initial Eulerian volume frac-
tion of the cross-linked polymer network. From Eqs. 共3兲 and
+ v0e 冋冉 冊
␸
␸0
1/3
−
␸
2␸0
册冎 . 共69兲

共62兲, we can also derive An equilibrium swelling state will be achieved when
␣ j = 冑1 + 2E j␣0j 共j = 1,2,3兲. 共63兲 the chemical potential of the interstitial liquid inside the hy-
drogels is equal to that of the bathing solution, i.e., 共␮ f = ␮
¯f
Substitution of Eq. 共62兲 into Eq. 共61兲, the Lagrangian true = p兲. The corresponding condition of the equilibrium swell-
volume density of the elastic free energy is obtained, ing is
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 174705-8 Xiaogui Wang J. Chem. Phys. 127, 174705 共2007兲

law of thermodynamics. In the framework of the Flory mean

field theory, the explicit expressions of the constitutive rela-
tionships were derived from the Helmholtz free energy
formed by the elastic and mixing contributions. The closed
set of governing equations consists of one Lagrangian satu-
rated continuity equation 关Eq. 共15兲兴, three Lagrangian mo-
mentum equations for the biphasic mixture media 关Eq. 共52兲兴,
and three Lagrangian momentum equations for the fluid con-
stitute 关Eq. 共53兲兴. The fluid pressure, the displacement of the
bulk hydrogels, and the displacement of the fluid can be
selected to be the independent unknown variables by taking
into account of the explicit constitutive relationships. The
FIG. 1. Equilibrium swelling of the neutral thermosensitive hydrogel biphasic mixture theory proposed here has the ability to char-
PNIPA. acterize the nonlinear large deformation kinetics of the vol-
ume phase transition of the thermosensitive hydrogels
共␦h − T␦s兲␸ PNIPA.
ln共1 − ␸兲 + ␸ + ␹2␸3 +
k BT ACKNOWLEDGMENTS

+ ␷v0e 冋冉 冊
␸
␸0
1/3
−
␸
2␸0
册= 0. 共70兲
This research was funded by National Natural Science
Foundation of China under Grant No. 10502045 and Zhe-
jiang Provincial Natural Science Foundation of China under
The comparison of the isotropic swelling-shrinking curves, Grant No. Y606231.
which were obtained by the experiment26 and predicted by
the developed theoretical model 关Eq. 共70兲兴 of the neutral 1
2
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