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International Journal of Solids and Structures Volume 51 Issue 25-26 2014 (Doi 10.1016 - J.ijsolstr.2014.09.014) Toh, William NG, Teng Yong Hu, Jianying Liu, Zishun - Mechanics of Inhomogeneous La
International Journal of Solids and Structures Volume 51 Issue 25-26 2014 (Doi 10.1016 - J.ijsolstr.2014.09.014) Toh, William NG, Teng Yong Hu, Jianying Liu, Zishun - Mechanics of Inhomogeneous La
School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
International Center for Applied Mechanics, State Key Laboratory for Strength and Vibration of Mechanical Structures, Xian Jiaotong University, Xian 710049, Peoples Republic
of China
b
a r t i c l e
i n f o
Article history:
Received 26 April 2014
Received in revised form 21 August 2014
Available online 5 October 2014
Keywords:
Photo-thermal sensitive hydrogel
Hyperelasticity
Large deformation
Phase transition
a b s t r a c t
A polymer network can imbibe copious amounts of solvent and swell, the resulting state is known as a
gel. Depending on its constituents, a gel is able to deform under the inuence of various external stimuli,
such as temperature, pH-value and light. In this work, we investigate the photo-thermal mechanics of
deformation of temperature sensitive hydrogels impregnated with light-absorbing nano-particles. The
eld theory of photo-thermal sensitive gels is developed by incorporating effects of photochemical heating into the thermodynamic theory of neutral and temperature sensitive hydrogels. This is achieved by
considering the equilibrium thermodynamics of a swelling gel through a variational approach. The phase
transition phenomenon of these gels, and the factors affecting their deformations, are studied. To facilitate the simulation of large inhomogeneous deformations subjected to geometrical constraints, a nite
element model is developed using a user-dened subroutine in ABAQUS, and by modeling the gel as a
hyperelastic material. This numerical approach is validated through case studies involving gels undergoing phase coexistence and buckling when exposed to irradiation of varying intensities, and as a microvalve in microuidic application.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
A three dimensional polymer network is formed by the covalent
crosslinking of polymer chains. When immersed in an aqueous
solution, the network swells due to absorption of the solution.
The resultant swollen state is known as a hydrogel. Light-sensitive
hydrogels are gaining popularity amongst researchers due to the
attractive properties of light being able to stimulate the gel remotely and precisely. Potential applications of light-sensitive gels
include, but are not limited to, photo-actuators (Mahimwalla
et al., 2012), photo-robotics (Mahimwalla et al., 2012), photopatterning (Kim et al., 2012) and articial muscles (Takashima
et al., 2012).
Depending on the type of photo-sensitive particle (photochrome) present, there will be different types of mechanisms
causing the deformation of the gel. The mechanisms of photoinduced deformation include pericyclic reaction (Yang, 2008),
cistrans isomerization (Finkelmann et al., 2001; Jiang et al.,
2006; Yang, 2008), intramolecular hydrogen transfer (Yang,
Corresponding author.
E-mail address: zishunliu@mail.xjtu.edu.cn (Z. Liu).
http://dx.doi.org/10.1016/j.ijsolstr.2014.09.014
0020-7683/ 2014 Elsevier Ltd. All rights reserved.
4441
@xi X K ; t
@X K
F iK
dWdV
Here we shall describe the mechanism of a hydrogel by considering the change in temperature due to light irradiation, as well as
the inhomogeneous large deformation theory for thermallysensitive hydrogels.
Bi dxi dV
T i dxi dS ls
dC s dV lp
dC p dV
3
where Cs and Cp represent the concentration of solvent and photochemical reactions in the reference state respectively.
Assuming that the free energy density in the current state is
dependent on the state of deformation, concentration of solvent
and photochemical reactions within the gel, i.e. W = W(FiK, Cs, Cp),
a small change in the free energy density can be written as
dW
2. Theoretical development
@W
@W
@W
dF iK
dC s
dC p
@F iK
@C s
@C p
Z
@W
@W
@W
siK dF iK
ls dC s
lp dC p dV 0
@F iK
@C s
@C p
5
Dh a I 0 /
4442
where siK is the nominal stress. This equation holds for arbitrary values of dFiK, dCs and dCp, which reduces the conservative form into
the differential form
@W
@F iK
@W
ls
@C s
@W
lp
@C p
siK
X hf ! Y
11
Y ! X heat
WF; C s ; C p W s F W m C s W p C p
Ws
1
NkhF iK F iK 3 2 ln det F
2
A hf kh ln
Y
X
12
Cp
W p C p hf kh ln
C g;0
13
W m kh C s ln
^ W l Cs l Cp
W
s
p
mC s
vC s
1 mC s 1 mC s
9
vh; / v0 v1 /
10
14
where a small change in this free energy density function will yield
the following relation
^ siK dF iK C s dl C p dl
dW
s
p
15
dWdV
Bi dxi dV
T i dxi dS
16
1 mC s det F
17
4443
E0 hf C p
18
Parameter
Value
Reference
A0
B0
A1
B1
12.947
0.04496 K1
17.92
0.0569 K1.
0.6 Km2 W1
488 nm
2.998 108 ms1
6.626 1034 m2 kg s1
1028 m3
4.18 106 Jm3 K1
2.4 107 Jm3 K1
3.44 106 Jm3 K1
77 106K1
67 106 K1
17 106 K1
f
c
h
m
c(polymer)
c(w)
c(cu)
a(p)
a(w)
a(Cu)
E0 qgel cgel Dh
19
Substituting the relations mgel = qgelJ and Dh = aI0/J into Eq. (19),
the thermal energy can be re-written as
E0 cg
aI 0
20
cg fccu 1 fcpolymer / cw 1 /
|{z}
21
cnetwork
where c(cu), c(polymer) and c(w) are the volumetric heat capacities
of copper, polymer and water, respectively. The volumetric heat
capacity of the dry network, c(network) is calculated using the rule
of mixtures consisting polymer molecules and copper chlorophyllin molecules with volume fractions (1 f) and f respectively.
Combining the two equations above, we obtain an expression
for Cp in terms of swelling ratio and light intensity
"
#
cw cnetwork cw aI0
Cp
J
hf
J2
22
Table 1
List of material parameters used in analysis.
"
h
i
^ 1 Nkh J 23I1 3 2 lnJ kh J 1 ln J 1
W
2
J
m
"
#
w
network
w
aI0 c
c
c
J1
ls
kh
hf
J
m
J2
v0
J
v1
!#
J2
23
#
J1
1 v0 v1 2v1
siK NkhF iK HiK
ln
3 JHiK
J
J
m
J2
J
"
#
network
w
w
aI0 2c
c c
l
kh
2 JHiK s JHiK
24
hf
m
J3
J
kh
"
4444
rij
siK F jK
det F
25
rij
"
#
Nkh
kh
J1
1 v v
2v
0 2 1 3 1 dij
F iK F jK dij
ln
J
J
J
m
J
J
"
!#
aI0 network w 2 w 1
l
dij s dij
kh
c
c 3c
26
hf
m
J
J2
ls;0
kh0
Nm
k30
k20 1 ln 1
1
k30
"
#
maI0 2 cp cw cw
6
hf
k90
k0
1
k30
v0 v1
k60
2v1
k90
27
v0;new ev0 A0 e B0 eh
v1;new ev1 A1 e B1 eh
28
4445
stationary points are not present, indicating that the gel undergoes
a continuous phase transition. In addition to stabilizing the phase
transition process, the addition of chromophores also increases
the phase transition temperature, and this is corroborated by the
higher curves Fig. 4 for higher chromophore concentration.
4.3. Hysteresis
Depending on values of the various factors discussed in the
preceding sections, the swellingdeswelling process of a hydrogel
may undergo hysteresis (Suzuki et al., 1996). From the plots
presented in Fig. 6, we see two different types of curves, one that
is monotonic, as shown in Fig. 6(a), and one that possesses stationary points, as shown in Fig. 6(b). The former monotonic curve
represents a smooth transition between the different phases,
whereas the latter curve suggests signs of hysteresis during the
swellingdeswelling process.
It was demonstrated that deformation caused by one stimulus
(light or heat) can be reversed by application of the other stimulus
(Suzuki et al., 1996). This property provides useful applications in
the area of optical switching where one stimulus can be used to
activate the switch, and the other to deactivate the switch.
4.4. Internal stress in a constrained gel
We now consider a gel, initially at a stress-free state of k0 which
is constrained on both lateral sides and allowed to deform only in
the longitudinal direction. Deformation is triggered by varying
light intensity at an isothermal condition. In the deformed state,
the stretches are k1 k2 k0 , whereas k3 is a variable. The in-plane
stresses are r1 = r2 = r while r3 = 0 as the gel is allowed to swell
freely in the 3-direction. With these denitions, Eq. (27) becomes
Nm
k20 k3
Nm
k20 k3
k23 1 n
29a
k20 1 n
29b
where n ln 1
1
k20 k3
1
k20 k3
v0 v1
2
k20 k3
2v 1
k20 k3
"
#
aI0 2 cp cw
cw
l
m
s
3
2
2
2
hf
kh
k k
k k
0 3
0 3
Eq. (29a) gives the longitudinal stretch while Eq. (29b) gives the
in-plane stress present in the gel at various light intensities.
Fig. 5. Parametric study of effects of changing light intensity on the phase transition path. The gels of crosslink density Nm = 0.01 are irradiated with light of wavelength
488 nm. The curves show the analytical results, while discrete points show the numerical results. (a) Light intensity is kept constant at I0 = 0, 40 and 80 mW while
temperature of the gel is varied from 293 to 313 K; and (b) Temperature of gel is kept constant at h0 = 300, 302, 304, 306 and 308 K as light intensity is varied from 0 to
300 mW.
4446
Fig. 6. (a) Continuous phase transition; (b) Discontinuous phase transition exhibiting hysteresis. The arrows above the curve represent the direction of deswelling and arrows
below the curve represent the direction of swelling.
From Fig. 7, we can see that a photothermal gel at xed deformation experiences a tensile internal stress when exposed to irradiation. As compared to the case of free swelling, the gel deswells
more in the case of constrained swelling.
5. Numerical examples
5.1. Coexistent phases of gel deformation
During the deformation process of a gel under external constraints, a part of the gel may undergo phase transition while other
parts remain in the original phase. This is known as the coexistent
phase where the collapsed gel is able to exist with the uncollapsed
gel. Although an analytical approach is possible by solving the governing equations (Eshelby, 1956) for temperature sensitive hydrogels (Cai and Suo, 2011), the phenomenon of coexistence within a
gel is a complex one and often requires numerical methods to predict the overall self-consistent behavior.
Here we will attempt to employ the developed FE formulation
to study this phenomenon. Consider a hydrogel rod immersed in
water (ls,0 = 0), xed at both ends and originally unexposed to
Fig. 7. A gel in contact with solvent with chemical potential ls,0 = 0 and maintained at h0 = 300, 302, 304, 306 and 308 K undergoing uni-axial deformation at various light
intensities. The gel experiences a (a) longitudinal stretch and (b) in-plane stress.
4447
Fig. 8. Cross-section view of a gel (Nm = 0.005, e = 0.78) subjected to irradiation of different intensities at 308 K. The contour plots show the deformation in the radial
direction.
Fig. 9. Contour plot of vertical displacement, l3of gel rings of (a) Ri/H = 2; (b) Ri/
H = 5; and (c) Ri/H = 10. Different wrinkling mode shapes are exhibited for various
radius-to-height ratios. Parameters used are Nm = 0.005, e = 0.78 subjected to
irradiation at 308 K.
4448
Fig. 10. (a) Conguration of valve when gel is not being irradiated, gel is swollen and blocks the orice, restricting ow; (b) Conguration of valve when gel is irradiated, gel
deswells and thus allowing ow across orice.
Fig. 11. Contour plot of the normal displacement of gel with parameters Nm = 0.005 and h0 = 308 K.
6. Concluding remarks
This paper proposes a eld theory of photo-thermal sensitive
gels by incorporating effects of photochemical heating into the
thermodynamic theory of neutral and temperature sensitive
hydrogels. The phase transition of the gel and its dependence on
light intensity are studied. The eld theory is implemented
through the development of a user-dened subroutine in a nite
element solver by modeling the material as a hyperelastic material.
Verication of the nite element formulation and source code is
performed by comparison with analytical results for the case of
free swelling of cubic gel. However, the nite element analysis cannot be completed for cases with discontinuous phase transitions as
the solution method is unable to overcome the turning point of the
instability. Furthermore, through several examples, we demonstrate that the developed eld theory and the nite element formulation can accurately and efciently predict the deformation
4449
f
@2 W
@J02
Appendix A
Supplementary information for details of the free energy function and its derivatives in the nite element implementation.
Due to singularity in the dry state, we assume an initial free
swelling condition of
k0
6
F0 4 0
0
0
k0
0
7
05
k0
Relative to the initial free swelling state, the current deformation of the gel is, as measured by ABAQUS, F0 . To obtain the actual
deformation gradient of the gel, we write F = F0 F0.
Therefore, in all subsequent implementation in ABAQUS, we
write J J 0 k30 ; where J denotes actual swelling ratio and J0 denotes
swelling ratio used in ABAQUS. The non-dimensionalized free
energy density is thus re-written as
(
^
i
mW
1 h 2 023
h
Nm k0 J I1 3 2 ln k30 J 0 k30 J 0 1
k
2
2
0
13
3 0
k
J
1
v
v
4ln 0 3 0 @ 30 0 1
2 A5
k0 J
k0 J
k30 J 0
)
"
!
!#
30
aI0 p w
1
1
w
~ s k0 J 1
c
l
m
c c
hf
k30 J 0
k60 J 02
4
1
Nm
N mk20 J 03I1 02
9
J
k30
2v0 v1
6v1
6 04
J 0 k30 J 0 1 J 02
k30 J 03
k0 J
"
!
!##
aI0 p w
6
2
w
c
h
m
c c
hf
k60 J 04
k30 J 03
Acknowledgments
The authors also would like to express their appreciation to
Nanyang Technological University (NTU) and Institute of High
Performance Computing (IHPC) for providing all the necessary
supercomputing resources. The authors are also grateful for the
support from the National Natural Science Foundation of China
through grant numbers 11372236 and 11321062.
"
f
@2 W
0
@I1 @I2
f 1
@2 W
2 013
h
N
m
k
J
0
3
@I1 @J
f
@2 W
0
@I2 @J
Third derivatives
f
@3 W
0
2
@ I1 @J
f
@3 W
0
2
@ I2 @J
f
@3 W
0
@I1 @I2 @J
f
4
@3 W
1
N m k20 J 03 h
2
9
@I1 @J
f
@3 W
0
2
@ I2 @J
f
@3 W
@J 3
7
4
Nm
Nmk20 J 03I1 2 0
27
J3
!
2 6v0 v1 24v1
0
60
2
J3
k0 J 5
k30 J 0 4
J 02 k30 J 0 1
"
!
!##
aI0 p w 24
6
w
m
c
h
c c
hf
k60 J 0 5
k30 J 0 4
k30 2k30 J 0 1
First derivatives
f 1
@W
2 023
h
N
m
k
J
0
2
@I1
f
@W
0
@I2
For the initial condition of k0 , we solve Eq. (27) at initial temperature h0, initial light intensity I0 and chemical potential l0.
f 1 2 01
@W
2
Nm k20 J 3I1 0
0
2
3
@J
J
"
#
k3 J 0 1 1 v v
2v
k30 ln 0 3 0 0 0 3 02 1 6 031 l k30
J
k0 J
k0 J
k0 J
"
!
!#)
aI0 p w
2
1
w
c
h
m
c c
hf
k60 J 03
k30 J 02
l0
Second derivatives
2f
@ W
0
@I21
f
@2 W
0
@ I22
kh
Nm
k30
k20 1 ln 1
"
maI0
hf
cp cw
2
J
1
k30
cw
1
k30
1
v0 v1
!#
k60
2v1
k90
J2
4450
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