International Journal of Solids and Structures 51 (2014) 44404451

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International Journal of Solids and Structures

journal homepage: www.elsevier.com/locate/ijsolstr

Mechanics of inhomogeneous large deformation of photo-thermal

sensitive hydrogels
William Toh a, Teng Yong Ng a, Jianying Hu b, Zishun Liu b,
a

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.

2008), intramolecular group transfer (Yang, 2008), dissociation

processes (Jiang et al., 2006; Yang, 2008) and change in crosslink
density (Jiang et al., 2006; Lendlein et al., 2005). Swelling of gels
typically takes place through the migration of solvent (Hong et al.,
2008; Toh et al., 2013) or ions (Hong et al., 2010; Toh et al., 2013)
through the polymer network, which constitutes a slow process.
However, it was reported that by incorporating light-absorbing
nano-particles (NPs) into a temperature sensitive hydrogel, photoinduced heating is able to achieve a much faster swelling rate
(Jiang et al., 2006; Suzuki and Tanaka, 1990; Yoon et al., 2012).
The phase transition of a temperature-sensitive hydrogel has
been widely observed and studied (Cai and Suo, 2011; Ding et al.,
2013). It is well accepted that hydrogels made of the same monomer, with the same crosslink density, will possess a unique transition temperature. However, it was shown that the phase transition
temperature of a temperature-sensitive hydrogel can be altered by
irradiation of light of varying intensities (Suzuki and Tanaka,
1990). It has also been reported that at a xed temperature below
the transition temperature, the gel is able to undergo phase transition by simply changing the intensity of light being irradiated on
the gel. Experimental ndings have proven the viability of photothermal sensitive hydrogels as a good material for remote controlling of devices in applications such as drug delivery (Sershen et al.,

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W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

2000), microuidics (Lo et al., 2011) and optical switching (Yoon

et al., 2012).
The photo-mechanics of light responsive polymer systems have
been extensively studied (Dunn and Maute, 2009; Dunn, 2007;
Long et al., 2011, 2009a,b, 2013; Mahimwalla et al., 2012;
Saphiannikova et al., 2009, 2011; Toshchevikov et al., 2012,
2011), but mainly as shape-memory polymers or liquid crystal
elastomer (LCE) systems. There is acutely limited literature on
the modeling of the mechanics and thermodynamics of photosensitive hydrogel systems.
Recent theories developed for hydrogels originate from traditional thermodynamics framework of energy balance and entropy
imbalance (Bowen, 1989; Truesdell, 1969). In view of the vast
literature available for the thermodynamics of deformation of a
swelling polymer network (Baek and Srinivasa, 2004; Chester
and Anand, 2010, 2011; Duda et al., 2010; Hong et al., 2008), we
will not repeat the highly involved classical derivations here, but
instead utilize the earlier results of these rigorous derivations to
advance the present theoretical model.
In the present study, we will develop a theory to model the
deformation of hydrogels due to photo-thermal effects by building
on earlier works on neutral gels (Hong et al., 2009; Toh et al.,
2013a,b) and temperature-sensitive gels (Ding et al., 2013). This
type of deformation mechanism is made possible through the
incorporation of light absorbing NPs into the temperature sensitive
polymers.
In what follows, Section 2 describes the thermodynamic
framework by expressing the stress and chemical potential in
terms of the free energy function. Section 3 specializes the free
energy function using the FloryRehner theory and describes
the physical constraints experienced by the gel. Section 4
describes the process of nite element (FE) implementation.
Section 5 investigates some potential applications of the present
theory and FE model, which include phenomena such as coexistent phases within the gel, its buckling during the deswelling
process, and its contact with a membrane in microuidic
applications.

2.2. Inhomogeneous large deformation of a temperature sensitive gel

With reference to Fig. 1, consider a gel subjected to geometrical
constraints, with an external weight of P hanging on the gel and
maintained in immersion with a solvent of chemical potential ls.
Concurrently, a monochromatic light is being irradiated onto the
gel. Using a thermodynamic approach on the irradiation, the light
possesses a non-zero chemical potential lp, produced by photochemical reactions (Ries and McEvoy, 1991; Herrmann and
Wurfel, 2005; Wurfel, 1982; Kelly, 1981; Haught, 1984).
In equilibrium, the weight is displaced by a distance dl, the
chemical potential is maintained by pumping dNs solvent molecules into the gel and the irradiation causes dNp photochemical
reactions at chemical potential lp. The work done on the gel would
be equal to the sum of the work done by the external weight, the
chemical potential pump and the irradiation, i.e. the sum of Pdl, lsdNs and lpdNp.
In a deformed state at any time t, a point originally at position
with reference coordinates XK relocates to the current position
with coordinates xi, we denote the deformation gradient by
Eq. (2), given by

@xi X K ; t
@X K

F iK

Thermodynamically, the change in free energy density of the gel

W, is balanced by the work done on the gel

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

Combining Eqs. (3) and (4), and applying the divergence

theorem, the equilibrium equation is re-written as Eq. (5),

Z 







@W
@W
@W
 siK dF iK
 ls dC s
 lp dC p dV 0
@F iK
@C s
@C p
5

2.1. Light irradiation induced temperature change

Due to the addition of light-absorbing NPs in the gel network,
light energy is converted into heat energy and transferred to the
polymer through local heat conduction. The use of different NPs
will result in different wavelengths required for absorption of
irradiation, with copper chlorophyllin absorbing best at 488 nm
(Suzuki and Tanaka, 1990), goldgold sulde at 1064 nm
(Sershen et al., 2000), gold nano-rods at 810 nm (Gorelikov et al.,
2004), graphene oxide at 808 nm (Zhu et al., 2012) and iron oxide
at 470 nm (Yoon et al., 2012).
Under irradiation, the temperature rise Dh is proportional to the
intensity I0 and polymer volume fraction /, as shown in the phenomenological Eq. (1) (Richardson et al., 2009; Suzuki and
Tanaka, 1990),

Dh a I 0 /

where a is the proportionality constant related to the heat capacity

of the gel.

Fig. 1. A hydrogel domain subjected to external weight P, exposed to an external

solvent of xed chemical potential ls, and irradiated with light.

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W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

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

Under steady state irradiation, X and Y will have concentrations

[X] and [Y] respectively. The afnity (free energy) associated with
one such chemical reaction, A, is given by (Parson, 1978)

3. Free energy function

From the approach of earlier works (Hong et al., 2009, 2008; Cai
and Suo, 2011; Ding et al., 2013), we assume that the free energy
density of the gel is the sum of the individual free energies of network stretch and mixing. For a photo-thermal sensitive gel, we
introduce an additional free energy density term due to photochemical reactions Wp, into the free energy density function of a
temperature sensitive hydrogel

WF; C s ; C p W s F W m C s W p C p

3.1. Free energies of network stretch and mixing

The free energy density of network stretch is taken to be (Flory,
1953)

Ws

This electronic transition can be represented as a series of two

consecutive chemical reactions, with the reactants being the
ground-state nano-particle (X) and a photon of relevant frequency
(hf), the intermediate product being the excited particle (Y), and
the product being the ground-state nano-particle and heat energy.
This series of chemical reactions is illustrated in Fig. 2 and written
as Eq. (11).

1
NkhF iK F iK  3  2 ln det F
2

A hf kh ln

 
Y
X

12

where hf corresponds to energy transition of the electron into the

excited state and the logarithmic term corresponds to the entropy
change associated with the transition.
The free energy density of the entire gel, Wp, resulting from
photochemical reactions is thus expressed as




Cp
W p C p hf kh ln
C g;0

13

where Cp = [Y] and Cg,0 = [X] is taken to be a nominal reference

value given that the concentration of excited particles is low
(Cp/Cg  1010) (Lavergne and Joliot, 2000).
3.3. Legendre transformation

where N is the number of crosslinks per unit reference volume of

the polymer network, kh the temperature in the unit of energy,
and det F the determinant of the deformation gradient.
The free energy density of mixing is assumed to take the Flory
Huggins form (Flory, 1942; Huggins, 1941)

As a standard approach to model hydrogels as hyperelastic

materials (Ding et al., 2013; Hong et al., 2009; Marcombe et al.,
^ which
2010), we introduce a new free energy density function W,
is obtained by a Legendre transformation of the free energy density
function W


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

where m the volume of a solvent molecule, v is the FloryHuggins

interaction parameter, which is dependent on polymer density /
and temperature. This relation is given by (Huggins, 1964)

vh; / v0 v1 /

10

where v0 = A0 + B0h and v1 = A1 + B1h, while A0, B0, A1 and B1 are

constants specic to the monomer. The temperature used in the calculation of the FloryHuggins interaction parameters is the real
temperature of the gel consisting of two parts, given by the equation h = h0 + aI0/, where h0 is the ambient temperature and aI0/ is
the temperature increment given in Eq. (1). In subsequent analyses,
all FloryHuggins interaction parameters are calculated based on
the real temperature, thus implicitly containing the temperature
increment due to irradiation.
3.2. Free energy of photochemical reaction
As the nano-particles absorb UV irradiation, molecular excitation occurs, promoting an electron to the next lowest unoccupied
orbital, with an energy jump corresponding to the product of the
Plancks constant and the frequency of the UV. The excited particle
decays back into the ground state immediately, thus releasing the
energy harvested during photon absorption.
For gold NPs (and other NP used for the purpose of photoheating), it has been shown that the quantum yield is of the order
of 106 (Dulkeith et al., 2004), resulting in a near unity conversion
of light energy into heat energy (Richardson et al., 2009).

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

Eq. (15) transforms the equilibrium Eq. (3) into

dWdV

Bi dxi dV

T i dxi dS

16

Eq. (16) is the equilibrium equation assumed by a hyperelastic

solid.
3.4. Constraint equations
During the deformation process, the stress induced is very
small, thus it is insignicant in relation to causing deformations
to the individual polymer and solvent molecules. Therefore the
volume of the swollen state is assumed to be equal to the sum of
the individual volumes of polymer and solvent components of
the gel. This assumption can be written as

1 mC s det F

17

Whilst the constituents of a temperature sensitive hydrogel

undergoes temperature changes and experience volumetric
changes due to thermal expansion/contraction, we note from the
order of magnitude of the coefcients of thermal expansion (see
Table 1) that the volumetric expansion of individual particles is
very small as compared to the volumetric change experienced during phase transition and therefore we assume that the effects from

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W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

Fig. 2. Excitation and decay of an atom absorbing a photon.

thermal expansion are negligible. This practice is also seen in

analyses of temperature sensitive gels (Birgersson et al., 2008;
Chester and Anand, 2011).
In photochemical reactions, the number of photons and chemical reactions is conserved, as dictated by the StarkEinstein equation, or second law of photochemistry (Rohatgi, 2006). The light
intensity is proportional to the amount of light energy absorbed.
In the irradiation of a material, the spatial distribution of photons
within a material follows the radiative transfer equation (Long
et al., 2013). However, we assume that at sub-millimeter dimensions, the spatial distribution of photochemical reactions taking
place within the gel is evenly distributed. This assumption can be
inferred from Eq. (1), as proportionality to / imply that the gel is
not optically thin, and the gel undergoing uniform temperature
change implies that there is no spatial distribution of photochemical reactions for gels of sub-millimeter dimensions.
The concentration of photochemical reactions is obtained by
considering conservation of energy, where all light energy is transformed into the rise in temperature of the system (Walker, 2009).
The amount of photonic energy released is the sum of energies
of all photons undergoing photo-excitation. For a monochromatic
light source of uniform frequency, this energy is equal to the product of the energy of a single photon with the number of photoexcited photons

E0 hf  C p

18

where E0 is a measure of the energy absorbed per unit reference

volume, h the Planck constant and f the frequency of irradiation.

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

Afroze et al. (2000)

Afroze et al. (2000)
Afroze et al. (2000)
Afroze et al. (2000)
Suzuki and Tanaka (1990)
Suzuki and Tanaka (1990)
Serway and Jewett (2013)
Barrow (2002)
Hong et al. (2008)
Birgersson et al. (2008)
Birgersson et al. (2008)
Serway and Jewett (2013)
Chester and Anand (2011)
Chester and Anand (2011)
Serway and Jewett (2013)

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

where c(g) = qgelcgel is the volumetric heat capacity, and J the

determinant of the deformation gradient, J = det F.
The volumetric heat capacity of the gel is taken to be the
volume weighted average of the constituents, i.e.



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

Substituting free energy functions into Eq. (14), we arrive at

Table 1
List of material parameters used in analysis.

The product hf measures the amount of energy possessed by a

single photon. The amount of thermal energy per unit reference
volume generated by the temperature rise is the product of mass,
specic heat and temperature change of the system, i.e.

" 

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

where I1 is the rst deviatoric invariant of the deformation gradient.

With the free energy density function, we are able to obtain an
explicit form of the nominal stress

#


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

"

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W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

Fig. 3. Gel in (a) dry state; and (b) reference state.

where HiK is the transpose of the inverse of the deformation

gradient, HiKFjK = dij. To convert the nominal stress into Cauchy
stress, we use the following relation

rij

siK F jK
det F

25

The Cauchy stress is thus given by

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

Fig. 4. Comparison of experimental (Suzuki, 1993) and analytical normalized

diameters of a free swelling gel. The discrete points correspond to experimental
data of gels with different amounts of copper chlorophyllin (Naming of experimental data set follows results presented by Suzuki (1993)), while the curves are
the analytical solutions of Eq. (27).

of the deformation gradient. Details of all required formulae in the

UHYPER subroutine are given in Appendix A.

3.5. Homogeneous state of free swelling

4.1. Phase transition of a photo-thermal sensitive hydrogel

Consider a dry cubic gel without any solvent imbibed in the

polymer network, the volume ratio of the gel is unity, J = 1. This
gives rise to a singularity in the free energy function. Therefore, a
second reference state of a freely swelling gel with mCs > 0 is
required, see Fig. 3. In the free swelling state, there is no stress
present (rik = 0) and the gel experiences stress free isotropic
stretches with k1 k2 k3 . Taking this free swelling state as the
reference, we denote the isotropic stretches as k0 , occurring at
the reference solvent chemical potential ls,0 and temperature h0
and exposed to light at intensity I0. In this conguration, Eq. (24)
becomes

The phase transition of temperature-sensitive hydrogels is a

commonly observed phenomenon, and has been widely studied
(Ding et al., 2013; Kondo et al., 1993; Suzuki and Ishii, 1999;
Suzuki and Kojima, 1994; Suzuki and Tanaka, 1990; Tanaka,
1978; Wang, 2007). The phase transition temperature is dependent
on several factors, including the crosslink density of the polymer
network (Harmon et al., 2003), the chemical potential of the solvent (Pastoor and Rice, 2012), and the intensity of light irradiation.
In the present study, we investigate the effects of varying light
intensity on the free swelling state of poly(N-isopropylacrylamide)
(PNIPAm) using the parameters listed in Table 1.
The values of A0, A1, B0 and B1 are material dependent and are
obtained by experimental tting (Afroze et al., 2000). Experimental
results have shown that for the same monomer, the addition of
chromophores will alter the swelling properties of the gel
(Suzuki, 1993), thus implying a change in the FloryHuggins interaction parameter (Caykara et al., 2006).
We dene a new FloryHuggins interaction parameter by introducing a factor e. to the experimental values obtained for a polymer
network without chromophores. Under this denition, we have

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

where v0 = A0 + B0h0, v1 = A1 + B1h0.

This homogeneous state of equilibrium serves as an initial condition during the FE analysis to circumvent the singularity in the
dry state. The variables in Eq. (27) are k0, h0, I0 and ls,0. Given
any three variables, we can nd the fourth using this equation, thus
providing the initial condition.
4. Finite element (FE) implementation
To facilitate the modeling and simulation of gel deformation
when subjected to external stimuli and constraints, we utilize
the powerful commercial FE numerical solver ABAQUS. Based on
earlier works which implement hydrogel properties as hyperelastic
materials (Ding et al., 2013; Hong et al., 2009; Marcombe et al.,
2010), we develop the user-dened subroutine UHYPER to carry
out FE analysis on the gel deformation. The denition of material
properties is based on the free energy function derived earlier in
Eq. (23) and its respective derivatives with respect to the invariants

v0;new ev0 A0 e B0 eh
v1;new ev1 A1 e B1 eh

28

Performing a curve tting process on the experimental results

reported, the FloryHuggins interaction parameters of the gel containing 5% and 8% copper chlorophyllin are obtained by multiplying the values A0, B0, A1 and B1 by a factor e = 0.78 and 0.85,
respectively, and the crosslink density corresponds to Nm = 0.004.
The change in transition prole is shown in Fig. 4, which shows a
comparison of experimental results with analytical results. Without any chromophores, the gel undergoes a discontinuous phase
transition as temperature is varied; and this is indicated by the
two turning points in the curve. The discontinuous phase transition
exhibits hysteresis phenomena which will be elaborated subsequently. Upon chromophore addition, it is evident that the two

4445

W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

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.

4.2. Effects of varying light intensity

In photo-thermal gels, the primary function of irradiation is to
create a temperature change in the temperature sensitive hydrogel. It might not appear obvious that light intensity plays a direct
role in the phase transition process but it does in fact affect the
transition. Experiments have shown that increasing the light intensity lowers the transition temperature and increases the tendency
for the gel to undergo a discontinuous phase transition (Suzuki and
Tanaka, 1990). Here we will rst study the effects of light intensity
on the free swelling. To verify that the FE subroutine developed is
numerically correct, we compare the simulation results with analytical results of free swelling by solving Eq. (27).
Fig. 5(a) shows that increasing intensity decreases the phase
transition temperature of the gel. In addition, the change in light
intensity may trigger a change in the mechanism of the phase transition from a continuous transition into a discontinuous one. For
continuous phase transitions, the FE analysis is able to fully simulate the entire transition process. In the case of discontinuous
phase transition, the simulations conclude when the turning points
are reached as the Newton method is not adapted to capture the
full resolution of the turning feature. When held at a constant temperature, phase transition takes place as we vary the intensity of
irradiation onto the gel. In Fig. 5(b), we hold temperature constant
and vary the light intensity from 0 to 300 mW. The curves obtained
show that an increase in light intensity decreases the transition
temperature and also increases the tendency for the gel to undergo
a discontinuous phase transition. These computed result shows
similar trends with experimental observations (Suzuki et al.,
1996; Suzuki and Tanaka, 1990; Suzuki, 1993).
The change in transition temperature and the existence of transition intensity suggests that in this photo-thermal deformation
process, irradiation does not simply act as a heating agent to
initiate temperature sensitive deformation, but also has a second
function to alter the phase transition pathway.

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.

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W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

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

irradiation. As light is being irradiated on the middle portion of

the rod, the exposed portion starts to undergo phase transition.
The process takes place under an isothermal condition of 308 K.
Axisymmetric four-node CAX4 elements were used for the mesh.
Fig. 8 shows the simulation results which successfully captures
the state of deformation when the gel is subjected to light with
different intensities. Under increasing intensities, the extent of
deswelling of the exposed rod increases. As the middle portion
shrinks, the interface between the two phases experiences tension,
which changes the proportion of the radial dimensions of the two
phases.
It should be noted, however, that the parameters used in this
simulation causes continuous phase transition, thus allowing the
simulation to be completed. Certain combinations of parameters
cause discontinuous phase transition and does not allow nite element analysis beyond the instability points.
5.2. Buckling due to deswelling phase transition
The wrinkling of hydrogel layers has been studied intensively,
mainly in the context of the swelling of neutral hydrogels and

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.

W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

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.

non-homogeneous polymer concentration. In this study, we study

the instabilities that arise in a constrained homogenous gel disc
and try to bridge this gap for the buckling of a deswelling gel with
homogeneous polymer concentration. Specically, we will investigate the wrinkling induced when a photo-thermal sensitive gel is
being irradiated.
A thin annulus ring with variable inner radius is studied to
investigate wrinkling phenomenon due to gel deswelling. The
thickness of the gel is xed at H and the outer radius of the annulus
is xed at 30H, as shown in Fig. 9. The inner radius is then varied at
Ri/H = 2, 5 and 10 to investigate the effects of geometry on the stability and wrinkling pattern of the gel. Eight-node brick elements
C3D8 were used in the simulations. To initiate the instability, we
introduce a small perturbation to the mesh in the form of a small
displacement to a random node.
With varying values of Ri/H, we observe that the thin annulus
buckles into different mode shapes, as shown in Fig. 9. This shows
that the buckling of gel sheets can be controlled simply by geometrical constraints, in addition to prescription of non-homogeneous
polymer concentrations. The presence of instabilities, when wellunderstood, provides a basis for potential utilization of the various
buckling modes in a diverse array of applications, such as microuidics, thin lm metrology, tunable wetting and particle sorting
(Chen and Yang, 2012).
5.3. Application in microvalves

temperature sensitive hydrogels. Moreover, most of earlier studies

are based on the swelling induced instabilities, with most studies
focusing on thin hydrogel lms (Hu et al., 2014; Liu et al., 2011,
2010; Mora and Boudaoud, 2006; Yang et al., 2010; Zhang et al.,
2014; Toh et al. 2014), surface instabilities (Huang and Suo,
2002; Huang et al., 2004; Wu et al., 2013; Zalachas et al., 2013)
and bifurcation (Ding et al., 2013; Okumura et al., 2014). In a
photo-thermal gel, a deswelling is more likely to take place as
the gel is suddenly being irradiated with light. There is currently
a lack of literature focusing on the wrinkling of gel layers due to
deswelling action. Thin gel discs have been demonstrated to be
able to transit into programmable congurations of buckling mode
shapes during unconstrained deswelling (Klein et al., 2007).
However, the tests were conducted on gels prescribed with

The large deformation present during irradiation of light to a

photo-thermal gel makes it a useful material as a remotely controlled ow regulator. Without irradiation exposure, the ow passage is blocked by the gel. Upon irradiation, the gel shrinks thus
allowing the liquid to ow across the channel. We study the deformation process of such an application using the FE model presently
developed. In this example, we investigate a hybrid hydrogelmembrane microuidic valve (He et al., 2012; Moore et al.,
2000), where a membrane in contact with a hydrogel is used to
control ow across an orice located directly below center of the
gel, see Fig. 10.
In this application of the photo-thermal gel, the gel is initially
not exposed to irradiation, and the gel is in a swollen state which

4448

W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

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.

prevents uid ow across the orice. However, as the gel is being

exposed to irradiation, the gel shrinks and thus removing the
blockage in the orice and allows ow. This action of shrinking
and swelling is reversible and thus would be a suitable material
as a ow control valve. In the valve, a gel originally in the dry state
is placed in contact with the membrane. There are no deformations
in the membrane. Next, the gel is being exposed to solvent of
chemical potential of l = 0 to reach the swollen state. This swollen
state inhibits ow in the channel. As the gel is being irradiated,
shrinkage occurs and unblocks the orice, thus allowing for ow
across the channel.
Using axisymmetric four-node elements, Fig. 11 illustrates the
simulation results of the deformation of the gel as it is being irradiated. The capability of presently developed FE model to capture
the gel deformations across various light intensities is clearly evident. Fig. 11(a) shows the valve being prepared by rst setting a
dry (l0 = 0.5) cylindrical gel in contact with the membrane,
while Fig. 11(b) shows the swollen gel at equilibrium with the
solvent of chemical potential l = 0. The swollen gel causes the
membrane to block the opening of the orice, thus restricting
ow. In Fig. 11(c), the gel deswells under 15 mW irradiation,
and in Fig. 11(d), it deswells further under 60 mW irradiation, and
is restored to a strain-free state. Although similar mechanisms

have been applied using pH-sensitive hydrogels, the slow

response mechanism of pH-sensitive hydrogels limits their application, whereas these photo-thermal gels would be a more viable
option as a microuidic valve.

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

W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

of photo-thermal sensitive gels with complex geometries. This is

shown through the analysis of deformation of the gel in coexistent
phases, buckling due to the deswelling action and a hybrid hydrogel-membrane light actuated microuidic valve.

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

Due to limitations of the UHYPER subroutine, only one loading

parameter can be applied in the form of a temperature eld. Therefore simulations are made by varying one eld (either temperature,
light intensity or chemical potential) and keeping the other two
xed.
The required loading parameter is thus represented by temperature in Abaqus. For example, to simulate effects of change in
chemical potential at xed temperature and intensity, we represent chemical potential as a temperature eld, with the xed
values of temperature and intensity as material inputs, together
with the crosslink density.

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W. Toh et al. / International Journal of Solids and Structures 51 (2014) 44404451

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