Mechanics of Materials 36 (2004) 411420

www.elsevier.com/locate/mechmat

Coupled chemo-electro-mechanical formulation for ionic

polymer gelsnumerical and experimental investigations
a,*
Thomas Wallmersperger plin a, Rainer W. G
, Bernd Kro ulch b,1

a
Institut f
ur Statik und Dynamik der Luft- und Raumfahrtkonstruktionen, Universitat Stuttgart, Pfaenwaldring 27,
D-70569 Stuttgart, Germany
b
Physiologisches Institut II, Universitat T
ubingen, Gmelinstr. 5, D-72076 Tubingen, Germany
Received 10 June 2002; received in revised form 8 November 2002

Abstract

Polyelectrolyte gels consist of a network of crosslinked polymers with attached electric charges and a liquid phase.
Variations of the chemical milieu surrounding the gel or application of an external electric eld lead to a change in the
swelling ratio of the gels. This phenomenon may be used for contraction and relaxation of chemo-electro-mechanical
actuators and in particular of articial muscles. In this paper electrically stimulated polymer gels, placed in a solution
bath, are investigated. For these gels, we present a volume- and surface-coupled chemo-electro-mechanical multi-eld
formulation. This formulation consists of a convectiondiusion equation describing the chemical eld, a Poisson
equation for the electric eld and a mechanical eld equation. The model is capable to describe the local swelling and
deswelling of ionic polymer gels as well as the ion concentrations and the electric potential in the gel and in the solution.
A chemo-electric simulation is performed for a gel ber at a given electric eld; the anionic and cationic ion concen-
trations as well as the electric potential inside and outside the gel are computed for a given number of bound anionic
groups. The resulting increase in the concentration dierences on the anode side of the anionic gel can be considered as
an indicator for a higher swelling ratio of the gel ber. Mechanical and electrical measurements on anionic polyelec-
trolyte gels are in good agreement with the numerical results. This demonstrates the validity of the employed numerical
model.

2003 Elsevier Ltd. All rights reserved.

Keywords: Polyelectrolyte gels; Chemo-electro-mechanical multi-eld formulation; Numerical simulation; Microelectrode technique;
Donnan potential; Ion concentrations; Osmotic pressure; Bending motion

1. Introduction

Certain polyelectrolyte gels are distinguished by

*
Corresponding author. Tel.: +49-711-685-2484; fax: +49-
711-685-3706.
E-mail addresses: wallmers@isd.uni-stuttgart.de (T. Wall-
mersperger), rw.guelch@uni-tuebingen.de (R.W. G ulch).
1
Tel.: +49-7071-29-73421; fax: +49-7071-29-5074.
enormous swelling capabilities under the inuence
of external physical and chemical stimuli. No other
kind of material attains comparable volume ex-
pansiveness. These unique properties make them
most attractive candidates for a new promising
generation of pseudomuscular actuators. The

0167-6636/$ - see front matter
2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0167-6636(03)00068-1
412 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420
Fig. 1. Schematic drawing of a polymer network with xed
anionic groups and mobile counter-ions.
typical architecture of a polyelectrolyte gel consists
of a network of crosslinked polymers to which
electric charges are attached. Suitable polyelec-
trolyte gels can be synthesized by crosslinked co-
polymerisation of weakly ionisable comonomers
often bonded chemically in a polymer network (see
Fig. 1).
Variations in the surrounding chemical milieu
or exposition to an external electric eld may in-
duce changes in the degree of ionisation of the
polyelectrolyte gel and in the distribution of ions
within the gel entailing a change in the swelling
capacity of the gel. The characteristic deforma-
tions of polyelectrolyte gels under the inuence of
external elds lead to reversible bending. In the
present study we want to model the mechanisms
behind the eect of external electric elds on ionic
polyelectrolyte gels leading to spatially dierent
swelling and deswelling and thus to bending mo-
tions. In contrast to various studies in this eld
assuming a constant Donnan potential throughout
the polyelectrolyte gels we investigate a coupled
chemo-electro-mechanical formulation which is
capable to describe the local swelling of a gel on
the basis of concentration dierences at the com-
plete gelsolution interface.
2. Chemo-electro-mechanical multi-eld formula-
tion
The dynamic behavior of ionic polymer gels in
electric elds has been investigated quasi-statically
by Doi et al. (1992), Shiga and Kurauchi (1990),
Shahinpoor (1995). Brock et al. (1994) have given
a coupled formulation for the ion-dynamics and a
theory for large displacements. Nemat-Nasser and
Li (2000) have presented an electro-mechanical
model for ionic polymer metal composites, while,
Neubrand (1999), Grimshaw et al. (1990), de
Gennes et al. (2000), Wallmersperger et al. (2001)
have published electro-chemical and electro-
mechanical formulations for ion-exchange mem-
branes and ionic gels.
In this section, a coupled chemo-electro-
mechanical multi-eld formulation will be pre-
sented to obtain a more precise insight into the
phenomena occurring in polyelectrolyte gels. The
ion concentrations and the electric eld can be
calculated by the chemical and electrical eld
equations. Based on the concentration dierences,
the swelling behavior of the polymer gels can be
described by the mechanical eld equation.
2.1. Chemical eld
The chemical eld is described by the convec-
tiondiusion equation for all the species a
c_ a Da ca;i za ca la W;i
;i  ca vi ;i ra ca 1
where ca is the concentration of the species a; Da ,
the diusion constant; la , the unsigned mobility;
za , the valence of the ions; W, the electric potential;
v, the convective velocity; ra , the source term re-
sulting from the chemical conversion.
The equation consists of
a diusive term resulting from the concentration
gradients,
a migrative term which stems from the gradient
in the electric potential,
 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420 413

a convective term which originates from an ap- rij Cijkl 
kl 

kl 5
plied convection of the solvent,
and a source term. where r is the stress tensor; , the strain tensor;
,
the prescribed strain; u, the displacement un-
The convectiondiusion equation (1) is an knowns; C, the elasticity tensor; f , the friction
elliptic PDE of rst order in time representing coecient; b, the body forces.
the conservation of mass and charge.
2.4. Coupling
2.2. Electric eld
The force equilibrium in the gel network can be
given by the electrostatic forces, the osmotic for-
The electric eld is described by the Poisson
ces, the cohesion between polymer and solvent and
equation
the viscoelastic restoring forces. All these forces
F X
Nf Nb
can be seen as a contribution to the inducement of
W;ii  za ca 2 a prescribed strain
.

r
0 a1
In our model we restrict to the concentration
where
0 is the permittivity of free space,
0 dierences between gel and solution resulting in an
8:8542  1012 A s/(V m);
r , the dielectric con- osmotic pressure dierence. This osmotic pressure
stant; F , the Faraday constant, F NA  e 96487 dierence can be given as
C/mol; Nf , the number of freely movable species; X
Nf


Nb , the number of bound species. Dp RT cs g
a  ca 6
The electric eld equation (2) is an elliptic PDE a1

in space. The velocity of propagation is much The normalized form as a measure for the local
higher in the electric eld than in the chemical swelling can be expressed by
eld. Hence, the quasi-static form of the Poisson
Dp X f
N

equation is sucient. Eq. (2) is based on the sec- p
D~ cag  cs
a 7
ond and fourth Maxwell equation. RT a1

The condition of neutrality From Eq. (5) follows

NX
f Nb rij Cijkl
kl  g~kl D~
p where

kl g~kl D~
p 8
za ca 0 3
a1
So, the prescribed strain
 can be given by the
normalized osmotic pressure D~ p multiplied by the
is obtained when W;ii in Eq. (2) is identical to zero. material parameters ~g.
This condition is satised in the whole domain (gel
and solution) outside the small region of the 2.5. Coupling strategy
boundary layer.
The chemo-electro-mechanical multi-eld for-
2.3. Mechanical eld mulation consists of a system of coupled PDEs:

Usually, dynamic processes are described by
partial dierential equations of second order in
time. Due to the relatively slow swelling process,
the inuence of the inertia term is very small; the
term of second order in time is therefore neglected.
Hence, the mechanical eld is described by a PDE
of rst order in time.
f u_ i rij;j qbi
the convectiondiusion equation (1) for the
concentrations ca of all species a,
the Poisson equation (2) for the electric poten-
tial W,
and the equation of motion (4) for the displace-
ment unknowns u.
Considering the coupled chemo-electric eld
4 only, for the (Nf Nb ) concentration unknowns
414 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420

and for the unknown electric potential, the
(Nf Nb ) convectiondiusion equations and the
Poisson equation are solved simultaneously (see
Fig. 2). The characteristics of the coupled formu-
lation are given in Table 1.
In order to obtain the deformation of the gel,
the equation of motion has to be solved subse-
quently to the chemo-electric eld (see Fig. 3). The
dierential osmotic pressure, resulting from the
concentration dierences of the mobile ions at
the gelsolution interface has to be used as an
input for the equation of motion. This pressure
dierence can be regarded as an external force or
as a kind of prescribed strain inside the gel.
3. Numerical simulation of electrical stimulation
In this section, electrical stimulation of an
electrolyte polymer gel ber is investigated.
The testcase is conducted for a xed gel ber
(4 10 mm2 ) with a concentration of bound an-
ionic groups cA 5 mM, placed between two
electrodes in a solution bath (50 50 mm2 ) having
s s
a concentration of cNa cCl 1 mM (see Fig.
4). The boundary conditions for Na and Cl in
the solution near the electrodes are set to
cNa cCl 1 mM. Since the concentrations of
H and OH ions are very small, they can be ne-
glected. An electric potential in the solution of

concentrations
convection-diffusion equations

bound ions A-
...
initial conditions output
boundary conditions Na + (actual solution)
Cl -
freely movable ions
OH -
H+
...

electric field
electric potential

Fig. 2. Chemo-electric coupling scheme.

Table 1
Characteristics of the coupled chemo-electric formulation
Unknowns/equations Number Eq. no.
Concentration, ca Nf Nb
Electric potential, W 1
Electric current density, j (1) postprocessing
Convectiondiusion equation Nf Nb Eq. (1)
Neutrality condition 0 Eq. (3)
Poisson equation 1 Eq. (2)
Faraday equation (1) postprocessing Eq. (9)

Transition conditions
Concentration gelsolution None
Electric potential None
Features One single integration domain for gel and solution
 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420 415

influence
coupling
initial conditions

concentrations boundary conditions

convection-diffusion equations

bound ions A-
...

Na +
Cl -
freely movable ions
OH -
H+
...

electric field equation of motion

electric potential
displacement

Fig. 3. Chemo-electro-mechanical coupling scheme.

)100 mV near to the cathode and of +100 mV near
to the anode is prescribed.
As the gel domain is xed, only the coupled
chemo-electric eld is considered. The convective
velocity of the solvent v equals zero and changes in
dissociation are neglected. Due to the large num-
ber of unknowns, a multi-grid (MG) method using
96 96 elements in space on 5 MG levels has been
applied for the computations. In order to obtain a
high resolution even in the small region of the
boundary layer at the gelsolution interface, an
adaptive mesh renement has been applied.
The stationary solution of the same testcase
without an external electric eld has been taken as
gel
- +
cathode
solution
0 0.01 0.02 0.03 0.04 0.05
x [m]
Fig. 4. Polymer gel in a solution bath under an applied electric
eld.
initial condition for this testcase. The concentra-
tions of Na and Cl in the whole gel region were
g g
set to cNa 5:193 mM and cCl 0:193 mM. In
the solution outside the gelsolution boundary
s s
layer, the concentrations were set to cCl cNa
1 mM const. Note, the initial conditions fulll
the given chemo-electric equations. From Eq. (7),
a normalized dierential osmotic pressure D~ p
3:386 mM between gel and solution is obtained at
the complete interface.
In Fig. 5, the initial conditions (dashed line) and
the stationary solution (solid line) of the testcase
with applied external electric eld are plotted for
the position y 0:025 m.
The stationary solution of the ion concentra-
tions and the electric potential in the gel and in the
0.05
solution bath with applied electric eld is depicted
0.04
in Fig. 6. The concentrations of the cations and
anions are higher on the cathode side and lower on
0.03 the anode side of the gel compared to the initial
y [m] conditions. Near the gelsolution interface, the ion
anode concentrations in the solution are also increased at
the cathode side and decreased at the anode side.
0.01
It has to be mentioned that the condition of
0 electroneutrality Eq. (3) is fullled in the whole
domaingel and solutionoutside the small
boundary layer at the interface.
The electric potential behaves nearly linear in
x-direction and constant in y-direction in the
416 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420

c Cl- [mM] PNThe

normalized
 pressure dierence D~ p
1.4
f
a1 cag  cs
a for the stationary solution as well
1.2 as for the initial conditions of the electrically
1 stimulated case is depicted in Fig. 8. It should be
0.8
0.6 noted that the concentrations in the gel and the
0.4 solution have been taken at the interface outside
0.2
0 the boundary layer (see Fig. 7). Without applied
electric eld, the pressure dierence at the interface
0 0.01 0.02 0.03 0.04 0.05 at all edges is D~ p0  3:39 mM, independent of the
x [m] x- or y-position. The stationary solution of the
dierential osmotic pressure with applied electric
c Na+ [mM]
eld shows the following behavior: at the edges
5.5
5
perpendicular to the electrodes, the course is
4.5 nearly linear. The pressure dierence D~ pcathode is
4
3.5 3.18 mM at x 0:023 m, at x 0:027 m D~ panode
3
2.5 is 3.62 mM. This behavior is also depicted in
2
1.5
1 Fig. 9 in detail.
0.5
At the edges parallel to the electrodes, a dier-
0 0.01 0.02 0.03 0.04 0.05
ent behavior can be determined: The normalized
x [m]
osmotic pressure at the boundary x 0:023 m has
a nearly quadratic behavior; in the middle of this
electric potential [V] edge (at y 0:025 m), it is minimal, i.e. the dif-
ference between the values with and without ap-
0.1
plied electric eld is maximal. At the boundary
0.05 x 0:027 m, D~ p at y 0:025 m is maximal, i.e. the
0 dierence between the dierential osmotic pres-
-0.05 sures is also maximal.
-0.1 The dierences over the y-coordinate are smal-
ler than the ones over x, hence in the following
0 0.01 0.02 0.03 0.04 0.05 they are neglected. Summarizing, a depolarisation
x [m] (smaller normalized osmotic pressure compared to
the initial conditions) on the cathode side and a
Fig. 5. Initial conditions (dashed line) and stationary solution
(solid line) of the concentrations and the electric potential at
hyperpolarisation on the anode side of the gel are
y 0:025 m. obtained as a result of the applied electric eld.

3.2. Electric current

solution. The increase over x in the gel is smaller
than in the solution. This is compensated by a The electric current density ji in i-direction can
smaller step at the cathode side and a larger one at be calculated by the Faraday equation
the anode side of the gel compared to the initial XNf   
oca oW
values without applied electric eld. ji F za  D a  za la ca vi ca
a1
oxi oxi
3.1. Dierential osmotic pressure 9
The computation of the current density is per-
In this subsection, the dierential osmotic pres- formed by a postprocessing using the nodal values
sure resulting from the concentration dierences and the local gradients of the unknowns.
between gel and solution at the interface outside The electric current density jx in x-direction for
the small boundary layer is investigated in detail. this testcase is depicted in Fig. 10. These uxes are
 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420 417

Fig. 6. 2D-plot of the ion concentrations (A (top left), Cl (bottom left), Na (bottom right)) and electric potential W (top right) in
the gel and the solution under an applied external electric eld.

(g) this value is larger, i.e. an additional ux enters the

c
gel at the boundaries perpendicular to the elec-
trodes. The electric current density in the solution
c far away from the gel (y < 0:01 m or y > 0:04 m) is
(s)
c/ nearly constant over the whole domain. In this
c region, assuming cs a  const, i.e. the gradients
of the concentrations in x-direction are vanishing,
c(g)

the (mean) value of the current density can be
estimated by
Fig. 7. Concentrations in the gel and in the solution at the
1
interface. jx jx
D
Nf 2   
1 X oca oW
F za  Da  za la ca
D a1 ox ox
normalized by a mean value of the diusion con-
 
1 X
Nf 2
stants D of all species. This allows to compare the oW 2 DW
uxes of salt solutions containing dierent ions.  F z2a la ca  F l

c
D a1 ox D Dx
Due to the second term of Eq. (9), a ux in neg-
ative x-direction can be determined. At the edge of C
3:06  107 10
the gel parallel to the electrodes at x 0:027 m, a m4
minimal current density is obtained. Inside the gel, where
c  c1  c2 .
418 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420

3.9 4
3.8
3.7
3.6
3.5 1 3
3.4
3.3
3.2 2
3.1
3
2.9

0.032
0.03
0.028
0.022 0.026
0.023 0.024 y [m]
0.024 0.022
0.025
0.026 0.02
x [m] 0.027
0.0280.018

Fig. 8. Normalized dierential osmotic pressure D~

p.

3.3. Deformation of the gel ber

3.9
3
3.7 Due to the dierent osmotic pressures, see
3.5 Section 3.1 a prescribed strain

ij according to
3.3 
2/4
3.1
1

ij
1

0
g~ij D~pcathode  D~ p0
2.9 
x  x0
D~ panode  D~ pcathode
0.022 0.023 0.024 0.025 0.026 0.027 0.028 lgel
x [m]
 
x  x0
g~ij  0:21 0:23   0:21 mM
Fig. 9. Normalized dierential osmotic pressure D~
p. lgel
11
where lgel x1  x0 ; x0 0:023 m; x1 0:027 m
can be given. The superscript [0] denotes the state
of the initial conditions, [1] the stationary solution
of this testcase. The constant g~ij depends on the
type of gel, the crosslink density, the anity be-
tween gel and solution and the number of anionic/
cationic groups bound to the polymer. To give
a realistic qualitative solution of the deformation
of the gel lm, this constant is chosen as
g~ 0:
3dij =mM
ij

From the equations given above, the following

prescribed strains for the mechanical testcase are
attained:
x  x0


11 0:07 0:14
6
Fig. 10. Normalized electric current density jx . lx
 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420
Fig. 11. Undeformed (left) and deformed gel ber (right).
x  x0


22 0:07 0:14

6
lx
For this two-dimensional testcase, the gel is xed
in y-direction

at y0 0:02
 m and xed in x-direc-
1
tion at x x0 x2
y y0 . The numerical simula-
tion is conducted on a three-level multi-grid using
24 24 shell elements.
Fig. 11 (left) depicts the undeformed gel and
Fig. 11 (right) the stationary solution of the de-
formed gel ber. A deswelling on the cathode side
(left) and an additional swelling on the anode side,
leading to a bending towards the cathode, can be
determined.
3.4. Comparative experiments
Mechanical and electrical measurements on
anionic polyelectrolyte gels exposed to an external
electric eld are in very promising agreement with
the model calculations of the previous sections.
Direct registrations of the potential prole inside
anionic polyacrylamide/polyacrylate gels by means
of a modied microelectrode technique (G ulch
et al., 2000) showed that the negative Donnan
potential within the gel is shifted by an external
eld in a characteristic manner as described by the
numerical results given in Figs. 5 and 6: The typ-
ical shifts were most pronounced at the current
inow and outow region of the gel specimen. On
419
the anode side of the gel a higher negativity was
induced which is classied as hyperpolarisation
whereas on the cathode side the opposite eect was
recorded in the sense of a depolarisation. The
alterations in the spatial distribution of the ions
inside and outside the gels causing the shifts in the
potential are presumed to aect swelling and de-
swelling of parts of the gel simultaneously thereby
promoting a bending movement of freely movable
gel specimen. Strips of anionic polyelectrolyte gels
which were xed at one end and superfused with a
given salt solution bent away from the anode when
they were exposed to an electric eld applied
through a pair of platinum electrodes in parallel to
the strips. These bending reactions are solely at-
tributed to the direct eect of the electric eld on
the gels. Any electrolytic processes due to the
electric currents have been strictly avoided by very
low stimulation voltages on the one hand and
continuous superfusion of the gel strips and the
electrodes with the bathing solution on the other
hand. Increasing the stimulation voltages intensi-
ed and accelerated the bending motion and in-
creased the hyperpolarisation and depolarisation.
By miniaturizing the specimen a speeding up of the
bending movements was obtained. In principle, the
bending of the anionic polyelectrolyte gels can be
characterized by its longitudinal axis being the
neutral line. This means that the boundary region
of the gel facing the anode will undergo a slight
swelling whereas the opposite side of the gel
420 T. Wallmersperger et al. / Mechanics of Materials 36 (2004) 411420
deswells under the inuence of a DC current. This
eect can be conrmed by the numerical simula-
tion (see Fig. 11).
4. Conclusion
In the present study, a coupled chemo-electro-
mechanical multi-eld formulation for polyelec-
trolyte gels has been presented. This formulation
consists of convectiondiusion equations de-
scribing the chemical eld, a Poisson equation for
the electric eld and a mechanical eld equation.
The model is capable to describe the local swelling
and deswelling of ionic polymer gels as well as the
ion concentrations and the electric potential in the
gel and in the solution.
Numerical simulations of the chemo-electric
eld have been performed for electrical stimula-
tion. The resulting dierences of the freely mov-
able ions, i.e. osmotic pressure dierences at the
interface, have been used as input for the me-
chanical eld. By this means, the increase/decrease
of the Donnan potential and of the dierential
osmotic pressure at the gelsolution interface can
be considered as indicators for a higher/lower
swelling ratio of the gel ber.
Experimental measurements are in good quali-
tative agreement with the numerical results. This
demonstrates the validity of the employed nu-
merical model.
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