Society for Experimental Mechanics, 2002 SEM Annual Conference Proceedings, Milwaukee, WI, 2002.
Mechanical Properties of a pH Sensitive Hydrogel
æ §
B. Johnson , D.J. Niedermaier , W.C. Crone
æ ¥
Department of Biomedical Engineering, Department of Engineering Physics, Engineering Mechanics Program
University of Wisconsin-Madison, Madison, WI 53706, USA
ABSTRACT
An experimental protocol was developed to determine the
basic mechanical properties of a poly(2-hydroxyethyl
methacrylate (HEMA)) hydrogel at various levels of pH
equilibrium. An Instron micromechanical testing machine
was modified such that tensile tests could be carried out in
temperature controlled pH solution. Values of Young’s
modulus were measured for a range of pH values from 2 to
12 and the experimental data was compared with theoretical
predictions of rubber elasticity. Although theory
overpredicted the decrease in modulus by 0.05 MPa, the
global decrease in modulus with increased swelling was
experimentally confirmed.
1 INTRODUCTION
There is a growing interest in developing engineered
actuation systems that have properties more in common with
soft biological materials, such as muscles and tendons, than
with traditional engineering materials. In an aqueous
environment, hydrogels will undergo a reversible phase
transformation that results in dramatic volumetric swelling
and shrinking upon exposure and removal of a stimulus.
Thus, these materials can be used as muscle-like actuators
[1], fluid pumps [2], and valves [3]. Interest in hydrogels has
gained momentum recently because these materials can be
actuated by a variety of stimuli such as pH [4], salinity [5],
electrical current [6], temperature [7], and antigens [8].
Since the rate of swelling and shrinking in a hydrogel is
diffusion-limited, the temporal response of macroscale
hydrogel structures to a given stimulus is typically measured
on time scales of hours or days. Thus, by reducing the size
of hydrogel structures to the microscale, volumetric
transitions occur within minutes or even seconds. The
favorable scaling of hydrogel dynamics has been the
essential element in the development of micro-fluidic devices
that employ hydrogel valves for flow control [9]. One benefit
of these devices is that they are completely autonomous,
and therefore require no external power source.
Our research considers a poly(2-hydroxyethyl methacrylate
(HEMA)) gel applied to the autonomous control of flow in
microfluidic devices [9]. HEMA based hydrogels are
¥ § æ æ
, J. Moorthy and D.J. Beebe
§
sensitive to the pH of their aqueous environment; expanding
at high pH and shrinking at low pH. The structures created
from this hydrogel for use in microfluidic devices must
endure forces imposed by flow of an aqueous solution, the
constraint of device walls during swelling, and the restoring
force of elastic membranes. Optimizing the design of these
devices demands an understanding of how the mechanical
properties of the gel change with its surroundings.
To assist device designers, material properties must be
known in order to ensure functional and reliable structures.
Additionally, there is a strong desire to better understand the
underlying mechanisms for swelling in hydrogels so that
more predictive models can be developed to guide the
design process [10]. Although our research focuses on
HEMA based gels, the methods outlined are applicable to a
variety of polymeric gels and biomaterials.
2 BACKGROUND INFORMATION
Theories describing the behavior of cross-linked polymer
networks were originally developed to understand the
elasticity of vulcanized rubber. While early molecular
theories were restricted to uniaxial tension, statistical
formulations successfully dealt with alternate states of strain
(e.g. simple shear or uniaxial compression). Kuhn [11] was
the first to relate the elastic modulus and the molecular
weight of the chains of a polymer network, however his
derivation did not account for large strains. Wall [12]
extended Kuhn’s work with a formulation for the elastic
modulus at any elongation:
 RTρ  2
ε =  1 + 3  , (1)
 M c  α 
where R is the universal gas constant, T is absolute
temperature, ρ is the density of the material, M c is the
molecular weight of the polymer chain, and α is the ratio of
the deformed length to the initial length in the direction of the
applied strain.
Flory and Rehner [13, 14] recognized the swelling
phenomenon exhibited by cross-linked polymers when
exposed to certain solvents and derived an expression for with an optical microscope and image analysis software
the elastic modulus of a swollen polymer network (Metamorph 4.6r6, Universal Imaging Corp.) after each test
was completed. All strain measurements were calculated
from the initial, stress-free state the gel assumes after
 RTρν 21 3 
ε ' =  1 + 23  , (2) reaching equilibrium with its respective pH solution.
M  α  Therefore, only strains due to mechanical deformation, and
 c  not swelling, were considered in the determination of
mechanical properties.
where ν2 is the volume ratio of unswollen gel to swollen gel.
Thus, the modulus of elasticity for a swollen cross-linked The experimental data was divided into swollen and
polymer network can be related to an unswollen network by unswollen regions for the purpose of comparison to the
theoretical predictions. The transition pH of 5.0 was based
1 3. (3)
ε ' = εν 2 on swelling experiments in which the diameters of cylindrical
hydrogel structures were measured after reaching
This relation is compared below to experimental results equilibrium with their respective pH environment [10]. An
found for a HEMA gel. average value of 0.29 MPa was calculated from the first four
data points of Figure 1 for tension samples tested in the
3 EXPERIMENTS unswollen state. The modulus value at pH 5.5 was excluded
since it was within the region of phase transformation. The
average of the remaining data points was 0.21 MPa.
Tension samples were fabricated from a prepolymer solution
of HEMA gel in the liquid state. The liquid prepolymer was
injected into a polydimethylsiloxane (PDMS) mold that took
the form of dumbbell shaped tension samples scaled down
from the Type IV geometry outlined in ASTM D 638-99.
Ultraviolet (UV) light from a Novacure UV source was
2
delivered at an intensity of 15 mW/cm for two minutes to
achieve proper polymerization within the PDMS mold. The
resulting samples had a 5.5 mm gage length, 1 mm neck
width, and an approximate thickness of 200 µ m. The
samples were washed with methanol and deionzed water
and were stored in the appropriate pH solution for at least 24
hours prior to testing. The 0.2 M ionic strength pH solutions
used in this study were made from NaH2PO4, Na2HPO4, HCl,
NaOH, and NaCl.

An Instron Model 5548 MicroTester, equipped with a 10 N

load cell, was used for measuring the mechanical properties
of the hydrogel. The position of the screw-driven actuator
could be determined to within ±6.0 µm over 100 mm of
travel, while loads could be measured to within ±0.25% of
Figure 1: Young’s modulus as a function of pH. The solid
the indicated force. A temperature controlled environmental
horizontal lines indicate the averaged modulus values for the
chamber added to the MicroTester allowed the samples to
unswollen and swollen states. The shaded area signifies the
be tested in solution. The buoyant force exerted by the test
region of phase transformation for which data points were
solution on the grip fixtures was accounted for by conducting
discarded. The dashed lines indicate values calculated from
a test in which the sample was absent from the experimental
equation (3) based on an initial unswollen modulus of 0.29
setup. The resulting force-displacement curve was
MPa.
subtracted from the tests in which the sample was present.

4 RESULTS
Young’s modulus was determined from the initial portion of
the stress/strain curve in tensile tests carried out to failure at
a constant crosshead displacement rate of 5 mm/min. A set
of five samples was tested for each pH value investigated. A
mean value of Young’s modulus was calculated from this
data set and is indicated with a data point in Figure 1, while
error bars denote the standard deviation within each data
set.
Young’s modulus was calculated from the slope of the
stress-strain curve within the region of 10% strain, where
axial strains were determined from crosshead position.
Cross-sectional areas for stress calculations were measured
The volume of the gage section of the tensile samples were
measured in the absence of strain and the values were
averaged amongst the swollen and unswollen groupings for
the purpose of calculating ν 2 . Similarly, cylinder volumes
were averaged from data provided by the aforementioned
swelling experiments. The swelling that takes place in the
swelling experiments is considered to be constrained in one
dimension due to rigid upper and lower channel walls.
Therefore, a fixed channel height of 0.180 mm was assumed
in the volume calculation. The impact of this constraint on
the final swelling volume, and thus ν2, is outlined in Table 1.
Taking the average unswollen elastic modulus as 0.29 MPa,
and ν2 as 0.19 for this particular gel chemistry, equation (3)
yields a value of 0.16 MPa for the elastic modulus of the gel
in its swollen state using the unconstrained volume data.
Using values from the swelling experiments collected under
constrained conditions yields a value of 0.18 MPa for the
elastic modulus.
Table 1: Volume data for constrained and free swelling
hydrogel, and the resulting volume ratios and moduli.
Avg. Unswollen Avg. Swollen
Volume (mm )
2
Volume (mm )
2 ν2
Constrained 1.45 × 10 −2
5.82 × 10 −2
0.25
Unconstrained 3.50 18.8 0.19
An additional study was undertaken to investigate the affect
of polymerization time on the elastic modulus.
Representative data is shown in Figure 2 for samples that
were exposed to UV light for durations varying from one to
ten minutes. For simplicity, tests were performed in
deionized water and sample cross sections were slightly
larger (1.5 mm by 0.5 mm) than those used in the pH study.
Figure 2: Young’s modulus as a function of polymerization
time. Data points indicate the average modulus of four
samples while error bars denote the standard deviation
within each sample set (the data set corresponding to a 6
minute polymerization time contains three samples).
5 DISCUSSION
The effectiveness of the theory to predict changes in
modulus with swelling, and the implications of mechanical
constraint on swelling will be discussed. The impact of
polymerization conditions on Young’s modulus will also be
addressed.
Although Figure 1 does not display a step wise change in
Young’s modulus at the pH where transformation occurs, the
data above and below phase transition was averaged such
that a constant value of modulus was assumed for each of
the swollen and unswollen states. This approach was
adopted primarily for the purpose of comparing experimental
results with theoretical predictions. The theoretical
formulation tends to predict a greater decrease in modulus
than what is revealed in the averaged experimental data
(Figure 1). Therefore, the theory discussed above may not
adequately describe the influence of swelling on the elastic
modulus.
Hydrogel swelling experiments show that the phase
transformation for this gel chemistry occurs around a pH
value of 5.0 [10]. They also reveal that cylindrical hydrogel
structures tend to expand to approximately twice their
original diameter (ν2 = 0.25) whereas samples used in the
ε'
tension tests swelled to a greater degree (ν 2 = 0.19). This
0.18
may be attributed to the fact that the swelling experiments
0.16
were conducted within a micro-channel where upper and
lower walls constrained expansion of the hydrogel structure
in one dimension. Conversely, the tension samples used in
this study were allowed to expand freely in bulk solution prior
to testing. The dependence of swelling on an applied stress
or strain was confirmed experimentally by Treloar [15]. His
experiments on natural rubber showed that an applied
uniaxial tensile stress produced an increase in swelling,
while a uniaxial compressive stress caused a reduction in
swelling.
In addition to the above discussion, the results shown in
Figure 1 provide essential information for the efficient design
of hydrogel structures in microfluidic devices. Young’s
modulus data has been implemented in mathematical
models that are able to predict the swelling characteristics of
the gel [10]. Specifically, radial displacements in a
cylindrical gel can be related to material constants (Young’s
modulus and Poisson’s ratio) and the osmotic pressure that
arises from the inflow of ions that maintain charge neutrality
in the presence of basic buffer solutions.
As demonstrated by the results presented in Figure 2, the
modulus of a hydrogel is also affected by the polymerization
process. Photo Differential Scanning Calorimetry (Photo-
DSC) experiments on a HEMA gel of similar composition
showed that there is a peak time during photopolymerization
when the reaction rate is maximum and then stalls to zero
upon further UV exposure [16]. As the reaction rate
increases, an increase in the conversion of monomer to
polymer is expected. This would also imply an increase in
cross-linking and thus modulus. Such a trend is represented
in Figure 2 for values of Young’s modulus corresponding to
polymerization times of one, two, and four minutes. The
modulus appears to reach a maximum at a polymerization
time of four minutes, after which it begins to decay. Photo-
DSC experiments reported a peak in the reaction rate
between two and four minutes of UV exposure [16]. The
location of this peak may be influenced by a number of
parameters including the UV source, type and concentration
of photo-initiator, and presence of other monomers.
After peak cross-linking is achieved, an apparent decay in
Young’s modulus is observed for polymerization times of six
and ten minutes. Because the conversion of monomer to
polymer should cease once the reaction stalls, the modulus
would be expected to maintain its peak value upon
prolonged exposure to UV. However, in the presence of UV,
oxygen forms ozone that can subsequently form oxygen
radicals. The oxygen radicals have the ability to break
bonds, thereby causing a decrease in the modulus.

6 CONCLUSIONS
Experiments were conducted on a pH sensitive hydrogel to
determine the dependence of Young’s modulus on two
parameters: the environmental pH and the time of exposure
to UV light during polymerization. Theoretical predictions
were in agreement with experiments in reference to the
global decrease in modulus with increased swelling.
However the magnitude of this decrease was slightly
overpredicted.
A brief investigation of the impact of mechanical constraint
on the ratio of unswollen to swollen volume (ν 2) was also
carried out. This study shows the need for further
investigation with experiments designed to test the change in
ν2 with varying levels of applied strain. This information may
be particularly useful in the design of improved microfluidic
devices that utilize the relationship between swelling and
strain.
Additionally, it was experimentally demonstrated that the
duration of UV exposure during photopolymerization
influences the mechanical properties of this hydrogel.
Accounting for differences in polymerization conditions and
chemical composition, the peak in the modulus coincides
reasonably well with reaction rate peaks measured with
photo-DSC experiments.
9. Beebe, D.J., et al., Functional hydrogel structures for
autonomous flow control inside microfluidic channels.
Nature, 404(6778), pp. 588-590, 2000.
10. De, S.K., et al., Equilibrium Swelling and Kinetics of pH-
responsive Hydrogels: Models, Experiments, and
Simulations. submitted for publication to the Journal of
Microelectromechanical Systems.
11. Kuhn, W., Kolloid-Zeitschrift, 76, pp. 258-271, 1936.
12. Wall, F.T., Statistical Thermodynamics of Rubber. II.
The Journal of Chemical Physics, 10, pp. 485-488,
1942.
13. Flory, P.J. and J. Rehner Jr., Statistical Mechanics of
Cross-Linked Polymer Networks: I. Rubberlike Elasticity.
The Journal of Chemical Physics, 11(11), pp. 512-520,
1943.
14. Flory, P.J. and J. Rehner Jr., Statistical Mechanics of
Cross-Linked Polymer Networks: II. Swelling. The
Journal of Chemical Physics, 11(11), pp. 521-526, 1943.
15. Treloar, L.R.G., The Swelling of Cross-Linked
Amorphous Polymers Under Strain. Transactions of the
Faraday Society, 46, pp. 783-789, 1950.
16. Lai, Y.C. and E.T. Quinn, The effects of initiator and
diluent on the photopolymerization of 2-hydroxyethyl
methacrylate and on properties of hydrogels obtained.
Photopolymerization, 673, pp. 35-50, 1997.

ACKNOWLEDGEMENTS

This research is sponsored by DARPA, AFRL, Air Force

Command, and USAF under agreement F30602-00-1-0570.
The authors would also like to thank Narayana Aluru, Joseph
Bauer, David Eddington, and Glennys Mensing for helpful
discussions and technical assistance.

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