Stimuli-responsive hydrogels are polymer gels possessing the ability to absorb or release solvent, resulting in a respective change of volume. This volume change can be triggered by applying a chemical or electrical stimulus to the gels placed in a solution bath.
To describe the chemo-electro-mechanical behavior of these hydrogels in the framework of the Theory of Porous Media, they have to be subdivided in a solid phase, fluid phase and an ionic phase. In this theory, the interaction of the different phases is directly incorporated. Due to the complexity of both, the material and the model, a large amount of material parameters is essential. The determination of these parameters is a challenging task. In this investigation, also the interaction between hydrogel (solid and fluid phase) and surrounding solution bath has to be considered in order to determine the viscoelastic behavior of the gel.
Hence, in the present work, polyelectrolyte hydrogels are investigated in consideration of the mechanical characteristics via a tensile test. In the experimental setup the stress is determined by a force sensor and the deformation is analyzed by using a gray scale correlation. Due to the fact, that the mechanical behavior of such multiphasic materials depends on the solid-fluid ratio, the gel is investigated under different swelling degrees. The acquired data then can be used to enhance the material equations. So, an enhanced prediction towards possible applications is gained.
This paper presents the design, simulation, assembly and testing of a force-compensated hydrogel-based pH sensor. In the conventional deflection method, a piezoresistive pressure sensor is used as a chemical-mechanical-electronic transducer to measure the volume change of a pH-sensitive hydrogel. In this compensation method, the pH-sensitive hydrogel keeps its volume constant during the whole measuring process, independent of applied pH value. In order to maintain a balanced state, an additional thermal actuator is integrated into the close-loop sensor system with higher precision and faster dynamic response. Poly (N-isopropylacrylamide) (PNIPAAm) with 5 mol% monomer 3-acrylamido propionic acid (AAmPA) is used as the temperature-sensitive hydrogel, while poly (vinyl alcohol) with poly (acrylic acid) (PAA) serves as the pH-sensitive hydrogel. A thermal simulation is introduced to assess the temperature distribution of the whole microsystem, especially the temperature influence on both hydrogels. Following tests are detailed to verify the working functions of a sensor based on pH-sensitive hydrogel and an actuator based on temperature-sensitive hydrogel. A miniaturized prototype is assembled and investigated in deionized water: the response time amounts to about 25 min, just half of that one of a sensor based on the conventional deflection method. The results confirm the applicability of t he compensation method to the hydrogel-based sensors.
In the last decade, ionic polymer–metal composites are emerged as viable intelligent materials working both as bending actuators and energy harvesting systems. Recently, the feasibility of actuation from mechanical buckling has been investigated. In the present research, we present relevant numerical experiments concerning the possible electromechanical transduction when different patterned electrodes are considered. The focus of this research is theoretical, numerical, and experimental. In particular, with reference to almost one–dimensional IPMC strips, we take into account the large influence of electrodes’ bending stiffness on the IPMC behavior. We consider an original continuous metal strip covering the ionic polymer, and the patterned electrodes with one or more gaps. The actuation response of the system to low and to high voltages is studied; a strong difference is evidenced in the two situations as, in presence of high voltage, the system shows a buckling in opposite direction which needs further investigations.
With the rapid development of micro systems technology and microelectronics, smart electronic systems are emerging
for the continuous surveillance of relevant parameters in the body and even for closed-loop systems with a sensor
feedback to drug release systems. With respect to diabetes management, there is a critical societal need for a sensor that
can be used to continuously measure a patient's blood glucose concentration twenty four hours a day on a long-term
basis. In this work, thin films of "stimuli-responsive" or "smart" hydrogels were combined with microfabricated
piezoresistive pressure transducers to obtain "chemomechanical sensors" that can serve as selective and versatile
wireless biomedical sensors. The sensitivity of hydrogels with regard to the concentration of glucose in solutions with
physiological pH, ionic strength and temperature was investigated in vitro. The response of the glucose-sensitive
hydrogel was studied at different regimes of the glucose concentration change and at different temperatures. Sensor
response time and accuracy with which a sensor can track gradual changes in glucose was estimated.
Hydrogels are viscoelastic active materials. They consist of a polymer network with bound charges and a liquid
phase with mobile anions and cations. In water based solutions these gels show large swelling capabilities under
the influence of different possible stimulation types, such as chemical, electrical or thermal stimulation.
In the present work a coupled chemo-electro-mechanical formulation for polyelectrolyte gels using the Finite
Element Method (FEM) is applied. In addition to the three given fields, the dissociation reactions of the bound
charges in the gel are considered. Thus, we are able to model and simulate pH-stimulation and to give the
different ion concentrations, the electric potential and the mechanical displacement. Depending on the initial
conditions and the dissociation ratio, different kinds of stimulation cycles can be simulated.
Concluding, the developed model is applicable for chemical stimulation and can model both, hydrogel actuators
and sensors.
Polyelectrolyte gels show adaptive viscoelastic characteristics. In water-based solutions they have enormous
swelling capabilities under the influence of various possible stimulation types, such as chemical, electrical or
thermal. In the present work a fully coupled 3-field formulation for polyelectrolyte gels using the Finite Element
Method (FEM) is applied. This formulation consists of a chemical, electrical, and mechanical field equation. The
mechanical field is coupled to the chemo-electrical field by a prescribed strain stemming from an osmotic pressure
term. In experiments it has been proven that there is a large dependency between the applied temperature and
the actual swelling degree of the gel. In the present research, the thermal stimulation is investigated. First, only
the actual temperature is considered in the osmotic pressure term. Then, additionally, temperature-dependent
material parameters obtained from experimental measurements are applied. The calibration of the numerical
simulation is performed with experimental results available in literature.
This work is motivated by a demand for inexpensive, robust and reliable biochemical sensors with high signal
reproducibility and long-term-stable sensitivity, especially for medical applications. Micro-fabricated sensors can
provide continuous monitoring and on-line control of analyte concentrations in ambient aqueous solutions. The
piezoresistive biochemical sensor containing a special biocompatible polymer (hydrogel) with a sharp volume phase
transition in the neutral physiological pH range near 7.4 can detect a specific analyte, for example glucose. Thereby the
hydrogel-based biochemical sensors are useful for the diagnosis and monitoring of diabetes. The response of the glucosesensitive
hydrogel was studied at different regimes of the glucose concentration change and of the solution supply.
Sensor response time and accuracy with which a sensor can track gradual changes in glucose was estimated.
Additionally, the influence of various recommended sterilization methods on the gel swelling properties and on the
mechano-electrical transducer of the pH-sensors has been evaluated in order to choose the most optimal sterilization
method for the implantable sensors. It has been shown that there is no negative effect of gamma irradiation with a dose
of 25.7 kGy on the hydrogel sensitivity. In order to achieve an optimum between sensor signal amplitude and sensor
response time, corresponding calibration and measurement procedures have been proposed and evaluated for the
chemical sensors.
Already eight years ago, the usage of piezoresistive sensors for chemical measurands was proposed at the Solid State
Electronics Laboratory of the Dresden University of Technology [1]. Adding functionalised polymer coating which shows
swelling due to chemical or biological values leads to a similar deflection of the thin silicon bending plate like for
pressure sensors.
The application of "stimuli-responsive" or "smart" cross-linked gels in chemical sensors is based on their ability to a
phase transition under the influence of external excitations (pH, concentration of additives in water, temperature).
Combining a "smart" hydrogel and a micro fabricated pressure sensor chip allows to continuously monitor the analytedependent
swelling of a hydrogel and hence the analyte concentration in ambient aqueous solutions. The sensitivity of
hydrogels with regard to the concentration of such additives as H+-ions (pH sensor), transition-metal ions, salts, organic
solvents and proteins in water was investigated. It has been demonstrated that the sensor's sensitivity depends on the
polymer composition as well as on the polymer cross-linking degree. Time constants down to a few ten seconds have
been found for thin hydrogel films deposited directly on the backside of the silicon bending plate. In order to achieve an
optimum between sensor signal amplitude and sensor response time, the gel swelling/deswelling kinetics was
investigated. Some methods improving the properties of the chemical sensors have been proposed. The long-term
measurements have shown that the lifetime of piezoresistive chemical sensors can be prolonged up to several years
provided that specific operation and storage conditions are fulfilled.
Environmentally responsive or smart hydrogels show a volume phase transition due to changes of external stimuli such
as pH or ionic strength of an ambient solution. Thus, they are able to convert reversibly chemical energy into mechanical
energy and therefore they are suitable as sensitive material to be integrated in biochemical microsensors and MEMS
devices. In this work, micro fabricated silicon pressure sensor chips with integrated piezoresistors were used as
transducers for the conversion of mechanical work into an appropriate electrical output signal due to the deflection of a
thin silicon bending plate. Within this work two different sensor designs have been studied. The biocompatible
poly(hydroxypropyl methacrylate-N,N-dimethylaminoethyl methacrylate-tetra-ethyleneglycol dimethacrylate) (HPMADMA-
TEGDMA) was used as an environmental-sensitive element in piezoresistive biochemical sensors. This
polyelectrolytic hydrogel shows a very sharp volume phase transition at pH values below about 7.4 which is in the range
of the physiological pH. The sensor's characteristic response was measured in-vitro for changes in pH of PBS buffer
solution at fixed ionic strength. The experimental data was applied to the Hill equation and the sensor sensitivity as a
function of pH was calculated out of it. The time-dependent sensor response was measured for small changes in pH,
whereas different time constants have been observed. The same sensor principal was used for sensing the ionic strength.
The time-dependent electrical output signal of both sensors was measured for variations in ionic strength at fixed pH
value using PBS buffer solution. Both sensor types showed an asymmetric swelling behavior between the swelling and
the deswelling cycle as well as different time constants, which was attributed to the different nature of mechanical
hydrogel confinement inside the sensor.
The application of stimuli-responsive or smart cross-linked gels in chemical sensors is based on their ability to a phase
transition under the influence of external excitations (temperature, pH, concentration of additives in water). The external
stimulus lowers the energy barrier between two possible gel states: a stable state (shrunk gel) and a metastable state
(swollen gel), and thereby makes possible the gel transition into the swollen state. The amount of the solvent absorbed
due to the external stimulus has been modeled and calculated taking into account the polymer parameters (concentrations
of the hydrophilic, hydrophobic, ionisable and ionised groups as well as polymer cross-linking degree) and the solution
parameters (analyte concentration, ionic strength, viscosity as well as temperature and temperature change rate).
Combining a smart hydrogel and a micro fabricated pressure sensor chip allows to continuously monitor the analytedependent
swelling of a hydrogel and hence the analyte concentration in ambient aqueous solutions. The sensitivity of
hydrogels with regard to the concentration of such additives as H+-ions (pH sensor), transition-metal ions and salts in
water was experimentally and numerically investigated at different temperatures. It has been demonstrated that the
sensor's sensitivity depends on the polymer composition as well as on the polymer cross-linking degree. A higher
sensitivity was observed for polyelectrolyte hydrogels with higher concentrations of ionisable groups. The long-term
measurements have shown that the lifetime of piezoresistive chemical sensors can be prolonged up to several years
provided that specific operation and storage conditions are fulfilled.
Polyelectrolyte gels are ductile elastic electroactive materials. They consist of a polymer network with charged
groups and a liquid phase with mobile ions. Changing the chemical or electric conditions in the gel-surrounding
solution leads to a change of the chemo-electro-mechanical state in the gel phase: diffusion and migration of ions
and solvent between the gel and solution phases trigger the swelling or shrinkage of the polymer gel. In case
of chemical stimulation (change of pH or salt concentration), a swelling ratio of up to 100% may be obtained.
Due to this large swelling ratio the gels exhibit excellent actuatoric capabilities. In this paper, a polyelectrolyte
gel placed in a solution bath is investigated. The actuatoric and sensoric capabilities are described by a chemo-electro-mechanical model. The chemical field is represented by a convection-migration-diffusion equation while
the electric field is described by a quasi-static Laplace equation. For the mechanical field a partial differential
equation of first order in time is applied. Inertia effects are neglected due to the relatively slow swelling/shrinkage
process. On the one hand, the coupling between the chemo-electrical and the mechanical field is realised by the
differential osmotic pressure stemming from the concentration differences between gel and solution. On the
other hand, the mechanical deformation influences the concentration of the bound charged groups in the gel.
The three fields are solved simultaneously by applying the Newton Raphson method using finite elements in
space and finite differences in time. The developed model is applicable for both, hydrogel actuators and sensors.
Numerical results of swelling and bending are given for chemically and electrically stimulated polymer gels. In
this paper we show the differences between the chemo-electric and the fully coupled chemo-electro-mechanical
formulation for polymer gels in different solution baths. The inverse (sensor-) effect is demonstrated by the
influence of the mechanical deformation on the gel, which results in a change of the chemical and electrical
unknowns in the gel. The validity of the employed numerical model is shown by a comparison of the obtained
results with experimental measurements.
pH-sensitive hydrogels are capable of reversibly converting chemical energy into mechanical energy and therefore they
are widely used as sensitive materials for pH sensors. However nonlinear effects such as hysteresis and drift are observed
in the swelling behaviour of the polyelectrolytic hydrogels complicating the calibration procedure for the pH sensor and
affecting the signal reproducibility.
In the present work, in order to realize a pH sensor with a high signal reproducibility and high long-term stable sensor
sensitivity, the complicated kinetics of gel swelling/deswelling processes is analysed and the origin of the hysteresis
nonlinearities is elucidated. It is found that the long-time drift in the sensor characteristic is caused by the drift of
hydrated ions and water into the gel or out of the gel in dependence on the pH range of the solution and on the chemical
reactions which occur in the gel during the swelling or shrinking processes. The rate of the water drift is determined by
the change rate of the concentration of ionized groups which increase the gel hydrophilicity and consequently the gel
swelling.
Temperature responsive hydrogels show a strong ability to change their swelling degree in dependence on organic solvent or salt concentration in aqueous solutions. This behavior can be used for appropriate sensors if a suitable transducer transforms the volume change into an electrical output signal. In the present work, piezoresistive sensors were used where the hydrogel led to a deflection of a silicon membrane within the sensor chip. This principle allows for a strict separation of the fluid from the piezoresistors as well as from other electronic components at the front side of the sensor chip. Poly(N-isopropylacrylamide) (PNIPAAm) as well as photo cross-linkable poly(N-isopropylacrylamide-co-dimethyl-acrylamide-co-2-(dimethyl maleimido)-N-ethyl-acrylamide) (PNIPAAm-DMAAm-DMIAAm) terpolymer have been applied and investigated for organic solvent concentration sensors and salt concentration sensors.
The sensor's output voltage was measured during the swelling of the hydrogel under influence of water solutions with different organic and inorganic solute concentrations at different temperatures. A complex "reentrant" swelling behavior of the hydrogel in mixed co-solvents as well as "salting in" and "salting out" effects of different salts were studied. It was found that the change in the gel volume phase transition temperature depends on the solution viscosity and the concentration of the additive affecting the stiffness of the polymer chain in the surrounding solution. The influence of an initial gel conditioning procedure on the signal value and the sensitivity of the proposed chemical sensors was investigated and the measurement conditions necessary for high signal reproducibility and long-term stability were determined.
The purpose of chemical sensors consists in converting chemical input data into output signals suitable for electronic measuring processes. The sensors are characterized by a material-recognizing element and a transducer. The transducer converts the non-electric measuring value into an electrical signal. Hydrogels are cross-linked polymers which swell in solvents to appreciable extent. The amount of solvent uptake depends on the polymer structure and can be made responsive to environmental factors, such as solvent composition, pH value, temperature, electrical voltage etc. Hydrogels are capable to convert reversibly chemical energy into mechanical energy making them interesting as sensitive material for appropriate sensors. In the present work, in order to realize pH sensors, poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blend hydrogels with a pH value dependent swelling behavior were used as chemo-mechanical transducers. The influence of the kinetics of the induced charge (in the swollen polyelectrolyte gel) on the response time, the signal value and the sensitivity of the proposed pH sensors were investigated and the measurement conditions necessary for high signal reproducibility were determined.
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