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From the liquid–liquid equilibrium (LLE) data of a linear polymer, an investigation of the Sanchez and Lacombe equation of state (SL-EOS) is performed with the goal of describing the swelling of th...

Visualization reveals that confinement in a granular medium hinders hydrogel swelling, with implications for agriculture., Hydrogels hold promise in agriculture as reservoirs of water in dry soil, potentially alleviating the burden of irrigation. However, confinement in soil can markedly reduce the ability of hydrogels to absorb water and swell, limiting their widespread adoption. Unfortunately, the underlying reason remains unknown. By directly visualizing the swelling of hydrogels confined in three-dimensional granular media, we demonstrate that the extent of hydrogel swelling is determined by the competition between the force exerted by the hydrogel due to osmotic swelling and the confining force transmitted by the surrounding grains. Furthermore, the medium can itself be restructured by hydrogel swelling, as set by the balance between the osmotic swelling force, the confining force, and intergrain friction. Together, our results provide quantitative principles to predict how hydrogels behave in confinement, potentially improving their use in agriculture as well as informing other applications such as oil recovery, construction, mechanobiology, and filtration.

Finite element modeling applied to analyze experimentally determined hydrogel swelling data provides quantitative description of the hydrogel in the aqueous solutions with well-defined ionic content and environmental parameters. In the present study, we expand this strategy to analysis of swelling of hydrogels over an extended concentration of salt where the Donnan contribution and specific ion effects are dominating at different regimes. Dynamics and equilibrium swelling were determined for acrylamide and cationic acrylamide-based hydrogels by high-resolution interferometry technique for step-wise increase in NaCl and NaBr concentration up to 2 M. Although increased hydrogel swelling volume with increasing salt concentration was the dominant trend for the uncharged hydrogel, the weakly charged cationic hydrogel was observed to shrink for increasing salt concentration up to 0.1 M, followed by swelling at higher salt concentrations. The initial shrinking is due to the ionic equilibration accounted for by a Donnan term. Comparison of the swelling responses at high NaCl and NaBr concentrations between the uncharged and the cationic hydrogel showed similar specific ion effects. This indicates that the ion non-specific Donnan contribution and specific ion effects are additive in the case where they are occurring in well separated ranges of salt concentration. We develop a novel finite element model including both these mechanisms to account for the observed swelling in aqueous salt solution. In particular, a salt-specific, concentration-dependent Flory&ndash, Huggins parameter was introduced for the specific ion effects. This is the first report on finite element modeling of hydrogels including specific ionic effects and underpins improvement of the mechanistic insight of hydrogel swelling that can be used to predict its response to environmental change.

Hydrogels are tridimensional elastic hydrophilic cross-linked polymers with the ability to absorb water in a process called swelling. The Flory-Huggins (FH) theory can be applied to model hydrogel swelling with appropriate adjustments. In the literature the FH model parameter is directly estimated from experimental data on swelling. The target of this paper is to evaluate the effect of using parameters estimated from liquid-liquid equilibria of the linear polymer directly in the swelling modeling of the respective cross-linked polymer as these data can be easily found in literature. Three methods that use different equations for the FH parameter and two methods for the mechanical contribution are evaluated. These models were applied to the polymer poly(N-isopropylacrylamide), PNIPA, and compared in three swelling intervals: the volume contraction region; the transition temperature; and the region of volume expansion. The most relevant and important behaviors of each region are shown, analyzed and discussed.

A biomedical sensor was developed to measure local pH near orthopedic implants to detect and study implant-associated infection. The sensor is read using plain radiography, a technique which is noninvasive, inexpensive, ubiquitously available in medical facilities, and routinely used in diagnosis and follow-up. The sensor comprises a radiopaque tungsten indicator pin embedded within a chemically responsive hydrogel that exhibits a pH-dependent swelling. A stainless steel well holds this hydrogel and attaches to an orthopedic plate. The local pH may be determined from the extent of hydrogel swelling by radiographically measuring the indicator position relative to the well. We calibrated the sensor in a series of standard pH buffers and tested it during bacterial growth in culture. The sensor was robust: its response was negligibly affected by changes in temperature, ionic strength within the normal physiological range, or long-term incubation with reactive oxygen species generated from hydrogen peroxide and copper. Pooled data from several sensors fabricated at different times and tested in different conditions had a root-mean-square deviation from a pH electrode reading of 0.24 pH units. Radiographic measurements were also performed in cadaveric tissue with the sensor attached to an orthopedic plate fixed to a tibia. Pin position readings varied by 100 μm between observers surveying the same radiographs, corresponding to 0.065 pH units precision in the range pH 4-8. The sensor was designed to augment standard radiographs of tissue, bony anatomy, and hardware by also indicating local chemical concentrations.

Various types of hydrogel swelling behaviors can be examined using one of two lattice-based thermodynamic models, a modified double lattice model (MDL) and a Xin model combined with the Flory-Erman theory as a contribution for network elasticity. Depending on the thermoresponsibility of the hydrogel, we investigate the swelling behaviors of lower critical solution temperature (LCST) and upper critical solution temperature (UCST) types. Hourglass, closed-loop, and LCST- and UCST-types are also hypothetically described. In addition, reentrant-type swelling behaviors are analyzed for the given hydrogel systems. The swelling equilibriums of the gel networks are calculated using predetermined molecular interaction parameters obtained from phase equilibrium of the corresponding linear polymer systems. The calculated results for the various types of swelling behaviors verify the applicability of the lattice-based thermodynamic models for swelling equilibrium of the given hydrogel systems.

Permeation through polymeric membranes can be controlled by surface coating of a polyethylene terephthalate (PET) membrane with poly(N-isopropylacrylamide) (PNIPAAm) and inserting pores of defined geometry. When the temperature of the system rises above the volume phase transition temperature, the pores open, which allows permeation of formerly blocked particles. The exact control of the temperature allows defined change of the pore size and therefore enables separation abilities. Free swelling experiments are conducted to obtain the swelling behaviour of PNIPAAm. Then, a temperature expansion model is derived in order to simulate this behaviour with the finite element tool ABAQUS. The gained results are in excellent agreement with the observed shape change. Membranes with permeation control of particles can be used for biomedical application in microfluidics to analyse the size distribution of cells or in chemical information processing as a transistor-like component for an information-bearing chemical species. The possibility to simulate the behaviour of such permeation systems allows computer aided design and prediction of permeation abilities in these areas.

The introduction of the work Makromolekule by Herman Staudinger in 1919 brings back an understanding of the very early days of polymer science when characterizing the molecular structure of exact networks was a main goal of research. Here, we present updates to a swollen polymer network hypothesis with a focus on hydrogel physical properties. We discuss the connections between hydrogel structure, swelling behavior, mechanical properties, and transport properties, including the most substantial developments since the original Flory-Rehner model (1944) of swollen polymer networks. In addition to analyzing well-established and recent contributions to the swollen polymer network hypothesis, we introduce novel amendments that combine the insights of existing models. We suggest that coordinating rubberlike elasticity theory, equilibrium swelling theory, and mesh size theory will help to develop a universal predictive model for swelling, stiffness, and solute diffusivities in a diverse array of hydrogel formulations.

In this paper, we demonstrate a low-cost and tunable pH-triggered smart switch which is based on the deflection of a conductive elastic membrane induced by the swelling of a pH-responsive hydrogel. The described switch comprises of a porous plate, a gel chamber, a deflectable conductive membrane, and an electrical isolation cell. The switching action is initiated through a sudden pH change (e.g., transition from acidic stomach to basic small intestine) which in turn results in diffusion/time controlled hydrogel swelling, making it suitable for ingestible capsules targeted for pH-controlled localized drug release in the gastrointestinal (GI) tract. A typical prototype (9 mm in diameter and 3.2 mm in thickness) responds to pH changes from 2 to 7 (transition from stomach to small intestine) with a response time of one hour.

This review highlights recent developments in the field of stimuli-responsive hydrogels, focusing primarily on thin films, with a thickness range between 100 nm to 10 μm. The theory and dynamics of hydrogel swelling is reviewed, followed by specific applications. Gels are classified based on the active stimulus—mechanical, chemical, pH, heat, and light—and fabrication methods, design constraints, and novel stimuli-responses are discussed. Often, these materials display large physiochemical reactions to a relatively small stimulus. Noteworthy materials larger than 10 μm, but with response times on the order of seconds to minutes are also discussed. Hydrogels have the potential to advance the fields of medicine and polymer science as useful substrates for “smart” devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1084–1099

In this research, an antibiotic was loaded in the composites of polyethylene glycol (PEG), acrylamide (AAm) and acrylic acid (AAc) hydrogels matrices and their drug deliveries were tested. Effect of some parameters on the drug delivery was checked by UV-spectrophotometer. Temperature enhancement considerably increased hydrogel swelling and the drug release in the AAc and AAm. A dynamic model based on the Maxwell–Stefan equation was developed to model the drug delivery of hydrogels. COMSOL software was also applied to simulate buffer diffusion inside the hydrogels.

The preliminary results of gel swelling experiments are reported, and then compared to predictions made by a recently-developed finite element model (FEM). This model utilises energy transport between different energy domains, and is being used to simulate gel swelling dynamics. Initial experiments have revealed the model does capture the general behaviour of polymer hydrogel swelling dynamics and further improvements are necessary for better accuracy.

Hydrogels, polymers and various other composite materials may be used in sensing applications in which the swelling or de-swelling of the material in response to some analyte is converted via a transducer to a measurable signal. In this paper, we analyze models used to predict the swelling behavior of hydrogels that may be used in applications related to hydration monitoring in humans. Preliminary experimental data related to osmolality changes in fluids is presented to compare to the theoretical models. Overall, good experimental agreement with the models is achieved.

DNA-polyacrylamide hybrid hydrogels designed with covalent and double-stranded (dsDNA) crosslinks respond to specific single-stranded DNA (ssDNA) probes by adapting new equilibrium swelling volume. The ssDNA probes need to be designed with a base pair sequence that is complementary to one of the strands in a dsDNA supported network junction. This work focuses on tuning the hydrogel swelling kinetics by introducing polyethylene glycol (PEG) as a pore-forming agent. Adding PEG during the preparation of hydrogels, followed by removal after polymerization, has been shown to improve the swelling dynamics of DNA hybrid hydrogels upon specific ssDNA probe recognition. The presence of porogen did not influence the kinetics of osmotic pressure-driven (2-acrylamido-2-methylpropane sulfonic acid)-co-acrylamide (AMPSA-co-AAm) hydrogels’ swelling, which is in contrast to the DNA-sensitive hydrogels. The difference in the effect of using PEG as a porogen in these two cases is discussed in view of processes leading to the swelling of the gels. © 2015 by the authors; license MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license (http://creativecommons.org/licenses/by/4.0/).

A facile method for the characterization of hydrogel swelling is described which is based on the determination of changes in the liquid phase concentration of an excluded tracer as gel swells in a constant volume system. The utility of this approach is demonstrated with two responsive hydrogel preparations, one where swelling is influenced by system pH, the other by changes in specific solute concentration.

Although studies of charged hydrogel swelling focus on the swelling transition, hydrogels display pre‐transition swelling which may affect their performance in applications such as sensors. In this paper we investigate the effect of system parameters on the pre‐transition swelling of charged poly methacrylic acid (PMAA) hydrogels. We find that the pre‐transition swelling can be quite significant in magnitude (in our case ∼40% of the maximal swelling). Increasing the sub‐chain molecular weight increases swelling in the pre‐transition region only in the case where no salt is added; Contrary to expectation, in moderate ionic strength solutions the degree of swelling of longer chains is lower than that of shorter sub‐chains. Also contrary to expectation, in the case of longer sub‐chains the addition of salt decreases the gel volume in the pre‐transition region, thereby indicating that in this system a significant number of charges are dissociated. These trends can be understood by accounting for the ...

In this paper, a three-dimensional dynamic model describing drug delivery and swelling behavior of polyelectrolyte gels was developed based on the Maxwell-Stefan equation and Bio-heat equation. COMSOL software was employed to simulate hydrogel swelling and the transportation of created automatically by COMSOL, and it had 78035 elements, which was unconcerned with the results. The results showed that Maxwell-Stefan equation and Bio-heat equation were suitable for modeling hydrogel behavior of swelling with temperature change. In addition, when temperature increased, the hydrogel swelling increased which also intensified drug release.Copyright © 2013 by ASME

To achieve pH detection of multi-points, a new pH sensor based on pH sensitive hydrogel swelling detection by a fiber Bragg grating is proposed. The deflection of a silica membrane due to pH value change induced hydrogel swelling is measured by the center wavelength shifts of a fiber Bragg grating epoxied on the membrane. The relation between center wavelength shifts of the fiber Bragg grating with the hydrogel swelling behavior was studied experimentally. Around 100pm shift of the fiber Bragg grating center wavelength was observed when the pH value was changed from 4 to 7 or from 7 to 10 by using pH standard solutions, which fundamentally proved the feasibility of this method for pH detection.

The ability of hydrogels to respond to relatively small changes in stimuli with relatively large changes in volume allows a wide variety of applications. This chapter addresses hydrogels with regard to the chemical identity of hydrophilic polymers and copolymers, polymer synthesis, the degree of crosslinking and hydrogel porosity, and bulk geometry of hydrogels in the form of matrix, membrane and erodible systems. The relationships between these features and hydrogel swelling behavior upon stimulation are also described. Finally, various exploitations of hydrogel swelling behavior in developing highly sensitive, real-time biosensors are discussed.

A method for hydrogel swelling kinetics measurement has been demonstrated by working with impedance analyzing technique.

Hydrogels containing benzo-18-crown-6 were used to modify microcantilevers for measurements of the concentration of Pb2+ in aqueous solutions. These microcantilevers undergo bending deflection upon exposure to solutions containing various Pb2+ concentrations as the result of a swelling of the hydrogels. It was found that a concentration of 10(-6) M Pb2+ can be detected using this technology. Other cations, such as Na+, have no effect on the deflection of this cantilever. The cation K+, which also complexes with benzo-18-crown-6, could interfere with Pb2+ detection, but only at high concentrations (> 10(-4) M).

We study the configuration of atomically-thin graphene membranes on tunable microhydrogel patterns. The polyethylene oxide microhydrogel structures patterned by electron-beam lithography show increase in height, with a persistent swelling ratio up to ?10, upon exposure to vapors of an organic solvent. We demonstrate that modifying the height fluctuations of the microhydrogel affects the strain and morphology of ultrathin graphene membrane over-layer. Raman spectroscopic investigations indicate that small lattice strains can be switched on in mechanically exfoliated few-layer graphene membranes that span these microhydrogel structures. In case of chemical-vapor deposited single-layer graphene, we observe Raman signatures of local depinning of the membranes upon swelling of microhydrogel pillars. We attribute this depinning transition to the competition between membrane-substrate adhesion energy and membrane strain energy, where the latter is tuned by hydrogel swelling. � 2014 AIP Publishing LLC.

An oligonucleotide–polymer hybrid hydrogel displaying swelling response in a logical AND and OR fashion depending on specific stimuli by probe oligonucleotides was prepared. The hydrogel acts as a transducer of the specific recognition of DNA sequences into micro- and macroscale mechanics. Input oligonucleotide probes induce hydrogel swelling ratio at two signal levels.