Gelation and Swelling Behavior of Semi-Interpenetrating Polymer Network Hydrogels Based on Polyacrylamide and Poly(vinyl alcohol)

Novel semi-Interpenetrating Polymer Network (semi-IPN) hydrogels based on partially Hydrolyzed Polyacrylamide (HPAM) and Poly(Vinyl Alcohol) (PVA) were prepared by solution crosslinking using chromium triacetate. Effects of PVA content on the gelation process and swelling behavior in tap water and different electrolyte solutions were investigated. Study of the gelation behavior using dynamic rheometery showed that the limiting storage modulus of the semi-IPN gels decreased with increasing PVA content. It was also found that increasing the PVA content increases the loss factor, indicating that the viscous properties of this gelling system increase more strongly than the elastic properties. The swelling ratio of the semi-IPN gels in tap water decreased as the concentration of the PVA increased. However, the semi-IPN gels showed lower salt sensitivity factor in synthetic oil reservoir water as compared with HPAM gels. Therefore, they are potentially good candidates for enhanced oil recovery applications.     

Study on the Dynamic Rheometry and Swelling Properties of the Polyacrylamide/Laponite Nanocomposite Hydrogels in Electrolyte Media

Polyacrylamide/laponite/chromium triacetate nanocomposite (NC) hydrogels were prepared by incorporation of the laponite nanoparticles in partially hydrolyzed polyacrylamide followed by cross-linking of their aqueous solutions with chromium triacetate. Influence of nanoparticle, cross-linker, polymer concentrations, and gelation media (water) temperature, salinity, and rheometer frequency on the viscoelastic behavior of the NC hydrogels were studied by probing the network properties. In addition, swelling behaviors of these NC gels in tap and oil reservoir water were evaluated. According to dynamic rheometry of the gelation process, the limiting storage modulus of the NC gels increased with increasing laponite content. The addition of laponite into the polyacrylamide gelling system increased their viscous properties more strongly than the elastic properties. The ultimate elastic modulus of the NC gels increased with increasing water salinity and temperature. Increasing rheometer frequency during gelation retarded the sol–gel transition and decreased the ultimate elastic modulus. The equilibrium swelling ratio of the NC hydrogels in tap water decreased with increasing laponite content. The salt sensitivity of the NC gels in oil reservoir water slightly decreased with increasing laponite content. These results suggest the superiority of the hydrolyzed polyacrylamide (HPAM)/chromium acetate/laponite NC hydrogels for water shut-off applications in oil reservoirs as compared with unfilled HPAM gels.     

Preparation and Swelling Behavior of Partially Hydrolyzed Polyacrylamide Nanocomposite Hydrogels in Electrolyte Solutions

In this research, nanocomposite hydrogels were prepared by cross‐linking of partially hydrolyzed polyacrylamide/sodium montmorillonite aqueous solutions with chromium triacetate. The gelation process and influence of nanoclay content and salt concentration on swelling behavior were investigated. Study of gelation behavior using dynamic rheometry method showed that increasing the nanoclay content decreases the storage modulus, due to the partial adsorption of polymer chains onto the clay surface and ionic interaction between negative layers of sodium montmorillonite and Cr.³⁺ By increasing the cross‐linker concentration of the gelation system, the viscous energy dissipation properties of the nanocomposite gel decreases. Swelling ratio of the nanocomposite gels in distilled water decreased as the concentration of the nanoclay increased. However, nanocomposite gels showed lower salt sensitivity in electrolyte media compared with unfilled gels.     

Swelling and Gelation Time Behavior of Sulfonated Polyacrylamide/Chromium Triacetate Hydrogels

A hydrogel was prepared by crosslinking of aqueous solutions of sulfonated polyacrylamide/chromium triacetate for use in water shut-off operations in oil reservoirs. The effects of pH, salinity, retarder and temperature, as well as co-polymer and crosslinker concentration, on the gelation time were investigated. The results indicated that as temperature increased, gelation occurred more rapidly. The activation energy was measured as about 86 kJ/mol. The effects of initial pH and retarder on the gelation time were also examined. The results showed that addition of retarder and increasing of pH increased and decreased the gelation time, respectively. The increase of co-polymer concentration in solution increased the gel swelling. However, the increase of crosslinker concentration decreased the gel swelling. In the presence of electrolytes, the gel swelling decreased by about 80%. Finally, some usable practical recommendations are offered for the gelling systems in reservoirs.     

Preparation,Characterization and Coreflood Investigation of Polyacrylamide/Clay Nanocomposite Hydrogel System for Enhanced Oil Recovery

The synthesis and characterization of polyacrylamide/clay nanocomposites for the development of hydrogel system used in enhanced oil recovery is described. The synthesized nanocomposite copolymer was crosslinked with Chromium (III) acetate to form the hydrogel which exhibited an acceptable gel strength, gelation time and gel stability. The nanocomposite gels prepared with low crosslinker concentration (2000 ppm chromium acetate) showed higher gel strength and required longer gelation time than the conventional polyacrylamide (PAAm) gel; these are desirable properties for the effective placement of gel during enhanced oil recovery operations. The effects of various parameters, such as polymer and crosslinker concentration, on the gelation time and gel strength were evaluated using the bottle testing method. X-ray diffraction (XRD) and field-emission scanning electron microscopy (FESEM) revealed the formation of intercalated and exfoliated clay morphologies. The effects of the clay content on the thermal stability and gel strength of the gel network were also investigated by thermogravimetric analysis (TGA) and rheological measurements (oscillatory time sweep profiles), respectively. Also, in-situ gelation and core flooding experiments revealed that a significant permeability reduction of the sand pack cores could be achieved at reservoir conditions when they were treated with the developed nanocomposite gel formulation. Hence, this nanocomposite gel system with low crosslinker concentration (10,000 ppm of nanocomposite polymer concentration containing 2000 ppm of clay with 2000 ppm chromium acetate crosslinker) may be suitable in water shut-off treatments required for enhanced oil recovery from the oil fields.     

Synthesis and Properties of Polyacrylamide-Based Conducting Gels with Enhanced Mechanical Strength

A nanocomposite conducting hydrogel, polyacrylamide/MWNT/clay (abbreviated as PAM/MWNT/clay), prepared through in situ free radical aqueous polymerization and crosslinked by both clay, as a functional physical crosslinker, and N,N′-methylenebisacrylamide (MBA) as a chemical crosslinker, is reported. The morphology of the gels was characterized by scanning electron microscopy (SEM). The mechanical properties and electrical conductivity were also studied. The results show that the prepared hydrogels had the expected chemical components, with a highly porous structure, and the gels also showed high mechanical strength. The mechanical strength and electrical conductivity value increased with increasing content of multi-walled nanotube (MWNT), and decreased with increasing content of water.     

Physicochemical properties and microstructure of composite surimi gels: The effects of ultrasonic treatment and olive oil concentration

This study was conducted to evaluate the effects of extra virgin olive (EVO) oil incorporation on the physicochemical properties and microstructure of surimi gels subjected to ultrasound-assisted water-bath heating. As the oil content was increased from 0 to 5 g/100 g, the breaking force and gel strength of the surimi gels significantly decreased, while the whiteness level exhibited the opposite tendency irrespective of the heating method. Compared with the traditional water-bath heating method, the ultrasonic heating promoted the unfolding of the α-helix structure and intensified the formation of β-sheet content and non-covalent bonds (ionic bonds, hydrogen bonds, and disulfide bonds), especially disulfide bonds, which contributed to the further crosslinking of the proteins and to gelation, thereby improving the gels’ strength. In addition, smaller cavities and compact microstructures were observed in the low-oil (≤3 g/100 g) surimi gels under ultrasonic treatment, which effectively prevented water migration in the gel network and resulted in a high water holding capacity and uniform water distribution. However, the ultrasonic treatment barely remedied the poor microstructures of the high-oil (>3 g/100 g) surimi gels owing to oil coalescence, which weakened the protein–protein interaction. In conclusion, ultrasonic treatment combined with water-bath heating significantly improved the gelation properties of the low-oil surimi gels, although it did not remarkably improve those of the high-oil gels. The choice of a suitable oil concentration could be of great importance for the production and functioning of surimi products via ultrasound-assisted treatments.     

Transglutaminase-induced gelation properties of soy protein isolate and wheat gluten mixtures with high intensity ultrasonic pretreatment

Soy protein isolate (SPI) and wheat gluten (WG) are widely used in commercial food applications in Asia for their nutritional value and functional properties. However, individually each exhibits poor gelation. In this study, we examined the microbial transglutaminase (MTGase)-induced gelation properties of SPI and WG mixtures with high intensity ultrasonic pretreatment. Ultrasonic treatment reduced the particle size of SPI/WG molecules, which led to improvements in surface hydrophobicity (H_o) and free sulfhydryl (SH) group content. However, MTGase crosslinking facilitated the formation of disulfide bonds, markedly decreasing the content of free SH groups. Ultrasonic treatment improved the gel strength, water holding capacity, and storage modulus and resulted in denser and more homogeneous networks of MTGase-induced SPI/WG gels. In addition, ultrasonic treatment changed the secondary structure of the gel samples as determined by Fourier transform infrared spectroscopic analysis, with a reduction in α-helices and β-turns and an increase in β-sheets and random coils. Thus, ultrasound is useful in facilitating the gelation properties of MTGase-induced SPI/WG gels and might expand their utilization in the food protein gelation industry.     

Polyvinyl Alcohol/Na-Montmorillonite Nanocomposite Hydrogels Prepared by Freezing–Thawing Method: Structural,Mechanical, Thermal,and Swelling Properties

Physically crosslinked nanocomposite hydrogels based on polyvinyl alcohol (PVA) containing Na-montmorillonite were prepared by the cyclic freezing–thawing method. The primarily exfoliated morphology of prepared nanocomposite hydrogels was confirmed by X-ray diffractometry (XRD) and transmission electron microscopy (TEM) as complementary techniques. It is shown that some interactions developed between the hydroxyl groups of PVA chains and Na-montmorillonite silicate layers in the nanocomposite hydrogels. Differential scanning calorimetry (DSC) results indicated some shifting in the glass transition temperature of the PVA hydrogel in the presence of the nanoclay. Swelling measurements showed that the swelling ratios of the nanocomposite hydrogels were increased either by decreasing the Na-montmorillonite content or by increasing the swelling medium temperature. Dynamic mechanical–thermal properties results showed higher storage modulus for nanocomposite hydrogels in temperature ranges both below and above 0°C. It was also found that the hardness of the nanocomposite hydrogels increased by increasing the nanoclay loading level.     

P(NIPAM-co-AA)/Clay nanocomposite hydrogels exhibiting high swelling ratio accompanied by excellent mechanical strength

In this paper, a series of P(NIPAM-co-AA)/Clay composite hydrogels (abbreviated as NAC gels) with high swelling ratio and excellent mechanical strength were synthesized and characterized by DMA, SEM, and IR. In NAC gels composed of a unique organic P(NIPAM-co-AA)/inorganic (clay) network, the inorganic clay acts as a multifunctional cross-linker in place of an organic cross-linker as used in the conventional chemically cross-linked hydrogels (abbreviated as OR gels). The NAC gels exhibit excellent swelling ratio, and there was no detectable change in properties on altering the concentration of clay, while the swelling ratio tends to decrease slightly when C _clay increases up to 25 wt%, which was revealed in swelling measurements. IR spectra show that clay has been intercalated by copolymers. Furthermore, results of DMA reveal that the composite hydrogel has an excellent mechanical strength by using a wide range of clay concentration, while the moduli improve with increasing C _clay.     

Swelling and Drying Mechanisms of Freeze-Thawed Polyvinyl Alcohol/Egg White/Montmorillonite Bionanocomposite Hydrogels

Abstract

Polyvinyl alcohol and egg white bionanocomposite hydrogels loaded with montmorillonite clay were fabricated by a freezing-thawing technique. The bionanocomposite hydrogels showed an exfoliated morphology and they had a more interconnected and dense network as compared with the clay-free sample. The montmorillonite layers acted as multifunctional crosslinkers and the bionanocomposite hydrogels had nanoscale, slit-shaped pores. The swelling ratios of the bionanocomposite hydrogels were increased either by decreasing the content of incorporated montmorillonite or by increasing the pH of the swelling medium. It was found that the bionanocomposite hydrogels having a higher content of montmorillonite exhibited a slightly slower drying process with a longer drying duration. Using the Ritger-Peppas model, it was shown that the swelling and drying mechanisms for all bionanocomposite hydrogels were non-Fickian diffusion. According to the Peppas-Sahlin model, it was found that the absorption of the swelling agent molecules during the swelling process and also the removal of water molecules during the drying process in the early stages of the processes occurred mostly due to their diffusion. At higher swelling or drying times, the contribution of the relaxation (for swelling) and shrinkage (for drying) of the polyvinyl alcohol polymeric chains and egg white protein chains was increased.     

Synthesis of Novel Double Network Hydrogels via Atom Transfer Radical Polymerization

Novel double network (DN) hydrogels were prepared via atom transfer radical polymerization (ATRP) of the first network using two different initiators, and followed by ultraviolet (UV) photo-initiated polymerization for the second network. The first networks of DN hydrogels were prepared by using two different initiators; one is a one-side initiator, and the other is a double-side initiator. The mechanical properties of various DN gels, such as water content and compressive strength, were studied. The network structure of the DN hydrogels was also characterized by dynamic light scattering. Thus, we demonstrated that the ATRP method is useful to control the network structure of the first network for DN gels. Extensive inhomogeneous structure of the first network was obtained by ATRP method and increased both the swelling degree and softness of DN gels.     

Gelation,Network Structure and Properties of Physically Crosslinked Gelatin Gels: Effect of Salt Cation Valence

A series of physically cross-linked gelatin networks with and without salts (NaCl, CaCl₂ and CrCl₃) were prepared. The effect of the valence of the cations at the same concentration on the gelation of the gelatin was investigated by a rheometer. It was found that both the gelation temperature and the distance between crosslinks of the networks increased with an increase in valence of the cations. However, the opposite trend was observed for the storage modulus of the gels. Moreover, the influences of the valence and concentration of cations on the swelling and thermal behaviors of the gelatin composite films were studied in detail. It was generally observed that the equilibrium swelling ratio (ESR) decreased with salt concentration for all three cations following the trend ESR for Cr³⁺ <Ca²⁺ <Na⁺. However, the glass transition temperature (T_g) showed an opposite dependence on the valence and concentration of the cations. The relationships between the network structure and the properties of the gelatin composite films are discussed based on two effects (shielding and crosslinking effect), caused by the introduction of the salts.     

Chemical semi-IPN hydrogels for the removal of adhesives from canvas paintings

Semi-interpenetrating (IPN) poly (2-hydroxyethyl methacrylate)/polyvinylpyrrolidone hydrogels were synthesized and used for the removal of adhesives from the back of canvas paintings. The high water retention capability and the specific mechanical properties of these gels allow the safe cleaning of water-sensitive artifacts using water-based detergent systems. The cleaning action is limited to the contact area and layer-by-layer removal is achieved while avoiding water spreading and absorption within water-sensitive substrates, which could lead, for example, to paint detachment. The use of these chemical gels also avoids leaving residues over the treated surface because the gel network is formed by covalent bonds that provide high mechanical strength. In this contribution, the physicochemical characterization of semi-IPN chemical hydrogels is reported. The successful application of an o/w microemulsion confined in the hydrogel for the removal of adhesives from linen canvas is also illustrated.     

Influence of environmental solution pH and microstructural parameters on mechanical behavior of amphoteric pH-sensitive hydrogels

Amphoteric hydrogels contain both ionizable acidic and basic groups attached on the polymer chains, which can change their volume in response to the slight alteration of the surrounding environmental p H. In this paper, a theory of equilibrium swelling of amphoteric p H-sensitive hydrogels which is an extension of the formalism proposed by Marcombe et al. and a new hybrid free-energy density function of amphoteric hydrogels composed of the Edwards-Vilgis slip-link model and the Flory-Huggins solution theory as well as the contributions of mixing the mobile ions with the solvent, and dissociating the acidic and basic groups are presented for the prediction of the influence of environmental solution p H, microstructural parameters and geometric constraints on mechanical behavior. The calculations were modeled on chitosan-genipin gels, and the results were compared to experimental data. Numerical calculations show that the model is able to predict the dependence of swelling on p H and crosslinker qualitatively well and quantitatively close to the experimental data. Each gel shows minimal swelling at low p H but an increase in swelling until a maximum was reached; for most of the p H range, a good fit was achieved except for where the maximum swelling occurs; for experimental data, the maximum swelling appears at about pH = 4 , but for modeled data the maximum swelling appears between pH = 4 and pH = 6 ; each gel swell decreasing with increasing crosslinker concentration was also successfully predicted. The calculated results also show that microstructural parameters and geometric constraints have a significant impact on the mechanical behavior of the amphoteric hydrogels; the gel swells less when the network is more densely entangled and the maximum swelling ratio of the gels under biaxial constraint is only about one-third of the maximum when the gels swell freely. The theory developed here is valuable for the design and optimization of a drug delivery system.     

Study on the Electrospinnability of Polyvinyl Alcohol Solutions by Using Water/N,N-dimethylacetamide or Water/N,N-dimethylformamide as Solvents

The electrospinning of poly(vinyl alcohol) (PVA) (99% hydrolysis degree) aqueous solution with added organic solvents N, N-dimethylacetamide (DMAc) or N, N-Dimethylformamide (DMF) was investigated. After the addition of the organic solvents to the PVA aqueous solutions, the surface tension and conductivity decreased and the viscosity significantly increased, which caused an improved electrospinnability of the PVA solutions. The micro-structures of the three solutions were investigated by dynamic light scattering (DLS), differential scanning calorimetry (DSC) and dynamic viscoelastic measurements. The DLS data revealed that the swelling of the PVA coils was slightly increased but the overlaps of PVA coils decreased greatly after one of the organic solvents was added to the aqueous solution. The DSC data showed both the water-rich phase and PVA-rich phase were destroyed and the solution became more homogenous after the addition due to the interaction between the organic solvent and water. Viscoelastic data showed there was an obvious difference in the storage modulus behavior between the aqueous solutions and the water/solvents solutions. These changes in the micro-structure and properties were the reason for the improved electrospinnability of the PVA solution. According to scanning electron microscopy (SEM), the average diameter of the electrospun PVA nanofibers was about 308 nm for the DMF/water system, and 255 nm for the DMAC/water system, as compared with uneven diameter nanofibers for the water system.     

Homogeneous and inhomogenous polyacrylamide gels as observed by small angle neutron scattering: A connection with elastic properties

Small angle neutron scattering of polyacrylamide solutions and gels is presented for different polymer and cross link concentrations. The gels are analyzed in connection with their elastic properties. For less than 11% of polymer concentration and for small cross link contents , it was found that the gels are no more heterogeneous than the solutions. This corresponds to the range of where the elastic modulus increases with . For larger cross link contents when the elastic modulus decreases if increases, the sample appears to be strongly heterogeneous with a large size distribution of the inhomogeneities. The results are compared with the recent model of Oshmyan and Benguigui of the elastic properties of the polyacrylamide gels. Thus a relation can be proposed between the observation of the inhomogeneities by scattering and the mechanical properties Received 30 December 1997 and Received in final form 26 June 1998     

Effect of high hydrostatic pressure and reducing sodium chloride and phosphate on physicochemical properties of beef gels

ABSTRACT

The effect of high hydrostatic pressure (HHP) treatment (100–200?MPa, 10?min, 20°C) combined with sodium chloride and sodium phosphate on the physicochemical properties of beef gels was investigated. The water content, cooking losses, color, protein composition by SDS-PAGE analysis and texture parameters of beef gels were determined. The beef gels treated with high pressure at 150?MPa showed a synergistic effect in the increased water content and the decreased cooking losses compared with the unpressurized gels. The L*, a* and b* color values of beef gels were slightly decreased under HHP treatment at 100–200?MPa. In the SDS-PAGE analysis, the staining intensity of the α-actinin protein band was decreased in pressurized samples. The cohesiveness, adhesiveness, gel strength and modulus of elasticity were improved after HHP treatment. Application of high pressure treatment (150–200?MPa) before heat treatment would be beneficial for the manufacturing of low salt and/or low phosphate meat products for a healthy diet.     

Effect of κ-carrageenan on volume phase transition for polyacrylamide (PAAm) hydrogel using the fluorescence technique

Steady-state fluorescence (SSF) technique was employed for studying swelling of polyacrylamide (PAAm) gels with various content of κ-carrageenan (κC). Disc shaped composite hydrogels were prepared by free-radical crosslinking copolymerization of acrylamide (AAm) with various amounts κC. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as crosslinker and initiator, respectively. Pyranine was introduced as a fluorescence probe. Fluorescence intensity of pyranine was monitored during in situ swelling processes of composite gels. It was observed that fluorescence intensity values decreased as swelling is proceeded. Li–Tanaka equation was used to determine the swelling time constants, τ and cooperative diffusion coefficients, D from intensity variations during the swelling processes. It was shown that swelling time constants, τ decreased and diffusion coefficients, D increased as the κC content in the composites are increased.     

Synthesis and Properties of Tannic Acid-Based Hydrogels

Hydrogels were synthesized by using tannic acid (TA) as a chemical cross-linker for the copolymer of allylglycidyl ether and acrylamide. The swelling ratio of the hydrogels increased with increasing amount of TA and decreased with increasing amounts of allylglycidyl ether. The hydrogels exhibited pH sensitivity; the swelling ratio increased with pH. Adsorption experiments of the hydrogel for Cu (II) ions suggested that the hydrogels can be used as an adsorbent for removal of Cu (II) heavy metal ions from dilute aqueous solutions.