Preparation of transparent poly(vinyl alcohol) hydrogel

A transparent hydrated gel is prepared from a poly(vinyl alcohol)(PVA) solution in a mixed solvent consisting of water and dimethyl sulfoxide(DMSO). Upon cooling the PVA solution below the room temperature, a gel is formed as a consequence of crystallization of PVA molecules. Exchange of DMSO in the formed gel with water gives the hydrated PVA gel which is high in tensile strength, water content, and light transmittance.     

Studies of reactions with polymers. II. The reaction of maleic anhydride with acrylonitrile onto PVA and the properties of the resultant

Graft terpolymers were prepared by graft polymerization of a mixture of acrylonitrile (AN) and maleic anhydride (MA) onto PVA in DMSO solution using KPS as an initiator. Structure and solubility of graft terpolymers varied with the concentrations of KPS and MA. Both lower and upper critical values of KPS concentration varied with MA concentration, and the resulting reaction could be divided into three regions—crosslinked, hydrophobic, and hydrophilic regions. Structures of graft terpolymers were considered to be composed of homopolymer side chain grafted onto PVA while gelation occurred from the surplus radicals in PVA backbone to carry on the coupling reaction. The mechanical properties and viscosities increased with the increase of the wt % of AN in graft terpolymers; however, to increase AN content in PVA by increasing KPS concentration would bring about the oxidation scission and do damage to mechanical properties. Thus it becomes obvious that KPS can only be used at a suitable amount.     

Effects of solvent adsorption on solution properties of poly(vinyl alcohol)/dimethylsulfoxide/water ternary systems

In this study, the solvent adsorption phenomena of poly(vinyl alcohol) (PVA) in cosolvent mixtures of dimethylsulfoxide (DMSO; solvent 1) and water (solvent 2) were investigated. Typically, this cosolvent mixture could form hydrogen‐bonded DMSO/(water)₂ complexes, involving one DMSO and two water molecules. Because of the complex formation in the cosolvent mixtures, PVA chains preferentially adsorb water molecules at DMSO mole fraction X₁ < 0.33, but preferentially adsorb DMSO molecules at X₁ > 0.33. The preferential adsorption of DMSO (a good solvent for PVA) could cause the relatively extended conformation of PVA chains in solutions because of the increase in excluded volume effect. Because of various interactions between PVA chains and cosolvent mixtures, the aggregation and gelation behaviors of PVA solutions were significantly affected by the composition of cosolvent mixture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3211–3217, 2004     

Study of cryostructuration of polymer systems. XIV. Poly(vinyl alcohol) cryogels: Apparent yield of the freeze–thaw‐induced gelation of concentrated aqueous solutions of the polymer

Poly(vinyl alcohol) (PVA) cryogels, which are formed as a result of freeze–thaw treatment of concentrated solutions of the polymer, were studied in respect to the amount of gel and sol fractions in these heterogeneous macroporous gel materials depending on the conditions of the thawing step of similar cryotropic gelation. It was shown that the yield of gel fraction (the efficiency of the gelation process) was not quantitative; this was controlled by the initial PVA concentration in the solution to be frozen, and to a higher extent, by the thawing rate, when the yield increased with slowing of the defrostation process. The sol fraction could be extracted from the PVA cryogels by their rinsing with water at room temperature; the extraction of the sol was accompanied with the variations of the swelling parameters of the gels (initial slight upswelling and subsequent gradual deswelling), as well as with analogous, in their character, variations of the gel strength. It was also demonstrated that at the evaluation of the fusion enthalpies of PVA cryogels with the aid of the Eldridge–Ferry equation a consideration of the values of gel‐fraction yield gave rise to the significantly higher ΔH values than in traditional cases commonly used for the thermoreversible gels, where such an yield was not taken into account. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1822–1831, 2000     

Preparation of porous TiO2 by a novel freeze casting

Highly porous and open interconnected pore structural TiO₂ were prepared by a novel freeze casting method. In the experiment, the well-dispersed aqueous slurries were first frozen, and then dried at a reduced vacuum. Since the sublimation of ice crystals developed in the freezing process, the green bodies with highly porous were obtained. The phase composition and the microstructure of the sintered samples were characterized by XRD, SEM, porosity and the pore size distribution was measured by mercury porosimetry. The results demonstrated that the PVA concentration in the slurries remarkably affect the microstructure of TiO₂ ceramics. The pore morphology of TiO₂ ceramics with 3 wt.% polyvinyl alcohol (PVA) addition was dendritic, and however, the pore morphology of TiO₂ ceramics with 6 wt.% PVA addition changed into columnar. The reason for the variation of the pore morphology was ascribed to the effect of the PVA gelation on the growth behavior of the ice crystals.     

Formation Mechanism Analysis of Shear-Induced Microgel Filaments during Microfluidic Gelation

Dynamic microfluidic gelation enables the fabrication of bundle-structured multiple parallel microgel filaments from an aqueous two-phase system. The formation mechanism of shear-induced filaments from an alginate (Alg)/polyvinyl alcohol (PVA) blend is studied using red-colored PVA and a titanium alkoxide PVA crosslinker. Bundle-structured Alg microgel filaments are formed through contact with a Ca²⁺ crosslinker. In this process, the PVA acts as a sacrificial polymer to maintain the Alg gel filaments because approximately 90% of the red-colored PVA is released from the Ca²⁺-crosslinked Alg gel filaments into the wash water. In addition, the fabrication of PVA gel filaments shows that the sacrificial PVA is also transformed into fibrillar domains under shear. However, the filament structure cannot be formed from a single-phase PVA/Alg solution. These results clearly show that the bundle-structured gel filaments are maintained by preventing the fusion of filaments during gelation based on the tendency of the non-crosslinked filaments to cause splitting of the gelled filaments.     

Mineralization of hydroxyapatite on a polymer substrate in a solution supersaturated by polyelectrolyte

In this article, a new method to construct composites of hydroxyapatite (HAP) and polymer material is introduced. A previously developed method for mineralization of CaCO₃ on a polymer substrate was applied to HAP. A solution that contained Ca²⁺, PO₄^3–, and OH‐ ions was supersaturated with polyacrylic acid (PAA) that, at the same time, formed a polymer complex with the substrate, a polyvinyl alcohol (PVA) film, at the substrate surface. In this thin surface layer, nucleation of HAP took place. Subsequently, the disklike domains of HAP that were generated spread until they covered the PVA film surface. By regulating the pH of the supersaturated solution at around 7.4, the domain size decreased and the quantity of deposited material increased. Approximately 20 mg of HAP coating was obtained on a PVA film of 1 cm radius when the film was soaked in single 200 mL batch of the supersaturated solution for 21 days. The junction between HAP layer and PVA substrate film was found to be very firm. When a crosslinked PVA/PAA was used as the substrate, the film swelled in the supersaturated solution to form a hydrogel. Then mineralization took place within the gel, and a transparent monolithic composite of HAP and the polymer network was obtained. In 13 days, the weight increase was 29 mg, which corresponded to a 71 wt % HAP mineralization ratio of the composite. By changing crosslinking degree and HAP mineralization ratio, the flexibility of composite will be controlled in a wide range. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1465–1470, 2006     

Effects of cononsolvency on gelation of poly(vinyl alcohol) in mixed solvents of dimethyl sulfoxide and water

We studied the rates of gelation and phase separation of poly(vinyl alcohol) (PVA) solutions in mixtures of dimethyl sulfoxide (DMSO) and water at 25 °C and found that both the rates show a maximum at a volume fraction of DMSO φ_DMSO=0.60 while gelation was not observed either in pure DMSO or pure water, suggesting that water-DMSO is a cononsolvent system for PVA. On the basis of the data by Cowie [Can J Chem 36 (1961) 2240] we concluded that the 1:2 stable complex between one DMSO molecule and two water molecules is the main cause of this cononsolvency.     

Preparation and properties of PVA/PVP hydrogels containing chitosan by radiation

Radiation can induce chemical reactions to modify polymers even when they are in the solid state or at a low temperature. Radiation crosslinking can be easily adjusted by controlling the radiation dose and is reproducible. The finished product contains no residuals of substances required to initiate the chemical crosslinking, which can restrict its application possibilities. In these studies, hydrogels for wound dressing were made from a mixture of chitosan and polyvinyl alcohol (PVA)/poly‐N‐vinylpyrrolidone (PVP) by freezing and thawing, gamma‐ray irradiation, or combined freezing and thawing and gamma‐ray irradiation. The physical properties of the hydrogel, such as gelation, water absorptivity, and gel strength, were examined to evaluate the usefulness of the hydrogels for wound dressing. The PVA/PVP composition was 60:40, PVA/PVP–chitosan ratio was in the range 9:1–7:3, and the concentration of, PVA/PVP–chitosan as a solid was 15 wt %. A mixture of PVA/PVP–chitosan was exposed to gamma irradiation doses of 25, 35, 50, 60 and 70 kGy to evaluate the effect of irradiation dose on the physical properties of hydrogels. Water‐soluble chitosan was used in these experiment. The physical properties of the hydrogels, such as gelation and gel strength, were higher when the combination of freezing and thawing and irradiation were used rather than just freezing and thawing. The PVA/PVP–chitosan composition and irradiation dose had a greater influence on swelling than gel content. Swelling percent increased as the composition of chitosan in PVA/PVP–chitosan increased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1787–1794, 2002     

Effect of ionizing irradiation and blending of natural rubber latex on polyvinylalcohol gelation by using chemical and freezing–thawing processes for use in the field of construction engineering

The aim of this work is to study the gelation behavior of polyvinylalcohol (PVA) and natural rubber latex (NRL) using two methods: The first was chemical gelation by adding sodium borate as a crosslinking to obtain a modeling clay gel able to draw easily under tension (using drum mill) or by using hand pressing. Irradiation was then applied at 2.5 Mrad to possess more crosslinking effect, where stable and rubbery‐gel shape in the dimension was obtained. The second method, where samples of liquid PVA were frozen and thawed for three consecutive cycles. The obtained gel was quite rubbery but completely soluble in hot water at 70°C. Irradiation was performed at 2.5 Mrad to produce a highly rubbery gel and resistant to boiled water. Also, blending of NRL with PVA induced a significant increase in gel‐elasticity and resistivity to boiled water. Factors affecting the properties of the prepared gel such as gel draw ability and gel strength were studied. The study was supported with thermal and scanning electron microscopy (SEM) to investigate the modification of PVA‐gel behavior through irradiation and blending with NRL processes. The results indicated that the PVA‐gel obtained by chemical method or blended with NRL through freezing–thawing gelation gave a superior ability for cement loading. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Properties and structure of poly(vinyl alcohol)/silica composites

The relationships between the properties and structure are discussed for poly(vinyl alcohol)(PVA)/silica composites prepared through the sol‐gel process. The composites became stiff and brittle with increasing the silica content. The properties of the composites were changed drastically at around the composition of PVA/silica = 70/30 wt %. For example, there was no large change in the Young's modulus above 30 wt % of silica content (Pure PVA: 31.8 MPa, silica 30%: 52.6 MPa, silica 50%: 55.2 MPa). Consequently, it was considered that the three‐dimensional network structure of silica could be formed in the composite with more than 30 wt % of silica in PVA. From this behavior, it could be considered that the crystal growth of PVA was remarkably inhibited by silica network. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 133–138, 1999     

Fabrication and characterization of electrospun psyllium husk-based nanofibers for tissue regeneration

The present study reports for first time the blending of psyllium husk (PH) powder/gelatin (G) in the polymer-rich composition of polyvinyl alcohol (PVA) to make an electrospinnable solution. The composite was prepared in 3 different ratios viz., 100% (wt/wt) (PVA + PH), 75% + 25% (PVA + 75PH + 25G) (wt/wt) and 50% + 50% (PVA + 50PH + 50G) (wt/wt) in 6% PVA solution. Optimum electrospinning parameters were evaluated for all the prepared blends. The fabricated nanofibers were characterized by scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared, differential scanning calorimetry, porosity percentage, and fiber orientation using ImageJ software. A qualitative in vitro degradation study at room temperature is supported by SEM images. The cellular interactions were characterized by MTT assay of NIH-3T3 fibroblast cells for 2 and 4 days with an optimum cell growth of >50% by fourth day of culture and long-term cultivation of L929-RFP cells was observed for 10 days. The nanofibers were formed in the range of 49–600 nm. PVA + 75PH + 25G when cultured with L929-RFP cells exhibited highest fluorescence intensity and thus supported cellular proliferation significantly. Based on the results obtained from various analyses, we anticipate that fabricated psyllium-based nanofiber can be used as a promising candidate for wound healing and other biomedical applications.     

Rheological characterization of shear‐induced structural formation in the solutions of poly(vinyl alcohol) in dimethyl sulfoxide

Gelation behavior of the solutions of poly(vinyl alcohol) (PVA), whose syndiotactic diad content was 52% and weight‐average molecular weight of PVA ranged from 89,000 to 186,000, in dimethyl sulfoxide (DMSO) was investigated in terms of shear rate, concentration, and molecular weight of the polymer. To trace time‐dependent gelation behavior, a programmed time sweep experiment was carried out by repeating the following procedure 3 times; 10 min of measurement followed by 5 min relaxation. All of the PVA solutions in DMSO exhibited time‐dependent rheological responses, particularly under low shear rate of 2 rad/s, indicative of the formation of physical structures. At high shear rate of 200 rad/s the rheological responses were independent of time. Referring to Winter's view on gelation, a weak shear produced a soft gel structure whereas a strong shear produced an irreversible strong gel. Gelation was more affected by molecular weight than by concentration over the period of shearing. At low frequency, relaxation time was increased with time, and then leveled off after prolonged shearing. At high frequency, however, little change of relaxation time was noticed. They can be interpreted as a consequence of formation of three‐dimensional gel structure through the polar interactions by hydroxyl groups whose strength was dependent on shearing conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 465–471, 2006     

Regimes of microstructural evolution as observed from rheology and surface morphology of crosslinked poly(vinyl alcohol) and hyaluronic acid blends during gelation

Hyaluronic acid (HA)‐based materials are being investigated because of their role in biological fluids and tissues. Poly(vinyl alcohol) (PVA) when blended with HA at different compositions leads to superior mechanical properties compared to pure HA. The PVAHA blend hydrogels are potential candidates for pharmaceutical, biomedical, and cosmetic applications. It is essential to understand the structure, gelation time, and morphological properties of these hydrogels. In this work, a blend system of PVA crosslinked with glutaraldehyde in the presence of HA is studied. Semidilute solutions of PVA and HA are blended, followed by gelation due to crosslinking. The crosslinked gels as well as the gel cast membranes were examined. The effect of HA on the gelation process is investigated using rheological characterization. It is shown that kinetics of gelation is influenced by HA content, though storage modulus of the gels is influenced marginally. The structural features of PVAHA gels were also probed with scanning electron microscopy and dynamic light scattering. It is argued that there is a complex interplay between intra‐ and intermolecular crosslinking of PVA and PVA–HA interactions during the gel formation. Based on the insights obtained from various probing techniques for PVAHA gels with different HA content, three broad structural features were identified. It is shown that the hydrogel is semi‐interpenetrating network at lower HA content (<10% HA), cocontinuous morphology at moderate HA content and with domains at high HA content (>20% HA). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41081.     

Preparation and characterization by radiation of poly(vinyl alcohol) and poly(N‐vinylpyrrolidone) hydrogels containing aloe vera

In these studies, hydrogels for wound dressings were made from a mixture of aloe vera and poly(vinyl alcohol) (PVA)/poly(N‐vinylpyrrolidone) (PVP) by freezing and thawing, γ‐Ray irradiation, or a two‐step process of freezing and thawing and γ‐ray irradiation. We examined the physical properties, including gelation, water absorptivity, gel strength, and degree of water evaporation, to evaluate the applicability of these hydrogels for wound dressings. The PVA:PVP ratio was 6:4, the dry weight of aloe vera was in the range 0.4–1.2 wt %, and the solid concentration of the PVA/PVP/aloe vera solution was 15 wt %. We used γ radiation doses of 25, 35, and 50 kGy to expose mixtures of PVA/PVP/aloe vera to evaluate the effect of radiation dose on the physical properties of the hydrogels. Gel content and gel strength increased as the concentration of aloe vera in the PVA/PVP/aloe vera gels decreased and as radiation dose increased and the number of freeze–thaw cycles was increased. The swelling degree was inversely proportional to the gel content and gel strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1477–1485, 2003     

Study of cryostructuration of polymer systems. XX. Foamed poly(vinyl alcohol) cryogels

Foamed poly(vinyl alcohol) (PVA) cryogels, which are formed as a result of freeze–thaw treatment of whipped PVA water solutions (polymer with MW of 69,000 Da and DD ～99 mol % was used), were obtained and their properties were studied. The rheological characteristics and macrostructure of these gel materials were controlled by the same factors as for the ordinary nonfoamed PVA cryogels (initial polymer concentration and freezing–thawing regimes) and also by the conditions of generation of fluid PVA foams. The study of the kinetics of the freeze–thaw‐induced gel formation of these foams revealed that the temperature dependence of the efficiency of cryotropic gelation showed a maximum at about ?1.5°C. The presence of low molecular weight admixtures in the initial polymer solution appears to be a rather important factor because the admixtures were capable of decreasing the stability of fluid PVA foams and weakening both foamed and nonfoamed cryogel samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1609–1619, 2001     

Molecular weight effect on theta-gel formation in poly(vinyl alcohol)–poly(ethylene glycol) mixtures

Injectable hydrogel formulations that undergo in situ gelation at body temperature are promising for minimally invasive tissue repair. This work focuses on the investigation of injectable poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG) mixtures. The injectable PVA–PEG aqueous solutions form a hydrogel as temperature is reduced to near body temperature, while filling a defect in the injection site. Gamma sterilization of these solutions compromises injectability presumably due to crosslinking of PVA. We hypothesized that by modifying the PEG molecular weight and its concentration, injectability of radiation sterilized PVA–PEG hydrogels can be optimized without compromising the mechanical properties of the resulting gel. The use of a bimodal mixture of higher and lower molecular weight PEG (600 and 200 g/mol) resulted in lower PVA/PEG solution viscosity, better injectability, and higher gel mechanical strength. The PVA/bimodal-PEG had a lower viscosity at 2733 ± 149 cP versus a viscosity of 5560 ± 278 cP for PVA/unimodal-PEG (400 g/mol). The gel formed with the bimodal PEG mixture had higher creep resistance (61% total creep strain under 0.5 MPa) than that formed with unimodal PEG (84%). These hydrogel formulations are promising candidates for minimally invasive tissue repair. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

New insights into phenol–formaldehyde‐based gel systems with ammonium salt for low‐temperature reservoirs

Polymer gels are effective tools that are still widely used in mature oilfield development to stop unwanted fluid production from oil and gas wells, but conventional gelant formulations have become increasingly difficult to apply at low and ultralow temperatures. Because of this situation, the gelation performance of phenol–formaldehyde‐based gel systems at a low temperature of 25°C is discussed in this article. The results show that the gelation time and strength of the gel systems can be perfectly controlled by the adjustment of the polymer concentration, the molecular weight, the crosslinking agent concentration, the ammonium salt concentration, and the composition. The polymer concentration and molecular weight can affect not only the gelation time and the gel strength but also its stability. The ammonium salt concentration affected not only the gelation time but also its viscosity before a detectable gel formed. Among them, the polymer concentration was the most important factor affecting the gel stability. For low‐temperature reservoirs, the phenol–formaldehyde‐based gel system achieved a much longer gelation time. Polymer gels formulated with a combination of 0.2–0.4 wt % polymer, 0.5–1.0 wt % formaldehyde or phenol–formaldehyde, and 0.1–0.6 wt % ammonium salt, and we added 0.02–0.03 wt % resorcinol to provide a gelation time between 2 h and 2 days. The maximum gel strength reached code I. The results of this study suggest that the formaldehyde‐based gel system could be used effectively in low‐temperature reservoirs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40657.     

Preparation and characterization by radiation of hydrogels of PVA and PVP containing Aloe vera

In these studies, hydrogels for wound dressing were made from a mixture of Aloe vera, poly(vinyl alcohol) (PVA) and poly(N‐vinylpyrrolidone) (PVP) by freeze‐thaw, gamma‐ray irradiation, or a two‐step process of freeze‐thaw and gamma‐ray irradiation. Physical properties, such as gelation, water absorptivity, gel strength and degree of water evaporation were examined to evaluate the applicability of these hydrogels to wound dressing. The PVA:PVP ratio was 6:4, and the dry weight of Aloe vera was in the range of 0.4‐1.2 wt %. The solid concentration of PVA/PVP/Aloe vera solution was 15 wt %. Mixtures of PVA/PVP/Aloe vera were exposed to gamma irradiation doses of 25, 35 and 50 kGy to evaluate the effect of irradiation dose on the physical properties of the hydrogels. Gel content and gel strength increased as the concentration of Aloe vera in PVA/PVP/Aloe vera decreased and as irradiation dose increased and freeze‐thaw was repeated. Swelling degree was inversely proportional to gel content and gel strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1612–1618, 2004     

A delicate ionizable-group effect on self-assembly and thermogelling of amphiphilic block copolymers in water

A carboxyl-capped PLGA-PEG-PLGA block copolymer (PLGA: poly(d,l-lactic acid-co-glycolic acid), PEG: poly(ethylene glycol)) was synthesized, and its self-assembly and thermogelling behaviors in water were studied at different pH values. While the aqueous solution of the virgin PLGA-PEG-PLGA block copolymer with the composition in this paper did not undergo sol-gel transition, that of the end-capped derivative exhibited four macroscopic states, sol, turbid sol, physical gel, and precipitate, dependent upon temperature and pH. Especially between pH 4.5 and 5.0, a concentrated aqueous system underwent sol-gel-(turbid sol)-precipitate transitions upon increase of temperature. Complex of dissociation constant pK_a of weak-acid groups on the micelle surfaces was illustrated. Dynamic light scattering, hydrophobic dye solubilization, transmission electron microscopy, NMR, and potentiometric titration were used to examine the relationship between ionization of the end groups of the polymer chains on the molecular level, micellization of the amphiphilic block copolymers on the supermolecular level, and physical gelation on the macroscopic level. The present research reveals the complex of the multi-scale self-assembly of amphiphilic polymer ionomers in a selective solvent.