Controlled mechanical and swelling properties of poly(vinyl alcohol)/sodium alginate blend hydrogels prepared by freeze–thaw followed by Ca2+ crosslinking

Poly(vinyl alcohol) (PVA)/sodium alginate (SA) blend hydrogels have immense potential for use as functional biomaterials. Understanding of influences of processing parameters and compositions on mechanical and swelling properties of PVA/SA blend hydrogels is very important. In this work, PVA/SA blend hydrogels with different SA contents were prepared by applying freeze–thaw method first to induce physical crosslinking of PVA chains and then followed by Ca²⁺ crosslinking SA chains to form interpenetrating networks of PVA and SA. The effects of number of freeze–thaw cycles, SA content and Ca²⁺ concentration on mechanical properties, swelling kinetics, and pH‐sensitivity of the blend hydrogels were investigated. The results showed that the blend hydrogels have porous sponge structure. Gel fraction, which is related to crosslink density of the blend hydrogels, increased with the increase of freeze–thaw cycles and strongly depended on SA content. The SA content exerts a significant effect on mechanical properties, swelling kinetics, and pH‐sensitivity of the blend hydrogels. The number of freeze–thaw cycles has marked impact on mechanical properties, but no obvious effect on the pH‐sensitivity of the PVA/SA blend hydrogels. Concentration of CaCl₂ aqueous solution also influences mechanical properties and pH‐sensitivity of the blend hydrogel. By altering composition and processing parameters such as freeze–thaw cycles and concentration of CaCl₂ aqueous solution, the mechanical properties and pH‐sensitivity of PVA/SA blend hydrogels can be tightly controlled. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High‐tensile‐strength polyvinyl alcohol films prepared from freeze/thaw cycled gels

The mechanical properties and molecular structure of a poly(vinyl alcohol) (PVA) film, which was obtained by eliminating water from a PVA hydrogel using repeated freeze/thaw cycles, were investigated by tensile tests, thermal analysis, and X‐ray diffraction measurements. The mechanical properties of PVA with 99.9% saponification were measured as a function of the number of freeze/thaw cycles performed. The tensile strength and Young's modulus increased and the elongation at break decreased with increasing freeze/thaw cycles. The tensile strength and Young's modulus of PVA films obtained after seven freeze/thaw cycles were as high as 255 MPa and 13.5 GPa after annealing at 130°C. Thermal analysis and X‐ray diffraction measurements revealed that this is because of a high crystallinity and a large crystallite size. A good relationship between the tensile strength and the glass transition temperature was obtained, regardless of the degree of saponification and annealing conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40578.     

Preparation and properties of physically crosslinked sodium carboxymethylcellulose/poly(vinyl alcohol) complex hydrogels

A series of physically crosslinked complex hydrogels of poly(vinyl alcohol) (PVA) and sodium carboxymethylcellulose (CMC) were prepared via physical mixing and a freeze/thaw technique. The morphology of the CMC/PVA complex gels was analyzed with differential scanning calorimetry and wide‐angle X‐ray diffraction. It was found that the crystallinity and melting temperature of the complex gels decreased, whereas the glass‐transition temperature increased, with an increase in the content of CMC. The reswelling of the complex gels was pH‐responsive and relied on the content of CMC and the freeze/thaw cycles. A network structure model of the complex gel was presented. PVA crystalline regions served as physical crosslinks; the interaction between CMC and PVA resulted in intramolecular entanglements. It was also found that the model drug hemoglobin was released completely from the complex hydrogels in 4 h, and its release rate increased with an increase in the content of CMC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of scleroglucan drug delivery films: The effect of freeze‐thaw cycling

This study examined the effect of the freeze‐thaw process on the physical properties of films prepared from scleroglucan (Scl) hydrogels, suitable for drug delivery applications. Films made from Scl, using glycerol as plasticizer, were prepared from hydrogels by two procedures: a room temperature drying (RTD) method and a freeze‐thaw cyclic process, before the application of RTD, which results in a reinforced physically cross‐linked network. Films were characterized by studies of water vapor transmission (WVT), swelling, tensile tests, ESEM microscopy, FTIR, and drug release measurements. These determinations showed significant differences between films obtained by both treatments. The films prepared through freeze‐thaw cycles showed an important increase of the tensile strength with respect to those corresponding to films only air dried and a decreasing swelling degree in direct relationship to the number of freeze‐thaw cycles. A model drug, Theophylline, was included in these biocompatible films for in vitro drug release measurements, using a flat Franz cell. The physical differences observed between Scl films prepared with both methods can be explained proposing that the number of crosslinking points by hydrogen bonding increase when increasing the number of freezing and thawing cycles used for film preparation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyaniline/Poly(acrylamide‐co‐sodium acrylate) Porous Conductive Hydrogels with High Stretchability by Freeze‐Thaw‐Shrink Treatment for Flexible Electrodes

With the development of alternatives to traditional fossil energy and the rise of wearable technology, flexible energy storage devices have attracted great attention. In this paper, a polyaniline/poly(acrylamide‐sodium acrylate copolymer) hydrogel (PASH) with high flexibility and excellent electrochemical properties for flexible electrodes is fabricated by freeze‐thaw‐shrink treatment of a highly water‐absorptive hydrogel, together with in‐situ polymerization of aniline at a low aniline concentration (0.1 mol L^?1). The PASH exhibits a conductivity of 4.05 S m^?1 and an elongation at break of 1245%. The freeze‐thaw‐shrink treatment greatly improves the electrochemical performance and stability of the conductive PASH. The area specific capacitance of PASH reaches 849 mF cm^?2 and the capacitance maintains 89% after 1000 galvanostatic charge–discharge cycles. All the raw materials are conventional industrialized materials and no additional templating agent is needed during the entire synthesis process. This study provides a cost‐efficient approach for the fabrication of conductive polymer hydrogels, which has a broad application prospect in flexible energy storage electronic devices.     

Nano-enabled poly(vinyl alcohol) based injectable bio-nanocomposite hydrogel scaffolds

We report development of poly(vinyl alcohol) (PVA)-based novel injectable hydrogel nanocomposite scaffolds. Nanocellulose (NC), synthesized from agricultural biomass, was used as reinforcement within PVA matrix. The hydrogels were formed using physical crosslinking process involving multiple freeze–thaw cycles. A range of bio-nanocomposite hydrogels were prepared with varying concentrations of NC. With increasing loading of NC, crystallinity was found to be increased, which could be attributed to nucleating effect and crystalline nature of nanofibrillar cellulose. Investigation of microstructural surface topology indicated reduced surface perturbations upon incorporation of NC. Fourier transform infrared spectroscopy studies further indicated presence of characteristic functional groups and possible interactions between PVA and NC. Enhanced structural integrity and dynamic stability of the bio-nanocomposite hydrogels were also confirmed by carrying out rheological investigations at different frequency, amplitude, temperature, and time sweeps. Further, the bio-nanocomposite hydrogels demonstrated excellent injectability and self-standing behavior, establishing the promising potential as injectable scaffolds. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48789.     

Preparation and characterization of biocompatible spongy cryogels of poly(vinyl alcohol)–gelatin and study of water sorption behaviour

Porous biocompatible spongy hydrogels of poly(vinyl alcohol) (PVA)–gelatin were prepared by the freezing–thawing method and characterized by infrared and differential scanning calorimetry. The prepared so‐called ‘cryogels’ were evaluated for their water‐uptake potential and the influence of various factors, such as the chemical architecture of the spongy hydrogels, pH and the temperature of the swelling bath, on the degree of water sorption by the cryogels was investigated. It was found that the water sorption capacity constantly decreased with increasing concentration of PVA while initially an increase and thereafter a decrease in swelling was obtained with increasing amounts of gelatin in the cryogel. The water sorption capacity decreased with an increase in the number of freeze–thaw cycles. The hydrogels were also swollen in salt solutions and various simulated biological fluids and a fall in swelling ratio was noticed. The effect of the drying temperature of the cryogel on its water sorption capacity was also investigated, and a decrease in swelling was obtained with increasing temperature of drying. The biocompatibility of the prepared materials was assessed by in vitro methods of blood‐clot formation, platelet adhesion, and per cent haemolysis. It was noticed that with increasing concentration of PVA and gelatin the biocompatibility increased, while a reduced biocompatibility was noted with an increasing number of freeze–thaw cycles. Copyright © 2005 Society of Chemical Industry     

Thermal and rheological properties of poly(vinyl alcohol) and water‐soluble chitosan hydrogels prepared by a combination of γ‐ray irradiation and freeze thawing

Poly(vinyl alcohol) (PVA)/water‐soluble chitosan (ws‐chitosan) hydrogels were prepared by a combination of γ‐irradiation and freeze thawing. The thermal and rheological properties of these hydrogels were compared with those of hydrogels prepared by pure irradiation and pure freeze thawing. Irradiation reduced the crystallinity of PVA, whereas freeze thawing increased it. Hydrogels made by freeze thawing followed by irradiation had higher degrees of crystallinity and higher melting temperatures than those made by irradiation followed by freeze thawing. ws‐Chitosan disrupted the ordered association of PVA molecules and decreased the thermal stability of both physical blends and hydrogels. All the hydrogels showed shear‐thinning behavior in the frequency range of 0.2–100 rad/s. Hydrogels made by freeze thawing dissolved into sol solutions at about 80°C, whereas those made by irradiation showed no temperature dependence up to 100°C. The chemical crosslinking density of the hydrogels made by irradiation followed by freeze thawing was much greater than that of hydrogels made by freeze thawing followed by irradiation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation on the formation mechanisms of hydrogels made by combination of γ‐ray irradiation and freeze‐thawing

Hydrogels based on poly(vinyl alcohol) (PVA)/water‐soluble chitosan (ws‐chitosan)/glycerol were prepared by γ‐ray irradiation, freeze‐thawing, and combination of γ‐ray irradiation and freeze‐thawing, respectively. The influence of freeze‐thawing cycles, the irradiation doses, and the sequence of freeze‐thawing and irradiation processes on the rheological, swelling, and thermal properties of these hydrogels was investigated to evaluate the formation mechanisms of hydrogels made by combination of irradiation and freeze‐thawing. For hydrogels made by freeze‐thawing followed by irradiation, the physical crosslinking is destroyed partially while chemical crosslinking is formed by irradiation. However, the chemical crosslinking density reduces with the increase of freeze‐thawing cycles. Hydrogels made by irradiation followed by freeze‐thawing bear less degree of physical crosslinking with the increase of irradiation dose for the increased chemical crosslinking density. It is found that these hydrogels own larger swelling capacity and better transparent appearance than those made by freeze‐thawing followed by irradiation. Moreover, the former hydrogels have larger mechanical strength than the latter at low freeze‐thawing cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

冻融环境下GFRP管混凝土柱轴压性能试验研究

通过对21个玻璃纤维增强聚合物（GFRP）管混凝土柱和21个素混凝土柱分别在水溶液和质量分数为3.5 %的氯化钠（NaCl）溶液中进行冻融循环试验及轴压试验，且对冻融后的GFRP管混凝土柱进行了超声波检测，研究冻融环境下不同冻融介质和冻融循环次数对GFRP管混凝土柱轴压性能的影响。结果表明，冻融介质相同的情况下，随着冻融循环次数的增加，质量损失率增大，相对动弹性模量降低，GFRP管混凝土柱内异常点增多，承载力下降，极限应变下降；冻融次数相同的情况下，经盐冻作用的GFRP管混凝土柱轴压极限承载力降低更为明显。GFRP管混凝土柱盐冻循环150次后极限承载力下降了29.45 %，下降量是相同条件下水冻结果的2.19倍。盐冻循环后的GFRP管混凝土柱极限应变小于相同条件下的水冻循环极限应变。     

Fabrication and characterization of novel macroporous cellulose–alginate hydrogels

Novel macroporous hydrogels were prepared by blending of cellulose and sodium alginate (SA) solution, and then cross-linking with epichlorohydrin. The resulting cellulose/SA hydrogels were characterized by solid-state ¹³C NMR, wide-angle X-ray diffraction (WXRD), thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), rheological measurement, dynamic mechanical analysis (DMA) and swelling test to evaluate their structure, interior morphology, gelation time, compressive modulus, and equilibrium swelling ratio. Our findings revealed that the cellulose acted as backbone in the hydrogels, whereas SA contributed to the higher equilibrium swelling ratio. The combination of cellulose having semi-stiff chains and SA containing –COOH groups in the cross-linking hydrogel created the macroporous structure. This work provided a new pathway for preparation of hydrogel with large porous structure through incorporation of stiff polymer as support of pore wall and acidic polysaccharide as expander of pore size because of high water-absorbency.     

Swelling behavior of sulfonated polyacrylamide nanocomposite hydrogels in electrolyte solutions: comparison of theoretical and experimental results

Nanocomposite hydrogels were prepared by cross-linking of aqueous solutions of sulfonated polyacrylamide/sodium montmorillonite with chromium triacetate as ionic cross-linker. The effect of montmorillonite content on equilibrium swelling in NaCl and CaCl₂ solutions, ultimate storage modulus and effective cross-link density was evaluated. The limiting storage modulus of the nanocomposite (NC) hydrogels dropped by increasing montmorillonite content up to 1,000?ppm, and then it increased by further montmorillonite loading. A mechanism is proposed for the formation of PAMPS/Na⁺-MMT/Cr³⁺ NC hydrogels. According to this mechanism, the drop in limiting storage modulus of the NC gels at low Na⁺-MMT concentration is due to ionic interactions between the negative layers of sodium montmorillonite and Cr³⁺, leading to decreased cross-link density. However, the increase of the limiting storage modulus of the NC gels at high clay concentration results from the strong interactions between the polyacrylamide chains and clay platelets. The equilibrium swelling ratio of the NC networks decreased with increase of montmorillonite content in both aqueous NaCl and CaCl₂ solutions. In addition, the experimental swelling data of these NC hydrogels were described by a modified Flory?CRehner theory. The modified model was sensitive to montmorillonite concentration and it described adequately the swelling data for NC gels in NaCl solutions. Nevertheless, theoretical predictions showed some deviations from experimental results for swelling of NC hydrogels in CaCl₂ solutions.     

Dissolution and stability of chitosan in a sodium hydroxide/urea aqueous solution

Medium‐molecular‐weight chitosan (MMWC; 157.5 kDa) and low‐molecular‐weight chitosan (LMWC; 53.4 kDa) samples were dissolved in an NaOH/urea solution by freeze–thaw treatment. The factors affecting dissolution were optimized, and the stability of chitosan in the produced solution was investigated. NaOH and urea concentrations of 2 and 0.67 mol/L, respectively, and a treatment temperature of ?18°C were optimized as the dissolving conditions. MMWC and LMWC could be completely dissolved in the 2 mol/L NaOH/0.67 mol/L urea solution after six and five cycles of freeze–thaw treatments, respectively. Dissolution and storage in the 2 mol/L NaOH/0.67 mol/L urea solution slightly increased the deacetylation degree of chitosan and slightly decreased the molecular weight. The solution stability of LMWC was better than that of MMWC. MMWC tended to form a gel during storage. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39819.     

Freeze–thaw resistance of unidirectional‐fiber‐reinforced epoxy composites

The freeze–thaw resistance of unidirectional glass‐, carbon‐, and basalt‐fiber‐reinforced polymer (GFRPs, CFRPs, and BFRPs, respectively) epoxy wet layups was investigated from ?30 to 30°C in dry air. Embedded optic‐fiber Bragg grating sensors were applied to monitor the variation of the internal strain during the freeze–thaw cycles, with which the coefficient of thermal expansion (CTE) was estimated. With the CTE values, the stresses developed in the matrix of the FRPs were calculated, and CFRPs were slightly higher than in the BFRP and GFRP cases. The freeze–thaw cycle showed a negligible effect on the tensile properties of both GFRP and BFRP but exhibited an adverse effect on CFRP, causing a reduction of 16% in the strength and 18% in the modulus after 90 freeze–thaw cycles. The susceptibility of the bonding between the carbon fibers and epoxy to the freeze–thaw cycles was assigned to the deterioration of CFRP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and rheological investigation of tough PAAm hydrogel by adding branched polyethyleneimine

In this article, tough hydrogels are prepared by introducing the polyethyleneimine (PEI) with branched structure and a large number of  NH₂ and  NH groups into permanently crosslinked polyacrylamide (PAAm) hydrogels matrix. To investigate the effects of B-PEI and chemical crosslinking agent (Bis) on the strength and toughness of hydrogels, a series of B-PEI/PAAm hydrogels with different mass percentage of Bis and B-PEI were manufactured and the rheological and swelling properties were compared. For all hydrogels, the storage modulus (G′) was much higher than the loss modulus (G″) in the linear viscoelastic region through the whole frequency range. The solid-like behavior and elastic nature (G′ > G″) are attributed to the permanent covalence crosslinking. Therefore, G′ increased when more Bis was added. For the nonlinear oscillatory shear measurement, hydrogels with B-PEI broke at larger γ than the pure PAAm hydrogels, indicating that the toughness of B-PEI/PAAm hydrogels has been improved by introducing B-PEI. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48541.     

Harmless hydrogels based on PVA/Na+‐MMT nanocomposites for biomedical applications: Fabrication and characterization

A series of nanocomposite hydrogels were prepared by a freeze‐thaw process, using polyvinyl alcohol (PVA) as polymer matrix and 0–10 wt% of hydrophilic natural Na‐montmorillonite (Na⁺‐MMT), free from any modification, as composite aggregates. The effect of nanoclay content and the sonication process on the nanocomposite microstructure and morphology as well as its properties (physical, mechanical, and thermal) were investigated. The microstructure and morphology were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and X‐ray diffraction technique. The thermal stability and mechanical properties of nanocomposite hydrogels were examined using thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis; moreover hardness and water vapor transmission rate measurements. It was concluded that the microstructure, morphology, physical (thermal) and mechanical properties of nanocomposite hydrogels have been modified followed by addition of nanoclay aggregates. The results showed that Na⁺‐MMT may act as a co‐crosslinker. Based on the results obtained, the nanocomposite hydrogel PVA/Na⁺‐MMT synthesized by a freeze‐thaw process, appeared to be a good candidate for biomedical applications. POLYM. COMPOS., 38:1135–1143, 2017. © 2015 Society of Plastics Engineers     

Effect of clinoptilolite on structure and drug release behavior of chitosan/thyme oil γ-Cyclodextrin inclusion compound hydrogels

Chitosan-based hydrogels involving γ-cyclodextrin inclusion compounds of thyme oil were prepared by freeze–thaw cycling method. Clinoptilolite as a natural zeolite was added to investigate its effects on the structural, mechanical, and drug release behaviors of the hydrogels. Zeolite compressed the structure and improved mechanical properties, which decreased swelling values. Release of thyme oil in prepared hydrogels were investigated by UV spectroscopy and drug release mechanism was evaluated by applying various mathematical methods. Rates of water vapor transmission of the samples were calculated as 2247–2998 g m⁻² day⁻¹ which are all in the range of an ideal wound dressing. Hydrogels with clinoptilolite had slower drug release (from 56% to 24% for hydrogels containing zeolite 1%) in comparison with that of without zeolite. Based on MTT assay, samples were low-toxic. Obtained results suggest that drug loaded hydrogels can be applied in biomedical field including drug delivery systems and wound dressings.     

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     

Contribution to the hydrothermal synthesis of zeolite beta and its modifications with gallium

The zeolite beta is a crystalline synthetic aluminosilicate with wide-pore size (6 to 9 Å) and a Si/Al ratio from 5 to 100. In this study, we have investigated the influence of several synthesis parameters on the physicochemical properties of the materials. The synthesis of zeolite beta has been performed by hydrothermal method, the aluminum source and gallium content in the structure being variable. The structural characterization was carried out by means of X-ray diffraction, SEM and ²⁷Al and ⁷¹Ga MAS NMR spectroscopy. When the aluminum sulfate is used as aluminium source, zeolite beta with higher crystallinity is generated. All the samples showed a XRD pattern similar to crystalline zeolite beta and the ²⁷Al and ⁷¹Ga MAS NMR spectrum demonstrated that the incorporation of both heteroatoms was efficient.     

Strain-induced crystallization of natural rubber as studied by high-resolution solid-state C NMR spectroscopy

A series of high-resolution solid-state ¹³C NMR experiments were performed on both unstretched and in situ stretched natural rubber samples. From the ¹³C CP/MAS spectra, it was found that natural rubber does form small crystals at room temperature though the degree of crystallinity is very small. Furthermore, from the ¹³C DD/MAS spectra, the crystalline signals were found to increase with the increase of draw ratio. ¹³C spin-lattice relaxation time (T₁) and ¹H spin-spin relaxation time (T₂) of in situ stretched natural rubber were measured for the first time, which provided further evidences for the conclusion that there exist crystals in both stretched and unstretched natural rubber samples. Quantitative ¹³C NMR measurements indicated that strain-induced crystallization occurs when the draw ratio reaches about 2.0 and the maximum crystallinity of our natural rubber samples can be as high as 19.3% upon stretching.