Light-induced water swelling/shrinking recovery of hydrogels based on chemically cross-linked poly (vinyl alcohol)

Photoresponsive hydrogels with high performance are of considerable interest because of their wide application. In this paper, a kind of smart poly (vinyl alcohol) (PVA) hydrogel is obtained using 4, 4′-azodibenzoic acid as cross-link agent. The hydrogels have the ability of swelling and shrinking reversibly under irradiation by ultraviolet or visible light because azobenzene groups show trans–cis isomerization under suitable light wavenumber. Under UV irradiation, azobenzene takes the cis structure which leads to volume decreases; macroscopically, shrinking can be observed. Under visible light irradiation, the volume recovers, and swelling can be observed macroscopically. Hydrogels have excellent swelling/shrinking recovery properties even after 12 cycles. The procedure achieves loop control of the transformation from light energy to mechanical energy.     

Swelling and scattering investigations on chemically cross-linked poly(vinyl alcohol) hydrogels

Swelling and scattering measurements are reported from chemically cross-linked polyvinyl alcohol) hydrogels and the corresponding semi-dilute polymer solutions. The mixing free energy in the swollen network is found to be significantly smaller than that of the corresponding polymer solution at identical concentration. Static light scattering and small-angle neutron scattering measurements indicate the presence of large-scale static structures in the solution. Reasonable agreement is found between the osmotic moduli obtained from light scattering measurements and macroscopic osmotic observations.     

Water and polymer dynamics in chemically cross-linked hydrogels of poly(vinyl alcohol): a molecular dynamics simulation study

A topologically extended model of a chemically cross-linked hydrogel of poly(vinyl alcohol) (PVA) at high hydration degree has been developed for a molecular dynamics simulation with atomic detail at 323 K. The analysis of the 5 ns trajectory discloses structural and dynamic aspects of polymer solvation and elucidates the water hydrogen bonding and diffusion in the network. The features of local polymer dynamics indicate that PVA mobility is not affected by structural constraints of chemical junctions at the investigated cross-linking density, with a prevailing dumping effect due to water interaction. Simulation results are validated by a favorable comparison with findings of an incoherent quasi-elastic neutron scattering study of the same hydrogel system.     

Synthesis, characterization and swelling properties of a chemically cross-linked poly(vinyl alcohol) hydrogel

A poly(vinyl alcohol) hydrogel was prepared by coupling poly(vinyl alcohol) with epichlorohydrin as the cross-linking agent. The structure of the hydrogel was characterized by FTIR and GPC techniques. Various amounts of water were added into the dry gel to swell it, and the quantity of water in various states in the partially swollen hydrogel was determined by DSC technique. The analytical results indicate that the water introduced into the dry gel first combines with the hydrophilic groups of the network chains through hydrogen bond forming non-freezable water. The weight ratio of the non-freezable water to dry gel in the hydrogels is about 0.20. After the non-freezable water is saturated, the additional water penetrates the network space and exists simultaneously both in the freezable and free water states until reaching equilibrium swelling. Translated from Acta Polymeric Sinica, 2006, (5): 671–675 (in Chinese)     

About the compatibility of polymer components in polymer complexes based on poly(acrylamide) and poly(vinyl alcohol)

The issue of applying the usual concepts of polymer compatibility to nonstoichiometric PVA/PAA mixtures of chemically complementary poly(vinyl alcohol) and poly(acrylamide), which form in water solution InterPC (intermolecular polymer complex) stabilyzed by H‐bonds, and PAA to PVA graft copolymers (PVA‐PAA_N) with different grafted chains number N, that are IntraPC (intramolecular polymer complexes) is discussed. PVA and PAA are compatible on molecular level. At the same time PVA/PAA mixture (50/50 W/W) is characterized by heterogeneous structure consists of InterPC with ϕ_char=9g_PVA/g_PAA and the excess of unconnected PAA. In the case of IntraPC, yet, only PVA‐PAA_N, where N=25, is characterized by a single glass transition temperature (Tg). At larger values of N separate PAA domains form giving rise to the corresponding Tg. These results are discussed in view of IntraPC structure peculiarities as a function of N investigated by IR spectroscopy.     

Stability of new optical pH sensing material based on cross-linked poly(vinyl alcohol) copolymer

Cross-linked poly(vinyl alcohol) (PVA)-silica gel copolymer has been employed as a optical pH sensor substrate for immobilisation of fluorescein. Cross-linking was carried out by the sol-gel process incorporating PVA in initial sol-gel solution of tetra-methoxysilane (TMOS) under acidic conditions. Three dimensional network formation could be achieved using compositions of PVA/TMOS=80-90/20-10 vol.% to result in crack-free films. The fluorescent sensor layers were prepared by dip-coating of gel solution onto glass slides. The dynamic fluorescence response towards different pH values was investigated in terms of the influence of sample ionic strength, membrane composition as well as age of sol-gel layers. Depending on the composition of the matrix pK_a values of 6.50, 6.68 and 7.06 were found 18 days after continues storage in buffer.     

Swelling kinetics of cross-linked polymer gels based on polystyrene and poly(vinyl alcohol) in aqueous solutions of electrolytes and sucrose

The swelling kinetics of polymer gels has been studied in water and aqueous solutions by optical micrometry. Cross-linked hydrophilic polymers based on polystyrene and poly(vinyl alcohol) have been used as gel-forming materials. The effects of the natures of the matrices and polar groups of the polymers and their cross-linking densities and granule sizes, as well as the properties of external phase, on the swelling kinetics of the polymer gels have been investigated. The experimental results have been processed in terms of a heterophase kinetic model. The applicability of the model to describing the behavior of all studied systems has been shown.     

Biodegradable hybrid polymer films based on poly(vinyl alcohol) and collagen hydrolyzate

Hybrid blends of poly(vinyl alcohol) (PVA) and collagen hydrolyzate (CH), an added value waste from leather indutry, have been converted by blown molding extrusion, to environmentally degradable films. Blown extruded films comprising 5-15% of CH, were tested as sel fertilizing mulching films and analyzed for their propensity to enviromental degradation. PVA/CH films rapidly disintegrate when buried in soil, and resulted promising for application such as transplanting films, with additional fertilizing action of CH.     

Sorption of water by poly(vinyl alcohol)

The isotherms of water sorption by poly(vinyl alcohol) have been obtained by static sorption methods in a wide range of vapor activities. The properties of poly(vinyl alcohol) at various values of relative humidity have been studied by DSC, X-ray diffraction analysis, and mechanical testing. It has been shown that the correct thermodynamic analysis of sorption isotherms for sorbents with complex organization requires knowledge of their structural features. A method of allowing for the effect of osmotic pressure on the polymer sorption capacity is proposed. The pair interaction parameters estimated in this study are compared with the published data.     

Morphology assessment of chemically modified cryostructured poly(vinyl alcohol) hydrogel

The morphology of hydrogels based on poly(vinyl alcohol) (PVA) in their frozen hydrated state, modified with biologically active di- and multifunctional molecules was studied by scanning electron microscopy (SEM) with cryo-attachment. The porosity of samples was found to be more regular and ordered in the case of samples containing difunctional, and especially multifunctional carboxylic acids as compared to the neat PVA hydrogel. The morphology is dependent not only from the hydrogel composition but also the number of freezing-thawing cycles. Resulted highly porous and oriented structure has significant influence on materials properties, such as compressive stress and crosslinking density.     

Sorption of water vapor by poly(vinyl alcohol): Influence of polymer crystallinity

The influence of crystallinity on water sorption behavior by poly(vinyl alcohol) (PVA) was studied by using a PVA of low crystallinity (15% crystalline by x-ray analysis) and an annealed sample there from (46%) crystalline. With the increase of crystallinity, the sigmoid shape (which is a characteristic for the sorption isotherm of the low crystalline polymer) diminishes. The B.E.T. plots of the isotherms are linear between the relative vapor pressures of 0.1 and 0.4 as usual, and deviate from straight lines in the higher pressure range in the direction of a larger sorbed quantity than that predicted by the B.E.T. theory. This tendency is regarded as a kind of dissolution, and the Flory-Huggins interaction parameter χ1 was calculated. In both polymers, the χ1 versus pressure relation has a maximum, while overall χ1 values are smaller in the polymer of low crystallinity. The maximum point (which lies in the higher pressure region in case of the less crystalline sample) is considered to be a transition point from a phenomenon controlled mainly by an adsorption mechanism to a phenomenon controlled mainly by a dissolution mechanism. Accordingly, the separation of the isotherm into adsorption and a dissolution components was made, and the polymer fraction which contributes to the dissolution mechanism versus pressure relation was calculated. The result indicates that the crystalline region observed by x-ray analysis may partly contribute to the dissolution process at room temperature.     

Miscible blends containing a crystallizable component: poly(vinyl alcohol)/poly(ethyleneimine)

Blends of poly(vinyl alcohol) (PVAI) with poly(ethyleneimine) (PEI) were prepared by casting from a common solvent. All blends show a single, composition dependent glass transition temperature (T_g), indicating that the blends are miscible in the amorphous state and in the melt. The overall crystallization rate of PVAI in the blend decreases with increasing PEI content. The crystallinity index of PVAI in the blend does not decrease greatly with PEI content up to a composition of 70/30 PVAI/PEI, since the T_g of the crystallizable component PVAI is larger than that of the non-crystallizable component PEI. The T_g of the system PVAI/PEI decreases with increasing PEI content. The interaction parameter B of the two polymers in the melt was found to be −24 J/cm³.     

New chemical hydrogels based on poly(vinyl alcohol)

The syntheses of two new types of chemical hydrogels based on poly(vinyl alcohol), PVA, are reported. Common to both synthetic routes is the preparation of a telechelic PVA (tel-PVA) obtained by periodate splitting of the vicinal diol units present in few percent along the chain. tel-PVA was then used as crosslinking agent with chitosan and PVA in two simple reactions in aqueous phase such as reductive alkylation of chitosan and acetalyzation of PVA. Both reactions yielded firm wall-to-wall networks showing marked differences in their swelling capability. © 1996 John Wiley & Sons, Inc.     

States of water in poly(vinyl alcohol) hydrogels

Poly(vinyl alcohol) (PVA) hydrogels with various water contents were prepared from 10 wt% aqueous solutions of mixtures of PVA and anionic poly(styrene sulfonic acid) sodium salt (NaPSS) by casting, dehydrating, and then extracting NaPSS. The existence of three types of ice were suggested by differential scanning calorimetry (DSC) measurements for every frozen hydrogel. In the frozen hydrogels the states of water, except unfrozen water, were ice of free water and disordered ice crystals. The mobility and activation energy for motion of water molecules in unfrozen hydrogels were investigated by using pulsed nuclear magnetic resonance (PNMR) measurements. It was concluded that there are two states of water in the unfrozen hydrogel, i.e. unfrozen water and disordered water which is mainly formed in narrow apertures in the hydrogel. The discrepancy between the DSC and PNMR measurements was explained by a structural transformation during cooling.     

Mechanism of formation and structure of polymer nanocomposites based on poly(vinyl alcohol) and magnetite

The mechanism of formation and structure of polymer nanocomposites based on poly(vinyl alcohol) and magnetite have been studied. The above nanocomposites are prepared by the in situ basic hydrolysis of a mixture of Fe(II) and Fe(III) chlorides in the matrix of a chemically crosslinked poly(vinyl alcohol) gel.     

Effects of microcrystallites on swelling behavior in chemically crosslinked poly(vinyl alcohol) gels

We report the swelling ratio and network structure of a poly(vinyl alcohol) (PVA) gel chemically crosslinked by glutaraldehyde with different degrees of crosslinks. Microcrystallites were formed in a chemical PVA gel during a drying process and were confirmed by X‐Ray diffraction (XRD) measurements and Fourier transform infrared (FTIR) spectroscopy. The formation of microcrystallites in the dried gels was suppressed by increasing the degrees of chemical crosslinks. When the dried samples were immersed in pure water at 25 °C, the swelling ratio depended on the degree of chemical crosslinks resulting from the destruction of physical crosslinks by microcrystallites. On the other hand, when the dried samples were immersed in a poor solvent of a mixture of dimethyl sulfoxide and water at 8 °C, the gels did not swell and stayed in the collapsed state. Starting from the collapsed state, the equilibrium swelling ratios were measured while the temperature was increased to 90 °C and then decreased to 8 °C. As a result, irreversible swelling behaviors were observed for all gels with different degrees of crosslinks, which were attributed to the destruction of microcrystallites. The swelling behavior is discussed in terms of the formation and destruction of additional physical crosslinks in the chemical PVA gels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Preparation of antimicrobial poly(vinyl alcohol) nanofibers containing silver nanoparticles

Polyvinyl alcohol (PVA) nanofibers containing Ag nanoparticles were prepared by electrospinning PVA/silver nitrate (AgNO₃) aqueous solutions, followed by short heat treatment, and their antimicrobial activity was investigated for wound dressing applications. Since PVA is a water soluble and biocompatible polymer, it is one of the best materials for the preparation of wound dressing nanofibers. After heat treatment at 155 °C for 3 min, the PVA/AgNO₃ nanofibers became insoluble, while the Ag⁺ ions therein were reduced so as to produce a large number of Ag nanoparticles situated preferentially on their surface. The residual Ag⁺ ions were reduced by subsequent UV irradiation for 3 h. The average diameter of the Ag nanoparticles after the heat treatment was 5.9 nm and this value increased slightly to 6.3 nm after UV irradiation. It was found that most of the Ag⁺ ions were reduced by the simple heat treatment. The PVA nanofibers containing Ag nanoparticles showed very strong antimicrobial activity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2468–2474, 2006     

Heterotactic poly(vinyl alcohol)

Bulky substituents in vinyl trialkylsilyl ethers and vinyl trialkylcarbinyl ethers led to heterotactic polymers (H = 66%). The polymers were converted into poly(vinyl alcohol) (PVA) and further to poly(vinyl acetate), and tacticity was determined as poly(vinyl acetate). Vinyl triisopropylsilyl ether in nonpolar solvents yielded a heterotactic polymer with a higher percentage of isotactic triads than syndiotactic triads (Hetero-I). Vinyl trialkylcarbinyl ethers in polar solvents gave a heterotactic polymer with more syndiotactic triads than isotactic (Hetero-II). Heterotactic PVA was soluble in water and showed characteristics infrared absorptions. Interestingly, Hetero-I PVA showed no iodine color reaction, but Hetero-II showed a much more intense color reaction than a commercial PVA. The mechanism of heterotactic propagation was discussed in terms of the Markóv chain model.     

Effect of the molecular weight of poly(vinyl alcohol) on the water stability of a syndiotactic poly(vinyl alcohol)/iodine complex film

To precisely identify the effect of the molecular weight of syndiotactic poly(vinyl alcohol) (s-PVA) on the water stability of a s-PVA/iodine complex film, we prepared four s-PVAs with similar syndiotactic diad (s-diad) contents of about 63% and with different number-average degrees of polymerization, P_n, of 900, 6,000, 10,000, and 17,000, respectively. The desorption behavior of iodine in the s-PVA/iodine complex film in water was investigated in relation to the solubility of s-PVA in water. The degree of solubility of a s-PVA film having different P_n in water at 80 °C was limited to about 0.3-10%, whereas the degrees of solubility of atactic PVA films with P_n of 6,000 and 10,000 were 100% at the same conditions. The degree of iodine desorption of the complex film decreased with increasing P_n of s-PVA. Especially, the degree of iodine desorption of a PVA drawn film having P_n of 17,000 was limited to 2%, regardless of soaking temperature from 40 to 80 °C. The desorption of iodine in water was strongly affected by the dissolution of PVA. In addition, the degree of iodine desorption of the drawn s-PVA/iodine film was larger than that of the undrawn one.