Study of cryostructuring of polymer systems. 32. Morphology and physicochemical properties of composite poly(vinyl alcohol) cryogels filled with hydrophobic liquid microdroplets

Cryogenic treatment (freezing at −20°C for 12 h followed by defrosting at a rate of 0.03°C/min) of decane, dodecane, or tetradecane emulsions in a poly(vinyl alcohol) solution (80 g/l) is employed to prepare composite cryogels containing microdroplets of liquid hydrophobic fillers entrapped into a macroporous hydrogel matrix. The effects of the type of a hydrocarbon, the degree of filling, and the addition of a surfactant (decaethylene glycol cetyl ether) on the physicomechanical properties, heat endurance, and morphology of the composites are studied. It is shown that, an increase in the content of liquid hydrophobic fillers within some range of their volume fraction enhances the rigidity of corresponding cryogels. Incorporation of the nonionic surfactant into the initial emulsions results in a complex dependence of the rigidity of the resulting composite cryogels on surfactant concentration and variations in the morphology of pores in the gel phase. At the same time, the heat endurance of all examined composite cryogels weakly depends on the type and concentration of the hydrocarbon fillers, as well as the presence of surfactant additives.     

A study of cryostructuring of polymer systems. 43. Characteristics of microstructure of chitosan-containing complex and composite poly(vinyl alcohol) cryogels

The microstructure of complex and composite poly(vinyl alcohol) (PVA) cryogels containing water-soluble chitosan hydrochloride (ChHC) of dispersed particles of water-insoluble chitosan base (Ch), respectively, has been studied by optical microscopy and attenuated total reflection FTIR spectroscopy. The macroporous morphology of cryogels has been studied using preparations in the form of thin (~10 μm) sections and discs 1 mm thick. The introduction of non-gelling additives (NaCl and ChHC) into an initial PVA solution causes significant changes in the size and shapes of macropores in the complex cryogels formed by freezing–defrosting, as compared with the pores in the samples obtained under the same conditions without additives. The reasons for the changes are the process of phase segregation and the influence of low- and high-molecular-weight electrolytes on crystallization of ice, which plays the role of a porogen upon cryotropic gelation of aqueous PVA solutions. As a result of an alkaline treatment of the complex cryogels, which transforms ChHC into Ch, microcoagulation of chitosan yields discrete, almost spherical, particles with sizes of about 1–5 μm. IR spectral studies have shown that concentration gradients of the gelling and nongelling polymers arise along the thickness of the gel discs, with PVA concentration prevailing near the lower surface and ChHC or Ch concentration dominating near the upper surface of the disc.     

A study of cryostructuring of polymer systems. 45. Effect of porosity of dispersed filler on physicochemical characteristics of composite poly(vinyl alcohol) cryogels

Composite cryogels simulating the properties of waterproof screens of hydraulic structures, such as protruding dykes and dams, have been obtained by a cryogenic treatment (freezing at –10…–30°C followed by incubation in the frozen state for 12 h and defrosting at a rate of 0.03°C/min) of suspensions of calcium-carbonate-containing (marble or coquina) or cellulose-containing (microcrystalline cellulose or sawdust) particles in aqueous poly(vinyl alcohol) solutions. Viscometric examinations of initial suspensions have shown that adhesion contacts arise between filler particles, as well as discrete and continuous phases, already at the stage of suspension preparation, thereby affecting the properties of resulting cryogels. This is most pronounced when high-porosity sawdust is used as a filler. It has been shown that all the dispersed materials used in the work are “active” fillers for poly(vinyl alcohol) cryogels, these fillers increasing the rigidity of the formed composites. Therewith, porous particles, into which the polymer solution can penetrate, are more efficient. The dependence of the composite rigidity on the temperature of the cryogenic treatment has, as a rule, a bell-shaped pattern with a maximum in the region of –20°C. Being tested for water permeability, the obtained model composite cryogels have exhibited pronounced antifiltration properties (the filtration coefficient is ≤(1–2) × 10^–9 cm/s), thus indicating that such materials are promising for solving problems relevant to the protection of fascine hydraulic structures from erosion with snow water.     

A Study of cryostructuring of polymer systems. 41. Complex and composite poly(vinyl alcohol) cryogels containing soluble and insoluble forms of chitosan,respectively

Complex macroporous poly(vinyl alcohol) (PVA) cryogels have been obtained by cryogenic treatment (freezing at–20°C for 12 h followed by defrosting at a rate of 0.03°C/min) of PVA–chitosan hydrochloride mixed solutions. The subsequent alkaline treatment of the cryogels has resulted in the transformation of the water-soluble salt form of chitosan into its insoluble basic form, which coagulates inside the bulk of the continuous phase of PVA cryogel into small particles with sizes of 2–5 µm. In the resulting composite cryogels, these particles play the role of an “active” filler, which increases the rigidity and heat endurance of the gel material. It has been shown that the sorption capacity of such chitosan particles entrapped into the bulk of composite cryogels with respect of bivalent copper ions is noticeably higher than the sorption capacity of ground chitosan particles incorporated as a discrete filler into the continuous phase PVA cryogels. The study of the properties of PVA–chitosan hydrochloride mixed solutions revealed that these polymers are, to a large extent, compatible with one another in a common solvent at a low ionic strength. Therefore, liquidliquid phase separation of these systems due to the thermodynamic incompatibility of macromolecules of different natures is observed only upon increasing the ionic strength by adding a low-molecular-mass salt (NaCl, 0.15 mol/L) to the solution.     

A study of cryostructuring of polymer systems. 46. physicochemical properties and microstructure of poly(vinyl alcohol) cryogels formed from polymer solutions in mixtures of dimethyl sulfoxide with low-molecular-mass alcohols

Poly(vinyl alcohol) (PVA) cryogels (PVACGs) are obtained and studied. The PVACGs are formed by freezing–defrosting of polymer solutions in dimethyl sulfoxide (DMSO) or its mixtures with one of the first members of the series low-molecular-mass aliphatic alcohols (methanol, ethanol, n-propanol, and n-butanol). PVA content in these solutions is 100 g/L, while the concentration of an aliphatic alcohol is varied in a range of 0.44–2.55 mol/L depending on its nature. The polymer solutions are subjected to the cryogenic treatment at temperatures 30, 40, or 50°C lower than the crystallization temperature of DMSO (+18.4°C). The frozen samples are defrosted at a heating rate of 0.03°C/min. It is shown that, in a certain range of lowmolecular-mass alcohol content in an initial system, its cryogenic treatment yields coarse-pored heterophase cryogels that have higher rigidity and heat endurance than those of DMSO–PVA cryogels. It has been shown that polymer cryoconcentration and phase separation play important roles in the formation of a cellular microstructure and an increase in the rigidity and heat endurance of PVACGs obtained in the presence of low-molecular-mass alcohols.     

Study of cryostructuring of polymer systems: 28. Physicochemical properties and morphology of poly(vinyl alcohol) cryogels formed by multiple freezing-thawing

Macroporous viscoelastic poly(vinyl alcohol) (PVA) cryogels are prepared from aqueous concentrated (80–120 g/l) PVA solutions subjected to 1–5 cycles of cryogenic treatment (freezing at ?20°C for 19 h and subsequent thawing at a rate of 0.3°C/min). Shear moduli and fusion temperatures of corresponding samples are determined and the structure of thin sections is studied by optical microscopy with subsequent processing and analysis of images obtained. The previously described effect of a substantial increase in the rigidity and thermal stability of PVA cryogels resulted from the repeated freezing-thawing cycles is confirmed. The largest (jumpwise) changes in the physicochemical characteristics of such gels and their macroporous morphology take place after the second cycle of cryogenic treatment. Moreover, depending on the PVA concentration in the initial solution, the mean cross section of micropores increases by a factor of 2–3 and the total porosity of cryogel rises by a factor of 1.5–2; i.e., the imperfection of material increases. Nevertheless, this negative (from view-point of the integral properties of cryogel) effect is completely overpowered by processes of additional structuring, which result in the strengthening of polymer phase proceeding during the repeated freezing-thawing cycles.     

Study of cryostructuring of polymer systems: 27. Physicochemical properties of poly(vinyl alcohol) cryogels and specific features of their macroporous morphology

Based on aqueous poly(vinyl alcohol) (PVA) solutions with different content of polymer having different molecular masses and chain tacticity, macroporous viscoelastic gels (PVA cryogels) are prepared in various regimes of freezing-storage in a frozen state-thawing. Shear modulus and fusion temperature of corresponding samples are measured; the structure of thin sections is studied by optical microscopy and the images are processed and analyzed. It is shown that the rigidity and heat endurance of cryogels rise with an increase in the concentration of initial PVA solution and a decrease in the rate of thawing. The influence of the temperature of cryogenic treatment and the PVA molecular mass has an extreme character. At the same time, the effect of the main parameters of cryotropic gelation on the macroporous morphology of PVA cryogels is manifested in the form of more complex dependences because of its multiple-factor character. Therefore, distinct structure-property correlations are not observed in many cases. Cluster analysis of the morphometric characteristics of cryogels in comparison with data on their rigidity makes it possible to classify these systems.     

Study of cryostructuring of polymer systems: 31. Effect of additives of alkali metal chlorides on physicochemical properties and morphology of poly(vinyl alcohol) cryogels

Macroporous viscoelastic poly(vinyl alcohol) (PVA) cryogels were prepared from aqueous PVA solutions containing additives (0–1.2 mol/l) of alkali metal chlorides (LiCl, NaCl, KCl, CsCl) by cryogenic treatment (freezing at −20°C for 12 h and subsequent thawing at a rate of 0.03°C/min). Shear moduli and fusion temperatures of corresponding samples were determined and the structure of thin sections was studied by optical microscopy with subsequent processing and analysis of images obtained. It was shown that the rigidity, heat endurance, and mean pore sizes of formed cryogels monotonically decrease with increasing content of chaotropic lithium chloride. In the case of other three salts, the dependences of rheological characteristics of cryogels on the concentration of low-molecular-weight electrolyte were extreme due to the competition between factors that promote and prevent PVA cryotropic gelation. At the same time, fusion temperatures of gel samples increased steadily with increasing content of these salts. Microscopic studies revealed substantial (by factor of two to three) decrease in macropore sizes even at low content of salt compared to mean cross sections of pores in cryogel containing no additive; morphometric analysis of obtained images makes it possible to reveal the linear correlations between the rheological characteristics of cryogels formed in the presence of LiCl and the sizes of their macropores.     

Study of cryostructuring of polymer systems. 33. Effect of rate of chilling aqueous poly(vinyl alcohol) solutions during their freezing on physicochemical properties and porous structure of resulting cryogels

Poly(vinyl alcohol) cryogels are obtained and investigated. The cryogels are prepared by freezing an initial polymer solution (100 g/L) at chilling rates of 1.85, 0.3, 0.03, or 0.003°C/min followed by defrosting the frozen (?20°C/12 h) preparations at heating rates of 0.3, 0.03, or 0.003°C/min. It is shown that a noticeable influence of the chilling rate on the rigidity and heat endurance of the gel matrix is observed at very slow regimes of chilling (on the order of thousandths of degree centigrade per minute). One of the reasons for a reduction in the rigidity of resulting cryogels and the fusion enthalpy of the nodes in their supramolecular networks is the formation of a homo-phase hydrogel during the long-term exposure of the concentrated polymer solution to low temperatures prior to the onset of ice crystallization. The effect of the regime of chilling the polymer solution being frozen on the porous structure of cryogels resulting from the thawing of the preparations is ambiguous due to the multifactor character of this effect; therefore, in many cases, well-defined structure-property correlations are not observed.     

Study of cryostructuring of polymer systems. 42. Physicochemical properties and microstructure of wide-porous covalently cross-linked albumin cryogels

Chemically cross-linked wide-porous protein cryogels have been obtained by freezing aqueous bovine serum albumin (BSA) solutions (30–50 g/L) at–15,–20, or–25°C in the presence of water-soluble carbodiimide (CDI) as a coupling agent. It has been shown that the gel-fraction yield and the swelling extent of the polymer phase of the formed spongy matrices depend primarily on the initial concentration of albumin and the amount of CDI added to a system, while the morphometric characteristics of the porous microstructure of the BSA cryogels are mainly determined by the temperature of the cryogenic treatment. The sizes of macropores in the obtained cryogels range from ≈50 to ≈200 μm. A high-sensitivity differential scanning calorimetric study of the conformational state of protein macromolecules incorporated into the spatial network of the polymer phase (gel walls of macropores) of the cryogels has shown that, during the cryotropic gelation, the native structure of albumin globules is subjected to “cold denaturation,” and the partly unfolded conformation of the protein is, simultaneously, fixed by intermolecular covalent cross links.     

A study of the microstructural and diffusion properties of poly(vinyl alcohol) cryogels containing surfactant supramolecular aggregates

Surfactant-containing poly(vinyl alcohol) (PVA) cryogels have been prepared by drying and reswelling hydrogel patches, previously obtained by the freeze/thaw procedure, in decyltrimethylammonium bromide (C10TAB) aqueous solutions. The microstructural and diffusive properties of the resulting material have been characterized by a combined experimental strategy. Gravimetric measurements show that the cryogel maximum swelling is not affected by the surfactant. The surfactant concentration within the cryogel, measured by ion chromatography, is the same as that in the rehydrating surfactant solution. Electron paramagnetic resonance (EPR) spin-probe and small-angle neutron scattering (SANS) measurements show that surfactant self-aggregation in the gel is similar to that in water, occurring at the same critical concentration and resulting in the formation of micellar aggregates whose structure is not affected by the cryogel polymeric scaffold. However, both the micelle intradiffusion coefficients, measured by PGSE-NMR, and the spin-probe correlation times, measured by EPR, indicate that dynamic processes in the hydrogel are much slower than in bulk water. A quantitative analysis of these results suggests that the cryogel polymer-poor domains, in which surfactant molecules are solubilized, have an average dimension of approximately 0.1 microm. Interestingly the experimental data also show that the polymer-poor phase contains more polymer than expected, suggesting that the spinodal decomposition, which occurs during the freezing step of cryogel preparation, is not complete or prevented by ice formation.     

Mechanical and thermal properties of cryogels and foamed cryogels produced from aqueous solutions of poly(vinyl alcohol)

The effect of sodium chloride and technical-grade carbon (carbon black) on the mechanical and thermal properties of cryogels and foamed cryogels produced from homogeneous and heterogeneous (foamed) solutions of poly(vinyl alcohol) was studied.     

Poly(vinyl alcohol) obtained through polymerization of some vinyl esters

Bulk and/or solution polymerizations of a series of vinyl esters, e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, and vinyl benzoate were conducted. Iodine-coloration, 1,2-glycol structure, molecular weight, and tacticity (triad and pentad) were measured for the resulting poly(vinyl alcohol)s (PVAs). The iodine-coloration abilities of PVAs, derived from poly(vinyl ester)s that were obtained through bulk polymerization at 60°C, depended on the starting monomer, increasing in the following order: vinyl benzoate < vinyl acetate < vinyl propionate < vinyl butyrate < vinyl pivalate. In solution polymerizations of vinyl propionate and vinyl butyrate, it was revealed that the tacticity of the derived PVAs apparently depended on the type and amount of polymerization solvent employed, as found previously in the case for vinyl acetate. The iodine-coloration of these PVA samples varied in the same order as their syndiotactic content, while no relationship was observed toward their 1,2-glycol content. The probabilities of the syndiotactic propagation at 60°C were estimated as 0.49 (benzoate), 0.54 (acetate), 0.55 (propionate), 0.56 (butyrate), and 0.60 (pivalate), respectively.     

Biomaterials of Poly(vinyl alcohol) and Natural Polymers

Polysaccharides and proteins are abundantly found in nature and are highly recommended for developing eco-friendly materials due to their special properties (biodegradability, biocompatibility, non-toxicity, low cost, etc.). However, they sometimes fail to meet specific requirements due to poor mechanical and physical properties. Poly(vinyl alcohol) (PVA) is one of the promising synthetic polymers with superior properties that can be blended with natural polymers for obtaining novel biomaterials with improved performances. This review addresses recent advance in PVA/polysaccharides and PVA/proteins biocomposites design and fabrication, mainly for the past two decades.     

Reduction of silver ions to silver with polyaniline/poly(vinyl alcohol) cryogels and aerogels

The macroporous conducting polymer cryogels were prepared by the oxidation of aniline hydrochloride in the frozen aqueous solutions of poly(vinyl alcohol) at ? 24 °C. Corresponding polyaniline aerogels supported with poly(vinyl alcohol) have been obtained after thawing of cryogels followed by freeze-drying. Silver was deposited on the composites using the ability of polyaniline to reduce silver ions after the immersion in silver nitrate solutions. Swollen cryogels were coated only on the surface with macroscopic silver particles due to the closed-pore structure in cryogels and limited penetration of silver ions into macropores. The diffusion of silver ions to freeze-dried aerogels was better and further improved by vacuum treatment. Silver microcubes were produced in the pores, the weight fraction of silver in dry composites being typically several per cent, a maximum 13 wt%. The conductivity of the aerogels compressed to pellets depended on the processing and the highest value was 0.27 S cm^?1. The aerogels containing silver were characterized in detail with Raman spectroscopy.     

Facile preparation of ferromagnetic alginate-g-poly(vinyl alcohol) microparticles

Alginate-g-poly(vinyl alcohol) was physically cross-linked with Fe(II) ion in a surfactant-free emulsion system to form microparticles via in situ precipitation. The microparticles were subjected to oxidation in aqueous of pH 13 at ambient temperature and transformed into magnetic ones within minutes. X-ray diffractometry showed that magnetic Fe₃O₄ was formed and it was further confirmed with a vibrating sample magnetometer measurement. Scanning electron microscopy examinations indicated that the iron oxide was well embedded into ferrous alginate and the size of particles was around 0.2-1.2 μm.     

Investigation of Miscibility of Linseed Oil Epoxy with Poly(vinyl alcohol)

Blending of two polymers in solution is a simple and cost effective technique to improve upon the physical and mechanical properties of the component polymers. Maximum synergism in the properties of the two polymers occurs when they are thermodynamically miscible. Poly(vinyl alcohol) (PVA) yields tough, flexible and water sensitive films. Linseed oil epoxy(LOE), a product from sustainable resource, used as a plasticizer and corrosion resistant coating, does not produce free standing film. A blend of PVA with LOE may yield films of good toughness and flexibility, and low water absorption if the two components are miscible with each other. Blends of PVA with LOE were prepared in weight ratios 80/20, 60/40, 40/60 and 20/80 through solution method by mixing in dimethyl sulphoxide. In the first instance, the miscibility the two components were investigated using the techniques of viscosity and ultrasonic measurements. The study revealed that the two components showed miscibility up to below 60 wt% PVA in the blend as at the composition LOE: PVA 40/60, phase inversion occurs. Above this composition, immiscibility is indicated; differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) delineates the above behavior in the solid phase.     

聚乙烯醇-碘复合物在水溶液中的形成

聚乙烯醇(PVA)在碘-碘化钾混合水溶液中能形成蓝色复合物,该复合材料在人们日常生活中已广泛应用.本文综述了在稀溶液条件下聚乙烯醇-碘复合物的形成,并对其复合物形成的可能影响因素,如:PVA的分子量、链结构的规整度、1,2-羟基结构、支链以及浓度、添加其它物质和反应时间等,进行了系统论述.从聚集模型观点看,在复合物中,碘主要是以线性多聚碘负离子形式存在的,如:T3-和I5-等;而PVA链通过分子间氢键作用形成链间聚集将多聚碘负离子包裹在内而形成复合物.     

Reaction of poly(vinyl alcohol) with formaldehyde and polymer stereoregularity. Model compounds

The reaction of stereoisomers of pentane-2, 4-diol and heptane-2, 4, 6-triol with formaldehyde was investigated as a model for the formalization reaction of poly(vinyl alcohol) in order to determine effect of the stereochemical configuration of the polyol molecules on the reaction. The isotactic (meso) diol portion reacted with formaldehyde to give cis-formal several times faster than did the syndiotactic (dl) diol portion to give trans-formal at 30–80°C. In the reaction of heterotactic (meso-dl) triol which provides both the isotactic and syndiotactic diol portions in a molecule, the proportion of trans-formal in the total formal decreased as the reaction proceeded. This shows that the formation of cis-formal is also favored thermodynamically to a greater extent, and hence the intramolecular migration of trans-formal to cis-formal did occur during the reaction. The rates of hydrolysis of formals of the diols were compared with those of the triols in order to see the effect of a hydroxyl group adjacent to the formal ring on the reaction. No appreciable rate difference was observed between the dimer and trimer models both in cis- and trans- formals. Therefore it was deduced from these results that the increase of the rate of hydrolysis of poly(vinyl formal) with the increase of hydroxyl groups along the polymer chain is a characteristic of macromolecules that is not observed in the low molecular weight models.     

氯化镁增塑改性聚乙烯醇

以氯化镁为增塑剂, 采用流延法制备了增塑改性聚乙烯醇(PVA). 研究了氯化镁与PVA的相互作用以及氯化镁增塑改性PVA的结晶性能、 热性能和机械性能. 研究结果表明, 氯化镁能与PVA大分子发生较强的相互作用, 从而破坏PVA分子链内和链间的氢键, 降低PVA的结晶度. 氯化镁对PVA的热性能影响显著, PVA在加入氯化镁后的热分解过程由纯PVA的两段失重过程转变成三段失重过程. 氯化镁可有效增塑PVA, 其玻璃化转变温度降低, 拉伸强度下降, 断裂伸长率上升, 储能模量下降.