Molecular dynamics simulation of oxygen diffusion in dry and water-containing poly(vinyl alcohol)

The kinetics and mechanisms of diffusion of oxygen and water in dry and water-containing amorphous syndiotactic poly(vinyl alcohol) were studied at 502 K and normal pressure by molecular dynamics simulation. Penetrant molecule trajectories were obtained in a system with 600 repeating units of poly(vinyl alcohol) and 0, 40 (2.6 wt%) and 80 (5.2 wt%) water molecules. Under dry conditions, oxygen molecules jumped in a cage-like fashion. The oxygen molecule diffused in a liquid-like fashion while water diffusion was cage-like in the system with 5.2 wt% water. The hydrogen bond lifetimes among the water molecules were significantly shorter than those formed between water and the polymer and between different polymer segments. The hydrogen bond lifetimes among all species were, within experimental error, unaffected by the content of water, even though the oxygen diffusivity increased exponentially and the water diffusivity increased to some extent with increasing water content. It seemed that the diffusivity was sensitive primarily to the decrease in concentration of polymer-polymer hydrogen bonds, which followed from the increase in water content. This finding was consonant with the analysis of the oxygen molecule motion relative to the nearest polymer backbone, which revealed that it jumped preferentially along the polymer chain and towards the backbone. This behavior was more pronounced when the dynamics were analyzed over longer distances (5 Å) and it was less pronounced in the water-rich systems. The simulations indicated that water clustering was absent and consequently that water was homogeneously distributed in the polymer systems.     

Cooperative behavior of poly(vinyl alcohol) and water as revealed by molecular dynamics simulations

An aqueous poly(vinyl alcohol) (PVA) model has been extensively studied by using the molecular dynamics (MD) simulation method. The employed molecular and force field models are validated against the available data in the literature. In particular, the glass transition temperature (T_g) is determined from the specific volume versus temperature, which compares well with the experimental observations. The diffusion coefficients of water (H₂O) through the PVA matrix follow the Arrhenius equations at both temperature regions separated by T_g, indicating the existence of free and bound water defined by hydrogen bonds (HBs). It has also been confirmed that HBs occur between PVA and H₂O, between PVA and PVA, between H₂O and H₂O, and all of them play the key roles in the glass transition. The local dynamics suggested by the decorrelations of various bond vectors can be well described by the Williams-Landel-Ferry (WLF) equation. This work demonstrates the cooperative behavior of PVA and H₂O which is responsible for the glass transition of the whole binary system.     

Water sorption in cross-linked poly(vinyl alcohol) networks

Poly(vinyl alcohol) (PVA) networks of different cross-linking densities were prepared by reaction with hexamethylene diisocyanate in solution and casting. The dynamic-mechanical properties of PVA films have been investigated in the temperature range of −150 to +150 °C. Two relaxations processes labeled α and β in order of decreasing temperature were observed. The α-relaxation shifts to lower temperature and the average molecular weight between cross-links decreases with increasing cross-linking density. Isothermal sorption from vapor and liquid water allowed determination of the Flory-Huggins interaction parameter between water and the polymer chain segments, which decreased with the water activity in the hydrogel and increased with the cross-linking density as a consequence of the hydrophobic character of the cross-linking agent. The water diffusion coefficients, D, in the networks obtained by means of dynamic sorption experiments increased with increasing water activity. This behavior is interpreted in terms of plasticization of the polymer by water molecules.     

Miscibility and interactions in poly(methylthiomethyl methacrylate)/poly(vinyl alcohol) blends

Poly(methylthiomethyl methacrylate) (PMTMA) is miscible with poly(vinyl alcohol) (PVA) over the whole composition range as shown by the existence of a single glass transition temperature in each blend. The interaction between PMTMA and PVA was examined by Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy. The interactions mainly involve the hydroxyl groups of PVA and the thioether sulfur atoms of PMTMA, and the involvement of the carbonyl groups of PMTMA in interactions is not significant. The measurements of proton spin-lattice relaxation time reveal that PMTMA and PVA do not mix intimately on a scale of 1-3 nm, but are miscible on a scale of 20-30 nm. In comparison, we have previously found that PMTMA is miscible with poly(p-vinylphenol) and the two polymers mix intimately on a scale of 1-3 nm.     

Microstructural studies on BaCl2 doped poly(vinyl alcohol)

We have studied the effect of BaCl₂ dopant on the optical and microstructural properties of a polymer poly(vinyl alcohol) (PVA). Pure and BaCl₂ doped PVA films were prepared using solvent casting method. These films were characterized using FTIR, UV-visible, XRD and DSC techniques. The observed peaks around 3425 cm⁻¹, at 1733 cm⁻¹ and 1640 cm⁻¹ in the FTIR spectra were assigned to O-H, CC stretching and acetyle CO group vibrations, respectively. In the doped PVA shift in these bands can be understood on the basis of intra/inter molecular hydrogen bonding with the adjacent OH group of PVA. The UV-visible spectra shows the absorption bands around 196 nm and shoulders around 208 nm with different absorption intensities for doped PVA, which are assigned to n→π* transition. This indicates the presence of unsaturated bonds mainly in the tail-head of the polymer. Optical band energy gap is estimated using UV-visible spectra and it decreases with increasing dopant concentration. The powder XRD shows an increase in crystallinity in the doped PVA, which arises due to the interaction of dopant with PVA causing a molecular rearrangement within the amorphous phase of polymer. These modifications also influence the optical property of the doped polymer. The DSC study also supports increasing crystalline thickness and degree of crystallinity due to doping.     

Mixed matrix membranes prepared from natural rubber/poly(vinyl alcohol) semi-interpenetrating polymer network (NR/PVA semi-IPN) incorporating with zeolite 4A for the pervaporation dehydration of water-ethanol mixtures

The pervaporation dehydration of water-ethanol mixtures was investigated using the mixed matrix (MM) membranes prepared from natural rubber (NR) and crosslinked poly(vinyl alcohol) (PVA) semi-IPN embedded with the zeolite 4A. With the presence of NR as well as zeolite, the swelling of MM membranes in water was effectively suppressed. Examined by DSC, the non-freezing bound water in the MM membranes was found decreasing with more zeolite loading because the water-polymer interaction is diminishing. The sorption study of MM membranes revealed a preferential sorption to water with improved water sorption selectivity as increasing the zeolite loading. For pervaporation at 5 vol% water in feed, the reversed trade-off with respect to the zeolite loading was encountered such that the total permeation flux increased along with an enhancement of the water separation factor. For higher feed water concentration, despite the greater total permeation flux, the separation factor was reduced owing to the extensive swelling of the polymer matrix. The temperature dependency of the partial water and ethanol fluxes followed the Arrhenius relationship and the estimated activation energies for water flux were lower than those of the ethanol flux, suggesting that the developed MM membranes are highly water selective.     

高分子量聚醋酸乙烯酯的醇解研究

探讨了催化剂浓度、醇解温度和反应时间等对高分子量聚醋酸乙烯酯醇解的影响,得出高分子量聚醋酸乙烯酯醇解的适合条件。     

Facile fabrication of poly(vinyl alcohol) gels and derivative aerogels

A facile preparation of poly(vinyl alcohol) (PVOH) hydrogels and their derivative PVOH/montmorillonite clay aerogels is reported, using water as solvent and divinylsulfone as crosslinking agent, making use of an environmentally friendly freeze drying process. The materials exhibit significantly increased mechanical properties after crosslinking. The compressive modulus of an aerogel prepared from an aqueous suspension containing 2 wt% PVOH/8 wt% clay increased 29-fold upon crosslinking, for example. Crosslinking of the polymer/clay aerogels decreased the onset decomposition temperature as measured by thermogravimetric analysis, and generated a more continuous structure at higher clay contents. Such polymer/clay aerogels are promising materials for low flammability applications.     

Thermal characteristics of poly(vinyl alcohol) and poly(vinylpyrrolidone) IPNs

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and 1‐vinyl‐2‐pyrrolidone (VP) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The thermal characterization of the IPNs was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depressions of the melting temperatures of PVA segments in IPNs were observed with increasing VP content via the DSC. The DEA was employed to ascertain the glass transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_gs indicating the presence of phase separation in the IPN. The thermal decomposition of IPNs was investigated using TGA and appeared at near 270°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1844–1847, 2002     

Transition of hydration states of poly(vinyl alcohol) in aqueous solution

A straightforward method for determination of the hydration number of polymer in aqueous solution based on ice-melting technique of DSC is proposed. The simple yet precise method has been applied to determine the hydration number of poly(vinyl alcohol) (PVA) in aqueous solution covering a wide range of concentrations, from 0.005 to 0.3 g(solute)/g(solution), for three samples with different molar masses. The hydration number of PVA maintains a constant lower value of 2.5 when the concentration exceeds 0.2 g(solute)/g(solution). It increases to a value of 7 when the concentration decreases to the overlap concentration C^∗ of the polymer, where C^∗ was estimated as the reciprocal of its intrinsic viscosity. For solutions of C < C^∗, the hydration number keeps constant again at the value of 7. This behavior evidently demonstrates that PVA has two hydration states, one occurs at the dilute regime and the other occurs at concentrated regime. The concentration dependent transition from one state to another is treated mathematically by a quantitative formula which involves two parameters: one denotes the transition concentration and the other denotes the width of the transition region. The transition concentration decreases linearly with increasing molar mass resembling the behavior of molar mass dependence of overlap concentration. The structural features for the two states of hydrated PVA are briefly discussed.     

Light scattering and viscoelasticity study of poly(vinyl alcohol)-borax aqueous solutions and gels

Poly(vinyl alcohol)-borate (PVA-borate) aqueous solutions properties with PVA concentrations ranging from 2 to 60 g/L and borax concentrations of 0.0 and 0.2 M were investigated at room temperature using static and dynamic light scattering (SLS and DLS), and dynamic viscoelasticity measurements. Light scattering and viscoelasticity data revealed that all the PVA-borate aqueous systems, except those with [PVA]≥40 g/L and [borax]=0.2 M, behaved as solutions. For PVA-borate aqueous systems with [PVA]≥40 g/L and [borax]=0.2 M, light scattering data revealed that these systems behaved like gels, but viscoelasticity data showed that these systems were in flow states. The experimental data suggest that PVA-borate aqueous systems with [PVA]≥40 g/L and [borax]=0.2 M are thermoreversible gels with finite equilibrium life time of thermoreversible borate-PVA di-diol crosslinks. The thermoreversible crosslinks can be observed by the non-perturbing light scattering technique but not by the pertubing rheometric method. These results indicate the advantage of light scattering relative to rheometers for studying the physical or reversible crosslink gels.     

Single wall carbon nanotube templated oriented crystallization of poly(vinyl alcohol)

Shearing of poly(vinyl alcohol) (PVA)/single wall carbon nanotube (SWNT) dispersions result in the formation of self-assembled oriented PVA/SWNT fibers or ribbons, while PVA solution results in the formation of unoriented fibers. Diameter/width and length of these self-assembled fibers was 5-45 μm and 0.5-3 mm, respectively. High-resolution transmission electron micrographs showed well resolved PVA (200) lattice with molecules oriented parallel to the nanotube axis. Nanotube orientation in the self-assembled fibers was also determined from Raman spectroscopy. PVA fibers exhibited about 48% crystallinity, while crystallinity in PVA/SWNT fibers was 84% as determined by wide angle X-ray diffraction. PVA and carbon nanotubes were at an angle of 25-40° to the self-assembled fiber axis. In comparison to PVA, PVA/SWNT samples exhibited significantly enhanced electron beam radiation resistance. This study shows that single wall carbon nanotubes not only nucleate polymer crystallization, but also act as a template for polymer orientation.     

Swelling and morphological properties of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA) hydrogels in solution with high salt concentration

Understanding the swelling properties of hydrogels and how they affect the hydrogel's morphology is of fundamental importance in the development of hydrogel-based artificial muscles, bio-actuators, sensors and other devices. In this paper, the swelling behavior of PVA-PAA hydrogel films in saline water and in buffer solutions of different pH values was investigated. It was observed that the swelling factor of the hydrogel decreases when the ionic strength of the solvent solution increases. Scanning Electron Microscopy (SEM) revealed structures with different pore shapes and sizes depending on the type of solution used for hydration. In saline water, Energy Dispersive X-Ray (EDS) analysis indicated the formation of NaCl crystals within the polymeric network. Finally, the PVA-PAA hydrogel was used as an actuator to strain a fiber Bragg grating sensor, thus providing an indirect measurement of the pH value of the surrounding solution.     

Synthesis and characterization of hydrophobically modified poly(vinyl alcohol) hydrogel membrane

Hydrophobically modified poly(vinyl alcohol), [PVA] was synthesized by graft copolymerization of N-tertiary butyl acrylamide [NTBA] onto PVA by free radical polymerization. The incorporation of NTBA onto PVA chains was confirmed by elemental analysis, FT-IR and NMR spectroscopy. A series of graft copolymers with different contents of NTBA were prepared and membranes were casted from these copolymer solutions in dimethyl sulfoxide. The increase in hydrophobicity with an increase in NTBA content was investigated by contact angle measurements. The swelling behaviour of membranes as a function of temperature, hydrophobic content, annealing temperature and period was studied. Permeability of solutes through these membranes was investigated as a function of solute size, membrane hydrophobicity and temperature. The swelling behaviour of the copolymer membranes showed that the lower content of NTBA gives discontinuous volume transition with respect to temperature whereas, the presence of higher amounts of NTBA showed decreased swelling ratios with very little influence of temperature on the swelling. The permeabilities of solutes through these membranes were strongly dependent on the size of the solute, solution temperature and hydrophobicity of the membrane. The copolymer membranes were further characterized using DSC, DMA and XRD. The peak becomes broader as the NTBA content increases.     

Poly(vinyl alcohol) hydrogel fixation on poly(ethylene terephthalate) surface for biomedical application

A surface modification technique was developed for the covalent immobilization of poly(vinyl alcohol) (PVA) hydrogel onto poly(ethylene terephthalate) (PET) to improve the biocompatibility of the film. The PET film was first graft copolymerized with poly(ethylene glycol) monomethacrylate (PEGMA) in the presence of ethylene glycol dimethacrylate (EGDMA) as crosslinker, and then oxidized with a mixture of acetic anhydride (Ac₂O) and dimethyl sulfoxide (DMSO) to produce aldehyde groups on the PET surface. Finally, the prepared PVA solution was cast onto the film and covalently immobilized on the film through the reaction between the aldehyde groups on the PET film and the hydroxyl groups of PVA. The good attachment of the PVA layer to the PET film was confirmed by observing the cross-section of the PET-PVA film using scanning electron microscopy (SEM). Heparin was immobilized on the PVA layered PET using two different methods, physical entrapment and covalent bonding, to further improve the biocompatibility of the film. Attenuated total reflectance (ATR) FT-IR spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize the chemical composition of the surface modified films. The biocompatibility of the various surface modified PET films was evaluated using plasma recalcification time (PRT) and platelet adhesion.     

Pure shear deformation of physical and chemical gels of poly(vinyl alcohol)

Pure shear deformation reveals the significant differences in elastic properties of the poly(vinyl alcohol) (PVA) gels with almost identical initial modulus, but with different types of crosslinks, physical crosslinks formed by microcrystallites and chemical crosslinks made of covalent bonds. The ratio of the two principal stresses steeply increases with elongation in the physical gels, while that remains almost constant independently of stretching in the chemical gels. The marked growth of the stress ratio with elongation in the physical gels leads to the negative values of the derivative of the elastic free energy (W₂) with respect to the second invariant of the deformation tensor in the whole range of deformation, which is firstly observed for elastomeric materials. By contrast, the chemical gels exhibit the positive values of W₂ like most chemically crosslinked rubbers. Among the existing theories of rubber elasticity, the classical non-Gaussian three-chain model considering the effect of finite chain-length is qualitatively successful in accounting for the steep increase of the stress ratio and the negative values of W₂ in the physical gels, although it fails to reproduce the large difference in the stress-strain behavior among uniaxial, pure shear and equi-biaxial deformations. These features of the physical gels are expected to stem from the structural characteristics such as fewer amounts of slippery-trapped entanglement along network strands compared to the chemical PVA gels.     

Preparation and characterization of poly(vinyl alcohol)‐poly(vinyl pyrrolidone) blend: A biomaterial with latent medical applications

Aqueous solutions of poly(vinyl alcohol) and poly(vinyl pyrrolidone) are blended and films are produced by casting method with the further intention of being used as bio‐materials with latent medical application. Glutaraldehyde, 4,4′‐diazido‐2,2′‐stilbenedisulfonic acid disodium salt tetra‐hydrate are used as crosslinker agents, whereas lactic acid is the plasticizer in the blend. The obtained films are characterized by differential scanning calorimetry (DSC), mechanical properties, swelling and solubility behavior. DSC measurements show that the blends exhibit a single glass transition temperature indicating that they are miscible, even in the presence of the plasticizer and crosslinker agents. By the combination of all mentioned additives, a relevant enhancement of the swelling is observed, accompanied by a stabilization of the solubility during the tested time. Finally, mechanical properties show an appropriate performance in the studied parameters. As a consequence, the obtained films could be suitable for use as medium or long‐term implants. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New production technologies and applications of poly(vinyl alcohol) film

The following aspects of the manufacture, properties and applications of biaxially oriented poly(vinyl alcohol) (PV-OH) films are discussed: selection of starting PV-OH; method of production by successive biaxial orientation: technical aspects of production; characteristics and applications of the film. Biaxially oriented PV-OH films have good antistatic properties, good thermal resistance, oil and solvent resistance, and excellent gas barrier properties, and are used in food packaging applications. The following aspects of the manufacture, properties and applications of poly(vinyl alcohol) film produced by a blown film technique are discussed: selection of starting PV-OH; process for the production of hot-water-soluble (HWS) film; technical aspects of film production; characteristics and applications of the film. Blown films, which are hot-water-soluble, are produced in tubular form, for conversion into disposable laundry bags.     

Effect of crosslinking on the mechanical and thermal properties of poly(vinyl alcohol)

Poly(vinyl alcohol) was crosslinked with hexamethylene diisocyanate in solution. A broad range of degrees of crosslinking, from 1.7 up to 74 mol% of reacted hydroxyl groups, was achieved. The variation of the thermal and mechanical properties of PVA with the crosslinking density show an initial decrease due to the diminution of the crystallinity of the system, caused by the crosslinking. After an abrupt rise at about 20%, the properties tend to level off independently on the increase of the crosslinking. This behaviour is explained as a result of the competitive action of at least three factors during the crosslinking: (i) weakening of the existing physical network due to hydrogen bonding; (ii) formation of a chemical network; and (iii) introduction of flexible moieties. The last factor is closely connected with the specific chemical structure of the crosslinker itself.