Preparation and characterization of reinforced poly(vinyl alcohol) films by a nanostructured,chiral, L-leucine based poly(amide-imide)/ZrO2 nanocomposite through a green method

In the present investigation, at first, the surface of ZrO₂ nanoparticles was modified with a bioactive and biocompatible diacid based on leucine amino acid as a coupling agent. The grafting of diacid on the surface of ZrO₂ was confirmed by Fourier transform infrared spectroscopy and thermogravimetric analysis. Then, the synthesis of poly(amide-imide)/ZrO₂ nanocomposite (PAI/ZrO₂ NC) was performed through ultrasonic technique. The obtained NCs demonstrated good thermal stability. Field emission scanning electron microscopy and transmission electron microscopy analysis showed that the average diameter of NP was around 15–20 nm. Finally, the resulting NC, was used as a nano-filler and was incorporated into the poly(vinyl alcohol) (PVA) in order to improve its mechanical and thermal properties. The PVA/PAI–ZrO₂ NC films were characterized by different techniques. The data indicated that the thermal and mechanical properties of the PVA/PAI–ZrO₂ NC were enhanced. It was attributed to the good dispersion of filler into the PVA matrix as a result of hydrogen bonding.     

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.     

聚乙烯醇/凹凸棒黏土纳米复合膜的制备及其性能

以聚乙烯醇(PVA)和提纯凹凸棒黏土(APT)为原料,采用溶液流延成膜法,制备了系列不同APT含量的PVA/APT纳米复合膜。采用XRD、FTIR和SEM对复合膜的结构进行了表征,测试了复合膜的热性能、力学性能和耐水性能。结果表明,APT可均匀分散在PVA基体中,APT的加入使得PVA的结晶度有所下降但并未改变其晶型。APT与PVA通过氢键作用,改善了复合膜的热稳定性、力学性能和耐水性。当APT含量为4%时,纳米复合膜有最优的性能。     

A straightforward preparation and characterization of novel poly(vinyl alcohol)/organoclay/silver tricomponent nanocomposite films

In the present investigation, novel poly(vinyl alcohol)/organoclay/silver (PVA/OMMT/Ag) tricomponent nanocomposite (NC) films with different compositions were prepared by solution intercalation method under ultrasonic irradiation process. The NC films were obtained by mixing a colloidal solution consisting of Ag nanoparticles (NPs) (3, 5, 7 and 9 wt%) with a water solution of PVA and OMMT (10 wt%) via solution casting method. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis (TGA) were utilized to characterize the morphology and properties of the PVA/OMMT/Ag NC films. TGA confirmed that the heat stability of the nanocomposite was improved. The enhancement in the thermal properties of the hybrid materials was due to strong hydrogen bonding between OH groups of PVA, free acid functionalized groups of OMMT, and the Ag NPs. SEM and TEM results also showed that the OMMT and Ag NPs were dispersed homogeneously in the PVA matrix on nanoscale.     

Preparation and properties of poly(vinyl alcohol)-clay nanocomposite materials

A series of polymer-clay nanocomposite (PCN) materials that consist of poly(vinyl alcohol) (PVA) and layered montmorillonite (MMT) clay are prepared by effectively dispersing the inorganic nanolayers of MMT clay in organic PVA matrix via an in situ free radical polymerization with AIBN as initiator. Organic vinyl acetate monomers are first intercalated into the interlayer regions of organophilic clay hosts and followed by a one-step free radical polymerization. The prepared poly(vinyl acetate)-clay (PVAc-clay) solution are then saponified via direct-hydrolysis with NaOH solution to form PVA-clay nanocomposite materials. The as-synthesized PCN materials are typically characterized by Fourier-Transformation infrared (FTIR) spectroscopy, wide-angle X-ray diffraction and transmission electron microscopy.The molecular weights of poly(vinyl alcohol) (PVA) extracted from polymer-clay nanocomposite (PCN) materials and bulk PVA are determined by gel permeation chromatography (GPC) analysis with THF as eluant. The viscosity property of PCN materials with different feeding amount of MMT clay is studied by an ubbelohode capillary viscometer. The morphological image of as-synthesized materials is studied by scanning electron microscopy (SEM) and optical polarizing microscope (OPM). Effects of the material composition on the thermal stability, mechanical strength, optical clarity of PVA along with a series of PCN materials, in the form of fine powder and free-standing film, are also studied by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analyzer (DMA) and UV-visible transmission spectra, respectively.     

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.     

Swelling and mechanical behavior of modified poly(vinyl alcohol)/laponite nanocomposite membranes

Nanocomposite (NC) membranes based on hydrophobically modified PVA and laponite were synthesized with varying laponite content in the feed. The incorporation of laponite in NC membranes was investigated by FTIR spectroscopy and thermogravimetric analysis. The swelling ratio of membranes was determined as a function of temperature and laponite content. Swelling studies of NC membranes exhibited the decrease in swelling with an increase in laponite content in the NC membranes. The swelling ratio of NC membrane with 20% laponite slightly increased with an increase in temperature. Dynamic mechanical analysis showed the systematic increase in storage modulus with laponite content, which indicates the enhancement of mechanical property upon laponite addition. There was also a decrease in the tan δ peak values of NC membranes with an increase in laponite content in NCs. The permeabilities through NC membranes as a function of solute size and laponite content were studied and the results showed molecular screening based on size. The permeability of solute reduced due to the presence of well‐dispersed laponite in the NC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2896–2903, 2007     

Preparation and characterization of α-chitin whisker-reinforced poly(vinyl alcohol) nanocomposite films with or without heat treatment

α-Chitin whisker-reinforced poly(vinyl alcohol) (PVA) nanocomposite films were prepared by solution-casting technique. The α-chitin whiskers were prepared by acid hydrolysis of α-chitin from shrimp shells. The as-prepared whiskers exhibited the length in the range of 150-800 nm and the width in the range of 5-70 nm, with the average length and width being about 417 and 33 nm, respectively. Thermal stability of the as-cast nanocomposite films was improved from those of the pure PVA film with increasing whisker content. The presence of the whiskers did not have any effect on the crystallinity of the PVA matrix. The tensile strength of α-chitin whisker-reinforced PVA films increased, at the expense of the percentage of elongation at break, from that of the pure PVA film with initial increase in the whisker content and leveled off when the whisker content was greater than or equal to 2.96 wt%. Both the addition of α-chitin whiskers and heat treatment helped improve water resistance, leading to decreased percentage degree of swelling, of the nanocomposite films.     

Novel ternary poly(vinyl pyrrolidone)/poly(amide-imide)/ZnO nanocomposite: Synthesis,characterization, thermal and optical performance

The present work describes the synthesis and properties of polymer composites based on poly(vinyl pyrrolidone) (PVP) as polymer shell and poly(amide-imide)(PAI)/ZnO nanocomposite (ZNC) as efficient filler. At first, the alanine amino acid containing dicarboxylic acid was grafted on the surface of ZnO NPs. Then, modified ZnO (12 wt%) was incorporated into the PAI matrix under ultrasonic irradiations. The obtained hybrid ZNC showed high thermal stability and the size of the NPs in the TEM image of ZNC was about 31 nm. Secondly, PVP NCs with different ZNC loadings such as 2, 4 and 6 wt% were prepared via ultrasonication. Transmission electron microscopy (TEM) observations showed that the ZnO NPs were uniformly and highly dispersed in the PVP matrix. The UV–vis results exposed that the high UV-shielding efficiency of the obtained composites. Thermal analysis represented that the onset decomposition temperatures of the obtained PVPNCs had remarkable increasing in compared to the neat PVP due to the presence of both ZnO NPs and PAI.     

Transparent and thermally stable improved poly (vinyl alcohol)/Cloisite Na/ZnO hybrid nanocomposite films: Fabrication,morphology and surface properties

A series of poly(vinyl alcohol)/Cloisite Na⁺-Tyrosine/Zinc oxide (PVA/Cloisite Na⁺-Tyr/ZnO) bionanocomposites were prepared by dispersing ZnO nanoparticles in solution containing mixture of the PVA and modified Cloisite Na⁺. Structure of nanocomposite coatings was investigated by X-ray diffraction and Fourier-transform infrared spectroscopy. The thermal stability and optical properties of bionanocomposite were characterized by thermogravimetric analysis and UV–vis spectroscopy, respectively. The introduction of ZnO nanoparticles into PVA/Cloisite Na⁺-Tyr mixed solutions significantly increased the thermal stability of the obtained films. The results revealed that the high UV-shielding efficiency of the composites: for a film containing 6.0 wt% of ZnO nanocrystals, over 92% of UV light at wavelengths of 368 nm was absorbed while the optical transparency in the visible region was slightly below that of a PVA/Cloisite Na⁺-Tyr film.     

Morphology-rheology relationship in hyaluronate/poly(vinyl alcohol)/borax polymer blends

In this work, we have prepared bioartificial polymer blends using hyaluronate (HA) as a biological component and poly(vinyl alcohol)-borax association (PVAs) as a synthetic component, and investigated the rheological properties as well as morphology of the blends. When plotted against the blend composition, the rheological properties showed both positive and negative deviation from the linear additive mixing rule depending on thermal history. The blend showed enhanced viscosity at the composition of 20 wt% of HA and 80 wt% of PVAs, when PVA was dissolved at high temperature. The viscosity enhancement was caused by the network formation of HA aggregates in the micrometer scale. In addition, the network structure of HA aggregates was found to be fractal with the fractal dimension of 1.7. As PVA system also forms a network structure in the nanometer scale between hydroxyl groups of PVA and borate anions, the blend system is unique in that it has network structures in both micrometer and nanometer scales in one material. On the contrary, HA formed aggregates but not any network structure in the blend of the same composition but of the negative deviation. In conclusion, we showed that HA/PVAs blend system may have diverse morphology as well as very broad spectrum of rheological properties, and could suggest that the rheology and morphology of HA/PVAs blends can be designed not only by controlling composition but also by controlling thermal and deformation history of the components.     

Drying of semicrystalline polymers: mathematical modeling and experimental characterization of poly(vinyl alcohol) films

A mathematical model was developed to predict the drying mechanism of semicrystalline polymers involving multiple solvents. Since drying of semicrystalline polymers can be accompanied by changes in polymer degree of crystallinity, the model integrates crystallization kinetics and the Vrentas-Duda diffusion model to provide a better understanding of the mechanism. The model considers the effect of external conditions such as temperature, film shrinkage and diffusion and evaporation of multiple solvents during drying. Poly(vinyl alcohol) (PVA)/water/methanol was chosen as a test system. The drying kinetics of PVA films swollen in water and methanol were investigated using gravimetric techniques. The model predicts that higher temperatures, lower film thicknesses and lower methanol to water ratios increase the drying rate. The model predictions were compared with experimental data and showed good agreement.     

Enhancing mechanical properties of poly(vinyl alcohol) blown films by drawing and surface crosslinking

Thermal blowing of poly(vinyl alcohol) (PVA) film was successfully realized based on molecular complexation. Ways to enhance the performance of the PVA blown films (drawing and surface crosslinking) were studied. The experimental results showed that water exists in PVA films in different states through hydrogen bonds with PVA and other modifiers and influences the drawability of PVA films, as well as the structure and properties of the stretched films. When the initial water content of the film was higher than 35.0%, the draw ratio of the PVA film was quite large because of the effects of the bound water with PVA, as well as the plasticization of free water. With the increase of the initial water content in PVA, the free water content and draw ratio of the films increased but the strength of the films decreased because of the higher residual water in the films. Surface crosslinking can improve the stretchability of PVA films because more water remains in the films and disrupts the hydrogen bonding of PVA. In addition, crosslinking enhances the mechanical properties of stretched PVA films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 774–779, 2005     

Viscoelastic properties of poly(vinyl alcohol) hydrogels and ferrogels obtained through freezing-thawing cycles

We report the preparation of poly(vinyl alcohol) (PVA) hydrogels obtained through freezing-thawing cycles. The viscoelastic properties of these gels using parallel-plate shear mode were evaluated as a function of temperature, time, degree of swelling, concentration and the number of freezing-thawing cycles. The storage modulus was analyzed on the basis of a theoretical model based on the scaling approach. These results provide additional evidence for a non-crystalline nature of the structure of PVA cryogels.Furthermore, PVA ferrogels have been prepared from PVA aqueous solutions and a ferrofluid through freezing-thawing cycles. The viscoelastic properties of these materials have been evaluated. It is shown that the variation of the storage modulus with ferrofluid concentration cannot be fitted using classical theories what has been attributed to the small dimensions of the particles in the ferrogels and to the magnetic interactions between particles.     

Synthesis and Characterization of Poly(vinyl alcohol)/Poly(vinyl pyrrolidone)-Iodine Nanofibers with Poloxamer 188 and Chitosan

This study focuses on the fabrication of poly(vinyl alcohol)/ poly(vinyl pyrrolidone)-Iodine nanofibers via electrospinning. Electrospun fibers were characterized by FT-IR, DSC and SEM techniques. DSC results indicated that the thermal stability of nanofibers were improved after the addition of chitosan and poloxamer 188. SEM images showed that the spongiform structure is much more compact and fibrous in the case of added chitosan, with an average fiber diameter of 374 nm, whereas the addition of poloxamer 188 resulted in a more porous and beaded composition, with average fiber diameter of 489 nm.     

Grafting and adsorption of poly(vinyl) alcohol in vinyl acetate emulsion polymerization

Poly(vinyl alcohol) is often used in vinyl acetate emulsion polymerization as a protective colloid, but its role is complex and controversial since it partakes in grafting reactions with the monomer, influencing process mechanisms, and affecting the colloidal properties of the latex. Furthermore, in industrial operations, the wide scatter of macromolecular properties of the commercial types of poly(vinyl alcohol) causes process irreproducibilities. In this work different types of polyvinyl alcohol were used to perform a series of polymerizations, and their kinetics were compared. A selective solubilization procedure was applied to separate the three fractions of poly(vinyl alcohol) in the final latex: free in the water phase, physically adsorbed onto the polymer particles and chemically grafted. These results were compared with those obtained from pure adsorption measurements of polyvinyl alcohol onto ‘emulsifier-free’ polyvinyl acetate dispersions. The rheological behavior of the different latexes was also compared, and the results were used to formulate an hypothesis on the interaction mechanisms acting in these systems.     

Fabrication of poly(vinyl alcohol)s (PVAs) nanotubes through the fusion of nanocapsules composed of PVAs multilayer films

Poly(vinyl alcohol) (PVA) nanocapsules were fabricated by the deposition of PVA multilayer films onto the surface of silica particles followed by the removal of the silica cores. When a water dispersion of PVA nanocapsules was dried on a substrate, PVA nanotubes were formed through the one-dimensional fusion of the nanocapsules. This fusion behavior of the PVA nanocapsules was strongly affected by the molecular weights and acetylation degrees of PVA, the capsule film thickness of the PVA nanocapsules and the temperature to dry a water dispersion of the nanocapsules. When nanocapsules composed of 20 layered films of acetylated PVA with a 14% acetylation degree were used, nanotube formation via the fusion of these nanocapsules occurred effectively upon drying the water dispersion at 20 °C.     

Structural properties of sodium ion implanted poly(vinyl alcohol) films

Poly(vinyl alcohol) (PVA) films were implanted with sodium ions at various energies and total doses. Modified films were characterized by Fourier transform IR (FTIR), UV–visible (UV–vis), X‐ray diffraction (XRD), and scanning electron microscopy (SEM). From FTIR studies, it was evident that scission of the main chain occurred together with removal of hydrogen and hydroxyl groups. Sodium ions formed weak bonds with oxygen from the neighboring chains. UV–vis studies of implanted PVA showed increases in the absorbance values with the various energies and total doses. XRD studies revealed that, as the energy and total dose increased overall, the crystallinity decreased and new peaks at different 2θ values appeared. Changes in the crystallinity were also studied for thermally annealed PVA films in order to correlate and understand the phenomena of recrystallization due to ion implantation. The morphological features of the films were investigated by SEM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 276–283, 2005     

Compression of poly(vinyl alcohol) gels by ultracentrifugal forces

Compression due to ultracentrifugal forces was investigated for poly(vinyl alcohol) (PVA) gels. The concentration gradient profiles for the gels were obtained by experiment and were then compared with a theoretical prediction. By the application of the centrifugal forces, the concentration gradient near the bottom increases sharply whereas the gradient inside the gel remains almost constant in the region far from the bottom. Further application of the centrifugal forces enhances the peak near the bottom. These are well explained by the theory proposed in the previous paper [Urayama et al. J Chem Phys 2005;122:024906.]. The frictional coefficient f for the PVA gels, which originates from the friction between the polymer network and solvent molecules, is estimated to be 3.5×10¹⁴ N s m⁻⁴.