Physico-mechanical properties of poly (vinyl alcohol), poly (vinyl alcohol)/boric acid,and poly (vinyl alcohol) nanocomposites incorporated with amino-functionalized and pristine halloysite nanotubes films

Eco-friendly poly(vinyl alcohol) (PVA), PVA/boric acid, PVA/halloysite nanotubes (HNTs), and PVA/amino-functionalized HNTs (APTES-HNTs) films were fabricated by a solution casting technique. The samples were characterized by fourier transform infrared, X-ray diffraction, differential scanning calorimetry, scanning electron microscope, and energy-dispersive spectroscopy. The characterization results proved the chemical and physical interactions between the PVA and different additives. The viscoelastic behavior of the films was evaluated by DMA and creep analysis. The storage modulus, loss factor, and both α_α and β_β transitions affected by APTES-HNTs as a potential filler to form effective cross-links. APTES-HNTs existence enhanced creep-recovery beyond expectations. Tensile and impact strength were measured to understand samples' mechanical stability. PVA/APTES-HNTs and PVA/boric acid showed more yield behavior after the elastic limit. Furthermore, the subsequent rupture and impact strength were increased significantly compared with neat PVA and PVA/HNTs. The viscoelastic and mechanical behaviors were linked to each other by the area under Tanδ curve and the work of rupture and impact strength, which their linear correlation coefficient is statistically significant at 95% confidence limits. It seems that the presence of APTES-HNTs provides new cross-links, which altered (improved) the physico-mechanical properties of PVA, offering a bionanocomposite suitable for further applications. From the literature, possible explanations are provided for these observations.     

A chitosan/poly(vinyl alcohol) nanocomposite film reinforced with natural halloysite nanotubes

Biodegradable polymer/clay nanocomposites have attracted tremendous attentions because of their excellent properties and ecofriendly advantages. In this article, a series of nanocomposite films were prepared by introducing of halloysite nanotubes (HTs) into chitosan (CS)/poly(vinyl alcohol) (PVA) matrix using the solution casting method, and the effect of HT as nanofillers on the properties of polymer/HT nanocomposites was explored. The results indicated that the tensile strength of CS/PVA/HT3 and elongation at break of CS/PVA/HT2 sharply increased by 39.72% and 26.14% in comparison with the pure CS/PVA film, respectively. The water resistance and thermal stability of polymer/HT nanocomposites were also improved compared with the pure CS/PVA film, but the optical property of the nanocomposite films was not affected by introducing HT into the CS/PVA matrix. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Microwave assisted improvement in physico-mechanical properties of poly(vinyl alcohol)/poly(ethylene imine)/gelatin blends

Blends of poly (vinyl alcohol) (PVA), poly-N-acyl ethyleneimine (PEI) and gelatin (PVA/ PEI/Gel) in the weight ratios 100/0/2, 95/5/2, 90/10/2, 85/15/2, 80/20/2 and 70/30/2 were prepared by solution casting method. The effects of poly (ethylene imine) component in the blend and microwave irradiation on the mechanical and microstructural properties have been investigated using various techniques along with Positron Annihilation Lifetime Spectroscopy (PALS). We observed tremendous improvement in mechanical properties after microwave irradiation for 60 s in 5 wt% of PEI component blend. These results are supported by the SEM data as well the optical data. The free volume data from positron results showed minimum free volume at 5 wt% of PEI after 60 s of irradiation due to cross linking through hydrogen bond formation and possible estrification among the blend components. These results correlate well the mechanical properties like tensile strength and modulus.     

Physicochemical and morphological evaluation of chitosan/poly(vinyl alcohol)/methylcellulose chemically cross-linked ternary blends

Chitosan/poly(vinyl alcohol)/methylcellulose (CS/PVA/MC) ternary blend was prepared and chemically cross-linked with glutaraldehyde. The prepared ternary blends were characterized by Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analysis (TGA), and X-ray diffraction (XRD). The FTIR results showed that the strong intermolecular hydrogen bonds took place between CS and PVA. TGA showed the thermostability of the blend is enhanced by glutaraldehyde as crosslink agent. Results of XRD indicated that the relative crystalline of pure CS film was reduced when the polymeric network was reticulated by glutaraldehyde. Finally, the results of scanning electron microscopy (SEM) indicated that the morphology of the blend is rough and heterogenous, further it confirms the interaction between the functional groups of the blend components.     

Medicated wound dressings based on poly(vinyl alcohol)/poly(N‐vinyl pyrrolidone)/chitosan hydrogels

Poly(vinyl alcohol)/poly(N‐vinyl pyrrolidone) (PVP)/chitosan hydrogels were prepared by a low‐temperature treatment and subsequent ⁶⁰Co γ‐ray irradiation and then were medicated with ciprofloxacin lactate (an antibiotic) and chitosan oligomer (molecular weight = 3000 g/mol). The gel content, swelling ratio, tensile strength, and crystallinity of the hydrogels were determined. The effects of the chitosan molecular weight, the low‐temperature treatment procedure, and the radiation dosage on the hydrogel properties were examined. The molecular weight of chitosan was lowered by the irradiation, but its basic polysaccharide structure was not destroyed. Repeating the low‐temperature treatment and γ‐ray irradiation caused effective physical crosslinking and chemical crosslinking, respectively, and contributed to the mechanical strength of the final hydrogels. The incorporation of PVP and chitosan resulted in a significant improvement in the equilibrium swelling ratio and elongation ratio of the prepared hydrogels. The ciprofloxacin lactate and chitosan oligomer were soaked into the hydrogels. Their in vitro release behaviors were examined, and they were found to follow diffusion‐controlled kinetics. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2453–2463, 2006     

Effect of graphene loading on thermomechanical properties of poly(vinyl alcohol)/starch blend

Polymer nanocomposites based on poly(vinyl alcohol) (PVA)/starch blend and graphene were prepared by solution mixing and casting. Glycerol was used as a plasticizer and added in the starch dispersion. The uniform dispersion of graphene in water was achieved by using an Ultrasonicator Probe. The composites were characterized by FTIR, tensile properties, X‐ray diffraction (XRD), thermal analysis, and FE‐SEM studies. FTIR studies indicated probable hydrogen bonding interaction between the oxygen containing groups on graphene surface and the –OH groups in PVA and starch. Mechanical properties results showed that the optimum loading of graphene was 0.5 wt % in the blend. XRD studies indicated uniform dispersion of graphene in PVA/starch matrix upto 0.5 wt % loadings and further increase caused agglomeration. Thermal studies showed that the thermal stability of PVA increased and the crystallinity decreased in the presence of starch and graphene. FE‐SEM studies showed that incorporation of graphene increased the ductility of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41827.     

Particle configuration and properties of poly(vinyl chloride)/halloysite nanotubes nanocomposites via in situ suspension polymerization

Poly(vinyl chloride) (PVC)/halloysite nanotubes (HNTs) nanocomposites were synthesized by in situ suspension polymerization of vinyl chloride (VC) in the presence of HNTs. The microstructure, mean particle size, and cold plasticizer absorption (CPA) of these resins and the rheological property, mechanical properties and thermal properties of PVC/HNTs nanocomposites were investigated. The results show that the mean particle size, the degree of porosity, and the CPA of PVC resins decrease with the addition of HNTs. The plasticization time and the equilibrium torque of PVC/HNTs nanocomposites are found to be longer and higher than that for the neat PVC. HNTs are uniformly distributed in the PVC matrix and effective in toughening and stiffening PVC nanocomposites when the addition of HNTs is 4.0 wt% or less. The glass transition temperatures of the PVC/HNTs nanocomposites were nearly identical to that of pure PVC. POLYM. COMPOS., 35:856–863, 2014. © 2013 Society of Plastics Engineers     

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.     

Pervaporation of water-ethanol through poly(vinyl alcohol)/chitosan blend membrane

Summary Blend membrane consisting of poly(vinyl alcohol)(PVA) and chitosan was prepared from solvent casting technique for effective separation of ethanol-water mixture by pervaporation. Selectivity toward water and the flux through the blend membrane, crosslinked with glutaraldehyde at the concention of 4×10^-6 mol/g, were450 and 0.47 kg/m².hr, respectively.     

Structural interpretations on tensile fracture mechanism and elongational rheology of poly(vinylidene fluoride)/halloysite nanotubes nanocomposites

Halloysite nanotubes (HNTs)‐filled poly(vinylidene fluoride) (PVDF) nanocomposites were fabricated using continuous mixing extrusion with and without water injection. The HNTs dispersion state was qualitatively and quantitatively analyzed by using transmission electron microscopy and the Halpin‐Tsai equation, suggesting better HNTs dispersion in the nanocomposites fabricated with water injection. To grasp the relationship between the structure and properties, the effect of the HNTs dispersion on the tensile fracture mechanism and melt elongational rheology of the nanocomposites was investigated. It was deduced from morphological observations on the fractured surfaces that for the nanocomposites fabricated without and with water injection, cracks initially formed at the vicinity of HNTs aggregates and the thinner brittle fracture edge region, respectively. This was attributed to the important roles of the PVDF crystallization behavior and HNTs dispersion on the formation of the voids, wedges and ridges, which are the origins for forming cracks and easily formed at region with more HNTs aggregates or lower crystallinity. The nanocomposites fabricated with water injection exhibited lower elongational viscosities and 17–60% increments for the draw ratios at break than those fabricated without water injection, due to better HNTs dispersion induced by injected water. POLYM. ENG. SCI., 59:773–780, 2019. © 2018 Society of Plastics Engineers     

Poly(vinylidene fluoride)/halloysite nanotubes nanocomposites: The structures,properties, and tensile fracture behaviors

Poly(vinylidene fluoride)/halloysite nanotubes (HNTs) nanocomposites with good dispersion were prepared. The effect of HNTs on the crystalline structure, dynamic rheological properties, dynamic mechanical properties, and tensile properties was investigated. Results showed that at low concentration, the effect of HNTs on the modulus was minor. However, at high concentration, improvement of the modulus can be observed. The tensile fracture behaviors were investigated, which showed that the addition of HNTs changed the fracture mode. When the concentration of HNTs was 20 phr, a fracture mode change from microductility/brittle to brittle/fibrillation occurred. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

PVC/G-POSS共混物的力学性能与热性能

考察了2,3-环氧丙氧乙基笼型倍半硅氧烷(G-POSS)对聚氯乙烯(PVC)共混物力学和热性能的影响。结果表明:加入G-POSS可缩短PVC的塑化时间;100 g PVC中G-POSS用量不超过7 g时共混物的拉伸强度得到提高;加入G-POSS可改善PVC的耐热性能,G-POSS用量为13 g时,共混物的维卡软化温度和初始分解温度分别提高12,27℃。     

Rheological and mechanical properties of poly(vinyl chloride)/chlorinated poly(vinyl chloride) miscible blends

The properties of poly(vinyl chlorlde)/ehlorinated poly(vinyl chloride) (61.6 percent C1) blends, prepared by melt and solution blending, were measured by various tests. Based on the chlorinated poly(vinyl chloride) (CPVC) composition, percent chlorine, and mole percent CC1₂ groups, these blends were expected to show intermediate properties between miscible and immiscible systems. Indicative of miscible behavior were the single glass transition temperatures over the entire composition range for both melt and solution blended mixtures. A single phase was also indicated by transmission electron microscopy. However, the yield stress showed a minimum value less than either of the pure components in the 50 to 75 percent CPVC range, which is characteristic of two-phased systems. Specific volume, glass transition temperature, and heat distortion temperature were linear with binary composition. The storage modulus showed a small maximum, suggesting a weak interaction between the two miscible polymers. Heats of melting for the residual PVC crystallinity were also less than expected from linear additivity. At 160°C and 210°C, the logarithm of the complex viscosity was essentially linear with volume fraction of CPVC, except for a very slight decrease in the 50 to 75 percent CPVC range, which may have been a result of lower crystallinity. At 140°C, the complex viscosity of the CPVC was less than that of PVC owing to the higher crystallinity of the latter. The viscosities were similar at 160°C, but at 210°C, where most of the crystallites had melted, the complex viscosity of the CPVC was higher because of its higher glass transition temperature.     

Sorption characterization of poly(vinyl alcohol)/chitosan interpenetrating polymer network hydrogels

Poly(vinyl alcohol) (PVA)/chitosan interpenetrating polymer networks (IPN) were prepared by UV irradiation. The water sorption behavior of the IPNs was measured at various temperatures and humidity levels. The water uptake of IPN13 is greater than that of other IPNs. Vapor sorption behavior is more affected by the density of water vapor than by hydrophilic properties with increasing temperature. Equilibrium water uptake increases as humidity increases, and the increase is more noticeable at high humidity. The sorption system of all IPNs is a relaxation‐controlled mechanism at a relative humidity (RH) of 90%, but it is a Fickian diffusion‐controlled mechanism when the RH is below 50%. With an increase in humidity, the diffusion coefficients were found to increase due to greater penetration of water into the IPNs. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 86–90, 2003     

Electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions

Chitosan bicomponent fibers were prepared via the electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions with different concentrations. With a 4% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were lower than 80/20, electrospinning nanofibers could be obtained. With a 90% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were less than 95/5, good nanofibers could be electrospun. The average diameter of the nanofibers gradually decreased, and its distribution became narrower as the poly(vinyl alcohol) concentration increased. Chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions could be electrospun at various concentrations by the adjustment of the chitosan and poly(vinyl alcohol) concentrations. The effects of the viscosity and conductivity of the blend solution on the morphologies of the fiber mats were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5692–5697, 2006     

Miscibility of poly(vinyl alcohol)/polyacrylamide blends before and after gamma irradiation

Films of polymer blends having various contents of poly(vinyl alcohol) (PVA) and polyacrylamide (PAM) were prepared by the solution casting technique using water as a common solvent. The thermal, mechanical and morphological properties of these blends before and after exposure to various doses of gamma radiation, up to 100 kGy, have been investigated. The visual observation and reflectance measurements show that PVA/PAM blends are miscible over a wide range of composition. Moreover, the differential scanning calorimetry (DSC) thermograms show only a single glass transition temperature (T_g), but not those of PVA or PAM homopolymers, giving further support to the complete compatibility of such blends. The T_g of PVA/PAM blends decreases with increasing content of PAM but increases after exposure to gamma irradiation, indicating the occurrence of crosslinking. These findings were demonstrated by the scanning electron micrographs of the fracture surfaces and the tensile mechanical properties. The TGA thermograms and percentage mass loss at different decomposition temperatures show that unirradiated PVA homopolymer possesses higher thermal stability than PAM homopolymer and their blends within the heating temperature range investigated, up to 250 °C. An opposite trend is observed within the temperature range 300–500 °C. In general, the thermal stability of homopolymers or their blends improves slighly after exposure to an irradiation dose of 100 kGy. These findings are clearly confirmed by the calculated activation energies of the thermal decomposition reaction of the homopolymers and the blends. © 2003 Society of Chemical Industry     

Miscibility and interactions in poly(n-propyl methacrylate)/poly(vinyl alcohol) blends

Poly(n-propyl methacrylate) (PPMA) 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 PPMA and PVA was examined by Fourier transform infrared spectroscopy and solid-state nuclear magnetic resonance spectroscopy. The interactions mainly involve the hydroxyl groups of PVA and the carbonyl groups of PPMA. The measurements of proton spin-lattice relaxation time reveal that PPMA and PVA do not mix intimately on a scale of 1-3 nm, but are miscible on a scale of 20-30 nm. A small negative interaction parameter value has been obtained by melting point depression measurement.     

Miscibility in poly(vinyl chloride)/chlorinated poly(vinyl chloride) blends,and blends of different chlorinated poly(vinyl chlorides)

Blends of poly(vinyl chloride) with chlorinated poly(vinyl chloride) (PVC), and blends of different chlorinated poly(vinyl chlorides) (CPVC) provide an opportunity to examine systematically the effect that small changes in chemical structure have on polymer-polymer miscibility. Phase diagrams of PVC/CPVC blends have been determined for CPVC's containing 62 to 38 percent chlorine. The characteristics of binary blends of CPVC's of different chlorine contents have also been examined using differential calorimetry (DSC) and transmission electron microscopy. Their mutual solubility has been found to be very sensitive to their differences in mole percent CCl₂ groups and degree of chlorination. In metastable binary blends of CPVC's possessing single glass transition temperatures (T_g) the rate of phase separation, as followed by DSC, was found to be relatively slow at temperatures 45 to 65° above the T_g of the blend.     

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.     

Structure and properties of poly(vinyl alcohol)/κ‐carrageenan blends

Blends of a commercial atactic poly(vinyl alcohol) (a‐PVA) derived from vinyl acetate and κ‐carrageenan were prepared by mixing the aqueous solutions of both samples. Blend films prepared by casting were transparent. In the DSC curves of the blend films, the endothermic peaks shifted to lower temperature with an increase of the content of κ‐carrageenan. The Young's modulus and the strength at break increased with an increase of the content of a‐PVA. As the standing temperature of the blend solutions decreased, the gelation region increased also at high content of carrageenan. In the amorphous regions of blend films, a‐PVA and κ‐carrageenan were miscible. © 2001 Society of Chemical Industry