Starch crosslinked with poly(vinyl alcohol) by boric acid

Starch was crosslinked with poly(vinyl alcohol) (PVA) by boric acid. A suitable plasticizer and defoamer were added to obtain the brei. A film from the starch and PVA (SP film) was prepared by casting. The effects of various factors, such as the crosslinking temperature, the PVA content, and the amounts of glycerol and boric acid, on the tensile strength and breaking elongation were studied. The results showed that the SP film prepared by boric acid crosslinking had excellent mechanical properties. The film‐forming properties, transmittance, and water resistance of the SP film were also investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1394–1397, 2005     

Thermal,mechanical, and surface characterization of starch–poly(vinyl alcohol) blends and borax‐crosslinked films

Starch–poly(vinyl alcohol) (PVA) blends with different compositions were prepared and crosslinked with borax by in situ and posttreatment methods. Various amounts of glycerol and poly(ethylene glycol) with a molecular weight of 400 were added to the formulations as plasticizers. The pure starch–PVA blends and the crosslinked blends were subjected to differential scanning calorimetry, thermogravimetry, and X‐ray photoelectron spectroscopic studies. Broido and Coats–Redfern equations were used to calculate the thermal decomposition kinetic parameters. The tensile strengths and elongation percentages of the films were also evaluated. The results suggested that the glass‐transition temperature (T_g) and the melting temperature strongly depended on the plasticizer concentration. The enthalpy relaxation phenomenon was dependent on the starch content in the pure blend. The crosslinked films showed higher stability and lower T_g's than pure PVA and starch–PVA blends, respectively. High‐resolution X‐ray photoelectron spectroscopy provided a method of differentiating the presence of various carbons associated with different environments in the films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1313–1322, 2005     

Poly(ether imide)s containing cyano substituents and thin films made from them

A series of poly(ether imide)s containing functional cyano groups has been prepared by polycondensation reaction of 2,6‐bis(m‐aminophenoxy)benzonitrile with different bis(ether dianhydride)s, such as 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]isopropane dianhydride, 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)‐phenyl]hexafluoroisopropane dianhydride, 1,1‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]cyclohexane dianhydride, and 3,3‐bis[4‐(3,4‐dicarboxyphenoxy) phenyl]phthalide dianhydride. The polymers were soluble in polar aprotic solvents and even in less polar solvents and were processed into thin films by casting their solutions. The properties of the polymers, particularly the crosslinking of macromolecular chains through cyano groups, were studied by using dynamic mechanical analysis (DMA), thermal stability, glass transition, and solubility measurements. Also, the molecular relaxations were evidenced by DMA and dielectric spectroscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High strength poly(vinyl alcohol) films obtained by drying and then stretching freeze/thaw cycled gel

The mechanical properties of stretched poly(vinyl alcohol) (PVA), which is formed by stretching a film prepared from a freeze/thaw cycled gel, were investigated as a function of the stretching ratio. The tensile strength and Young's modulus of 800% stretched PVA annealed at 130°C were 3.4 and 119 GPa, respectively. These values were much higher than those for a PVA film prepared without freeze/thaw cycling. For a film stretched more than 600% before annealing, two melting peaks, assignable to folded and extended chain crystals, were observed around 220°C and 230°C, respectively. This indicates that a shish‐kebab structure is formed as the stretching ratio increases. After annealing at 130°C, the folded‐chain crystal transformed to an extended‐chain crystal if an extended‐chain crystal was present in the stretched film before annealing. High tensile strength and Young's modulus after annealing were due to the formation of extended‐chain crystal. Therefore, the presence of extended‐chain crystal for annealing is important to provide good mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41318.     

Preparation of resistant starch/poly(vinyl alcohol) blend films with added plasticizer and crosslinking agents

We report on the physical properties of films synthesized with native corn starch (NCS) and resistant starch (RS4) prepared with NCS. NCS and RS4/poly(vinyl alcohol) (PVA) blend films were synthesized with a mixing process and casting method. Glycerol (GL) and citric acid (CA) were used as additives. Glutaraldehyde (GLU) was used as a crosslinking agent of the films. RS4 was synthesized with sodium trimetaphosphate and sodium tripolyphosphate as a crosslinker. Then, the RS4 thus synthesized was confirmed by the pancreatin–gravimetry method, swelling power, differential scanning calorimetry, and X‐ray diffraction. The tensile strength, elongation, swelling behavior, and solubility of the films were measured. The results of the measurements indicated that the RS4‐added film was better than the NCS‐added film. In particular, the RS4/PVA blend film with CA as an additive showed physical properties superior to those of the other films. Also, the physical properties with GLU added as a crosslinking agent to the films were investigated. With increasing GLU contents, the tensile strength increased but the elongation, swelling behavior, and solubility values of the GL‐added and CA‐added films decreased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Easy preparation of crosslinked polymer films from polyoxyalkylene diamine and poly(styrene–maleic anhydride) for electrostatic dissipation

The curing reaction of polyoxyalkylene diamine and poly(styrene–maleic anhydride) was able to produce polymer films that were hygroscopic in nature. The process involved the formation of an imine intermediate by dissolving the diamine monomers in a ketone solvent, followed by instant casting into films before the solution self‐cured into a gel product. Hydrophilic films were formed by the fast reaction of amine with anhydride while evaporating the solvent under vacuum. The resulting films exhibited dissipation of electrostatic charges over a wide range, from 10^9.4 to 10^4.1 Ω/sq surface resistivity. The low resistivity was attributed to the functionality of hydrophilic polyoxyethylene (POE), which was able to adsorb moisture and optionally to the added metal ion salts. Furthermore, the slightly crosslinked network prevented POE from having crystallinity and rendered the films solvent resistant, thermally stable, and suitable for applications as antistatic and polymeric electrolytes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 716–723, 2007     

Poly(vinyl alcohol)‐controlled synthesis of monodispersed crosslinked poly(methyl methacrylate) microparticles with significantly improved mechanical properties

A facile synthesis concept focusing on the poly(vinyl alcohol) (PVA) concentration induced interfacial energy effects in seed swelling polymerization was realized for the successful fabrication of a series of monodispersed poly(methyl methacrylate) (PMMA) microparticles with four crosslinking agents, 2,2‐bis[(methacryloyloxy)methyl]butyl methacrylate, 1,2‐ethanediyl bis(2‐methylacrylate), 1,3‐divinylbenzene and 1,2‐ethanediyl diacetate. We revealed a special role of PVA in regulating the diffusion of crosslinking agents as well as the swelling degree of latex seeds and, more noticeably, the consequent improved mechanical properties of the crosslinked PMMA microparticles formed. The highest recovery rate obtained from the PMMA microparticles with 0.6 wt% PVA approached 67%, which is higher than or comparable to reported values. This work not only developed a new facile synthesis approach for producing highly uniform tough crosslinked PMMA microparticles for more potential applications but also provided valuable insights into fundamental aspects of seed swelling polymerization. © 2019 Society of Chemical Industry     

Effect of nano‐silica on the mechanical,thermal, and crystalline properties of poly(vinyl alcohol)/nano‐silica films

Poly(vinyl alcohol)/nano‐silica (PVA/nano‐SiO₂) films were prepared through extrusion blowing with the addition of water and glycerin as plasticizer. The characteristic properties of PVA/nano‐SiO₂ films were investigated by differential scanning calorimetry, dynamic mechanical analysis, Haake torque rheometry, and atomic force microscopy (AFM). The results showed that the mechanical properties of PVA/nano‐SiO₂ were improved dramatically. The tensile strength of the nanofilms increased from 62 MPa to 104 MPa with loading 0.3 wt % nano‐SiO₂ and the tear strength was improved from 222 KN/m to 580 KN/m. The crystallinity of the films loaded with 0.4 wt. % nano‐SiO₂ decreased from 32.2% to 21.0% and the AFM images indicated that the amorphous region of nanofilms increased with increasing nano‐SiO₂ content. The storage modulus and loss modulus increased to two and nearly three times with 0.3 wt % nano‐SiO₂ loading. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

On the viscoelastic properties of poly(vinyl alcohol) and chemically crosslinked poly(vinyl alcohol)

Poly(vinyl alcohol)(PVA) films chemically crosslinked with glutaraldehyde(GA) in the presence of HCl were prepared by casting from aqueous solutions. The PVA and PVA gels were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical analysis (DMA); their swelling characteristics and tensile strength were also determined. The DSC results for the gels displayed depressions of the melting and crystallization temperatures, as well as a decrease of the heat of fusion, when compared to those of PVA free of crosslinker. The DMA analysis revealed that: (1) The glass transition temperature of the wet PVA was lower than that of the dry one, indicating that the water had a plasticizing effect. (2) The gels had a lower glass transition temperature than PVA. (3) The glass transition temperature of the wet gels increased with increasing crosslink density. Possible explanations are provided for these observations. Whereas the thermogravimetric curves of PVA exhibited a single degradation peak, two degradation peaks were detected for the crosslinked PVA. The wet PVA and PVA gels displayed lower tensile strengths and higher elongations than the dried ones. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1816–1823, 2001     

Mechanism of paper wet strength development by polycarboxylic acids with different molecular weight and glutaraldehyde/poly(vinyl alcohol)

In our previous research, we found that crosslinking paper using poly(carboxylic acid)s with different molecular weight or using the combination of glutaraldehyde and poly(vinyl alcohol) (PVA) significantly improved the wet strength of the paper. In this research, we studied the mechanism of paper wet strength development using crosslinking systems with different molecular weight by measuring scanning electron microscopic (SEM) images, wet strength, folding endurance, wet thickness, water retention, and Z‐direction tensile strength of the treated paper. The paper crosslinked by a high‐molecular weight (MW) poly(carboxylic acid) shows more swelling by water than that crosslinked by a low‐MW polycarboxylic acid in the SEM micrographs even though both treated paper samples have similar wet strength. Thus, the data suggest that high‐MW poly(carboxylic acid)s promote the formation of interfiber crosslinking. Crosslinking paper by glutaraldehyde, a crosslinking agent of small molecular size, improves wet strength and reduces flexibility and swellability of paper because of the formation of intrafiber crosslinking. Combining glutaraldehyde with PVA as a coreactant increases wet strength and also retains flexibility and swellability of the treated paper because of the formation of interfiber crosslinking. The hypothesis that PVA reacts with glutaraldehyde to form a polymeric pentanedialated‐PVA crosslinking system and promotes the formation of interfiber crosslinking on the paper is supported by the data of wet strength, folding endurance, wet thickness, water retention, and Z‐direction tensile strength of the treated paper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 277–284, 2006     

Synthetic absorbent for dyestuffs based on gamma crosslinked poly(vinyl alcohol) (PVA)

This work reports on the characterization and uses of gamma radiation‐crosslinked poly(vinyl alcohol) (PVA) films as absorbents for different classes of dyestuffs normally released from textile factors. Dyestuffs were selected from different producers. These dyestuffs were Remacryl Blue (basic dye), Remazol Golden Orange (reactive dye), Solar Orange (direct dye), and Sandolan (acid dye). The percentage dye sorption by PVA was determined by spectroscopic analysis and color‐strength measurements of the PVA films after absorbing the different dyestuffs. The results showed that the concentration of dimethylbisacrylamide as a crosslinking agent has a great effect on the gel fraction and percentage swelling in water of the PVA polymer. In general, crosslinked PVA showed a low tendency to absorb the different dyestuffs under investigation at room temperature. This tendency was shown to increase with an increasing temperature of the dye solution from room temperature to 70°C. Meanwhile, the highest percentage of dye sorption was found in the case of the basic dye and the lowest one in the case of the reactive dye depending on the active groups on the dyes. Moreover, the percentage dye sorption by PVA was slightly higher in the acid medium rather than in the alkaline one. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 349–354, 2003     

Preparation and characterization of poly(vinyl alcohol) and 1,2,3‐propanetriol diglycidyl ether incorporated soy protein isolate‐based films

Novel biodegradable films were prepared from soy protein isolate (SPI), poly(vinyl alcohol) (PVA), glycerol, and 1,2,3‐propanetriol diglycidyl ether (PTGE). The mechanical, hydrophilic, and compatible properties of the films were investigated. The influence of PTGE as a crosslinker on the properties of the SPI/PVA/PTGE films was examined with Fourier transform infrared spectroscopy, X‐ray diffraction (XRD), thermogravimetric analysis, mechanical analysis, contact angle measurements, and scanning electron microscopy. XRD and contact angle examination confirmed that the addition of PTGE altered the film microstructure to a crystalline one. The mechanical properties and water resistance of the SPI/PVA/PTGE films increased notably compared with those of the unmodified SPI films. All results indicate that the networks were formed between SPI and PTGE and played an important role in forming a homogeneous structure in the obtained films. The novel biodegradable films provide a convenient and promising way for preparing environmentally friendly film materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42578.     

Effect of copper sulfate pentahydrate on the structure and properties of poly(vinyl alcohol)/graphene oxide composite films

Poly(vinyl alcohol) (PVA)/graphene oxide (GO)/copper sulfate pentahydrate (CuSO₄·5H₂O) composite films were prepared by the solution casting method, and the effect of CuSO₄·5H₂O on the structure and properties of the PVA/GO composites was investigated. Fourier transform infrared (FTIR) analysis proved the crosslinking interaction between CuSO₄·5H₂O and the ? OH group of PVA. The crystallinity of the composite films increased first and then decreased. For the composite films, the tensile strength, Young's modulus, and yield stress values improved with increasing CuSO₄·5H₂O, whereas the elongation at break decreased compared with that of the neat PVA/GO composite film. The thermogravimetric analysis (TGA) and derivative thermogravimetry (DTG) patterns of the PVA/GO/CuSO₄·5H₂O composite films showed that the thermal stability decreased; this was consistent with the TGA–FTIR analysis. A remarkable improvement in the oxygen‐barrier properties was achieved. The oxygen permeability coefficient was reduced by 60% compared to that of the neat PVA/GO composite film. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44135.     

Thin polymer films based on poly(vinyl alcohol) containing graphene oxide and reduced graphene oxide with functional properties

In this article, the effect of the addition of graphene oxide (GO) and reduced graphene oxide (rGO) on the mechanical properties, thermal stability, and electrical conductivity of polyvinyl alcohol (PVA) has been investigated. Different weight percentages of nanofillers ranging from 0.5 to 5 wt% have been combined with PVA. The ultrasonic technique has been applied to disperse nanofillers in the PVA solution. The nanocomposite films have been prepared via solution casting technique and the dispersion of nanofillers into the PVA has been studied through optical microscopy. The microstructure, crystallization behavior, and interfacial interaction were characterized through X-ray diffraction and Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis have been applied to study the thermal properties of the prepared nanocomposites. The DSC results revealed that the crystallization temperature and melting temperature were enhanced in the presence of GO nanofiller. Besides, the tensile strength at break was improved along with the addition of GO; however, elongation at break for PVA/GO and PVA/rGO was diminished. Moreover, all specimens showed insulating behavior and the only sample was electrically conducting, which contain a high amount of rGO (5 wt%).     

Influence of crosslinking methods toward poly(vinyl alcohol) properties: Microwave irradiation and conventional heating

In this study, crosslinking of poly(vinyl alcohol) (PVA) with tartaric acid, as crosslinker, is performed using microwave irradiation. A comparison between the properties of PVA crosslinked using microwave irradiation and conventional heating methods is also discussed. While the water absorption, tensile and thermal properties of PVA crosslinked by either of the methods are comparable, microwave irradiation took only one‐eighth (14 min) of the time compared to conventional heating. In comparison with PVA (42 MPa), the strength of PVA crosslinked with 35% TA increased to 145 and 153 MPa for conventional heating and microwave irradiation, respectively. Water absorption of crosslinked PVA film is successively reduced to less than 30% in comparison with PVA (～200%). Moreover, the crosslinked films are stable at higher temperatures in comparison with PVA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46125.     

Effect of postcrosslinking modification with glutaraldehyde on the properties of thermoplastic starch/poly(vinyl alcohol) blend films

Thermoplastic starch (TPS)/poly(vinyl alcohol) (PVA) blend films were modified by crosslinking through soaking the films in glutaraldehyde aqueous solution and then heating in an oven. The effects of the concentration of the glutaraldehyde aqueous solution, soaking time, reaction temperature, and time on the crosslinking reaction were investigated. The moisture absorption and mechanical properties of the films were measured to characterize the influence of the crosslinking modification. It was found that the crosslinking modification significantly reduced the moisture sensitivity of the TPS/PVA blend films and increased the tensile strength and Young's modulus but decreased the elongation at break of the TPS/PVA blend films. The described method could be used for posttreating TPS/PVA‐based products to optimize their properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Properties of chitosan/poly(vinyl alcohol) films for drug‐controlled release

With bovine serum albumin (BSA) as a model drug, drug‐loaded films of chitosan (CS) and poly(vinyl alcohol) (PVA) were obtained by a casting/solvent evaporation method and crosslinked by tripolyphosphate (TPP). The films were characterized by FTIR, XRD, and SEM. The influential factors of drug‐loaded films on drug‐controlled release were studied. These factors included, primarily, the component ratio of CS and PVA, the loaded amount of BSA, the pH and ionic strength of the release solution, and the crosslinking time with TPP. The results showed that within 25 h, when the weight ratios of CS to PVA in the drug‐loaded films were 90 : 10, 70 : 30, 50 : 50, and 30 : 50, the cumulative release rates of BSA were 63.3, 72.9, 81.8, and 91.8%, respectively; when the amounts of model drug were 0.1, 0.2, and 0.3 g, the release rates were 100, 81.8, and 59.6%, respectively; when the pH values of the drug release medium were 1.0, 3.8, 5.4, and 7.4, the release rates reached 100, 100, 37.9, and 7.8%, respectively; the cumulative release rates of BSA were 78.4, 82.3, 84.3, and 91.7% when the ionic strengths of the release solution were, respectively, 0.1, 0.2, 0.3, and 0.4M; when the crosslinking times of these drug films in the TPP solution were 0, 5, 15, 30, and 60 min, the release rates attained 100, 100, 81.8, 65, and 43.3%, respectively. All the results indicated that the CS/PVA film was useful in drug delivery systems. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 808–813, 2005     

Preparation and characterization of poly(vinyl alcohol) and gelatin blend films

Poly(vinyl alcohol) (PVA) is a water-soluble polymer that has been studied intensively because of several interesting physical properties that are useful in technical applications, including biochemical and medical applications. In this article, we report the effects of the addition of gelatin on the optical, microstructural, thermal, and electrical properties of PVA. Pure and PVA/gelatin blend films were prepared with the solution-casting method. These films were further investigated with Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), ultraviolet–visible (UV–vis) spectroscopy, and dielectric measurements. The FTIR spectrum shows a strong chemical interaction between PVA and gelatin molecules with the formation of new peaks. These peaks are due to the presence of gelatin in the blend films. The DSC results indicate that the addition of gelatin to PVA changes the thermal behavior, such as the melting temperature of PVA, and this shows that the blends are compatible with each other. This also shows that the interaction of gelatin and PVA molecules changes the crystallite parameters and the degree of crystallinity, and this supports the XRD results. The UV–vis optical study also reflects the formation of the complex and its effect on the microstructure of the blend film. Moreover, the addition of gelatin also gives rise to changes in the electrical properties of PVA/gelatin blend films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Macroporous poly(vinyl alcohol) foam crosslinked with epichlorohydrin for microorganism immobilization

Macroporous poly(vinyl alcohol) foam with epichlorohydrin as a crosslinking agent was investigated. The average molecular weight between crosslinks, crosslinking density, and mesh size were determined through the equilibrium swelling theory. The characterization of foams with different crosslinking ratios was also investigated through the testing of the thermal properties, specific surface areas, and diffusion coefficients. The biomass densities and activity yields were measured by detection of the protein concentration and oxygen uptake rate. Thermogravimetry and differential scanning calorimetry tests showed an increase in the thermal stability and a decrease in the polymeric crystallinity with increasing crosslinking ratio. The biomass densities increased with increasing crosslinking ratio, with the highest value shown at 0.0638 ± 0.0093 g of volatile suspended solid (VSS)/g of carrier. However, the activity yields decreased with increasing crosslinking ratio, with the highest value at 69.38%. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(vinyl alcohol) nanocomposite films: Thermooptical properties,morphology, and gas permeability

Poly(vinyl alcohol) (PVA)/saponite nanocomposites were prepared with various clay concentrations with the solution intercalation method. The intercalations of the polymer chains in the clay were examined with wide‐angle X‐ray diffraction and transmission electron microscopy. The variations of the dispersion, morphology, thermal properties, and gas permeability of the nanocomposites with clay concentrations in the range of 0–10 wt % were examined. Up to a 5 wt % clay loading, the clay particles were highly dispersed in the PVA matrix without any agglomeration of particles. However, some agglomerated structures formed in the polymer matrix above a 7 wt % clay concentration. The thermal stability of the hybrids increased linearly with increases in the clay loading up to 10 wt %. To measure the oxygen permeability and optical properties of the PVA hybrid films, the PVA hybrid solutions were coated onto both biaxially oriented polypropylene and poly(ethylene terephthalate) films, which were used as polymer substrates. The oxygen permeability values monotonically decreased with increases in the clay loading in the range of 0–10 wt %. The optical properties, such as the haze and gloss of the hybrid films when coated onto the matrix films, were nearly constant, that is, independent of the clay loading. These improvements arose because of the largely nanometer‐scale dispersion of the clay layers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 591–596, 2006