Mechanical properties of individual fiber segments of electrospun lignocellulose‐reinforced poly(vinyl alcohol)

The influence of lignocellulosic nanofibers (LCNF) additive on the inherent mechanical properties of submicron electrospun poly(vinyl alcohol) (PVA) fibers is reported. LCNF with a diameter of 25 ± 15 nm and a length of 220 ± 90 nm obtained from hemp shives were dispersed in aqueous PVA solutions to produce homogeneous nanocomposite fibers with 0, 5, and 10 w/w % LCNF loads in solid PVA. Tensile tests on mats show that LCNF additive causes up to sevenfold increase in stiffness and significant decrease in elongation at yield. AFM‐based 3‐point bending tests on single LCNF‐doped fibers reveal up to 11.4 GPa Young's modulus in the diameter range of 300 to 500 nm, indicating a 2.4 times increase compared to neat PVA fibers. Mechanical properties of both neat and LCNF‐doped PVA fibers are found to be strongly size‐dependent at lower fiber diameters, with Young's modulus values exceeding 100 GPa at below 100 nm diameters. The results can be explained by extensive restructuration of hydrogen bonding network due to the LCNF additive. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44361.     

Enhancement of the mechanical properties and thermostability of poly(vinyl alcohol) nanofibers by the incorporation of sodium chloride

The mechanical properties and thermostability of poly(vinyl alcohol) (PVA) nanofiber mats have been obviously improved by the incorporation of sodium chloride (NaCl). The tensile properties including tensile strength and modulus of membranes with an addition of 1.0 wt % NaCl increased from 2.51 to 4.22 MPa and 33.0 to 176.30 MPa, respectively, more than 160 and 700% of those of the electrospun pure PVA membranes. Moreover, thermogravimetric analysis showed that the initial decomposition temperature (T_i) and the half decomposing temperature (T_50%) of PVA nanofibers with the addition of NaCl were at least 26 and 59 °C higher than that of pure PVA nanofibers, respectively, indicating a strong interaction between the PVA and the salt ions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45981.     

Release of diclofenac through gluteraldehyde crosslinked poly(vinyl alcohol)/poly(acrylic acid) alloy membranes

A controlled‐release preparation of diclofenac sodium for transdermal administration has been developed. Poly(vinyl alcohol) (PVA) and PVA/poly(acrylic acid) (PAA) alloy membranes were prepared from a solvent‐casting technique using different PVA/PAA (v/v) ratios. The release of the drug from the membrane was evaluated under in vitro conditions at pH 7.4. The delivery system provided linear release without time lag, burst effect, and boundary layer resistance. Effects of variables such as film thickness and PVA/PAA ratio on the permeation behavior of the polymeric membranes were discussed. The optimal PVA/PAA was determined as 50/50. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 72–77, 2004     

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.     

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     

Optimizing the step‐by‐step forming processes for fabricating a poly(DL‐lactic‐co‐glycolic acid)‐sandwiched cell/hydrogel construct

A poly(DL ‐lactic‐co‐glycolic acid) (PLGA)‐sandwiched cell/fibrin construct was fabricated to overcome the weak mechanical properties of cell/hydrogel mixtures. This construct was formed with a step‐by‐step mold/extraction method to generate a middle smooth muscle layer of natural blood vessels. A desired three‐layer construct, as an integrated entity with optimized inner structures, was achieved by the control of the size of the molds, the concentration of the polymer systems, and the temperature of the extraction and polymerization processes. The constructs were fabricated with the following dimensions: length = 10–25 mm, diameter >2 mm, and wall thickness = 0.6–2 mm. Different microstructures in different layers of the sandwiched structure resulted in different functions. The pore structure in the inner PLGA and middle fibrin layers was beneficial for nutrient transference, whereas the solid structure without pores in the outmost surface of the outer PLGA layer could prevent fluid from leaking during in vitro culturing and in vivo implantation. This study showed that this can be a promising approach for the fabrication of synthetic‐polymer‐sandwiched viable cell/hydrogel constructs for wide potential application in complex organ manufacturing. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and property of poly(vinyl alcohol) grafted with butyl glycidyl ether

The crosslinked polyvinyl alcohol (CPVA) and alkyl chain grafted CPVA (CPVA‐g‐BGE) were prepared through the addition reaction of epoxy group of epichlorohydrin and butyl glycidyl ether (BGE) with the hydroxyl group of PVA. By FTIR and ¹HNMR analysis, BGE was confirmed to be grafted onto the molecular chain of PVA successfully. By grafting with BGE, the area of the stress–strain curves of CPVA increased, and the elongation at break increased remarkably with little drop of the tensile strength. Much rougher fractured surface with folds was observed, indicating the increased toughness of CPVA. The relaxation peak corresponding to the glass transition temperature (T_g) of CPVA shifted to low temperature with increasing grafting ratio of BGE. When compared with CPVA, the crystallization ability of CPVA‐g‐BGE decreased, indicating that although the intermolecular hydrogen bonding of PVA was weakened by grafting with alkyl chain, appropriate intermolecular association of alkyl chain facilitated the formation of physical entanglement of molecular chains to strengthen and toughen the PVA matrix. Ink contact angles of CPVA‐g‐BGE decreased with increasing grafting ratio of BGE, indicating the increasing compatibility of CPVA with ink, which was advantageous for PVA to be used as surface sizing agent in papermaking. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical,morphological, and thermal properties of nanotalc reinforced PA6/SEBS‐g‐MA composites

Ternary butylene‐styrene‐g‐maleic anhydride (SEBS‐g‐MA) (100/20 w/w) blend with varying content of nanotalc (1, 3, and 5 wt %) were prepared by melt compounding followed by injection molding. Thermal properties were investigated by thermogravimetric analysis (TGA) and the results show that the thermal properties of nanocomposites are slightly improved by the addition of nanotalc content. The morphology of nanocomposites using wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) revealed the delamination of talc layers in the ternary nanocomposites. The dynamic mechanical properties of the samples were analyzed by using dynamic mechanical thermal analyzer (DMTA). The results show that the storage modulus of the blend monotonically increased while tan δ curve show the diffuse pattern with the nanotalc content. The mechanical properties of PA6/SEBS‐g‐MA nanocomposites were studied by tensile, flexural, and impact tests. The tensile and flexural properties continuously increased while izod impact and elongation‐at‐break decreased with nanotalc content. Various theoretical predictive models were used to correlate tensile modulus with the experimental data. The experimental data shows the positive deviation with the applied models. Bela Pukanszky model has been used to calculate the value of parameter B by employing tensile strength data. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41381.     

Physical and antibacterial properties of polyvinyl alcohol films reinforced with quaternized cellulose

Hydroxypropyltrimethylammonium chloride cellulose (CM) was homogeneously synthesized in a NaOH/urea aqueous solution. CM was blended in a polyvinyl alcohol (PVA) matrix to produce composite films via co‐regeneration from the alkaline solution. The PVA film and the blend films were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction measurements and scanning electron microscopy. The mechanical properties, water swelling ratio, hydrophobicity, light transmission, and antibacterial activity against Staphylococcus aureus and Escherichia coli were also evaluated. The results showed that CM could interact with PVA by hydrogen bonding and exhibit an obvious reinforcement effect. The addition of CM improved the surface roughness, hydrophobicity and water swelling ratio, especially, the antibacterial activity. However, compared with neat PVA film, the elasticity and optical transmission decreased. The increased tensile strength, powerful antibacterial activity, and medium light transmission indicate that the biocompatible blend film will become an exceptional alternative in functional bio‐material field. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43552.     

High‐tensile‐strength polyvinyl alcohol films prepared from freeze/thaw cycled gels

The mechanical properties and molecular structure of a poly(vinyl alcohol) (PVA) film, which was obtained by eliminating water from a PVA hydrogel using repeated freeze/thaw cycles, were investigated by tensile tests, thermal analysis, and X‐ray diffraction measurements. The mechanical properties of PVA with 99.9% saponification were measured as a function of the number of freeze/thaw cycles performed. The tensile strength and Young's modulus increased and the elongation at break decreased with increasing freeze/thaw cycles. The tensile strength and Young's modulus of PVA films obtained after seven freeze/thaw cycles were as high as 255 MPa and 13.5 GPa after annealing at 130°C. Thermal analysis and X‐ray diffraction measurements revealed that this is because of a high crystallinity and a large crystallite size. A good relationship between the tensile strength and the glass transition temperature was obtained, regardless of the degree of saponification and annealing conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40578.     

In vitro silver ion release kinetics from nanosilver/poly(vinyl alcohol) hydrogels synthesized by gamma irradiation

A nanosilver (nano‐Ag)/poly(vinyl alcohol) (PVA) hydrogel device was synthesized with γ irradiation because it is a highly suitable tool for enhanced nano‐Ag technologies and biocompatible controlled release formulations. The amount of the Ag⁺ ions released in vitro by the nano‐Ag/PVA hydrogel device was in the antimicrobial parts per million concentration range. The modeling of the Ag⁺ ion release kinetics with the elements of the drug‐delivery paradigm revealed the best fit solution (R² > 0.99) for the Kopcha and Makoid–Banakar's pharmacokinetic dissolution models. The term A/B, derived from the Kopcha model, indicated that the nano‐Ag/PVA hydrogel was mainly an Ag⁺‐ion diffusion‐controlled device. Makoid–Banakar's parameter and the short time approximated Ag⁺‐ion diffusion constant reflected the importance of the size of the Ag nanoparticles. However, it appeared that the cell oxidation potential of the Ag nanoparticles depended on the diffusion characteristics of the fluid penetrating into the Ag/PVA nanosystem. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40321.     

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.     

The optical properties of PVA/TiO2 composite nanofibers

The electrospun nanofibers emerge several advantages because of extremely high specific surface area and small pore size. This work studies the effect of PVA nanofibers diameter and nano‐sized TiO₂ on optical properties as reflectivity of light and color of a nanostructure assembly consisting polyvinyl alcohol and titanium dioxide (PVA/TiO₂) composite nanofibers prepared by electrospinning technique. The PVA/TiO₂ composite spinning solution was prepared through incorporation of TiO₂ nanoparticles as inorganic optical filler in polyvinyl alcohol (PVA) solution as an organic substrate using the ultrasonication method. The morphological and optical properties of collected composites nanofibers were highlighted using scanning electron microscopy (SEM) and reflective spectrophotometer (RS). The reflectance spectra indicated the less reflectance and lightness of composite with higher nanofiber diameter. Also, the reflectance and lightness of nanofibers decreased with increasing nano‐TiO₂ concentration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of a new type poly(vinyl alcohol)/peat/bamboo charcoal/KNO3 composite bead used as biofilter material

A new type poly(vinyl alcohol) (PVA)/peat/bamboo charcoal (BC)/KNO₃ composite bead was prepared, which has a diameter of 2.4–6.0 mm and a density of 1.133 g/cm³ and is a porous spherical particle. The biochemical kinetic behaviors of n‐butyl acetate in PVA/peat/BC/KNO₃ spherical composite bead biofilter (BC biofilter) and PVA/peat/granular activated carbon (GAC)/KNO₃ spherical composite bead biofilter (GAC biofilter) were investigated. The values of half‐saturation constant K_s for BC biofilter and GAC biofilter were 27.89 and 27.95 ppm, respectively. The values of maximum reaction rate V_m for BC biofilter and GAC biofilter were 13.49 and 13.65 ppm/s, respectively. Zero‐order kinetic with the diffusion limitation was regarded as the most adequate biochemical reaction model for the two biofilters. The microbial growth rate and biochemical reaction rate for two biofilters were inhibited at higher inlet concentration, and the degree of inhibitive effect was more pronounced in the inlet concentration range of 100–800 ppm. The biochemical kinetic behaviors of the two biofilters were similar. The maximum elimination capacity of BC biofilter and GAC biofilter were 111.65 and 122.67 g C/h m³ bed volume, respectively. The PVA/peat/BC/KNO₃ composite bead was suitable as a biofilter material. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of structural,thermal, and electrical properties of PVA by addition of silicon carbide nanocrystals

SiC‐PVA nanocomposite films, synthesized using solution‐casting technique were structurally characterized using X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. Morphological studies of the SiC‐PVA nanocomposite films were carried out using Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM). TEM analysis confirms that the size of SiC nanocrystals present in PVA matrix are 23 ± 9 nm, which is consistent with size calculated using XRD. SiC‐PVA nanocomposite films were further characterized for their thermal and electrical properties. Thermogravimetric/differential thermal analysis (TG/DTA) indicates that the char yield of nanocomposite films containing 3 wt % SiC nanocrystal is ～30% more than PVA. This increase in char yield is an indication of the potency of flame retardation of SiC‐PVA nanocomposite films. I‐V analysis reveals that Schottky mechanism is the dominant conduction mechanism which is responsible for the increase in conductivity of PVA with the addition of SiC nanocrystals. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42464.     

Poly(vinyl alcohol)–lignin blended resin for cellulose‐based composites

Wood has limitations in strength because of its biostructural defects, including vessels. To overcome this limitation, composite materials can be innovated by breaking wood down into cellulose and lignin and reassembling them for bio‐originating strong structural materials. In this study, an ecofriendly resin was developed that was suitable for cellulose‐based composites. To overcome the low dimensional stability of lignin and to increase its interactions with cellulose, it was blended with poly(vinyl alcohol) (PVA). The PVA–lignin resin was characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, thermal analysis, mechanical tensile testing, and lap‐shear joint testing. The adhesion properties of the PVA–lignin resin increased with increasing PVA content. PVA played the role of synthetic polymer and that of linker between the cellulose and lignin, like hemicellulose does in wood. The PVA–lignin resin exhibited a high miscibility, mechanical toughness, and good adhesion properties for nanocellulose composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46655.     

Properties of soy protein isolate/poly(vinyl alcohol) blend “green” films: Compatibility,mechanical properties,and thermal stability

Blend films from nature soy protein isolates (SPI) and synthetical poly(vinyl alcohol) (PVA) compatibilized by glycerol were successfully fabricated by a solution‐casting method in this study. Properties of compatibility, mechanical properties, and thermal stability of SPI/PVA films were investigated based on the effect of the PVA concentration. XRD tests confirm that the SPI/PVA films were partially crystalline materials with peaks of 2θ = 20°. And, the addition of glycerol will insert the crystalline structure and destroy the blend microstructure of SPI/PVA. Differential scanning calorimetry (DSC) tests show that SPI/PVA blend polymers have a single glass transition temperature (T_g) between 80 and 115.0°C, which indicate that SPI and PVA have good compatibility. The tension tests show that SPI/PVA films exhibit both higher tensile strength (σ_b) and percentage elongation at break point (P.E.B.). Thermogravimetric analysis (TGA) and water solubility tests show that SPI/PVA blend polymer has more stable stability than pure SPI. All the results reflect that SPI/PVA/glycerol blend film provides a convenient and promising way to prepare soy protein plastics for practical application. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Bio‐nanocomposite films based on cellulose nanocrystals filled polyvinyl alcohol/chitosan polymer blend

Bio‐nanocomposite films based on polyvinyl alcohol/chitosan (PVA/CS) polymeric blend and cellulose nanocrystals (CNC) were prepared by casting a homogenous and stable aqueous mixture of the three components. CNC used as nanoreinforcing agents were extracted at the nanometric scale from sugarcane bagasse via sulfuric acid hydrolysis; then they were characterized and successfully dispersed into a PVA/CS (50/50, w/w) blend to produce PVA/CS–CNC bio‐nanocomposite films at different CNC contents (0.5, 2.5, 5 wt %). Viscosity measurement of the film‐forming solutions and structural and morphological characterizations of the solid films showed that the CNC are well dispersed into PVA/CS blend forming strong interfacial interactions that provide an enhanced load transfer between polymer chains and CNC, thus improving their properties. The obtained bio‐nanocomposite films are mechanically strong and exhibit improved thermal properties. The addition of 5 wt % CNC within a PVA/CS blend increased the Young's modulus by 105%, the tensile strength by 77%, and the toughness by 68%. Herein, the utilization of Moroccan sugarcane bagasse as raw material to produce high quality CNC has been explored. Additionally, the ability of the as‐isolated CNC to reinforce polymer blends was studied, resulting in the production of the aforementioned bio‐nanocomposite films with improved properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42004.     

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     

Synthesis and processability into textile structures of radiopaque,biodegradable polyesters and poly(ester‐urethanes)

Radiopaque biodegradable polymers have been synthesized by ring‐opening polymerization of l /dl ‐lactide and caprolactone with the iodine‐containing starter molecule 2,2‐bis(hydroxymethyl)propane‐1,3‐diyl bis(2,3,5‐triiodobenzoate) followed by chain elongation with a diacid chloride or diisocyanates. The resulting polyesters and poly(ester‐urethanes) exhibited a radiopacity of 60?124% relative to an aluminium sample of the same thickness. The polymers were processed into monofilament fibres by melt‐spinning and into fibre meshes by electrospinning. All polymers were biodegradable in simulated body fluid medium under in vitro conditions and showed an excellent in vitro cytocompatibility even after several months of hydrolytic degradation. A current drawback is the relatively low tensile strength of the polymer monofilaments, which needs to be improved for applications as textile structures. Nevertheless, the new radiopaque and biodegradable polymers are promising candidates in fields of application where radiopacity of implants is an important parameter.