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.     

Heat‐sealing properties of soy protein isolate/poly(vinyl alcohol) blend films: Effect of the heat‐sealing temperature

To promote the heat‐sealing properties of soy protein isolate (SPI) films applied in the packaging field, we mixed a synthetic polymer of poly(vinyl alcohol) (PVA) with SPI to fabricate blend films by a solution‐casting method in this study. To clarify the relationship between the heat‐sealing properties and the heat‐sealing temperature, strength, melting process, crystalline structure, and microstructure, variations of the heat‐sealing parts of the films were evaluated by means of differential scanning calorimetry, tensile testing, scanning electron microscopy, X‐ray diffraction, and Fourier transform infrared spectroscopy, respectively. The test results showed that both the PVA and glycerol contents greatly affected the melting behavior and heat of fusion of the SPI/PVA blends; these blend films had a higher melting temperature than the pure SPI films. The peel strength and tensile strength tests indicated that the long molecular chain of PVA had a main function of enhancing the mechanical properties above the melting temperature. With increasing heat‐sealing temperature, all of the mechanical properties were affected by the microstructure of the interface between the laminated films including the chain entanglement, crystallization, and recrystallization. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of starch‐based plastic films by electron beam irradiation

Starch‐based plastic films were prepared by the electron beam irradiation of starch and poly(vinyl alcohol) (PVA) in a physical gel state at room temperature. The influence of starch/PVA composition, irradiation dose, and plasticizer (glycerol) on the properties of the plastic films was investigated. The gel fraction of the starch/PVA films increased with both the radiation dose and PVA content in the plastic film and decreased with increasing glycerol concentration. The starch/PVA compatibility was determined by measurement of the thermal properties of the starch/PVA blends with various compositions with differential scanning calorimetry. The swelling of the starch/PVA films increased with increasing PVA content and decreasing irradiation dose. Mechanical studies were carried out, and the tensile strength of the films decreased at high starch ratios in the starch‐based mixture. This was due to the decrease in the degree of crosslinking of starch. Furthermore, when PVA, a biodegradable and flexible‐chain polymer, was incorporated into the starch‐based films, the properties of the films, such as the flexibility (elongation at break), were obviously improved. The tensile strength of the films decreased with increasing glycerol concentration, but elongation at break increased up to a maximum value at a 20% glycerol concentration, and then, it leveled off and decreased slightly. Biodegradation of the starch/PVA plastic films was indicated by weight loss (%) after burial in soil and morphological shape, which was detected by scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 504–513, 2007     

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.     

Poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride)/silica nanocomposites derived from in situ suspension polymerization

Poly(vinyl chloride‐co‐vinyl acetate‐co‐maleic anhydride) (PVVM)/silica nanocomposites were prepared by the suspension radical copolymerization of the monomers in the presence of fumed silica premodified with γ‐methylacryloxypropl trimethoxy siliane. Morphological observation showed that the silica particles of nanometer scale were well dispersed in the copolymer matrix of the nanocomposites films, whereas silica particles tended to agglomerate in the composites films prepared by the solution blending of PVVM with silica. The experimental results show that the thermal stability, glass‐transition temperature, tensile strength, and Young's modulus were significantly enhanced by the incorporation of silica nanoparticles. The enhancement of properties was related to the better dispersion of silica particles in polymer matrix and the interaction between the polymer chains and the surfaces of the silica particles. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology and mechanical properties of pullulan/poly(vinyl alcohol) blends crosslinked with glyoxal

We prepared pullulan/poly(vinyl alcohol) (PVA) blend films by casting the polymer solution in dimethyl sulfoxide. Their morphology and mechanical properties were investigated. Scanning electron micrographs revealed that the pullulan was immiscible with PVA over the entire composition range. The tensile strength and modulus of the blend films were lower than those predicted by the upper bound composite equation. To improve the mechanical properties, we investigated the reaction of the 40/60 blend with glyoxal. The infrared spectral change and the increase in the glass‐transition temperature (corresponding to the PVA component) accompanying the reaction indicated that crosslinking with glyoxal had proceeded. The crosslinked films were homogeneous and had higher tensile strengths and moduli than the simple blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2273–2280, 2001     

Poly(vinyl alcohol)‐g‐lactic acid copolymers and films with silver nanoparticles

Poly(vinyl alcohol) (PVA), a well‐known synthetic biodegradable, biocompatible, and hydrophilic polymer is susceptible to several structural modifications, due to the presence of hydroxyl groups in its backbone. PVA was grafted with L (+)‐lactic acid (LA) in molar ratios VA/LA (1/1, 1.5/1, and 2.2/1), manganese acetate as catalyst, by solution polycondensation procedure, resulting the poly(vinyl alcohol)‐g‐lactic acid copolymers. Aqueous solutions of copolymers with glycerol as plasticizer, silver nanoparticles (Ag^o), and sodium tetraborate as crosslinking agent were used for films casting. The copolymers were characterized by FTIR and ¹H RMN spectroscopy, gel permeation chromatography, thermal analyses (DTG and DSC), silver particles size, while films were characterized by mechanical properties and mechanodynamic analyses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Glycerol‐plasticized spirulina–poly(vinyl alcohol) films with improved mechanical performance

Spirulina–poly(vinyl alcohol) (PVA)–glycerol (SPG) films with improved mechanical performance, especially tensile strength (TS) and the elongation at break (EAB), are fabricated by a casting method. The integrity, color, solubility, microstructure, thermal properties, tensile strength, and compatibility of the SPG films are assessed. SPG films became smooth, homogeneous, and flexible after plasticizing with glycerol. The presence of PVA and hydrogen bonding of PVA with glycerol and spirulina protein improves the water resistance of SPG films by decreasing water absorption of spirulina protein and decreasing water diffusion through the films. The amount of carbonaceous residues decreases from 31% to 14% because of the co‐pyrolysis of spirulina, PVA, and glycerol. TS increases from 2.5 to 26 Mpa and modulus from 53 to 610 Mpa with increasing PVA content. Glycerol enhances film flexibility and EAB up to 50%. Spirulina can be composited with hydrophilic polymers to fabricate compatible, processable and thermally recyclable films with desirable mechanical performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44842.     

Preparation and characterization of a novel gelatin–poly(vinyl alcohol) hydrogel film loaded with Zataria multiflora essential oil for antibacterial–antioxidant wound‐dressing applications

This study was performed to evaluate the properties of poly(vinyl alcohol) (PVA), gelatin, and PVA–gelatin dispersions and films enriched with Zataria multiflora essential oil (ZO). The results reveal that the ζ potential, particle size, and viscosity values and the antioxidant and antibacterial activities of the dispersions changed significantly with the addition of ZO to the polymer matrix. Changes in the properties of the dispersions suggested the presence of interactions between PVA or gelatin and ZO. Such interactions could affect the mechanical and water‐barrier properties of the films. ZO induced remarkable decreases in the tensile strength, elastic modulus, and swelling and increases in the elongation at break, solubility, and water‐vapor permeability of the films. Scanning electron microscopy analyses proved the impact of ZO on the film morphology, which affected the film properties, including the mechanical and water‐barrier properties. The addition of ZO to the polymer led to a coarse film microstructure because of the hydrophobic ZO aggregates, which produced discontinuities in the film matrix. ZO considerably increased the antioxidant and antibacterial activities of the dispersions. Pseudomonas aeruginosa was the most resistant bacteria. The improved antioxidant and antimicrobial activities of the PVA–ZO and gelatin–ZO indicated that such products could effectively be used as wound dressings. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45351.     

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     

Syndiotacticity‐rich ultrahigh molecular‐weight poly(vinyl alcohol) film. I. Determination of optimum polymer concentration by zone‐drawing method in film preparation

A new method using a simple zone‐drawing technique has been suggested for determining the optimum initial concentration of a polymer solution that has suitable macromolecular entanglements. This method was developed to replace the incorrect inherent viscosity‐measuring method for syndiotacticity‐rich (syndiotactic diad content of 63.4%) ultrahigh molecular‐weight (number‐average degree of polymerization of 12,300) (UHMW) poly(vinyl alcohol) (PVA) solution. Syndiotacticity‐rich UHMW PVA films were prepared from dimethyl sulfoxide (DMSO) solutions with different initial concentrations: of 0.1, 0.2, 0.3, 0.4, and 0.5 g/dL. In order to investigate the drawing behavior of the syndiotacticity‐rich UHMW PVA films with different solution concentrations, the films were drawn under various zone‐drawing conditions. Through a series of experiments, it was discovered that the initial concentration of PVA solution in DMSO caused significant changes in the draw ratio of the syndiotacticity‐rich UHMW PVA film. That is, the one‐step and maximum zone draw ratios of the film at an initial concentration of 0.3 g/dL exhibited its maximum values and gradually decreased at higher or lower concentrations. Thus, it was disclosed that the initial concentration of 0.3 g/dL is the optimum polymer concentration to produce a maximum draw ratio in this work. Based on the above results, it may be concluded that the optimum concentration of the initial PVA solution can be determined directly by measuring the zone draw ratio. The draw ratio, birefringence, crystallinity, degree of crystal orientation, tensile strength, and tensile modulus of the maximum drawn PVA film were 32.9, 0.0449, 0.61, 0.991, 1.91, and 46.2 GPa, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 123–134, 2000     

Preparation of poly(vinyl alcohol) and hydroxypropyl‐β‐cyclodextrin inclusion complex through polymer processing

In this study, inclusion complexes (ICs) between host hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) and guest poly(vinyl alcohol) (PVA) were prepared through polymer processing with water as plasticizer and solvent. The structure of PVA/HP‐β‐CD ICs was confirmed by FTIR, ¹H‐NMR and 2D‐NOESY NMR. The yields of PVA/HP‐β‐CD ICs were 62.5%, 51.4%, and 46.8% in twin‐screw, rotor and single‐screw processing, respectively. The crystallinity, thermal properties and mechanical properties of the PVA/HP‐β‐CD ICs were characterized by X‐ray diffraction, differential scanning calorimetry, thermal gravimetric analysis and tensile tests, respectively. The results indicated that HP‐β‐CD could establish strong interfacial interaction with PVA through hydrogen bonding and form ICs with PVA. As a result, crystallinity and melting temperature decomposition temperature of PVA were decreased. Compared with pure PVA, PVA/HP‐β‐CD ICs exhibited remarkable improvement in thermal stability. Moreover, the tensile strength, elongation at break and torque of ICs with different content of HP‐β‐CD were discussed. POLYM. ENG. SCI., 55:1988–1993, 2015. © 2014 Society of Plastics Engineers     

Studies on the properties of poly(vinyl alcohol) film plasticized by urea/ethanolamine mixture

This study investigated the effects of urea/ethanolamine mixture (UE) on the crystallinity, thermal, and mechanical properties of poly(vinyl alcohol) (PVA) films. PVA films were prepared from solutions containing PVA, urea, ethanolamine, and water by casting and evaporating at 50°C for 12 h. The plasticization efficiency of UE was compared with that of glycerol (GL), the conventional plasticizer for PVA. The properties of PVA films plasticized by UE and GL, abbreviated to UE-plasticized PVA film and GL-plasticized PVA film, respectively, were investigated by Fourier-transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and mechanical testing. It was proved that UE could form more stable hydrogen bonding with the hydroxyl group of PVA molecule and was more effective in breaking the hydrogen bonds between the hydroxyl groups. Thus, the crystallinity of UE-plasticized PVA films was lower than that of GL-plasticized PVA films. The melting temperatures of UE-plasticized PVA films were lower than those of GL-plasticized PVA films. It was found that UE-plasticized PVA film showed a higher degradation temperature compared with GL-plasticized PVA film. The degree of swelling of UE-plasticized PVA film was higher than that of GL-plasticized PVA film but solubility (S) of UE-plasticized PVA film was lower in aqueous solution. Furthermore, UE-plasticized PVA films show lower tensile strength and higher elongation at break (E) than those of GL-plasticized PVA films. The tensile strength, E, and Young's modulus of PVA film containing 30% UE mixture reached 50.78 MPa, 591.19% and 76.9 MPa, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Electrical properties of sorbitol‐doped poly(vinyl alcohol)–poly(acrylamide‐co‐acrylic acid) polymer membranes

Solid polymer membranes from poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐acrylic acid) (PAA) with varying doping ratios of sorbitol were prepared using the solution casting method. The films were examined with Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and AC impedance spectroscopy. The impedance measurements showed that the ionic conductivity of PVA–PAA polymer membrane can be controlled by controlled doping of sorbitol within the polymer blends. The PVA–PAA–sorbitol membranes were found to exhibit excellent thermal properties and were stable for a wide temperature range (398–563K), which creates a possibility of using them as suitable polymers for device applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure evolution of melt‐spun poly(vinyl alcohol) fibers during hot‐drawing

The drawability of melt‐spun poly(vinyl alcohol) (PVA) fibers and its structure evolution during hot‐drawing process were studied by differential scanning calorimetry (DSC), two dimensional X‐ray diffraction (2‐D WAXD) and dynamic mechanical analysis (DMA). The results showed that the water content of PVA fibers should be controlled before hot‐drawing and the proper drying condition was drying at 200°C for 3 min. PVA fibers with excellent mechanical properties could be obtained by drawing at 200°C and 100 mm/min. The melt point and crystallinity of PVA fibers increased with the draw ratio increasing. The 2‐D WAXD patterns of PVA fibers changed from circular scattering pattern to sharp diffraction point, confirming the change of PVA fibers from random orientation to high degree orientation. Accordingly, the tensile strength of PVA fibers enhanced by hot‐drawing, reaching 1.85 GPa when the draw ratio was 16. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of graphene/poly(vinyl alcohol) nanocomposites with enhanced mechanical properties and water resistance

The control and dispersal of graphene nanosheets in polymer hosts are challenges in the development of high‐performance graphene‐based nanocomposites due to the strong interlayer cohesive energy and surface inertia. Here we report a simple and practical approach to synthesize graphene‐reinforced poly(vinyl alcohol) (PVA) composite films by incorporating graphene oxide and graphene into PVA aqueous solution. The resulting nanocomposites revealed increases of up to 212% in tensile strength and 34% in elongation at break with only 0.5 wt% graphene content. Water absorption measurements showed that the water absorption ratio of the graphene/PVA composites decreased from 105.2 to 48.8%, and the barrier properties were obviously improved. Contact angle measurements showed that the composites were hydrophobic (θ > 90°) in contrast to the highly hydrophilic (θ < 90°) pure PVA. Copyright © 2011 Society of Chemical Industry     

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     

Nanofibrillated cellulose,poly(vinyl alcohol), montmorillonite clay hybrid nanocomposites with superior barrier and thermomechanical properties

Nanocomposites of poly(vinyl alcohol) (PVA), nanofibrillated cellulose (NFC), and montmorillonite (MMT) clay were prepared via solvent casting. In addition to investigating the effect of clay loading, PVA matrices crosslinked with poly(acrylic acid) (PAA) were prepared and compared with linear (noncrosslinked) PVA nanocomposites. ¹³C NMR and infrared spectroscopy confirmed the presence of crosslinks. Scanning electron microscopy revealed effective NFC and MMT clay dispersion throughout the nanocomposites, while X‐ray diffraction highlighted the effectiveness of PAA to encourage clay dispersion. MMT clay provided a barrier against the diffusion of water and oxygen (molecules) through the nanocomposite films. Permeability and adsorption were further reduced by crosslinking, while oxygen barrier properties were remarkably enhanced at elevated relative humidities. Thermal stability of the PVA segments was strengthened by the presence of MMT clay and crosslinks. MMT clay–reinforced PVA and NFC within the films, increasing the Young's modulus, tensile strength, and glass transition temperature. Crosslinking further enhanced the thermomechanical properties by imparting physical restraints on polymer chain segments, providing elasticity, and ductility. The hybrid films were successfully reinforced at elevated humidities, with nanocomposites displaying enhanced storage moduli and near‐complete recovery. POLYM. COMPOS., 35:1117–1131, 2014. © 2013 Society of Plastics Engineers     

Properties of starch‐based blend films using citric acid as additive. II

Starch/polyvinyl alcohol (PVA) blend films were prepared by using corn starch, polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA) as additives and glutaraldehyde (GLU) as crosslinking agent for the mixing process. The additives, drying temperature, and the influence of crosslinker of films on the properties of the films were investigated. The mechanical properties, tensile strength (TS), elongation at break (% E), degree of swelling (DS), and solubility (S) of starch/PVA blend film were examined adding GL and CA as additives. At all measurement results, except for DS, the film adding CA was better than GL because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA, and additives. CA improves the properties of starch/PVA blend film compared with GL. TS, % E, DS, and S of film adding GLU as crosslinking agent were examined. With increasing GLU contents, TS increases but % E, DS, and S value of GL‐added and CA‐added films decrease. When the film was dried at low temperature, the physical properties of the films were clearly improved because the hydrogen bonding was activated at low temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2554–2560, 2006