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.     

Heat‐sealing properties of soy protein isolate/polyvinyl alcohol film made compatible by glycerol

Heat‐sealing properties are necessary for packaging materials. Soy protein isolate/polyvinyl alcohol (SPI/PVA) blend film is a biodegradable potential packaging material. We analyzed the effects of PVA content (0–20%), glycerol content (1–3%), and sealing temperature (180–230°C) on the heat‐sealing properties of SPI/PVA blend film. Results showed that SPI/PVA film obtained the desired sealing properties when the PVA content exceeded 15%. The sealing strength increased with the PVA content, reaching a maximum upon blending with 20% PVA and 1% glycerol at 220°C. The temperature at sealing strength was approximately twice that at 180°C. However, glycerol migrated to the surface and hindered the entanglement of macromolecular chains in the sealing interface, thereby resulting in reduction of seal strength. Glycerol vaporization at 204°C led to aesthetically unacceptable blistering in the sealing area. Therefore, the optimum sealing temperature of the blended film was ～200°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40308.     

High‐strength biodegradable poly(vinyl alcohol)/fly ash composite films

We prepared biodegradable composite films of poly(vinyl alcohol) (PVA) and fly ash (FA) spanning 5, 10, 15, 20, and 25 wt % concentrations by casting aqueous solutions. The tensile strengths of the composite films were increased proportionally via the addition of FA. The strength of the film was enhanced by 193% with 20% FA compared to the neat PVA control. Further addition of FA deviated from the linear trend. The moduli of the composites also increased proportionally with FA addition to 212% at 20 wt % FA addition compared to the control. The percentage strain at break exponentially decreased with the addition of FA. In the dynamic mechanical behavior, the storage and loss moduli both increased with FA content. The tan δ peaks corresponding to the glass‐transition temperature shifted 5–10°C higher above the control sample (73°C). This shift was attributed to a reduction in the mobility of PVA segments because they were anchored by the FA surface. The reductions in mobility manifested in strong interfacial interactions were indicative of hydrogen bonding. Broadening and reduction in the intensities of the stretching and bending peaks of ? OH, ? CH and ? C?O of PVA in the Fourier transform infrared spectra were observed. This suggested that hydrogen bonding was active between the functional groups in the FA and PVA chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Fabrication of water‐soluble poly(vinyl alcohol)‐based composites with improved thermal behavior for potential three‐dimensional printing application

Water‐soluble support materials are essential for fabrication of three‐dimensional printing component, in particular of fused deposition modeling (FDM) process. Poly(vinyl alcohol) (PVA) was considered as a potential ideal candidate used in rapid prototyping technology, while its properties and process‐ability need to be improved for the wide application. This article attempts to use urea/caprolatam (UC) as modification additive for tuning the thermal and mechanical properties of PVA. PVA‐based films with different content of additives were prepared by solution casting method. The results showed that with the increase of UC, PVA films showed decreased crystallinity and melting temperature, while the initial degradation temperature and melt index were increased. The corporation of UC decreased the melting temperature to 173.04 °C and PVA composite with 4.5% crystallinity was fabricated. Due to the formation of hydrogen bonding between UC and the hydroxyl group of PVA, the tensile strength and modulus of PVA were slightly decreased, while strain‐at‐break was significantly enhanced, as high as 470.24%, indicating UC behaved as good plasticizing effect. The microstructure examination via scanning electron microscopy showed that when the content of UC was less than 30% in the composites, homogeneous phase could be observed, indicating good compatibility between these two components. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44966.     

Novel high-strength montmorillonite/polyvinyl alcohol composite film enhanced by chitin nanowhiskers

Nanomaterials can be used as reinforcement phase to improve the performance of polymers. A simple method to prepare a composite film with super high tensile strength was used in this study. The properties of montmorillonite (MMT)/polyvinyl alcohol (PVA) films reinforced by chitin nanowhisker (CNW) have been evaluated. The structures and properties of films were analyzed by atomic force microscope (AFM), Fourier transforms infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and tensile testing. The results of FTIR and XRD showed that no chemical interaction occurred among MMT, PVA, and CNW. The SEM and AFM images suggested that the obtained composite films with the three substances had a relatively uniform layered structure and relatively smooth. The temperature at the onset of decomposition of the composite films was increased from 262.0 to 282.3°C by the addition of CNW. The tensile strength of the MMT/PVA/CNW film was reached 263.5 MPa, which was increased approximately 382% compared with the MMT/PVA film. According to these results, the composite film could be potentially used in packaging materials.     

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     

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 of poly(vinyl alcohol) films with promising physical properties in comparison with commercial polyethylene film

Poly(vinyl alcohol) (PVA) films with different thicknesses (0.08, 0.2, 0.23, 0.42 mm) were prepared by a casting technique. The transmission and the absorption of the PVA films were measured as functions of the wavelengths. PVA film with a thickness of 0.42 mm showed zero transmission in the wavelength range of 190–350 nm. The transmission spectrum of a commercial polyethylene film with a thickness of 0.21 mm was compared to the transmission spectrum of PVA film with a thickness of 0.42 mm. A correlation was found between the two transmission spectra in the region 190–350 nm and a 20% increase in the transmission of the PVA film in comparison with the transmission of commercial polyethylene in the region 350–1500 nm. The near‐infrared region of the transmission of commercial polyethylene was increased by 15% with respect to the transmission of the PVA film. The stress–strain measurements were done for PVA and commercial polyethylene films. The Young's modulus and the strength at break for PVA films are higher by two orders of magnitude than those for commercial polyethylene film. The strain at break for commercial polyethylene is 17% lower than that for PVA film. Radiation effects on the optical properties of PVA and commercial polyethylene films were investigated. The PVA and commercial polyethylene films were irradiated with a xeon arc lamp at 3.5–5 W/cm². The optical properties for PVA and commercial polyethylene films were studied after irradiation. The obtained results showed that PVA film with a thickness of 0.42 mm gave promising properties which could be used in technological applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1219–1226, 2002     

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     

Preparation and performance of PANI–PVA composite film doped with HCl

The polyaniline (PANI)–poly (vinyl alcohol) (PVA) composite film doped with HCl was prepared by adopting PVA as matrix. Effects of PVA content and film drying temperature on properties of HCl–PANI–PVA composite film were studied. A comparison was made for tensile strength, elasticity, conductivity and thermal stability of PVA, HCl–PANI or HCl–PANI–PVA. PVA film presented the highest tensile strength and elasticity (150.8?MPa and 300.0%), but its conductivity was the lowest. The conductivity of HCl–PANI–PVA was the highest (1500?S?m^?1), and tensile strength and elasticity of HCl–PANI–PVA were higher than those of HCl–PANI. The order of their thermal stability is PVA?>?HCl–PANI?>?HCl–PANI–PVA before 260°C, and the order of their thermal stability is HCl–PANI?>?HCl–PANI–PVA?>?PVA after 260°C. At the same time, the structure and conductive mechanism of composite materials were characterised and analysed through infrared and scanning electron microscopy (SEM).     

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.     

Morphology,crystalline features,and tensile properties of syndiotactic polypropylene blends

Syndiotactic polypropylene (sPP) was modified with ethylene–octene copolymer (EOC) and ethylene–propylene rubber (EPR), with test samples prepared in a twin‐screw extruder and then injection‐molded. The phase morphology, rheology, and thermal and tensile properties of the modified sPP were investigated. Atomic force microscopy studies showed how the phase morphology of the sPP blends with elastomers depended on the blend compositions, and the results compared with the storage modulus at low frequency. EOC and EPR were dispersed phase in an sPP matrix with spherical shapes when the dispersed content was 20 wt % or lower. The phase cocontinuity started around 40 wt % EOC for the sPP–EOC blends and around 60 wt % EPR for the sPP–EPR. The dispersed phase then formed more complex elongated shapes. The rheological and thermal properties were affected by the sPP–elastomer interphase. EOC promoted the crystallization of sPP; this increased the crystallization temperature and rate. In contrast, EPR had the opposite effect on the crystallization behavior, and the results indicate that sPP and EPR were not completely separated. The tensile properties were studied from ?20 to 100 °C. We found that the tensile properties at low temperature could be improved without a loss in high‐temperature properties. In the particular case of 20 wt % EOC, both the strain at yield and strain at break of the sPP–EOC blend were improved at both ?20 and 100 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44611.     

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     

Preparation of PANI–PVA composite film with good conductivity and strong mechanical property

The polyaniline (PANI)–polyvinyl alcohol (PVA) conductive composite films [doped with hydrochloride (HCl), dodecylbenzene sulphonic acid and amino sulphonic acid (NH₂SO₃H) aqueous solution] were synthesised by ‘in situ’ polymerisation, and their conductivities were compared. Among these composite films, HCl–PANI–PVA composite film possessed the highest conductivity that reached 1360?S·m^??1 [w_(PVA)?=?40%]. Meanwhile, the effects of PVA content, HCl concentration, oxidant ammonium persulphate (APS) dosage, reaction time and film drying temperature on tensile strength of the HCl–PANI–PVA composite films were studied. The tensile strength of the film was improved greatly due to effective mixture of PANI and PVA. When the PVA content was 40%, C_(HCl)?=?1.0?mol·L^??1, reaction time was 4.0?h, n_(APS)/n_(aniline)?=?1.0 and film drying temperature was 80°C, and the tensile strength of the HCl–PANI–PVA composite film reached the maximum of 60.8?MPa. At the same time, the structure of composite materials was characterised and analysed through ultraviolet spectrum and SEM.     

Preparation and Characterization of Gelatin-Based PVA Film: Effect of Gamma Irradiation

Gelatin-based polyvinyl alcohol (PVA) films were prepared (using a casting process) by mixing aqueous solutions of gelatin and PVA in different ratios. Monomer 1, 4-butanediol diacrylate (BDDA) was dissolved in methanol. Films containing 95% gelatin + 5% PVA were soaked in 3% BDDA monomer (w/w). These films were then irradiated under gamma radiation (⁶⁰Co) at different doses (50–500 krad) at a dose rate of 350 krad/h. The physico-mechanical and thermal properties of these films were evaluated. It was evident that 5% PVA-containing gelatin blend film exhibited the highest tensile strength (TS) value at 50 krad (51 MPa), which was 46% higher than that of non-irradiated blend films. It was also found that incorporation of PVA significantly reduced the TS value of the blend films compared to the raw film, whereas elongation at break (Eb) value was increased. A significant improvement of the blend films was also confirmed by thermogravimetric analysis (TGA) and thermo-mechanical analysis (TMA) when the acrylate group (from BDDA) was introduced into the film.     

The reversible plasticization of the aromatic copolyester of poly(ethylene terephthalate) and 60 mol % p-acetoxybenzoic acid with 1,1,1,3,3,3-hexafluoro-2-propanol

In recent mechanooptical studies with solution cast films of the aromatic copolyester of poly(ethylene terephthalate) and 60 mol % p-acetoxybenzoic acid from 1,1,1,3,3,3-hexafluoro-2-propanol, a volatile solvent with bp 59°C, we observed that the solvent plasticizes and affects considerably the stress–strain behavior of the copolyester at ambient temperature. Whereas a dry copolyester film is typically brittle failing at ≤ 10% strain, a film containing 12% w/w 1,1,1,3,3,3-hexafluoro-2-propanol can be stretched readily to ≥ 300% strain. When the solvent is removed by evaporation or by heating at an elevated temperature (≥ 120°C), the films lose their ductility, indicating that the plasticization is reversible.     

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.     

Improving the moisture barrier and mechanical properties of semi-refined carrageenan films

Semi-refined carrageenan (SRC) films are sensitive to moisture and generally have poor mechanical properties. These factors limit their use in applications where moisture levels are high and good mechanical strength is required. This work investigated the incorporation of nanoclay (NC) into SRC film in combination with surface lamination using a thin layer of poly(caprolactone) (PCL) to enhance the barrier properties and hydrophobicity of the SRC film and concurrently improved the mechanical properties. The water vapor permeability, moisture uptake, and water solubility decreased by 92, 24, and 11%, respectively, and the water contact angle increased from 72° to 95°. The tensile strength and elongation at break increased by 17.9 and 2.8%, respectively, and the thermal stability also increased slightly. The PCL lamination was the main contributor to the enhanced barrier and mechanical properties of the films, whereas the NC inclusion contributed more to the enhanced thermal properties.     

Mechanical strain modulation of domain wall currents across LiNbO3 nanosensors

Recently, studies on low-dimensional conducting domain walls (DWs) in insulating ferroelectrics have opened up new research areas that allow information to be mechanically written and electrically read on the nanoscale. Large strains in thin films can change the polarization gradient across the DW region and thus increasing the DW current significantly. This phenomenon can enable the development of high sensitivity mechanical vibration sensors. In this study, the effects of variable uniaxial strain on the structures of 180° conducting DWs in LiNbO₃ (LNO) single-crystal thin films bonded onto Si/SiO₂ substrates were investigated. After the creation of antiparallel domains within each LNO nanosensor integrated at the film surface, strain modulation of DW currents was observed through simple mechanical bending of the film. The DW current increases under application of tensile strain along the axis of polarization, but decreases under application of in-plane compression by a factor of approximately 25. Phase field simulations showed the dramatic change in polarization gradients around the DW regions under the increase in tensile strain, which reduced the band gap. Repetitive band-gap narrowing/broadening with change in local electric field intensity under vibrating mechanical forces can periodically modulate both the carrier density and the DW conduction in the sensors. This finding not only provides the new fundamental physics to enrich the ferroelectric theory, but also paves the way to the near-future development of bending actuators, piezolighters, and micro-/nano-manipulators, etc.     

Superhard and superelastic films of polymeric C60

The C₆₀ thin film deposited on steel substrate was transformed by high pressure–high temperature treatment to a superhard and superelastic material. The films were studied by Raman spectroscopy in situ at 20 GPa after heating at 300°C and ex situ after the quenching. The hardness and elastic properties of the high-pressure phases have been characterized with nanoindentation. The hardness of the films were determined to be 0.5±0.1 GPa and 61.9±9 GPa for unmodified C₆₀ and HPHT treated films, respectively. The hardness of the pressurized film is higher than for cubic BN but lower than hardness values reported for ultrahard fullerite samples prepared from powders. An interesting observation was that the HPHT treated film showed an extreme elastic response with an elastic recovery of approximately 90%.