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.     

PVA/接枝改性淀粉热塑性生物降解材料的制备及应用

以过硫酸铵为引发剂,采用固相法合成了乙酸乙烯酯(VAC)/玉米淀粉接枝共聚物.将其与聚乙烯醇(PVA)、加工助剂在流变仪中共混,制备了PVA/接枝改性淀粉热塑性生物降解材料;分别研究了淀粉接枝共聚物对PVA/淀粉/接枝改性淀粉共混物的加工流动性、耐水性、力学性能和生物降解性能及形态结构的影响.结果表明,PVA/淀粉/接...     

The Effect of glycerol on the crystalline,thermal, and tensile properties of CaCl2‐doped starch/PVA films

Starch/poly(vinyl alcohol) (PVA) films with the addition of 10 wt% CaCl₂ and various content of glycerol were prepared. The effect of glycerol on the crystalline, thermal, and tensile properties of CaCl₂‐doped starch/PVA films was studied by X‐ray diffraction, thermogravimetric analysis (TGA), and tensile testing, respectively. The effect of glycerol on the miscibility of CaCl₂‐doped starch/PVA films was studied by scanning electron microscopy. The CaCl₂‐doped starch/PVA film became more homogeneous after the addition of glycerol. The addition of glycerol would increase the crystallinity of CaCl₂‐doped starch/PVA film. With the addition of 10 wt% glycerol and 10 wt% CaCl₂, the starch/PVA film showed the highest degree of crystallinity. The TGA results show that the thermal stability of CaCl₂‐doped starch/PVA film increased after the addition of glycerol. The toughness of CaCl₂‐doped starch/PVA films was enhanced with the addition of glycerol. The starch/PVA film with the addition of 10 wt% CaCl₂ and 20 wt% glycerol showed the tensile strength of 17 MPa and the elongation at break of 428%. Moreover, the water sorption of CaCl₂‐doped starch/PVA film decreased after the addition of glycerol at the low and intermediate relative humidity of 33 and 54%. POLYM. COMPOS., 37:3191–3199, 2016. © 2015 Society of Plastics Engineers     

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     

纳米SiO_2对聚乙烯醇/淀粉熔融吹塑薄膜性能的影响

用甘油和水为增塑剂对高醇解度聚乙烯醇和玉米淀粉复配增塑改性,并选用不同的纳米SiO2,对聚乙烯醇/玉米淀粉基体进行纳米改性,熔融吹塑制备聚乙烯醇/玉米淀粉/纳米SiO2薄膜。结果表明:加入纳米SiO2后,聚乙烯醇/玉米淀粉/纳米SiO2薄膜的拉伸性能显著提高,热性能也发生了较明显的变化;探讨了纳米SiO2对薄膜性能影响的机理。     

Modified cassava starch/poly(vinyl alcohol) blend films plasticized by glycerol: Structure and properties

We report a systematic investigation on the structure–property relationships in glycerol-plasticized poly(vinyl alcohol) (PVA)/cassava starch blends prepared via solution casting. In particular, PVA mixed with native, low-oxidized, high-oxidized, and pregelatinized cassava starches were characterized by means of SEM, XRD, FTIR, thermal analysis and mechanical testing and the immiscible systems were received. Burial tests over a period of several days suggested the preferential degradation of the starch and glycerol component (as indicated by the absence of FTIR signatures of those components) and the amorphous phase of PVA (as indicated by the enhanced crystallinity index of the degraded samples). The rheological properties of the blends seem to dictate their morphological characteristics that, in turn, have a profound impact on their mechanical properties. In that sense, the study highlights promising strategies for the development of a new family of polymeric materials that combine their biodegradable nature within superior mechanical properties. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48848.     

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     

Morphological,barrier, and mechanical properties of cassava starch films reinforced with cellulose and starch nanoparticles

A comparative performance study of cellulose and starch nanoparticles on plasticized starch reinforcement has been presented. Starch nanoparticles were obtained by ultrasound and acid hydrolysis, and cellulose nanoparticles were extracted by acid hydrolysis from microcrystalline cellulose and sisal fibers. The nanoparticles were characterized according to the zeta potential, the particle-size distribution, transmission electron microscopy, X-ray diffraction, and thermogravimetric analysis. The influence of the addition of these nanoparticles to starch films on the morphology, water vapor permeability (WVP), and mechanical properties of the nanocomposites films were investigated. The cellulose nanoparticles exhibited higher electrical stability than those originating from starch. Acid hydrolysis produced starch nanoparticles with higher crystallinity than ultrasound. All the nanoparticles significantly reduced the WVP. The cellulose nanoparticles significantly increased the tensile strength of the starch films; however, they reduced the flexibility of the nanocomposites. The results of this work support the application of starch and cellulose nanostructures for the development of reinforced biodegradable materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47001.     

A starch‐based biodegradable film modified by nano silicon dioxide

The purpose of this work was to improve the properties of the starch/poly(vinyl alcohol) (PVA) films with nano silicon dioxide (nano SiO₂). Starch/PVA/nano‐SiO₂ biodegradable blend films were prepared by a solution casting method. The characteristics of the films were assessed by Fourier Transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray photoelectron spectroscopy (XPS). The results obtained in this study indicated that the nano‐SiO₂ particles were dispersed evenly within the starch/PVA coating and an intermolecular hydrogen bond and a strong chemical bond C? O? Si were formed in the nano‐SiO₂ and starch/PVA. That the blending of starch, PVA and nano‐SiO₂ particles led to uniform starch/PVA/nano‐SiO₂ blend films with better mechanical properties. In addition, the nano‐SiO₂ particles can improve the water resistance and light transmission of the blend films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of co‐plasticization of acetyl tributyl citrate and glycerol on the properties of starch/PVA films

Starch/polyvinyl alcohol (PVA) nanocomposite films by film blowing process were successfully obtained. Starch (1700 g), PVA (300 g), and organically modified montmorillonite (OMMT, 200 g) were blended and plasticized with acetyl tributyl citrate (ATBC) and glycerol (GLY) at weight ratios of 0/100, 5/95, 10/90, 15/85, 20/80, and 25/75. The structural, morphology, barrier, mechanical, and thermal properties of the films, as well as molecular interactions in the nanocomposites were analyzed. The 3.98 nm d‐spacing was the highest in starch/PVA nanocomposite films plasticized with ATBC/GLY ratio of 10/90. The film with ATBC/GLY (5/95) had the lowest WVP (3.01 × 10^?10 g m^?1 s^?1 Pa^?1). The longitudinal tensile strength (TS) of starch/PVA nanocomposite films gradually increased from 4.46 to 6.81 MPa with the increase of ATBC/GLY ratios. The T_g steadily increased from 49.2°C to 55.2°C and the ΔH of the nanocomposite films decreased from 81.77 to 51.43 J/g at the presence of ATBC. The addition of ATBC into GLY plasticized starch/PVA/OMMT system enhanced the intermolecular interaction in the nanocomposites. This study proved that ATBC was an excellent compatibilizer in the preparation of starch/PVA/OMMT nanocomposite films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42544.     

淀粉基聚乙烯醇完全生物降解塑料薄膜的结构与性能

通过优化工艺条件，制备了高淀粉填充量的淀粉／聚乙烯醇完全生物降解塑料薄膜，研究了提高淀粉用量对淀粉／聚乙烯醇（PVA）完全生物降解塑料薄膜的力学性能和耐水性影响；并分析了耐水改性助剂尿素用量对薄膜的吸水率和生物降解性能的影响。结果表明，通过先糊化、后共混、再交联的薄膜制备工艺过程，能够获得高淀粉填充量的淀粉／聚乙烯醇完全生物降解塑料薄膜；先糊化打破了淀粉颗粒的原有形态结构，促进了淀粉与聚乙烯醇的共混相容性，从而获得了优良的力学性能；耐水改性助剂尿素的使用，能够大幅度地降低材料的吸水率，同时提高材料的生物降解性和环境友好程度。     

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.     

Hybrid composite based on poly(vinyl alcohol) and fillers from renewable resources

Hybrid composite laminates consisting of polyvinyl alcohol (PVA) as continuous phase (33% by weight) and lignocellulosic fillers, derived from sugarcane bagasse, apple and orange waste (22% by weight) were molded in a carver press in the presence of water and glycerol such as platicizers agents. Corn starch was introduced as a biodegradation promoter and gluing component of the natural filler and synthetic polymeric matrix in the composite (22% by weight). The prepared laminates were characterized for their mechanical properties and degradative behavior in simulated soil burial experiments. The fibers type and content in composite impacted mechanical properties. Materials based on PVA and starch with apple wastes and sugarcane bagasse fillers were much harder (Young's Modulus respectively, 57, 171 MPa) than materials prepared with orange wastes (17 Mpa). Respirometric test revealed that soil microbes preferentially used natural polymers and low molecular weight additive as a carbon source compared to biodegradable synthetic polymer. The presence of PVA in formulations had no negative effect on the degradation of lignocellulosic fibers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Water resistance,mechanical properties,and biodegradability of poly(3‐hydroxybutyrate)/starch composites

Composites of poly(3‐hydroxybutyrate), P(3HB), and starch were prepared by solution casting technique. To improve adhesion of starch to P(3HB), stearic acid was added as a compatibilizer and glycerol as a plasticizer. The water resistance, mechanical, and biodegradable properties of the P(3HB)/starch composites were studied. Diffusion and penetration coefficients of water increased with increasing starch content in the composites. The results showed that the elastic modulus and strain at rupture of the P(3HB)/starch composites were enhanced by increasing starch content upto 10 wt % and the tensile strength increased from 21.2 to 93.9 MPa. The presence of starch content higher than 10 wt % had an adverse effect on the mechanical properties of the investigated composites. The biodegradation rate using Actinomycetes increased proportionally to the starch content in the composite and accelerated in a culture medium of pH ≈ 7.0 at 30°C. Enzymatic degradation experiments showed that lipase produced by Streptomyces albidoflavus didnot degrade P(3HB)/starch composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Impact of the starch source on the physicochemical properties and biodegradability of different starch‐based films

Concern about environmental issues has motivated research into the development of biodegradable packaging from renewable sources. Natural polymers such as starch constitute a good alternative for diminishing the use of nonbiodegradable and nonrenewable components in the packaging industry. However, depending on the botanical source, films with different properties are formed. The aim of this study was to evaluate the film‐forming capacity of different starch sources (cassava, corn, potato, and wheat) by casting with starch contents from 2 to 6%. Principal component analysis methodology was used to evaluate the correlation between the formulations and their physicochemical and mechanical properties. It was not possible to produce continuous films based on potato starch, probably because of its very low amylose content (10%). The corn‐, cassava‐, and wheat‐starch‐based films were characterized by their thicknesses (0.06–0.22 mm), moisture contents (19–26%), water solubilities (13.7–26.5%), water‐vapor permeabilities (WVPs; 0.19–0.48 g mm h^?1 m^?2 kPa^?1), wettabilities (35–106°), biodegradabilities in soil, and thermal and mechanical properties (tensile strength = 1.9–6.7 MPa, elongation = 41–166%, and Young's modulus = 8–127 MPa). The wheat starch films presented higher WVPs and lower mechanical properties. The cassava starch films presented lower wettabilities and good mechanical properties; this suggested that their use in packaging for products, such as fruits and vegetables, with higher water activities could be feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46564.     

Dynamic–Mechanical Properties of Bioartificial Polymeric Materials

Bioartificial polymeric materials represent a new class of polymeric materials based on blends of synthetic and natural polymers, designed with the purpose of producing new materials with enhanced properties with respect to the single components. The mechanical properties of bioartificial materials prepared using poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) as synthetic components, and collagen (SC), gelatin, starch, hyaluronic acid (HA) and dextran as biological components, were investigated by dynamic mechanical thermal analysis. The materials were prepared in the form of films or hydrogels and treated by glutaraldehyde (GTA) vapour or thermal dehydration in order to reduce their solubility in water. The results indicate that SC/PVA, gelatin/PVA and starch/PVA films behave as biphasic systems, showing good mechanical properties over a wide range of temperature. It was observed that the GTA procedure affects only the biological component of the SC/PVA and gelatin/PVA blends, whilst the thermal treatment influences mainly the synthetic polymer. In the case of HA/PVA hydrogels, a modulus variation was found with the HA content related to the organization degree and perfection of the PVA network structure. It seems evident that, in the experimental conditions used, dextran/PAA mixtures behave as miscible blends showing a glass transition intermediate between those of the pure components. With both untreated and GTA-treated gelatin/PMAA blends, it was not possible to evaluate the miscibility of the systems; it could only be affirmed that these materials show good mechanical properties over a wide range of temperature. © 1997 SCI.     

Starch–recycled gelatin composite films produced by extrusion: Physical and mechanical properties

This article describes using recycled gelatin in production of blends of starch (Manihot esculenta Crantz). Films were produced by extrusion using varying percentages of recycled gelatin (2.5, 5, 7.5, 10, 12.5, and 15% relative to the starch weight), plasticized with glycerol (20 wt % relative to the starch weight), and then characterized. The morphology results showed films with a cohesive matrix and no phase separation. The crystallinity analysis showed that the extrusion process eliminated crystalline zones of the granules and produced low‐crystallinity films. The addition of recycled gelatin caused an increased thermal stability and significantly increased the mechanical strength and solubility in water of the films. It also accelerated the biodegradation process. It was concluded that the process of recycling and reprocessing did not affect the properties of gelatin, even as it has significantly influenced the properties of the films. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46254.     

Preparation and characterization of LDPE/PVA blend films filled with glycerin‐plasticized polyvinyl alcohol

A series of LDPE/PVA blend films were prepared via a twin‐screw extruder, and their morphology, thermal property, oxygen and water vapor permeation, surface properties, and mechanical properties were investigated as a function of the PVA content. During the extrusion process of the blend films, glycerin improved the compatibility and processing conditions between LDPE and PVA. The melting temperature (T_m), melting enthalpy (ΔH_m), crystallinity (%), and thermal stability of the thermal decomposition temperature (T_5%) of the LDPE/PVA blend films decreased with increasing PVA content. The oxygen permeabilities of the blend films decreased from 24.0 to 11.4 cm³·cm (m²·day·atm)^?1 at 23°C. The WVTR increased from 7.8 to 15.0 g(m² day)^?1 and the water uptake increased from 0.13 to 9.31%, respectively. The mechanical properties of blend films were slightly enhanced up to 2% PVA and then decreased. The physical properties of the blend films strongly varied with the chemical structure and morphology depending on the PVA and glycerin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41985.     

Antioxidant,antifungal, water binding,and mechanical properties of poly(vinyl alcohol) film incorporated with essential oil as a potential wound dressing material

In this study, the properties of poly (vinyl alcohol) (PVA) films incorporated with Zataria multiflora essential oil (ZMO) as a potential antioxidant/antibacterial material was investigated. PVA films were prepared from PVA solutions (2% w/v) containing different concentrations of ZMO. Water solubility, moisture absorption, water swelling, and water vapor permeability for pure PVA films were 57 ± 1.1, 99 ± 3.2%, 337 ± 8%, and 0.453 ± 0.015 g mm/m² h, respectively. Incorporation of ZMO into PVA films caused a significant decrease in water swelling and moisture absorption and increase in solubility and water vapor permeability. Tensile strength, elastic modulus, and elongation at break for pure PVA films were 13.5 ± 0.61 MPa, 15.2 ± 0.8 MPa, and 216 ± 4%, respectively. Incorporation of ZMO into the PVA films caused a significant decrease in tensile strength and elastic modulus and increase in elongation at break of the films. Pure PVA film showed UV‐visible light absorbance ranging from 280 to 440 nm with maximum absorbance at 320 nm. Addition of ZMO caused a significant increase in light absorbance and opacity. PVA films exhibited no antioxidant and antifungal activities, whereas PVA/ZMO films exhibited excellent antioxidant and antifungal properties. Although the bioactivity PVA films were improved by the addition of ZMO, however, the mechanical properties and water binding capacity of the films were weaken slightly. Thus, ZMO emulsified in the ethanol not compatible with PVA matrix and more suitable emulsifier was needed in order to obtain strong film with higher mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40937.     

Preparation and properties of poly(vinyl alcohol) films using carbohydrates as plasticizers

Three nontoxic carbohydrates (ribose, xylose, fructose) were used as poly(vinyl alcohol) (PVA) plasticizers to prepare PVA films using a casting method. Fourier transform infrared spectra demonstrated that hydrogen bonds formed between the carbohydrate and PVA. The crystallinity of raw PVA and PVA film plasticized by carbohydrate was characterized by X‐ray diffraction. Differential scanning calorimetry showed that carbohydrate decreased the melting point (T_m) of PVA. The decomposition temperature of PVA increased with addition of carbohydrate. The thermal stability of PVA film plasticized by carbohydrate (CAPF) was higher than that of PVA film plasticized by glycerol (GLPF). The thermal processing window of CAPF was broader than that of GLPF. The water vapor resistance of CAPF was better than that of GLPF. The mechanical properties of PVA films stored at different relative humidity were studied. Generally, the tensile strength of CAPF was larger than that of GLPF, while the elongation at break of CAPF was close to that of GLPF. Our experimental results indicate that carbohydrates are effective plasticizers for PVA. J. VINYL ADDIT. TECHNOL., 25:E181–E187, 2019. © 2018 Society of Plastics Engineers