Starch- polyvinyl alcohol crosslinked film— performance and biodegradation

Starch-PVOH cast films were prepared with and without crosslinking agent (hexamethoxymethylmelamine) in the absence of plasticizer. Moisture absorption in films without crosslinking agent at a low relative humidity was similar to that of PVOH and increased as the relative humidity increased. Films with crosslinking agent showed moisture absorption linearly proportional to the relative humidity. Significant improvement in resistance to water disintegration for crosslinked starch-PVOH films was observed. While the tensile strength decreased with increased relative humidity, crosslinking significantly improved the tensile strength. Increased PVOH content improved elongation of films even when the relative humidity was 80% or higher. Biodegradation studies revealed that the degradation rate was negatively correlated with the PVOH content in films and crosslinking generated more converged degradation curves. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Properties of Wheat-Gluten/Montmorillonite Nanocomposite Films Obtained by a Solvent-Free Extrusion Process

This is, to our knowledge, the first study of wheat-gluten-based nanocomposite films prepared by a solvent-free extrusion process. Wheat gluten/montmorillonite nanocomposite films were obtained in a single screw-extruder using urea as a combined denaturant and plasticizer. The oxygen permeability and water vapor transmission rate of the films decreased by respectively factors of 1.9 and 1.3 when 5 wt.% clay was added. At the same time, the stiffness increased by a factor of 1.5, without any critical loss of extensibility. Field emission scanning electron microscopy (FE-SEM) and Energy-dispersive X-ray analysis indicated that the clay particles were layered mainly in the plane of the extruded film. It was possible to identify individual platelets/tactoids with FE-SEM and, together with findings from transmission electron microscopy, atomic force microscopy and X-ray diffraction, it was concluded that the clay existed as individual clay platelets, intercalated tactoids and agglomerates. Thermogravimetric analysis showed that the thermal stability of the extrudates was improved by the addition of clay.     

Mechanical and Barrier Properties of Biodegradable Films Made from Chitosan and Poly (Lactic Acid) Blends

Biodegradable film blends of chitosan with poly(lactic acid) (PLA) were prepared by solution mixing and film casting. The main goal of these blends is to improve the water vapor barrier of chitosan by blending it with a hydrophobic biodegradable polymer from renewable resources. Mechanical properties of obtained films were assessed by tensile test. Thermal properties, water barrier properties, and water sensitivity were studied by differential scanning calorimeter analysis, water vapor permeability measurements, and surface-angle contact tests, respectively. The incorporation of PLA to chitosan improved the water barrier properties and decreased the water sensitivity of chitosan film. However, the tensile strength and elastic modulus of chitosan decreased with the addition of PLA. Mechanical and thermal properties revealed that chitosan and PLA blends are incompatible, consistent with the results of Fourier transform infrared (FTIR) analysis that showed the absence of specific interaction between chitosan and PLA.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Physical Characterization of Biodegradable Films Based on Chitosan,Polyvinyl Alcohol and <Emphasis Type="Italic">Opuntia</Emphasis> Mucilage

This study aimed to develop and characterize biodegradable films containing mucilage, chitosan and polyvinyl alcohol (PVA) in different concentrations. The films were prepared by casting on glass plates using glycerol as plasticizer. Mechanical properties, water vapor and oxygen barrier, as well as the interaction with water, were measured. The compatibility of the film-forming components and the uniformity of the films were determined by zeta potential and SEM, respectively. The glycerol and mucilage allowed obtaining more hydrophilic films. The barrier properties of the films made from 100 % chitosan were similar to composed films containing PVA up to 40 %. The results of this study suggest that the interaction between chitosan and mucilage could increase water vapor permeability. The films prepared from either 100 % chitosan or PVA showed a more hydrophobic behavior as compared to the composed films. The films were homogenous since no boundary or separation of components was observed, indicating a good compatibility of the components in the films.     

Structural Features and Water Interactions of Etherified Xylan Thin Films

In this paper, the model film approach was used to investigate the structural features and humidity induced changes of the etherified xylan derivatives by using surface sensitive methods. Two routes to modify the birch xylan to generate either cross-linking xylan or more hydrophobic xylan were mastered via allylation and butylation, respectively. Thin nanometer scale model films were prepared by spin-coating and the films were further treated by UV-radical treatment and heat. The structural changes and wetting behaviour of the films before and after the post-treatment procedures were studied using atomic force microscopy and water contact angle measurements. In addition, the water vapour uptake of the xylan derivative films was monitored using quartz crystal microbalance with dissipation (QCM-D) equipped with the humidity module. With the QCM-D, the mass uptake due to the water vapour binding was defined. Simultaneously the changes in the viscoelastic properties of the films when subjected to different relative humidity conditions were determined. We show that the water sensitivity and wetting behaviour of the water soluble xylan derivatives can be altered by cross-linking the film structure and through the molecular rearrangements. Cross-linking and the conformational rearrangements of the allylated xylan reduced the water vapour uptake ability approximately 80?%. Butylated xylan as being a more hydrophobic derivative showed lower ability to uptake water vapour when compared to more hydrophilic xylan derivative. This ability was even further reduced after the post-treatments mainly due to the reassembly of the hydrophobic groups.     

Water transport in polylactic acid (PLA), PLA/ polycaprolactone copolymers, and PLA/polyethylene glycol blends

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester, and water vapor permeability may have a significant influence on the rate of degradation. A method is devised to use bags prepared from PLA films and filled with molecular sieves to determine the water vapor permeability in the polymer, its copolymers with caprolactone, and blends with polyethylene glycol. The “solution-diffusion” model is used to determine the permeability parameters. These include the solubility coefficient,S, a measure of the equilibrium water concentration available for hydrolysis and the diffusion coefficient,D, which characterizes the rate of water vapor diffusion into the film under specific conditions. Values ofS andD at 50‡C and 90% relative humidity ranged from 400 × 10^-6 to 1000 × 10^-6 cm³ (STP)/(cm³ Pa) and 0.20 × 10^-6 to 1.0 × 10^-6 cm²/s, respectively. TheS andD coefficients were also measured at 20 and 40‡C and compared to those of other polymers. The degree of crystallinity was found to have little influence on the measured permeability parameters. The heat of sorption, δH_S, and the activation energy of diffusion, E_D, were used to show that the permeability process is best described by the “water cluster” model for hydrophobic polymers. Finally, the diffusion coefficient is used to compare the rate of water diffusion to the rate of water consumption by ester hydrolysis. Results indicate that hydrolytic degradation of PLA is reaction-controlled.     

Biodegradable Polymer Composites as Coating Materials for Granular Fertilizers

The composites consisting of poly(vinyl alcohol), horn meal, rapeseed cake, glycerol and phosphogypsum were proposed for the encapsulation of mineral fertilizers. Poly(vinyl alcohol) was used as a binder. The other components making ca. 70% of the mass of the composites were waste materials or by-products. They contain phosphorus, nitrogen, calcium, potassium and sulphur, which are useful nutrients for plants. The effect of the amount of glycerol and of the composition of the mixture of the fillers on the mechanical, sorption properties, water vapour permeability, solubility in water, dimensional stability of the composite films was studied. The addition of phosphogypsum and increase of the concentration of glycerol in the composites lead to the decrease of the tensile strength, water vapour permeability and to the increase of elongation at break and of the solubility of the composite films in water. The composites prepared were used for encapsulation of fertilizers. It was established that encapsulation resulted in the increase of the time of release of the fertilizers. In addition, encapsulation improved mechanical properties of the fertilizers. The fertilizer granules were coated with composite films and tested in the cultivation of tomato sprouts. They showed considerable positive effect on the development of the roots of the plants.     

Characterization of Biodegradable Composite Films Prepared from Blends of Poly(Vinyl Alcohol), Cornstarch,and Lignocellulosic Fiber

Several composite blends of poly(vinyl alcohol) (PVA) and lignocellulosic fibers were prepared and characterized. Cohesive and flexible cast films were obtained by blending lignocellulosic fibers derived from orange waste and PVA with or without cornstarch. Films were evaluated for their thermal stability, water permeability and biodegradation properties. Thermogravimetric analysis (TGA) indicated the suitability of formulations for melt processing, and for application as mulch films in fields at much higher temperatures. Composite films were permeable to water, but at the same time able to maintain consistency and composition upon drying. Chemical crosslinking of starch, fiber and PVA, all hydroxyl functionalized polymers, by hexamethoxymethylmelamine (HMMM) improved water resistance in films. Films generally biodegraded within 30 days in soil, achieving between 50–80% mineralization. Both starch and lignocellulosic fiber degraded much more rapidly than PVA. Interestingly, addition of fiber to formulations enhanced the PVA degradation.     

Effect of Manufacturing Process and Xanthan Gum Addition on the Properties of Cassava Starch Films

The objective of this work was to manufacture biodegradable films by two different processes (casting and extrusion), from different combinations of cassava starch and xanthan gum. These films were produced by casting and by extrusion from six different starch-xanthan gum combinations (0, 2, 4, 6, 8 and 10% w/w), containing glycerol as plasticizer (20% w/w) and were also characterized according to their microstructure, optical, mechanical, and barrier properties. Scanning electron microscopy of the starch-xanthan gum extruded films showed reticulated surface and smooth interior, suggesting that xanthan was driven to the surface and gelatinized starch to the interior of the films during extrusion. Films manufactured by casting were entirely homogeneous. In general, casted films presented lower opacity and water vapor permeability and higher stress at break than films manufactured by extrusion. Xanthan gum addition affected mechanical properties of starch films, improving their stress and strain at break, especially for extruded samples, but these properties did not show stability at different RH conditions.     

Studies on enhanced degradable plastics. III. The effect of weathering of polyethylene and (ethylene-carbon monoxide) copolymers on moisture and carbon dioxide permeability

Two enhanced-photodegradable polyethylenes were studied to determine the effect of photooxidative degradation upon transport properties. Water vapor permeability of LDPE films containing metal compound prooxidants, weathered to different extents under outdoor exposure was studied. A film made of LDPE blended with 20 wt% of polycaprolactone was also examined to determine if biodegradation over a 40-day period resulted in a measurable change in its water vapor transport characteristics. A gravimetric technique was used to study the effects of outdoor and weather-ometer exposures on the permeability of carbon dioxide of both the LDPE film and (ethylene-carbon monoxide) copolymer films. Generally, photooxidative degradation was seen to be accompanied by a change in transport characteristics of the polymer films.     

TiO2气溶胶快速去除空气中的芥子气模拟剂

在自制反应器内,通过喷射法将纳米TiO_2分散成气溶胶形式,用以降解空气中的芥子气模拟剂二乙基硫醚(DES)。利用自行设计的一套气溶胶沉降行为评价装置,对TiO_2气溶胶的释放条件进行了优化。系统研究了相对湿度、反应温度、光强、催化剂加入量、反应物浓度等因素对DES降解速率和彻底矿化速率的影响。结果表明:TiO_2气溶胶对2.80 mg/L(近似芥子气快速致死浓度)DES降解的半衰期由涂覆型TiO_2的34.5 min缩短至8.5 min;TiO_2气溶胶光催化降解DES的最佳相对湿度为35%,此时CO_2最快生成速率可达34.64μg/(L·min),150 min内彻底矿化比例达66.1%;对于1.5 L反应器,催化剂加入量为30 mg时降解DES的量效比达到最佳状态;TiO_2气溶胶光催化适用于含低浓度DES空气的快速净化。     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Natural Oil-Based Alkyd-Acrylic Copolymers: New Candidates for Barrier Materials

The feasibility of using alkyd-acrylic copolymers as a barrier material was studied. Copolymers of tall oil fatty acid or rapeseed oil-based alkyd resin and polyacrylates were synthesized and films of these copolymers were prepared. Nuclear magnetic resonance spectroscopy revealed that after copolymerization the proportion of double bonds in alkyd resin was diminished due to grafting reactions. The mechanical properties, such as strength and flexibility, of the copolymer films were tested, and the performance of the films as water, oil, and oxygen barrier was evaluated. An increased amount of alkyd resin made the films more brittle and increased their oxygen permeability, however, at the same time their hydrophobicity was increased.     

Light Stability of Oriental Lacquer Films Irradiated by a Fluorescent Lamp

Oriental lacquer film was prepared and exposed to a fluorescent lamp. The color difference and gloss of the surface of the film decreased compared to those of film kept in a dark place by irradiation with the fluorescent light. The percentage of discoloration was 7.0% on a relative scale with an irradiation of 3600 h. The surface of the film was characterized by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The oxygen content of the surface increased considerably with the decrease in triene groups with exposure time. These changes were also observed when the film was exposed in a glass or acrylic plate box. The change of the above properties was not observed when the film was kept in a dark place for more than 4800 h. The results suggest that oriental lacquer film deteriorates even under irradiation with visible light.     

平板陶瓷膜回收烟气水热的实验研究

将平板陶瓷膜组成膜组件对烟气水分和余热进行回收,考察了烟气的温度、相对湿度、流速和冷却水温度等参数对膜组件水热回收性能的影响。在实验工况下,水通量和水回收效率随着烟气温度、烟气相对湿度的增加和冷却水温度的降低而上升;水通量随着烟气流速的加快而上升,水回收效率随着烟气流速的加快先上升后降低;膜组件的水通量和水回收效率最高分别可达22.0 kg/(m²·h)和36.3%。平板陶瓷膜回收的热量主要来自烟气潜热,烟气潜热换热量与水通量呈正相关变化趋势。在实验工况下,平板陶瓷膜组件的总传热系数最高为412 W/(m²·℃),高于多通道管式陶瓷膜和单通道管式陶瓷膜。     

A Processing,Characterization and Marine Biodegradation Study of Melt-Extruded Polyhydroxyalkanoate (PHA) Films

A series of polyhydroxyalkanoates (PHA), all containing 1% nucleating agent but varying in structure, were melt-processed into films through single screw extrusion techniques. This series consisted of three polyhydroxybutyrate (PHB) and three polyhydroxybutyrate-valerate (PHBV) resins with varying valerate content. Processing parameters of temperature in the barrel (165–173 °C) and chill rolls (60 °C) were optimized to obtain cast films. The gel-permeation chromatography (GPC) results showed a loss of 8–19% of the polymer’s initial molecular weight due to extrusion processing. Modulated differential scanning calorimetry (MDSC) displayed glass transition temperatures of the films ranging from −4.6 to 6.7 °C depending on the amount of crystallinity in the film. DSC data were also used to calculate the percent crystallinity of each sample and slightly higher crystallinity was observed in the PHBV series of samples. X-ray diffraction patterns did not vary significantly for any of the samples and crystallinity was confirmed with X-ray data. Dynamic mechanical analysis (DMA) verified the glass transition trends for the films from DSC while loss modulus (E′) reported at 20 °C showed that the PHBV (3,950–3,600 MPa) had the higher E′ values than the PHB (3,500–2,698 MPa) samples. The Young’s modulus values of the PHB and PHBV samples ranged from 700 to 900 MPa and 900 to 1,500 MPa, respectively. Polarized light microscopy images revealed gel particles in the films processed through single-screw extrusion, which may have caused diminished Young’s modulus and tensile strength of these films. The PHBV film samples exhibited the greatest barrier properties to oxygen and water vapor when compared to the PHB film samples. The average oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) for the PHBV samples was 247 (cc-mil/m²-day) and 118 (g-mil/m²-day), respectively; while the average OTR and WVTR for the PHB samples was 350 (cc-mil/m²-day) and 178 (g-mil/m²-day), respectively. Biodegradation data of the films in the marine environment demonstrated that all PHA film samples achieved a minimum of 70% mineralization in 40 days when run in accordance with ASTM 6691. For static and dynamic incubation experiments in seawater, microbial action resulting in weight loss as a function of time showed all samples to be highly biodegradable and correlated with the ASTM 6691 biodegradation data.     

A Solvent-Free Approach for Production of Films from Pectin and Fungal Biomass

Self-binding ability of the pectin molecules was used to produce pectin films using the compression molding technique, as an alternative method to the high energy-demanding and solvent-using casting technique. Moreover, incorporation of fungal biomass and its effects on the properties of the films was studied. Pectin powder plasticized with 30% glycerol was subjected to heat compression molding (120 °C, 1.33 MPa, 10 min) yielding pectin films with tensile strength and elongation at break of 15.7 MPa and 5.5%, respectively. The filamentous fungus Rhizopus oryzae was cultivated using the water-soluble nutrients obtained from citrus waste and yielded a biomass containing 31% proteins and 20% lipids. Comparatively, the same strain was cultivated in a semi-synthetic medium resulting in a biomass with higher protein (60%) and lower lipid content (10%). SEM images showed addition of biomass yielded films with less debris compared to the pectin films. Incorporation of the low protein content biomass up to 15% did not significantly reduce the mechanical strength of the pectin films. In contrast, addition of protein-rich biomass (up to 20%) enhanced the tensile strength of the films (16.1–19.3 MPa). Lastly, the fungal biomass reduced the water vapor permeability of the pectin films.     

Improvement of permeability of waste sludge by mixing with slag or construction and demolition waste

To determine the allowable ratio of waste sludge required to ensure an aerobic zone in the landfill, we investigated sludge permeability, which involved mixing sludge, the major landfill waste in Japan, at different mixing ratios with other wastes (slag and construction and demolition waste (C&D)). We measured parameters of sample permeability and analyzed parameters that exert a large influence on oxygen penetration depth with a simulation model accounting for both diffusion and convection driven by temperature gradients. We also determined the critical volumetric contents in which gas and/or water permeability change significantly when sludge is mixed with sand or gravel. From the results of the simulations, gas permeability of the layer, the difference between inside and outside temperatures and the oxygen consumption rate exert a large influence on the resulting oxygen penetration depth. The allowable ratio of sludge required to ensure an aerobic zone in the landfill was determined by considering the balance of the above three parameters. By keeping volumetric sludge content to below 25%, air convection and oxygen penetration depth of several meters were achieved in the modeling.     

Characteristic Properties of Novel Organosolv Lignin/Polylactide/Delta-Valerolactone Terpolymers

Compostable terpolymers of l-lactide (LLA), delta-valerolactone (DVL), and switchgrass organosolv lignin (OSL) were synthesized via ring-opening polymerization to improve on polylactide homopolymer properties for commercial applications. OSL has properties that improve some of the deficiencies of polylactide, including polylactide’s limitations for use in food, beverage and medical applications due to its high water permeability and low ultraviolet light (UV) blocking capabilities. DVL was incorporated into these polymers to add flexibility. The addition of DVL to the polymer had a positive effect on the tensile strain properties of the resultant terpolymer, resulting in a more flexible polymer with a reduced Young’s modulus. Water vapor transmission rate calculations confirmed that water vapor was transported more slowly through terpolymer films than through the PLLA homopolymer under varying hygrostatic conditions. While the addition of DVL increased UV permeability, the addition of even a small amount of lignin can effectively counteract this effect.