Polyvinyl Alcohol (PVA)/Starch Bioactive Packaging Film Enriched with Antioxidants from Spent Coffee Ground and Citric Acid

The bioactive packaging polyvinyl alcohol (PVA)/starch films were prepared by incorporating combined antioxidant agents i.e. extracted spent coffee ground (ex-SCG) and citric acid. Effect of citric acid content on chemical compatibility, releasing of antioxidant, antibacterial activities, and physical and mechanical properties of PVA/starch incorporated ex-SCG (PSt-E) films was studied. The results of ATR-FTIR spectra showed that antioxidant agents of ex-SCG can penetrate into the film and the ester bond of blended films by citric acid was also observed. The presence of ex-SCG increased efficiency of antioxidant release and antimicrobial activity. The PSt-E film incorporated 30 wt% citric acid showed minimum inhibitory concentration against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The incorporation of ex-SCG and citric acid into film showed a synergistic effect on antibacterial activity. The water resistance and kinetic moisture sorption improved with incorporation of citric acid. The tensile strength and biodegradability of samples were in range of 5.63–7.44 MPa and 65.28–86.64%, respectively. Based on this study, PSt-E film incorporated 30 wt% citric acid can be applied as novel food packaging materials.     

The Effect of Polymeric Chain Extenders on Physical Properties of Thermoplastic Starch and Polylactic Acid Blends

The effects of a polymeric chain extender on the properties of bioplastic film made from blends of plasticized polylactic acid (p-PLA) and thermoplastic starch (TPS) were studied. Joncryl^? ADR 4370S, a polymeric chain extender, was blended with TPS and p-PLA at a level of 1% (w/w). A co-rotating twin-screw extrusion process was used to prepare films with various ratios of TPS and p-PLA. Mechanical and physical properties of films, including film tensile properties, surface energy, moisture content, hydrophilicity, moisture sorption behaviour and thermal mechanical properties were determined. During extrusion, films enhanced by 1% Joncryl addition demonstrated more desirable and consistent qualities, such as smoother film edge and surface. Addition of Joncryl significantly improved film tensile strength, 0.2% offset yield strength, and elongation, especially evident with the 250% elongation of 70/30 (TPS/p-PLA) film. Total surface energy of films was not significantly influenced by addition of Joncryl. However, the polar contribution to the total surface energy of 70/30 (TPS/p-PLA) film increased after the addition of Joncryl. The study showed that blending TPS with p-PLA transformed TPS film from being highly hydrophilic to highly hydrophobic. On the other hand, addition of Joncryl had limited effects on moisture content, water solubility, glass transition temperature and moisture sorption behaviour of TPS/p-PLA blend films.     

Effects of washing with water on enzymatic saccharification and d-lactic acid production from steam-exploded sugarcane bagasse

This study investigated the production of d-lactic acid from unutilized sugarcane bagasse using steam explosion pretreatment. The optimal steam pressure for a steaming time of 5?min was determined. The steam-exploded sugarcane bagasse was hydrolyzed using cellulase (Meicelase) and then the hydrolyzate was subjected to fermentation substrate. By enzymatic saccharification using Meicelase, the highest recovery of glucose from raw bagasse, 73.7?%, was obtained at a steam pressure of 20?atm. For extracted residue with water after steam explosion, the glucose recovery increased up to 94.9?% at a steam pressure of 20?atm. These results showed that washing with water is effective in removing enzymatic reaction inhibitors. After steam pretreatment (steam pressure of 20?atm), d-lactic acid was produced by Lactobacillus delbrueckii NBRC 3534 from the enzymatic hydrolyzate of steam-exploded bagasse and washed residue. The conversion rate of d-lactic acid obtained from the glucose concentration was 66.6?% for the hydrolyzate of steam-exploded bagasse without washing with water and 90.0?% for that derived from the extracted residue with water after steam explosion. These results also demonstrated that the hydrolyzate of steam-exploded bagasse (without washing with water) contains fermentation inhibitors and washing with water can remove them.     

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.     

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.     

Preparation and Biodegradation of Starch/Polycaprolactone Films

Starch granules were modified with trisodium trimetaphosphate (TSTP) and characterized by P³¹-NMR, FTIR and DSC. Seventy-micron films were prepared from modified starch and polycaprolactone blends by solvent casting technique. Three different types of films—PCL (100% polycaprolactone), MOD-ST/PCL (50% modified starch and 50% polycaprolactone blend) and NONMOD-ST/PCL (50% nonmodified starch and 50% polycaprolactone blends)—were prepared, and their thermal, mechanical, and morphologic properties were investigated to show the increased performance of PCL with the addition of starch and also the effect of modification. It was observed that with the addition of starch the Young's modulus of polycaprolactone was increased and became less ductile, whereas tensile strength and elongation at break values decreased. Biodegradation of these films was inspected under different aerobic environments with the presence of Pseudomonas putida, activated sludge, and compost. It was observed that whereas P. putida had almost no effect on degradation during 90 days, with the presence of activated sludge, considerable deformation of films was observed even in the first 7 days of degradation. In a compost environment, degradation was even faster, and all polymer films were broken into pieces within first 7 days of degradation and no film remained after 15 days.     

Active Bio-composite Sodium Alginate/Maltodextrin Packaging Films for Food Containing Azolla pinnata Leaves Extract as Natural Antioxidant

The aim of the current work was to produce sodium alginate (SA) maltodextrins (MD) based functional films incorporated with phenolic extract of Azolla pinnata leaves fern (AF) by solution molding technique. AF with different concentrations (0.8, 1.2 and 1.6% w/w) were integrated inside SA.MD films. The resulted films were characterized to investigate the surface structure by scanning electron microscope (SEM), thermal disposal by (DSC), crystallization by X-ray diffraction (XRD), potential interaction by (FT-IR) and some mechanical properties. The SEM micrographs indicated that the higher concentration (1.6%) of AF extract caused development of wrinkles on the surface of films. And as a result, there were a significant decrease of elongation at break (EB) and tensile strength properties of films to 55.01 and 58.42%, respectively. By continues addition of AF extract to SA.MD films, the film thickness increased from 0.124 to 0.181 mm, the scavenging and antimicrobial properties were enhanced by the attendance of ferulic acid, rutin, thiamine, tamarixetin, astragalin, quercetin, chlorogenic acid and epicatechin inside extracts. Furthermore, the films solubility, swelling degree and water vapor permeability were decreased to 13.08%, 26.41% and 1.662?×?10^??10 g H₂O/m s p.a. The resulted films could be utilized as composite packaging material for different food applications.

     

Leaching of heavy metals by citric acid from fly ash generated in municipal waste incineration plants

The leaching behavior of heavy metals from municipal waste incineration (MWI) fly ash was investigated in this study. The leaching process includes two steps, i.e., fly ash was firstly washed with water, and then subjected to citric acid leaching. The main parameters of the washing process such as liquid/solid ratio, washing time, and number of washing were tested. The optimum conditions for water washing were found as follows: washing time 5–10 min, liquid/solid ratio 10:1 (ml:g), and number of washing was twice; under these conditions, 86% Na, 70% K, 12% Ca, 1.2% Al, and 0.5% Pb were removed from the fly ash in the prewashing. From the results of screening tests of leaching lixiviants, citric acid was found to be the most effective leaching agent, taking account of its environmentally benign characteristics. Optimum metal extraction can be achieved with citric acid under the following conditions: pH 3.0, liquid/solid ratio 40 (ml:g), citric acid concentration 0.10 mol/dm³, contact time 20 min at room temperature.     

Biodegradability of Chemically Modified Starch (RS4)/PVA Blend Films: Part 2

Biodegradable films were successfully prepared by using cornstarch (CS), chemically modified starch (RS4), polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA). The physical properties and biodegradability of the films using CS, RS4, and additives were investigated. The results of the investigation revealed that the RS4-added film was better than the CS-added film in tensile strength (TS), elongation at break (%E), swelling behavior (SB) and solubility (S). Especially, the RS4/PVA blend film with CA as an additive showed physical properties superior to other films. Furthermore, when the film was dried at low temperature, the properties of the films clearly improved because the hydrogen bonding was activated at low temperature. The biodegradation of films was carried out using the enzymatic, microbiological and soil burial test. The enzyme used in this study was amyloglucosidase (AMG), α-amylase (α-AM) and β-amylase (β-AM). At the enzymatic degradation test, the GL-added films had an approximately 60% degradation, while the CA-added films were degraded about 25%. The low degradation value on CA-added film is attributed to low pH of film added CA that deactivated the enzymatic reaction. The microbiological degradation teat was performed by using Bacillus subtilis and Aspergillus niger.     

Blends of Zein and Nylon-6

Blends of zein and nylon-6 (55?k) in formic acid were used to produce solution cast films and electrospun fibers. When the amount of nylon-6 was 8?% or less blends were formed that had improved tensile strength and reduced solubility. The blends were analyzed using physical property measurements, DSC and IR spectra. Using between 2 and 8?% nylon-6 provided a 33?% increase in tensile strength. Young??s modulus increased by over 50?% in this range. In general elongation was lower for all formulations. Surprisingly the cast films having 0.5?C8?% nylon-6 had improved solvent resistance to 90?% ethanol/water. Electrospun fibers were produced from formic acid solutions of zein and nylon-6 where the amount of nylon was 0, 2 and 6. Fibers produced from 27?% spinning solids had average diameters on the order of 0.5???m. Reducing the spinning solids to 21?% provide slightly smaller fibers however, the fibers had more defects.     

Microbial Degradation of UV-Pretreated Low-Density Polyethylene Films by Novel Polyethylene-Degrading Bacteria Isolated from Plastic-Dump Soil

Eleven effective low-density polyethylene (LDPE)-degrading bacterial strains were isolated and identified from landfill soil containing large amounts of plastic materials. The isolates belonged to 8 genera, and included Pseudomonas (areroginosa and putida), Sphingobacterium (moltivorum), Delftia (tsuruhatansis), Stentrophomonas (humi and maltophilia), Ochrobacterum (oryzeae and humi), Micrococcus (luteus), Acinetobacter (pitti), and Citrobacter (amalonaticus). Abiotic degradation of LDPE films by artificial and natural ultraviolet (UV)-exposure was analyzed by FT-IR spectroscopy. LDPE films treated with UV-radiation were also inoculated with the isolates and biofilm production and LDPE degradation were measured. Surface changes to the LDPE induced by bacterial biofilm formation were visualized by Scanning Electron Microscopy. The most active bacterial isolate, IRN19, was able to degrade polyethylene film by 26.8?±?3.04% gravimetric weight over 4 weeks. Analysis of 16S rRNA sequence of this isolate revealed 96.97% similarity in sequence to Acinetobacter pitti, which has not previously been identified as a polyethylene-degrading bacterium. Also, most the effective biofilm forming isolate, IRN11, displayed the highest cell mass production (6.29?±?0.06 log cfu/cm²) after growth on LDPE films, showed 98.74% similarity to Sphingobacterium moltivourum.     

Topographic Controls of Nitrogen,Sulfur, and Carbon Transport from a Tolerant Hardwood Hillslope

The lateral down-slope movement of water, NO₃ ^-, NH₄ ⁺, SO₄ ^2-, H⁺ and DOC through an ablation till was examined from 1987 to 1990 for a one hectaresoil catena on a steep hillslope with uniform forest cover at the Turkey Lakes Watershed (TLW), Ontario, Canada. Natural variation in the export of nutrients from the soil profile via soil water to Little Turkey Lake was assessed in relation to nutrient distribution in soil at different topographic positions.Subsurface throughflow exhibited dramatic differences in nutrientconcentrations and fluxes with slope position, largely reflectingthat of the soil horizons through which the water passed. GreaterNO₃ ^-, SO₄ ^2-, and DOC concentrations in subsurface water in the upper, well-drained hillslope were a reflection of enrichment by contact with more acidic, more developed podzols, and more favorable soil physical and biological conditions for NO₃ ^- retention in solution.Nutrient inputs to the lake were strongly influenced by increaseddown-slope transport of water, and increased SO₄ ^2-, N, and C retention in wetter, less-developed podzolic soils that characterize lower slope positions. An understanding of water movement and soil development variation withtopographic position was required to accurately estimate nutrient budgets for steep slopes at TLW.     

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.     

Biodegradable Films Based on Blends of Gelatin and Poly (Vinyl Alcohol): Effect of PVA Type or Concentration on Some Physical Properties of Films

The aim of this work was to develop biodegradable films based on blends of gelatin and poly (vinyl alcohol) (PVA), without a plasticizer. Firstly, the effect of five types of PVA with different degree of hydrolysis (DH) on the physical properties of films elaborated with blends containing 23.1% PVA was studied. One PVA type was then chosen for the study of the effect of the PVA concentration on the mechanical properties, color, opacity, gloss, and water solubility of the films. The five types of PVA studied allowed for films with different characteristics, but with no direct relationship with the DH of the PVA. Therefore, the PVA Celvol^®418 with a DH = 91.8% was chosen for the second part, because they produced films with greater tensile strength. The PVA concentration affected all studied properties of films. These results could be explained by the results of the DSC and FTIR analyses, which showed that some interactions between the gelatin and the PVA occurred depending on the PVA concentration, affecting the crystallinity of the films.     

Development of Regenerated Cellulose/Citric Acid Films with Ionic Liquids

Nowadays, the importance of green and biodegradable plastics as viable substitutes for non-degradable petroleum-based materials is felt more than ever. Regenerated cellulose (RC) as a potential candidate suffers from poor processability and inferior properties, limiting its wide applications. In this study, it is demonstrated that citric acid (CA) enhances physical, mechanical, and thermal properties of RC films, due to RC-citric acid compatibility. 1-ethyl-3-methylimidazolium chloride (EMIMCl) as a green ionic liquid was employed for the processing of RC. The optimum properties in terms of thermal stability, mechanical strength, contact angle, water uptake, and oxygen permeability were achieved at 10 wt% of CA. However, further incorporation of CA adversely affected the film properties. This behaviour was explained by the crosslinking and plasticizing effects of CA. Furthermore, in vitro cytotoxicity test demonstrated that RC/CA films are cytocompatible, suggesting the potential advantage of using these biopolymeric films for biomaterial and biological applications.

     

Addition of Saturated Fatty Acids to Biodegradable Films: Effect on the Crystallinity and Viscoelastic Characteristics

Biodegradable films were produced by extrusion from blends of starch, glycerol and poly(butylene adipate co-terephthalate), a biodegradable polyester, with the addition of 1.5 % (wt/wt) saturated fatty acids (caproic, lauric or stearic). Films containing fatty acids had higher crystallinity than control films and the longer the carbon chain of the acid was, the more crystalline the film. Fatty acids with up to 12 carbon atoms did not alter the viscoelastic characteristic of the films. Further, the incorporation of fatty acids did not decrease the hydrophilicity of the films in comparison with the control film without a fatty acid.     

Feasibility study of the separation of chlorinated films from plastic packaging wastes

This study describes the possible separation of chlorinated plastic films (PVC and PVDC) from other heavy plastic packaging waste (PPW) by selective twist formation and gravity separation. Twists formation was mechanically induced in chlorinated plastic films, whereas twist formation did not occur in PS and PET films. After twist formation, all the films had the apparent density of less than 1.0 g/cm³ and floated in water even though the true density was more than 1.0 g/cm³. However, the apparent density of the PS and the PET films increased with agitation to more than 1.0 g/cm³, whereas that of chlorinated plastic films was kept less than 1.0 g/cm³. The main reason would be the air being held inside the chlorinated plastic films which was difficult to be removed by agitation. Simple gravity separation after twist formation was applied for artificial film with 10 wt.% of the chlorinated films and real PPW films with 9 wt.% of the chlorinated films. About 76 wt.% of the artificial PPW films and 75 wt.% of real PPW films after the removal of PP and PE were recovered as settling fraction with 4.7 wt.% and 3.0 wt.% of chlorinated plastic films, respectively. These results indicate that simple gravity separation process after twist formation can be used to reduce the chlorinated plastic concentration from mixed heavy PPW films.     

Biodegradation of pretreated polyethylene film by Pseudomonas aeruginosa AMB-CD-1

A comparative study evaluated the acid, alkali, and heat-treated polyethylene biodegradation efficiency of Pseudomonas aeruginosa AMB-CD-1. The polyethylene (PE) pieces were separately treated with heat (50°C), acid (1N HCl), and alkali (1N NaOH) and then washed with water before use. All the treated samples were analyzed through thermogravimetric analysis. In addition, weight and temperature changes during the decomposition reactions were also measured and determined. In these treatments, the PE films of heat-treated and acid-treated low-density polyethylene (LDPE) indicated more significant weight loss at 120°C (48.99% and 40.75%, respectively) as compared to their control or untreated PE and alkali-treated LDPE (21.84% and 24.68%, respectively). A biodegradation assay was then conducted with treated and untreated LDPE films with P. aeruginosa AMB-CD-1 strain. Fourier transform infrared spectroscopy analysis revealed that the heat or acid-pretreated samples with isolate AMB-CD-1 displayed peaks at 2922.84, 2923.97, and 1450.31, 874.22 cm⁻¹ for C–H stretching deformation vibration, CH₂ scissoring vibration, –CHO stretching, and strong alkyl structure, respectively. Furthermore, the new peaks with a significant difference at 2500–2000 cm⁻¹ (O═C═O, O–H stretching vibration: carboxylic acid) and 1500–1000 cm⁻¹ (–CHO and C═O stretching) were noticed in the infrared spectral range of LDPE degradation. Modifications in the functional group provided evidence that biodegradation had impacted the chemical structure of the LDPE film. Additionally, it was demonstrated that pretreating LDPE films with heat or acid could speed up their biodegradation.     

Degradation of a Terephthalate-containing Polyester by Thermophilic Actinomycetes and <Emphasis Type="Italic">Bacillus</Emphasis> Species Derived from Composts

We intended to find thermophilic degraders of terephthalate-containing Biomax^® films. Films in mesh bags were buried in composts (inside temperature: approximately 55–60 °C), resulting in the degradation of them in 2 weeks. Fluorescent microscopy of films recovered from composts showed that microorganisms gradually covered the surface of a film during composting. DGGE analysis of microorganisms on the composted film indicated the presence of Bacillus species as main species (approximately 80% of microbial flora) and actinomycetes (approximately 10–20%) as the second major flora. Isolation of Biomax^®-utilizing bacteria was focused on these two genera: two actinomycetes and one Bacillus species were isolated as pure best degraders from the composted polymer films, which were fragmented into small pieces. All the strains were thermophilic and identified, based on their 16S rDNA analyses. Degradation of polymer films was confirmed by (1) accelerated fragmentation of films in composts, compared with a control (no inoculum) and resultant decrease in molecular weights, (2) growth in a powdered Biomax^® medium, compared with a control without powdered Biomax^®, and (3) production of terephthalate in a powdered Biomax^® medium. In this way, we concluded that these bacteria were useful for degradation of thermostable Biomax^® products.     

Preparation and Optimization of Starch/Poly Vinyl Alcohol/ZnO Nanocomposite Films Applicable for Food Packaging

Pollution and destruction of the environment due to the accumulation of non-degradable plastics are some of the most important concerns in the world. A significant amount of this waste is related to the polymers used in food packaging. Therefore, experts in the food industry have been looking for suitable biodegradable alternatives to synthetic polymers. Preparing biocompatible and biodegradable films based on starch is a good choice. In this study, various factors affecting films of starch/polyvinyl alcohol (PVA)/containing ZnO nanoparticles such as the amount of starch, PVA, glycerol, and ZnO were evaluated by response surface methodology (RSM). Film formation by solvent casting method, mechanical properties, swelling, solubility, and water vapor permeability (WVP) were selected as responses of RSM. The results showed that hydrogen bonding interactions between polyvinyl alcohol and starch improved the film formation. The effect of glycerol and PVA content on the mechanical strength was contrary to each other. As the amount of PVA increased, the tensile strength first decreased and then increased. The value of WVP was for all Runs from 0 to 6.77?×?10^??8 g m^??1 s^??1 Pa^??1. Finally, films with high film formation, maximum tensile strength, and high elongation at break, minimum solubility, permeability, and swelling were optimized.