Effect of Varying Filler Concentration on Zinc Oxide Nanoparticle Embedded Chitosan Films as Potential Food Packaging Material

Prevailing scenario of non-biodegradable food packaging materials worldwide was the motivation for this research. More than half of the packaging materials used today are non-biodegradable and lack one or the other feature that keeps it from being an ideal food packaging material. Based on the current need of food grade packaging materials, the present study illustrates the amelioration of the properties of biodegradable chitosan films with the incorporation of zinc oxide (ZnO) nanoparticles in varying concentration. The ZnO nanoparticles (ZnONPs) used as fillers in the chitosan films were synthesized by supersaturation method. They were characterized using UV–visible spectrophotometry, X-ray diffraction and field emission scanning electron microscopy (FE-SEM). The particles were observed to be around 100–200 nm in size. The chitosan films with varying concentration of ZnONPs were synthesized and characterized using Fourier transform infrared spectroscopy and FE-SEM. The films were studied for their thermal stability, water vapor transmission rate (WVTR) and mechanical properties. The thermal stability, as determined by Thermo Gravimetric Analysis and Differential Scanning Calorimetry increased slightly with increasing percentage of embedded ZnONPs while a substantial decrease in WVTR was observed. Mechanical properties also showed improvements with 77% increment in tensile modulus and 67% increment in tensile strength. The antimicrobial activity of the films was also studied on gram positive bacterium Bacillus subtilis (B. subtilis) and gram negative bacterium Escherichia coli (E. coli) by serial dilution method. A twofold and 1.5-fold increment in the antimicrobial activity was observed for B. subtilis and E. coli, respectively, with increased ZnONPs concentration in the films from 0(w/w) to 2%(w/w). Films thus prepared can prove to be of immense potential in the near future for antimicrobial food packaging applications.     

Role of Hydrophilic and Hydrophobic Interactions in Structure Development of Zein Films

Zein has been studied for its potential as a biobased polymeric material. Due to the fact that films made exclusively from zein are brittle, composites of zein and oleic acid were prepared in our lab and formed into flexible films. Film properties were believed related to their structure. X-ray scattering measurements on zein films suggested the formation of layers along the plane of the film. Oleic acid seemed to play an important role in layer formation. However, X-ray measurements could not yield information on the nature of the interface between oleic acid and zein. Surface plasmon resonance (SPR) was used to further investigate interaction between zein and oleic acid. Dynamic adsorption of zein from alcoholic solutions onto hydrophilic and hydrophobic surfaces generated by self-assembled monolayers of 11-mercaptoundecanoic acid or 1-octanethiol was monitored by SPR. It was observed that zein had a greater affinity for hydrophilic than for hydrophobic surfaces under the prevalent experimental conditions. A mechanism for structure development of zein-oleate films was proposed based on these results and previous X-ray measurements. It is suggested that the structure development involves hydrophilic adsorption of fatty acids onto the zein surface followed by hydrophobic associations leading to a layered film structure organization.     

Effect of Gamma Radiation on the Properties of Crosslinked Chitosan Nano-composite Film

Chitosan nano-composite film crosslinked by citric acid and with glycerol as plasticizer and MgO as antibacterial agent was prepared by casting method. MgO nanoparticles were synthesized via calcination method in furnace at 500 °C for 4 h and characterized by X-ray diffraction and transmission electron microscope. The chitosan nano-composite film with composition chitosan/citric/glycerol/magnesium oxide (1 wt%:1 wt%:75 vol%:10 wt%) has high mechanical properties than other films. The effects of different irradiation doses on the mechanical, thermal and antibacterial activity were investigated. The tensile strength enhanced by increasing irradiation dose up to 10 kGy and the elongation negligible changed as irradiation dose increased. The thermal stability slightly increased up to dose 2.5 kGy then decreased with dose increment. The antimicrobial activity film was studied against white mulberry-borne bacterial pathogens either Gram positive or Gram negative bacteria and has positive impact of gamma irradiation on the antimicrobial activity. The use of the selected chitosan nano-composite film which irradiated by dose of 2.5 kGy and has magnesium oxide of average particle size 54.3 nm as new packaging materials found to improve storage quality and shelf-life of mulberry fruit.     

Experimental Investigation of Cellulose/Silver Nanocomposites Using In Situ Generation Method

Cellulose gel films were prepared by regeneration process using pre-cooled aq.(8 wt% LiOH + 15 wt% urea) mixture as solvent and ethyl alcohol as non solvent. The Terminus cattapa leaf extract diffused wet cellulose films were then dipped in 1–5 mM aq.AgNO₃ solutions to allow in situ generation of silver nanoparticles (AgNPs). Besides the in situ generation, some AgNPs were also formed outside the wet films in the solution. The AgNPs formed outside the films were observed under transmission electron microscope and scanning electron microscope. The nanocomposite films were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis and tensile test. The thermal stability of the composite films was lower than that of the matrix up to a temperature of ~300 °C and afterwards showed a reverse trend. The tensile strength of the nanocomposite films was found to be higher than the matrix but decreased with increasing concentration of aq.AgNO₃. The cellulose/AgNPs composite films showed good antibacterial activity against E. coli (gram positive) and Bacillus sp. (gram negative). Based on the aforementioned properties, the cellulose/AgNPs composite films can be considered for antibacterial packaging and medical applications.     

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.     

Compatible Blends of Zein and Polyvinylpyrrolidone

Blends of zein and polyvinylpyrrolidone (PVP) were compared based on their tensile properties, thermal properties and morphology. Zein was blended with polyvinylpyrrolidone of varying molecular weights (10, 55, and 1,300 kDa) and films were cast from ethanol solutions. Films cast using the higher molecular weight polymers showed an improvement in tensile strength, up to a 24% increase, compared to control. Differential scanning calorimetry data for the blends showed single T_m and T_g values of an intermediate value between those of zein and PVP control samples. Field emission scanning electron microscopy images show no obvious inhomogeneities, and confocal fluorescence microscopy showed no decreased uniformity in the PVP/zein films compared to control. Electrospun fibers of the zein/PVP blends were also obtained. These findings suggest that zein and polyvinylpyrrolidone combine to form a compatible blend, the first such blend of zein with a synthetic polymer.     

Biodegradable Water Soluble Copolymer for Antimicrobial Applications

Synthesis and characterization of novel biodegradable, water soluble and optically active DL-malic acid (DMA) and citric acid (CA) copolymers were studied for possible use as antibacterial agents. The copolymers were synthesized by direct bulk melt condensation in the absence of a catalyst above 150 °C. Characterization of obtained copolymers was carried out with the help of infrared absorption spectra, differential scanning calorimetry and thermo gravimetric analysis. The antibacterial activity of copolymers against bacteria was investigated. The results obtained shows the above copolymers possess a broad wound dressing activity against different types of bacteria and may be useful as antibacterial agents.     

Properties of Composite Panels Made from Tetra-Pak and Polyethylene Waste Material

The objective of this study was to evaluate some of the properties of experimental composite panels manufactured from waste packaging materials without using any additional binders. Particles from three types of materials, namely Tetra-Pak, food packaging films (FPEF) as recycled stretch wraps, and candy polyethylene wrappers (CPEW) were used at different ratios in the panels at a target density of 900 kg/m³. Modulus of rupture (MOR), screw holding strength and dimensional stability in the form of thickness swelling and water absorption of the panels were determined according to European (EN) standards. Based on the findings in this work it was determined that the ratio of different raw materials significantly influenced overall properties of the samples. The highest MOR value of 15.5 MPa was determined for the samples having 40 % Tetra-Pak and 60 % CPEW particles. Modulus of rupture values of the panels decreased with decreasing content of CPEW in the samples. The increased content of Tetra-Pak particles in the samples also resulted in reduction of their strength characteristics and dimensional stability. Properties of the samples considered in this work satisfied minimum requirements of typical particleboard stated in EN standards. It appears that such waste material would have potential to be used as raw material for value-added composite production using no adhesive in the panels and, therefore, such panels would possibly create significant ecological impact as green product.     

Thermoplastic Blends from Albumin and Zein: Plastic Formation and Mechanical Properties Including Modeling

The use of proteins in blending with traditional polymers in the formation of thermoplastics can produce plastics with properties that are superior to traditional petroleum-based plastics. We investigated the physical and thermal properties of albumin and zein thermoplastic blends plasticized with glycerol and mixed with varying amounts of low-density polyethylene (LDPE). Several mechanical models were utilized to determine how tensile properties will be altered when varying amounts of protein/LDPE were added into the thermoplastic blend. When analyzed for thermal properties, we found that as the amount of LDPE in the thermoplastic blend increased, the resulting plastic possessed thermal properties that were more similar to pure LDPE plastics. In terms of mechanical properties, comparison between the experimental data and model predictions points to a synergistic effect between albumin and LDPE that leads to higher modulus, while a potential lack of compatibility between zein and LDPE leads to a plastic with lower modulus. Based on our results, the use of albumin and zein proteins when blended with LDPE in the production of thermoplastics has potential use in the areas of medical and food packaging applications.     

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.

     

Investigation of Thermoplasticity of Zein and Kafirin Proteins: Mixing Process and Mechanical Properties

Conventional direct melt mixing technology was investigated on zein and kafirin, two vegetable proteins extracted, respectively, from maize and sorghum. A lab scale internal mixer has been used to thoroughly study the thermo-plasticization process of the proteins with several plasticizers. Different compositions were investigated under different processing conditions. In particular, the lengthy procedures of forming the protein/solvent/plasticizer solution followed by drying or the protein/plasticizer emulsion followed by the precipitation of the extrudable resin, reported in the literature for these systems, were avoided and the protein and plasticizer were directly fed into the mixer to obtain a plastic-like material. The effect of plasticizer type and content and mixing process variables on the mechanical properties was analyzed. Compression molded slabs were transparent, strong and flexible, with properties similar to the cast films reported in the literature, prepared with the same type of plasticizers. However, lower plasticizer content was sufficient to produce equally flexible films, proving an enhanced plasticization efficiency of the mixing process, as compared to casting.     

Influence of Glutaraldehyde Crosslinking and Alkaline Post-treatment on the Properties of Chitosan-Based Films

Depending on the modifications proposed, chitosan films present different characteristics, for instance correlated to hydrophilicity, chemical and mechanical properties. The aim of this study was to evaluate the influence of glutaraldehyde crosslinking and an alkaline post-treatment with NaOH on the characteristics of chitosan based films. Films were obtained by casting and characterized by thickness, swelling degree, mechanical and thermal properties and chemical structure. The water vapor permeability (WVP) was also evaluated for food packaging application. It was observed that crosslinking and NaOH post-treatment have great influence on the chitosan films characteristics. Crosslinking reduced the swelling degree of films and increased its fragility, whereas NaOH treatment also reduces the swelling degree and changes mechanical properties, acting in the same way as a crosslinker. The WVP analyses showed that the basic treatment could substitute the glutaraldehyde crosslinking for film water stability, without greatly compromising the barrier properties of chitosan based films.     

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.     

Mechanical,Barrier and Antioxidant Properties of Chitosan Films Incorporating Cinnamaldehyde

Chitosan films (CF) [1 and 2% w/v] alone and with cinnamaldehyde (CNE) [0.25, 0.5 and 1% v/v] were prepared using an emulsion method, and the obtained films were characterized in terms of water vapor permeability (WVP), water solubility and optical, mechanical and antioxidant properties. The incorporation of CNE at 1% (v/v) significantly decreased the water solubility of the film by approximately 4% for the 1 and 2% CF films, whereas the WVP increased (2.5–3.5 times). The incorporation of CNE (0.25 and 0.5%) into 2% CF significantly increased the tensile strength (TS) (62 and 34%, respectively) and the percent elongation (%E) values, 26, 30 and 52% for CF that contained 0.25, 0.5 and 1% CNE, respectively. The largest value of the elasticity modulus (EM) was observed for 2% CF with 0.25% CNE. All films exhibited a yellow appearance (b*), but the CNE content had a marked impact on the coloration of the films. The CNE recoveries of the CF films (1 and 2%) with 1% of CNE were high (43 and 67%). The antioxidant activities indicated that the incorporation of 1% CNE into CF films (1 and 2%) increased the antioxidant activity. The protective effects of the films with and without CNE on erythrocytes were very strong (36–72% hemolysis inhibition). These results suggest there are potential applications for CF-CNE films as active packaging for the preservation of food products.     

Biodegradation of Coproducts from Industrially Processed Corn in a Compost Environment

Information pertaining to biodegradability of renewable polymeric material is critical for the design and development of single-use biodegradable consumer products. The rate and extent of biodegradation of corn fiber, corn zein, cornstarch, distillers grain, and corn gluten meal were evaluated in compost environments under variable temperature, pH, and moisture conditions. Generally, composts with higher temperature (40°C), neutral pH (7.0), and 50%–60% moisture appeared to be ideal for corn coproduct biodegradation, particularly for corn gluten meal and corn zein. Low moisture conditions slowed biodegradation considerably, but degradation rates improved when moisture content increased up to 60%. Thereafter, increased moisture particularly slowed the degradation of corn gluten meal and corn zein, whereas cornstarch degradation remained unaffected. At low pH (4.0) and high pH (11.0) the rate of degradation of most coproducts was slowed somewhat. Cornstarch degradation was slower at pH 7.0, but degradation improved with increased temperatures. Increase in compost temperature from 25 to 40°C (in 5°C increments) also improved biodegradation of corn fiber and distillers grain. Addition of 1% urea to compost as a nitrogen source decreased the extent of biodegradation nearly 40% for corn gluten meal and corn zein, and 20% for cornstarch samples. Treatment of compost with 0.02% azide inhibited biodegradation of all coproducts, suggesting that the presence of metabolically active microbial cells is required for effective degradation of biobased materials in a compost environment.     

Preparation and Properties of Propylene Glycol Plasticized Wheat Protein Isolate Novel Green Films

Novel bio-based green films were prepared using wheat protein isolate (WPI) by solution casting method using Propylene Glycol as a plasticizer for packaging applications. The effect of the plasticizer content (10, 15, 20 and 25 wt%) on mechanical properties (tensile strength, young’s modulus and  % of elongation) was investigated. A thermal degradation and phase transition of the prepared WPI was assessed by means of TGA and DSC analysis. The results showed that the tensile strength and young’s modulus decreased and  % of elongation increased with increasing PG content. The ATR-FTIR and SEM were used for structural characterization and morphology of the films, respectively. FTIR studies reveals that the intensity of the bands corresponding to the amide groups increases with increasing PG content tending to increase protein–PG interactions. Further, the glass transition temperature was decreased and the thermal stability of the WPI was found to be increased by plasticization. The overall thermal stability of the films was improved and is attributed to the increase in mobility of the polymer chains.     

Transfer of Graphene CVD to Surface of Low Density Polyethylene (LDPE) and Poly(butylene adipate-co-terephthalate) (PBAT) Films: Effect on Biodegradation Process

Here, the influence of graphene as a coating on the biodegradation process for two different polymers is investigated, poly(butylene adipate-co-terephthalate) (PBAT) (biodegradable) and low-density polyethylene (LDPE) (non-biodegradable). Chemical vapor deposition graphene was transferred to the surface of two types of polymers using the Direct Dry Transfer technique. Polymer films, coated and uncoated with graphene, were buried in a maturated soil for up to 180 days. The films were analyzed before and after exposure to microorganisms in order to obtain information about the integrity of the graphene (Raman Spectroscopy), the biodegradation mechanism of the polymer (molecular weight and loss of weight), and surface changes of the films (atomic force microscopy and contact angle). The results prove that the graphene coating acted as a material to control the biodegradation process the PBAT underwent, while the LDPE covered by graphene only had changes in the surface properties of the film due to the accumulation of solid particles. Polymer films coated with graphene may allow the production of a material that can control the microbiological degradation, opening new possibilities in biodegradable polymer packaging. Regarding the possibility of graphene functionalization, the coating can also be selective for specific microorganisms attached to the surface.     

A Novel Biodegradable Green Poly(l-Aspartic Acid-Citric Acid) Copolymer for Antimicrobial Applications

Poly (l-aspartic acid-citric acid) green copolymers were developed using thermal polymerization of aspartic acid (ASP) and citric acid (CA) followed by direct bulk melt condensation technique. Antibacterial properties of copolymer of aspartic acid based were investigated as a function of citric acid content. This study is focused on the microorganism inhibition performance of aspartic acid based copolymers. Results showed that inhibition properties increase with increasing citric acid content. Characterization of obtained copolymers was carried out with the help of infrared absorption spectra (FTIR), x-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA). The antibacterial activity of copolymers against bacteria like E-coli, Bacillus and pseudomonas was investigated. The copolymers showed excellent antimicrobial activities against three types of microorganisms. Overall studies indicated that the above copolymers possess a broad wound dressing activity against above three types of bacteria and may be useful as antibacterial agents.     

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.

     

Material and energy recovery in integrated waste management systems. An evaluation based on life cycle assessment

This paper reports the environmental results, integrated with those arising from mass and energy balances, of a research project on the comparative analysis of strategies for material and energy recovery from waste, funded by the Italian Ministry of Education, University and Research. The project, involving the cooperation of five University research groups, was devoted to the optimisation of material and energy recovery activities within integrated municipal solid waste (MSW) management systems. Four scenarios of separate collection (overall value of 35%, 50% without the collection of food waste, 50% including the collection of food waste, 65%) were defined for the implementation of energetic, environmental and economic balances. Two sizes of integrated MSW management system (IWMS) were considered: a metropolitan area, with a gross MSW production of 750,000 t/year and an average province, with a gross MSW production of 150,000 t/year. The environmental analysis was conducted using Life Cycle Assessment methodology (LCA), for both material and energy recovery activities. In order to avoid allocation we have used the technique of the expansion of the system boundaries. This means taking into consideration the impact on the environment related to the waste management activities in comparison with the avoided impacts related to the saving of raw materials and primary energy. Under the hypotheses of the study, both for the large and for the small IWMS, the energetic and environmental benefits are higher than the energetic and environmental impacts for all the scenarios analysed in terms of all the indicators considered: the scenario with 50% separate collection in a drop-off scheme excluding food waste shows the most promising perspectives, mainly arising from the highest collection (and recycling) of all the packaging materials, which is the activity giving the biggest energetic and environmental benefits. Main conclusions of the study in the general field of the assessment of the environmental performance of any integrated waste management scheme address the importance of properly defining, beyond the design value assumed for the separate collection as a whole, also the yields of each material recovered; particular significance is finally related to the amount of residues deriving from material recovery activities, resulting on average in the order of 20% of the collected materials.