Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

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.     

Influence of the Concentrations of Chitosan and Glycerol on Edible Film Properties Showed by Response Surface Methodology

The individual and interactive effects of glycerol and chitosan concentrations on edible film properties were investigated using response surface methodology. The results of ANOVA indicated that all the independent variables exhibited significant effect on the film properties. Chitosan concentration had a positive effect on CO₂ permeability and negative effect on O₂ while the glycerol concentration had a positive effect on permeability to both gases. Regarding water vapor permeability, the chitosan concentration had a negative effect, whereas the glycerol had no influence. Moreover, both chitosan and glycerol concentration influenced the elongation at break point (%A), and only glycerol concentration had a significant effect on tensile strength. Optimization by desirability approach was carried out on the independent variables to get the optimum levels within the experimental conditions. It was found that 1.5 % of chitosan and 25 % of glycerol (wt/wt of chitosan) retarded respiration and showed a strong permeability to water vapor.     

Improvement of Physico-Mechanical Properties of Photo-Cured Chitosan Films with Ethylene Glycol Dimethacrylate and (2-Hydroxyethyl) Methacrylate

Chitosan, a natural polymer, was prepared by deacetylation of chitin which was obtained from dried prawn shell and was characterized. Thin chitosan film of chitosan was prepared by casting method from 0.2 % chitosan in 2 % acetic acid solution. Five formulations were developed with ethylene glycol dimethacrylate and (2-hydroxyethyl) methacrylate along with photo-initiator, Darocur-1664 (4 %). The chitosan film was soaked in the formulations at different soaking times and irradiated under UV-radiation at different intensities for the improvement of its physical and mechanical properties. The cured chitosan films were then subjected to various mechano-chemical tests like tensile strength, elongation at break, polymer loading, water absorption and gel content. The formulation containing 30 % ethylene glycol dimethacrylate and 66 % (2-hydroxyethyl) methacrylate showed the best performance at the 30th UV pass of UV-radiation for 3 min soaking time.     

Biodegradation by Composting of Surface Modified Starch and PVA Blended Films

Several starch/PVA/glycerol polymer blends were prepared by a solution casting technique and examined for biodegradation by composting over 45 days. Within this time frame, the starch and glycerol components were fully degraded, leaving the PVA component essentially intact. The lowest PVA content film (20%) was selected as a polymer with enough PVA to impart important physical characteristics, but also enough starch to be considered biodegradable. The film characteristics were further improved by surface modification with chitosan. This modification did not interfere with the biodegradation of the starch component. Furthermore, there was slight evidence that PVA biodegradation had been initiated in composted, surface modified starch/PVA blends.     

Characterization of Urea Encapsulated by Biodegradable Starch-PVA-Glycerol

The influence of the blending ratio of biodegradable starch/polyvinyl alcohol (PVA)/glycerol in encapsulating urea has been investigated. It is found that water absorption capacity increased approximately 135 % as the amounts of starch, PVA and glycerol in the composite film increase. Therefore, the swell ability of the composite film is increased and the urea is released from the composite film in the wet environment. The FTIR shows that the urea had been encapsulated successfully in the composite films. Moreover, the soil burial biodegradation results indicated that the biodegradability of the starch/PVA/glycerol/urea composite film strongly depended on the PVA proportion in the composite film matrix. The DSC results show that the higher the amount of PVA in the composite film, the less change of the melting enthalpy value. The crystalline region of PVA remains after biodegradation.     

Properties of Poly(Vinyl Alcohol)/Chitosan Nanocomposite Films Reinforced with Oil Palm Empty Fruit Bunch Amorphous Lignocellulose Nanofibers

The objective of this study was to investigate the properties of poly(vinyl alcohol)/chitosan nanocomposite films reinforced with different concentration of amorphous LCNFs. The properties analyzed were morphological, physical, chemical, thermal, biological, and mechanical characteristics. Oil palm empty fruit bunch LCNFs obtained from multi-mechanical stages were more dominated by amorphous region than crystalline part. Varied film thickness, swelling degree, and transparency of PVA/chitosan nanocomposite films reinforced with amorphous part were produced. Aggregated LCNFs, which reinforced PVA/chitosan polymer blends, resulted in irregular, rough, and uneven external surfaces as well as protrusions. Based on XRD analysis, there were two or three imperative peaks that indicated the presence of crystalline states. The increase in LCNFs concentration above 0.5% to PVA/chitosan polymer blends led to the decrease in crystallinity index of the films. A noticeable alteration of FTIR spectra, which included wavenumber and intensity, was obviously observed along with the inclusion of amorphous LCNFs. That indicated that a good miscibility between amorphous LCNFs and PVA/chitosan polymer blend generated chemical interaction of those polymers during physical blending. Reinforcement of PVA/chitosan polymer blends with amorphous LCNFs influenced the changes of T_g (glass transition temperature), T_m (melting point temperature), and T_max (maximum degradation temperature). Three thermal phases of PVA/chitosan/LCNFs nanocomposite films were also observed, including absorbed moisture evaporation, PVA and chitosan polymer backbone structural degradation and LCNFs pyrolysis, and by-products degradation of these polymers. The addition of LCNFs 0.5% had the highest tensile strength and the addition of LCNFs above 0.5% decreased the strength. The incorporation of OPEFB LCNFs did not show anti-microbial and anti-fungal properties of the films. The addition of amorphous LCNFs 0.5% into PVA/chitosan polymer blends resulted in regular and smooth external surfaces, enhanced tensile strength, increased crystallinity index, and enhanced thermal stability of the films.     

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.     

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.     

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.

     

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.     

Preparation and Thermo-Mechanical Characterization of Chitosan Loaded Methylcellulose-Based Biodegradable Films: Effects of Gamma Radiation

Chitosan (0.1–1%, w/w), dissolved in 2% acetic acid solution, was added into 1% methylcellulose (MC)-based formulation containing 0.5% vegetable oil, 0.25% glycerol and 0.025% Tween^?80. Films were prepared by casting. Puncture strength (PS), puncture deformation (PD), viscoelasticity coefficient and water vapour permeability (WVP) of the films were measured. The PS value of 312 N/mm was observed for MC-based films containing 0.25% chitosan. Values of PD, viscoelasticity coefficient and WVP of these films were 5.0 mm, 44.1%, and 6.0 g mm/m² day kPa, respectively. The MC-based films containing 0.25% chitosan were also exposed to gamma radiation (0.5–50 kGy). The PS of the treated films decreased significantly from 312 at 0 kGy to 201 N/mm when treated at a dose of 50 kGy. However, WVP values were not affected by increasing irradiation the dose used. The Fourier Transform Infrared spectroscopy supported the molecular interactions due to addition of chitosan in MC-based films. Thermo gravimetric analysis and differential scanning calorimetric experiments showed that thermal properties of the films were significantly improved by chitosan loading. Surface topography of the films was studied by scanning electron microscopy and found rougher due to chitosan addition.     

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.     

Novel Biodegradable Cast Film from Carbon Dioxide Based Copolymer and Poly(Lactic Acid)

Poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) blends with different levels of chain extender were prepared and cast into films. The effect of chain extender on the mechanical, thermal and barrier properties of the films were investigated. With the inclusion of the chain extender, the compatibility and interfacial adhesion between the two polymer phases were significantly improved by a mean of forming a PLA–chain extender–PPC copolymer. Reactions between the chain extender, PLA and PPC were observed through FTIR study. SEM study also confirmed the improved compatibility and interfacial adhesion. The elongation at break of the compatibilized film with optimal amount of chain extender showed dramatic increase by up to 1940 %. DSC studies revealed that chain extender hindered the crystallization of the film which explained the decrease in both water and oxygen barrier when adding chain extender. PLA was found to be able to enhance both oxygen and water barrier of the blend as compared to neat PPC, while in the case of the blend with chain extender, oxygen and water barrier properties exhibited reduction at the beginning. However, when increasing chain extender concentration, these two barrier performance exhibited an upward trend. It was found that PLA/PPC blend showed much better oxygen barrier property than both parent polymers, which can be ascribed to the acceleration effect of PPC on the crystallization of PLA.     

Effect of Hexadecyl Lactate as Plasticizer on the Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) Films for Food Packaging Applications

In this study, poly(l-lactide) (PLA) films were fabricated by melt processing and the plasticizing effect of hexadecyl lactate (HL) (0, 5, 7.5, 10, and 12.5 wt% on PLA were investigated by scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis, tensile, transparency, and water vapor permeability tests. The SEM analysis revealed that PLA with 10 wt% HL appeared uniform with extra small bumps, confirmed the interaction between PLA and HL. The thermal analysis revealed a glass transition temperature of 57.4 °C for neat PLA film, but the addition of HL elicited a decrease in the temperature of the peak (43.8 °C). The incorporation of plasticizer into PLA resulted in the increase of elongation at break, as well as the decrease of tensile strength and tensile modulus. Even though a decrease in transparency was recorded, the PLA/HL blend films appeared transparent by visually observation. The water vapor permeability of PLA/HL blend films increased with the increase of HL. The PLA/HL blend films could effectively extend the shelf-life of fresh-cut pears as the commercial low density polyethylene films. The results indicated that the properties of PLA films can be modified with the addition of HL and PLA/HL blend films could serve as an alternative as food packaging materials to reduce environmental problems associated with synthetic packaging films.     

Properties of Starch/PVA Blend Films Containing Citric Acid as Additive

Starch/polyvinyl alcohol (PVA) blend films were prepared successfully by using starch, polyvinyl alcohol (PVA), glycerol (GL) sorbitol (SO) and citric acid (CA) for the mixing process. The influence of mixing time, additional materials and drying temperature of films on the properties of the films was investigated. With increase in mixing time, the tensile strength (TS), elongation (%E), degree of swelling (DS) and solubility (S) of the film were equilibrated. The equilibrium for TS, %E, DS and S value was 20.12 MPa, 36.98%, 2.4 and 0.19, respectively. The mixing time of equilibrium was 50 min. TS, %E, DS and S of starch/PVA blend film were examined adding glycerol (GL), sorbitol (SO) and citric acid (CA) as additives. At all measurement results, except for DS, the film adding CA was better than GL or SO because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA and additives. Citric acid improves the properties of starch/PVA blend film compared to glycerol and sobitol. When the film was dried at low temperature, the properties of the films were clearly improved because the hydrogen bonding was activated at low temperature.     

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.     

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.     

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.     

Preparation and Properties of Carboxymethyl Cellulose (CMC)/Sodium alginate (SA) Blends Induced by Gamma Irradiation

Carboxymethyl Cellulose (CMC)/Sodium alginate (SA) blends have been prepared by casting solution method. The effect of different irradiation doses (2.5, 5, 10, 15, and 20 kGy) of gamma rays on the physical properties of the CMC/SA blend containing different ratios of SA (20, 30, and 40 %) such as gel fraction (%) and swelling (%) of CMC/SA blends were investigated. It was found that the gel fraction increases with increasing irradiation dose up to 20 kGy while the swelling of CMC/SA blend films tends to increase with increasing SA content and reduced with increasing irradiation doses. Mechanical and thermal properties of the blend films were improved when CMC content increased and with increasing irradiation dose up to 20 kGy. Morphology of the blend was examined by SEM, which indicates compatibility between CMC and SA. The blend rich in SA content possessed good antimicrobial activity against Gram +ve Bacteria (Bacillus subtilis).