Biodegradable films made from low density polyethylene (LDPE), wheat starch and soluble starch for food packaging applications. Part 2

Blends of LDPE and wheat or soluble starch were extruded, hot pressed and studied, after conditioning at various relative humidities, with regard to their mechanical properties and gas/water permeabilities before and after storage. Several theoretical and semiempirical calculations for mechanical properties and gas permeability are applied and possible interpretations are provided for occasionally observed deviations between the experimental and the theoretical values. Some of the semiempirical models predicted reasonably well the mechanical behaviour of the films. The presence of starch, at contents >30%, had an adverse effect on the mechanical properties of LDPE/starch blends. The degradability of several LDPE/starch blends and the accompanying changes in their mechanical properties are also assessed. Gas permeability and water vapour transmission rate increased proportionally with the starch content in the blend.     

Edible films made from natural resources; microcrystalline cellulose (MCC), methylcellulose (MC) and corn starch and polyols-Part 2

Aqueous blends of microcrystalline cellulose (MCC) or methyl cellulose (MC) and corn starch with or without polyols were extruded, hot pressed and studied, after their conditioning at different relative humidities, in terms of their thermal, mechanical and water and gas permeability properties. An increase in water or polyol content showed a considerable increase in percentage elongation but also a decrease in the tensile strength of films. The presence of high cellulose contents increased the tensile strength and decreased the water vapour transmission of films. The development of crystallinity with time resulted in a decrease of both gas and water permeability. Several semiempirical models for calculation of gas permeability and tensile strength and tensile and flexural moduli were applied. The obtained values were compared to those experimentally determined and with the ones reported in the literature. On several occasions, quite significant discrepancies were found which were attributed to differences in molecular weight, percentage crystallinity and polymorphism.     

Green composite films prepared from cellulose,starch and lignin in room-temperature ionic liquid

A series of novel biobased composite films derived from cellulose, starch and lignin were prepared from an ionic liquid (IL), 1-allyl-3-methylimidazolium chloride (AmimCl) by coagulating in a nonsolvent condition. The ionic liquid can be recycled with a high yield and purity after the green film was prepared. The uniform design method was applied to investigate mechanical properties of the biobased composite films. The effect of each component and their associated interactive effects were investigated. The experimental results showed that contents of cellulose, lignin and starch had a significant influence on the mechanical properties of composite films. The composite films showed relatively excellent mechanical properties in dry and wet states owing to the mutual property supplement of different components. The composite films were characterized via FT-IR, X-ray diffraction (XRD) and scanning electron microscope (SEM). Their thermal stability and gas permeability were also investigated, and the results showed that the composite films had good thermal stability and high gas barrier capacity and give a CO₂:O₂ permeability ratio close to 1.     

Processing and characterization of porous structures from chitosan and starch for tissue engineering scaffolds

Natural biodegradable polymers were processed by different techniques for the production of porous structures for tissue engineering scaffolds. Potato, corn, and sweet potato starches and chitosan, as well as blends of these, were characterized and used in the experiments. The techniques used to produce the porous structures included a novel solvent-exchange phase separation technique and the well-established thermally induced phase separation method. Characterization of the open pore structures was performed by measuring pore size distribution, density, and porosity of the samples. A wide range of pore structures ranging from 1 to 400 microm were obtained. The mechanisms of pore formation are discussed for starch and chitosan scaffolds. Pore morphology in starch scaffolds seemed to be determined by the initial freezing temperature/freezing rate, whereas in chitosan scaffolds the shape and size of pores may have been determined by the processing route used. The mechanical properties of the scaffolds were assessed by indentation tests, showing that the indentation collapse strength depends on the pore geometry and the material type. Bioactivity and degradation of the potential scaffolds were assessed by immersion in simulated body fluid.     

Nano clay reinforced PCL/starch blends obtained by high energy ball milling

Sodium montmorillonite was incorporated into a poly(ε-caprolactone)–starch blend by means of a ball mill. The structural organization and physical (mechanical, thermal and barrier) properties were analyzed and correlated with the milling conditions. Scanning electron microscopy and X-ray characterization show that the milling process can improve the compatibilization between the PCL and the starch phases, while promotes the dispersion of clay minerals at nanometric level. The milling time strongly influences the mechanical and barrier properties. In particular, the best results in terms of elastic modulus and permeability coefficient were achieved with a complete delamination of the pristine clay structure. In summary, the milling process not only has demonstrated to be a promising compatibilization method for immiscible PCL–starch blends, but it can be also used to improve the dispersion of nanoparticles into the polymer blends.     

Extrusion of pectin/starch blends plasticized with glycerol

The microstructural and thermal dynamic mechanical properties of extruded pectin/starch/glycerol (PSG) edible and biodegradable films were measured by scanning electron microscopy (SEM) and thermal dynamic mechanical analysis (TDMA). SEM revealed that the temperature profile (TP) in the extruder and the amount of water present during extrusion could be used to control the degree to which the starch was gelatinized. TDMA revealed that moisture and TP during extrusion and by inference the amount of starch gelatinization had little effect on the mechanical properties of PSG films. Furthermore, TDMA revealed that PSG films underwent a glass transition commencing at about −50°C and two other thermal transitions above room temperature. Finally, it was concluded that the properties of extruded PSG films were comparable to those cast from solution.     

Preparation of poly(l-lactide) blends and biodegradation by Lentzea waywayandensis

As a biodegradable polyester, polylactide (PLA) has applications as a packaging material, in biomedical fields and tissue engineering. With the dual aim of improving its properties and biodegradability, PLA was blended with other polymers such as gum arabic, thermoplastic starch, microcrystalline cellulose, polyethylene glycol and polyhydroxy butyrate in 1:1 (w/w) by melt-blending technique. The thermal properties of the blends were compared with that of unblended PLA by thermo-gravimetric analysis. Biodegradation using Lentzea waywayandensis was in the order of PLA–gum arabic?>?PLA–thermoplastic starch?>?PLA(virgin)?>?PLA–microcrystalline cellulose?>?PLA–polyethylene glycol?>?PLA–polyhydroxy butyrate. Weight loss of 99?% (w/w) was noted within 4?days for PLA–thermoplastic starch and PLA-gum arabic blends.     

Mechanical Properties of Thermo-moulded Biofilms in Relation to Proteins/Starch Interactions

The effects of hydrophilic and hydrophobic characteristics of proteins on the interactions with corn starch were investigated in this study. The model system included corn starch and proteins, i.e. zein, gliadin, gluten, soy protein and rapeseed protein. The blend films were prepared by thermo-moulding in gentle conditions at 70 °C in order to avoid starch gelatinization, with respect to water content, and avoid protein denaturation. The effects of different kinds of proteins on structure and mechanical behaviour of blend biomaterials were characterised by scanning electron microscopy (SEM) and tensile test, respectively. The effects of different kinds of proteins on intermolecular interactions between proteins and starch were investigated by dynamical mechanical thermal analysis. Based on the solubility measurement results, almost all protein films showed the similar solubility to the natural protein powders, resulting from the weak influence of mild thermo-moulding treatment on protein inner structure. Different morphologies were observed for different proteins and corresponding blends, which are relatively loose protein architecture that appeared for hydrophobic protein and blend films, and uniform and densely packed architecture for hydrophilic ones. Moreover, different mechanical behaviours were obtained for different proteins and corresponding blends. No significantly increased strength for hydrophilic protein blends with starch added can be explained that there is weak intermolecular interaction between both components based on SEM observation. However, the addition of corn starch granules in hydrophobic protein networks was assumed that starch destroyed or weakened the protein network, resulting in the decrease of mechanical strength.     

Study of the thermal stability of blends based on synthetic polymers and natural polysaccharides

The thermal properties of biodegradable blends based on polyethylene and natural polysaccharides prepared in an extruder were studied by thermogravimetric analysis. It was demonstrated that polymer blends are characterized by a higher thermal degradation temperature than that of the initial polysaccharides. The effects of photooxidative treatment were investigated, as well as the influence of polyethylene glycol on the thermal stability of the studied polymer blends.     

The plasticizing effect of alginate on the thermoplastic starch/glycerin blends

Corn starch and corn starch–alginate (5–15%) blends plasticized with 35% glycerin were prepared, water was intentionally excluded from the formulations. Torque rheometry measurements were carried out during the processing of the blends in a batch counterrotating twin screw mixer. A progressive decrease in the plasticization energy of the blends was observed as the alginate content was increased, with a 5-fold decrease for the blend with the higher alginate content (15%). The steady state torque of the plasticized melted blends also showed a decrease as alginate content was increased; with a drastic drop occurring for the formulation with higher alginate content. After mixing, test specimens for mechanical, thermal and microstructural testing were made by compression molding. A decrease in the elastic properties and an increase in elongation at break and impact resistance was observed when alginate content was increased in the blends. The transition of the materials towards a more viscous behavior, as alginate content was increased, was confirmed by differential scan calorimetric analysis. For the corn starch–alginate blends glass transitions were detected in the temperature range −60 to −90 °C. Scanning electron microscopy was used to examine the morphology of cryofractured surfaces of the molded test specimens. A reduction of the granular crystalline structures typical of corn starch was observed as alginate content was increased in the blends. The experimental evidence presented in this work indicates that, when water is excluded from thermoplastic corn starch preparation, alginate acts synergistically with glycerin increasing the degree and efficiency of the plasticization process.     

Fabrication and Characterization of Native and Oxidized Potato Starch Biodegradable Films

The need to replace conventional polymers due to environmental pollution caused by them has led to increased production of biodegradable polymers such as starch. Thus, the application possibilities of starch have increased. In this study, we produced and characterized biodegradable films derived from native and oxidized potato starch. The film-forming solution was prepared with different concentrations of extracted starch (native or oxidized) and a plasticizer (glycerol or sorbitol). Then, the mechanical, barrier, morphological, and structural properties of the films were characterized. The moisture content of the films varied from 15.35?±?1.31 to 21.78?±?0.49%. The elastic modulus of the films ranged from 219?±?14.97 to 2299?±?62.91 MPa. The film of oxidized starch plasticized with sorbitol in the lowest content was the most resistant and flexible; moreover, this film also presented lower water vapor permeability and low solubility in water. Fourier-transform infrared spectroscopic analysis of the biodegradable films indicated the presence of same functional groups as those of starch with bands in the same regions. The film thickness was lower for the films plasticized with glycerol whereas the color variation (Δ?) was lower for the ones plasticized with sorbitol. In case of both plasticizers, the increase in their content decreased the Δ? value. All the biodegradable films presented stability against water absorption owing to their low solubility in water. Morphological evaluation revealed the presence of partially gelatinized starch granules in the films. The roughness parameter (Rq) of the films varied from 3.39 to 10.9 nm, indicating that their surfaces are smooth. X-ray diffraction studies showed a B-type pattern for the starches, which is representative of tubers. Further, the films present higher relative crystallinity (RC) compared to the starches. The biodegradable starch films are uniform, transparent and with low solubility in water. The oxidation of starch and use of sorbitol as a plasticizer resulted in improved properties of the starch films, which is suitable for application.     

Chitosan and gelatin based edible films: state diagrams, mechanical and permeation properties

Films of chitosan and gelatin were prepared by casting their aqueous solutions (pH≈4.0) at 60°C and evaporating at 22 or 60°C (low- and high-temperature methods, respectively). The physical (thermal, mechanical and gas/water permeation) properties of these composite films, plasticized with water or polyols, were studied. An increase in the total plasticizer content resulted in a considerable decrease of elasticity modulus and tensile strength (up to 50% of the original values when 30% plasticizer was added), whereas the percentage elongation increased (up to 150% compared to the original values). The low-temperature preparation method led to the development of a higher percentage renaturation (crystallinity) of gelatin which resulted in a decrease, by one or two orders of magnitude, of CO₂ and O₂ permeability in the chitosan/gelatin blends. An increase in the total plasticizer content (water, polyols) of these blends was found to be proportional to an increase in their gas permeability.     

Preparation and characterization of konjac glucomannan/poly(diallydimethylammonium chloride) antibacterial blend films

A novel antibacterial film was prepared by blending konjac glucomannan (KGM) and poly(diallydimethylammonium chloride) (PDADMAC) in an aqueous system. The antibacterial activity of the films against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa, and Saccharomyces were measured by the halo zone test and the double plate method. The films exhibited an excellent antibacterial activity against B. subtilis and S. aureus but not against E. coli, P. aeruginosa or Saccharomyces. The miscibility, morphology, thermal stability, water vapour permeability and mechanical properties of the blend films were investigated by density determination, SEM, ATR-IR, XRD, DSC, TGA, WVA and tensile tests. The results of density determination predicted that the blends of KGM and PDADMAC were miscible when the PDADMAC content was less than 70 wt%. Moreover, SEM and XRD confirmed the result. ATR-IR showed that strong intermolecular hydrogen bonds and electrostatic interactions occurred between KGM and PDADMAC in the blends. The tensile strength and the break elongation of the blends were improved largely to 106.5 MPa and 32.04% and the water vapour permeability decreased when the PDADMAC content was 20 wt%. The thermal stability of the blends was higher than pure KGM. The blends should be good antibacterial materials.     

Preparation and characterization of biodegradable poly-3-hydroxybutyrate-starch blend films

Bacterial polyesters have attracted much attention as biodegradable biocompatible polymers. Poly-3-hydroxybutyrate, a microbially produced thermoplastic, has similar material properties to polypropylene. Its potential application as biodegradable and biocompatible plastics is well documented. However, due to high cost it is used mainly in biomaterials for medical applications. Materials with useful properties may result from blending bacterial polyhydroxybutyrate (PHB) with other polymers. In this paper, the compatibility of PHB with starch for improved properties and cost reduction is discussed. The thermal and mechanical properties of the blended films were studied by means of thermogravimetry, differential scanning calorimetry and an automated material testing system. The results revealed that blend films had a single glass transition temperature for all the proportions of PHB:starch tested. The nature of all combinations was found to be crystalline. The tensile strength was optimum for the PHB:starch ratio of 0.7:0.3 (wt/wt). The variation in tensile strength, Young's modulus, extension needed to break, thermal stability, glass transition temperature, melting temperature, for the different proportions of PHB:starch are discussed.     

Effect of gelatinization and additives on morphology and thermal behavior of corn starch/PVA blend films

The blend films of ungelatinized and gelatinized starch/polyvinyl alcohol (PVA) were prepared with a solution casting method by the introduction of additives (glycerol/urea) or not. The phase morphologies and thermal behaviors of the blends were carefully analyzed. A droplet phase was observed in the blends containing ungelatinized starch and a laminated phase was observed in the blends containing gelatinized starch. For both ungelatinized and gelatinized starch/PVA blends, the melting temperature (T(m)) (210-230°C) of PVA was detected, and the T(m) of gelatinized starch/PVA blends was higher than that of the ungelatinized starch/PVA blends. Blend films containing 16.8wt% of glycerol or urea exhibited a decreased T(m). The introduction of additives (glycerol or urea) reduced the decomposition onset temperature of the blend films. These various morphologies and thermal behaviors could be attributed to the different hydrogen bonding interaction characteristics between starch and polyvinyl alcohol at different conditions.     

Characterization of films made with chayote tuber and potato starches blending with cellulose nanoparticles

The aim of this study was to characterize chayotextle starch films reinforced with cellulose (C) and cellulose nanoparticle (CN) (at concentrations of 0.3%, 0.5%, 0.8% and 1.2%), using thermal, mechanical, physicochemical, permeability, and water solubility tests. C was acid-treated to obtain CN. The films were prepared by casting; potato starch and C were used as the control. The solubility of the starch films decreased with the addition of C and CN compared with its respective film without C and CN. No statistical difference (α = 0.05) was found in the films added with different concentrations of C and CN. In general, the mechanical properties were improved with the addition of C and CN, and higher values of tensile strength and elastic modulus were determined in the films reinforced with CN. The melting temperature and enthalpy increased with the addition of C and CN, and the values of both thermal parameters were higher in the films with CN than with C; the enthalpy value of the film decreased when the concentration of C or CN increased in the composite. Low concentration of C and CN is better distributed in the matrix film. The addition of C and CN in the starch films improved some mechanical, barrier, and functional properties.     

Biodegradation of polyurethane acrylate with acrylated epoxidized soybean oil blend elastomers by Chaetomium globosum

This paper studies the biodegradation features of a novel blend of polyurethane acrylate-acrylated epoxidized soybean oil-based cross-linked polyurethane elastomers in the presence of the soft-rot fungus Chaetomium globosum. After the specimens were incubated at 28 °C for 90 and 130 days, the degree of fungal damage was measured by analysis of weight loss and mechanical properties. The biodegradation of the films was also evidenced by SEM and FTIR spectroscopic studies. After fungal attack, the FTIR spectra indicate a degradation of urethane and ester groups of the polyurethane and especially of the ester groups from the modified soybean oil part. The polyurethane blend films exposed to fungal attack suffered a loss in strength of up to 55% and a loss in elongation of up to 80%, depending on the content of acrylated epoxidized soybean oil. The biodegradation of the blends was also confirmed by SEM analyses. The biodegradation results show that samples with a high content of acrylated epoxidized soybean oil are more biodegradable than mere polyurethane acrylate. These biodegradable polymer blends present an optimum balance of physical properties and biodegradable properties with the potential for application as eco-friendly biomaterials.     

Properties and Antioxidant Action of Actives Cassava Starch Films Incorporated with Green Tea and Palm Oil Extracts

There is an interest in the development of an antioxidant packaging fully biodegradable to increase the shelf life of food products. An active film from cassava starch bio-based, incorporated with aqueous green tea extract and oil palm colorant was developed packaging. The effects of additives on the film properties were determined by measuring mechanical, barrier and thermal properties using a response surface methodology design experiment. The bio-based films were used to pack butter (maintained for 45 days) under accelerated oxidation conditions. The antioxidant action of the active films was evaluated by analyzing the peroxide index, total carotenoids, and total polyphenol. The same analysis also evaluated unpacked butter, packed in films without additives and butter packed in LDPE films, as controls. The results suggested that incorporation of the antioxidants extracts tensile strength and water vapor barrier properties (15 times lower) compared to control without additives. A lower peroxide index (231.57%), which was significantly different from that of the control (p<0.05), was detected in products packed in film formulations containing average concentration of green tea extracts and high concentration of colorant. However, it was found that the high content of polyphenols in green tea extract can be acted as a pro-oxidant agent, which suggests that the use of high concentration should be avoided as additives for films. These results support the applicability of a green tea extract and oil palm carotenoics colorant in starch films totally biodegradable and the use of these materials in active packaging of the fatty products.     

Properties of biodegradable citric acid-modified granular starch/thermoplastic pea starch composites

Pea starch-based composites reinforced with citric acid-modified pea starch (CAPS) and citric acid-modified rice starch (CARS), respectively, were prepared by screw extrusion. The effects of granular CAPS and CARS on the morphology, thermal stability, dynamic mechanical thermal analysis, the relationship between the mechanical properties and water content, as well as the water vapor permeability of the composite films were investigated. Scanning electron microscope and X-ray diffraction reveal that the reinforcing agents, the granules of CAPS and CARS, are not disrupted in the thermoplastic process, while the pea starch in the matrix is turned into a continuous TPS phase. Granular CAPS and CARS can improve the storage modulus, the glass transition temperature, the tensile strength and the water vapor barrier, but decrease thermal stability. CARS/TPS composites exhibit a better storage modulus, tensile strength, elongation at break and water vapor barrier than CAPS/TPS composites because of the smaller size of the CARS granules.     

Biodegradability and mechanical properties of starch films from Andean crops

Different Andean crops were used to obtain starches not previously reported in literature as raw material for the production of biodegradable polymers. The twelve starches obtained were used to prepare biodegradable films by casting. Water and glycerol were used as plasticizers. The mechanical properties of the starch based films were assessed by means of tensile tests. Compost tests and FTIR tests were carried out to assess biodegradability of films. The results show that the mechanical properties (UTS, Young's modulus and elongation at break) of starch based films strongly depend on the starch source used for their production. We found that all the starch films prepared biodegrade following a three stage process and that the weight loss rate of all the starch based films tested was higher than the weight loss rate of the cellulose film used as control.