Marianne Ayumi Shirai

Development of biodegradable flexible films of starch and poly(lactic acid) plasticized with adipate or citrate esters

Biodegradable films were produced from blends contained a high amount of thermoplastic starch (TPS) and poly(lactic acid) (PLA) plasticized with different adipate or citrate esters. It was not possible to obtain pellets for the production of films using only glycerol as a plasticizer. The plasticization of the PLA with the esters and mixture stages added through extrusion was critical to achieve a blend capable of producing films by blow extrusion. Adipate esters were the most effective plasticizers because they interacted best with the PLA and yielded films with appropriate mechanical properties.

Mixture design applied for the study of the tartaric acid effect on starch/polyester films.

Tartaric acid (TA), a dicarboxylic acid, can act as a compatibiliser in starch/polyester blends. A mixture design was proposed to evaluate the effect of TA on the properties of starch/poly (butylene adipate co-terephthalate) (PBAT) blown films plasticised with glycerol. The interaction between the starch/PBAT and the TA has a positive effect on the tensile strength and puncture force. Additionally, greater proportions of TA increased Youngs modulus. The starch+PBAT/TA and Gly/TA interactions contributed to a reduction in the water vapour permeability of the films. The inclusion of TA did not change the crystallinity of the samples. Formulations with intermediate proportions of TA (0.8 g/100 g) were shown to produce the best compatibilising effect. This was observed by DMA analysis as a consequence of the perfect equilibrium between the contributions of TA as a compatibiliser and in the acidolysis of starch, resulting in films with a tensile strength of 5.93 MPa, a possible alternative to non-biodegradable packaging.

Thermoplastic starch/polyester films: Effects of extrusion process and poly (lactic acid) addition

Biodegradable films were produced using the blown extrusion method from blends that contained cassava thermoplastic starch (TPS), poly(butylene adipate-co-terephthalate) (PBAT) and poly(lactic acid) (PLA) with two different extrusion processes. The choice of extrusion process did not have a significant effect on the mechanical properties, water vapor permeability (WVP) or viscoelasticity of the films, but the addition of PLA decreased the elongation, blow-up ratio (BUR) and opacity and increased the elastic modulus, tensile strength and viscoelastic parameters of the films. The films with 20% PLA exhibited a lower WVP due to the hydrophobic nature of this polymer. Morphological analyses revealed the incompatibility between the polymers used.

Adipate and Citrate Esters as Plasticizers for Poly(Lactic Acid)/Thermoplastic Starch Sheets

Poly(lactic acid) (PLA) and thermoplastic starch (TPS) sheets plasticized with different adipate and citrate esters were produced by a calendering-extrusion process. The incorporation of plasticizers significantly reduced the glass transition temperature and increased the PLA chain mobility thus improving the mechanical properties. Among the plasticizers employed, diethyl adipate significantly increased the elongation of the sheets and slightly increased the water vapor permeability. Micrographs revealed the incompatibility between starch and PLA, and there was no plasticizer phase separation, suggesting that the plasticizer concentration was adequate. The incorporation of adipate or citrate esters improves the mechanical properties and processability of PLA/TPS sheets produced by calendering extrusion at a pilot scale.

Biodegradable blends of starch/polyvinyl alcohol/glycerol: multivariate analysis of the mechanical properties

The aim of the work was to study the mechanical properties of extruded starch/polyvinyl alcohol (PVA)/glycerol biodegradable blends using multivariate analysis. The blends were produced as cylindrical strands by extrusion using PVAs with different hydrolysis degrees and viscosities, at two extrusion temperature profiles (90/170/170/170/170 °C and 90/170/200/200/200 °C) and three conditioning relative humidities of the samples (33, 53, and 75%). The mechanical properties showed a great variability according to PVA type, as well as the extrusion temperature profile and the conditioning relative humidity; the tensile strength ranged from 0.42 to 5.40 MPa, elongation at break ranged from 10 to 404% and Young’s modulus ranged from 0.93 to 13.81 MPa. The multivariate analysis was a useful methodology to study the mechanical properties behavior of starch/PVA/glycerol blends, and it can be used as an exploratory technique to select of the more suitable PVA type and extrusion temperature to produce biodegradable materials.

Effect of drying method on mechanical, thermal and water absorption properties of enzymatically crosslinked gelatin hydrogels

Enzymatically crossliked gelatin hydrogel was submitted to two different drying methods: air drying and freeze drying. The resulting polymeric tridimensional arrangement (compact or porous, respectively) led to different thermal and swelling properties. Significant differences (p < 0.05) on thermal and mechanical characteristics as well as swelling in non-enzymatic gastric and intestinal simulated fluids (37 ºC) were detected. Water absorption data in such media was modelled according to Higuchi, Korsmeyer-Peppas, and Peppas-Sahlin equations. Freeze dried hydrogel showed Fickian diffusion behavior while air dried hydrogels presented poor adjustment to Higuchi model suggesting the importance of the relaxation mechanism at the beginning of swelling process. It was possible to conclude that the same gelatin hydrogel may be suitable to different applications depending on the drying process used.

Poly(lactic acid)/thermoplastic starch sheets: effect of adipate esters on the morphological, mechanical and barrier properties

Blends of poly(lactic acid) (PLA) and thermoplastic starch (TPS) plasticized with adipate esters (diisodecyl adipate and diethyl adipate) having different molecular weight were used to produce sheets. The calendering-extrusion process at a pilot scale was used, and the mechanical, barrier, and morphological characterization of the obtained materials were performed. The increase in the TPS content affected the mechanical properties of the sheets by increasing the elongation and decreasing the rigidity. TPS conferred a more hydrophilic character to the sheets, as observed from the water vapor permeability results. The sheets plasticized with diisodecyl adipate (DIA), having a higher molecular weight, had better mechanical and barrier properties than diethyl adipate (DEA) plasticized sheets, indicating that DIA was more effective as plasticizer. Micrographs obtained by confocal laser microscopy and scanning electron microscopy showed different morphologies when different proportions of PLA and TPS were used (dispersed or co-continuous structures), which were strongly associated with the mechanical and barrier properties.

Active Food Packaging From Botanical, Animal, Bacterial, and Synthetic Sources

Abstract The use of bioactive substances, especially those that present antimicrobial and antioxidant activities, has attracted considerable attention toward the development of a novel generation of materials with functional properties. In particular, one of the greatest challenges of the food-packaging area is the development of sustainable and biodegradable materials containing active substances capable of being gradually released to the food surface or matrix during its shelf life, ensuring sensorial, nutritional, and microbiological characteristics maintenance, without compromising the mechanical, thermal, and barrier properties quality of food packaging materials. In this context, this chapter presents an overview of the existing strategies to develop viable products by combining biodegradable polymeric matrices of natural or synthetic origin with natural additives able to confer specific functionalities (e.g., natural extracts, essential oils, enzymes, vitamins, and bacteriocins) or improve their mechanical properties (nanoreinforcements from organic or inorganic sources).

The effect of gelatin amount on the properties of PLA/TPS/gelatin extruded sheets

Films and sheets composed by poly (lactic acid) (PLA)/thermoplastic starch (TPS) and TPS/gelatin blends have already been produced and characterized in the ...