Alfonso Jiménez

Effects of modified cellulose nanocrystals on the barrier and migration properties of PLA nano-biocomposites.

The aim of this paper is to report the impact of the addition of cellulose nanocrystals on the barrier properties and on the migration behaviour of poly(lactic acid), PLA, based nano-biocomposites prepared by the solvent casting method. Their microstructure, crystallinity, barrier and overall migration properties were investigated. Pristine (CNC) and surfactant-modified cellulose nanocrystals (s-CNC) were used, and the effect of the cellulose modification and content in the nano-biocomposites was investigated. The presence of surfactant on the nanocrystal surface favours the dispersion of CNC in the PLA matrix. Electron microscopy analysis shows the good dispersion of s-CNC in the nanoscale with well-defined single crystals indicating that the surfactant allowed a better interaction between the cellulose structures and the PLA matrix. Reductions of 34% in water permeability were obtained for the cast films containing 1 wt.% of s-CNC while good oxygen barrier properties were detected for nano-biocomposites with both 1 wt.% and 5 wt.% of modified and un-modified cellulose nanocrystals, underlining the improvement provided by cellulose on the PLA films. Moreover, the migration level of the studied nano-biocomposites was below the overall migration limits required by the current normative for food packaging materials in both non-polar and polar simulants.

Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles

Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

Thermal degradation of mixtures of polycaprolactone with cellulose derivatives

Abstract Thermal degradation processes for a series of mixtures based on polycaprolactone (PCL), with microcrystalline cellulose (MC) and sisal fiber (SF) powder, were investigated by thermogravimetric analysis (TGA), in order to predict the thermal behaviour of biodegradable matrixes reinforced with cellulose derivatives. The maximum degradation temperature of each component in the mixture was higher than those of the individual components; thus an increase in thermal stability was expected. Apparent activation energies were obtained from Friedman isoconversional plots. Mixtures were considered as multistage processes. Predicted apparent activation energies agreed well with the increment in thermal stability due to the presence of the co-components. This effect was associated with either, solid–solid or solid–gas interactions between cellulose derivatives and PCL during thermal degradation.

Development of novel nano-biocomposite antioxidant films based on poly (lactic acid) and thymol for active packaging

Novel nano-biocomposite films based on poly (lactic acid) (PLA) were prepared by incorporating thymol, as the active additive, and modified montmorillonite (D43B) at two different concentrations. A complete thermal, structural, mechanical and functional characterization of all nano-biocomposites was carried out. Thermal stability was not significantly affected by the addition of thymol, but the incorporation of D43B improved mechanical properties and reduced the oxygen transmission rate by the formation of intercalated structures, as suggested by wide angle X-ray scattering patterns and transmission electron microscopy images. The addition of thymol decreased the PLA glass transition temperature, as the result of the polymer plasticization, and led to modification of the elastic modulus and elongation at break. Finally, the amount of thymol remaining in these formulations was determined by liquid chromatography (HPLC-UV) and the antioxidant activity by the DPPH spectroscopic method, suggesting that the formulated nano-biocomposites could be considered a promising antioxidant active packaging material.

Combined Effect of Poly(hydroxybutyrate) and Plasticizers on Polylactic acid Properties for Film Intended for Food Packaging

Poly(lactic acid) PLA, and poly(hydroxybutyrate) PHB, blends were processed as films and characterized for their use in food packaging. PLA was blended with PHB to enhance the crystallinity. Therefore, PHB addition strongly increased oxygen barrier while decreased the wettability. Two different environmentally-friendly plasticizers, poly(ethylene glycol) (PEG) and acetyl(tributyl citrate) (ATBC), were added to these blends to increase their processing performance, while improving their ductile properties. ATBC showed higher plasticizer efficiency than PEG directly related to the similarity solubility parameters between ATBC and both biopolymers. Moreover, ATBC was more efficiently retained to the polymer matrix during processing than PEG. PLA–PHB–ATBC blends were homogeneous and transparent blends that showed promising performance for the preparation of films by a ready industrial process technology for food packaging applications, showing slightly amber color, improved elongation at break, enhanced oxygen barrier and decreased wettability.

Thermal degradation of ethylene (vinyl acetate)

Ethylene (vinyl acetate), EVA, is a copolymer which is thermally degraded at high temperatures, with acetic acid release at approximately 620 K. This release can be studied by using thermal methods, and in particular thermogravimetric analysis.The present work was focused on establishing the polymer weight loss with temperature in order to calculate the activation energy of the overall deacetylation process. To obtain the final results, a Mettler TC50 instrument coupled with a Mettler TC11 microprocessor was used.The activation energies of four different industrial EVA formulations were calculated. The results obtained by applying different kinetic methods reported in the literature agreed reasonably well; they were compared in order to select the best method of reporting EVA deacetylation results.

Migration study of carvacrol as a natural antioxidant in high-density polyethylene for active packaging

The migration behaviour of low molecular weight compounds from food packaging materials is one of the key issues in assessing the possibility of use in such applications. The aim of this work was to study the migration of carvacrol (1% and 2% w/w) when added to high-density polyethylene. All materials were exposed to the food simulants olive oil and distilled water separately at 40°C and 25°C. Three significant variables influencing the migration process were considered: incubation temperatures, the initial concentration of antioxidant, and the type of simulant (oil and aqueous). The amount of carvacrol migrating to olive oil was significantly higher than in water because of the higher solubility of this antioxidant in oil. Experimental results agreed reasonably well with those obtained by the application of a simple model derived from Ficks Second Law. Carvacrol could therefore be used in active packaging formulations as its release from the polymer matrix can be controlled.

Determination of aromatic amines formed from azo colorants in toy products.

A study for the determination of the aromatic amines formed after reduction of the azo colorants mostly used in toys was conducted. Sodium dithionite was used in the reductive cleavage of the azo group for the dyes, and the released amines were subsequently analysed by high-performance liquid chromatography with UV detection. The influence of different variables related to the reduction process was investigated by the use of a full-level factorial design, where most significant parameters as well as order interactions were studied. Reduction profiles for each colorant were obtained by studying the changes in the amount of amine obtained with different dithionite/colorant ratios. The expected aromatic amines forming azo colorants were detected, and in the presence of a nitro group a further reduction was observed. The yield of the total reduction process was determined by using standard addition of different quantities of amines to the colorants.

Thermal degradation of poly(vinyl chloride) plastisols based on low-migration polymeric plasticizers

The analysis of the thermal degradation of poly(vinyl chloride) (PVC) plastisols formulated with low-toxicity polymeric plasticizers is reported. Dynamic and isothermal thermogravimetric analyses are applied to study the behavior of these materials at high temperatures and to evaluate their degradation kinetics. The results used for the optimization of the processing conditions, in particular the cure time and temperature, to maximize the thermal stability of the plastisol. The optimum plasticizer concentration is also determined. TGA results have been used to determine the parameters of the degradation kinetic model using Friedman and Horowitz methods. A comparison with the thermal behavior of traditional plastisols normally employed in industrial applications is reported.

Thermal degradation of recycled polypropylene toughened with elastomers

Commercial polyolefins, such as polypropylene (PP), are widely used because of their easy processing and their excellent properties. Although their recycling is well established, the mechanical and thermal properties of the recycled products are normally lower than those of the virgin material. The introduction of an elastomeric additive can improve the toughness, without compromising the processability and recycling capabilities. However the thermal properties of these blends should be assessed in order to limit degradation during recycling. This work presents a study of the thermal degradation of blends based on recycled PP with different elastomeric systems. Thermogravimetric analysis in dynamic and isothermal modes is used to develop a kinetic model for the decomposition reaction of the studied blends. The effect of the introduction of the elastomer is analysed through the variation of the apparent activation energies as well as the reaction order and pre-exponential factor. The correspondence between experimental and calculated results demonstrates the validity of the proposed model.