Novel Epoxidized Brazil Nut Oil as a Promising Plasticizing Agent for PLA.

This work evaluates for the first time the potential of an environmentally friendly plasticizer derived from epoxidized Brazil nut oil (EBNO) for biopolymers, such as poly(lactic acid) (PLA). EBNO was used due to its high epoxy content, reaching an oxirane oxygen content of 4.22% after 8 h of epoxidation for a peroxide/oil ratio of 2:1. Melt extrusion was used to plasticize PLA formulations with different EBNO contents in the range of 0-10 phr. The effects of different amounts of EBNO in the PLA matrix were studied by performing mechanical, thermal, thermomechanical, and morphological characterizations. The tensile test demonstrated the feasibility of EBNO as a plasticizer for PLA by increasing the elongation at break by 70.9% for the plasticized PLA with 7.5 phr of EBNO content in comparison to the unplasticized PLA. The field-emission scanning electron microscopy (FESEM) of the fractured surfaces from the impact tests showed an increase in porosity and roughness in the areas with EBNO addition, which was characteristic of ductile failure. In addition, a disintegration test was performed, and no influence on the PLA biodegradation process was observed. The overall results demonstrate the ability of EBNO to compete with other commercial plasticizers in improving the ductile properties of PLA.

The Influence of Different Sustainable Silk-Based Fillers on the Thermal and Mechanical Properties of Polylactic Acid Composites.

In this work, different silk fillers combined with maleinized corn oil (MCO), as environmentally friendly plasticizers, were used to modify the mechanical and thermal properties of polylactic acid (PLA) composites. Melt extrusion and injection were used to obtain samples with a content of 10 wt.% of MCO and 0.5 phr of different silk fillers: crushed silk (CS), silk fibroin microparticles (SFM), and silk fibroin nanoparticles (SFN). PLA formulation with 10 wt.% of MCO and 0.5 g of CS per hundred grams of composite (phr) showed the highest increase in mechanical ductile properties with an increase in elongation at break of approximately 1400%, compared with PLA. Differential scanning calorimetry (DSC) showed a decrease of 2 °C in their glass transition temperature with the addition of different silk fillers. In addition, SFM and SFN increase the degree of crystallinity of PLA. This increment was also confirmed by infrared spectroscopy analysis. Field emission scanning electron microscopy (FESEM) images revealed a good dispersion of the different silk fillers. Among them, PLA formulation with 10 wt.% MCO and 0.5 phr of SFN, showed an optimal balance between maximum resistance and elongation at break, with 52.0 MPa and 10.8%, respectively, improving elongation at break by 635%. Furthermore, all samples were satisfactorily disintegrated under composting conditions.

Effect of Epoxidized and Maleinized Corn Oil on Properties of Polylactic Acid (PLA) and Polyhydroxybutyrate (PHB) Blend.

The present work analyzes the influence of modified, epoxidized and maleinized corn oil as a plasticizing and/or compatibilizing agent in the PLA-PHB blend (75% PLA and 25% PHB wt.%). The chemical modification processes of corn oil were successfully carried out and different quantities were used, between 0 and 10% wt.%. The different blends obtained were characterized by thermal, mechanical, morphological, and disintegration tests under composting conditions. It was observed that to achieve the same plasticizing effect, less maleinized corn oil (MCO) is needed than epoxidized corn oil (ECO). Both oils improve the ductile properties of the PLA-PHB blend, such as elongation at break and impact absorb energy, however, the strength properties decrease. The ones that show the highest ductility values are those that contain 10% ECO and 5% MCO, improving the elongation of the break of the PLA-PHB blend by more than 400% and by more than 800% for the sample PLA.

Comparative Study of the Properties of Plasticized Polylactic Acid with Maleinized Hemp Seed Oil and a Novel Maleinized Brazil Nut Seed Oil.

In this study, for the first time, Brazil nut seed oil was chemically modified with maleic anhydride to obtain maleinized Brazil nut seed oil (MBNO). The same process was developed to obtain maleinized hemp seed oil (MHO). The use of MBNO and MHO was studied as bio-based plasticizers by incorporating them with different contents ranging from 0 to 10 phr in a polylactic acid (PLA) matrix. By means of mechanical, thermal and thermomechanical characterization techniques, the properties of the different formulations were studied to evaluate the plasticizing effect of the MBNO and MHO. With the addition of both plasticizers, a significant increase in ductile properties was observed, reaching an increase in elongation at break of 643% with 7.5 phr MBNO and 771% with 10 phr MHO compared to neat PLA. In addition, it has been observed that the mechanical resistant properties do not decrease, since the oils enhance the crystallization of PLA by increasing the free volume between its chains and counteracting the effect. Finally, a disintegration test was carried out under thermophilic conditions at 58 °C for 27 days, demonstrating that the incorporation of MHO and MBNO does not significantly affect the biodegradability of neat PLA.

Gum Rosin as a Size Control Agent of Poly(Butylene Adipate-Co-Terephthalate) (PBAT) Domains to Increase the Toughness of Packaging Formulations Based on Polylactic Acid (PLA).

Gum rosin (GR) was used as a natural additive to improve the compatibility between polylactic acid, PLA, and poly(butylene adipate-co-terephthalate, PBAT, blended with 20 wt.% of PBAT (PLA/PBAT). The PBAT was used as a soft component to increase the ductility of PLA and its fracture toughness. The coalescence of the PBAT domains was possible due to the plasticization effect of the GR component. These domains contributed to increasing the toughness of the final material due to the variation and control of the PBAT domains' size and consequently, reducing the stress concentration points. The GR was used in contents of 5, 10, 15, and 20 phr. Consequently, the flexural properties were improved and the impact resistance increased up to 80% in PLA/PBAT_15GR with respect to the PLA/PBAT formulation. Field emission scanning electron microscope (FESEM) images allowed observing that the size of PBAT domains of 2-3 µm was optimal to reduce the impact stress. Differential scanning calorimetry (DSC) analysis showed a reduction of up to 8 °C on the PLA melting temperature and up to 5.3 °C of the PLA glass transition temperature in the PLA/PBAT_20GR formulation, which indicates an improvement in the processability of PLA. Finally, transparent films with improved oxygen barrier performance and increased hydrophobicity were obtained suggesting the potential interest of these blends for the food packaging industry.

Films Based on Mater-Bi® Compatibilized with Pine Resin Derivatives: Optical, Barrier, and Disintegration Properties.

Mater-Bi® NF866 (MB) was blended with gum rosin and two pentaerythritol esters of gum rosin (labeled as LF and UT), as additives, to produce biobased and compostable films for food packaging or agricultural mulch films. The films were prepared by blending MB with 5, 10, and 15 wt.% of each additive. The obtained films were characterized by optical, colorimetric, wettability, and oxygen barrier properties. Moreover, the additives and the MB-based films were disintegrated under composting conditions and the effect of each additive on the biodegradation rate was studied. All films were homogeneous and optically transparent. The color of the films tended to yellow tones due to the addition of pine resin derivatives. All the formulated films presented a complete UV-transmittance blocking effect in the UVA and UVB region, and those with 5 wt.% of pine resin derivatives increased the MB hydrophobicity. Low amounts of resins tend to maintain the oxygen transmission rate (OTR) values of the neat MB, due to its good solubilizing and compatibilizing effects. The disintegration under composting conditions test revealed that gum rosin completely disintegrates in about 90 days, while UT degrades 80% and LF degrades 5%, over 180 days of incubation. As expected, the same tendency was obtained for the disintegration of the studied films, although Mater-Bi® reach 28% of disintegrability over the 180 days of the composting test.

Dual Plasticizer/Thermal Stabilizer Effect of Epoxidized Chia Seed Oil (Salvia hispanica L.) to Improve Ductility and Thermal Properties of Poly(Lactic Acid).

The use of a new bio-based plasticizer derived from epoxidized chia seed oil (ECO) was applied in a poly(lactic acid) (PLA) matrix. ECO was used due to its high epoxy content (6.7%), which led to an improved chemical interaction with PLA. Melt extrusion was used to plasticize PLA with different ECO content in the 0-10 wt.% range. Mechanical, morphological, and thermal characterization was carried out to evaluate the effect of ECO percentage. Besides, disintegration and migration tests were studied to assess the future application in packaging industry. Ductile properties improve by 700% in elongation at break with 10 wt.% ECO content. Field emission scanning electron microscopy (FESEM) showed a phase separation with ECO content equal or higher than 7.5 wt.%. Thermal stabilization was improved 14 °C as ECO content increased. All plasticized PLA was disintegrated under composting conditions, not observing a delay up to 5 wt.% ECO. Migration tests pointed out a very low migration, less than 0.11 wt.%, which is to interest to the packaging industry.

Dynamic-Mechanical and Decomposition Properties of Flax/Basalt Hybrid Laminates Based on an Epoxidized Linseed Oil Polymer.

This contribution focuses on the development of flax and flax/basalt hybrid reinforced composites based on epoxidized linseed oil (ELO) resin, exploiting the feasibility of different ratios of glutaric anhydride (GA) to maleinized linseed oil (MLO) in the hardener system (50:0, 40:10 and 30:20 wt.%) to provide crosslinked thermosets with balanced properties. The hybrid laminates have been manufactured by resin transfer molding (RTM) and subjected to dynamic-mechanical (DMA) and thermal gravimetry (TGA) analysis. The presence of glutaric anhydride (GA) resulted in hard and relatively brittle flax and flax/basalt laminates, whose loss moduli decreased as the number of basalt plies diminished. Furthermore, the increase in MLO content in the GA:MLO hardener system shifted the glass transition temperatures (Tg) from 70 °C to 59 and 56 °C, which is representative of a decrease in brittleness of the crosslinked resin. All samples exhibited two stages of their decomposition process irrespective of the MLO content. The latter influenced the residual mass content that increased with the increase of the MLO wt.% from 10 to 30 wt.%, with shifts of the final degradation temperatures from 410 °C to 425 °C and 445 °C, respectively.

Motives and Commitment to Sport in Amateurs during Confinement: A Segmentation Study.

The current COVID-19 pandemic has paralysed whole countries, which have had to confine their entire population and this changed people's lives worldwide. The aim of this study is to identify the reasons for and the level of commitment to physical activity among the Spanish population during confinement and the return to the "new normal". A sample of 1025 amateurs, 534 males and 491 females with an average age of 35 years old were interviewed using an online survey that collected their motives for practising sport and their commitment to physical activity. A cluster analysis combining hierarchical and non-hierarchical methods was performed, identifying three groups of amateurs: High Commitment (n = 650), Moderate Commitment (n = 324), and Low Commitment (n = 81). The main motives shown by the different groups were psychological motives related to an improved or managed general or emotional well-being. Regarding commitment, all the groups showed higher scores in enthusiasm for physical activity than affliction from sport. The variables referring to gender, educational level and sports habits showed differences that enabled the identification of the different groups. These findings highlight the importance of conducting segmentation studies that provide specific population profiles to improve the action strategies of governments and specialists.

Interference of Biodegradable Plastics in the Polypropylene Recycling Process.

Recycling polymers is common due to the need to reduce the environmental impact of these materials. Polypropylene (PP) is one of the polymers called 'commodities polymers' and it is commonly used in a wide variety of short-term applications such as food packaging and agricultural products. That is why a large amount of PP residues that can be recycled are generated every year. However, the current increasing introduction of biodegradable polymers in the food packaging industry can negatively affect the properties of recycled PP if those kinds of plastics are disposed with traditional plastics. For this reason, the influence that generates small amounts of biodegradable polymers such as polylactic acid (PLA), polyhydroxybutyrate (PHB) and thermoplastic starch (TPS) in the recycled PP were analyzed in this work. Thus, recycled PP was blended with biodegradables polymers by melt extrusion followed by injection moulding process to simulate the industrial conditions. Then, the obtained materials were evaluated by studding the changes on the thermal and mechanical performance. The results revealed that the vicat softening temperature is negatively affected by the presence of biodegradable polymers in recycled PP. Meanwhile, the melt flow index was negatively affected for PLA and PHB added blends. The mechanical properties were affected when more than 5 wt.% of biodegradable polymers were present. Moreover, structural changes were detected when biodegradable polymers were added to the recycled PP by means of FTIR, because of the characteristic bands of the carbonyl group (between the band 1700⁻1800 cm-1) appeared due to the presence of PLA, PHB or TPS. Thus, low amounts (lower than 5 wt.%) of biodegradable polymers can be introduced in the recycled PP process without affecting the overall performance of the final material intended for several applications, such as food packaging, agricultural films for farming and crop protection.