Preparation and Characterization of New Bioplastics Based on Polybutylene Succinate (PBS).

Sea and environmental pollution due to microplastics are global problems that in recent years have attracted particular interest in the scientific community. The increase in the world population and the consequent consumerism of non-reusable materials are amplifying these problems. In this manuscript, we present novel bioplastics, which are completely biodegradable, for their potential use in food packaging, to replace fossil-fuel-derived plastic films and slow food degradation due to oxidative processes or microbial contamination. In this study, thin films based on polybutylene succinate (PBS) were prepared to reduce pollution, and different percentages by weight (1, 2 and 3 wt%) of extra virgin olive oil (EVO) and coconut oil (CO) were included to improve the chemico-physical properties of the polymer and possibly improve the functionality of the films in terms of prolonged food preservation. Attenuated total reflectance Fourier transform infrared (ATR/FTIR) spectroscopy was used to evaluate the interactions between the polymer and the oil. Furthermore, the mechanical properties and thermal behavior of the films were evaluated as a function of the oil content. A scanning electron microscopy (SEM) micrograph showed the surface morphology and the thickness of the materials. Finally, apple and kiwi were selected for a food-contact test, and the wrapped sliced fruit was monitored and evaluated for 12 days to macroscopically evaluate the oxidative process and/or eventually occurring contamination. The films were shown to reduce the browning of sliced fruit due to oxidation, and no molds were evidenced up to 10/12 days of observation with the addition of PBS, with 3 wt% of EVO achieving the best outcomes.

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.

Mechanical, Dynamic-Mechanical, Thermal and Decomposition Behavior of 3D-Printed PLA Reinforced with CaCO3 Fillers from Natural Resources.

This study evaluates the effect of CaCO3 fillers extracted from waste eggshells on 3D-printed PLA performance. Samples of neat PLA and PLA reinforced with CaCO3 fillers embedded with different wt.% were prepared using an FDM (fused deposition modeling) technology. The samples were examined using mechanical, dynamic mechanical, thermal, and thermal decomposition analyses. The results revealed increasing elastic moduli, tensile strength, and flexure as the filler content increased. The rheological results from the MFR tests showed that the filler content did not influence the PLA-based samples' processability. Further, the thermal degradation of neat and various CaCO3-wt.%-reinforced PLA specimens revealed relatively small discrepancies in their exposure to the temperature increase, mainly concerning the eggshell organic components and volatile components, from their processability up to 300 °C. By contrast, the increased filler content positively shifted the peaks along the temperature scale at the maximum degradation rate. Additionally, the weight content of the natural reinforcement strongly influenced the surface wettability and appearance of the samples. Further, the SEM analysis featured both the presence of interlayer disturbances and the interfacial compatibility the PLA with the selected fillers.

Influence of Ultraviolet Radiation Exposure Time on Styrene-Ethylene-Butadiene-Styrene (SEBS) Copolymer.

The effect of ultraviolet radiation on styrene-ethylene-butadiene-styrene (SEBS) has been studied at different exposures times in order to obtain a better understanding of the mechanism of ageing. The polymer materials were mechanically tested and then their surfaces were analyzed using a scanning electron microscope (SEM) and atomic force microscopy (AFM). Moreover, the optical analysis of contact angle (OCA) was used to evaluate the surface energy (γs) and the yellowing index (YI) and attenuated total reflectance infrared spectroscopy (ATR-FTIR) were used to observe structural and physical changes in aging SEBS. The results obtained for the SEBS, in relation to the duration of exposure, showed superficial changes that cause a decrease in the surface energy (γs) and, therefore, a decrease in surface roughness. This led to a reduction in mechanical performance, decreasing the tensile strength by about 50% for exposure times of around 200 h.

Improved Toughness in Lignin/Natural Fiber Composites Plasticized with Epoxidized and Maleinized Linseed Oils.

The use of maleinized (MLO) and epoxidized (ELO) linseed oils as potential biobased plasticizers for lignin/natural fiber composites formulations with improved toughness was evaluated. Arboform®, a lignin/natural fiber commercial composite, was used as a reference matrix for the formulations. The plasticizer content varied in the range 0-15 wt % and mechanical, thermal and morphological characterizations were used to assess the potential of these environmentally friendly modifiers. Results from impact tests show a general increase in the impact-absorbed energy for all the samples modified with bio-oils. The addition of 2.5 wt % of ELO to Arboform (5.4 kJ/m2) was able to double the quantity of absorbed energy (11.1 kJ/m2) and this value slightly decreased for samples containing 5 and 10 wt %. A similar result was obtained with the addition of MLO at 5 wt %, with an improvement of 118%. The results of tensile and flexural tests also show that ELO and MLO addition increased the tensile strength as the percentage of both oils increased, even if higher values were obtained with lower percentages of maleinized oil due to the possible presence of ester bonds formed between multiple maleic groups present in MLO and the hydroxyl groups of the matrix. Thermal characterization confirmed that the mobility of polymer chains was easier in the presence of ELO molecules. On the other hand, MLO presence delayed the crystallization event, predominantly acting as an anti-nucleating agent, interrupting the folding or packing process. Both chemically modified vegetable oils also efficiently improved the thermal stability of the neat matrix.

Effect of Different Compatibilizers on Injection-Molded Green Fiber-Reinforced Polymers Based on Poly(lactic acid)-Maleinized Linseed Oil System and Sheep Wool.

A method to modify polymers is that of introducing fibers in a matrix to produce a fiber-reinforced polymer (FRP). Consequently, the aim of this work was to study the compatibility effect of four coupling agents on wool FRP properties, using poly(lactic acid) plasticized with maleinized linseed oil as polymer matrix. The content of wool assessed was 1 phr. The compatibilizers were (3-(2-aminoethylamino)propyl)-trimethoxysilane, trimethoxy (2-(7-oxabicyclo (4.1.0)hept-3-yl) ethyl) silane, tris(2-methoxyethoxy)(vinyl) silane and titanium (IV) (triethanolaminate)isopropoxide. Initially, wool was modified with coupling agents in an acetone/water (50/50) solution. Mechanical properties were evaluated by tensile and flexural properties, hardness by Shore D measurement and impact resistance by Charpy's energy. Differential scanning calorimetry, dynamic thermo-mechanical analysis, and thermogravimetric analysis were conducted to evaluate the interaction among components and the effect of the coupling agents on the thermal properties of the original material. Color, wettability and scanning electron microscopy were used to describe physical and microstructural properties. Modification of fibers allows achieving improved mechanical properties and changes the thermal properties of the FRPs slightly. Coupling agent treatment helps to formulate PLA-MLO and sheep wool materials and to improve their performance, thereby creating a broader spectrum of applications for PLA maintaining the bio-based character of the material.

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.

Novel methodology to isolate microplastics from vegetal-rich samples.

Microplastics are small plastic particles, globally distributed throughout the oceans. To properly study them, all the methodologies for their sampling, extraction, and measurement should be standardized. For heterogeneous samples containing sediments, animal tissues and zooplankton, several procedures have been described. However, definitive methodologies for samples, rich in algae and plant material, have not yet been developed. The aim of this study was to find the best extraction protocol for vegetal-rich samples by comparing the efficacies of five previously described digestion methods, and a novel density separation method. A protocol using 96% ethanol for density separation was better than the five digestion methods tested, even better than using H2O2 digestion. As it was the most efficient, simple, safe and inexpensive method for isolating microplastics from vegetal rich samples, we recommend it as a standard separation method.

On the Use of PLA-PHB Blends for Sustainable Food Packaging Applications.

Poly(lactic acid) (PLA) is the most used biopolymer for food packaging applications. Several strategies have been made to improve PLA properties for extending its applications in the packaging field. Melt blending approaches are gaining considerable interest since they are easy, cost-effective and readily available processing technologies at the industrial level. With a similar melting temperature and high crystallinity, poly(hydroxybutyrate) (PHB) represents a good candidate to blend with PLA. The ability of PHB to act as a nucleating agent for PLA improves its mechanical resistance and barrier performance. With the dual objective to improve PLAPHB processing performance and to obtain stretchable materials, plasticizers are frequently added. Current trends to enhance PLA-PHB miscibility are focused on the development of composite and nanocomposites. PLA-PHB blends are also interesting for the controlled release of active compounds in the development of active packaging systems. This review explains the most relevant processing aspects of PLA-PHB based blends such as the influence of polymers molecular weight, the PLA-PHB composition as well as the thermal stability. It also summarizes the recent developments in PLA-PHB formulations with an emphasis on their performance with interest in the sustainable food packaging field. PLA-PHB blends shows highly promising perspectives for the replacement of traditional petrochemical based polymers currently used for food packaging.