PLA Electrospun Fibers Reinforced with Organic and Inorganic Nanoparticles: A Comparative Study.

In this work, different poly (lactic acid) (PLA)-based nanocomposite electrospun fibers, reinforced with both organic and inorganic nanoparticles, were obtained. As organic fibers, cellulose nanocrystals, CNC, both neat and functionalized by "grafting from" reaction, chitosan and graphene were used; meanwhile, hydroxyapatite and silver nanoparticles were used as inorganic fibers. All of the nanoparticles were added at 1 wt% with respect to the PLA matrix in order to be able to compare their effect. The main aim of this work was to study the morphological, thermal and mechanical properties of the different systems, looking for differences between the effects of the addition of organic or inorganic nanoparticles. No differences were found in either the glass transition temperature or the melting temperature between the different electrospun systems. However, systems reinforced with both neat and functionalized CNC exhibited an enhanced degree of crystallinity of the electrospun fibers, by up to 12.3%. From a mechanical point of view, both organic and inorganic nanoparticles exhibited a decreased elastic modulus and tensile strength in comparison to neat electrospun PLA fibers, improving their elongation at break. Furthermore, all of the organic and inorganic reinforced systems disintegrated under composting conditions after 35 days.

Foaming of 3D-Printed PLA/CaCO3 Composites by Supercritical CO2 Process for Sustainable Food Contact Materials.

In the last decade, among the emerging technologies in the area of bioplastics, additive manufacturing (AM), commonly referred to as 3D printing, stands out. This technology has gained great interest in the development of new products, mainly due to its capability to easily produce customized and low-cost plastic products. This work aims to evaluate the effect of supercritical foaming of 3D-printed parts based on a commercial PLA matrix loaded with calcium carbonate, for single-use sustainable food contact materials. 3D-printed PLA/CaCO3 parts were obtained by 3D printing with a 20% and 80% infill, and two infill patterns, rectilinear and triangular, were set for each of the infill percentages selected. Supercritical fluid foaming of PLA/CaCO3 composite printed parts was performed using a pressure of 25 MPa, a temperature of 130 °C for 23 min, with a fast depressurization rate (1 s). Closed-cell foams were achieved and the presence of CaCO3 did not influence the surface of the foams or the cell walls, and no agglomerations were observed. Foam samples with 80% infill showed subtle temperature fluctuations, and thermogravimetric analysis showed that samples were thermally stable up to ~300 °C, while the maximum degradation temperature was around 365 °C. Finally, tensile test analysis showed that for lower infill contents, the foams showed lower mechanical performance, while the 80% infill and triangular pattern produced foams with good mechanical performance. These results emphasize the interest in using the supercritical CO2 process to easily produce foams from 3D-printed parts. These materials represent a sustainable alternative for replacing non-biodegradable materials such as Expanded Polystyrene, and they are a promising option for use in many industrial applications, such as contact materials.

Biodegradable nanocomposite poly(lactic acid) foams containing carvacrol-based cocrystal prepared by supercritical CO2 processing for controlled release in active food packaging.

Compounds derived from essential oils have been used in active packaging, but their volatility and degradability negatively affect stability and leads to high release rates. The present study aimed to develop PLA bionanocomposite foams loaded with carvacrol cocrystal by supercritical CO2 and its release into a food simulant for control release in food packaging. For this purpose, 4,4'-bipyridine was used as coformer and carvacrol as active agent. Cocrystallized closed cell foams were obtained using supercritical CO2 and were characterized in terms of their physicochemical and mechanical properties, and release kinetics to a D1 simulant were evaluated as well as the antioxidant ability. A better overall mechanical behavior due to the nanoclay promoting a higher interfacial adhesion with the polymeric matrix was revealed. A higher incorporation of carvacrol was observed in samples with higher C30B content. The incorporated cocrystals showed a decrease of one order of magnitude in the estimated effective diffusion coefficient of carvacrol and showed antioxidant activity. These results suggest that the nanocomposite foam containing carvacrol-based cocrystals could be used in active packaging systems with controlled release characteristics, especially with highly volatile compounds, and can be proposed for other fields such as biomedical applications.

Effect of Operational Variables on Supercritical Foaming of Caffeic Acid-Loaded Poly(lactic acid)/Poly(butylene adipate-co-terephthalate) Blends for the Development of Sustainable Materials.

Expanded polystyrene will account for 5.3% of total global plastic production in 2021 and is widely used for food packaging due to its excellent moisture resistance and thermal insulation. However, some of these packages are often used only once before being discarded, generating large amounts of environmentally harmful plastic waste. A very attractive alternative to the conventional methods used for polymer processing is the use of supercritical carbon dioxide (scCO2) since it has mass-transfer properties adapted to the foam morphology, generating different path lengths for the diffusion of active compounds within its structure and can dissolve a wide range of organic molecules under supercritical conditions. The objective of this research was to evaluate the effect of operational variables on the process of caffeic acid (CA) impregnation and subsequent foaming of polylactic acid (PLA) as well as two PLA/poly(butylene-co-terephthalate-adipate) (PBAT) blends using scCO2. The results showed an increase in the degree of crystallinity of the CA-impregnated samples due to the nucleation effect of the active compound. On the other hand, SEM micrographs of both films and foams showed significant differences due to the presence of PBAT and its low miscibility with PLA. Finally, the results obtained in this work contribute to the knowledge of the important parameters to consider for the implementation of the impregnation and foaming process of PLA and PLA/PBAT blends with potential use in food packaging.

Study of Ethylene-Removing Materials Based on Eco-Friendly Composites with Nano-TiO2.

Ethylene is a phytohormone that is responsible of fruit and vegetable ripening. TiO2 has been studied as a possible solution to slowing down unwanted ripening processes, due to its photocatalytic capacity which enables it to remove ethylene. Thus, the objective of this study was to develop nanocomposites based on two types of eco-friendly materials: Mater-Bi® (MB) and poly(lactic acid) (PLA) combined with nano-TiO2 for ethylene removal and to determine their ethylene-removal capacity. First, a physical-chemical characterization of nano-TiO2 of different particle sizes (15, 21, 40 and 100 nm) was done through structural and morphological analysis (DRX, FTIR and TEM). Then, its photocatalytic activity and the ethylene-removal capacity were determined, evaluating the effects of time and the type of light irradiation. With respect to the analysis of TiO2 nanoparticles, the whole samples had an anatase structure. According to the photocatalytic activity, nanoparticles of 21 nm showed the highest activity against ethylene (~73%). The results also showed significant differences in ethylene-removal activity when comparing particle size and type and radiation time. Thus, 21 nm nano-TiO2 was used to produce nanocomposites through the melt-extrusion process to simulate industrial processing conditions. With respect to the nanocomposites' ethylene-removing properties, there were significant differences between TiO2 concentrations, with samples with 5% of active showed the highest activity (~57%). The results obtained are promising and new studies are needed to focus on changes in material format and the evaluation in ethylene-sensitive fruits.

Processing Compostable PLA/Organoclay Bionanocomposite Foams by Supercritical CO2 Foaming for Sustainable Food Packaging.

This article proposes a foaming method using supercritical carbon dioxide (scCO2) to obtain compostable bionanocomposite foams based on PLA and organoclay (C30B) where this bionanocomposite was fabricated by a previous hot melt extrusion step. Neat PLA films and PLA/C30B films (1, 2, and 3 wt.%) were obtained by using a melt extrusion process followed by a film forming process obtaining films with thicknesses between 500 and 600 µm. Films were further processed into foams in a high-pressure cell with scCO2 under constant conditions of pressure (25 MPa) and temperature (130 °C) for 30 min. Bionanocomposite PLA foams evidenced a closed cell and uniform cell structure; however, neat PLA presented a poor cell structure and thick cell walls. The thermal stability was significantly enhanced in the bionanocomposite foam samples by the good dispersion of nanoclays due to scCO2, as demonstrated by X-ray diffraction analysis. The bionanocomposite foams showed improved overall mechanical performance due to well-dispersed nanoclays promoting increased interfacial adhesion with the polymeric matrix. The water uptake behavior of bionanocomposite foams showed that they practically did not absorb water during the first week of immersion in water. Finally, PLA foams were disintegrated under standard composting conditions at higher rates than PLA films, showing their sustainable character. Thus, PLA bionanocomposite foams obtained by batch supercritical foaming seem to be a sustainable option to replace non-biodegradable expanded polystyrene, and they represent a promising alternative to be considered in applications such as food packaging and other products.

Biopolymers from Natural Resources.

During the last decades, the increasing ecology in the reduction of environmental impact caused by traditional plastics is contributing to the growth of more sustainable plastics with the aim to reduce the consumption of non-renewable resources for their production [...].

Upgrading Recycled Polypropylene from Textile Wastes in Wood Plastic Composites with Short Hemp Fiber.

This research reports the manufacturing and characterization of green composites made from recycled polypropylene obtained from the remnants of polypropylene non-woven fabrics used in the textile industry and further reinforced with short hemp fibers (SHFs). To improve the interaction of the reinforcing fibers with the recycled polymeric matrix, two types of compatibilizing agents (maleic anhydride grafted, PP-g-MA, and maleinized linseed oil, MLO) were added during melt-processing, the percentage of which had to remain constant concerning the amount of fiber loading to ensure complete reactivity. Standardized test specimens were obtained by injection molding. The composites were characterized by mechanical (tensile, impact, and hardness), thermal (DSC, TGA), thermomechanical, FTIR, and FESEM microscopy tests. In addition, color and water uptake properties were also analyzed. The results show that the addition of PP-g-MA to rPP was satisfactory, thus improving the fiber-matrix interaction, resulting in a marked reinforcing effect of the hemp fibers in the recycled PP matrix, which can be reflected in the increased stiffness of the samples. In parallel to the compatibilizing effect, a plasticizing effect was obtained by incorporating MLO, causing a decrease in the glass transition temperature of the composites by approximately 6 °C and an increase in ductility compared to the unfilled recycled polypropylene samples.

Effect of Yerba Mate and Silk Fibroin Nanoparticles on the Migration Properties in Ethanolic Food Simulants and Composting Disintegrability of Recycled PLA Nanocomposites.

The main objective of the present research is to study the effect of the incorporation of low amounts of silk fibroin nanoparticles (SFNs) and yerba mate nanoparticles (YMNs) on the migration phenomenon into ethanolic food simulants as well as on the disintegrability under composting conditions of mechanically recycled polylactic acid (PLA). Recycled PLA was obtained under simulated recycling conditions by melt processing virgin PLA into films and further subjecting them to an accelerated aging process, which involved photochemical, thermal, and hydrothermal aging steps followed by an intense washing step. SFNs were extracted from Bombyx mori cocoons and YMNs from yerba mate waste. Then, recycled PLA was melted, reprocessed, and reinforced with either 1%wt. of SFNs or YMNs, by melt extrusion, and further processed into films by compression molding. The obtained nanocomposites were exposed to ethanolic food simulants (ethanol 10% v/v, simulant A and ethanol 50% v/v, simulant D1) and the structural, thermal, and mechanical properties were studied before and after the exposure to the food simulants. The migration levels in both food simulants were below the overall migration limits required for food contact materials. The materials were disintegrated under simulated composting conditions at the laboratory scale level and it was observed that the nanoparticles delayed the disintegration rate of the recycled PLA matrix, but nanocomposites were fully disintegrated in less than one month.

Evaluation of the Technical Viability of Distributed Mechanical Recycling of PLA 3D Printing Wastes.

3D printing PLA wastes were recovered from a well-known reference grade and from different sources. The recovered wastes were subjected to an energic washing step and then reprocessed into films by melt-extrusion, followed by compression molding to simulate the industrial processing conditions. The obtained materials were characterized and the optical, structural, thermal and crystallization behavior are reported. The mechanical recycling process leads to an increase of the crystallinity and a decrease of the intrinsic viscosity of the formulations, particularly in the sample based on blends of different 3D-PLA wastes. Moreover, the obtained films were disintegrated under composting conditions in less than one month and it was observed that recycled materials degrade somewhat faster than the starting 3D-PLA filament, as a consequence of the presence of shorter polymer chains. Finally, to increase the molecular weight of the recycled materials, the 3D-PLA wastes were submitted to a solid-state polymerization process at 110, 120, and 130 °C, observing that the recycled 3D-wastes materials based on a well-known reference grade experiences an improvement of the intrinsic viscosity, while that coming from different sources showed no significant changes. Thus, the results show that 3D printing PLA products provides an ideal environment for the implementation of distributed recycling program, in which wastes coming from well-known PLA grades can successfully be processed in films with good overall performance.

A Deeper Microscopic Study of the Interaction between Gum Rosin Derivatives and a Mater-Bi Type Bioplastic.

The interaction between gum rosin and gum rosin derivatives with Mater-Bi type bioplastic, a biodegradable and compostable commercial bioplastic, were studied. Gum rosin and two pentaerythritol esters of gum rosin (Lurefor 125 resin and Unik Tack P100 resin) were assessed as sustainable compatibilizers for the components of Mater-Bi® NF 866 polymeric matrix. To study the influence of each additive in the polymeric matrix, each gum rosin-based additive was compounded in 15 wt % by melt-extrusion and further injection molding process. Then, the mechanical properties were assessed, and the tensile properties and impact resistance were determined. Microscopic analyses were carried out by field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and atomic force microscopy with nanomechanical assessment (AFM-QNM). The oxygen barrier and wettability properties were also assayed. The study revealed that the commercial thermoplastic starch is mainly composed of three phases: A polybutylene adipate-co-terephthalate (PBAT) phase, an amorphous phase of thermoplastic starch (TPSa), and a semi-crystalline phase of thermoplastic starch (TPSc). The poor miscibility among the components of the Mater-Bi type bioplastic was confirmed. Finally, the formulations with the gum rosin and its derivatives showed an improvement of the miscibility and the solubility of the components depending on the additive used.

Study of the Properties of a Biodegradable Polymer Filled with Different Wood Flour Particles.

Lignocellulosic wood flour particles with three different sizes were used to reinforce Solanyl® type bioplastic in three compositions (10, 20, and 30 wt.%) and further processed by melt-extrusion and injection molding to simulate industrial conditions. The wood flour particles were morphologically and granulometric analyzed to evaluate their use as reinforcing filler. The Fuller method on wood flour particles was successfully applied and the obtained results were subsequently corroborated by the mechanical characterization. The rheological studies allowed observing how the viscosity was affected by the addition of wood flour and to recover information about the processing conditions of the biocomposites. Results suggest that all particles can be employed in extrusion processes (shear rate less than 1000 s-1). However, under injection molding conditions, biocomposites with high percentages of wood flour or excessively large particles may cause an increase in defective injected-parts due to obstruction of the gate in the mold. From a processing point of view and based on the biocomposites performance, the best combination resulted in Solanyl® type biopolymer reinforced with wood flour particles loaded up to 20 wt.% of small and medium particles size. The obtained biocomposites are of interest for injected molding parts for several industrial applications.

Hybrid Biocomposites Based on Poly(Lactic Acid) and Silica Aerogel for Food Packaging Applications.

Bionanocomposites based on poly (lactic acid) (PLA) and silica aerogel (SiA) were developed by means of melt extrusion process. PLA-SiA composite films were plasticized with 15 wt.% of acetyl (tributyl citrate) (ATBC) to facilitate the PLA processability as well as to attain flexible polymeric formulations for films for food packaging purposes. Meanwhile, SiA was added in four different proportions (0.5, 1, 3 and 5 wt.%) to evaluate the ability of SiA to improve the thermal, mechanical, and barrier performance of the bionanocomposites. The mechanical performance, thermal stability as well as the barrier properties against different gases (carbon dioxide, nitrogen, and oxygen) of the bionanocomposites were evaluated. It was observed that the addition of 3 wt.% of SiA to the plasticized PLA-ATBC matrix showed simultaneously an improvement on the thermal stability as well as the mechanical and barrier performance of films. Finally, PLA-SiA film formulations were disintegrated in compost at the lab-scale level. The combination of ATBC and SiA sped up the disintegration of PLA matrix. Thus, the bionanocomposites produced here show great potential as sustainable polymeric formulations with interest in the food packaging sector.

Electrospinning of PCL-Based Blends: Processing Optimization for Their Scalable Production.

In this work poly(ε-caprolactone) (PCL) based electrospun mats were prepared by blending PCL with microcrystalline cellulose (MCC) and poly(3-hydroxybutyrate) (PHB). The electrospinning processing parameters were firstly optimized with the aim to obtain scalable PCL-based electrospun mats to be used in the industrial sector. Neat PCL as well as PCL-MCC and PCL-PHB based mats in different proportions (99:1; 95:5; 90:10) were prepared. A complete morphological, thermal and mechanical characterization of the developed materials was carried out. Scanning electron microscopy (SEM) observations showed that the addition of PHB to the PCL matrix considerably reduced the formation of beads. Both the addition of MCC and PHB reduced the thermal stability of PCL, but obtained materials with enough thermal stability for the intended use. The electrospun PCL fibers show greatly reduced flexibility with respect to the PCL bulk material, however when PCL is blended with PHB their stretchability is increased, changing their elongation at break from 35% to 70% when 10 wt% of PHB is blended with PCL. However, the mechanical response of the different blends increases with respect to the neat electrospun PCL, offering the possibility to modulate their properties according to the required industrial applications.

Effect of Iignocellulosic Nanoparticles Extracted from Yerba Mate (Ilex paraguariensis) on the Structural, Thermal, Optical and Barrier Properties of Mechanically Recycled Poly(lactic acid).

In this work, yerba mate nanoparticles (YMNs) were extracted from Ilex paraguairiencis yerba mate wastes and further used to improve the overall performance of mechanically recycled PLA (PLAR). Recycled PLA was obtained by melt reprocessing PLA subjected to an accelerated ageing process, which involved photochemical, thermal and hydrothermal ageing steps, as well as a final demanding washing step. YMNs (1 and 3 wt. %) were added to the PLAR during the melt reprocessing step and further processed into films. The main goal of the development of PLAR-YMNs bionanocomposites was to increase the barrier properties of recycled PLA, while showing good overall performance for food packaging applications. Thus, optical, structural, thermal, mechanical and barrier properties were evaluated. The incorporation of YMNs led to transparent greenish PLAR-based films with an effective blockage of harmful UV radiation. From the backbone FTIR stretching region (bands at 955 and 920 cm-1), it seems that YMNs favor the formation of crystalline domains acting as nucleating agents for PLAR. The morphological investigations revealed the good dispersion of YMNs in PLAR when they are used in the lowest amount of 1 wt. %, leading to bionanocomposites with improved mechanical performance. Although the addition of high hydrophilic YMNs increased the water vapor transmission, the addition of 1 wt. % of YMNs enhanced the oxygen barrier performance of the produced bionanocomposite films. These results show that the synergistic revalorization of post-consumer PLA and nanoparticles obtained from agri-food waste is a potential way for the production of promising packaging materials that meet with the principles of the circular economy.

Improvement of PBAT Processability and Mechanical Performance by Blending with Pine Resin Derivatives for Injection Moulding Rigid Packaging with Enhanced Hydrophobicity.

Polybutylene adipate-co-terephthalate (PBAT) is a biodegradable polymer with good features for packaging applications. However, the mechanical performance and high prices of PBAT limit its current usage at the commercial level. To improve the properties and reduce the cost of PBAT, pine resin derivatives, gum rosin (GR) and pentaerythritol ester of GR (UT), were proposed as sustainable additives. For this purpose, PBAT was blended with 5, 10, and 15 wt.% of additives by melt-extrusion followed by injection moulding. The overall performance of the formulations was assessed by tensile test, microstructural, thermal, and dynamic mechanical thermal analysis. The results showed that although good miscibility of both resins with PBAT matrix was achieved, GR in 10 wt.% showed better interfacial adhesion with the PBAT matrix than UT. The thermal characterization suggested that GR and UT reduce PBAT melting enthalpy and enhance its thermal stability, improving PBAT processability. A 10 wt.% of GR significantly increased the tensile properties of PBAT, while a 15 wt.% of UT maintained PBAT tensile performance. The obtained materials showed higher hydrophobicity than neat PBAT. Thus, GR and UT demonstrated that they are advantageous additives for PBAT-resin compounding for rigid food packaging which are easy to process and adequate for industrial scalability. At the same time, they enhance its mechanical and hydrophobic performance.

Oxygen reduction using a metal-free naphthalene diimide-based covalent organic framework electrocatalyst.

A novel naphthalene diimide-based covalent organic framework (NDI-COF) has been synthesized and successfully exfoliated into COF nanosheets (CONs). Electrochemical measurements reveal that the naphthalene diimide units incorporated into NDI-CONs act as efficient electrocatalyst for oxygen reduction in alkaline media, showing its potential for the development of metal-free fuel cells.

Antioxidant Bilayers Based on PHBV and Plasticized Electrospun PLA-PHB Fibers Encapsulating Catechin.

The main objective of this work was to develop bio-based and biodegradable bilayer systems with antioxidant properties. The outer layer was based on a compression-molded poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)-based material while antioxidant electrospun fibers based on poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) blends formed the inner active layer. In particular, PLA was blended with 25 wt% of PHB to increase the crystallinity of the fibers and reduce the fiber defects. Moreover, in order to increase the stretchability and to facilitate the electrospinning process of the fiber mats, 15 wt% of oligomeric lactic acid was added as a plasticizer. This system was further loaded with 1 wt% and 3 wt% of catechin, a natural flavonoid with antioxidant activity, to obtain antioxidant-active mats for active food packaging applications. The obtained bilayer systems showed effective catechin release capacity into a fatty food simulant. While the released catechin showed antioxidant effectiveness. Finally, bilayer films showed appropriate disintegration in compost conditions in around three months. Thus, showing their potential as bio-based and biodegradable active packaging for fatty food products.

Polymeric Materials: Surfaces, Interfaces and Bioapplications.

This special issue "Polymeric Materials: Surfaces, Interfaces and Bioapplications" was proposed to cover all the aspects related to recent innovations on surfaces, interfaces and bioapplications of polymeric materials. The collected articles show the advances in polymeric materials, which have tremendous applications in agricultural films, food packaging, dental restoration, antimicrobial systems and tissue engineering. We hope that readers will be able to enjoy highly relevant topics that are related to polymers. Therefore, we hope to prove that plastics can be a solution and not a problem.

Bio-Based Polymers with Antimicrobial Properties towards Sustainable Development.

This article concisely reviews the most recent contributions to the development of sustainable bio-based polymers with antimicrobial properties. This is because some of the main problems that humanity faces, nowadays and in the future, are climate change and bacterial multi-resistance. Therefore, scientists are trying to provide solutions to these problems. In an attempt to organize these antimicrobial sustainable materials, we have classified them into the main families; i.e., polysaccharides, proteins/polypeptides, polyesters, and polyurethanes. The review then summarizes the most recent antimicrobial aspects of these sustainable materials with antimicrobial performance considering their main potential applications in the biomedical field and in the food industry. Furthermore, their use in other fields, such as water purification and coating technology, is also described. Finally, some concluding remarks will point out the promise of this theme.