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The development of biomaterials with gradient surface modification capable of spatially controlled cell adhesion and migration is of great importance for tissue engineering and regeneration. In this study, we proposed a method for the covalent modification of PLA-based materials with a cationic polypeptide (polylysine, PLys) via a thiol-ene click reaction carried out under a light gradient. With this aim, PLA-based films were fabricated and modified with 2–aminoethyl methacrylate (AEMA) as a double bond source. The latter was introduced by reacting pre-formed and activated surface carboxyl groups with the amino group of AEMA. The success of the modification was confirmed by 1H NMR, Raman and X-ray photoelectron spectroscopy data. A further photoinduced thiol-ene click reaction in the presence of a photosensitive initiator as a radical source was further optimized using cysteine. For grafting of PLys via the thiol-ene click reaction, PLys with a terminal thiol group was synthesized by ring-opening polymerization using Cys(Acm) as an amine initiator. Deprotection of the polypeptide resulted in the formation of free thiol groups of Cys-PLys. Successful gradient grafting of Cys-PLys was evidenced by covalent staining with the fluorescent dye Cy3-NHS. In addition, PLys gradient-dependent adhesion and migration of HEK 293 cells on PLys-PLA-based surfaces was confirmed.

Replacing traditional disposable, non-biodegradable plastic packaging with biodegradable plastic packaging is one of the key approaches to address the issue of “white pollution”. PBAT/PLA/inorganic filler composites are widely utilized as a biodegradable material, commonly employed in the field of packaging films. However, the poor dispersion of inorganic fillers in the polymer matrix and the limited compatibility between PBAT and PLA have led to inferior mechanical properties and elevated costs. In this work, we propose a simple and effective strategy to improve the dispersion of nano-CaCO3 in a PBAT/PLA matrix through solid-state shear- milling (S3M) technology, combined with mechanochemical modification and in situ compatibilization to enhance the compatibility between PBAT and PLA. The impact of varying milling conditions on the structure and performance of the PBAT/PLA/CaCO3 composites was investigated. During the milling process, PBAT and PLA undergo partial molecular chain fragmentation, generating more active functional groups. In the presence of the chain extender ADR during melt blending, more branched PBAT-g-PLA is formed, thereby enhancing matrix compatibility. The results indicate that the choice of milling materials significantly affects the structure and properties of the composite. The film obtained by milling only PBAT and CaCO3 exhibited the best performance, with its longitudinal tensile strength and fracture elongation reaching 22 MPa and 437%, respectively. This film holds great potential for application in the field of green packaging.

Poly(L-lactic acid) (PLLA) and poly(ε-caprolactone) (PCL), two biodegradable and biocompatible polymers that are commonly used for biomedical applications, are, respectively, the result of the ring-opening polymerization of LA and ε-CL, cyclic esters, which can be produced according to several mechanisms (cationic, monomer-activated cationic, anionic, and coordination-insertion), except for L-lactide, which is polymerized only by anionic, cationic, or coordination-insertion polymerization. A series of well-defined PLLA-b-PCL block copolymers have been obtained starting from the same PLLA homopolymer, having a molar mass of 2500 g·mol−1, and being synthesized by coordination-insertion in the presence of tin octoate. PCL blocks were obtained via a cationic-activated monomer mechanism to limit transesterification reactions, and their molar masses varied from 1800 to 18,500 g·mol−1. The physicochemical properties of the copolymers were determined by 1H NMR, SEC, and DSC. Moreover, a series of nanoparticles (NPs) were prepared starting from these polyester-based copolymers by an emulsification/evaporation method. The sizes of the obtained NPs varied between 140 and 150 nm, as a function of the molar mass of the copolymers. Monomodal distribution curves with PDI values under 0.1 were obtained by Dynamic Light Scattering (DLS) and their spherical shape was confirmed by TEM. The increase in the temperature from 25 to 37 °C induced only a very slight decrease in the NP sizes. The results obtained in this preliminary study indicate that NPs have a temperature stability, allowing us to consider their use as drug-loaded nanocarriers for biomedical applications.

Amid the current environmental crisis caused by plastic accumulation, one of the proposed solutions to manage this problem is using biodegradable polymers. However, the impact of adding biodegradable polymers to the well-established circular economy of recyclable polymers, such as HDPE, has not been fully considered. Therefore, there is a need to reconsider the way we consume, dispose of, and manage biodegradable polymers after use. This study evaluates the effect of varying the contents of a biodegradable polymer, taking poly(lactic acid) (PLA) as a model biodegradable polymer, on the thermal and mechanical properties of HDPE. The study highlights the importance of identifying and disposing of biodegradable polymers to avoid mixtures with HDPE, in order not to affect mechanical performance when considering reprocessing and a new life cycle of this conventional polymer.

In this study, a twin-screw extruder was used to fabricate poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends and blend-based nanocomposites with carbon nanotube (CNT) or nanocarbon black (CB) as nanofillers. The fabricated samples were subsequently treated with supercritical carbon dioxide (scCO2) to fabricate the corresponding foams. Bi-phasic morphology and selective distribution of CNTs or CBs in the PBAT phase were observed in the blends/composites through scanning electron microscopy. After the scCO2 treatment, the selective foaming of the PBAT phase in the prepared blends/composites was confirmed. The cellular structure of PBAT phase in scCO2-treated blends is similar to the size/shape of PBAT domains in untreated blends or treated neat PBAT foam. The addition of CNTs or CBs in the blends led to a slight reduction in cell size of the foamed PBAT phase, demonstrating CNT/CB-induced cell nucleation. Differential scanning calorimetry (DSC) results showed that CNTs and CBs played as nucleating agents and increased the initial crystallization temperature up to 14 °C compared with neat PBAT for PBAT in different composites during cooling. The scCO2 treatment induced the bimodal stability of PBAT crystals in different samples, which melted mainly in two temperature regions in DSC studies. Thermogravimetric analyses revealed that compared with parent blends, the addition of CNTs or CBs increased the temperature at 80 wt.% loss (degradation of PBAT portion) up to 6 °C. The electrical resistivity decreased by more than six orders of magnitude for certain CNT- or CB-added composites compared with the parent blends. The hardness of the blends slightly increased after forming the corresponding composites and then declined after the scCO2 treatment.

Polymer blends of poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-PEG-PLLA) and high-density polyethylene (HDPE) with different blend ratios were prepared by a melt blending method. The thermal, morphological, mechanical, opacity, and biodegradation properties of the PLLA-PEG-PLLA/HDPE blends were investigated and compared to the PLLA/HDPE blends. The blending of HDPE improved the crystallization ability and thermal stability of the PLLA-PEG-PLLA; however, these properties were not improved for the PLLA. The morphology of the blended films showed that the PLLA-PEG-PLLA/HDPE blends had smaller dispersed phases compared to the PLLA/HDPE blends. The PLLA-PEG-PLLA/HDPE blends exhibited higher flexibility, lower opacity, and faster biodegradation and bioerosion in soil than the PLLA/HDPE blends. Therefore, these PLLA-PEG-PLLA/HDPE blends have a good potential for use as flexible and partially biodegradable materials.

The manufacturing method influences the properties of the produced components. This work investigates the influence of manufacturing methods, such as fused deposition modeling (3D printing) and injection molding, on the water absorption and mechanical and thermal properties of the specimens produced from neat bio-based poly(lactic acid) (PLA) polymer and poly(lactic acid)/wood composites. Acrylonitrile butadiene styrene (ABS) acts as the reference material due to its low water absorption and good functional properties. The printing layer thickness is one of the factors that affects the properties of a 3D-printed specimen. The investigation includes two different layer thicknesses (0.2 mm and 0.3 mm) while maintaining uniform overall thickness of the specimens across two manufacturing methods. 3D-printed specimens absorb significantly higher amounts of water than the injection-molded specimens, and the increase in the layer thickness of the 3D-printed specimens contributes to further increased water absorption. However, the swelling due to water absorption in 3D-printed specimens decreases upon increased layer thickness. The tensile, flexural, and impact properties of all of the specimens decrease after water absorption, while the properties improve upon decreasing the layer thickness. Higher porosity upon increasing the layer thickness is the predominant factor. The results from dynamic mechanical analysis and microscopy validate the outcomes. The results from this experimental study highlight the limitations of additive manufacturing.

High-molecular-weight poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-PEG-PLLA) is a flexible and biodegradable bioplastic that has promising potential in flexible food packaging but it has no antibacterial ability. Thus, in this work, the effect of zinc oxide nanoparticles (nano-ZnOs) which have antimicrobial activity on various properties of PLLA-PEG-PLLA was determined. The addition of nano-ZnOs enhanced the crystallization, tensile, UV-barrier, and antibacterial properties of PLLA-PEG-PLLA. However, the crystallization and tensile properties of nanocomposite films decreased again as the nano-ZnO increased beyond 2 wt%. The nano-ZnO was well distributed in the PLLA-PEG-PLLA matrix when the nano-ZnO content did not exceed 2 wt% and exhibited some nano-ZnO agglomerates when the nano-ZnO content was higher than 2 wt%. The thermal stability and moisture uptake of the PLLA-PEG-PLLA matrix decreased and the film’s opacity increased as the nano-ZnO content increased. The PLLA-PEG-PLLA/ZnO nanocomposite films showed good antibacterial activity against bacteria such as Escherichia coli and Staphylococcus aureus. It can be concluded that nano-ZnOs can be used as a multi-functional filler of the flexible PLLA-PEG-PLLA. As a result, the addition of nano-ZnOs as a nucleating, reinforcing, UV-screening, and antibacterial agent in the flexible PLLA-PEG-PLLA matrix may provide protection for both the food and the packaging during transportation and storage.

A quantitative analysis of the morphology, as well as an analysis of the distribution of components and surface/interfacial properties in poly(lactic acid)(PLA) InegoTM 3251D, poly(ε-caprolactone) (PCL) Capa 6800 and nano-silica (SiO2) Aerosil®200 blends, was conducted in this research. The study aimed to improve the understanding of how PLA, PCL, and nano-SiO2 interact, resulting in the specific morphology and surface properties of the blends. Samples were produced by varying the concentration of all three components. They were analyzed using SEM, EDS mapping, water contact angle measurements, surface free energy calculation, adhesion parameter measurements, and FTIR-ATR spectroscopy. The results showed that the addition of SiO2 nanoparticles led to an increase in the contact angle of water, making the surface more hydrophobic. SEM images of the blends showed that increasing the PCL content reduced the size of spherical PCL elements in the blends. FTIR-ATR analysis showed that SiO2 nanoparticles influenced the structure ordering of PLA in the blend with equal portions of PLA and PCL. In the samples with a higher PCL content, the spherical elements present in the samples with a higher PLA/PCL ratio have been reduced, indicating better interactions at the interface between PLA, PCL, and SiO2. SEM-EDS mapping of the PLA/PCL 100/0 blend surfaces revealed the presence of SiO2 clusters and the silicon (Si) concentration reaching up to ten times higher than the nominal concentration of SiO2. However, with the addition of 3% SiO2 to the blend containing PCL, the structure became more granular. Specifically, Si protrusions in the sample PLA/PCL 90/10 with 3% SiO2 displayed 29.25% of Si, and the sample PLA/PCL 70/30 with 3% SiO2 displayed an average of 10.61% of Si at the protrusion locations. The results confirmed the affinity of SiO2 to be encapsulated by PCL. A better understanding of the interactions between the materials in the presented blends and the quantitative analysis of their morphology could improve the understanding of their properties and allow the optimization of their application for different purposes.

Polymeric materials, renowned for their lightweight attributes and design adaptability, play a pivotal role in augmenting fuel efficiency and cost-effectiveness in railway vehicle development. The tailored formulation of compounds, specifically designed for additive manufacturing, holds significant promise in expanding the use of these materials. This study centers on poly(lactic acid) (PLA), a natural-based biodegradable polymeric material incorporating diverse halogen-free flame retardants (FRs). Our investigation scrutinizes the printability and fire performance of these formulations, aligning with the European railway standard EN 45545-2. The findings underscore that FR in the condensed phase, including ammonium polyphosphate (APP), expandable graphite (EG), and intumescent systems, exhibit superior fire performance. Notably, FR-inducing hydrolytic degradation, such as aluminum hydroxide (ATH) or EG, reduces polymer molecular weight, significantly impacting PLA’s mechanical performance. Achieving a delicate balance between fire resistance and mechanical properties, formulations with APP as the flame retardant emerge as optimal. This research contributes to understanding the fire performance and printability of 3D-printed PLA compounds, offering vital insights for the rail industry’s adoption of polymeric materials.

Biodegradable polylactic acid (PLA) has been widely used in fused deposition modeling (FDM) 3D printing. In order to improve its comprehensive properties in 3D printing, in this study, 0-40% content of polybutylene adipate terephthalate(PBAT) was selected to be blended with PLA in a twin-screw extruder; the resulting pellets were drawn into a homogeneous filament; then, PBAT/PLA samples were prepared by FDM 3D printing, and the effects of the dosage of PBAT on the mechanical properties, thermal behavior, surface wettability and melt flowability of the samples were investigated. The results showed that all the samples could be printed smoothly, and the ductility was slightly improved by the increase in the PBAT dosage; the thermal stability of PLA was enhanced by blending with PBAT, and the crystallinity increased monotonically with the increase in PBAT. After blending with PBAT, the surfaces of the samples were more hydrophilic and flowable. The important conclusion achieved in this work was that the PBAT/PLA blends, especially those containing 30%PBAT, showed great potential to replace petroleum-based plastics and are suitable for use in FDM 3D printing technologies for different applications.

This study investigates the use of low molecular weight poly(ethylene glycol) (PEG) as a plasticizer for poly(lactic acid) (PLA). PLA/PEG blend films were prepared using the solvent casting method with varying mixing ratios. The films were analyzed using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and dynamic rheological analysis. The results indicate that the addition of PEG as a plasticizer affects the thermal and mechanical properties of the PLA/PEG blend films. The study found that the glass transition and cold crystallization temperatures decreased with increasing PEG content up to 20 wt%, while the crystallinity and crystallization rate increased. The blends with up to 20 wt% PEG were miscible, but phase separation occurred when the plasticizer content was increased to 30 wt%. Subsequently, amorphous samples of neat PLA and PLA plasticized with 10 wt% of PEG underwent annealing at various temperatures (Ta = 80–120 °C) for durations ta of 1 and 24 h. The samples were then analyzed using DSC and DMA. The addition of PEG to PLA altered the content of α′ and α crystalline forms compared to neat PLA at a given (Ta; ta) and favored the formation of a mixture of α′ and α crystals. The crystallinity achieved upon annealing increased with increasing Ta or ta and with the incorporation of PEG.

Poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-PEG-PLLA) shows promise for use in bioplastic applications due to its greater flexibility over PLLA. However, further research is needed to improve PLLA-PEG-PLLA’s properties with appropriate fillers. This study employed zinc phenylphosphate (PPZn) as a multi-functional filler for PLLA-PEG-PLLA. The effects of PPZn addition on PLLA-PEG-PLLA characteristics, such as crystallization and thermal and mechanical properties, were investigated. There was good phase compatibility between the PPZn and PLLA-PEG-PLLA. The addition of PPZn improved PLLA-PEG-PLLA’s crystallization properties, as evidenced by the disappearance of the cold crystallization temperature, an increase in the crystallinity, an increase in the crystallization temperature, and a decrease in the crystallization half-time. The PLLA-PEG-PLLA’s thermal stability and heat resistance were enhanced by the addition of PPZn. The PPZn addition also enhanced the mechanical properties of the PLLA-PEG-PLLA, as demonstrated by the rise in ultimate tensile stress and Young’s modulus. We can conclude that the PPZn has potential for use as a multi-functional filler for the PLLA-PEG-PLLA composite due to its nucleating-enhancing, thermal-stabilizing, and reinforcing ability.

Essential oils have been identified as effective natural compounds to prevent bacterial infections and thus are widely proposed as bioactive agents for biomedical applications. Across the literature, various essential oils have been incorporated into electrospun fibres to produce materials with, among others, antibacterial, anti-inflammatory and antioxidant activity. However, limited research has been conducted so far on the effect of these chemical products on the physical characteristics of the resulting composite fibres for extended periods of time. Within this work, electrospun fibres of poly(lactic acid) (PLA) were loaded with the essential oil limonene, and the impact of storage conditions and duration (up to 12 weeks) on the thermal degradation, glass transition temperature and mechanical response of the fibrous mats were investigated. It was found that the concentration of the encapsulated limonene changed over time and thus the properties of the PLA–limonene fibres evolved, particularly in the first two weeks of storage (independently from storage conditions). The amount of limonene retained within the fibres, even 4 weeks after fibre generation, was effective to successfully inhibit the growth of model microorganisms Escherichia coli, Staphylococcus aureus and Bacillus subtilis. The results of this work demonstrate the importance of evaluating physical properties during the ageing of electrospun fibres encapsulating essential oils, in order to predict performance modification when the composite fibres are used as constituents of medical devices.

The development of high-performance filtration materials is essential for the effective removal of airborne particles, and metal–organic frameworks (MOFs) anchored to organic polymer matrices are considered to be one of the most promising porous adsorbents for air pollutants. Nowadays, most air filters are generally based on synthetic fiber polymers derived from petroleum residues and have limited functionality, so the use of MOFs in combination with nanofiber air filters has received a lot of attention. Here, a conjugated electrostatic spinning method is demonstrated for the one-step preparation of poly(lactic acid) (PLA) nanofibrous membranes with a bimodal diameter distribution and the anchoring of Zeolitic Imidazolate Framework-8 (ZIF-8) by the introduction of TiO2 and in situ generation to construct favorable multiscale fibers and rough structures. The prepared PLA/TZ maintained a good PM2.5 capture efficiency of 99.97%, a filtration efficiency of 96.43% for PM0.3, and a pressure drop of 96.0 Pa, with the highest quality factor being 0.08449 Pa−1. Additionally, ZIF-8 was uniformly generated on the surface of PLA and TiO2 nanofibers, obtaining a roughened structure and a larger specific surface area. An enhanced filtration retention effect and electrostatic interactions, as well as active free radicals, can be generated for the deep inactivation of bacteria. Compared with the unmodified membrane, PLA/TZ prepared antibacterial characteristics induced by photocatalysis and Zn2+ release, with excellent bactericidal effects against S. aureus and E. coli. Overall, this work may provide a promising approach for the development of efficient biomass-based filtration materials with antimicrobial properties.

In the current contribution, bacterial nanocellulose obtained from a by-product of Kombucha tea production and vegetal nanocellulose isolated from milled rice husks were employed as fillers of PLA-based composites prepared by intensive mixing followed by compression molding. Given the challenges associated with the incorporation of nanocelluloses—initially obtained as aqueous suspensions—into melt compounding processes, and also with achieving a proper dispersion of the hydrophilic nanofillers within PLA, three different nanofibrils incorporation strategies were studied: i.e., direct mixing of dried milled nanocelluloses and PLA; masterbatching by solvent casting of native nanocelluloses followed by melt compounding; and masterbatching by solvent casting of acetylated nanocelluloses followed by melt compounding. Composites with varying filler content (from 0.5 wt.% to 7 wt.%) were characterized in terms of morphology, optical properties, and mechanical performance. Results revealed the relative suitability of each strategy employed to promote nanocelluloses dispersion within the PLA matrix. PLA/nanocellulose masterbatches prepared by solvent casting proved to be particularly useful for feeding the nanocelluloses into the processing equipment in a dry state with limited hornification. Acetylation also contributed to a better dispersion of both nanocelluloses within the PLA matrix, although no clear positive impact on the mechanical properties of the films was observed. Finally, filler loading played an important role in the films’ properties by increasing their stiffness while reducing their translucency.

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.

The brittle behavior of poly(lactic acid) (PLA) and PLA composites with inorganic filler limits their applications; the addition of a toughening agent, such as a rubbery phase, was selected to transform the brittle to ductile behavior for versatility in various applications. This work aims to study the properties of PLA and PLA composite with filled nanosized hydroxyapatite (nHA) after adding modified natural rubber (MoNR), which acts as a toughening agent. MoNR refers to poly(acrylic acid-co-acrylamide)-grafted deproteinized natural rubber. nHA was prepared from fish scales. Its characteristics were investigated and was confirmed to be comparable to those of commercial grade. PLA-MoNR at various MoNR contents and PLA/nHA composites with/without MoNR were prepared by melt mixing. Their morphology, mechanical, and thermal properties were observed and investigated. Samples with MoNR added showed the dispersion of spherical particles, indicating incompatibility. However, the mechanical properties of PLA-MoNR, which had MoNR added at 10 phr, showed toughening behavior (increased impact strength by more than two times compared to that of neat PLA). The PLA/nHA composite with MoNR showed the same result. The addition of MoNR in the composite increased its impact strength by 1.27 times compared to the composite without MoNR. MoNR can be a stress concentrator, resulting in toughened PLA and PLA/nHA composite.

NMR analysis combined with statistical modeling offers a useful approach to investigate the microstructures of polymers. This article provides a selective review of the developments in both the NMR analysis of biobased polymers and the statistical models that can be used to characterize these materials. The information obtained from NMR and statistical models can provide insights into the microstructure and stereochemistry of appropriate biobased polymers and establish a systematic approach to their analysis. In suitable cases, the analysis can help optimize the synthetic procedures and facilitate the development of new or modified polymeric materials for various applications. Examples are given of the studies of poly(hydroxyalkanoates), poly(lactic acid), and selected polysaccharides, e.g., alginate, pectin, and chitosan. This article may serve as both a reference and a guide for future workers interested in the NMR sequence analysis of biobased materials.

Recent studies have shown that astronauts experience altered immune response behavior during spaceflight, resulting in heightened susceptibility to illness. Resources and resupply shuttles will become scarcer with longer duration spaceflight, limiting access to potentially necessary medical treatment and facilities. Thus, there is a need for preventative health countermeasures that can exploit in situ resource utilization technologies during spaceflight, such as additive manufacturing (i.e., 3D printing). The purpose of the current study was to test and validate recyclable antimicrobial materials compatible with additive manufacturing. Antimicrobial poly(lactic acid)- and polyurethane-based materials compatible with 3D printing were assessed for antimicrobial, mechanical, and chemical characteristics before and after one closed-loop recycling cycle. Our results show high biocidal efficacy (>90%) of both poly(lactic acid) and polyurethane materials while retaining efficacy post recycling, except for recycled-state polyurethane which dropped from 98.91% to 0% efficacy post 1-year accelerated aging. Significant differences in tensile and compression characteristics were observed post recycling, although no significant changes to functional chemical groups were found. Proof-of-concept medical devices developed show the potential for the on-demand manufacturing and recyclability of typically single-use medical devices using antimicrobial materials that could serve as preventative health countermeasures for immunocompromised populations, such as astronauts during spaceflight.

Commercially available poly(lactic acid) exhibits poor hydrolytic stability, which makes it impossible for use in durable applications. Therefore, a novel hydrolysis inhibitor based on an aziridine derivative as well as a novel stabilizer composition, containing an aziridine derivative and an acid scavenger, were investigated to improve the hydrolytic stability. To evaluate the stabilizing effect, the melt volume rate (MVR) and molecular weight were monitored during an accelerated hydrolytic aging in water at elevated temperatures. Temperatures were selected according to the glass transition temperature (~60 °C) of PLA. It was shown that the novel hydrolysis inhibitor as well as the novel stabilizer composition exhibited excellent performance during hydrolytic aging, exceeding commercially available alternatives, e.g., polymeric carbodiimides. A molecular weight analysis resulted in a molecular weight decrease of only 10% during approximately 850 h and up to 20% after 1200 h of hydrolytic aging, whereas poly(lactic acid) stabilized with a commercial polycarbodiimide revealed comparable molecular weight reductions after only 300 h. Furthermore, the stabilization mechanism of the aziridine derivative alone, as well as in the synergistic combination with the acid scavenger (calcium hydrotalcite), was investigated using nuclear magnetic resonance (NMR) spectroscopy. In addition to an improved hydrolytic stability, the thermal properties were also enhanced compared to polymeric carbodiimides.

Nanofibers are some of the most attractive materials that can modify functionalities for developing new kinds of specific applications and are mainly used as a biomedical material. Herein, we designed and prepared antibacterial nonwoven fiber mats of PLA and PLA composited with Ag nanoparticles by electrospinning. The effects of varying filler contents on their chemical, surface morphology, thermal, water absorbency, and antibacterial properties were investigated using FTIR, SEM/EDS, DSC, swelling ratio, and qualitative and quantitative antibacterial tests. FTIR and EDS spectra indicated that Ag nanoparticles were incorporated in the PLA without chemical bonding. SEM revealed that the average diameter of the PLA nanofibers containing the Ag nanoparticles was more significant than those without those particles. In addition, fiber diameters are proportional to the amount of Ag nanoparticle contents. DSC indicated that the Ag nanoparticles can be incorporated within the PLA matrix without strongly affecting their thermal properties. Moreover, the crystallinity of the composite nonwoven fiber mats was higher than those of fiber mats in the neat PLA. However, TGA revealed that the loaded Ag can improve the thermal stability of the PLA electrospun fiber mats. Accordingly, the antibacterial activities revealed that all the composite nanofiber mats exhibited excellent resistance against S. aureus and E. coli bacterial strains. In addition, in the cell toxicity study, all produced hybrids of nonwoven fiber mats induced a reduction in cell viability for the L929 fibroblast cells. Our results suggest that the designed and prepared nonwoven fiber mats may have good potential for use in the biomedical field, particularly in wound dressing applications.

Poly(lactic acid) (PLA), derived from renewable resources, plays a significant role in the global biodegradable plastic market. However, its widespread adoption faces challenges, including high brittleness, hydrophobicity, limited biodegradability, and higher costs compared to traditional petroleum-based plastics. This study addresses these challenges by incorporating thermoplastic pineapple stem starch (TPSS) and modified natural rubber (MNR) into PLA blends. TPSS, derived from pineapple stem waste, is employed to enhance hydrophilicity, biodegradability, and reduce costs. While the addition of TPSS (10 to 40 wt.%) marginally lowered mechanical properties due to poor interfacial interaction with PLA, the inclusion of MNR (1 to 10 wt.%) in the PLA/20TPSS blend significantly improved stretchability and impact strength, resulting in suitable modulus (1.3 to 1.7 GPa) and mechanical strength (32 to 52 MPa) for diverse applications. The presence of 7 wt.% MNR increased impact strength by 90% compared to neat PLA. The ternary blend exhibited a heterogeneous morphology with enhanced interfacial adhesion, confirmed by microfibrils and a rough texture on the fracture surface. Additionally, a downward shift in PLA’s glass transition temperature (Tg) by 5–6 °C indicated improved compatibility between components. Remarkably, the PLA ternary blends demonstrated superior water resistance and proper biodegradability compared to binary blends. These findings highlight the potential of bio-based plastics, such as PLA blends with TPSS and MNR, to contribute to sustainable economic models and reduce environmental impact for using in plastic packaging applications.

Poly(lactic acid) (PLA) and Poly(butylene succinate) (PBS) were chosen as raw materials and melt blended by a twin screw extruder and pelletized; then, the pellets were extruded into filaments; after that, various PBS/PLA blending samples were prepared by Fused Deposition Molding (FDM) 3D printing technology using the filaments obtained and the effect of the dosage of PBS on technological properties of 3D-printed specimens was investigated. For comparison, the PLA specimen was also prepared by FDM printing. The tensile strength, tensile modulus, thermal stability, and hydrophilicity became poorer with increasing the dosage of PBS, while the flexural strength, flexural modulus, impact strength, and crystallinity increased first and then decreased. The blend containing 10% PBS (10% PBS/PLA) had the greatest flexural strength of 60.12 MPa, tensile modulus of 2360.04 MPa, impact strength of 89.39 kJ/m2, and crystallinity of 7.4%, which were increased by 54.65%, 61.04%, 14.78%, and 51.02% compared to those of printed PLA, respectively; this blend also absorbed the least water than any other specimen when immersed in water. Different from the transparent PLA filament, 10% PBS/PLA filament presented a milky white appearance. The printed 10% PBS/PLA specimen had a smooth surface, while the surface of the printed PLA was rough. All the results indicated that the printed 10% PBS/PLA specimen had good comprehensive properties, including improved mechanical properties, crystallization performance, and surface quality than PLA, as well as proper wettability and water absorption. The prominent conclusion achieved in this work was that 10% PBS/PLA should be an ideal candidate for biodegradable feedstock among all the PBS/PLA blends for FDM 3D printing.

This study investigates the fluoride release, rechargeability and degradation behaviors of newly developed anticariogenic poly(lactic acid) (PLA) composites. The PLA composite with various concentrations (0%, 5%, 10%, 15% and 20% by weight) of glass ionomer cement (GIC) and sodium fluoride (NaF) were prepared using solvent casting method. The fluoride release, fluoride rechargeability and degradation behavior were evaluated. All experimental groups demonstrated fluoride-releasing ability. The highest level of fluoride ions released was found in PLA composite with sodium fluoride (PLA/NaF). Following the 28-day period, both groups showed a gradual reduction in fluoride ion released, ranging between 0.03 ± 0.01 and 0.53 ± 0.06 ppm, although remaining within the effective range for tooth remineralization. However, the rechargeability was only observed in PLA composite with GIC (PLA/GIC). Following an eight-week in vitro degradation test, all PLA/NaF groups displayed a significantly higher percentage of weight change and water absorption compared to the PLA/GIC and the control group. In SEM analysis, the formation of surface porosities was clearly noticed in all PLA/NaF. All specimens retained their structural integrity throughout the study. In conclusion, the newly developed PLA/GIC displays promising possibilities as an anticariogenic material. Furthermore, the rechargeability of these ions are repeatable, ensuring their long-term utility.

Flexible poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) block copolymer (PLLA-PEG-PLLA) bioplastic has been blended with low-cost thermoplastic starch (TPS) to prepare fully biodegradable bioplastics. However, the mechanical properties of PLLA-PEG-PLLA matrix decrease after the addition of TPS. In this work, citric acid (CA) was used as a compatibilizer to improve the phase compatibility and mechanical properties of PLLA-PEG-PLLA/TPS blends. TPS was first modified with CA (1.5 %wt, 3 %wt, and 4.5%wt) before melt blending with PLLA-PEG-PLLA. The PLLA-PEG-PLLA/modified TPS ratio was constant at 60/40 by weight. CA modification of TPS suppressed the crystallinity and enhanced the thermal stability of the PLLA-PEG-PLLA matrix, as determined through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. The compatibility between the dispersed TPS and PLLA-PEG-PLLA phases was improved through modification of TPS with CA, as revealed by the smaller size of the co-continuous TPS phase from scanning electron microscopy (SEM) analysis. Increasing the hydrophilicity of the blends containing modified TPS confirmed the improvement in phase compatibility of the components. From the tensile test, the ultimate tensile strength, elongation at break, and Young’s modulus of the blends increased with the CA content. In conclusion, CA showed a promising behavior in improving the phase compatibility and mechanical properties of PLLA-PEG-PLLA/TPS blends. These PLLA-PEG-PLLA/modified TPS blends have potential to be used as flexible bioplastic products.

The present work deeply studied the mechanical behavior of woven non-woven PLA/OLA/MgO electrospun fibers, efibers, by using Box–Wilson surface response methodology. This work follows up a previous one where both the diameters and the thermal response of such efibers were discussed in terms of both the different amounts of magnesium oxide nanoparticles, MgO, as well as of the oligomer (lactic acid), OLA, used as plasticizer. The results of both works, in term of diameters, degree of crystallinity, and mechanical response, can be strongly correlated to each other, as reported here. In particular, the strain mechanism of PLA/OLA/MgO efibers was studied, showing an orientation of efibers parallel to the applied stress and identifying the mechanically weakest points that yielded the start of the breakage of efibers. Moreover, we identified 1.5 wt% as the critical amount of MgO, above which the plasticizing effect of OLA was weaker as the amount of both components increased. Moreover, the minimum elastic modulus value took place at 15 wt% of OLA, in agreement with the previously reported convergence point in the evolution of the degree of crystallinity. Regarding the yield point, a concentration of OLA between 20 and 30 wt% led to a slight improvement in the yielding capability in terms of tensile strength in comparison with neat PLA efibers. Therefore, the approach presented here permits the design of tailor-made electrospun nanocomposites with specific mechanical requirements.

Wood flour–poly(butylene succinate)–poly(lactic acid) biocomposite samples were prepared by fused-deposition-molding 3D-printing technology, and modifications with glycerol and a silane coupling agent (KH550) were carried out. The samples were then hydrothermally aged. Modification with glycerol and KH550 enhanced the hydrophilicity of the samples and increased their tensile strength. Hydrothermal aging clearly whitened the surfaces of all the samples and made them more hydrophobic. Meanwhile, their tensile properties and thermal stability became poor; a higher hydrothermal aging temperature affected the mechanical properties more negatively. The modified samples turned out to be more resistant to the hydrothermal aging, and modification with KH550 could improve the anti-hydrothermal aging properties of the samples better than that with glycerol, where the tensile properties and the cross-sectional morphologies of the fractured specimens were concerned. Generally, the effects of hydrothermal aging temperature on the physico-mechanical properties of the printed specimens were greater than those by hydrothermal aging time.

Replacing traditional disposable, non-biodegradable plastic packaging with biodegradable plastic packaging is one of the key approaches to address the issue of "white pollution". PBAT/PLA/inorganic filler composites are widely utilized as a biodegradable material, commonly employed in the field of packaging films. However, the poor dispersion of inorganic fillers in the polymer matrix and the limited compatibility between PBAT and PLA have led to inferior mechanical properties and elevated costs. In this work, we propose a simple and effective strategy to improve the dispersion of nano-CaCO 3 in a PBAT/PLA matrix through solid-state shear- milling (S 3 M) technology, combined with mechanochemical modification and in situ compatibilization to enhance the compatibility between PBAT and PLA. The impact of varying milling conditions on the structure and performance of the PBAT/PLA/CaCO 3 composites was investigated. During the milling process, PBAT and PLA undergo partial molecular chain fragmentation, generating more active functional groups. In the presence of the chain extender ADR during melt blending, more branched PBAT-g-PLA is formed, thereby enhancing matrix compatibility. The results indicate that the choice of milling materials significantly affects the structure and properties of the composite. The film obtained by milling only PBAT and CaCO 3 exhibited the best performance, with its longitudinal tensile strength and fracture elongation reaching 22 MPa and 437%, respectively. This film holds great potential for application in the field of green packaging.

The development of biomaterials with gradient surface modification capable of spatially controlled cell adhesion and migration is of great importance for tissue engineering and regeneration. In this study, we proposed a method for the covalent modification of PLA-based materials with a cationic polypeptide (polylysine, PLys) via a thiol-ene click reaction carried out under a light gradient. With this aim, PLA-based films were fabricated and modified with 2-aminoethyl methacrylate (AEMA) as a double bond source. The latter was introduced by reacting pre-formed and activated surface carboxyl groups with the amino group of AEMA. The success of the modification was confirmed by 1 H NMR, Raman and X-ray photoelectron spectroscopy data. A further photoinduced thiol-ene click reaction in the presence of a photosensitive initiator as a radical source was further optimized using cysteine. For grafting of PLys via the thiol-ene click reaction, PLys with a terminal thiol group was synthesized by ring-opening polymerization using Cys(Acm) as an amine initiator. Deprotection of the polypeptide resulted in the formation of free thiol groups of Cys-PLys. Successful gradient grafting of Cys-PLys was evidenced by covalent staining with the fluorescent dye Cy3-NHS. In addition, PLys gradient-dependent adhesion and migration of HEK 293 cells on PLys-PLA-based surfaces was confirmed.

Poly(L-lactic acid) (PLLA) and poly(ε-caprolactone) (PCL), two biodegradable and biocompatible polymers that are commonly used for biomedical applications, are, respectively, the result of the ring-opening polymerization of LA and ε-CL, cyclic esters, which can be produced according to several mechanisms (cationic, monomer-activated cationic, anionic, and coordination-insertion), except for L-lactide, which is polymerized only by anionic, cationic, or coordination-insertion polymerization. A series of well-defined PLLA-b-PCL block copolymers have been obtained starting from the same PLLA homopolymer, having a molar mass of 2500 g·mol -1 , and being synthesized by coordination-insertion in the presence of tin octoate. PCL blocks were obtained via a cationic-activated monomer mechanism to limit transesterification reactions, and their molar masses varied from 1800 to 18,500 g·mol -1 . The physicochemical properties of the copolymers were determined by 1 H NMR, SEC, and DSC. Moreover, a series of nanoparticles (NPs) were prepared starting from these polyester-based copolymers by an emulsification/evaporation method. The sizes of the obtained NPs varied between 140 and 150 nm, as a function of the molar mass of the copolymers. Monomodal distribution curves with PDI values under 0.1 were obtained by Dynamic Light Scattering (DLS) and their spherical shape was confirmed by TEM. The increase in the temperature from 25 to 37 °C induced only a very slight decrease in the NP sizes. The results obtained in this preliminary study indicate that NPs have a temperature stability, allowing us to consider their use as drug-loaded nanocarriers for biomedical applications.

With the continuous improvement of the standard of living, people are increasingly inclined towards natural, green, and environmentally friendly products. Plant-based products that are safe, natural, non-toxic, and beneficial to human health are often more favored. Poly(lactic acid) (PLA) is a polymer obtained through lactate polymerization using renewable plant resources such as corn and has excellent biocompatibility and biodegradability. It is widely used in the field of food packaging. Wormwood oil (WO) is an oil extracted from the stems and leaves of Artemisia plants, and it has broad-spectrum antibacterial properties. In this article, through electrospinning technology, wormwood oil was directly incorporated into PLA, giving the PLA nanofiber membrane antioxidant and antibacterial functions. Various parameters such as voltage (11 KV, 13 KV, 15 KV), spinning solution concentration (8%, 10%, 12%), distance (15 cm, 17 cm, 19 cm), and feeding rate (0.4 mL/h, 0.5 mL/h, 0.6 mL/h) were explored, and the resulting spun fibers were characterized. Through SEM characterization, it was found that when the spinning voltage was 13 KV, the spinning solution concentration was 10%, the distance was 17 cm, and the feeding rate was 0.5 mL/h, the nanofiber membrane had a smooth morphology without bead formation, with an average diameter of 260 nm. The nanofiber membrane was characterized using FTIR, TG, and SEM, confirming the successful incorporation of artemisia essential oil into PLA. The prepared antimicrobial nanofilm was subjected to antimicrobial testing, and the results showed that as the concentration of the essential oil increased, the inhibition zones also increased. When wormwood oil concentration was 4%, the diameter of the inhibition zone for Staphylococcus aureus increased from 1.0 mm to 3.5 mm, while the diameter of the inhibition zone for Escherichia coli increased from 2.0 mm to 4.5 mm.

The multiple roles of organic nanofillers in biodegradable nanocomposites (NC) with a blend-based matrix is not yet fully understood. This work highlights combination of reinforcing and structure-directing effects of chitin nanowhiskers (CNW) with different degrees of deacetylation (DA), i.e., content of primary or secondary amines on their surface, in the nanocomposite with the PCL/PLA 1:1 matrix. Of importance is the fact that aminolysis with CNW leading to chain scission of both polyesters, especially of PLA, is practically independent of DA. DA also does not influence thermal stability. At the same time, the more marked chain scission/CNW grafting for PLA in comparison to PCL, causing changes in rheological parameters of components and related structural alterations, has crucial effects on mechanical properties in systems with a bicontinuous structure. Favourable combinations of multiple effects of CNW leads to enhanced mechanical performance at low 1% content only, whereas negative effects of structural changes, particularly of changed continuity, may eliminate the reinforcing effects of CNW at higher contents. The explanation of both synergistic and antagonistic effects of structures formed is based on the correspondence of experimental results with respective basic model calculations.

Composite materials containing natural reinforcement fibers, generally called biocomposites, have attracted the interest of both researchers and manufacturers, but the most environmentally advantageous combinations include a bio-based matrix, as well. With this in mind, a poly(lactic acid) (PLA) matrix was reinforced with natural fibers from hemp, both untreated strands (UHSs) and soda-bleached fibers (SBHFs). The preparation of the subsequent fully bio-sourced, discontinuously reinforced composites involved kinetic mixing, intensive single-screw extrusion, milling, and injection molding. Up to a fiber content of 30 wt%, the tensile modulus increased linearly with the volume fraction of the dispersed phase. Differences between SBHFs (up to 7.6 Gpa) and UHSs (up to 6.9 Gpa) were hardly significant (p = 0.1), but SBHF-reinforced composites displayed higher strain at failure. In any case, for the same fiber load (30 wt%), the Young’s modulus of PLA/hemp biocomposites was greater than that of glass fiber (GF)-reinforced polypropylene (5.7 GPa), albeit lower than that of PLA/GF (9.8 GPa). Considering all the measurements, the contribution of each phase was analyzed by applying the Hirsch model and the Tsai-Pagano model. As a concluding remark, although the intrinsic tensile modulus of SBHFs was lower than that of GF, the efficiency of those natural fibers as reinforcement (according to the rule of mixtures) was found to be higher.

This manuscript details the preparation and characterization of a renewable biocomposite material intended as a soil conditioner based on low-molecular-weight poly(lactic acid) (PLA) and residual biomass (wheat straw and wood sawdust). The swelling properties and biodegradability of the PLA-lignocellulose composite under environmental conditions were evaluated as indicators of its potential for applications in soil. Its mechanical and structural properties were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). Results showed that the incorporation of lignocellulose waste material into PLA increased the swelling ratio of the biocomposite by up to 300%. The application of the biocomposite of 2 wt% in soil enhanced its capacity for water retention by 10%. In addition, the cross-linked structure of the material proved to be capable of swelling and deswelling repeatedly, indicating its good reusability. Incorporating lignocellulose waste in the PLA enhanced its stability in the soil environment. After 50 days of the experiment, almost 50% of the sample had degraded in the soil.

Astragalus residue powder (ARP)/thermoplastic starch (TPS)/poly(lactic acid) (PLA) biocomposites were prepared by fused-deposition modeling (FDM) 3D-printing technology for the first time in this paper, and certain physico-mechanical properties and soil-burial-biodegradation behaviors of the biocomposites were investigated. The results showed that after raising the dosage of ARP, the tensile and flexural strengths, the elongation at break and the thermal stability of the sample decreased, while the tensile and flexural moduli increased; after raising the dosage of TPS, the tensile and flexural strengths, the elongation at break and the thermal stability all decreased. Among all of the samples, sample C—which was composed of 11 wt.% ARP, 10 wt.% TPS and 79 wt.% PLA—was the cheapest and also the most easily degraded in water. The soil-degradation-behavior analysis of sample C showed that, after being buried in soil, the surfaces of the samples became grey at first, then darkened, after which the smooth surfaces became rough and certain components were found to detach from the samples. After soil burial for 180 days, there was weight loss of 21.40%, and the flexural strength and modulus, as well as the storage modulus, reduced from 82.1 MPa, 11,922.16 MPa and 2395.3 MPa to 47.6 MPa, 6653.92 MPa and 1476.5 MPa, respectively. Soil burial had little effect on the glass transition, cold crystallization or melting temperatures, while it reduced the crystallinity of the samples. It is concluded that the FDM 3D-printed ARP/TPS/PLA biocomposites are easy to degrade in soil conditions. This study developed a new kind of thoroughly degradable biocomposite for FDM 3D printing.

Poly(lactic acid) (PLA) composites with 0.5 wt% lignin or nanolignin were prepared with two different techniques: (a) conventional melt-mixing and (b) in situ Ring Opening Polymerization (ROP) by reactive processing. The ROP process was monitored by measuring the torque. The composites were synthesized rapidly using reactive processing that took under 20 min. When the catalyst amount was doubled, the reaction time was reduced to under 15 min. The dispersion, thermal transitions, mechanical properties, antioxidant activity, and optical properties of the resulting PLA-based composites were evaluated with SEM, DSC, nanoindentation, DPPH assay, and DRS spectroscopy. All reactive processing-prepared composites were characterized by means of SEM, GPC, and NMR to assess their morphology, molecular weight, and free lactide content. The benefits of the size reduction of lignin and the use of in situ ROP by reactive processing were demonstrated, as the reactive processing-produced nanolignin-containing composites had superior crystallization, mechanical, and antioxidant properties. These improvements were attributed to the participation of nanolignin in the ROP of lactide as a macroinitiator, resulting in PLA-grafted nanolignin particles that improved its dispersion.

FDM (Fused Deposition Modeling) is one of the most used and industrially applied additive manufacturing processes due to its fast prototyping and manufacturing, simplicity, and low cost of the equipment. However, the mechanical properties of the printed products have a large dependence on orientation and interface strength between layers which is mainly related to the thermal union obtained. This thermal union has a large dependence on the melting and cooling down process. Additionally, the materials used must be extruded in a continuous filament before their use, which limits the materials used. However, a pellet extruder could be used directly in the printing equipment, avoiding filament extrusion. In this work, specimens of PLA (Poly(lactic acid)) with different bead orientations have been produced via filament or pellet extrusion to compare the effect of the different melting processes in the manufacturing methodology. Pellet extruded specimens showed higher infill and mechanical properties. These results were related to better adhesion between layers due to the longer melting and cooling process. The result was confirmed using DSC and XRD techniques, where a higher crystallinity was observed. A bicomponent specimen (50% pellet–50% filament) was prepared and tested, showing higher mechanical results than expected, which was, again, due to the better thermal union obtained in the pellet extruder.

This review paper presents an overview of the state of the art on process-induced degradation of poly(lactic acid) (PLA) and the relative importance of different processing variables. The sensitivity of PLA to degradation, especially during melt processing, is considered a significant challenge as it may result in deterioration of its properties. The focus of this review is on degradation during melt processing techniques such as injection molding and extrusion, and therefore it does not deal with biodegradation. Firstly, the general processing and fundamental variables that determine the degradation are discussed. Secondly, the material properties (for example rheological, thermal, and mechanical) are presented that can be used to monitor and quantify the degradation. Thirdly, the effects of different processing variables on the extent of degradation are reviewed. Fourthly, additives are discussed for melt stabilization of PLA. Although current literature reports the degradation reactions and clearly indicates the effect of degradation on PLA’s properties, there are still knowledge gaps in how to select and predict the processing conditions that minimize process-induced degradation to save raw materials and time during production.

Thermoplastic starch was blended with commercially available biodegradable polyesters of poly(butylene adipate-co-terephthalate) (PBAT) and poly(lactic acid) (PLA) for its improved performance and processability. The morphology and elemental composition of these biodegradable polymer blends were observed by scanning electron microscopy and energy dispersive X-ray spectroscopy, respectively, while their thermal properties were analyzed using thermogravimetric analysis and differential thermal calorimetry. For rheological analysis, the steady shear and dynamic oscillation tests of three samples at various temperatures were investigated using a rotational rheometer. All three samples exhibited significant shear thinning at all measured temperatures, and their shear viscosity behavior was plotted using the Carreau model. The frequency sweep tests showed that the thermoplastic starch sample exhibited a solid state at all temperatures tested, whereas both starch/PBAT and starch/PBAT/PLA blend samples exhibited viscoelastic liquid behavior after the melting temperature such that their loss modulus at low frequencies was greater than the storage modulus, and inversion occurred at high frequencies (storage modulus > loss modulus).

Poly(lactic acid) (PLA) is a common biobased film-former made from renewable biomass, such as polysaccharides from sugarcane, corn, or cassava. It has good physical properties but is relatively expensive when compared to the plastics used for food packaging. In this work, bilayer films were designed, incorporating a PLA layer and a layer of washed cottonseed meal (CSM), an inexpensive agro-based raw material from cotton manufacturing, where the main component is cottonseed protein. These bilayer films were made through the solvent casting method. The combined thickness of the PLA/CSM bilayer film was between 47 and 83 μm. The thickness of the PLA layer in this film was 10%, 30%, or 50% of the total bilayer film’s thickness. Mechanical properties of the films, opacity, water vapor permeation, and thermal properties were evaluated. Since PLA and CSM are both agro-based, sustainable, and biodegradable, the bilayer film may be used as an eco-friendlier food packaging material, which helps reduce the environmental problems of plastic waste and microplastics. Moreover, the utilization of cottonseed meal may add value to this cotton byproduct and provide a potential economic benefit to cotton farmers.

Production of biocompatible composite scaffolds shifts towards additive manufacturing where thermoplastic biodegradable polymers such as poly(lactic acid) (PLA) are used as matrices. Differences between industrial- and medical-grade polymers are often overlooked although they may affect properties and degradation behaviour as significantly as the filler addition. In the present research, composite films based on medical-grade PLA and biogenic hydroxyapatite (HAp) with 0, 10, and 20 wt.% of HAp were prepared by solvent casting technique. The degradation of composites incubated in phosphate-buffered saline solution (PBS) at 37 °C after 10 weeks showed that the higher HAp content slowed down the hydrolytic PLA degradation and improved its thermal stability. Morphological nonuniformity after degradation was indicated by the different glass transition temperatures (Tg) throughout the film. The Tg of the inner part of the sample decreased significantly faster compared with the outer part. The decrease was observed prior to the weight loss of composite samples.

Astragalus is widely cultivated in China, and the residue of Astragalus particles (ARP) can be used as reinforcements in fused filament-fabricated (FFF) natural fiber/Poly(lactic acid)(PLA) biocomposites. To clarify the degradation behavior of such biocomposites, 3D-printed 11 wt% ARP/PLA samples were buried in soil, and the effects of soil burial duration on the physical appearance, weight, flexural properties, morphology, thermal stability, melting, and crystallization properties were investigated. At the same time, 3D-printed PLA was chosen as a reference. The results showed that, with prolonged soil burial, the transparency of PLA decreased (but not obviously), while the surface photographs of ARP/PLA became gray with some black spots and crevices; especially after 60 days, the color of the samples became extremely heterogeneous. After soil burial, the weight, flexural strength, and flexural modulus of the printed samples all reduced, and greater losses happened to ARP/PLA pieces than pure PLA. With an increase in soil burial time, the glass transition, cold crystallization, and melting temperatures, as well as the thermal stability of PLA and ARP/PLA samples, all increased gradually. Additionally, soil burial had a greater effect on the thermal properties of ARP/PLA. The results showed that the degradation behavior of ARP/PLA was more significantly affected by soil burial than the behavior of PLA. Additionally, ARP/PLA more easily degraded in soil than PLA.

The paper presents the influence of the loading modelling on the simulation process results of the bending behaviour for 3D printed structures. The study is done on structures having different geometries of the cross section, and the type of structure is bar or tube. The materials used for 3D printing are poly(lactic) acid and poly(lactic acid) mixed with glass fibres. The simulation was carried out both based on a simple modelling (schematization) of the bending loading and a complex one. The complex modelling reproduces the bending of 3D printed structures more accurately but is also more time-consuming for the computer-aided design stage. Analysis of the study results shows that in terms of the Von Mises stresses determined by simulation, they are in line with those of the tests but with a slight advantage for the complex modelling compared to the simple one. In terms of deformations, the simulation introduces errors compared to the test results, but the source of the errors is the high elasticity of some 3D printed structures. The study also shows that the high elasticity is due to both the shape of the structure cross section and its arrangement during the bending test.

Different parts of bones possess different properties, such as the capacity for remodeling cell content, porosity, and protein composition. For various traumatic or surgical tissue defects, the application of tissue-engineered constructs seems to be a promising strategy. Despite significant research efforts, such constructs are still rarely available in the clinic. One of the reasons is the lack of resorbable materials, whose properties can be adjusted according to the intended tissue or tissue contacts. Here, we present our first results on the development of a toolbox, by which the scaffolds with easily tunable mechanical and biological properties could be prepared. Biodegradable poly(lactic acid) and nanocrystalline cellulose methacrylated particles were obtained, characterized, and used for preparation of three-dimensional scaffolds via cryogelation and 3D printing approaches. The composition of particles-based ink for 3D printing was optimized in order to allow formation of stable materials. Both the modified-particle cytotoxicity and the matrix-supported cell adhesion were evaluated and visualized in order to confirm the perspectives of materials application.

The effect of shear history on structure development during post-processing annealing was studied using poly(lactic acid) PLA. Since PLA shows a low crystallization rate, quenched films had no crystallinity. Moreover, molecular orientation was not detected in the films. During the annealing procedure beyond its glass transition temperature, however, molecular orientation to the flow direction occurred with the crystallization growth in the films having an appropriate shear history. This peculiar crystal growth during the annealing was most probably attributed to the crystallization from extended chain crystals generated during the applied shear history, although the amount of extended chain crystals was low. The results obtained in this study should be noted because the molecular orientation proceeded due to the annealing history applied. Furthermore, this phenomenon will be used to suppress dimensional change and increase product rigidity.

Poly(L-lactide) (PLLA) is a promising candidate as a bioplastic because of its non-toxicity and biodegradability. However, the low flexibility of PLLA limits its use in many applications. Poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-b-PEG-b-PLLA) block copolymer is of interest for bioplastic applications due to its superior flexibility compared to PLLA. The aim of this work is to modify PLLA-b-PEG-b-PLLA using a low-cost calcium carbonate (CaCO3) filler to improve material properties compared to PLLA/CaCO3 composites. The addition of CaCO3 enhanced the crystallinity and thermal stability for the PLLA-b-PEG-b-PLLA matrix but not for the PLLA matrix, as determined by differential scanning calorimetry (DSC), X-ray diffractometry (XRD), and thermogravimetric analysis (TGA). Phase morphology investigation using scanning electron microscopy (SEM) revealed that the interfacial adhesion between PLLA-b-PEG-b-PLLA and CaCO3 was stronger than between PLLA and CaCO3. Additionally, tensile testing was carried out to determine the mechanical properties of the composites. With the addition of CaCO3, the tensile stress and Young’s modulus of the PLLA-b-PEG-b-PLLA matrix were increased, whereas these properties of the PLLA matrix were significantly decreased. Thus, CaCO3 shows great promise as an inexpensive filler that can induce nucleation and reinforcing effects for PLLA-b-PEG-b-PLLA bioplastics.

Ternary-blended, melt-blown films of polylactide (PLA), polycaprolactone (PCL) and cellulose acetate butyrate (CAB) were prepared from preliminary miscibility data using a rapid screening method and optical ternary phase diagram (presented as clear, translucent, and opaque regions) as a guide for the composition selection. The compositions that provided optically clear regions were selected for melt blending. The ternary (PLA/PCL/CAB) blends were first melt-extruded and then melt-blown to form films and characterized for their tensile properties, tensile fractured-surface morphology, miscibility, crystallinity, molecular weight and chemical structure. The results showed that the tensile elongation at the break (%elongation) of the ternary-blended, melt-blown films (85/5/10, 75/10/15, 60/15/25 of PLA/PCL/CAB) was substantially higher (>350%) than pure PLA (ca. 20%). The range of compositions in which a significant increase in %elongation was observed at 55–85% w/w PLA, 5–20% w/w PCL and 10–25% w/w CAB. Films with high %elongation all showed good interfacial interactions between the dispersed phase (PCL and CAB) and matrix (PLA) in FE-SEM and showed improvements in miscibility (higher intermolecular interaction and mixing) and a decrease in the glass transition temperature, when compared to the low %elongation films. The decrease in Mw and Mn and the formation of the new NMR peaks (1H NMR at 3.68–3.73 ppm and 13C NMR at 58.54 ppm) were observed in only the high %elongation films. These are expected to be in situ compatibilizers that are generated during the melt processing, mostly by chain scission. In addition, mathematical modelling was used to study the optimal ratio and cost-effectiveness of blends with optimised mechanical properties. These ternary-blended, melt-blown films have the potential for use in both packaging and medical devices with excellent mechanical performance as well as inherent economic and environmental capabilities.

In this study, the effects of the post-ultraviolet-curing process on the flexural, absorptive, and morphological properties of poly(lactic acid) specimens produced using a fused deposition modelling technique 3D printer were experimentally investigated. In this direction, 15, 30, 45, and 60 min post-UV-curing processes were applied to poly(lactic acid) three-point bending and absorption specimens produced at 190 and 200 °C. Three-point bending tests and morphological analyses were applied after the post-ultraviolet-curing process, and absorption tests were applied by immersing the post-ultraviolet-cured specimens in a distilled water bath for 1-, 3-day, and 1-, 2-, and 4-week exposure times. The changes in flexural strain properties for each experimental parameter were also simulated by the computer-aided finite element analysis and compared with the experimental results. It was observed that the post-ultraviolet-curing process increased the flexural strength of the poly(lactic acid) specimens produced at both 190 and 200 °C with the same increasing trend up to 30 min of exposure, and the most significant increase was determined in the specimens that were subjected to post-ultraviolet-curing for 30 min. Although the flexural strengths of the post-ultraviolet-cured specimens were higher than the non-cured specimens in all conditions, it was detected that they tended to decrease after 30 min.

Amid the current environmental crisis caused by plastic accumulation, one of the proposed solutions to manage this problem is using biodegradable polymers. However, the impact of adding biodegradable polymers to the well-established circular economy of recyclable polymers, such as HDPE, has not been fully considered. Therefore, there is a need to reconsider the way we consume, dispose of, and manage biodegradable polymers after use. This study evaluates the effect of varying the contents of a biodegradable polymer, taking poly(lactic acid) (PLA) as a model biodegradable polymer, on the thermal and mechanical properties of HDPE. The study highlights the importance of identifying and disposing of biodegradable polymers to avoid mixtures with HDPE, in order not to affect mechanical performance when considering reprocessing and a new life cycle of this conventional polymer.