Poly Lactic Acid Research Articles

Recent advancements in bio-based dielectric and piezoelectric polymers and their biomedical applications.

The advent of polymer-based dielectrics marked a significant breakthrough in dielectric materials. However, despite their many advantages, they pose serious environmental threats. Therefore, in recent years, there has been growing interest in bio-based polymers as a sustainable alternative to traditional petroleum-based polymers. Their renewable nature and reduced environmental impact can fulfil the rising demand for eco-friendly substitutes. Beyond their ecological benefits, bio-based polymers also possess distinctive electrical properties that make them extremely attractive in a variety of applications. Considering these, herein, we present recent advancements in bio-based dielectric polymers and nanocomposites. First, the fundamental concepts of dielectric and polymer-based dielectric materials are covered. Then, we will delve into the discussion of recent advancements in the dielectric properties and thermal stability of bio-based polymers, including polylactic acid, polyhydroxyalkanoates, polybutylene succinate, starch, cellulose, chitosan, chitins, and alginates, and their nanocomposites. Other novel bio-based dielectric polymers and their distinct dielectric characteristics have also been pointed out. In an additional section, the piezoelectric properties of these polymers and their recent biomedical applications have been highlighted and discussed thoroughly. In conclusion, this paper thoroughly discusses the recent advances in bio-based dielectric polymers and their potential to revolutionize the biomedical industry while cultivating a more sustainable and greener future.

Experimental study on the effect of filament-extrusion rate on the structural, mechanical and thermal properties of material extrusion 3D-printed polylactic acid (PLA) products

AbstractMaterial extrusion (MEX), also commonly referred to as fused deposition modeling (FDM) or fused filament fabrication (FFF) is currently one of the most commonly used additive manufacturing techniques. The quality of the 3D-printed objects fabricated by MEX methods highly relies on various printing parameters, one of which is the so-called filament extrusion multiplier (k). In this study, 3D-printed parts were prepared by MEX technique during which the material feeding rate was adjusted by varying the extrusion multiplier in the range of 97–105% (k = 0.97–1.05). The fabricated parts were tested for their geometrical, structural, mechanical, and thermal conductivity properties. Based on computed tomographic analysis and scanning electron microscopic images, increasing the k parameter resulted in smaller voids, along with gradually decreasing porosity (from 5.82 to 0.05%). Parallel to the decreasing defects, the thermal conductivity of the parts improved from 0.157 to 0.188 W/mK as determined by light-flash analysis technique. On the other hand, when k was set to ≥ 1.03 the geometrical accuracy declined, the size of the specimens considerably increased relative to the nominal values, especially in the X–Y directions due to excess material getting “squeezed” on the sides of the specimens. This latter phenomenon also resulted in the formation of a number of stress concentration sites, which manifested in the decrease of mechanical properties. Accordingly, the tensile, flexural, and impact strength of the samples improved up to k = 1.03; however, above that it dropped considerably.

Glycine/alginate-based piezoelectric film consisting of a single, monolithic β-glycine spherulite towards flexible and biodegradable force sensor

Abstract Development of piezoelectric biomaterials with high piezoelectric performance, while possessing excellent flexibility, biocompatibility, and biodegradability still remains a great challenge. Herein, a flexible, biocompatible and biodegradable piezoelectric β-glycine-alginate-glycerol (Gly-Alg-Glycerol) film with excellent in vitro and in vivo sensing performance was developed. Remarkably, a single, monolithic β-glycine spherulite, instead of more commonly observed multiple spherulites, was formed in alginate matrix, thereby resulting in outstanding piezoelectric property, including high piezoelectric constant (7.2 pC/N) and high piezoelectric sensitivity (1.97 mV/kPa). The Gly-Alg-Glycerol film exhibited superior flexibility, enabling complex shape-shifting, e.g. origami pigeon, 40% tensile strain, and repeated bending and folding deformation without fracture. In vitro, the flexible Gly-Alg-Glycerol film sensor could detect subtle pulse signal, sound wave, and recognize shear stress applied from different directions. In addition, we have demonstrated that the Gly-Alg-Glycerol film sensor sealed by polylactic acid and beeswax could serve as an in vivo sensor to monitor physiological pressure signals such as heartbeat, respiration, and muscle movement. Finally, the Gly-Alg-Glycerol film possessed good biocompatibility, supporting the attachment and proliferation of rat mesenchymal stromal cells, and biodegradability, thereby showing great potential as biodegradable piezoelectric biomaterials for biomedical sensing applications.

Modifying the Backbone Chemistry of PEG-based Bottlebrush Block Copolymers for the Formation of Long-Circulating Nanoparticles.

Nanoparticle physicochemical properties have received great attention in optimizing the performance of nanoparticles for biomedical applications. For example, surface functionalization with small molecules or linear hydrophilic polymers is commonly used to tune the interaction of nanoparticles with proteins and cells. However, it is challenging to control the location of functional groups within the shell for conventional nanoparticles. Nanoparticle surfaces composed of shape-persistent bottlebrush polymers allow hierarchical control over the nanoparticle shell but the effect of the bottlebrush backbone on biological interactions is still unknown. We report the synthesis of novel heterobifunctional poly(ethylene glycol) (PEG)-norbornene macromonomers modified with various small molecules to form bottlebrush polymers with different backbone chemistries. We demonstrate that micellar nanoparticles composed of poly(lactic acid) (PLA)-PEG bottlebrush block copolymer (BBCP) with neutral and cationic backbone modifications exhibit significantly reduced cellular uptake compared to conventional unmodified BBCPs. Furthermore, the nanoparticles display long blood circulation half-lives of ∼22h and enhanced tumor accumulation in mice. Overall, our work sheds light on the importance of the bottlebrush polymer backbone and provides a strategy to improve the performance of nanoparticles in biomedical applications. This article is protected by copyright. All rights reserved.

Green Synthesis and Characterization of Silver Anchored ZnO Nanoparticle as the Antimicrobial Reinforcement for Polylactide (PLA) Films

AbstractThe aqueous extract of endophytic fungi (Periconia sp.) was effectively used as a reducing agent to anchor Ag nanoparticles on the ZnO surface. The XRD, UV‐Vis, SEM‐EDX and TEM analyses were performed to ensure the formation of AgNP@ZnO architecture. TEM analysis confirmed that the 4‐20 nm sized Ag nanoparticles were anchored evenly on the surface of ZnO with 16‐78 nm in size. The antimicrobial study showed the superior performance of AgNP@ZnO functional nanoparticles than the pristine ZnO against pathogenic bacteria Staphylococcus aureus (gram‐positive) and Escherichia coli (gram‐negative). Hence, AgNP@ZnO functional particles were effectively explored as antimicrobial reinforcement for fabricating composite films using polylactic acid (PLA) as a matrix. The obtained nanocomposite films showed excellent antibacterial activity, which increases with increasing AgNP@ZnO loading.This article is protected by copyright. All rights reserved.

Synergistic flame retardancy of aluminum diethylphosphinate and piperazine pyrophosphate/β‐cyclodextrin in polylactic acid

AbstractPolylactic acid has good biodegradability and processability, but its flammability and serious droplet characteristics limit its development and application. Therefore, developing safer flame‐retardant PLA materials is crucial. This research develops a novel flame‐retardant polylactic acid (PLA) material blend, utilizing aluminum diethylphosphinate (AlPi), piperazine pyrophosphate (PAPP), and β‐cyclodextrin. Optimal synergy occurs at a 5:1 PAPP/β‐CD mass ratio with 4 wt.% AlPi. This combination significantly reduces the heat release peak from 294.89 to 144.21 kW·m−2 and generates non‐combustible residues. The sample forms a stable, uniform carbon layer during combustion due to hydrogen bond crosslinking and Lewis acid–base reactions. The activation energy (Eα) is raised from 264.99 to 281.08 kJ·mol−1 between 312 and 402°C. Thus, an AlPi‐PAPP‐β‐CD based P‐C‐N composite flame retardant is investigated, offering a promising research direction for developing fire‐safe polylactic acid materials. This research may yield valuable insights for diverse applications.

Study on the characteristics of Napier grass fibre reinforced porcelain filler particulates poly lactic acid matrix biocomposite

This study investigates the complex properties of a novel biocomposite by a conventional process, which is composed of poly (lactic acid) (PLA) as the matrix, porcelain particles as fillers, and Napier grass fibre as reinforcement. The primary objective was to evaluate the mechanical, crystalline, water absorption, morphological, and antibacterial properties of the biocomposites in relation to the individual components and their synergistic impacts. When 25 g porcelain particles were added to PLA with Napier grass fibre, mechanical tests demonstrated a 25% increase in tensile strength (maximum tensile strength of 39.76 MPa) and a 30% increase in flexural strength (maximum flexural strength of 41.29 MPa). Scanning electron microscopy (SEM) revealed a strong interfacial bond between the fibre and matrix, with porcelain particles serving as bridges to facilitate stress transmission. The biocomposite exhibited reduced water absorption due to the inherent hydrophobic nature of porcelain, which enhances its resistance to bacterial growth. The study demonstrates that combining Napier grass fibre with porcelain filler particles synergistically enhances the properties of PLA, creating a viable biocomposite material suitable for use in packaging, automotive, and sustainable building industries.

Optimizing FDM process parameters: predictive insights through taguchi, regression, and neural networks

Fused deposition modelling (FDM) is a popular additive manufacturing process used for rapid prototyping and the production of complex geometries. Despite its popularity, FDM’s susceptibility to variations in numerous process parameters can significantly impact the quality, design, functionality, and mechanical properties of 3D printed parts. This study explores thirteen FDM process parameters and their influence on the mechanical properties of polylactic acid (PLA) polymer, encompassing surface roughness, warpage, tensile and bending strength, elongation at break, deformation, and microhardness. The optimum parameters were identified alongside key contributors by applying the Taguchi method, signal-to-noise ratios, and analysis of variances (ANOVA). Notably, specific FDM parameters significantly affect the surface profile, with layer thickness contributing 32.65% and fan speed contributing 8.59% to the observed variations. Similarly, warping values show notable influence from nozzle temperature (29.53%), wall thickness (16.74%), layer thickness (16.56%), and retraction distance (12.80%). Tensile strength is primarily determined by wall thickness (31.83%), followed by infill percentage (26.73%) and infill pattern (16.18%). Elongation at break predominantly correlates with wall thickness (44.82%), with a supplementary contribution from nozzle temperature (10.90%). Microhardness lacks a dominant parameter. Bending strength variations primarily arise from layer thickness (38%), wall thickness (37.6%), and infill percentage (9.17%). Deformation tendencies are influenced by layer thickness (19.20%), print speed (11.37%), wall thickness, and fan speed (10.9% each). The optimized dataset of FDM process parameters was then employed in two prediction models: multiple-regression and artificial neural network (ANN). Evaluation based on the correlation coefficient (R2) and root mean squared error (RMSE) indicates that the ANN model outperforms the multiple-regression approach. The results indicate that precise control of FDM parameters, coupled with ANN predictions, facilitates the fabrication of 3D printed parts with the desired mechanical characteristics.

Digital Light Processing Route for 3D Printing of Acrylate-Modified PLA/Lignin Blends: Microstructure and Mechanical Performance

In this study, digital light processing (DLP) was utilized to generate 3D-printed blends composed of photosensitive acrylate-modified polylactic acid (PLA) resin mixed with varying weight ratios of lignin extracted from softwood, typically ranging from 5 wt% to 30 wt%. The microstructure of these 3D-printed blends was examined through X-ray microtomography. Additionally, the tensile mechanical properties of all blends were assessed in relation to the weight ratio and post-curing treatment. The results suggest that post-curing significantly influences the tensile properties of the 3D-printed composites, especially in modulating the brittleness of the prints. Furthermore, an optimal weight ratio was identified to be around 5 wt%, beyond which UV light photopolymerization experiences compromises. These findings regarding acrylate-modified PLA/lignin blends offer a cost-effective alternative for producing 3D-printed bio-sourced components, maintaining technical performance in reasonable-cost, low-temperature 3D printing, and with a low environmental footprint.

Experimental consideration of the effects of calcium lignosulfonate and tannic acid on the flammability and thermal properties of polylactide composites

The purpose of this study was to determine the quantitative and qualitative effects of the form of natural phenolic compounds (NPCs) on the decomposition of polylactide (PLA) under different measurement conditions. For this purpose, thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), and pyrolysis-combustion flow calorimetry (PCFC) analyses were carried out not only on individual raw materials like calcium lignosulfonate (BX), tannic acid (TA), BX chemically modified with TA (BMT), but also on PLA/BX, PLA/TA, and PLA/BMT composites with 3, 6, and 9 wt.% of filler. Moreover, the work checked whether to obtain satisfactory results it is necessary to carry out chemical modification lasting many hours, or whether simple physical mixing of ingredients (TABX) is enough, e.g. in proportions 1:2, 2:4, 3:6. The results of these analyses showed that TA is neither a good flame retardant nor a highly swelling material, but when combined with BX physically or chemically, it can produce an interesting synergistic effect. This work proves that chemically obtained BMT hybrid material allows to reduce flammability by 30 % compared to PLA which cannot be achieved by physically mixing these components in a polymer melt. On the other hand, the addition of TABX is sufficient to achieve a good thermal stabilization effect under processing conditions.

Dimethyl-Dioctadecyl-Ammonium Bromide/Poly(lactic acid) Nanoadjuvant Enhances the Immunity and Cross-Protection of an NM2e-Based Universal Influenza Vaccine.

For most frequent respiratory viruses, there is an urgent need for a universal influenza vaccine to provide cross-protection against intra- and heterosubtypes. We previously developed an Escherichia coli fusion protein expressed extracellular domain of matrix 2 (M2e) and nucleoprotein, named NM2e, and then combined it with an aluminum adjuvant, forming a universal vaccine. Although NM2e has demonstrated a protective effect against the influenza virus in mice to some extent, further improvement is still needed for the induction of immune responses ensuring adequate cross-protection against influenza. Herein, we fabricated a cationic solid lipid nanoadjuvant using poly(lactic acid) (PLA) and dimethyl-dioctadecyl-ammonium bromide (DDAB) and loaded NM2e to generate an NM2e@DDAB/PLA nanovaccine (Nv). In vitro experiments suggested that bone marrow-derived dendritic cells incubated with Nv exhibited ∼4-fold higher antigen (Ag) uptake than NM2e at 16 h along with efficient activation by NM2e@DDAB/PLA Nv. In vivo experiments revealed that Ag of the Nv group stayed in lymph nodes (LNs) for more than 14 days after initial immunization and DCs in LNs were evidently activated and matured. Furthermore, the Nv primed T and B cells for robust humoral and cellular immune responses after immunization. It also induced a ratio of IgG2a/IgG1 higher than that of NM2e to a considerable extent. Moreover, NM2e@DDAB/PLA Nv quickly restored body weight and improved survival of homo- and heterosubtype influenza challenged mice, and the cross-protection efficiency was over 90%. Collectively, our study demonstrated that NM2e@DDAB/PLA Nv could offer notable protection against homo- and heterosubtype influenza virus challenges, offering the potential for the development of a universal influenza vaccine.

Dosimetric characteristics of 3D-printed and epoxy-based materials for particle therapy phantoms

Objective3D printing has seen use in many fields of imaging and radiation oncology, but applications in (anthropomorphic) phantoms, especially for particle therapy, are still lacking. The aim of this work was to characterize various available 3D printing methods and epoxy-based materials with the specific goal of identifying suitable tissue surrogates for dosimetry applications in particle therapy.Methods3D-printed and epoxy-based mixtures of varying ratios combining epoxy resin, bone meal, and polyethylene powder were scanned in a single-energy computed tomography (CT), a dual-energy CT, and a µCT scanner. Their CT-predicted attenuation was compared to measurements in a 148.2 MeV proton and 284.7 MeV/u carbon ion beam. The sample homogeneity was evaluated in the respective CT images and in the carbon beam, additionally via widening of the Bragg peak. To assess long-term stability attenuation, size and weight measurements were repeated after 6–12 months.ResultsFour 3D-printed materials, acrylonitrile butadiene styrene polylactic acid, fused deposition modeling printed nylon, and selective laser sintering printed nylon, and various ratios of epoxy-based mixtures were found to be suitable tissue surrogates. The materials’ predicted stopping power ratio matched the measured stopping power ratio within 3% for all investigated CT machines and protocols, except for µCT scans employing cone beam CT technology. The heterogeneity of the suitable surrogate samples was adequate, with a maximum Bragg peak width increase of 11.5 ± 2.5%. The repeat measurements showed no signs of degradation after 6–12 months.ConclusionWe identified surrogates for soft tissue and low- to medium-density bone among the investigated materials. This allows low-cost, adaptable phantoms to be built for quality assurance and end-to-end tests for particle therapy.

Biobased Triesters as Plasticizers for Improved Mechanical and Biodegradable Performance of Polylactic Acid Fibrous Membranes as Facemask Materials

Biobased Triesters as Plasticizers for Improved Mechanical and Biodegradable Performance of Polylactic Acid Fibrous Membranes as Facemask Materials

3D hydrogel microfibers promote the differentiation of encapsulated neural stem cells and facilitate neuron protection and axon regrowth after complete transactional spinal cord injury

Spinal cord injury (SCI) can cause permanent impairment to motor or sensory functions. Pre-cultured neural stem cell (NSC) hydrogel scaffolds have emerged as a promising approach to treat SCI by promoting anti-inflammatory effects, axon regrowth, and motor function restoration. Here, in this study, we performed a coaxial extrusion process to fabricate a core-shell hydrogel microfiber with high NSC density in the core portion. Oxidized hyaluronic acid, carboxymethyl chitosan, and matrigel blend were used as a matrix for NSC growth and to facilitate the fabrication process. During the in vitro differentiation culture, it was found that NSC microfibers could differentiate into neurons and astrocytes with higher efficiency compared to NSC cultured in petri dishes. Furthermore, during in vivo transplantation, NSC microfibers were coated with polylactic acid nanosheets by electrospinning for reinforcement. The coated NSC nanofibers exhibited higher anti-inflammatory effect and lesion cavity filling rate compared with the control group. Meanwhile, more neuron- and oligodendrocyte-like cells were visualized at the lesion epicenter. Finally, axon regrowth across the whole lesion site was observed, demonstrating that the microfiber could guide renascent axon regrowth. Experiment results indicate that the NSC microfiber is a promising bioactive treatment for complete SCI treatment with superior outcomes.

Investigation of Fiber Orientation of Fused Filament Fabricated CFRP Composites via an External Magnetic Field

Abstract For carbon fiber-reinforced plastic (CFRP) composites, controlling the interior fiber distribution and orientation during the manufacturing process is a common approach to optize the structural performance of fabricated parts. However, few studies have been conducted to investigate fiber alignment during the additive manufacturing of CFRP composites. This study proposes a magnetic field controlled (MFC) method to control the fiber orientation during the fused filament fabrication (FFF) of nickel-coated carbon fiber (NCF) reinforced polymer composites. Firstly, a theoretical analysis model is established to explore the suitable magnetic field intensity for fiber rotation. Secondly, a customized FFF system with MFC components is implemented, and a polylactic acid matrix composite containing 10 wt% NCF is printed to validate the feasibility of the proposed approach. The microstructure of the printed samples is examined to assess the effectiveness of the method. Finally, uniaxial tensile tests are performed to investigate the impact of fiber orientation adjustment on mechanical properties. The experimental results reveal that the MFC method can effectively align the interior fiber orientation of CFRP composites, leading to a significant increase in the tensile strength (approximately 8.8%) and Young's modulus (around 10.5%) of the printed samples.

Utilization of Silica Filler as Reinforcement Material of Polylactic Acid (PLA) in 3D Printing Applications: Thermal, Rheological, and Mechanical Performance

Glass was introduced as an additive to filaments used for the manufacturing of composite materials, employed by Additive Manufacturing applications. Glass accounts for a large waste electric and electronic equipment (WEEE) percentage, and its recovery and recycling can lead to the production of sustainable composite materials. In this work, poly(lactic acid) (PLA)/commercially available silicon oxide composite filaments were manufactured and their structural, thermal, rheological, and mechanical properties were assessed. Scanning Electron Microscopy confirmed the 1:2 ratio of silicon: oxygen, along with the relatively low adhesion between the filler and the matrix. Differential Scanning Calorimetry presented steady glass transition and melting temperatures of composites, whereas a crystallization temperature of 10% wt. and a crystallinity of 15% wt. composite slightly increased. Rheological analysis showcased that the viscosity of the composite filaments decreased compared to PLA (10–100 compared to 300–400 Pa·s), with a more shear-thinning behavior. Dynamic mechanical analysis exhibited increased elastic, flexural moduli, and flexural strength of composites (up to 16, 23, and 11%, respectively), whereas tensile strength and elongation decreased. The affordability of raw materials (with the future introduction of recycled ones) and the minimal processing steps can lead to the potential scaling up of the study.

Experimental analysis of 3D printed continuous carbon/glass hybrid fiber reinforced PLA composites: Revealing synergistic mechanical properties and failure mechanisms

AbstractThis study investigates the mechanical properties of continuous carbon/glass hybrid fiber‐reinforced polylactic acid (PLA) composites (HFRC) produced through the three dimensions (3D) printing process, comparing them with single carbon fiber‐reinforced PLA composites (CFRC). Initially, composite prepreg filaments are prepared using an impregnation device, followed by fabrication using a 3D printer. The mechanical performance results reveal a 13% increase in tensile strength for HFRC compared with CFRC. Due to differing elongation rates of carbon and glass fibers, HFRC exhibits two strength peaks, while CFRC demonstrates a 37% higher bending strength than HFRC. Scanning electron microscope images indicate that the tensile failure mechanism involves fiber brittle fracture and fiber‐matrix interface debonding, while the bending failure mechanism includes fiber pullout, fiber debonding, fiber cluster buckling, and interlayer interface failure.Highlights To realize the moldless rapid manufacturing of continuous hybrid fiber‐reinforced PLA composites. The stress–strain curves of single fiber‐reinforced composites and hybrid fiber‐reinforced composites are obviously different. Elucidating the effect of single fiber/hybrid fiber in composites on mechanical properties and failure mechanism according to micro‐morphology.

Green Synthesis of Bioplastics from Microalgae: A State-of-the-Art Review

The synthesis of conventional plastics has increased tremendously in the last decades due to rapid industrialization, population growth, and advancement in the use of modern technologies. However, overuse of these fossil fuel-based plastics has resulted in serious environmental and health hazards by causing pollution, global warming, etc. Therefore, the use of microalgae as a feedstock is a promising, green, and sustainable approach for the production of biobased plastics. Various biopolymers, such as polyhydroxybutyrate, polyurethane, polylactic acid, cellulose-based polymers, starch-based polymers, and protein-based polymers, can be produced from different strains of microalgae under varying culture conditions. Different techniques, including genetic engineering, metabolic engineering, the use of photobioreactors, response surface methodology, and artificial intelligence, are used to alter and improve microalgae stocks for the commercial synthesis of bioplastics at lower costs. In comparison to conventional plastics, these biobased plastics are biodegradable, biocompatible, recyclable, non-toxic, eco-friendly, and sustainable, with robust mechanical and thermoplastic properties. In addition, the bioplastics are suitable for a plethora of applications in the agriculture, construction, healthcare, electrical and electronics, and packaging industries. Thus, this review focuses on techniques for the production of biopolymers and bioplastics from microalgae. In addition, it discusses innovative and efficient strategies for large-scale bioplastic production while also providing insights into the life cycle assessment, end-of-life, and applications of bioplastics. Furthermore, some challenges affecting industrial scale bioplastics production and recommendations for future research are provided.

Green Engineering: Poly (lactic acid) Composite Materials Fortified with Surface-Modified Nanocellulose from Borassus flabellifer Leaves

Green Engineering: Poly (lactic acid) Composite Materials Fortified with Surface-Modified Nanocellulose from Borassus flabellifer Leaves

Synthesis and dyeing performance of novel heterocyclic azo disperse dyes for polylactic acid fiber

Synthesis and dyeing performance of novel heterocyclic azo disperse dyes for polylactic acid fiber