Search Results (47)

Poly(butylene adipate-co-terephthalate) (PBAT) is a promising degradable polymer for replacing non-degradable traditional plastics to mitigate pollution. However, its low softening temperature and poor hardness impede its application. Herein, PBAT and stereocomplex polylactide (sc-PLA) blends were fabricated through a melt-blending process to balance the heat resistance and mechanical strength of PBAT in this research. The effects of the PLA content and hot embossing temperature on the blend properties were comprehensively investigated. The results demonstrate that the sc-crystal content in the PBAT/sc-PLA blend increased by 493% as the PLA content rose from 10% to 30%. The blend with 15% PLLA and 15% PDLA, hot embossed at 190 °C, exhibited the highest sc-PLA crystallinity of 23.3% and the largest fraction of sc-crystallites at 66%, leading to the optimal comprehensive performance. Its Vicat softening temperature (VST) reached 92.2 °C, and a nonlinear increase trend in accordance with the power-law model between VST and the mass ratio of sc-crystal was obtained. Compared with the mechanical properties of neat PBAT, a maximum tensile yield stress of 9.7 MPa and a Young’s modulus of 82.5 MPa were achieved and improved approximately by 107% and 361%, respectively. This research offers an effective strategy for synergistically enhancing the heat resistance and mechanical strength of PBAT. Full article

The formation of polylactide stereocomplex (sc-PLA), involving the blending of poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA), enhances PLA materials by making them stronger and more heat-resistant. This study investigated the competitive crystallization behavior of homocrystals (HCs) and stereocomplex crystals (SCs) in a 50/50 PLLA/PDLA blend with added polyethylene glycol (PEG). PEG, with molecular weights of 400 g/mol and 35,000 g/mol, was incorporated at concentrations ranging from 5% to 20% by weight. Differential scanning calorimetry (DSC) analysis revealed that PEG increased the crystallization temperature, promoted SC formation, and inhibited HC formation. PEG also acted as a plasticizer, lowering both melting and crystallization temperatures. The second heating DSC curve showed that the pure PLLA/PDLA blend had a 57.1% fraction of SC while adding 5% PEG with a molecular weight of 400 g/mol resulted in complete SC formation. In contrast, PEG with a molecular weight of 35,000 g/mol was less effective, allowing some HC formation. Additionally, PEG consistently promoted SC formation across various cooling rates (2, 5, 10, or 20 °C/min), demonstrating a robust influence under different conditions. Full article

Polymeric nanoparticles (PNPs) are frequently researched and used in drug delivery. The degradation of PNPs is highly dependent on various properties, such as polymer chemical structure, size, crystallinity, and melting temperature. Hence, a precise understanding of PNP degradation behavior is essential for optimizing the system. This study focused on enzymatic hydrolysis as a degradation mechanism by investigation of the degradation of PNP with various crystallinities. The aliphatic polyester polylactide ([C₃H₄O₂]n, PLA) was used as two chiral forms, poly l-lactide (PlLA) and poly d-lactide (PdLA), and formed a unique crystalline stereocomplex (SC). PNPs were prepared via a nanoprecipitation method. In order to further control the crystallinity and melting temperatures of the SC, the polymer poly(3-ethylglycolide) [C₆H₈O₄]n (PEtGly) was synthesized. Our investigation shows that the PNP degradation can be controlled by various chemical structures, crystallinity and stereocomplexation. The influence of proteinase K on PNP degradation was also discussed in this research. AFM did not reveal any changes within the first 24 h but indicated accelerated degradation after 7 days when higher EtGly content was present, implying that lower crystallinity renders the particles more susceptible to hydrolysis. QCM-D exhibited reduced enzyme adsorption and a slower degradation rate in SC-PNPs with lower EtGly contents and higher crystallinities. A more in-depth analysis of the degradation process unveiled that QCM-D detected rapid degradation from the outset, whereas AFM exhibited delayed changes of degradation. The knowledge gained in this work is useful for the design and creation of advanced PNPs with enhanced structures and properties. Full article

Fibers made from biopolymers are one solution for conserving both resources and the environment. However, these fibers currently have limited strengths, which limit their use for textile applications. In this paper, a biopolymer stereocomplex poly(-lactide) (scPLA) formation on a technical scale of high-molecular-weight poly(D-lactide) (PDLA) and poly(L-lactide) (PLLA) is presented. This scPLA material is the basis for further research to develop scPLA yarns in melt spinning with technical strengths for technical application. scPLA is compared with standard and commercially available semi-crystalline PLA for the production of fibers in melt spinning (msPLA) with textile strengths. Differential scanning calorimetry (DSC) gives a degree of crystallization of 59.7% for scPLA and 47.0% for msPLA. X-ray diffraction (XRD) confirms the pure stereocomplex crystal structure for scPLA and semi-crystallinity for msPLA. scPLA and msPLA are also compared regarding their processing properties (rheology) in melt spinning. While complex viscosity of scPLA is much lower compared to msPLA, both materials show similar viscoelastic behavior. Thermal gravimetric analysis (TGA) shows the influence of the molecular weight on the thermal stability, whereas essentially the crystallinity influences the biodegradability of the PLA materials. Full article

Polylactides (PLAs) and lactide copolymers are biodegradable, compostable, and derived from renewable resources, offering a sustainable alternative to petroleum-based synthetic polymers owing to their advantages of comparable mechanical properties with commodity plastics and biodegradability. Their hydrolytic stability and thermal properties can affect their potential for long-lasting applications. However, stereocomplex crystallization is a robust method between isomer PLAs that allows significant amelioration in copolymer properties, such as thermal stability, mechanical properties, and biocompatibility, through substantial intermolecular interactions amid l-lactyl and d-lactyl sequences, which have been the key approach to initial degradation rate and further PLA applications. It was demonstrated that the essential parameters affecting stereocomplexation are the mixing ratio and the chain length of each unit sequence. This study deals with the molecular weight, one of the specific interactions between isomers of PLAs. A solution polymerization method was applied to control molecular weight and chain architecture. The stereocomplexation was monitored with DSC. It was confirmed that the lower molecular weight polymer showed a higher degradation rate, as a hydrolyzed fragment having a molecular weight below a certain length dissolves into the water. To systematically explore the critical contribution of molecular weights, the Langmuir system was used to observe the stereocomplexation effect and the overall degradation rate. Full article

Medical titanium alloy Ti-6Al-4V (TC4) has been widely used in the medical field, especially in human tissue repair. However, TC4 has some shortcomings, which may cause problems with biocompatibility and mechanical compatibility in direct contact with the human body. To solve this problem, physical gels are formed on the surface of TC4, and the storage modulus of the formed physical gel matches that of the human soft tissue. 2-bromoisobutyryl bromide (BIBB) and dopamine (DA) were used to form initiators on the surface of hydroxylated medical titanium alloy. Different initiators were formed by changing the ratio of BIBB and DA, and the optimal one was selected for subsequent reactions. Under the action of the catalyst, L-lactide and D-lactide were ring-opened polymerized with hydroxyethyl methacrylate (HEMA), respectively, to form macromolecular monomers HEMA-PLLA₂₉ and HEMA-PDLA₂₉ with a polymerization degree of 29. The two macromolecular monomers were stereo-complexed by ultrasound to form HEMA-stereocomplex polylactic acid (HEMA-scPLA₂₉). Based on two monomers, 2-(2-methoxyethoxy) ethyl methacrylate (MEO₂MA) and oligo (ethylene oxide) methacrylate (OEGMA), and the physical crosslinking agent HEMA-scPLA_29, physical gels are formed on the surface of TC4 attached to the initiator via Atom Transfer Radical Addition Reaction (ATRP) technology. The hydrogels on the surface of titanium alloy were characterized and analyzed by a series of instruments. The results showed that the storage modulus of physical glue was within the range of the energy storage modulus of human soft tissue, which was conducive to improving the mechanical compatibility of titanium alloy and human soft tissue. Full article

This review paper analyzes the development of advanced class polylactide (PLA) materials through a combination of stereocomplexation and nanocomposites approaches. The similarities in these approaches provide the opportunity to generate an advanced stereocomplex PLA nanocomposite (stereo-nano PLA) material with various beneficial properties. As a potential “green” polymer with tunable characteristics (e.g., modifiable molecular structure and organic–inorganic miscibility), stereo-nano PLA could be used for various advanced applications. The molecular structure modification of PLA homopolymers and nanoparticles in stereo-nano PLA materials enables us to encounter stereocomplexation and nanocomposites constraints. The hydrogen bonding of D- and L-lactide fragments aids in the formation of stereococomplex crystallites, while the hetero-nucleation capabilities of nanofillers result in a synergism that improves the physical, thermal, and mechanical properties of materials, including stereocomplex memory (melt stability) and nanoparticle dispersion. The special properties of selected nanoparticles also allow the production of stereo-nano PLA materials with distinctive characteristics, such as electrical conductivity, anti-inflammatory, and anti-bacterial properties. The D- and L-lactide chains in PLA copolymers provide self-assembly capabilities to form stable nanocarrier micelles for encapsulating nanoparticles. This development of advanced stereo-nano PLA with biodegradability, biocompatibility, and tunability properties shows potential for use in wider and advanced applications as a high-performance material, in engineering field, electronic, medical device, biomedical, diagnosis, and therapeutic applications. Full article

Biodegradable polylactic acid (PLA) foams with open-cell structures are good candidates for oil–water separation. However, the foaming of PLA with high-expansion and uniform cell morphology by the traditional supercritical carbon dioxide microcellular foaming method remains a big challenge due to its low melting strength. Herein, a green facile strategy for the fabrication of open-cell fully biodegradable PLA-based foams is proposed by introducing the unique stereocomplexation mechanism between PLLA and synthesized star-shaped PDLA for the first time. A series of star-shaped PDLA with eight arms (8-s-PDLA) was synthesized with different molecular weights and added into the PLLA as modifiers. PLLA/8-s-PDLA foams with open-cells structure and high expansion ratios were fabricated by microcellular foaming with green supercritical carbon dioxide. In detail, the influences of induced 8-s-PDLA on the crystallization behavior, rheological properties, cell morphology and consequential oil–water separation performance of PLA-based foam were investigated systemically. The addition of 8-s-PDLA induced the formation of SC-PLA, enhancing crystallization by acting as nucleation sites and improving the melting strength through acting as physical cross-linking points. The further microcellular foaming of PLLA/8-s-PDLA resulted in open-cell foams of high porosity and high expansion ratios. With an optimized foaming condition, the PLLA/8-s-PDLA-13K foam exhibited an average cell size of about 61.7 μm and expansion ratio of 24. Furthermore, due to the high porosity of the interconnected open cells, the high-absorption performance of the carbon tetrachloride was up to 37 g/g. This work provides a facile green fabrication strategy for the development of environmentally friendly PLA foams with stable open-cell structures and high expansion ratios for oil–water separation. Full article

Current biodegradable drinking straws suffer from poor heat resistance and rigidity when wet, causing user dissatisfaction. Here, a fully biodegradable straw formed by stereocomplexation of poly (lactic acid) (SC-PLA) is reported. Because of the unique strong interaction and high density of link chains between stereocomplex crystallites (over 70% crystallinity), SC-PLA straws outperform their counterparts on the market. This coupled with the advantages of simple processing (solution casting and annealing) and relatively low cost (~2.06 cents per straw) makes SC-PLA drinking straws a superior substitute for plastic ones. Commercially available PLLA straws lose almost 60% of their flexural strength when wet compared to less than 5% of the SC-PLA straws proposed in this study. Full article

Aligned with the Sustainability Development Goals (SDGs), we present the complete methodology of preparing bio-based polymer filaments to be used in additive manufacturing, specifically by means of so-called Fused Filament Fabrication (FFF) in 3D printing. Filament production and 3D printing were both developed and optimised in this work. First, we focused on the steps of producing and optimising the extrusion process of unreinforced polylactic acid (PLA) composite filaments. Second, we studied the resulting material properties by discussing the selection of a specimen geometry and the international standards adequate for FFF 3D printing. Moreover, we investigated the process parameters in order to achieve reliable structures. Based on the reinforcement material (stereocomplex fibres (Sc-PLA fibre) and bi-component fibres (bi-co PLA fibre), base-matrices were selected for producing un-reinforced filaments. In this way, we present the complete preparation approach by identifying problems and pitfalls for fostering studies of bio-based polymer filaments. Full article

A scalable continuous manufacturing method to produce stereocomplex PLA was developed and optimized by melt-blending a 1:1 blend of high molecular weight poly(L-lactide) (PLLA) and high molecular weight poly(D-lactide) (PDLA) in a co-rotating twin-screw extruder. Thermal characteristics of stereocomplex formation were characterized via DSC to identify the optimal temperature profile and time for processing stereocomplex PLA. At the proper temperature window, high stereocomplex formation is achieved as the twin-screw extruder allows for alignment of the chains; this is due to stretching of the polymer chains in the extruder. The extruder processing conditions were optimized and used to produce >95% of stereocomplex PLA conversion (melting peak temperature T_pm = 240 °C). ATR-FTIR depicts the formation of stereocomplex crystallites based on the absorption band at 908 cm⁻¹ (β helix). The only peaks observed for stereocomplex PLA’s WAXD profile were at 2θ values of 12, 21, and 24°, verifying >99% of stereocomplex formation. The total crystallinity of stereocomplex PLA ranges from 56 to 64%. A significant improvement in the tensile behavior was observed in comparison to the homopolymers, resulting in a polymer of high strength and toughness. These results lead us to propose stereocomplex PLA as a potential additive/fiber that can reinforce the material properties of neat PLA. Full article

Poly(lactide) (PLA) and poly(ethylene glycol) (PEG)-based hydrogels were prepared by mixing phosphate buffer saline (PBS, pH 7.4) solutions of four-arm (PEG-PLA)₂-R-(PLA-PEG)₂ enantiomerically pure copolymers having the opposite chirality of the poly(lactide) blocks. Dynamic Light Scattering, rheology measurements, and fluorescence spectroscopy suggested that, depending on the nature of the linker R, the gelation process followed rather different mechanisms. In all cases, mixing of equimolar amounts of the enantiomeric copolymers led to micellar aggregates with a stereocomplexed PLA core and a hydrophilic PEG corona. Yet, when R was an aliphatic heptamethylene unit, temperature-dependent reversible gelation was mainly induced by entanglements of PEG chains at concentrations higher than 5 wt.%. When R was a linker containing cationic amine groups, thermo-irreversible hydrogels were promptly generated at concentrations higher than 20 wt.%. In the latter case, stereocomplexation of the PLA blocks randomly distributed in micellar aggregates is proposed as the major determinant of the gelation process. Full article

Due to their high sensitivity to temperature and humidity, the applications of polylactic acid (PLA) products are limited. The stereo-complexation (SC) formed by poly(L-lactic acid) (PLLA) and its enantiomer poly(D-lactic acid) (PDLA) can effectively improve the heat resistance and hydrolysis resistance of PLA products. In this work, the blended melt-spinning process of PLLA/PDLA was carried out using a polyester fiber production line to obtain PLA fiber with a complete SC structure. The effects of high-temperature tension heat-setting on the crystalline structure, thermal properties, mechanical properties, and hydrolysis resistance were discussed. The results indicated that when the tension heat-setting temperature reached 190 °C, the fiber achieved an almost complete SC structure, and its melting point was 222.5 °C. An accelerated hydrolysis experiment in a 95 °C water bath proved that the SC crystallites had better hydrolysis resistance than homocrystallization (HC). The monofilament strength retention rate of SC−190 fiber reached as high as 78.5% after hydrolysis for 24 h, which was significantly improved compared with PLLA/PDLA drawn fiber. Full article

High-molecular-weight poly(L-lactide) (HMW-PLLA) is a promising candidate for use as a bioplastic because of its biodegradability and compostability. However, the applications of HMW-PLLA have been limited due to its poor crystallizability. In this work, stereocomplex polylactide (scPLA) powder was prepared by precipitation of a low-molecular-weight poly(L-lactide)/poly(D-lactide) (LMW-PLLA/LMW-PDLA) blend solution and investigated for use as a fully-biodegradable nucleating agent for HMW-PLLA compared to LMW-PLLA powder. The obtained LMW-PLLA and scPLA powders with a nearly spherical shape showed complete homo- and stereocomplex crystallites, respectively. HMW-PLLA/LMW-PLLA powder and HMW-PLLA/scPLA powder blends were prepared by melt blending. The LMW-PLLA powder was homogeneously melted in the HMW-PLLA matrices, whereas the scPLA powder had good phase compatibility and was well-dispersed in the HMW-PLLA matrices, as detected by scanning electron microscopy (SEM). It was shown that the enthalpies of crystallization (ΔH_c) upon cooling scans for HMW-PLLA largely increased and the half crystallization time (t_1/2) dramatically decreased as the scPLA powder content increased; however, the LMW-PLLA powder did not exhibit the same behavior, as determined by differential scanning calorimetry (DSC). The crystallinity content of the HMW-PLLA/scPLA powder blends significantly increased as the scPLA powder content increased, as determined by DSC and X-ray diffractometry (XRD). In conclusion, the fully biodegradable scPLA powder showed good potential for use as an effective nucleating agent to improve the crystallization properties of the HMW-PLLA bioplastic. Full article

This review covers the development of eco-friendly, bio-based materials based on polylactide (PLA) and cellulose nanowhiskers (CNWs). As a biodegradable polymer, PLA is one of the promising materials to replace petroleum-based polymers. In the field of nanocomposites, CNWs offer many advantages; they are made from renewable resources and exhibit beneficial mechanical and thermal properties in combination with polymer matrix. A wide range of surface modifications has been done to improve the miscibility of CNW with the PLA homopolymer, which generally gives rise to hydrophobic properties. PLA–CNW nanocomposite materials are fully degradable and sustainable and also offer improved mechanical and thermal properties. Limitations pertaining to the miscibility of CNWs with PLA were solved through surface modification and chemical grafting on the CNW surfaces. Further development has been done by combining PLA-based material via stereocomplexation approaches in the presence of CNW particles, known as bio-stereo-nanocomposite PLA–CNW. The combination of stereocomplex crystalline structures in the presence of well-distributed CNW particles produces synergetic effects that enhance the mechanical and thermal properties, including stereocomplex memory (melt stability). The bio-based materials from PLA and CNWs may serve as eco-friendly materials owing to their sustainability (obtained from renewable resources), biodegradability, and tunability properties. Full article