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.

Poly(ethylene 2,5-furandicarboxylate) (PEF)-based nanocomposites containing Ce–bioglass, ZnO, and ZrO₂ nanoparticles were synthesized via in situ polymerization, targeting food packaging applications. The nanocomposites were thoroughly characterized, combining a range of techniques. The successful polymerization was confirmed using attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy, and the molecular weight values were determined indirectly by applying intrinsic viscosity measurements. The nanocomposites’ structure was investigated by depth profiling using time-of-flight secondary ion mass spectrometry (ToF-SIMS), while color measurements showed a low-to-moderate increase in the color concentration of all the nanocomposites compared to neat PEF. The thermal properties and crystallinity behavior of the synthesized materials were also examined. The neat PEF and PEF-based nanocomposites show a crystalline fraction of 0–5%, and annealed samples of both PEF and PEF-based nanocomposites exhibit a crystallinity above 20%. Furthermore, scanning electron microscopy (SEM) micrographs revealed that active agent nanoparticles are well dispersed in the PEF matrix. Contact angle measurements showed that incorporating nanoparticles into the PEF matrix significantly reduces the wetting angle due to increased roughness and introduction of the polar -OH groups. Antimicrobial studies indicated a significant increase in inhibition of bacterial strains of about 9–22% for Gram-positive bacterial strains and 5–16% for Gram-negative bacterial strains in PEF nanocomposite films, respectively. Finally, nanoindentation tests showed that the ZnO-based nanocomposite exhibits improved hardness and elastic modulus values compared to neat PEF.

This work describes the synthesis of poly(lactic acid) by the ring-opening polymerization of L-lactide in the presence of oligo(butylene succinate) with two different molecular weights (M_n = 6100 and 16300 g/mol) as a macroinitiator during reactive processing. The macroinitiators were added in concentrations 1 wt%, 2.5 wt%, 5 wt%, 10 wt% and 15 wt% in respect to the L-lactide mass in the premix. The properties of the received copolymers were extensively studied with spectroscopic techniques, GPC, DSC, XRD, TGA as well as nanoindentation. Blocky copolymers were received with number average molecular weights ranging from 30 to 100 kg/mol, which decreased with increasing the PBSu content in the feed. The introduction of the flexible PBSu chains decreased the single glass transition detected, while DSC and XRD gave indications that both components crystallized in the copolymers with PBSu premix content > 5 wt%. Thermal stability was maintained and depended on the composition and molecular weight. Nanoindentation showed that despite the decreasing trend of hardness and elastic modulus with increasing PBSu content, the PLA-PBSu 2.5% copolymers had simultaneously higher elasticity modulus and strength compared to the other compositions, possibly because of a complementary effect of their high molecular weight and crystallinity. These copolymers were promising for production with continuous reactive extrusion, a novel, fast and economically viable method to commercially produce PLA-based polymers.

Hierarchically porous polymers can unite macro-scale architected voids with micro-scale pores, enabling unique combinations of low density, high surface area, and controlled transport properties that are difficult to achieve with traditional methods. This review outlines the current advancements in creating such multiscale architectures using fused filament fabrication (FFF), the most widely used polymer additive manufacturing technique. Unlike earlier reviews that consider lattice architectures and foaming chemistries separately, this work integrates both within a single analysis. It begins with an overview of FFF fundamentals and how process parameters affect macropore formation. Design strategies for achieving macroporosity (≳100 µm) with a single thermoplastic are presented and categorized: 2D infill patterns, strut-based lattices, triply periodic minimal surfaces (TPMS), and Voronoi structures, along with functionally graded approaches. The discussion then shifts to functional filaments incorporating chemical or physical blowing agents, thermally expandable or hollow microspheres, and sacrificial porogens, which create microporosity (≲100 µm) either in situ or through post-processing. Each material approach is connected to case studies that demonstrate its application. A comparative analysis highlights the advantages of each method. Key challenges such as viscosity control, thermal gradient management, dimensional instability during foaming, environmental concerns, and the absence of standardized porosity measurement techniques are addressed. Finally, emerging solutions and future directions are explored. Overall, this review provides a comprehensive perspective on strategies that enhance FFF’s capability to fabricate hierarchically porous polymer structures.

Esophageal cancer is a complex and challenging tumor to treat, with esophageal stenting being used as a palliative measure to improve the quality of life of patients. Self-expandable metal stents (SEMS), self-expandable plastic stents (SEPS), and biodegradable stents are the most commonly used types of stents. However, complications can arise, such as migration, bleeding, and perforation. To address issues of migration, this study developed a novel 3D printed bioinspired esophageal stent utilizing a highly flexible and ductile TPU material. The stent was designed to be self-expanding and tubular with flared ends to provide secure anchorage at both the proximal and distal ends of the structure. Suction cups were strategically placed around the shaft of the stent to prevent migration. The stent was evaluated through compression–recovery, self-expansion, and anti-migration tests to evaluate its recovery properties, self-expansion ability, and anchoring ability, respectively. The results indicated that the novel stent was able to recover its shape, expand, keep the esophagus open, and resist migration, demonstrating its potential for further research and clinical applications. Finite element analysis (FEA) was leveraged to analyze the stent’s mechanical behavior, providing insights into its structural integrity, self-expansion capability, and resistance against migration. These results, supported by FEA, highlight the potential of this innovative stent for further research and its eventual application in preclinical settings.

Gradient stiffness structures are increasingly recognized for their excellent energy absorption capabilities, particularly under challenging loading conditions. Most studies focus on varying the thickness of the structure in order to produce gradient stiffness. This work introduces an innovative approach to design honeycomb architectures with controlled gradient stiffness along the out-of-plane direction achieved by materials’ microstructure variations. The gradient is achieved by combining three types of thermoplastic polyurethane (TPU) materials: porous TPU, plain TPU, and carbon fiber (CF)-reinforced TPU. By varying the material distribution across the honeycomb layers, a smooth transition in stiffness is formed, improving both mechanical resilience and energy dissipation. To fabricate these structures, a dual-head 3D printer was employed with one head printed processed TPU with a chemical blowing agent to produce porous and plain sections, while the other printed a CF-reinforced TPU. By alternating between the two print heads and modifying the processing temperatures, honeycombs with up to three distinct stiffness zones were produced. Compression testing under out-of-plane loading revealed clear plateau and densification regions in the stress–strain curves. Pure CF-reinforced honeycombs absorbed the most energy at stress levels above ~4.5 MPa, while porous TPU honeycombs were more effective under stress levels below ~1 MPa. Importantly, the gradient stiffness honeycombs achieved a balanced energy absorption profile across a broader range of stress levels, offering enhanced performance and adaptability for applications like protective equipment, packaging, and automotive structures.