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Robust materials in medical applications are sought after and researched, especially for 3D printing in bone tissue engineering. Poly[ε-caprolactone] (PCL) is a commonly used polymer for scaffolding and other medical uses. Its strength is a drawback compared to other polymers. Herein, PCL was mixed with hydroxyapatite (HAp). Composites were developed at various concentrations (0.0-8.0 wt. %, 2.0 step), aiming to enhance the strength of PCL with a biocompatible additive in bioplotting. Initially, pellets were derived from the shredding of filaments extruded after mixing PCL and HAp at predetermined quantities for each composite. Specimens were then manufactured by bioplotting 3D printing. The samples were tested for their thermal and rheological properties and were also mechanically, morphologically, and chemically examined. The mechanical properties included tensile and flexural investigations, while morphological and chemical examinations were carried out employing scanning electron microscopy and energy dispersive spectroscopy, respectively. The structure of the manufactured specimens was analyzed using micro-computed tomography with regard to both their dimensional deviations and voids. PCL/HAp 6.0 wt. % was the composite that showed the most enhanced mechanical (14.6% strength improvement) and structural properties, proving the efficiency of HAp as a reinforcement filler in medical applications.

In this study, titanium nitride (TiN) was selected as an additive to a high-density polyethylene (HDPE) matrix material, and four different nanocomposites were created with TiN loadings of 2.0-8.0 wt. % and a 2 wt. % increase step between them. The mixtures were made, followed by the fabrication of the respective filaments (through a thermomechanical extrusion process) and 3D-printed specimens (using the material extrusion (MEX) technique). The manufactured specimens were subjected to mechanical, thermal, rheological, structural, and morphological testing. Their results were compared with those obtained after conducting the same assessments on unfilled HDPE samples, which were used as the control samples. The mechanical response of the samples improved when correlated with that of the unfilled HDPE. The tensile strength improved by 24.3%, and the flexural strength improved by 26.5% (composite with 6.0 wt. % TiN content). The dimensional deviation and porosity of the samples were assessed with micro-computed tomography and indicated great results for porosity improvement, achieved with 6.0 wt. % TiN content in the composite. TiN has proven to be an effective filler for HDPE polymers, enabling the manufacture of parts with improved mechanical properties and quality.

Polyethylene terephthalate glycol (PETG) and silicon nitride (Si 3 N 4 ) were combined to create five composite materials with Si 3 N 4 loadings ranging from 2.0 wt.% to 10.0 wt.%. The goal was to improve the mechanical properties of PETG in material extrusion (MEX) additive manufacturing (AM) and assess the effectiveness of Si 3 N 4 as a reinforcing agent for this particular polymer. The process began with the production of filaments, which were subsequently fed into a 3D printer to create various specimens. The specimens were manufactured according to international standards to ensure their suitability for various tests. The thermal, rheological, mechanical, electrical, and morphological properties of the prepared samples were evaluated. The mechanical performance investigations performed included tensile, flexural, Charpy impact, and microhardness tests. Scanning electron microscopy and energy-dispersive X-ray spectroscopy mapping were performed to investigate the structures and morphologies of the samples, respectively. Among all the composites tested, the PETG/6.0 wt.% Si 3 N 4 showed the greatest improvement in mechanical properties (with a 24.5% increase in tensile strength compared to unfilled PETG polymer), indicating its potential for use in MEX 3D printing when enhanced mechanical performance is required from the PETG polymer.

The goal of this paper is to investigate tungsten carbide (WC) as a reinforcement in the popular material extrusion (MEX) additive manufacturing (AM) procedure. The impressive characteristics of WC demonstrate its potential as a valuable additive for commonly used polymeric matrices in MEX 3D printing, offering reinforcement and stabilization properties. The mechanical properties of hybrid polymer/ceramic nanocomposites made up of various filler loadings (0-10 wt. %) of medical-grade polylactic acid (PLA) and WC were studied. The mechanical characteristics, structure, and thermomechanical properties of the resulting compounds were fully characterized following the respective standards. The fracture mechanisms were revealed with Scanning Electron Microscopy. Overall, a laborious effort was implemented with fifteen different tests to fully characterize the nanocomposites prepared. In comparison to the raw PLA material, the tensile strength of the 4.0 wt. % WC PLA/WC nanocomposite was improved by 42.5% and the flexural strength by 41.9%. In the microhardness test, a 120.4% improvement was achieved, justifying the properties of WC ceramic. According to these findings, PLA nanocomposites reach high-performance polymer specifications, expanding their potential use, especially in wear-related applications.

Bone tissue engineering has emerged as a promising strategy to overcome the limitations of current treatments for bone-related disorders, but the trade-off between mechanical properties and bioactivity remains a concern for many polymeric materials. To address this need, novel polymeric blends of poly-L-lactic acid (PLLA), polycaprolactone (PCL) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) have been explored. Blend filaments comprising PLLA/PCL/PHBV at a ratio of 90/5/5 wt% have been prepared using twin-screw extrusion. The PLLA/PCL/PHBV blends were enriched with nano-hydroxyapatite (nano-HA) and strontium-substituted nano-HA (Sr-nano-HA) to produce composite filaments. Three-dimensional scaffolds were printed by fused deposition modelling from PLLA/PCL/PHBV blend and composite filaments and evaluated mechanically and biologically for their capacity to support bone formation in vitro. The composite scaffolds had a mean porosity of 40%, mean pores of 800 µm, and an average compressive modulus of 32 MPa. Polymer blend and enriched scaffolds supported cell attachment and proliferation. The alkaline phosphatase activity and calcium production were significantly higher in composite scaffolds compared to the blends. These findings demonstrate that thermoplastic polyesters (PLLA and PCL) can be combined with polymers produced via a bacterial route (PHBV) to produce polymer blends with excellent biocompatibility, providing additional options for polymer blend optimization. The enrichment of the blend with nano-HA and Sr-nano-HA powders enhanced the osteogenic potential in vitro.

There is a growing concern about wound care, since traditional dressings such as bandages and sutures can no longer meet existing needs. To address the demanding requirements, naturally occurring polymers have been extensively exploited for use in modern wound management. Polysaccharides, being the most abundant biopolymers, have some distinct characteristics, including biocompatibility and biodegradability, which render them ideal candidates for wound healing applications. Combining them with inorganic and organic moieties can produce effective multifunctional composites with the desired mechanical properties, high wound healing efficiencies and excellent antibacterial behavior. Recent research endeavors focus on the development of stimuli-responsive polysaccharide composites for biomedical applications. Polysaccharide composites, being sensitive to the local environment, such as changes of the solution temperature, pH, etc., can sense and react to the wound conditions, thus promoting an effective interaction with the wound. This review highlights the recent advances in stimuli-responsive polysaccharide hydrogels and their composites for use in wound healing applications. The synthetic approaches, physical, chemical, and biochemical properties as well as their function in wound healing will be discussed.

Metal nanoparticles are used to modify/enhance the properties of a polymer matrix for a broad range of applications in bio-nanotechnology. Here, we study the properties of polymer/gold nanoparticle (NP) nanocomposites through atomistic molecular dynamics, MD, simulations. We probe the structural, conformational and dynamical properties of polymer chains at the vicinity of a gold (Au) NP and a functionalized (core/shell) Au NP, and compare them against the behavior of bulk polyethylene (PE). The bare Au NPs were constructed via a systematic methodology starting from ab-initio calculations and an atomistic Wulff construction algorithm resulting in the crystal shape with the minimum surface energy. For the functionalized NPs the interactions between gold atoms and chemically adsorbed functional groups change their shape. As a model polymer matrix we consider polyethylene of different molecular lengths, from the oligomer to unentangled Rouse like systems. The PE/Au interaction is parametrized via DFT calculations. By computing the different properties the concept of the interface, and the interphase as well, in polymer nanocomposites with metal NPs are critically examined. Results concerning polymer density profiles, bond order parameter, segmental and terminal dynamics show clearly that the size of the interface/interphase, depends on the actual property under study. In addition, the anchored polymeric chains change the behavior/properties, and especially the chain density profile and the dynamics, of the polymer chain at the vicinity of the Au NP.

The design and synthesis of new biomaterials with adjustable physicochemical and biological properties for tissue engineering applications have attracted great interest. In this work, chitosan- graft -poly(l-lactide) (CS- g -PLLA) copolymers were prepared by chemically binding poly(l-lactide) (PLLA) chains along chitosan (CS) via the " grafting to " approach to obtain hybrid biomaterials that present enhanced mechanical stability, due to the presence of PLLA, and high bioactivity, conferred by CS. Two graft copolymers were prepared, CS- g -PLLA(80/20) and CS- g -PLLA(50/50), containing 82 wt % and 55 wt % CS, respectively. Degradation studies of compressed discs of the copolymers showed that the degradation rate increased with the CS content of the copolymer. Nanomechanical studies in the dry state indicated that the copolymer with the higher CS content had larger Young modulus, reduced modulus and hardness values, whereas the moduli and hardness decreased rapidly following immersion of the copolymer discs in alpha-MEM cell culture medium for 24 h. Finally, the bioactivity of the hybrid copolymers was evaluated in the adhesion and growth of MC3T3-E1 pre-osteoblastic cells. In vitro studies showed that MC3T3-E1 cells exhibited strong adhesion on both CS- g -PLLA graft copolymer films from the first day in cell culture, whereas the copolymer with the higher PLLA content, CS- g -PLLA(50/50), supported higher cell growth.