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In this study, we investigated the performance improvement caused by the addition of copper (Cu) nanoparticles to high-density polyethylene (HDPE) matrix material. Composite materials, with filler percentages of 0.0, 2.0, 4.0, 6.0, 8.0, and 10.0 wt% were synthesized through the material extrusion (MEX) 3D printing technique. The synthesized nanocomposite filaments were utilized for the manufacturing of specimens suitable for the experimental procedure that followed. Hence, we were able to systematically investigate their tensile, flexural, impact, and microhardness properties through various mechanical tests that were conducted according to the corresponding standards. Broadband Dielectric Spectroscopy was used to investigate the electrical/dielectric properties of the composites. Moreover, by employing means of Raman spectroscopy and thermogravimetric analysis (TGA) we were also able to further investigate their vibrational, structural, and thermal properties. Concomitantly, means of scanning electron microscopy (SEM), as well as atomic force microscopy (AFM), were used for the examination of the morphological and structural characteristics of the synthesized specimens, while energy-dispersive X-ray spectroscopy (EDS) was also performed in order to receive a more detailed picture on the structural characteristics of the various synthesized composites. The corresponding nanomaterials were also assessed for their antibacterial properties regarding Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) with the assistance of a method named screening agar well diffusion. The results showed that the mechanical properties of HDPE benefited from the utilization of Cu as a filler, as they showed a notable improvement. The specimen of HDPE/Cu 4.0 wt% was the one that presented the highest levels of reinforcement in four out of the seven tested mechanical properties (for example, it exhibited a 36.7% improvement in the flexural strength, compared to the pure matrix). At the same time, the nanocomposites were efficient against the S. aureus bacterium and less efficient against the E. coli bacterium. The use of such multi-functional, robust nanocomposites in MEX 3D printing is positively impacting applications in various fields, most notably in the defense and security sectors. The latter becomes increasingly important if one takes into account that most firearms encompass various polymeric parts that require robustness and improved mechanical properties, while at the same time keeping the risk of spreading various infectious microorganisms at a bare minimum.

Abstract The development of efficient and sustainable composites remains a primary objective of both research and industry. In this study, the use of biochar, an eco-friendly reinforcing material, in additive manufacturing (AM) is investigated. A high-density Polyethylene (HDPE) thermoplastic was used as the matrix, and the material extrusion (MEX) technique was applied for composite production. Biochar was produced from olive tree prunings via conventional pyrolysis at 500 °C. Composite samples were created using biochar loadings in the range of 2.0–10.0 wt. %. The 3D-printed samples were mechanically tested in accordance with international standards. Thermogravimetric analysis (TGA) and Raman spectroscopy were used to evaluate the thermal and structural properties of the composites. Scanning electron microscopy was used to examine the fractographic and morphological characteristics of the materials. The electrical/dielectric properties of HDPE/biochar composites were studied over a broad frequency range (10–2 Hz–4 MHz) at room temperature. Overall, a laborious effort with 12 different tests was implemented to fully characterize the developed composites and investigate the correlations between the different qualities. This investigation demonstrated that biochar in the MEX process can be a satisfactory reinforcement agent. Notably, compared to the control samples of pure HDPE, biochar increased the tensile strength by over 20% and flexural strength by 35.9% when added at a loading of 4.0 wt. %. The impact strength and microhardness were also significantly improved. Furthermore, the Direct current (DC) conductivity of insulating HDPE increased by five orders of magnitude at 8.0 wt. % of biochar content, suggesting a percolation threshold. These results highlight the potential of C-based composites for the use in additive manufacturing to further exploit their applicability by providing parts with improved mechanical performance and eco-friendly profiles. Graphical Abstract

Acrylonitrile butadiene styrene (ABS) composites were prepared in filament form compatible with the material extrusion (MEX) 3D printing method, using biochar as a filler at various loadings of up to 10.0 wt %. Samples were fabricated to experimentally investigate their mechanical performance. The ABS/biochar composites were characterized using thermogravimetric analysis, differential scanning calorimetry, Raman spectroscopy, and rheological tests. The electrical properties of the composites were investigated using broadband dielectric spectroscopy. Scanning electron microscopy was utilized to analyze the morphological features of the fabricated specimens by examining their side and fracture surfaces. The results indicate that the composite with 4.0 wt % biochar content compared to pure ABS showed the highest mechanical response between the prepared composites (24.9 % and 21 % higher than the pure ABS tensile and flexural strength respectively). The composites retained their insulating behavior. These findings contribute to expanding the utilization of the material extrusion (MEX) 3D printing method while also unlocking prospects for potential applications in microelectronics, apart from mechanical reinforcement.

This research focused on developing medical-grade polypropylene (PP)/silver (Ag) nanocomposites for the production of components through material extrusion (MEX) three-dimensional printing (3DP). The objective was to improve the performance of PP by enhancing its mechanical properties and imparting antibacterial characteristics. An industrially scalable process was utilized to fabricate PP/Ag nanocomposites through the reactive melt mixing technique. Polyethylene glycol (PEG) served as the reduction agent, and silver nitrate (AgNO3) was incorporated as the additive. During the extrusion of the three-dimensional printing (3DP) filaments, reactive melt mixing occurred, resulting in the production of specimens for various standard tests. The addition of 5.0 wt% AgNO3 and 2.5 wt% PEG in the PP thermoplastic led to a slight improvement in mechanical performance, with a 9.9 % increase in tensile strength observed. The antibacterial properties of the composites were assessed through agar well diffusion tests against Escherichia coli (E-coli) and Staphylococcus aureus (S. aureus). A more significant biocidal effect was observed for S. aureus compared to E-coli. These composites have the potential to be utilized in industrial applications that require enhanced mechanical properties and durability, as well as important biocidal properties, such as in the medical equipment industry or the defense sector.

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.

In this study, poly (ethylene terephthalate) (PETG) was combined with Antimony-doped Tin Oxide (ATO) to create five different composites (2.0–10.0 wt.% ATO). The PETG/ATO filaments were extruded and supplied to a material extrusion (MEX) 3D printer to fabricate the specimens following international standards. Various tests were conducted on thermal, rheological, mechanical, and morphological properties. The mechanical performance of the prepared nanocomposites was evaluated using flexural, tensile, microhardness, and Charpy impact tests. The dielectric and electrical properties of the prepared composites were evaluated over a broad frequency range. The dimensional accuracy and porosity of the 3D printed structure were assessed using micro-computed tomography. Other investigations include scanning electron microscopy and energy-dispersive X-ray spectroscopy, which were performed to investigate the structures and morphologies of the samples. The PETG/6.0 wt.% ATO composite presented the highest mechanical performance (21% increase over the pure polymer in tensile strength). The results show the potential of such nanocomposites when enhanced mechanical performance is required in MEX 3D printing applications, in which PETG is the most commonly used polymer.

Polyethylene terephthalate glycol (PETG) and silicon nitride (Si3N4) were combined to create five composite materials with Si3N4 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 Si3N4 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.% Si3N4 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.

High-density polyethylene polymer (HDPE) and carbon black (CB) were utilized to create HDPE/CB composites with different filler concentrations (0.0, 2.0, 4.0, 6.0, 8.0, 10.0, 16.0, 20.0, and 24.0 wt.%). The composites were extruded into filaments, which were then utilized to fabricate 3D-printed specimens with the material extrusion (MEX) method, suitable for a variety of standard mechanical tests. The electrical conductivity was investigated. Furthermore, thermogravimetric analysis and differential scanning calorimetry were carried out for all the HDPE/CB composites and pure HDPE. Scanning electron microscopy in different magnifications was performed on the specimens’ fracture and side surfaces to investigate the morphological characteristics. Rheological tests and Raman spectroscopy were also performed. Eleven different tests in total were performed to fully characterize the composites and reveal connections between their various properties. HDPE/CB 20.0 wt.% showed the greatest reinforcement results in relation to pure HDPE. Such composites are novel in the MEX 3D printing method. The addition of the CB filler greatly enhanced the performance of the popular HDPE polymer, expanding its applications.

In this study, innovative nanocomposite materials for material extrusion (MEX) 3D printing were developed using a polypropylene (PP) polymer with tungsten carbide (WC) nanopowder. The raw materials were converted into filaments using thermomechanical extrusion. The samples were then fabricated for testing according to the international standards. Extensive mechanical testing was performed on the 3D-printed specimens, including tensile, impact, flexural, and microhardness assessments. In addition, the impact of ceramic additive loading was examined. The thermal and stoichiometric characteristics of the nanocomposites were examined using thermogravimetric analysis, energy-dispersive X-ray spectroscopy, differential scanning calorimetry, and Raman spectroscopy. The 3D-printed shape, quality, and fracture process of the specimens were examined using scanning electron microscopy. The results showed that the filler significantly enhanced the mechanical characteristics of the matrix polymer without reducing its thermal stability or processability. Notably, the highest level of nanocomposite mechanical responsiveness was achieved through the inclusion of 6.0 and 8.0 wt. % fillers. The 10.0 wt. % loading nanocomposite showed significantly increased microhardness, indicating a possible high resistance to wear.

Herein, polytetrafluoroethylene (PTFE) is evaluated as a reinforcement agent in material extrusion (MEX) additive manufacturing (AM), aiming to develop nanocomposites with enhanced mechanical performance. Loadings up to 4.0 wt.% were introduced as fillers of polylactic acid (PLA) and polyamide 12 (PA12) matrices. Filaments for MEX AM were prepared to produce corresponding 3D-printed samples. For the thorough characterization of the nanocomposites, a series of standardized mechanical tests were followed, along with AFM, TGA, Raman spectroscopy, EDS, and SEM analyses. The results showed an improved mechanical response for filler concentrations between 2.0 and 3.0 wt.%. The enhancement for the PLA/PTFE 2.0 wt.% in the tensile strength reached 21.1% and the modulus of elasticity 25.5%; for the PA12/PTFE 3.0 wt.%, 34.1%, and 41.7%, respectively. For PLA/PTFE 2.0 wt.%, the enhancement in the flexural strength reached 57.6% and the modulus of elasticity 25.5%; for the PA12/PTFE 3.0 wt.%, 14.7%, and 17.2%, respectively. This research enables the ability to deploy PTFE as a reinforcement agent in the PA12 and PLA thermoplastic engineering polymers in the MEX AM process, expanding the potential applications.

In this study, nanocomposites were fabricated with polycarbonate (PC) as the matrix material. Cellulose Nanofiber (CNF) at low filler loadings (0.5 wt.% and 1.0 wt.%) was used as the filler. Samples were produced using melt mixing extrusion with the Fused Filament Fabrication (FFF) process. The optimum 3D-printing parameters were experimentally determined and the required specimens for each tested material were manufactured using FFF 3D printing. Tests conducted for mechanical performance were tensile, flexural, impact, and Dynamic Mechanical Analysis (DMA) tests, while images of the side and the fracture area of the specimens were acquired using Scanning Electron Microscopy (SEM), aiming to determine the morphology of the specimens and the fracture mechanism. It was concluded that the filler’s ratio addition of 0.5 wt.% created the optimum performance when compared to pure PC and PC CNF 1.0 wt.% nanocomposite material.