Mechanical and Electrical Properties of Polyethylene Terephthalate Glycol/Antimony Tin Oxide Nanocomposites in Material Extrusion 3D Printing.

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.

Scanning Micro X-ray Fluorescence and Multispectral Imaging Fusion: A Case Study on Postage Stamps.

Scanning micrο X-ray fluorescence (µ-XRF) and multispectral imaging (MSI) were applied to study philately stamps, selected for their small size and intricate structures. The µ-XRF measurements were accomplished using the M6 Jetstream Bruker scanner under optimized conditions for spatial resolution, while the MSI measurements were performed employing the XpeCAM-X02 camera. The datasets were acquired asynchronously. Elemental distribution maps can be extracted from the µ-XRF dataset, while chemical distribution maps can be obtained from the analysis of the multispectral dataset. The objective of the present work is the fusion of the datasets from the two spectral imaging modalities. An algorithmic co-registration of the two datasets is applied as a first step, aiming to align the multispectral and µ-XRF images and to adapt to the pixel sizes, as small as a few tens of micrometers. The dataset fusion is accomplished by applying k-means clustering of the multispectral dataset, attributing a representative spectrum to each pixel, and defining the multispectral clusters. Subsequently, the µ-XRF dataset within a specific multispectral cluster is analyzed by evaluating the mean XRF spectrum and performing k-means sub-clustering of the µ-XRF dataset, allowing the differentiation of areas with variable elemental composition within the multispectral cluster. The data fusion approach proves its validity and strength in the context of philately stamps. We demonstrate that the fusion of two spectral imaging modalities enhances their analytical capabilities significantly. The spectral analysis of pixels within clusters can provide more information than analyzing the same pixels as part of the entire dataset.

Investigation of the Effectiveness of Silicon Nitride as a Reinforcement Agent for Polyethylene Terephthalate Glycol in Material Extrusion 3D Printing.

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/Carbon Black Composites in Material Extrusion Additive Manufacturing: Conductivity, Thermal, Rheological, and Mechanical Responses.

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.

Nanostructured Single-ion Polymer Blend Electrolytes Composed of Polyanionic Particles and Low Molecular Weight PEO.

The development of single-ion solid polymer electrolytes with high ion conductivity holds the key to the realization of safe, long-lasting, high-energy batteries. Here we introduce the use of core-shell nanostructured polyanionic particles, composed of polyanion asymmetric miktoarm stars with a large number of glassy polystyrene-based polyanion arms that complement longer poly(ethylene oxide), PEO, arms, as additives to low molecular weight, liquid PEO. Due to the proposed macromolecular design approach, the polyanion particles are well dispersed for wt % ≤ 55 that enables the formation of a nanostructured single-ion electrolyte with highly interconnected channels composed of liquid PEO that promotes fast ion transport. Noticeably, while the ion conductivity remains fairly unaffected and close to 10-5 S/cm at room temperature with nanoparticle loading, the shear modulus monotonically increases by several order of magnitudes indicating a very strong decoupling between the antagonistic properties of mechanical modulus and ion conductivity.

Medical-Grade PLA Nanocomposites with Optimized Tungsten Carbide Nanofiller Content in MEX Additive Manufacturing: A Rheological, Morphological, and Thermomechanical Evaluation.

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.

Label-Free Human Disease Characterization through Circulating Cell-Free DNA Analysis Using Raman Spectroscopy.

Circulating cell-free DNA (ccfDNA) is a liquid biopsy biomaterial attracting significant attention for the implementation of precision medicine diagnostics. Deeper knowledge related to its structure and biology would enable the development of such applications. In this study, we employed Raman spectroscopy to unravel the biomolecular profile of human ccfDNA in health and disease. We established reference Raman spectra of ccfDNA samples from healthy males and females with different conditions, including cancer and diabetes, extracting information about their chemical composition. Comparative observations showed a distinct spectral pattern in ccfDNA from breast cancer patients taking neoadjuvant therapy. Raman analysis of ccfDNA from healthy, prediabetic, and diabetic males uncovered some differences in their biomolecular fingerprints. We also studied ccfDNA released from human benign and cancer cell lines and compared it to their respective gDNA, confirming it mirrors its cellular origin. Overall, we explored for the first time Raman spectroscopy in the study of ccfDNA and provided spectra of samples from different sources. Our findings introduce Raman spectroscopy as a new approach to implementing liquid biopsy diagnostics worthy of further elaboration.

A novel SATB1 protein isoform with different biophysical properties.

Intra-thymic T cell development is coordinated by the regulatory actions of SATB1 genome organizer. In this report, we show that SATB1 is involved in the regulation of transcription and splicing, both of which displayed deregulation in Satb1 knockout murine thymocytes. More importantly, we characterized a novel SATB1 protein isoform and described its distinct biophysical behavior, implicating potential functional differences compared to the commonly studied isoform. SATB1 utilized its prion-like domains to transition through liquid-like states to aggregated structures. This behavior was dependent on protein concentration as well as phosphorylation and interaction with nuclear RNA. Notably, the long SATB1 isoform was more prone to aggregate following phase separation. Thus, the tight regulation of SATB1 isoforms expression levels alongside with protein post-translational modifications, are imperative for SATB1's mode of action in T cell development. Our data indicate that deregulation of these processes may also be linked to disorders such as cancer.

Three-Dimensional-Printed Photocatalytic Sponges Decorated with Mn-Doped ZnO Nanoparticles.

The present work reports on the fabrication of high-density polyethylene sponges, decorated with Mn-doped ZnO nanostructures. The sponges were developed utilizing three-dimensional printing technology, while Mn-doped ZnO nanostructures, with varying doping levels, were grown at mild temperatures. The nanostructures were fully characterized by means of scanning electron microscopy, X-ray diffraction, and Raman spectroscopy, revealing the existence of Mn doping. Moreover, their photocatalytic properties were investigated using the degradation/decolorization of a commercially available liquid laundry detergent, based on synthetic, less foaming ingredients, under UV irradiation. The Mn-doped ZnO nanostructures show better photocatalytic activity at higher doping levels. This study demonstrates that it is possible to achieve the adequate degradation of a typical detergent solution in water by means of low-cost and environmentally friendly approaches, while Mn-doped ZnO/HDPE nanostructures are good candidates for real environmental applications.

The Effect of Nano Zirconium Dioxide (ZrO2)-Optimized Content in Polyamide 12 (PA12) and Polylactic Acid (PLA) Matrices on Their Thermomechanical Response in 3D Printing.

The influence of nanoparticles (NPs) in zirconium oxide (ZrO2) as a strengthening factor of Polylactic Acid (PLA) and Polyamide 12 (PA12) thermoplastics in material extrusion (MEX) additive manufacturing (AM) is reported herein for the first time. Using a melt-mixing compounding method, zirconium dioxide nanoparticles were added at four distinct filler loadings. Additionally, 3D-printed samples were carefully examined for their material performance in various standardized tests. The unfilled polymers were the control samples. The nature of the materials was demonstrated by Raman spectroscopy and thermogravimetric studies. Atomic Force Microscopy and Scanning Electron Microscopy were used to comprehensively analyze their morphological characteristics. Zirconium dioxide NPs showed an affirmative reinforcement tool at all filler concentrations, while the optimized material was calculated with loading in the range of 1.0-3.0 wt.% (3.0 wt.% for PA12, 47.7% increase in strength; 1.0 wt.% for PLA, 20.1% increase in strength). PA12 and PLA polymers with zirconium dioxide in the form of nanocomposite filaments for 3D printing applications could be used in implementations using thermoplastic materials in engineering structures with improved mechanical behavior.

Nanocomposites with Optimized Polytetrafluoroethylene Content as a Reinforcement Agent in PA12 and PLA for Material Extrusion Additive Manufacturing.

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.

Optimizing the Rheological and Thermomechanical Response of Acrylonitrile Butadiene Styrene/Silicon Nitride Nanocomposites in Material Extrusion Additive Manufacturing.

The current research aimed to examine the thermomechanical properties of new nanocomposites in additive manufacturing (AM). Material extrusion (MEX) 3D printing was utilized to evolve acrylonitrile butadiene styrene (ABS) nanocomposites with silicon nitride nano-inclusions. Regarding the mechanical and thermal response, the fabricated 3D-printed samples were subjected to a course of standard tests, in view to evaluate the influence of the Si3N4 nanofiller content in the polymer matrix. The morphology and fractography of the fabricated filaments and samples were examined using scanning electron microscopy and atomic force microscopy. Moreover, Raman and energy dispersive spectroscopy tests were accomplished to evaluate the composition of the matrix polymer and nanomaterials. Silicon nitride nanoparticles were proved to induce a significant mechanical reinforcement in comparison with the polymer matrix without any additives or fillers. The optimal mechanical response was depicted to the grade ABS/Si3N4 4 wt. %. An impressive increase in flexural strength (30.3%) and flexural toughness (47.2%) was found. The results validate that these novel ABS nanocomposites with improved mechanical properties can be promising materials.

Mechanical strength predictability of full factorial, Taguchi, and Box Behnken designs: Optimization of thermal settings and Cellulose Nanofibers content in PA12 for MEX AM.

Optimization of reinforced nanocomposites for MEX 3D-printing remain strong industrial claims. Herein, the efficacy of three modeling methods, i.e., full factorial (FFD), Taguchi (TD), and Box-Behnken (BBD), on the performance of MEX 3D printed nanocomposites was investigated, aiming to reduce the experimental effort. Filaments of medical-grade Polyamide 12 (PA12) reinforced with Cellulose NanoFibers (CNF) were evolved. Besides the CNF loading, 3D printing settings such as Nozzle (NT) and Bed (BΤ) Temperatures were optimization goals aiming to maximize the mechanical response. Three parameters and three levels of FFD were compliant with the ASTM-D638 standard (27 runs, five repetitions). An L9 orthogonal TD and a 15 runs BBD were compiled. In FFD, wt.3%CNF, 270 °C NT, and 80 °C BΤ led to 24% higher tensile strength compared to pure PA12. TGA, RAMAN, and SEM analyses interpreted the reinforcement mechanisms. TD and BBD exhibited fair approximations, requiring 7.4% and 11.8% of the FFD experimental effort.

Mechanical Reinforcement of ABS with Optimized Nano Titanium Nitride Content for Material Extrusion 3D Printing.

Acrylonitrile Butadiene Styrene (ABS) nanocomposites were developed using Material Extrusion (MEX) Additive Manufacturing (AM) and Fused Filament Fabrication (FFF) methods. A range of mechanical tests was conducted on the produced 3D-printed structures to investigate the effect of Titanium Nitride (TiN) nanoparticles on the mechanical response of thermoplastic polymers. Detailed morphological characterization of the produced filaments and 3D-printed specimens was carried out using Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). High-magnification images revealed a direct impact of the TiN concentration on the surface characteristics of the nanocomposites, indicating a strong correlation with their mechanical performance. The chemical compositions of the raw and nanocomposite materials were thoroughly investigated by conducting Raman and Energy Dispersive Spectroscopy (EDS) measurements. Most of the mechanical properties were improved with the inclusion of TiN nanoparticles with a content of 6 wt. % to reach the optimum mechanical response overall. ABS/TiN 6 wt. % exhibits remarkable increases in flexural modulus of elasticity (42.3%) and toughness (54.0%) in comparison with pure ABS. The development of ABS/TiN nanocomposites with reinforced mechanical properties is a successful example that validates the feasibility and powerful abilities of MEX 3D printing in AM.

Thermomechanical Response of Polycarbonate/Aluminum Nitride Nanocomposites in Material Extrusion Additive Manufacturing.

Polycarbonate-based nanocomposites were developed herein through a material extrusion (MEX) additive manufacturing (AM) process. The fabrication of the final nanocomposite specimens was achieved by implementing the fused filament fabrication (FFF) 3D printing process. The impact of aluminum nitride (AlN) nanoparticles on the thermal and mechanical behavior of the polycarbonate (PC) matrix was investigated thoroughly for the fabricated nanocomposites, carrying out a range of thermomechanical tests. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) provided information about the morphological and surface characteristics of the produced specimens. Using energy dispersive spectroscopy (EDS), the elemental composition of the nanocomposite materials was validated. Raman spectroscopy revealed no chemical interactions between the two material phases. The results showed the reinforcement of most mechanical properties with the addition of the AlN nanoparticles. The nanocomposite with 2 wt.% filler concentration exhibited the best mechanical performance overall, with the highest improvements observed for the tensile strength and toughness of the fabricated specimens, with a percentage of 32.8% and 51.6%, respectively, compared with the pure polymer. The successful AM of PC/AlN nanocomposites with the MEX process is a new paradigm, which expands 3D printing technology and opens a new route for the development of nanocomposite materials with multifunctional properties for industrial applications.

Three-Dimensional Printed Polyamide 12 (PA12) and Polylactic Acid (PLA) Alumina (Al2O3) Nanocomposites with Significantly Enhanced Tensile, Flexural, and Impact Properties.

The effect of aluminum oxide (Al2O3) nanoparticles (NPs) as a reinforcing agent of Polyamide 12 (PA12) and Polylactic acid (PLA) in fused filament fabrication (FFF) three-dimensional printing (3DP) is reported herein for the first time. Alumina NPs are incorporated via a melt-mixing compounding process, at four different filler loadings. Neat as well as nanocomposite 3DP filaments are prepared as feedstock for the 3DP manufacturing of specimens which are thoroughly investigated for their mechanical properties. Thermogravimetric analyses (TGA) and Raman spectroscopy (RS) proved the nature of the materials. Their morphological characteristics were thoroughly investigated with scanning electron and atomic force microscopy. Al2O3 NPs exhibited a positive reinforcement mechanism at all filler loadings, while the mechanical percolation threshold with the maximum increase of performance was found between 1.0-2.0 wt.% filler loading (1.0 wt.% for PA12, 41.1%, and 56.4% increase in strength and modulus, respectively; 2.0 wt.% for PLA, 40.2%, and 27.1% increase in strength and modulus, respectively). The combination of 3DP and polymer engineering using nanocomposite PA12 and PLA filaments with low-cost filler additives, e.g., Al2O3 NPs, could open new avenues towards a series of potential applications using thermoplastic engineering polymers in FFF 3DP manufacturing.

Multifunctional Medical Grade Resin with Enhanced Mechanical and Antibacterial Properties: The Effect of Copper Nano-Inclusions in Vat Polymerization (VPP) Additive Manufacturing.

Vat photopolymerization (VPP) is an additive manufacturing process commonly used in medical applications. This work aims, for the first time in the literature, to extend and enhance the performance of a commercial medical-grade resin for the VPP process, with the development of nanocomposites, using Copper (Cu) nanoparticles as the additive at two different concentrations. The addition of the Cu nanoparticles was expected to enhance the mechanical properties of the resin and to enable biocidal properties on the nanocomposites since Cu is known for its antibacterial performance. The effect of the Cu concentration was investigated. The nanocomposites were prepared with high-shear stirring. Specimens were 3D printed following international standards for mechanical testing. Their thermal and spectroscopic response was also investigated. The morphological characteristics were examined. The antibacterial performance was evaluated with an agar well diffusion screening process. The experimental results were analyzed with statistical modeling tools with two control parameters (three levels each) and eleven response parameters. Cu enhanced the mechanical properties in all cases studied. 0.5 wt.% Cu nanocomposite showed the highest improvement (approximately 11% in tensile and 10% in flexural strength). The antibacterial performance was sufficient against S. aureus and marginal against E. coli.

Silicon Carbide Nanoparticles as a Mechanical Boosting Agent in Material Extrusion 3D-Printed Polycarbonate.

In this work, the effect of silicon carbide (carborundum, SiC), as a boosting agent of the mechanical response of the polycarbonate (PC) polymer, was investigated. The work aimed to fabricate nanocomposites with an improved mechanical performance and to further expand the utilization of 3D printing in fields requiring an enhanced material response. The nanocomposites were produced by a thermomechanical process in various SiC concentrations in order to evaluate the filler loading in the mechanical enhancement. The samples were 3D printed with the material extrusion (MEX) method. Their mechanical performance was characterized, following international standards, by using dynamic mechanical analysis (DMA) and tensile, flexural, and Charpy's impact tests. The microhardness of the samples was also measured. The morphological characteristics were examined, and Raman spectra revealed their structure. It was found that SiC can improve the mechanical performance of the PC thermoplastic. A 19.5% increase in the tensile strength was found for the 2 wt.% loading nanocomposite, while the 3 wt.% nanocomposite showed a 16% increase in the flexural strength and a 35.9% higher impact strength when compared to the unfilled PC. No processability issues were faced for the filler loadings that have been studied here.

Interplay of plastic pollution with algae and plants: hidden danger or a blessing?

In the era of plastic pollution, plants have been discarded as a system that is not affected by micro and nanoplastics, but contrary to beliefs that plants cannot absorb plastic particles, recent research proved otherwise. The presented review gives insight into known aspects of plants' interplay with plastics and how plants' ability to absorb plastic particles can be utilized to remove plastics from water and soil systems. Microplastics usually cannot be absorbed by plant root systems due to their size, but some reports indicate they might enter plant tissues through stomata. On the other hand, nanoparticles can enter plant root systems, and reports of their transport via xylem to upper plant parts have been recorded. Bioaccumulation of nanoplastics in upper plant parts is still not confirmed. The prospects of using biosystems for the remediation of soils contaminated with plastics are still unknown. However, algae could be used to degrade plastic particles in water systems through enzyme facilitated degradation processes. Considering the amount of plastic pollution, especially in the oceans, further research is necessary on the utilization of algae in plastic degradation. Special attention should be given to the research concerning utilization of algae with restricted algal growth, ensuring that a different problem is not induced, "sea blooming", during the degradation of plastics.

Trilateral Multi-Functional Polyamide 12 Nanocomposites with Binary Inclusions for Medical Grade Material Extrusion 3D Printing: The Effect of Titanium Nitride in Mechanical Reinforcement and Copper/Cuprous Oxide as Antibacterial Agents.

In this work, for the first time, polyamide 12 (PA12) nanocomposites with binary inclusions in material extrusion (MEX) 3D printing were developed. The aim was to achieve an enhanced mechanical response with the addition of titanium nitride (TiN) and antibacterial performance with the addition of copper (Cu) or cuprous oxide (Cu2O), towards the development of multi-functional nanocomposite materials, exploiting the 3D printing process benefits. The prepared nanocomposites were fully characterized for their mechanical properties. The thermal properties were also investigated. Morphological characterization was performed with atomic force microscopy (AFM) and scanning electron microscopy (SEM). The antibacterial performance was investigated with an agar-well diffusion screening process. Overall, the introduction of these nanofillers induced antibacterial performance in the PA12 matrix materials, while at the same time, the mechanical performance was significantly increased. The results of the study show high potential for expanding the areas in which 3D printing can be used.