Synthesis, Crystal Structure, and Broadband Emission of (CH3)3SSnCl3.

We report here on the synthesis, crystal structure, optoelectronic and vibrational properties, as well as the DFT calculations of the novel trimethylsulfonium tin trichloride (CH3)3SSnCl3. The air-stable compound is prepared by reacting the (CH3)3SCl and SnCl2 solid precursors in evacuated silica tubes at 100 °C. According to powder X-ray diffraction and Rietveld refinement, it crystallizes at room temperature in the orthorhombic space group Pbca (No. 61) with isolated pyramids of [SnCl3]- and (CH3)3S+ units. UV-vis reflectance and photoluminescence spectroscopies reveal a direct energy band gap of 3.85 eV, accompanied by a broad Stokes-shifted luminescence signal. Photoexcitation of the compound at room temperature and at -196 °C results in broadband luminescence with weak magenta emission centered at 400 nm using an excitation at 250 nm. First principal calculations provide insight into the physical properties through the electron and phonon density of states. Multitemperature Raman spectroscopy and differential scanning calorimetry reveal a reversible phase transition at ca. 70 °C that affects the vibrational modes of the [SnCl3]-. By dissolving (CH3)3SSnCl3 in dimethylformamide in ambient air for a week, oxidation of tin occurs in the "defect" perovskite ((CH3)3S)2SnCl6. The crystal structure of ((CH3)3S)2SnCl6 is also determined with high accuracy via single-crystal X-ray diffraction (cubic space group Pa-3 (No. 205)) and compared with (CH3)3SSnCl3 via Hirshfeld surface analysis.

Utilization of Silica Filler as Reinforcement Material of Polylactic Acid (PLA) in 3D Printing Applications: Thermal, Rheological, and Mechanical Performance.

Glass was introduced as an additive to filaments used for the manufacturing of composite materials, employed by Additive Manufacturing applications. Glass accounts for a large waste electric and electronic equipment (WEEE) percentage, and its recovery and recycling can lead to the production of sustainable composite materials. In this work, poly(lactic acid) (PLA)/commercially available silicon oxide composite filaments were manufactured and their structural, thermal, rheological, and mechanical properties were assessed. Scanning Electron Microscopy confirmed the 1:2 ratio of silicon: oxygen, along with the relatively low adhesion between the filler and the matrix. Differential Scanning Calorimetry presented steady glass transition and melting temperatures of composites, whereas a crystallization temperature of 10% wt. and a crystallinity of 15% wt. composite slightly increased. Rheological analysis showcased that the viscosity of the composite filaments decreased compared to PLA (10-100 compared to 300-400 Pa·s), with a more shear-thinning behavior. Dynamic mechanical analysis exhibited increased elastic, flexural moduli, and flexural strength of composites (up to 16, 23, and 11%, respectively), whereas tensile strength and elongation decreased. The affordability of raw materials (with the future introduction of recycled ones) and the minimal processing steps can lead to the potential scaling up of the study.

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.

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.

A Coherent Assessment of the Compressive Strain Rate Response of PC, PETG, PMMA, and TPU Thermoplastics in MEX Additive Manufacturing.

In this study, we successfully address a significant research and engineering gap by quantitatively assessing the impact of varying compressive loading rates on the mechanical behavior of four popular thermoplastic polymers in material-extrusion-based (MEX) 3D printing. Raw powders of polycarbonate (PC), polyethylene terephthalate glycol (PETG), polymethyl methacrylate (PMMA), and thermoplastic polyurethane (TPU) were processed through melt extrusion, and the filaments were used to 3D-print the test samples. For completeness, thermogravimetric analysis and a compressive test following the ASTM-D695 standard were conducted. Ultimately, the compressive strength and yield stress, the compressive modulus of elasticity and toughness, and the maximum compressive sensitivity index were thoroughly documented. Specimens were tested in strain rates from 1.3 mm/min to 200 mm/min. The compressive strength (40% for the PMMA) and stiffness (29% for the TPU) increased with the increase in the strain rate in all polymers tested. PC had the highest strain rate sensitivity. Significant variations in deformation and fracture modes were observed and thoroughly documented throughout this study. Our findings can be useful in industrial engineering as valued design optimization input parameters in various applications involving the above-mentioned polymeric materials.

Photocatalysis as an advanced reduction process (ARP): The reduction of 4-nitrophenol using titania nanotubes-ferrite nanocomposites.

TiO2 photocatalysis is an advanced process, employed worldwide for the oxidation of organic compounds, that leads to significant technological applications in the fields of health and environment. The use of the photocatalytic approach in reduction reactions seems very promising and can open new horizons for green chemistry synthesis. For this purpose, titanium dioxide nanotubes (TNTs) were developed in autoclave conditions using TiO2 P25 as a precursor material. Based on these nanotubular substrates, TiO2/CoFe2O4 (TCF) nanocomposites were further obtained by wet impregnation method. The materials were thoroughly characterized and their structural, textural, vibrational, optoelectronic and magnetic properties were determined. The composite materials combine absorbance in the visible optical range and high BET surface area values (˜100 m2/g), showing extremely high yield in the photocatalytic reduction of 4-nitrophenol (4-NP), exceeding 94% within short illumination time (only 35 min). The developed nanocomposites were successfully reused in consecutive photocatalytic experiments and were easily removed from the reaction medium using magnets. Both remarkable recycling ability and high-performance stability in the photocatalytic reduction of nitrophenol were observed, thus justifying the significant economic potential and industrial perspectives for this advanced reduction process.