Search Results (19)

Understanding cellular interaction with nanomaterials represents a subject of great interest for the validation of new diagnostic and therapeutic tools. A full characterization of a designed product includes the evaluation of its impact on specific biological systems, including the study of cell behavior as a response to that particular interaction. Copper and copper-based nanoparticles (CuO NPs) have emerged as valuable building blocks for various biomedical applications such as antibacterial and disinfecting agents for infectious diseases, and the evaluation of the metabolism of food, including the iron required for proteins and enzymes or as drug delivery systems in cancer therapy. In this study, the biological impact of manganese-doped crystalline copper oxide (CuO:Mn) nano-platelets on human normal BJ fibroblasts and human A375 skin melanoma was assessed. The particles were synthesized at room temperature via the hydrothermal method. A complete physicochemical characterization of the materials was performed by employing various techniques including X-ray diffraction, electron microscopy, X-Ray photoelectron spectroscopy, and dynamic light scattering. Morphological investigations revealed a flat structure with nearly straight edges, with sizes spanning in the nanometer range. XRD analysis confirmed the formation of the CuO phase with good crystallinity, while XPS provided insights into the Mn doping. The findings indicate that nano-platelets interact with cells actively by mediating essential molecular processes. The exogenous manganese triggers increased MnSOD production in mitochondria, compensating ROS produced by external stress factors (Cu²⁺ ions), and mimics the endogenous SODs production, which compensates internal ROS production as it normally results from cell biochemistry. The effect is differentiated in normal cells compared to malignant cells and deserves investigation. Full article

Waste Zn-Mn batteries represent a significant contributor to e-waste, which is typically a hazardous material. Furthermore, Zn-Mn batteries possess more valuable metals than primary ore minerals, making them a crucial secondary resource for Zn and Mn extractive metallurgy. Current hydrometallurgy techniques primarily use acids as leaching agents, and the products are then purified by precipitating, extraction, etc. However, the Mn-Zn spinel formed in spent batteries exhibits exceptional structural stability, which can only be dissolved under strong acidic conditions. Therefore, eliminating the spinel’s effects helps improve recovery efficiency. This study introduces an innovative approach for selectively recovering Zn and Mn from spent batteries by integrating reduction roasting with acid leaching, utilizing spent graphite electrodes as environmentally friendly reductants. Meanwhile, the effect of roasting and leaching on recovery efficiency is explored, as well as the phase transformation of Zn-Mn oxides during the total component recovery process. In addition, high-value-added products, nano-ZnO whiskers, are in situ synthesized via a two-stage atmosphere-controlled process. Finally, Mn and Zn recoveries of 99.8% and 99.5% are obtained under optimal conditions, and hexagonal nano-ZnO with a crystallinity of 99.9% with a grain size of 46.3 nm is synthesized successfully. Full article

MnZn ferrite powders were prepared based on the novel nano in situ composite method and through chemical sol-spray drying–calcination technology. The precursor powders were calcined at 1060 °C at different calcination times (1–9 h) to research the influences of the calcination time on MnZn ferrite powders. The research results revealed that all samples had similar morphologies composed of fine particles. The pure MnZn ferrite spinel phase can only be obtained when the calcination time does not exceed 3 h. Otherwise, some α-Fe₂O₃ or γ-Fe₂O₃ impurities will appear. The particle size descended with an increasing calcination time and then ascended. After 3 h of preservation, the smallest particle size was obtained, and it exhibited a unimodal distribution. The saturation magnetization (M_s) increased at first and decreased later with an increasing calcination time, and the optimal value (53.4 emu/g) was reached after holding for 3 h. In view of this work, the optimal calcination time is 3 h. Full article

[Carbonatotetraamminecobalt(III)] permanganate monohydrate was synthesized first in the metathesis reaction of [Co(NH₃)₄CO₃]NO₃ and NaMnO₄ in aqueous solution. Its thermal dehydration at 100 °C resulted in phase-pure [Co(NH₃)₄CO₃]MnO₄ (compound 1). Compounds 1 and 2 (i.e., the hydrated form) were studied with IR, far-IR, and low-temperature Raman spectroscopies, and their vibrational modes were assigned. The lattice parameters were determined by powder X-ray diffraction (PXRD) and single crystal X-ray diffraction (SXRD) methods for the triclinic and orthorhombic compounds 1 and 2, respectively. The detailed structure of compound 2 was determined, and the role of hydrogen bonds in the structural motifs was clarified. UV studies on compounds 1 and 2 showed the distortion of the octahedral geometry of the complex cation during dehydration because of the partial loss of the hydrogen bonds between the crystal water and the ligands of the complex cation. The thermal decomposition consists of a solid phase quasi-intramolecular redox reaction between the ammonia ligands and permanganate anions with the formation of ammonia oxidation products (H₂O, NO, N₂O, and CO₂). The solid phase reaction product is amorphous cobalt manganese oxide containing ammonium, carbonate (and nitrate) anions. The temperature-controlled thermal decomposition of compound 2 in toluene at 110 °C showed that one of the decomposition intermediates is ammonium nitrate. The decomposition intermediates are transformed into Co_1.5Mn_1.5O₄ spinel with MnCo₂O₄ structure upon further heating. Solid compound 2 gave the spinel at 500 °C both in an inert and air atmosphere, whereas the sample pre-treated in toluene at 110 °C without and with the removal of ammonium nitrate by aqueous washing, gave the spinel already at 300 and 400 °C, respectively. The molten NH₄NO₃ is a medium to start spinel crystallization, but its decomposition stops further crystal growth of the spinel phase. By this procedure, the particle size of the spinel product as low as ~4.0 nm could be achieved for the treatments at 300 and 400 °C, and it increased only to 5.7 nm at 500 °C. The nano-sized mixed cobalt manganese oxides are potential candidates as Fischer-Tropsch catalysts. Full article

Aluminium metal is not typically added to the submerged arc welding (SAW) process because it is easily oxidised to form unwanted slag in the weld pool. The successful application of aluminium as a de-oxidiser is illustrated in this study by preventing oxidation of Cr and Co to their oxides, thereby preventing element loss to the slag. Unconstrained pure metals of Al, Cr, Co and Cu were applied to investigate the gas formation behaviour of these elements in the SAW arc cavity. Of interest is the effect of copper in the arc cavity in terms of its possible substitution for aluminium. The results confirmed that the Al-Cr-Co-Cu alloyed weld metal total oxygen content was lowered to 176 ppm O, in comparison to 499 ppm O in the weld metal formed from welding with the original flux, which excluded metal powder additions. This lower ppm O value of 176 ppm O confirms that the added aluminium powder effectively lowered the original flux-induced partial oxygen pressure in the arc cavity, and at the molten flux–weld pool interface. Carbon steel was alloyed to 5.3% Co, 5.5% Cr, 5.3% Cu and 4.5% Al at 78% Co yield, 82% Cr yield, 78% Cu yield and 66% Al yield. Thermochemical equilibrium calculations confirm the partial oxygen pressure-lowering effect of aluminium when considering the gas–slag–alloy equilibrium. BSE (backscattered electron) images of the three-dimensional (3D) post-weld slag sample show dome structures which contain features of vapour formation and re-condensation. SEM-EDX (scanning electron microscope-energy dispersive X-ray) maps show that the dome surface matrix phase consists of Al-Mg-Ca-Si-Na-K-Ti-Fe-Mn oxy-fluoride. The spherical 3D structures of 10–40 µm in diameter consist of Fe-Mn-Si fluorides with some Cr, Cu and Co contained in some of the spheres. Cr and Co were observed in distinctive porous structures of approximately 10 µm in size, consisting partly of Cr oxy-fluoride and partly of Co oxy-fluoride. Nano-sized oxy-fluoride strands and spheres in the dome structures confirm vaporisation and re-condensation of oxy-fluorides. Cu and Na formed a distinct condensation pattern on the surface of the Si-Cu-Na-Mn-Fe-Co oxy-fluoride sphere. The results confirm the importance of including gas phase reactions in the interpretation of SAW process metallurgy. Full article

Soft magnetic composite (SMC) cores have been obtained by Spark Plasma Sintering (SPS) using pseudo core–shell powders. Pseudo core–shell powders are formed by a core of soft magnetic particle (nanocrystalline permalloy or supermalloy) surrounded by a thin layer (shell) of nanosized soft ferrite (Mn_0.5Zn_0.5Fe₂O₄). Three compositions of pseudo core–shell powders were prepared, with 1, 2 and 3 wt.% of manganese–zinc mixt ferrite. The pseudo core–shell powders were compacted by SPS at temperatures between 500 and 700 °C, with a holding time ranging from 0 to 10 min. Several techniques have been used for characterization of the samples, both, powders and compacts X-ray diffraction (XRD, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), magnetic hysteresis measurements (DC and AC) and electrical resistivity. The electrical resistivity is in the order of 1 × 10⁻² Ωm, 3–4 orders of magnitude higher than supermalloy electrical resistivity. The SPS at lower temperatures (500 °C) conserves the initial phases of the composite, but increasing the sintering temperature and/or sintering time produces a solid-state reaction between the alloy and ferrite phases, with negative consequence on the magnetic properties of the compacts. The initial relative permeability is around 40 and remains constant until to 2000 Hz. The power losses are lower than 2 W/kg until to 2000 Hz. Full article

One of the current problems in the environmental catalysis is the design of an effective and less costly catalytic system for the oxidation of CO. The nano-sized α-Mn₂O₃ oxide has been prepared and modified with 0.5 wt.% Pt. The catalysts have been characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), temperature-programmed reduction (TPR) and diffuse-reflectance infrared spectroscopy (DRIFTS). Finely divided PtO and Pt(OH)₂ are being formed on the Mn₂O₃ surface as a result of the strong interaction between platinum and the nano-oxide. Based on DRIFTS investigations and the model calculations, a Langmuir–Hinshelwood type of mechanism is supposed for CO oxidation on Pt/Mn₂O₃. The CO and oxygen are adsorbed on different types of sites. The Mars–van Krevelen mechanism is the most probable one over pure Mn₂O₃, thus suggesting that CO₂ is adsorbed on the oxidized sites. The CO adsorption in the mixture CO + N₂ or in the presence of oxygen (CO + N₂ + O₂) leads to a partial reduction in the Pt⁺ surface species and the formation of linear Pt¹⁺−CO and Pt⁰−CO carbonyls. Both of them take part in the CO oxidation reaction. Full article

The present paper reports on MnCoFeO₄ spinels with peculiar composition and their catalytic behavior in the reactions of complete oxidation of hydrocarbons. The samples were synthesized by solution combustion method with sucrose and citric acid as fuels. All samples were characterized by powder X-ray diffraction, N₂-physisorption, scanning electron microscopy, thermal analysis, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy. The catalytic properties of the spinels with Mn:Co:Fe = 1:1:1 composition were studied in reactions of complete oxidation of methane, propane, butane, and propane in the presence of water as model pollutants. Both prepared catalysts are nanosized materials. The slight difference in the compositions, structure, and morphology is due to the type of fuel used in the synthesis reaction. The spinel, prepared with sucrose, shows a higher specific surface area, pore volume, higher amount of small particles fraction, higher thermal stability, and as a result, more exposed active sites on the sample surface that lead to higher catalytic activity in the studied oxidation reactions. After the catalytic tests, both samples do not undergo any substantial phase and morphological changes; thus, they could be applied in low-temperature hydrocarbon oxidation reactions. Full article

Here, we report synthesis and investigations of bulk and nano-sized La_(0.7−x)Eu_xBa_0.3MnO₃ (x ≤ 0.4) compounds. The study presents a comparison between the structural and magnetic properties of the nano- and polycrystalline manganites La_(0.7−x)Eu_xBa_0.3MnO₃, which are potential magnetocaloric materials to be used in domestic magnetic refrigeration close to room temperature. The parent compound, La_0.7Ba_0.3MnO₃, has Curie temperature T_C = 340 K. The magnetocaloric effect is at its maximum around T_C. To reduce this temperature below 300 K, we partially replaced the La ions with Eu ions. A solid-state reaction was used to prepare bulk polycrystalline materials, and a sol-gel method was used for the nanoparticles. X-ray diffraction was used for the structural characterization of the compounds. Transmission electron spectroscopy (TEM) evidenced nanoparticle sizes in the range of 40–80 nm. Iodometry and inductively coupled plasma optical emission spectrometry (ICP-OES) was used to investigate the oxygen content of the studied compounds. Critical exponents were calculated for all samples, with bulk samples being governed by tricritical mean field model and nanocrystalline samples governed by the 3D Heisenberg model. The bulk sample with x = 0.05 shows room temperature phase transition T_C = 297 K, which decreases with increasing x for the other samples. All nano-sized compounds show lower T_C values compared to the same bulk samples. The magnetocaloric effect in bulk samples revealed a greater magnetic entropy change in a relatively narrow temperature range, while nanoparticles show lower values, but in a temperature range several times larger. The relative cooling power for bulk and nano-sized samples exhibit approximately equal values for the same substitution level, and this fact can substantially contribute to applications in magnetic refrigeration near room temperature. By combining the magnetic properties of the nano- and polycrystalline manganites, better magnetocaloric materials can be obtained. Full article

High-energy cathode materials that are Li- and Mn-rich lithiated oxides—for instance, 0.35Li₂MnO₃^.0.65LiNi_0.35Mn_0.45Co_0.20O₂ (HE-NCM)—are promising for advanced lithium-ion batteries. However, HE-NCM cathodes suffer from severe degradation during cycling, causing gradual capacity loss, voltage fading, and low-rate capability performance. In this work, we applied an effective approach to creating a nano-sized surface layer of Li₂SO₄ on the above material, providing mitigation of the interfacial side reactions while retaining the structural integrity of the cathodes upon extended cycling. The Li₂SO₄ coating was formed on the surface of the material by mixing it with nanocrystalline Li₂SO₄ and annealing at 600 °C. We established enhanced electrochemical behavior with ~20% higher discharge capacity, improved charge-transfer kinetics, and higher rate capability of HE-NCM cathodes due to the presence of the Li₂SO₄ coating. Online electrochemical mass spectrometry studies revealed lower CO₂ and H₂ evolution in the treated samples, implying that the Li₂SO₄ layer partially suppresses the electrolyte degradation during the initial cycle. In addition, a ~28% improvement in the thermal stability of the Li₂SO₄-treated samples in reactions with battery solution was also shown by DSC studies. The post-cycling analysis allowed us to conclude that the Li₂SO₄ phase remained on the surface and retained its structure after 100 cycles. Full article

Mn_0.5Zn_0.5Fe₂O₄ nano-powder was coated on Fe microparticles by mechanical ball milling combined with high-temperature annealing. The effects of milling time on the particle size, phase structure and magnetic properties of core–shell powder were studied. Scanning electron microscopy (SEM), energy-dispersive spectroscopy and X-ray diffraction showed that the surface of the milled composite powder was composed of thin layers of uniform Mn_0.5Zn_0.5Fe₂O₄ insulating powder. SEM also revealed a cell structure of Fe particles, indicating that the Fe particles were well separated and isolated by the thin Mn_0.5Zn_0.5Fe₂O₄ layers. Then, Fe/Mn_0.5Zn_0.5Fe₂O₄ soft magnetic composites were prepared by spark plasma sintering. The amplitude permeability of Fe/Mn_0.5Zn_0.5Fe₂O₄ SMCs in the Fe/Mn_0.5Zn_0.5Fe₂O₄ soft magnetic composites was stable. The resistivity decreased with the increase in sintering temperature. The loss of the composite core was obviously less than that of the iron powder core. Hence, the preparation method of Mn_0.5Zn_0.5Fe₂O₄ insulating iron powder is promising for reducing core loss and improving the magnetic properties of soft magnetic composites. Full article

In this paper, the interface between yttria stabilized zirconia (Y_0.08Zr_0.92O₂, YSZ) electrolyte and Sr-doped lanthanum manganite (La_0.80Sr_0.20MnO₃, LSM) cathode for solid oxide fuel cells (SOFCs) is studied. For such a purpose, the combination of a suitable synthesis route for obtaining fine powders and simple aqueous colloidal shaping routes is proposed. The synthesis of nanosized particles of La_0.80Sr_0.20MnO₃ by a citrate route and their full characterization, including the colloidal stability and the densification and phase development determined by X-ray diffraction and electron microscopy at different temperatures, is reported. In a second step, YSZ tapes were obtained by aqueous tape casting and used as substrates for the preparation of LSM coatings by dip-coating using aqueous slurries. YSZ tapes were used either in the green state or after a pre-sintering treatment. Co-sintering at 1350 °C led to a sharp interface with excellent adhesion, also achieved when coating pre-sintered tapes. In both cases, the substrates are dense and the coatings are porous, with thicknesses of 85 and 60 μm for green and pre-sintered tapes, respectively. No diffusion of Zr and Y occurs at the LSM layer, but some diffusion of La and Mn towards the YSZ layer takes place. Full article

Among lithium battery cathode materials, Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ (LR-NMC) has a high theoretical capacity, but suffers from voltage and capacity fade during cycling. This is partially ascribed to transition metal cation migration, which involves the local transformation of the honeycomb layered structure to spinel-like nano-domains. Determination of the honeycomb layered/spinel phase ratio from powder X-ray diffraction data is hindered by the nanoscale of the functional material and the domains, diverse types of twinning, stacking faults, and the possible presence of the rock salt phase. Determining the phase ratio from transmission electron microscopy imaging can only be done for thin regions near the surfaces of the crystals, and the intense beam that is needed for imaging induces the same transformation to spinel as cycling does. In this article, it is demonstrated that the low electron dose sufficient for electron diffraction allows the collection of data without inducing a phase transformation. Using calculated electron diffraction patterns, we demonstrate that it is possible to determine the volume ratio of the different phases in the particles using a pair-wise comparison of the intensities of the reflections. Using this method, the volume ratio of spinel structure to honeycomb layered structure is determined for a submicron sized crystal from experimental three-dimensional electron diffraction (3D ED) and precession electron diffraction (PED) data. Both twinning and the possible presence of the rock salt phase are taken into account. After 150 charge–discharge cycles, 4% of the volume in LR-NMC particles was transformed irreversibly from the honeycomb layered structure to the spinel structure. The proposed method would be applicable to other multi-phase materials as well. Full article

La_0.7Sr_0.3MnO₃ (LSMO) and Nd_0.7Sr_0.3MnO₃ (NSMO) possess excellent colossal magnetoresistance (CMR). However, research work on the neodymium-based system is limited to date. A comparative study between LSMO and NSMO prepared by sol–gel and solid-state reaction methods was undertaken to assess their structural, microstructural, magnetic, electrical, and magneto-transport properties. X-ray diffraction and structure refinement showed the formation of a single-phase composition. Sol–gel-synthesised NSMO was revealed to be a sample with single crystallite grains and exhibited intriguing magnetic and electrical transport behaviours. Magnetic characterisation highlighted that Curie temperature (T_C) decreases with the grain size. Strong suppression of the metal–insulator transition temperature (T_MI) was observed and attributed to the magnetically disordered grain surface and distortion of the MnO₆ octahedra. The electrical resistivity in the metallic region was fitted with theoretical models, and the conduction mechanism could be explained by the grain/domain boundary, electron–electron, and electron–magnon scattering process. The increase in the scattering process was ascribed to the morphology changes. Enhancement of low-field magnetoresistance (LFMR) was observed in nano-grained samples. The obtained results show that the grain size and its distribution, as well as the crystallite formation, strongly affect the physical properties of hole-doped manganites. Full article

Mn-Ce-Zr-O catalysts doped with varying Mn content were prepared and assessed for the catalytic combustion of chlorobenzene (CB). Nanosized MCZ-0.67 catalyst with amorphous phase exhibited a high and stable catalytic activity among the studied catalysts, achieving 90% CB conversion at 226 °C and withstanding stability tests, including time-based stability and the successive influence of various operating conditions. Meanwhile, the MCZ-0.67 catalyst used showed good recyclability by calcination in air. Characterization results suggested that Mn doping played a dominant role in improving the catalytic performance, resulting in larger surface area, better redox properties and greater amounts of surface active oxygen. In addition, the introduction of Zr was also indispensable for maintaining the good catalytic performance of catalysts. Finally, trace amounts of polychlorinated by-products during CB oxidation were monitored and the oxidation process was discussed. Full article