Search Results (459)

The structural features of Sb–doped (Ti,Zr)NiSn and (Ti,Zr,Hf)NiSn half-Heusler (HH) thermoelectrics have been identified down to the atomic scale using a combination of transmission electron microscopy (TEM) techniques. TEM sheds light on the morphology, phases present, size distributions and elemental variations between the two samples. Both materials consist of the HH phase, at both micro- and nanoscale levels, and comprise particles with two size ranges, 115 and 223 nm, on average, for large HH particles and 4–17 nm for nanoparticles for both materials. Hf incorporation in the HH lattice brought upon significant elemental fluctuations, manifested in chemical profiles and lattice parameter variations measured by post-experimental image analysis. The increased elemental variations induced by Hf substitution significantly contributed to the low thermal conductivity values and high power factor, leading to an enhanced figure of merit of 0.76 at 762 K for (Ti,Zr,Hf)NiSn, demonstrating the capability of TEM to confirm the structural features that are responsible for improved TE performance. Full article

In this study, we present a comprehensive theoretical analysis of modifications in the physical and chemical properties of MoSe₂ upon the introduction of substitutional transition metal impurities, specifically, Ti, V, Cr, Fe, Co, Ni, Cu, W, Pd, and Pt. Wet systematically calculated the adsorption enthalpies for various representative analytes, including O₂, H₂, CO, CO₂, H₂O, NO₂, formaldehyde, and ethanol, and further evaluated their free energies across a range of temperatures. By employing the formula for probabilities, we accounted for the competition among molecules for active adsorption sites during simultaneous adsorption events. Our findings underscore the importance of integrating temperature effects and competitive adsorption dynamics to predict the performance of highly selective sensors accurately. Additionally, we investigated the influence of temperature and analyte concentration on sensor performance by analyzing the saturation of active sites for specific scenarios using Langmuir sorption theory. Building on our calculated adsorption energies, we screened the catalytic potential of doped MoSe₂ for CO₂-to-methanol conversion reactions. This paper also examines the correlations between the electronic structure of active sites and their associated sensing and catalytic capabilities, offering insights that can inform the design of advanced materials for sensors and catalytic applications. Full article

In this study, high-energy milled (HEM) samples of natural phosphorites from Estonian deposits were investigated. The activation was performed via planetary mill with Cr-Ni grinders with a diameter of 20 mm. This method is an ecological alternative, since it eliminates the disadvantages of conventional acid methods, namely the release of gaseous and solid technogenic products. The aim of the study is to determine the changes in the structure to follow the solid-state transitions and the isomorphic substitutions in the anionic sub-lattice in the structure of the main mineral apatite in the samples from Estonia, under the influence of HEM activation. It is also interesting to investigate the influence of HEM on structural-phase transformations on the structure of impurity minerals-free calcite/dolomite, pyrite, quartz, as well as to assess their influence on the thermal behavior of the main mineral apatite. The effect of HEM is monitored by using a complex of analytical methods, such as chemical analysis, powder X-ray diffraction (PXRD), wavelength-dispersive X-ray fluorescence (WD-XRF) analysis, and Fourier-transformed infrared (FTIR) analysis. The obtained results prove the correlation in the behavior of the studied samples with regard to their quartz content and bonded or non-bonded carbonate ions. After HEM activation of the raw samples, the following is established: (i) anionic isomorphism with formation of A and A-B type carbonate-apatites and hydroxyl-fluorapatite; (ii) solid-phase synthesis of calcium orthophosphate-CaHPO₄ (monetite) and dicalcium diphosphate-β-Ca₂P₂O₇; (iii) enhanced chemical reactivity by approximately three times by increasing the solubility via HEM activation. The dry milling method used is a suitable approach for solving technological projects to improve the composition and structure of soils, increasing soil fertility by introducing soluble forms of calcium phosphates. It provides a variety of application purposes depending on the composition, impurities, and processing as a soil improver, natural mineral fertilizer, or activator. Full article

A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (^tBuN4) for supporting nitrene transfer to olefins. The known [(^tBuN4)M^II(MeCN)₂]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(MeCN)]⁺ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold. Full article

TiVCr-based alloys are well-explored body-centered cubic (BCC) materials for hydrogen storage applications that can potentially store higher amounts of hydrogen at moderate temperatures. The challenge remains in optimizing the alloy-hydrogen stability, and several transition elements have been found to support the reduction in the hydride stability. In this study, Ni and Nb transition elements were incorporated into the TiVCr alloy system to thoroughly understand their influence on the (de)hydrogenation kinetics and thermodynamic properties. Three different compositions, (TiVCr)₉₅Ni₅, (TiVCr)₉₀ Ni₁₀, and (TiVCr)₉₅Ni₅Nb₅, were prepared via arc melting. The as-prepared samples showed the formation of a dual-phase BCC solid solution and secondary phase precipitates. The samples were characterized using hydrogen sorption studies. Among the studied compositions, (TiVCr)₉₀Ni₁₀ exhibited the highest hydrogen absorption capacity of 3 wt%, whereas both (TiVCr)₉₅Ni₅ and (TiVCr)₉₀Ni₅Nb₅ absorbed up to 2.5 wt% hydrogen. The kinetics of (de)hydrogenation were modeled using the JMAK and 3D Jander diffusion models. The kinetics results showed that the presence of Ni improved hydrogen adsorption at the interface level, whereas Nb substitution enhanced diffusion and hydrogen release at room temperature. Thus, the addition of Ni and Nb to Ti-V-Cr-based high-entropy alloys significantly improved the hydrogen absorption and desorption properties at room temperature for gas-phase hydrogen storage. Full article

Milk powder is a key nutritional alternative to breastfeeding, but its thermal properties, which vary with temperature, can affect its quality and shelf life. However, there is little information about the physical and chemical properties of powdered milk in several countries. This dataset contains the result of an analysis of the aflatoxins, macroelement and microelement concentrations, oxidative stability, and fatty acid profile of infant formula milk powder. The concentrations of Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Se, V, and Zn in digested powdered milk samples were quantified through inductively coupled plasma optical emission spectrometry (ICP OES). Thermogravimetry (TG) and differential scanning calorimetry (DSC) were used to estimate the oxidative stability of infant formula milk powder, while the methyl esters of the fatty acids were analyzed by gas chromatography. Most milk samples showed significant concentrations of As (0.5583–1.3101 mg/kg) and Pb (0.2588–0.0847 mg/kg). The concentrations of aflatoxins G2 and B2 are below the limits established by Brazilian regulatory agencies. The thermal degradation behavior of the samples is not the same due to their fatty acid compositions. The data presented may be useful in identifying compounds present in infant milk powder used as a substitute for breast milk and understanding the mechanism of thermal stability and degradation, ensuring food safety for those who consume them. Full article

Low-permittivity microwave dielectric ceramics are essential for high-frequency communication and radar systems, as they minimize signal delay and interference, thereby enabling compact and high-performance devices. In this study, LiAl_5−xNi_xO_8−0.5x (x = 0.1–0.5) ceramics were synthesized via a solid-state reaction method to investigate the effects of Ni²⁺ substitution on crystal structure, microstructure, and dielectric properties. X-ray diffraction and Rietveld refinement reveal a phase transition from the P4₃32 to the Fd$\stackrel{-}{3}$m spinel structure at x ≈ 0.3, accompanied by a systematic increase in the lattice parameter (7.909–7.975 Å), attributed to the larger ionic radius of Ni²⁺ compared to Al³⁺. SEM analysis confirms dense microstructures with relative densities exceeding 95% and grain size increases from less than 1 μm at x = 0.1 to approximately 2 μm at x = 0.5. Dielectric measurements show a decrease in permittivity (ε_r) from 8.24 to 7.77 and in quality factor (Q × f) from 34,605 GHz to 20,529 GHz with increasing Ni content, while the temperature coefficient of the resonant frequency (τ_f) shifts negatively from −44.8 to −69.1 ppm/°C. Impedance spectroscopy indicates increased conduction losses and reduced activation energy with higher Ni²⁺ concentrations. Full article

The nanostructural features of a mechanically alloyed Sb-doped (Ti_0.4Zr_0.6)_0.7Hf_0.3NiSn thermoelectric (TE) Half-Heusler (HH) compound were addressed using Transmission Electron Microscopy (TEM) coupled with Energy Dispersive Spectroscopy measurements and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The EXAFS measurements at the Ni-K, Sn-K, Zr-K, and Hf-L₃-edge were implemented in an effort to reveal the influence of Hf and Zr incorporation into the crystal with respect to their previously measured TE properties. The substitution of Ti by Hf and Zr is expected to yield local lattice distortions due to the different atomic sizes of the dopants or/and electronic charge redistribution amongst the cations. However, the material is characterised by a high degree of crystallinity in both the short and long-range order, on average, and the nominal stoichiometry is identified as (Zr_0.42Hf_0.30Ti_0.28)NiSn_0.98Sb_0.02. The synergistic effect of minimization of extended structural defects or lattice distortions and considerable alloying-induced point defect population contributes to the improved TE properties and leads to the previously reported enhancement of the figure of merit of the mixed HHs. Full article

Spinel-structured hausmannite (Mn(II)Mn(III)₂O₄) is a vital intermediate in Mn mineralogy and a key player in redox chemistry in the environment. Its transformation into other Mn oxides is a critical factor in controlling its environmental occurrence and reactivity. Yet structural impurities and solution pH, as well as the fate of impurities during transformation, which influence hausmannite transformation processes and products, remain largely unknown. In the present work, we address this knowledge gap by investigating pristine and metal-substituted hausmannite, specifically nickel (Ni) or cobalt (Co), equilibrated at two time periods (8 h and 30 days) and three different pH levels (4, 5, and 7). Solution chemistry data revealed that both the equilibration period and pH had a significant impact on hausmannite dissolution rates and the concomitant repartitioning of Ni or Co. Hausmannite with Ni or Co substitution exhibited lower dissolution rates than pristine mineral under acidic conditions. Mineralogy and crystal chemistry data indicated that hausmannite was the major host phase after 30-day equilibration, followed by minor transformed products, including birnessite and manganite. Although minor, birnessite became more abundant than manganite at low pHs. Analytical high-resolution transmission electron microscopy (HRTEM) analyses revealed a poorly crystalline, nano-scaled MnO₂ formed from hausmannite and the majority of metal impurities remaining in the host hausmannite. Yet Co was associated with both hausmannite and the newly formed birnessite, whereas Ni was only found with hausmannite, indicating the strong sequestration of Co by Mn(II/III) and Mn(IV) mineral phases. This study highlights the significant impacts of metal impurities and pH on the stability of hausmannite and its transformation into birnessite, as well as the control of Mn-oxide minerals on the solubility and sequestration of transition metals in the environment. Full article

A series of para-trifluoromethoxy-substituted and fluorobenzhydryl-functionalized 1,2-bis(imine)acenaphthene ligands: 1-[2,6-{(4-F-C₆H₄)₂CH}₂-4-F₃COC₆H₂N]-2-(ArN)C₂C₁₀H₆ (Ar = 2,6-Me₂C₆H₃ L1, 2,6-Et₂C₆H₃ L2, 2,6-iPr₂C₆H₃ L3, 2,4,6-Me₃C₆H₂ L4, 2,6-Et₂-4-MeC₆H₂ L5), were synthesized and used to generate their corresponding nickel(II) bromide complexes (Ni1–Ni5). Elemental analysis, ¹⁹F NMR, and FT-IR spectroscopy were employed to characterize these five nickel complexes. Single-crystal X-ray diffraction of Ni2 and Ni4 confirmed distorted tetrahedral geometries. Upon activation with either EtAlCl₂ (ethylaluminum dichloride) or EASC (ethyl aluminum sesquichloride), these complexes showed exceptional high activities (up to 22.0 × 10⁶ g PE mol⁻¹ (Ni) h⁻¹) and remarkable thermal stability (4.82 × 10⁶ g PE mol⁻¹(Ni) h⁻¹ at 80 °C) towards ethylene polymerization. The resulting polyethylenes are highly branched, with the type and extent of branches tunable by temperature, solvent, and co-catalyst choice. Moreover, these polymers demonstrated excellent tensile strength (σ_b up to 20.7 MPa) and elastic recovery (up to 58%), characteristic of thermoplastic elastomers (TPEs). These results highlight the dual role of trifluoromethoxy and fluorobenzhydryl groups in enhancing catalytic performance and polymer properties. Full article

Investigations of the synthesis of multicomponent coatings and their subsequent application to metal substrates to increase the wear resistance of materials is relevant for industry. Nickel compounds obtained from oxidized magnesia-iron nickel ores with a desorption rate of more than 94% were used to create Ni-MoO₃-WO₃ electroplating. Such composite samples formed from an aqueous alcohol solution reduced the content of sodium and ammonium chlorides. The annealing and dehydration of samples at a temperature of 725 °C in an air atmosphere made it possible to achieve the highest level of crystallinity. In this case, an isomorphic substitution of W atoms by Mo occurs, which is confirmed by electron paramagnetic resonance (EPR) spectroscopy studies. The invariance of the shape of the EPR spectrum with a sequential increase in microwave radiation power revealed the stability of the bonds between the particles. The surface morphology of Ni-MoO₃-WO₃ films deposited on an Al substrate is smooth and has low roughness. In this case, an increased degree of wear resistance has been achieved. Thus, a recipe for the formation of an electroplating with stable bonds between the components and increased wear resistance was obtained. Full article

This paper presents the results of a study of the catalytic hydrogenation of phenanthrene using catalysts based on chrysotile modified with nickel and titanium (chrysotile/NiTi), as well as coal shale. Complex characterization of catalysts in terms of acid, texture and morphological properties was carried out. Pre-reduction in the catalysts has been found to increase the yield of partially and fully hydrogenated products, including tetrahydronaphthalene, trans-decalin and dihydrophenanthrene. Particular attention is paid to the role of coal shale as a donor source of hydrogen in thermolysis conditions. The results of hydrogenation revealed complex mechanisms of phenanthrene transformations, including partial saturation of aromatic rings, desulfurization and the formation of alkyl-substituted compounds. The obtained data emphasize the prospects of using the studied catalysts in the processes of processing heavy and solid hydrocarbon raw materials, which opens up opportunities for creating new technologies for the production of liquid fuel. Full article

Dispersive liquid–liquid microextraction (DLLME) is an economical, rapid, sensitive, and environmentally friendly miniaturized liquid–liquid extraction format. It has been successfully applied in trace element analysis since 2006 when it was first proposed. This article describes a new dispersive liquid–liquid microextraction method for the determination of trace amounts of Co²⁺. In brief, this method involves the extraction of Co²⁺ from the sample to the trichloromethane phase by the dispersive action of methanol after the formation of a complex with a novel 9-(methylaminomethyl)anthracene-Ni(II) phthalocyanine (MAMA Ni(II)Pc 2) as a sensor. The first step in this study was the synthesis and characterisation of the sensor. Later, the proposed method was optimized with respect to various parameters such as extraction and dispersive solvents and their amounts, pH, sensor concentration, and centrifugation time and rate. The calibration graph was linear between 0.40 and 260 µg/L, with an R² of 0.9978. The limit of detection and limit of quantification were found to be 0.19 µg/L and 0.46 µg/L, respectively. To evaluate the precision of this method, the analysis of a 50 µg/L Co²⁺ solution was carried out. The intra-day and inter-day relative standard deviation values were calculated as 1.7% and 2.4%, respectively (n = 7). The accuracy of the proposed method was investigated by means of a standard addition/recovery test. Full article

Chalcopyrite (CuFeS₂) has attracted interest as a thermoelectric material due to its narrow bandgap and its ability to tailor its carrier concentration through doping. In this study, we investigated the effects of Ni²⁺ substitution at Cu⁺ sites in chalcopyrite (Cu_1−xNi_xFeS₂) on its structural, microstructural, and thermoelectric properties. Samples were synthesized using mechanical alloying followed by hot pressing to ensure high-density compaction. X-ray diffraction analysis confirmed the formation of the tetragonal chalcopyrite phase without detectable secondary phases. The observed reduction in lattice parameters with increasing Ni content provided evidence of successful Ni incorporation at Cu sites within the chalcopyrite structure. Microstructural analysis and elemental mapping further supported the uniform distribution of Ni within the chalcopyrite matrix. Thermoelectric property measurements revealed that Ni-doped chalcopyrite exhibited n-type conduction. As the Ni concentration increased, the carrier concentration and electrical conductivity increased significantly, with Cu_0.92Ni_0.08FeS₂ achieving the highest electrical conductivity of 2.5 × 10⁴ Sm⁻¹ at 723 K. However, the absolute value of the Seebeck coefficient decreased with increasing Ni doping, following the expected trade-off between electrical conductivity and thermopower. The optimized composition, Cu_0.96Ni_0.04FeS₂, exhibited the highest thermoelectric performance, with a power factor of 0.50 mWm⁻¹K⁻² and a maximum dimensionless figure of merit (ZT) of 0.18 at 623 K. Compared to undoped chalcopyrite, these enhancements represent a 43% increase in power factor and a 50% improvement in ZT. Full article

316L stainless steel is widely employed in various industrial sectors, including shipbuilding, offshore plants, high-temperature/high-pressure (HTHP) piping systems, and hydrogen infrastructure, due to its excellent mechanical stability, superior corrosion resistance, and robust resistance to hydrogen embrittlement. This study presents 316L stainless steel alloys fabricated via hot isostatic pressing (HIP), conducted at 1300 °C and 100 MPa for 2 h, incorporating Cr₂N powder and an optimized Ni/Mn ratio based on the nickel equivalent (Ni_eq). During HIP, Cr₂N decomposition yielded a uniformly refined, dense austenitic microstructure, with enhanced corrosion resistance and mechanical performance. Corrosion resistance was evaluated by potentiodynamic polarization in 3.5 wt.% NaCl after 1 h of OCP stabilization, using a scan range of −0.25 V to +1.5 V (Ag/AgCl) at 1 mV/s. Optimization of the Ni/Mn ratio effectively improved the pitting corrosion resistance and mechanical strength. It is cost-effective to partially substitute Ni with Mn. Of the various alloys, C13Ni-N exhibited significantly enhanced hardness (~30% increase from 158.3 to 206.2 HV) attributable to nitrogen-induced solid solution strengthening. E11Ni-HM exhibited the highest pitting corrosion resistance given the superior PREN value (31.36). In summary, the incorporation of Cr₂N and adjustment of the Ni/Mn ratio effectively improved the performance of 316L stainless steel alloys. Notably, alloy E11Ni-HM demonstrated a low corrosion current density of 0.131 μA/cm², indicating superior corrosion resistance. These findings offer valuable insights for developing cost-efficient, mechanically robust corrosion-resistant materials for hydrogen-related applications. Further research will evaluate alloy resistance to hydrogen embrittlement and investigate long-term material stability. Full article