Search Results (177)

Micron-sized near-spherical α-Al₂O₃ powders are widely used as thermal fillers due to their high thermal conductivity, high packing density, good flowability, and low cost. During the high-temperature calcination, the resulting α-Al₂O₃ powders often exhibit an aggregated worm-like morphology owing to limitations in solid-state mass transfer. Researchers have employed various mineralizers to regulate the morphology of α-Al₂O₃ powders; however, the preparation of micron-sized highly spherical α-Al₂O₃ powders via solid-state calcination is still a great challenge. In this work, micron-sized near-spherical α-Al₂O₃ powders were synthesized through high-temperature calcination using hydratable alumina (ρ-Al₂O₃) as precursor with water-soluble mineralizer ammonium fluoroborate (NH₄BF₄). ρ-Al₂O₃ can undergo a hydration reaction with water to form AlO(OH) and Al(OH)₃ intermediates, serving as an excellent precursor. With the addition of 0.1 wt% NH₄BF₄, the product exhibits an optimal near-spherical morphology. Excessive addition (>0.2 wt%), however, significantly promotes the transformation of α-Al₂O₃ from a near-spherical to a plate-like structure. Further studies reveal that the introduction of NH₄BF₄ not only modulates the crystal morphology but also effectively reduces the content of sodium impurities in the powder through a high-temperature volatilization mechanism, thereby enhancing the thermal conductivity of the powder. It is shown that the thermal conductivity of the micron-sized α-Al₂O₃/ epoxy resin composites reaches 1.329 ± 0.009 W/(m·K), which is 7.4 times that of pure epoxy resin. Full article

This study evaluates the impact of mineralogy, elemental composition, and reaction pathways on hydrogen (H₂) generation in seven ultramafic and mafic (basaltic) rocks. Experiments were conducted under typical low-temperature hydrothermal conditions (150 °C) and captured early and evolving stages of fluid–rock interaction. Pre- and post-interactions, the solid phase was analyzed using X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS), while Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to determine the composition of the aqueous fluids. Results show that not all geologic H₂-generating reactions involving ultramafic and mafic rocks result in the formation of serpentine, brucite, or magnetite. Our observations suggest that while mineral transformation is significant and may be the predominant mechanism, there is also the contribution of surface-mediated electron transfer and redox cycling processes. The outcome suggests continuous H₂ production beyond mineral phase changes, indicating active reaction pathways. Particularly, in addition to transition metal sites, some ultramafic rock minerals may promote redox reactions, thereby facilitating ongoing H₂ production beyond their direct hydration. Fluid–rock interactions also regenerate reactive surfaces, such as clinochlore, zeolite, and augite, enabling sustained H₂ production, even without serpentine formation. Variation in reaction rates depends on mineralogy and reaction kinetics rather than being solely controlled by Fe oxidation states. These findings suggest that ultramafic and mafic rocks may serve as dynamic, self-sustaining systems for generating H₂. The potential involvement of transition metal sites (e.g., Ni, Mo, Mn, Cr, Cu) within the rock matrix may accelerate H₂ production, requiring further investigation. This perspective shifts the focus from serpentine formation as the primary driver of H₂ production to a more complex mechanism where mineral surfaces play a significant role. Understanding these processes will be valuable for refining experimental approaches, improving kinetic models of H₂ generation, and informing the site selection and design of engineered H₂ generation systems in ultramafic and mafic formations. Full article

Mg₂TiO₄:Mn⁴⁺ (MTO:Mn⁴⁺) red phosphor has important applications in areas such as red LEDs and forensic science, but the preparation of MTO:Mn⁴⁺ through the solid-state reaction method requires a high sintering temperature. Herein, MTO:Mn⁴⁺ red phosphor was synthesized using the solid-state reaction method with LiCl flux, and its crystallographic structure and photoluminescence properties were studied to determine the influence of experimental parameters like the amount of fluxing agent added and sintering temperature in producing a bright red phosphor suitable for LEDs. The experimental results showed that samples with added LiCl could form pure MTO after sintering at 950 °C, whereas those without LiCl still contained a mixture of MTO and MgTiO₃, even when sintered at 1400 °C. The optimal performance was achieved with a sample doped with 0.2 mol% Mn⁴⁺, synthesized using 50 wt% LiCl flux and sintered at 950 °C for 12 h. This sample exhibited a broad excitation band and a narrow red emission band peaking at 662 nm, confirming its excellent luminescence properties. Furthermore, a prototype red LED fabricated with a 377 nm chip and MTO:0.2% Mn⁴⁺ phosphor achieved photoelectric conversion efficiency of 78.5% at a 100 mA drive current, confirming its viability for high-performance red LED manufacturing. Full article

Facing energy and environmental issues is recognized globally as one of the major challenges for sustainable development, to which sustainable chemistry can make significant contributions. Strontium ferrate-based materials belong to a little-known class of perovskite-type compounds in which iron is primarily stabilized in the unusual 4+ oxidation state, although some Fe³⁺ is often present, depending on the synthesis and processing conditions and the type and amount of dopant. When doped with cerium at the Sr site, the SrFeO_3−δ cubic structure is stabilized, more oxygen vacancies form and the Fe⁴⁺/Fe³⁺ redox couple plays a key role in its functional properties. Alone or combined with other materials, Ce-doped strontium ferrates can be successfully applied to wastewater treatment. Specific doping at the Fe site enhances their electronic conductivity for use as electrodes in solid oxide fuel cells and electrolyzers. Their oxygen storage capacity and oxygen mobility are also exploited in chemical looping reactions. The main limitations of these materials are SrCO₃ formation, especially at the surface; their low surface area and porosity; and cation leaching at acidic pH values. However, these limitations can be partially addressed through careful selection of synthesis, processing and testing conditions. This review highlights the high versatility and efficiency of cerium-doped strontium ferrates for energy and environmental applications, both at low and high temperatures. The main literature on these compounds is reviewed to highlight the impact of their key properties and synthesis and processing parameters on their applicability as sustainable thermocatalysts, electrocatalysts, oxygen carriers and sensors. Full article

Pyrochlore Bi_1.8Mn_0.5Ni_0.5Ta₂O_9-Δ (sp.gr. Fd-3m, a = 10.5038(9) Å) was synthesized by the solid-phase reaction method and characterized by vibrational and X-ray spectroscopy. According to scanning electron microscopy, the ceramics are characterized by a porous microstructure formed by randomly oriented oblong grains. The average crystallite size determined by X-ray diffraction is 65 nm. The charge state of transition element cations in the pyrochlore was analyzed by soft X-ray spectroscopy using synchrotron radiation. For mixed pyrochlore, a characteristic shift of Bi4f and Ta4f and Ta5p spectra to the region of lower energies by 0.25 and 0.90 eV is observed compared to the binding energy in Bi₂O₃ and Ta₂O₅ oxides. XPS Mn2p spectrum of pyrochlore has an intermediate energy position compared to the binding energy in MnO and Mn₂O₃, which indicates a mixed charge state of manganese (II, III) cations. Judging by the nature of the Ni2p spectrum of the complex oxide, nickel ions are in the charge state of +(2+ζ). The relative permittivity of the sample in a wide temperature (up to 350 °C) and frequency range (25–10⁶ Hz) does not depend on the frequency and exhibits a constant low value of 25. The minimum value of 4 × 10⁻³ dielectric loss tangent is exhibited by the sample at a frequency of 10⁶ Hz. The activation energy of conductivity is 0.7 eV. The electrical behavior of the sample is modeled by an equivalent circuit containing a Warburg diffusion element. Full article

In order to elucidate the high-temperature reaction process of solid waste-based high belite sulphoaluminate cement containing residual gypsum in clinker (NHBSAC) and obtain the formation laws of each mineral in clinker, this article studied its high-temperature reaction kinetics. Through QXRD analysis and numerical fitting methods, the formation of C₄A₃$\overline{\mathrm{S}}$, β-C₂S, and CaSO₄ in clinker under different calcination systems was quantitatively characterized, the corresponding high-temperature reaction kinetics models were established, and the reaction activation energies of each mineral were obtained. The results indicate that the content of C₄A₃$\overline{\mathrm{S}}$ and β-C₂S increases with the prolongation of holding time and the increase in calcination temperature, while CaSO₄ is continuously consumed. Under the control mechanism of solid-state reaction, the formation and consumption of minerals follow the kinetic equation. C₄A₃$\overline{\mathrm{S}}$ and β-C₂S satisfy the D₄ equation under diffusion mechanism control, and CaSO₄ satisfies the R₃ equation under interface chemical reaction mechanism control. The activation energy required for mineral formation varies with different temperature ranges. The activation energies required to form C₄A₃$\overline{\mathrm{S}}$ at 1200–1225 °C, 1225–1275 °C, and 1275–1300 °C are 166.28 kJ/mol, 83.14 kJ/mol, and 36.58 kJ/mol, respectively. The activation energies required to form β-C₂S at 1200–1225 °C and 1225–1300 °C are 374.13 kJ/mol and 66.51 kJ/mol, respectively. This study is beneficial for achieving flexible control of the mineral composition of NHBSAC clinker, providing a theoretical basis and practical experience for the preparation of low-carbon cement and the optimization design of its mineral composition. 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

Microwave dielectric ceramics are indispensable in modern communication technologies, playing a pivotal role in components such as filters, oscillators, and antennas. Among these materials, ZnAl₂O₄ ceramics have garnered attention for their excellent quality factor (Q × f) and low dielectric constant (ε_r). However, their high sintering temperature (~1650 °C) limits practical applications. This study investigates ZnAl_2-x(Zn_0.5Si_0.5)_xO₄ (ZAZS) (x = 0.1–0.9) ceramics, where [Zn_0.5Si_0.5]³⁺ substitutes Al³⁺, to reduce sintering temperature while maintaining high-performance microwave dielectric properties. ZAZS ceramics were synthesized via the solid-state reaction method and characterized for their structural, morphological, and dielectric properties. X-ray diffraction analysis confirmed the formation of a single-phase solid solution up to x = 0.8, with minor secondary phases appearing at x = 0.9. The substitution increased lattice parameters and enhanced material densification, as observed through SEM and relative density calculations. Microwave dielectric measurements showed that ZAZS ceramics achieved a maximum Q × f of 20,200 GHz and a τ_f value reduced to −62 ppm/°C at x = 0.8, while ε_r decreased from 7.90 to 6.98. Bond-valence calculations reveal that the reduction of the average Al/Zn/Si–O bond valence weakens octahedral rigidity, systematically tuning τ_f toward zero. These results demonstrate that ZAZS ceramics, with a reduced sintering temperature of 1400 °C, exhibit excellent potential for application in low-loss microwave devices. Full article

Complex antimony pyrochlores Bi_2.7M_0.46Ni_0.70Sb₂O_10+Δ (M = Zn, Mg) were synthesized from oxide precursors, using the solid-state reaction method. For each composition variant, the pyrochlore phase formation process was studied during solid-state synthesis in the range of 500–1050 °C. The influence of zinc and magnesium on the phase formation process was established. The interaction of oxide precursors occurs at a temperature of 600 °C and higher, resulting in the formation of bismuth stibate (Bi₃SbO₇) as a binary impurity phase. Oxide precursors, including bismuth(III) and antimony(III,V) oxides, are fixed in the samples up to 750 °C, at which point the intermediate cubic phase Bi₃M_2/3Sb_7/3O₁₁ (sp. gr. Pn-3, M = Zn, Ni) is formed in the zinc system. Interacting with transition element oxides, it is transformed into pyrochlore. An intermediate phase with the Bi_4.66Ca_1.09VO_10.5 structure (sp. gr. Pnnm) was found in the magnesium system. The unit cell parameter of pyrochlore for two samples has a minimum value at 800 °C, which is associated with the onset of high-temperature synthesis of pyrochlore. The synthesis of phase-pure pyrochlores is confirmed by high-resolution Raman spectroscopy. The data interpretation showed that the cations in Ni/Zn pyrochlore are more likely to be incorporated into bismuth positions than in Ni/Mg pyrochlore. The nickel–magnesium pyrochlore is characterized by a low-porosity microstructure, with grain sizes of up to 3 μm, according to SEM data. Zinc oxide has a sintering effect on ceramics. Therefore, the grain size in ceramics is large and varies from 2 to 7 μm. Full article

Na₂Ti₃O₇ (NTO), with low sodium insertion potential (~0.3 V vs. Na⁺/Na) and potential for high-energy-density batteries, is regarded as one of the most promising anode materials for sodium-ion batteries (SIBs). However, its practical application is hindered by poor electronic conductivity, sluggish Na⁺ (de)intercalation kinetics, and interfacial instability, leading to inferior cycling stability, low initial Coulombic efficiency, and poor rate capability. In this work, micron-sized rod-like NTO and Al-doped NTO (NTO-Al) samples were synthesized via a one-step high-temperature solid-state method. Al doping slightly reduced the size of NTO microrods while introducing oxygen vacancies and generating Ti³⁺, thereby enhancing electronic conductivity and reducing ionic diffusion resistance. H₂-TPR confirms that doping activates lattice oxygen and promotes its participation in the reaction. The optimized NTO-Al0.03 electrode delivered a significantly improved initial charge capacity of 147.4 mA h g⁻¹ at 0.5 C, surpassing pristine NTO (124.7 mA h g⁻¹). Moreover, it exhibited the best cycling stability (49.5% capacity retention after 100 cycles) and rate performance (36.3 mA h g⁻¹ at 2 C). Full article

Low-loaded copper-exchanged mordenite samples (3 wt.% of copper) were prepared by a solid-state milling method using controlled conditions. The milled samples were then submitted to a calcination process where trimeric copper active species were formed, according to XPS, EPR, IR, and UV–vis recorded spectra. To verify the interaction of the active site with methane at mild conditions, a test experimental design was developed in a batch reactor configuration using mild two-step conditions: (1) activation temperature at 400 °C in an air atmosphere, and (2) isothermal conversion process at 200 °C with 6 bar methane. The analyzed samples were active in methanol conversion in batch conditions, nonetheless less efficient than the usually reported copper mono $\mu$-oxo sites using harder experimental conditions. The herein reported copper active sites are as follows: a trinuclear copper active cluster [Cu₃($\mu$-O)₃]²⁺ and a possible intermediate during methane contact detected as bis($\mu$-oxo) dicopper species were identified and studied on each reaction step. This study revealed that trinuclear copper active sites can be obtained through grinding. Nonetheless, they stabilize after a calcination stage in an air atmosphere. Their stability is then maintained during the whole cyclic experimental test, suggesting their potential use for multicyclic processes. Full article

Hydrogen is critical for achieving carbon neutrality as a clean energy source. However, its low ambient energy density poses challenges for storage, making efficient and safe hydrogen storage a bottleneck. Metal hydride-based solid-state hydrogen storage has emerged as a promising solution due to its high energy density, low operating pressure, and safety. In this work, the thermodynamic and kinetic characteristics of the hydrogenation and dehydrogenation processes are investigated and analyzed in detail, and the effects of initial conditions on the thermochemical hydrogen storage reactor are discussed. Multiphysics field modeling of the magnesium-based hydrogen storage tank was conducted to analyze the reaction processes. Distributions of temperature and reaction rate in the reactor and temperature and pressure during the hydrogen loading process were discussed. Radially, wall-adjacent regions rapidly dissipate heat with short reaction times, while the central area warms into a thermal plateau. Inward cooling propagation shortens the plateau, homogenizing temperatures—reflecting inward-to-outward thermal diffusion and exothermic attenuation, alongside a reaction rate peak migrating from edge to center. Axially, initial uniformity transitions to bottom-up thermal expansion after 60 min, with sustained high top temperatures showing nonlinear decay under $∆$t = 20 min intervals, where cooling rates monotonically accelerate. The greater the hydrogen pressure, the shorter the period of the temperature rise and the steeper the curve, while lower initial temperatures preserve local maxima but shorten plateaus and cooling time via enhanced thermal gradients. Full article

As a third-generation advanced high-strength steel (AHSS), δ-TRIP steel exhibits the characteristics of high strength, high plasticity, and low density. However, the addition of Al to steel will affect solidification and segregation, which may impact the final microstructure and mechanical properties of the product. In this study, thermodynamic calculations and microsegregation model analysis were employed to investigate the effects of Al addition on the solidification path, peritectic reaction range, equilibrium partition coefficients, and microsegregation behavior of δ-TRIP steel. The results show that with an increase in the Al content, the carbon content range in which δ ferrite is retained without complete transformation during the solid-state phase transition becomes broader. Simultaneously, the carbon concentration range of the peritectic zone expands. The segregation of the C, Si, Mn, P, and S elements increases with increasing Al content, whereas the segregation of Al decreases as the Al content increases. Under non-equilibrium solidification conditions, unlike equilibrium solidification, the temperature difference between the solid and liquid phases initially increases, then decreases, and subsequently levels off with further Al addition. This study provides information for the composition design and production process optimization of δ-TRIP steel, and the research results can provide a reference for similar high-aluminum, low-density steels. Full article

This research explores the modification of marl by the incorporation of diopside (CaMgSi₂O₆) to develop a composite material with improved dielectric properties, while addressing environmental and economic challenges through the use of abundant natural resources. X-ray fluorescence (XRF) analysis reveals a high silicate content in the raw marl, mainly SiO₂ (68.12%) and Al₂O₃ (12.54%), while laser particle size analysis indicates a homogeneous grain size distribution centered around 100 µm. The composite was synthesized by the solid-state reaction method, achieving good phase homogeneity. X-ray diffraction (XRD) and infrared spectroscopy confirm the incorporation of diopside, while SEM analysis shows a porous morphology with granular aggregates. The modified material has an average particle size of 11.653 µm, optimizing the electrical properties. Impedance spectroscopy demonstrates improved dielectric performance, with accumulated permittivity and reduced losses, which improves energy storage and dissipation. Tests showed the remarkable stability of dielectric properties over a wide frequency range (10 Hz to 10 MHz) and low-temperature dependence. The performance was demonstrated on a single sample with a thickness of 0.63 mm, demonstrating consistent efficiency. These results position the diopside-modified marl as a promising candidate for electrochemical and microelectronic applications. Full article

Cesium tungsten bronzes (Cs_xWO₃), as functional materials with excellent near-infrared shielding properties, demonstrate significant potential for applications in smart windows. However, traditional synthesis methods, such as solid-state reactions and solvothermal/hydrothermal approaches, typically require harsh conditions, including high temperatures (above 200 °C), high pressure, inert atmospheres, or prolonged reaction times. In this study, we propose an optimized microwave-assisted solvothermal synthesis strategy that significantly reduces the severity of reaction conditions through precise parameter control. When benzyl alcohol was employed as the solvent, Cs_xWO₃ nanoparticles could be rapidly synthesized within a relatively short duration of 15 min at 180 °C, or alternatively obtained through 2 h at a low temperature of 140 °C. However, when anhydrous ethanol, which is cost-effective and environmentally friendly, was substituted for benzyl alcohol, successful synthesis was also achieved at 140 °C in 2 h. This method overcomes the limitations of traditional high-pressure reaction systems, achieving efficient crystallization under low-temperature and ambient-pressure conditions while eliminating safety hazards and significantly improving energy efficiency. The resulting materials retain excellent near-infrared shielding performance and visible-light transparency, providing an innovative solution for the safe, rapid, and controllable synthesis of functional nanomaterials. Full article