Search Results (173)

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

Marble waste is produced on a large scale in many countries, resulting in serious pollution problems. This investigation aimed to study the valorization potential of marble waste from the ornamental rock industry used in the synthesis of a novel calcium niobate–magnesium niobate composite powder prepared by a solid-state reaction between 1000 °C and 1200 °C. The chemical and mineralogical characteristics of the marble waste were determined. Structural and morphological characterizations of the synthesized calcium niobate–magnesium niobate composite powders were conducted by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The thermophysical properties were measured using open photoacoustic cell and photothermal techniques. Structurally, at all synthesis temperatures, the calcium niobate–magnesium niobate powders were found to be composed of a complex mixture of CaNb₂O₆/Ca₂Nb₂O₇/MgNb₂O₆/CaMg_0.33Nb_0.67O₃. In addition, the calcium niobate–magnesium niobate composite powders exhibited low values of thermal diffusivity (1.88–2.15 × 10⁻⁷ m²/s) and thermal conductivity (0.12–0.16 W/mK). The findings of this investigation highlight the potential of marble waste as a promising sustainable source of carbonate for obtaining calcium niobate–magnesium niobate composite powder, which has thermophysical properties that should be explored in low-thermal-conductivity applications. Full article

Finding reliable, sustainable, and economical methods for addressing the relentless increase in plastic production and the corresponding rise in plastic waste within terrestrial and marine environments has garnered significant attention from environmental organizations and policymakers worldwide. This study presents a comprehensive analysis of the low-heating-rate thermal degradation of high-density polyethylene (HDPE) plastic in conjunction with date seed powder (DSP), utilizing thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (TGA/FTIR), machine learning convolutional deep neural networks (CDNNs), multiple linear regression model (MLRM) and thermokinetics. The TGA/FTIR experimental measurements indicated a synergistic interaction between the selected materials, facilitated by the presence of hemicellulose and cellulose in the DSP biomass. In contrast, the presence of lignin was found to hinder degradation at elevated temperatures. The application of machine learning CDNNs facilitated the formulation and training of learning algorithms, resulting in an optimized architectural composition comprising three hidden neurons and employing 27,456 epochs. This modeling approach generated predicted responses that are closely aligned with experimental results ($R^2~0.939$) when comparing the responses from a formulated MLRM model ($R^2~0.818$). The CDNN models were utilized to estimate interpolated thermograms, representing the limits of experimental variability and conditions, thereby highlighting temperature as the most sensitive parameter governing the degradation process. The Borchardt and Daniels (BD) model-fitting and Kissinger–Akahira–Sunose (KAS) model-free kinetic methods were employed to estimate the kinetic and thermodynamic parameters of the degradation process. This yielded activation energy estimates ranging from 40.419 to 91.010 kJ·mol⁻¹ and from 96.316 to 226.286 kJ·mol⁻¹ for the selected kinetic models, respectively, while the D2 and D3 diffusion models were identified as the preferred solid-state reaction models for the process. It is anticipated that this study will aid plastic manufacturers, environmental organizations, and policymakers in identifying energy-reducing pathways for the end-of-life thermal degradation of plastics. Full article

Solid-state lithium batteries are considered ideal due to the safety of solid-state electrolytes. The Na superionic conductor-type Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) is a solid electrolyte with high ionic conductivity, low cost, and stability. However, LATP is reduced upon contact with metallic lithium, leading to lithium dendrite growth on the anode during charging. In this study, LATP was synthesized, and the relationship between crystallinity and ionic conductivity was investigated at different heat treatment temperatures. Optimal sintering conditions and ionic conductivity were analyzed for sintering temperatures from 800 to 1000 °C. To suppress reactions with Li metal, 50 nm thick Ag and 10 nm thick Al₂O₃ layers were deposited on LATP via DC sputtering and plasma-enhanced atomic layer deposition. The electrochemical stability was tested under three conditions: uncoated LATP, Al₂O₃-coated LATP, and Ag+Al₂O₃-coated LATP. The stability improved in the following order: uncoated < Al₂O₃-coated < Ag+Al₂O₃-coated. The Al₂O₃ coating suppressed secondary phase formation by preventing direct contact between LATP and Li, while Ag coating mitigated charge concentration, inhibiting dendrite growth. These findings demonstrate that Ag and Al₂O₃ nano-layers enhance electrolyte stability, advancing solid-state battery reliability and commercialization. Full article

Thin films of gadolinium-doped ceria (GDC) nanoparticles were fabricated as electrolytes for low-temperature solid oxide fuel cells (SOFCs) by combining electrophoretic deposition (EPD) and the successive ionic layer adsorption and reaction-air spray plus (SILAR-A+) method. The Ce_1−xGd_xO_2−x/2 solid solution was synthesized using hydrothermal (HY) and solid-state (SS) procedures to produce high-quality GDC nanoparticles suitable for EPD fabrication. The crystalline structure, cell parameters, and phases of the GDC products were analyzed using X-ray diffraction. Variations in oxygen vacancy concentrations in the GDC samples were achieved through the two synthetic methods. The ionic conductivities of pressed pellets from the HY, SS, and commercial G_0.2DC samples, measured at 150 °C, were 0.6 × 10⁻⁶, 2.6 × 10⁻⁶, and 2.9 × 10⁻⁶ S/cm, respectively. These values were determined using electrochemical impedance spectroscopy (EIS) with a simplified equivalent circuit method. The morphologies of G_0.2DC thin films prepared via EPD and SILAR-A+ processes were characterized, with particular attention to surface cracking. Crack-free GDC thin films, approximately 730–1200 nm thick, were successfully fabricated on conductive substrates through the hybridization of EPD and SILAR-A+, followed by hydrothermal annealing. EIS and ionic conductivity (1.39 × 10⁻⁹ S/cm) measurements of the G_0.2DC thin films with thicknesses of 733 nm were performed at 300 °C. Full article