Search Results (67)

This study investigates the thermally induced phase transformation of Ni-exchanged LTA zeolite as a dual-purpose method for nickel immobilization and the synthesis of stable ceramic pigments. The process describes a cost-effective and sustainable alternative to conventional pigment production, aligning with circular economy principles. Upon thermal treatment at temperatures ranging between 900 °C and 1300 °C, Ni-exchanged LTA zeolite undergoes a transformation to NiAl₂O₄ spinel, confirmed by XRPD, FTIR, and thermal analysis. Initially, NiO is formed, but as the temperature increases, it dissolves and transforms into NiAl₂O₄. Colorimetric studies revealed intensified blue pigmentation with increasing temperature, correlating with crystallite growth and structural evolution. SEM analysis showed morphological changes from cubic particles to sintered agglomerates, enhancing pigment stability and hardness. The Ni-LTA sample calcined at 1300 °C showed the highest hue angle, which was consistent with the formation of over 99 wt.% of the nickel aluminate crystalline phase at this temperature. The results demonstrate that Ni-LTA zeolite can be effectively transformed into durable greenish-blue pigments suitable for application in porcelain. This transformation is especially evident at 1300 °C, where a spinel phase (NiAlSi₂O₄) forms, with colorimetric values: L = 58.94, a* = –16.08, and b* = –15.90. Full article

Microstructure evolution and cracking behavior of a four-layer thermal barrier coating (TBC) with double YSZ layers during thermal cycle tests were studied in the current work. The temperature range of the thermal cycle test ranged from room temperature to 1100 °C under atmospheric conditions. The TBC consisted of tetragonal t′ and t phases as well as monoclinic yttrium oxide. After 500 thermal cycles, the m-ZrO₂ phase was formed through the phase transformation from t′-ZrO₂ to m-ZrO₂ and c-ZrO₂. A large number of bulk thermally grown oxides (TGO), including chromium, spinel, and yttrium aluminates, were formed around pores in the transition layer (TL). Furthermore, the thickness of the TGO layer increased with a relatively low increase rate during the test (where k_p was about 0.17 μm²/h). This may be attributed to the formation of bulk TGO around pores within the TL, which could consume some of the oxygen. The results show that large horizontal cracks are likely to form at the TSL/TIL and TIL/TL interfaces, while vertical cracks tend to occur near the surface of the TSL, and the propagation rate is relatively low. The propagation of horizontal cracks is the primary cause of failure in this four-layer structure. After the thermal cycle test, the porosity of TSL decreased significantly, from 7.17% to 0.76%. The results in this study may help optimize the design and preparation of TBCs with double YSZ layers. Full article

This study investigates the effect of the exsolution behavior of alumina-rich spinel on the formation and distribution of CA₆ (CaAl₁₂O₁₉) in corundum castables bonded with calcium aluminate cement. In this study, alumina-rich spinel is substituted for tabular corundum in the same proportions and grain size. The matrices after curing were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The phase composition and microstructure of the matrices containing alumina-rich spinel were analyzed after firing at 1600 °C. These results showed that the addition of alumina-rich spinel significantly improved the mechanical strength of the castables. This improvement was attributed to the alumina produced by spinel exsolution during firing at 1600 °C, which reacted in situ with CA₂ (CaAl₄O₇) to form CA₆. CA₆ connects the different particles and forms an interspersed interlocking structure within the spinel. The CA₆-MA interspersed interlocking structure replaces part of the CA₆-Al₂O₃ structure and significantly improves the mechanical strength of the castables. Full article

Magnesium aluminates (MgO)_x(Al₂O₃)_1−x belong to a class of refractory materials with important applications in glass and glass–ceramic technologies. Typically, these materials are fabricated from high-temperature molten phases. However, due to the difficulties in making measurements at very high temperatures, information on liquid-state structure and properties is limited. In this work, we employed the method of aerodynamic levitation with CO₂ laser heating at large scale facilities to study the structure of liquid magnesium aluminates in the system (MgO)_x(Al₂O₃)_1−x, with x = 0.33, 0.5, and 0.75, using X-ray and neutron diffraction. We determined the structure factors and corresponding pair distribution functions, providing detailed information on the short-range structural order in the liquid state. The local structures were similar across the range of compositions studied, with average coordination numbers of ${\overline{n}}_{\mathrm{A}\mathrm{l}}^{\mathrm{O}}\sim 4.5$ and ${\overline{n}}_{\mathrm{M}\mathrm{g}}^{\mathrm{O}}\sim 5.1$ and interatomic distances of $r_{\mathrm{AlO}}=1.76-1.78 \mathrm{\AA }$ and $r_{\mathrm{MgO}}=1.93-1.95 \mathrm{\AA }$. The results are in good agreement with previous molecular dynamics simulations. For the spinel endmember MgAl₂O₄ (x = 0.5), the average Mg-O and Al-O coordination numbers gave rise to conflicting values for the inversion coefficient χ, indicating that the structural formula used to describe the solid-state order-disorder transition is not applicable in the liquid state. Full article

Slags from the Silesia–Cracow Upland (Poland), including ten historical slags (deposited in waste dumps) and four contemporary slags (from current production), were examined to compare their chemical and mineralogical properties as well as to assess their potential for the recovery of selected metals and critical raw materials. The historical slags associated with the smelting of polymetallic ores originating from Mississippi Valley-type (MVT) deposits consisted primarily of gypsum. The contemporary slags, obtained from industrial waste rich in zinc and lead, were predominantly spinels (magnesium-aluminate and ferric) that exhibited higher iron content (up to 46.6 wt% of Fe₂O₃) compared to the historical slags (up to 26.1 wt% of Fe₂O₃). The zinc content was similar for both the slag types (3.5 wt% Zn). The average titanium and arsenic contents in the old and contemporary slags were at the same level as well, with 0.21 wt% (Ti) and 0.13 wt% (As), respectively. The contemporary slags contained higher levels of critical raw materials, such as cobalt, nickel, copper, and manganese, compared to the historical slags. Rare earth elements (REEs) were also more abundant in the contemporary slags, with an average content of 212 ppm, while the historical slags averaged 124 ppm. These findings underscore the potential for recovering valuable metals and critical raw materials from such slags, presenting opportunities for resource optimisation and environmental management. Full article

Inorganic cool pigments are widely used as cooling agents in residential coatings due to their ability to achieve near-infrared reflectance. These coatings can be designed to exhibit a variety of colors independent of their reflectivity and absorption properties. Recent studies have highlighted the development of novel near-infrared (NIR) blue pigments, with an increasing emphasis on environmentally sustainable options that demonstrate high NIR reflectivity. This trend highlights the importance of creating novel and eco-friendly NIR reflective blue pigments. This study presents the synthesis of cobalt aluminates with varying concentrations of coloring ions (Co²⁺), achieved through the recycling of aluminum can seals via chemical precipitation. The formation of the spinel phase was confirmed through X-ray diffraction (XRD), and a colorimetric analysis was performed in the CIEL*a*b* color space. The synthesized pigments exhibited high near-infrared solar reflectance, with R% values ranging from 34 to 54%, indicating their potential as energy-efficient color pigments for use in coatings. Full article

Thermal degradation is a leading cause of automotive catalyst deactivation. Because high-entropy oxides are uniquely stabilized at high temperatures via an increase in configurational entropy, these materials may offer new mechanisms for preventing the thermal deactivation of precious metal catalysts. In this work, we evaluated platinum loaded on simple and high-entropy aluminate spinels (MAl₂O₄, where M = Co, Cu, Mg, Ni, or mixtures thereof) in carbon monoxide oxidation before and after aging at 800 °C. Pt supported on all simple spinels showed significant deactivation after thermal aging compared to the fresh samples, with T₉₀ increasing by at least 60 °C. However, Pt on high-entropy spinels had nearly the same or better activity after aging, with T₉₀ increasing by only 6 °C at most. During aging and reduction, copper exsolved from the spinel supports and alloyed with platinum. This interaction promoted low temperature oxidation activity, presumably through weakened CO binding, but did not prevent deactivation. On the other hand, Co, Mg, and Ni constituents promoted stronger CO bonding, as evidenced by apparent negative order kinetics and poor activity at low temperatures. High-entropy spinels, containing a variety of active metals, displayed synergetic reactant adsorption capacity and cooperative effects with supported platinum particles, which collectively prevented thermal deactivation. Full article

U75V heavy rail steel production uses an aluminum-free deoxidation process; however, large particles of MgO–Al₂O₃ inclusions form in the steel, which has a great impact on product quality. In this paper, we try to explain how spinel inclusions, which affect the metallurgical quality of heavy rail steel, are produced by thermodynamic and experimental methods, and then determined measures for avoiding such inclusions. The formation mechanism of spinel inclusions in U75V heavy rail steel was determined through the analysis of nozzle clogging in the pouring process and typical inclusions in steel. The results show that there are two types of spinel inclusions in heavy rail steel: one is pure Mg–Al spinel inclusions and the other is Mg–Al spinel inclusions coated with calcium aluminate. The small, pure Mg–Al spinel inclusions were precipitated during the solidification of the molten steel, and the precipitation temperature was related to the composition of the molten steel. The large spinel inclusions were derived from clogging of the submersed nozzle. Mg–Al spinel inclusions coated with calcium aluminate were transformed from CaO–SiO₂–Al₂O₃–MgO complex inclusions in the steel during cooling, and the formation temperature was related to the content of Al₂O₃ and MgO in the inclusions. The content of Al₂O₃ and MgO in the inclusions was the key to the formation of the Mg–Al spinel inclusions. Therefore, in order to control the production of spinel inclusions in steel, it is necessary to strictly control the content of impurity elements such as magnesium and aluminum in the alloy auxiliary materials, to reduce the secondary oxidation of liquid steel and to reduce the erosion of refractory materials. Full article

A synthetic single crystal of magnesium-aluminate spinel was irradiated perpendicularly to the (111) plane with swift heavy xenon ions with an energy of 220 MeV. The modified layer was attested based on Raman scattering spectra recorded while focusing on the surface. A decrease in surface crystallinity was observed, reflected in the changes in fundamental optical characteristics such as the band gap and the energies of static and dynamic disorder. In this study, we demonstrate, along with the modification of optical characteristics and the formation of a disordered layer, the creation of new optically active centers. The luminescent properties of these centers were analyzed. The effect of temperature flare-up in the 3.4 eV band of the excitation spectrum was determined. The low sensitivity of Cr³⁺ luminescence to SHI is demonstrated. Full article

Deep red phosphors have attracted much attention for their applications in lighting, medical diagnosis, health monitoring, agriculture, etc. A new phosphor host material based on fluorine-doped lithium aluminate (ALFO) was proposed and deep red emission from Cr³⁺ in this host material was demonstrated. Cr³⁺ in ALFO was excited by blue (~410 nm) and green (~570 nm) rays and covered the deep red to near-infrared region from 650 nm to 900 nm with peaks around 700 nm. ALFO was a fluorine-doped form of the spinel-type compound LiAl₅O₈ with slightly Li-richer compositions. The composition depended on the preparation conditions, and the contents of Li and F tended to decrease with preparation temperature, such as Al_4.69Li_1.31F_0.28O_7.55 at 1100 °C, Al_4.73Li_1.27F_0.17O_7.65 at 1200 °C, and Al_4.83Li_1.17F_0.10O_7.78 at 1300 °C. The Rietveld analysis revealed that ALFO and LiAl₅O₈ were isostructural with respect to the spinel-type lattice and in a disorder–order relationship in the arrangement of Li⁺ and Al³⁺. The emission peak of Cr³⁺ in LiAl₅O₈ resided at 716 nm, while Cr³⁺ in ALFO showed a rather broad doublet peak with the tops at 708 nm and 716 nm when prepared at 1200 °C. The broad emission peak indicated that the local environment around Cr³⁺ in ALFO was distorted, which was also supported by electron spin resonance spectra, suggesting that the local environment around Cr³⁺ in ALFO was more inhomogeneous than expected from the diffraction-based structural analysis. It was demonstrated that even a small amount of dopant (in this case fluorine) could affect the local environment around luminescent centers, and thus the luminescence properties. Full article

The thermal decomposition processes of coprecipitated Cu-Ni-Al and Cu-Ni-Fe hydroxides and the formation of the mixed oxide phases were followed by thermogravimetry and derivative thermogravimetry analysis (TG – DTG) and in situ X-ray diffraction (XRD) in a temperature range from 25 to 800 °C. The as-prepared samples exhibited layered double hydroxide (LDH) with a rhombohedral structure for the Ni-richer Al- and Fe-bearing LDHs and a monoclinic structure for the CuAl LDH. Direct precipitation of CuO was also observed for the Cu-richest Fe-bearing samples. After the collapse of the LDHs, dehydration, dehydroxylation, and decarbonation occurred with an overlapping of these events to an extent, depending on the structure and composition, being more pronounced for the Fe-bearing rhombohedral LDHs and the monoclinic LDH. The Fe-bearing amorphous phases showed higher reactivity than the Al-bearing ones toward the crystallization of the mixed oxide phases. This reactivity was improved as the amount of embedded divalent cations increased. Moreover, the influence of copper was effective at a lower content than that of nickel. Full article

Copper (Cu²⁺)-and-magnesium (Mg²⁺)-doped Zinc aluminate ZnAl₂O₄ is a promising material with diverse applications in electronic and energy storage devices. In this study, the synthesis of Zn_0.9M_xAl₂O₄ (M = Cu²⁺ and Mg²⁺; x = 0.00 and 0.10) was conducted via the sol–gel combined combustion technique. The structural, spectral, optical and dielectric parameters of the synthesized spinel aluminates were analysed to explore the substitution effect of Cu²⁺ and Mg²⁺ content. The formation and crystallinity analyses of the single-phase cubic spinel structure in the synthesized spinel aluminates were confirmed using XRD patterns. The lattice parameter and grain size were ascertained from the XRD data. The crystallite size of Cu²⁺ and Mg²⁺ substituted into ZnAl₂O₄ using Scherrer’s formula was found to be around 22 nm. The spinel structure formations in the prepared spinel aluminates were ascertained through an FT-IR study. The UV-Vis spectra exhibited a broad absorption band in the UV-Vis region, indicating the presence of electronic transitions. The band gap energy of the prepared aluminates was estimated from the absorption edge, with values varying between 2.90 eV and 3.03 eV, revealing its suitability for optoelectronic applications. Measurement of the dielectric parameters was performed in the frequency range of 100 Hz to 20 MHz at temperatures ranging from 30 °C to 250 °C. The dielectric constant (ε′) and dielectric loss (ε”) were determined as a function of frequency at different temperatures. The results showed that the dielectric constant decreased with increasing frequency for all the observed temperatures, while the dielectric loss exhibited a peak at a specific temperature. The conductivity results indicate that the conduction mechanism occurred due to polaron hopping. The Arrhenius relation was adopted to calculate the activation energies E_a for all the samples, and the values were between 0.70 eV and 0.38 eV. The obtained results were discussed and interpreted. These findings contribute to our understanding of the electrical behaviour of doped zinc aluminate materials and their useful applications in different electronic and energy systems. Full article

Non-oxidative propane dehydrogenation (PDH) is becoming an increasingly important approach to propylene production, while cobalt-containing catalysts have recently demonstrated great potential for use in this reaction, providing efficiencies comparable to those of industrially employed Pt- and Cr-based catalytic systems. It is therefore essential to clarify the nature of their active sites, especially since contradictory opinions on this issue are expressed in the literature. In this study, efforts were made to determine the state of Co in cobalt aluminates (CoAl₂O₄-Al₂O₃) responsible for PDH under typical operating conditions (600 °C, 1 atm). It is shown that the catalyst with a low cobalt content (Co/Al = 0.1) ensured the highest selectivity to propylene, ca. 95%, while maintaining significant propylene conversion. The structural motifs such as cobalt oxide and metallic cobalt nanoparticles, in addition to tetrahedral Co²⁺ species in the CoAl₂O₄ spinel system, were evaluated as potential active-site ensembles based on the obtained catalytic performance data in combination with the XRD, H₂-TPR, TEM and XPS characteristics of as-synthesized, spent and spent–regenerated catalysts. It is revealed that the most likely catalytic sites linked to PDH are the Co-oxide forms tightly covering alumina or embedded in the spinel structure. However, additional in situ tuning is certainly needed, probably through the formation of surface oxygen vacancies rather than through a deeper reduction in Co⁰ as previously thought. Full article

In In this study, the optical properties of magnesium-aluminate spinel were examined after being irradiated with 220 MeV Xe ions. The research aimed to simulate the impact of nuclear fuel fission fragments on the material. The following measurements were taken during the experiments: transmission spectra in the IR region (190–7000) nm, optical absorption spectra in the range (1.2–6.5) eV, and Raman spectra were measured along the depth of ion penetration from the surface to 30 µm. A peak with a broad shape at approximately 5.3 eV can be observed in the optical absorption spectrum of irradiated spinel crystals. This band is linked to the electronic color centers of F⁺ and F. Meanwhile, the band with a maximum at ~(3–4) eV is attributed to hole color centers. Apart from the typical Raman modes of an unirradiated crystal, additional modes, A1g* (720 cm⁻¹), and Eg* (385 cm⁻¹), manifested mainly as an asymmetric shoulder of the main Eg mode, are also observed. In addition, the Raman spectroscopy method showed that the greatest disordering of crystallinity occurs in the near-surface layer up to 4 μm thick. At the same time, Raman scattering spectroscopy is sensitive to structural changes almost up to the simulated value of the modified layer, which is an excellent express method for certifying the structural properties of crystals modified by swift heavy ions. Full article

A series including single and mixed Ni-Co aluminates was obtained using the precursor method, with malic acid as a ligand. The malate precursors (polynuclear coordination compounds) were isolated and characterized by Fourier Transform Infrared (FTIR), Ultraviolet/Visible/Near Infrared (UV–Vis–NIR) spectroscopy, and thermal analysis. The UV–Vis–NIR spectra of the synthesized complex compounds highlighted the presence of Co²⁺ and Ni²⁺ in an octahedral environment. The thermal decomposition of these precursors led to Co_1−xNi_xAl₂O₄ (x = 0, 0.1, 0.25, 0.5, 0.75, 0.9, and 1) spinels. The effect of Ni²⁺ substitution on the structure, morphology, and optical properties of the obtained oxides was studied with the help of different characterization tools. XRD, FTIR, and Raman spectra evidenced the formation of the spinel phase. The size of the crystallites and the agglomeration degree of the particles decrease when the nickel content increases. The band gap (BG) value is not significantly influenced by the Ni substitution. The fluorescence spectra recorded for all samples show a similar pattern, but different intensities of the emission bands. Full article