Chromium Spinel Research Articles

Oxidation kinetics and electrical properties of oxide scales formed under exposure to air and Ar–H2-H2O atmospheres on the Crofer 22 H ferritic steel for high-temperature applications such as interconnects in solid oxide cell stacks

A 100 h isothermal oxidation kinetics study for Crofer 22H was conducted in air and the Ar–H2-H2O gas mixture (p(H2)/p(H2O) = 94/6) in the range of 973–1123 K. The parabolic rate constant was independent of oxygen partial pressure in the range from 6.2 × 10−24 to 0.21 atm at 1023 and 1073 K, while at 973 and 1123 K it was higher in air than in Ar–H2-H2O. The scales consisted of Cr2O3 and manganese chromium spinel with an Mn:Cr ratio dependent on the oxidation conditions. Cross-scale resistance was evaluated with regards to the application of the steel in solid oxide fuel cells using a number of methods, including X-ray diffraction, scanning electron microscopy, confocal Raman imaging and area-specific resistance measurements.

Stabilities and Transformations of Manganese Incorporated Magnesium–Chromium Spinels

Stabilities and Transformations of Manganese Incorporated Magnesium–Chromium Spinels

Three-dimensional checkerboard spin structure on a breathing pyrochlore lattice

The standard approach to realize a spin-liquid state is through magnetically frustrated states, relying on ingredients such as the lattice geometry, dimensionality, and magnetic interaction type of the spins. While Heisenberg spins on a pyrochlore lattice with only antiferromagnetic nearest-neighbor interactions are theoretically proven disordered, spins in real systems generally include longer-range interactions. The spatial correlations at longer distances typically stabilize a long-range order rather than enhancing a spin-liquid state. Both states can, however, be destroyed by short-range static correlations introduced by chemical disorder. Here, using disorder-free specimens with a clear long-range antiferromagnetic order, we refine the spin structure of the Heisenberg spinel ZnFe2O4 through neutron magnetic diffraction. The unique wave vector (1,0,12) leads to a spin structure that can be viewed as alternatively stacked ferromagnetic and antiferromagnetic tetrahedra in a three-dimensional checkerboard form. Stable coexistence of these opposing types of clusters is enabled by the bipartite breathing pyrochlore crystal structure, leading to a second-order phase transition at 10 K. The diffraction intensity of ZnFe2O4 is an exact complement to the inelastic scattering intensity of several chromate spinel systems which are regarded as model classical spin liquids. Our results challenge this attribution, and suggest instead of the six-spin ring mode, spin excitations in chromate spinels are closely related to the (1,0,12) type of spin order and the four-spin ferromagnetic cluster locally at one tetrahedron. Published by the American Physical Society 2024

Corrosion behavior of CaO–Al2O3–SiO2–MgO-Cr2O3 slag on MgO refractory brick for smelting of chromite

The MgO bricks were generally used as the refractory linings in electric furnace smelting of chromite ore. The reaction mechanisms between the MgO refractory and CaO-Al2O3-SiO2-MgO-Cr2O3 slags were experimentally investigated. The elemental distribution and phase compositions at the contact surface between slags and refractory bricks were studied using thermodynamic calculations and SEM-EDS techniques analysis. The main phase of the refractory brick was MgO, while the main phases of slag were pyroxene ((Ca, Mg) AlSi2O6), chromium spinel (Mg (Al, Cr)2O4), and magnesium olivine (2MgO·SiO2). The EDS analysis showed that the main phases at the contact surface of slag and refractory brick were calcium magnesium olivine and magnesium olivine, and the proportion of calcium magnesium olivine phase increased with the increase of slag basicity. Furthermore, the thermodynamic calculation indicated that the melting temperature and the slag viscosity decreased with the increase of slag basicity, and then the molten slag more easily penetrated the pores of refractory brick and caused brick corrosion.

Signatures of a magnetic superstructure phase induced by ultrahigh magnetic fields in a breathing pyrochlore antiferromagnet

The mutual coupling of spin and lattice degrees of freedom is ubiquitous in magnetic materials and potentially creates exotic magnetic states in response to the external magnetic field. Particularly, geometrically frustrated magnets serve as a fertile playground for realizing magnetic superstructure phases. Here, we observe an unconventional two-step magnetostructural transition prior to a half-magnetization plateau in a breathing pyrochlore chromium spinel by means of state-of-the-art magnetization and magnetostriction measurements in ultrahigh magnetic fields available up to 600 T. Considering a microscopic magnetoelastic theory, the intermediate-field phase can be assigned to a magnetic superstructure with a three-dimensional periodic array of 3-up-1-down and canted 2-up-2-down spin molecules. We attribute the emergence of the magnetic superstructure to a unique combination of the strong spin-lattice coupling and large breathing anisotropy.

Effect of sodium aluminate on chromium spinels oxidation in chromite lime-free roasting process

The reaction between Na2O·Al2O3 and chromium spinels or chromite in the roasting process was systemically investigated to reveal the effects of Na2O·Al2O3 on chromium oxidation. The results of Na2O·Al2O3 roasted with MgO·Cr2O3 illustrate that only about 50% of the chromium in MgO·Cr2O3 can convert into Na2CrO4, while the remaining chromium converts into an Al-bearing spinel Mg(CrAl)O4. Mg(CrAl)O4 is found to be difficult to further react with Na2O·Al2O3. The oxidative roasting of Na2O·Al2O3 with chromite further confirms that Na2O·Al2O3 cannot fully react with some chromium spinels, which reveals the cause of the low chromium oxidation rate in the traditional chromite lime-free roasting process. Based on the experiment results, a strategy for eliminating the impacts of Na2O·Al2O3 in the lime-free roasting process was proposed, in which adding more Na2CO3 for forming Na2O·Al2O3 is considered. The chromium oxidation rate can rise close to 100% with the new strategy. This study contributes to better understanding the chromite lime-free roasting process and provides a new idea for developing the chromate salts manufacturing process more efficiently and cleanly.

Origin of Low-26Al/27Al Corundum/Hibonite Inclusions in Meteorites

Most meteoritic calcium-rich, aluminum-rich inclusions formed from a reservoir with 26Al/27Al ≈ 5 × 10−5, but some record lower , demanding they sampled a reservoir without live 26Al. This has been interpreted as evidence for “late injection” of supernova material into our protoplanetary disk. We instead interpret the heterogeneity as chemical, demonstrating that these inclusions are strongly associated with the refractory phases corundum or hibonite. We name them “low-26Al/27Al corundum/hibonite inclusions” (LAACHIs). We present a detailed astrophysical model for LAACHI formation in which they derive their Al from presolar corundum, spinel, or hibonite grains 0.5–2 μm in size with no live 26Al; live 26Al is carried on smaller (<50 nm) presolar chromium spinel grains from recent nearby Wolf–Rayet stars or supernovae. In hot (≈1350–1425 K) regions of the disk, these grains and perovskite grains would be the only survivors. These negatively charged grains would grow to sizes 1–103 μm, even incorporating positively charged perovskite grains, but not the small, negatively charged 26Al-bearing grains. Chemical and isotopic fractionations due to grain charging was a significant process in hot regions of the disk. Our model explains the sizes, compositions, oxygen isotopic signatures, and the large, correlated 48Ca and 50Ti anomalies (if carried by presolar perovskite) of LAACHIs, and especially how they incorporated no 26Al in a solar nebula with uniform, canonical 26Al/27Al. A late injection of supernova material is obviated, although formation of the Sun in a high-mass star-forming region is demanded.

Synthesis and characterization of silver doped calcium chromate spinel Nano- particles and Ca effect on its band gap and optical properties

Silver chromates catalysts have newly been discussed by different preparation and utilization approaches. The results of all discussion explain that silver chromates is a proficient catalyst using for catalyses programmes at national and commercial level including worldwide environmental control of pollution. Various applications of silver chromates in energy clean, laboratory. Eco-friendly approach naming sol-gel is used to get final sample and characterized by SEM, XRD, EDS and photoluminescence. Final sample approach is affected by various parameters. Furnance was used to sinter at 750-900 o C for 4 hours.I intended 1.56 eV band gap value, 28.881 nm crystalline size for doped sample and EDS describes silver was successfully doped and emerged completely.

Bacterial mineralization of chromium-copper spinel with highly performance in electroplating effluent

Cr (VI) contamination has posed severe challenges to water quality, food safety, and land resources. Microbial reduction of Cr(VI) to Cr(III) has drawn considerable attention due to its low cost and environmental friendliness. However, recent reports have shown that Cr(VI) generates highly migratable organo-Cr(III) rather than stable inorganic chromium minerals during the biological reduction process. In this work, it was reported for the first time that spinel structure CuCr2O4 was formed by Bacillus cereus in Cr biomineralization process. Different from known biomineralization models (biologically controlled mineralization and biologically induced mineralization), the chromium-copper minerals here appeared as specialized minerals with extracellular distribution. In view of this, a possible mechanism of biologically secretory mineralization was proposed. In addition, Bacillus cereus demonstrated a high conversion ability in the treatment of electroplating wastewater. The Cr(VI) removal percentage reached 99.7%, which satisfied the Chinese emission standard of pollutants for electroplating (GB 21,900–2008), indicating its application potential. Altogether, our work elucidated a bacterial chromium spinel mineralization pathway and evaluated the potential of this system for application in actual wastewater, opening a new avenue in the field of chromium pollution treatment and control.

Electronic origin of half-metal to semiconductor transition and colossal magnetoresistance in spinel HgCr2Se4

Half-metals are ferromagnets hosting spin-polarized conducting carriers and crucial for spintronics applications. The chromium spinel HgCr2Se4 represents a unique type of half-metal, which features a half-metal to semiconductor transition (HMST) and exhibits colossal magnetoresistance (CMR) across the ferromagnetic-paramagnetic (FM-PM) transition. Using angle-resolved photoemission spectroscopy (ARPES), we find that the Fermi surface of n-type HgCr2Se4 (n-HgCr2Se4) consists of a single electron pocket which moves above the Fermi level (EF) upon the FM-PM transition, leading to the HMST. Such a Lifshitz transition manifests a giant band splitting which originates from the exchange interaction unveiled with a specific chemical nonstoichiometry. The exchange band splitting and the chemical nonstoichiometry are two key ingredients to the HMST and CMR, consistent with our ab-initio calculation. Our findings provide spectroscopic evidences of the electronic origin of the anomalous properties of HgCr2Se4, which address the unique phase transition in half-metals.

Magnesian Basalts of the Medvezhia Caldera: Main Magmas and Their Sources on the Example of the Menshiy Brat Volcano (Iturup Island)

The paper represents new data on the formation conditions of basalts from post-caldera volcano Menshiy Brat (Medvezhia caldera, Iturup Island). Liquidus mineral assemblage is composed of olivine (Fo up to 90.1 mol. %) and chromium spinel (Cr# = 0.46–0.6), which crystallized at 1090–1170°С and oxygen fugacity NNO +0.6 (σ = 0.2) – NNO +0.2 (σ = 0.14). The study of melt inclusions in the liquidus olivine demonstrated that its parental melts have low-alumina, low-potassium compositions with up to 15.5 wt. % MgO and with an average water content of 5.5 wt. %. The data on volatile contents in the olivine-hosted melt inclusions suggest that the basic melts appeared due to partial melting of essentially peridotitic source with a small admixture of an olivine-free component at 1225°С under active influence of the slab-related fluids. These fluids were separated from the subducting slab at 670–705°С and depths of 95–105 km beneath the Iturup Island. The results of this study enhance our understanding of the evolution of basic magmas that serve as a heat and volatile supply during the formation of large calderas.

The origin of olivine basalts from Medvezhya Mount (Avachinsky group of volcanoes, Kamchatka): The evidence of assimilation of sulfide-bearing cumulates

The role and conditions of liquid immiscibility and crystallization of sulfide phase during evolution of subduction related magmas remains to be a debated topic, which bears relevance to mechanisms of porphyry copper deposit formation and evolution of the continental crust. We studied rare volcanic rocks with inclusions of magmatic sulfides in olivine – the basalts of Medvezhya Mount in the Avachinsky group of volcanoes. The rocks belong to primitive (Mg# = 66 mol. %) middle-K island arc olivine basalts. Olivine with normal zoning predominate (~98%) among phenocrysts. The olivine compositions are typical for Kamchatka basalts, except for an unusual trend of increase of MnO content from 0.20 to 0.55 wt. % and decrease of Fe/Mn from 60 to 35 with change of olivine composition from Fo87.8 to Fo78.2. Olivines of this group contain numerous inclusions of minerals of the spinel group varying in composition from chromium spinel to magnesian magnetite. Olivine phenocrysts with sulfide inclusions are characterized by the absence or weak reverse zoning and reduced contents of Ca, Ni, Mn, Cr, and Al. The estimated crystallization temperatures for olivines of the prevailing type are 1036–1241°C, for sulfide-bearing olivines – 1010–1062°C. The data suggest that crystallization of the main olivine population occurred under relatively shallow conditions and was accompanied by strong oxidation of the magmas. On the contrary, the zoning and composition features of sulfide-bearing olivine suggest its xenogenic origin and probable crystallization at conditions of deep crust from low temperature water-rich and/or low-Ca magmas. The results obtained confirm the possibility of saturation of oxidized island-arc magmas with sulfide phase at lower crustal conditions, but show that this process is rare and not typical for low-pressure crystallization stage.

Synthesis of Pyrope Garnet with High Samarium Content at 5 GPa and 1300 °C

In natural garnets associated with diamonds, an increased content of "light" rare-earth elements, especially samarium, is often noticed. There are various estimates of the composition of the crystallization medium. Experimental data on the synthesis of Cr-rich garnets containing rare-earth elements are still scarce. The experiments were carried out on a multi-anvil apparatus of the “split-sphere” type (BARS) at a pressure of 5 GPa and a temperature of 1300 °С. The high pressure cell was made of Zr02 and CaO. A tubular graphite element was used as a heater. The measurement error of pressure and temperature was ± 0.2 GPa and ± 25 °С. The starting materials for the experiments were natural serpentine-antigorite, chromium spinel, and corundum. As a result of the experiments, pyrope crystals with a high content of samarium were synthesized in the range of 0.77 to 2.34 wt% Sm2O3. The study demonstrates that the interaction of components in the serpentine-chromite-corundum-Sm system in the presence of fluid leads to crystallization of pyrope garnet with samarium content exceeding the values known for natural garnets associated with diamond.

Accessory Minerals in the Chromitite Ores of Dzharlybutak Ore Group of Kempirsai Massif (Southern Urals, Kazakhstan): Clues for Ore Genesis

The paper provides results of a detailed mineralogical study of some chromitite ores from two deposits in the Southern Urals of Kazakhstan: Almaz-Zhemchuzhina and Geofizicheskoe-VII. It is revealed that the main ore minerals are Cr-spinel with high Cr# (Cr/(Cr + Al) = 0.8–0.83), as well as serpentine and chlorite, replacing primary olivine. Chromium spinel grains contain mineral inclusions, which are distributed rather unevenly. The most common mineral inclusions are olivine (serpentine) and amphibole; phlogopite, pyroxenes, and base metal sulfides are rare. Olivine from inclusions in chromite is the highest in magnesium (Fo97–98), and is anomalously high in nickel (up to 1.8 wt.% NiO). The closure of exchange reactions between olivine and chromite occurred in the temperature range of 700–850 °C and in the oxygen fugacity range of −1.04 … +2.8 ΔFMQ, which most likely corresponds to the upper mantle settings of the fore-arc basin. A few tens of monomineral grains and polymineral intergrowths of platinum group minerals (PGMs) were found in chromite aggregates. Notably, monomineral grains are mainly represented by Ru, Os, and Ir disulfides, while in polymineral inclusions, iridium prevails (with widespread native phases, sulfides, and sulfoarsenides). PGM grains included in chromite are often associated with hydrous silicates: amphibole, and less often with phlogopite or chlorite. Discussed in the paper is the possible genesis of ores and inclusions. As a preliminary conclusion, we suggest that the solid-phase processes played the most significant role in the crystallization of Cr-spinel in the investigated chromitite ores.

Mineralogical and Geochemical Evidence of Paragenetic Unity of Igneous Silicate and Carbonatite Rocks of the Tomtor Massif in the North-East of the Siberian Platform

The Tomtor massif is a polychronous ring zonal complex of alkaline ultramafic and carbonatite rocks containing unique Nb and REE deposits. Mineralogical and geochemical studies of minerals from different types of silicate rocks and carbonatites of the Tomtor massif were performed. For excluding traces of the interaction between silicate and carbonatite melts, we limited ourselves to the study of independent small secant bodies located in the immediate vicinity of the massif itself. The presence of through mineral series in various silicate igneous rocks and carbonatite ores of high-titanium chromium spinels, rare-metal, ore and other exotic phases with similar compositional trends was defined. Such studies will help reveal the mineralogical criteria for the genetic relationship between silicate melts and associated carbonatite derivatives, which can form rich rare elements mineralization. Also, such studies help to improve the petrochemical and mineralogical criteria for dividing potentially diamond-bearing magmatites (typical kimberlites) from non-diamond-bearing kimberlites, alpicrites and other non-diamond-bearing rocks convergent to kimberlites, which are formed under different physicochemical conditions. The existence of polychronous complex ore–magmatic ring complexes, such as the Tomtor massif, indicates the existence of large deep intraplate magma-generating chambers in the lithospheric mantle.

Pressure-Induced Structural Phase Transitions in the Chromium Spinel LiInCr4O8 with Breathing Pyrochlore Lattice

This study reports high-pressure structural and spectroscopic studies on polycrystalline cubic chromium spinel compound LiInCr4O8. According to pressure-dependent X-ray diffraction measurements, three structural phase transitions occur at ∼14 GPa, ∼19 GPa, and ∼36 GPa. The first high-pressure phase is indexed to the low-temperature tetragonal phase of the system which coexists with the ambient phase before transforming to the second high-pressure phase at ∼19 GPa. The pressure-dependent Raman and infrared spectroscopic measurements show a blue-shift of the phonon modes and the crystal field excitations and an increase in the bandgap under compression. During pressure release, the sample reverts to its ambient cubic phase, even after undergoing multiple structural transitions at high pressures. The experimental findings are compared to the results of first principles based structural and phonon calculations.

Effect of Al2O3 on migration and distribution of chromium and chromium fixation effect in stainless-steel slag glass-ceramics

Stainless-steel slag was used to prepare glass-ceramics, which could solidify chromium (Cr) in the slag. The migration and distribution state of chromium in the slag during the preparation of the glass-ceramics have a great influence on the chromium fixation ability of the glass-ceramics. In this paper, the effects of Al2O3 content in the glass-ceramics on the migration and distribution of chromium during the nucleation and crystallization steps, and on the chromium fixation effect of the glass-ceramics were systematically studied. The results show that in the nucleation stage, with the increase of Al2O3 content, the number of chromium spinel (Cr-spinel) nanocrystals formed in the glass first increases and then decreases, and Cr in the glass phase gradually migrates to Cr-spinel nanocrystals. TEM and XPS analyses show that during crystallization, part of Cr in Cr-spinel diffuses into diopside lattice, and the other part of Cr still exists in Cr-spinel wrapped by diopside. Cr in the glass phase also diffuses and migrates into the diopside lattice with the formation of diopside crystals. The optimal Al2O3 content is 11.8wt.%, which results in 97.94wt.% of the total Cr being fixed in the diopside crystalline phase. The ability of chromium fixation is very high giving a very low Cr leaching concentration of 0.004mg/l. The research results provide theoretical and technical support for increased chromium fixation and realizing harmless and high-value utilization of stainless-steel slag.

INFLUENCE OF STRUCTURAL FACTORS ON THE MECHANICAL STRENGTH OF GLASS-CERAMIC PROPANTS

The results of studying the influence of the chemical composition, material structure, crystallization features and isomorphic substitutions in pyroxene solid solutions of the augite type on the mechanical characteristics of glass ceramics are presented. The mechanism of structure formation is shown, which consists in the crystallization of chromium spinel and subsequent growth on its surface of crystals of a pyroxene solid solution of the augite type in the form of spherical intergrowths, which ensures high mechanical strength of glass-ceramic proppants. It has been established that during the course of isomorphic substitutions in the diopside-augite series, the mechanical strength of glass-ceramic proppants increases, which is associated with a decrease in bond lengths, an increase in their number, and compaction of the unit cell.

Facile preparation of thermal insulation materials by microwave sintering of ferronickel slag and fly ash cenosphere

A novel approach for preparing thermal insulation materials by microwave sintering of ferronickel slag (FNS) in the presence of fly ash cenosphere (FAC) was proposed and evaluated. The study showed that during microwave radiation, the contact interface between FNS and FAC would preferentially form magnesium iron chromate spinel and magnesium iron aluminate spinel particles as hot spots by absorbing microwave vigorously, promoting decomposition and transformation of the raw materials into the thermal insulation phases, mainly cordierite and enstatite. After sintering at 900 °C by microwave for only 20 min with the addition of 25 wt% FAC, a thermal insulation material with thermal conductivity of 0.41 W/(m·K), bulk density of 1.46 g/cm3, compressive strength of 30.72 MPa, water absorption of 21.07%, and linear shrinkage of 7.06% was obtained. Compared with the conventional sintering method, the temperature was reduced by 300 °C, with the sintering time shortened by 6 times. This study represents a good example for clean and efficient value-added utilization of FNS, FAC and other relavent solid wastes.

Structural, elastic, thermodynamic, electronic, magnetic, thermoelectric and optical investigation of chromate spinels TCr2O4 [T = V2+, Mn2+, Fe2+] for optoelectronic applications

Spinel oxides (TM2O4) containing transition metals are gaining vast momentum not only for advanced exploration of fundamental properties but also because of their potential as promising materials for various technological applications, such as microwaves, fuel cells, sensors, information storage, supercapacitors, magnetic fluids, photocatalysis and biomedical devices. In this regard, the structural, elastic, thermodynamic, electronic, magnetic, thermoelectric and optical properties of three related chromate spinels (TCr2O4) with 3d transition metals (T2+ = V, Mn, Fe) have been systematically investigated. The Perdew-Burke-Ernzerh (PBE) functional and the exchange-correlation method (PBE + U) based on the generalized gradient approximation were used to investigate these properties. The elastic parameters confirm that TCr2O4 compounds are mechanically stable and possess stiffness and anisotropic properties. The calculated band structures, DOSs and magnetic moments show that the cubic TCr2O4 (Fd-3m) are half-metallic (HM) ferromagnetic compounds due to strong hybridization between their T-3d, Cr-3d and O-2p states. The thermodynamic properties are explained by calculating the melting temperature (Tm), average sound velocity (vm) and Debye temperature (ƟD). High values of these parameters, Tm, νm and ƟD, indicate the high thermodynamic stability of TCr2O4, which allows them to maintain their ground state structures at high temperatures. The thermoelectric properties as a function of temperature illustrate the stability of the current spinel structures. We have also calculated the optical properties, including real ε1(ω) and imaginary ε2(ω) parts of dielectric function ε(ω), conductivity σ(ω), absorption coefficient α(ω), reflectivity R(ω), refractive index n(ω), extinctive index k(ω) and energy loss function L(ω). TCr2O4 exhibits high dielectric constants; low reflectivity and minimal energy loss in the range VL-UV, making these FM-HM compounds promising materials for many optoelectronics devices.