Interaction of Al2O3-rich slag with MgO–C refractories during VOD refining—MgO and spinel layer formation at the slag/refractory interface

The interaction mechanisms between a pitch-bonded MgO–C refractory and an Al₂O₃ rich (～15 wt%) stainless steelmaking slag were investigated by rotating finger tests in a vacuum induction furnace. A porous MgO layer (instead of a dense MgO layer) was observed at the hot face of the MgO–C bricks. This implies that under the present low oxygen pressure conditions, the oxygen supply from the slag is insufficient to meet the demand of reoxidising the entire amount of Mg vapor generated from the MgO–C reaction to form a fully dense MgO layer. A Mg(Al,Cr)₂O₄ spinel layer with zoning was found at the slag/brick interface in the top slag zone specimen of Test 3 (CHS3). Based on the thermodynamic analyses with and experimental data, a mechanism of Mg(Al,Cr)₂O₄ spinel formation is proposed. Initially, hot face periclase grains take up Cr₂O₃, and to a much lesser extent, Al₂O₃ from the slag. The further diffusion of Cr₂O₃ and Al₂O₃ from the slag establishes a spinel layer of three distinct compositions of the type MgAl_2(1?x)Cr_2xO₄, with x decreasing when moving from the interior to the exterior spinel layer. Due to the low oxygen pressures, the thermodynamically less stable, dissolved Cr₂O₃ in the hot face periclase decomposes and forms chromium-rich metal droplets.     

In situ observation of the direct and indirect dissolution of MgO particles in CaO–Al2O3–SiO2-based slags

The dissolution of magnesia particles in synthetic CaO–Al₂O₃–SiO₂ (CAS)-based slags with and without MgO addition was investigated in situ with a confocal scanning laser microscope (CSLM) at 1500 and 1600 °C. The dissolution process was recorded. The effects of slag composition and temperature on the dissolution process and the time dependency of the MgO particle size during dissolution were obtained. Increasing the temperature increases the dissolution rate. However, MgO addition to the slag retards the dissolution rate significantly. The rate limiting steps are discussed. It is shown that boundary layer diffusion is responsible for the dissolution. By combining in situ observations with post mortem analyses, thermodynamic calculations of local and global equilibrium, and kinetic considerations, the conditions under which MgAl₂O₄ spinel can be formed at the particle–slag interface are clarified.     

Evolution of elastic properties and microstructural changes versus temperature in bonding phases of alumina and alumina–magnesia refractory castables

The microstructural evolutions of high alumina refractory concretes, based on the systems CaO–Al₂O₃ and CaO–Al₂O₃–MgO, have been studied by the way of ultrasonic high temperature measurements. Since such a refractory concrete can be considered as a composite material with two constituents, a continuous matrix (so called bonding phase) and aggregates, investigations of matrices made of mixtures containing cement, reactive alumina and/or magnesia, constitute a preliminary study which is presented in this paper. The elastic behaviour of these matrices has been followed from room temperature to 1550 °C via a specific ultrasonic method. During the first thermal treatment, different changes of slope are observed in the curve E = f(T). Between 200 °C and 400 °C, dehydration mechanisms involve a microstructural reorganisation correlated with a strong decrease of the elastic properties. At high temperature, the Young's modulus evolutions are associated with the expansive formations of CA₂^b and/or in-situ spinel at 1100 °C and then CA₆ (see endnote b) at 1450 °C, which directly depend on the CaO/Al₂O₃ and MgO/Al₂O₃ ratios in the mix. The forming of bond linkage between CA₆ and in-situ spinel grains in the matrix is believed to enhance the elastic properties at high temperature.     

Synthesis and characterization of S2O82 −/ZnFexAl2 − xO4 solid acid catalysts for the esterification of acetic acid with n-butanol

New spinel-types of S₂O₈^2 −/ZnFe_xAl_2 − xO₄ solid acid catalysts were prepared by sol–gel method. Their catalytic performances for the synthesis of n-butyl acetate were investigated. The catalysts were characterized by means of XRD, IR, XPS, FT-IR of adsorbed pyridine and NH₃-TPD. The experimental results showed that S₂O₈^2 −/ZnFe_xAl_2 − xO₄ solid acid catalysts maintained the spinel structure as well as the support of ZnFe_xAl_2 − xO₄. Fe^3 + ions were well incorporated and highly dispersed into the spinel lattice. S₂O₈^2 −/ZnFe_0.15Al_1.85O₄ exhibited the maximum conversion of acetic acid with 98.2%. Moreover, S₂O₈^2 −/ZnFe_0.15Al_1.85O₄ showed better reusability, which remained above 72.7% conversion of acetic acid even after being used five times.     

Highest UV–vis transparency of MgAl2O4 spinel ceramics prepared by hot pressing with LiF

Reaction sintering of MgO and Al₂O₃ with addition of LiF as sintering additive was used to prepare MgAl₂O₄ spinel ceramic by hot pressing. The process parameter (temperature, pressure, dwell time), the stoichiometric ratio of MgO to Al₂O₃ and the selection of the alumina raw powder are equally important for highest transparency of the spinel ceramic. With this optimization highest transparency of 86% in the visible range at λ = 640 nm together with UV transmission of 62% at 200 nm for spinel ceramic with 4 mm thickness was reached.     

Investigation of slag-refractory interactions for the Ruhrstahl Heraeus (RH) vacuum degassing process in steelmaking

In order to determine the effect of slag composition during the RH process on refractory wear, magnesia–carbon and magnesia–chromite refractories were immersed for 10 min at 1600 °C in a ladle slag, two FeO-rich slags (20 and 40 wt% FeO) and two CaO–Al₂O₃ slags. Corrosion of magnesia–carbon refractory by the ladle and CaO–Al₂O₃ slags was limited as the refractory carbon phase efficiently prevented slag infiltration. Severe degradation was observed in contact with FeO-rich slags. FeO oxidized the carbon phase with formation of Fe droplets at the hot face. Regarding magnesia–chromite refractory, the corrosion mechanism consisted of severe slag infiltration, high temperature inactivation of the secondary chromite and primary chromite dissolution in the infiltrating slag. The FeO-rich slags seem to have generated more severe conditions as the infiltrating slag pushed apart the periclase grains, leading to severe refractory erosion. The degradation mechanisms are discussed by combining experimental results and thermodynamic calculations.     

Dissolution behavior of a novel Al2O3-SiC-SiO2-C composite refractory in blast furnace slag

Al₂O₃-SiC-SiO₂-C composite refractories are interesting potential blast furnace hearth lining materials that feature several advantageous properties. In this study, the corrosion resistance of a novel Al₂O₃-SiC-SiO₂-C composite refractory to blast furnace slag was investigated by adopting a rotating immersion method (25 r/min) at 1450–1550 °C and comparing it against a conventional corundum-based refractory at 1550 °C as a benchmark. The results showed that the apparent activation energy of Al₂O₃-SiC-SiO₂-C composite refractory over the dissolution process in the slag is 150.4 kJ/mol. Dissolution of the Al₂O₃ and 3Al₂O₃·2SiO₂ phases appeared to be the main cause of Al₂O₃-SiC-SiO₂-C composite refractory corrosion. High-melting-point compounds in the slag layer formed a protective layer which mitigated the corrosion. The novel Al₂O₃-SiC-SiO₂-C composite refractory is better suited to blast furnace hearth lining than the conventional corundum-based refractory, because the carbon phase and SiC phase in the material are not readily wetted by the blast furnace slag and therefore are more resistant to slag penetration. Higher melting point phases also may crystallize on the hot face of the hearth lining due to the high thermal conductivity of the Al₂O₃-SiC-SiO₂-C composite refractory, promoting a more stable protective layer.     

Hot bending strength and creep behaviour at 1000–1400 °C of high alumina refractory castables with spinel,periclase and dolomite additions

The modulus of rupture and creep behaviour of refractory castables at high temperature (1000–1400 °C) with additions of spinel, periclase and dolomite has been studied. Three processing routes for obtaining refractory concretes within the alumina-rich zone of the Al₂O₃–MgO–CaO ternary system were employed. To achieve high temperature mechanical properties special attention was paid to the processing route (synthetic spinel, periclase and dolomite additions), and the composition (effect of synthetic or self-forming spinel and CaO contents).The results demonstrate that these refractory castables show a highly viscoplasticity behaviour at temperatures >1100 °C and a hot bending strength depending on the loading rate. Refractory castables made with synthetic spinel have lower high temperature bending strength values than castables made with periclase additions owing to their less viscoplastic behaviour. In this work neither the amount of spinel nor processing route chosen were found to have any significant influence on the hot bending tests between 1100 and 1400 °C. The creep tests show that in the temperature range of 1100–1300 °C the main reaction governing deformation is the interaction between the alumina and the calcium aluminate cement phases. Above 1300 °C, castables made first with dolomite, then with periclase and finally with synthetic spinel are more prone to deformation in that order.     

Phase structure and electrochemical performance of layered-spinel integrated LiNi0.5Mn0.5O2-LiMn1.9Al0.1O4 composite cathodes for lithium ion batteries

In recent years, multi-component integrated composite cathodes for lithium ion batteries have attracted considerable attention. In this work, novel layered-spinel integrated cathode materials of (1−x)LiNi_0.5Mn_0.5O₂-xLiMn_1.9Al_0.1O₄ were synthesized by a sol-gel method, and their phase structures, morphologies and electrochemical performance were investigated. The crystal structure of the (1−x)LiNi_0.5Mn_0.5O₂-xLiMn_1.9Al_0.1O₄ is changed from layered to spinel structure with increasing x. All the samples exhibit nanoscale grains with the minimum grain size of ~130 nm when x = 0.5. The composite electrode with x = 0.5 exhibits the optimal discharge capacity, presenting a large initial discharge capacity of 236 mAh g⁻¹ at the current density of 20 mA g⁻¹. Good rate capability is also obtained at the composite electrode with x = 0.5 where the electrode displays the relatively high discharge capacity of 64.9 mAh g⁻¹ at the high rate of 5 C. The improved electrochemical performance is related to the introduction of spinel structure into layered structure and small grain size. The spinel structure can stabilize the layered structure, which leads to the improvement in the electrochemical performance of the composites; and the small grain size in the sample with x = 0.5 provides short lithium ion diffusion way and thus enhances the electrochemical performance.     

Electronic conductivity,oxygen permeability and thermal expansion of Sr0.7Ce0.3Mn1−xAlxO3−δ

The maximum solubility of aluminum cations in the perovskite lattice of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ is approximately 15%. The incorporation of Al³⁺ increases oxygen ionic transport due to increasing oxygen nonstoichiometry, and decreases the tetragonal unit cell volume and thermal expansion at temperatures above 600 °C. The total conductivity of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ (x = 0–0.2), predominantly electronic, decreases with aluminum additions and has an activation energy of 10.2–10.9 kJ/mol at 350–850 °C. Analysis of the electronic conduction and Seebeck coefficient of Sr_0.7Ce_0.3Mn_0.9Al_0.1O_3−δ, measured in the oxygen partial pressure range from 10⁻¹⁸ to 0.5 atm at 700–950 °C, revealed trends characteristic of broad-band semiconductors, such as temperature-independent mobility. The temperature dependence of the charge carrier concentration is weak, but exhibits a tendency to thermal excitation, whilst oxygen losses from the lattice have an opposite effect. The role of the latter factor becomes significant at temperatures above 800 °C and on reducing p(O₂) below 10⁻⁴ to 10⁻² atm. The oxygen permeability of dense Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ (x = 0–0.2) membranes, limited by both bulk ionic conduction and surface exchange, is substantially higher than that of (La, Sr)MnO₃-based materials used for solid oxide fuel cell cathodes. The average thermal expansion coefficients of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ ceramics in air are (10.8–11.8) × 10⁻⁶ K⁻¹.     

Influence of the structure of MgO·nAl2O3 spinel lattices on transparent ceramics processing and properties

It is demonstrated that a complete elimination of pores on sintering is governed not only by the size of the ceramic powder particles and by the homogeneity of their mutual coordination but similarly strongly by the state of the crystal lattice: with different cation disorder at fixed stoichiometry (n = 1) the sintering temperatures may differ by as much as 200 °C at constant powder particle size and equal homogeneity of the green bodies. Additionally, the impact of stoichiometry was investigated over the range between n = 1 and n = 3 with retarded reactive sintering at moderately increased Al₂O₃ concentrations but promoted densification of alumina-rich compositions. Taking advantage of the observed effects, sintered spinel ceramics were derived by reactive sintering of undoped MgO/Al₂O₃ mixtures resulting in an in-line transmittance which equals spinel single crystals of similar composition from 200 nm wave length up to the IR range.     

Crystallisation of amorphous spray-dried precursors in the Al2O3–SiO2 system

The crystallisation of amorphous precursors has been studied in the whole range of composition in the Al₂O₃–SiO₂ system. The amorphous precursors have been obtained by hydrolysing TEOS directly in a diluted aqueous solution of aluminium nitrate, spray drying the clear solution and heating the resulting powder. Up to 70 mol % Al₂O₃, only mullite crystallises around 980–1000 °C; between 70 and 80 mol % Al₂O₃ mullite and spinel crystallise together; and for more than 80 mol % Al₂O₃ only spinel is formed. In the 70–80 mol % Al₂O₃ range of composition, when both mullite and spinel crystallise, low heating favours the crystallisation of mullite and it is nearly possible to crystallise only mullite from a 75 mol % Al₂O₃ sample. By rapid heating it is also possible to crystallise only spinel from the same 75 mol % Al₂O₃ precursor. The enthalpy and the activation energy for crystallisation are maximum for 60–80 mol % Al₂O₃. Heating the samples up to 1700 °C for 1 h, the phase equilibrium is not reached, particularly when both mullite and spinel crystallise together, and θ-Al₂O₃ is still present.     

Dilatometric sintering study of fine-grained ceramics from ultradispersed admixture composed of Ce0.09Zr0.91O2 and MgO–Al2O3

The experiment was carried out to produce fine-grained ceramics with a grain size of less than 5 μm. Ultradispersed oxide mixture MgO–Al₂O₃ (weight ratio MgO/Al₂O₃ value was 3/97) and solid solution Ce_0.09Zr_0.91O_2?δ were used as initial nanopowders with a crystallite size less than 10 nm. Dilatometric investigation was carried out at the temperature interval 1100–1550 °C using three temperature modes, included various heating and cooling rates and isothermal plots. Initial metal oxide powders were obtained by modified sol–gel technique using N-containing organic compounds for sol stabilization. It was shown that the role of MgO in nanopowdery composition for sintering is to accelerate the sintering due to the formation of the liquid phase with spinel MgAl₆O₁₀. It was determined, that the presence of interim isotherms on the temperature rise curves does not impact the rate and quality of sintering.     

Microwave dielectric properties and cation distributions of Zn1-3xAl2+2xO4 ceramics with defect structures

The spinel-structured Zn_1-3xAl_2+2xO₄ (x = 0–0.2) ceramics having defective structures were synthesized using the molten salt method, and their microwave dielectric properties and cation distributions were assessed. The ²⁷Al solid-state nuclear magnetic resonance spectra of these ceramics demonstrate that they have an intermediate spinel structure in which the tetrahedral site occupancy increases from 0.03 to 0.64 as x increases. Moreover, crystal structure refinements suggest that cation vacancies are located at octahedral sites for x = 0.1 and 0.2. Based on these data, the introduction of cation vacancies at octahedral sites appears to enhance the preferential occupation of tetrahedral sites by Al³⁺. The ε_r of these ceramics slightly decreased from 8.5 to 8.2 with increasing x, while the Q·f value increased significantly, from 127,532 to 202,468 GHz, upon the introduction of cation vacancies. An intermediate spinel structure with preferential occupancy of tetrahedral sites by trivalent cations exhibits an enhanced Q·f value.     

Synthesis and characterization of a MgO-MgAl2O4-ZrO2 composite with a continuous network microstructure

Using analytically pure MgO, analytically pure Al₂O₃ and analytically pure ZrO₂ as raw materials, Mg_4.68Al_2.64Zr_1.68O₁₂ was prepared at 1993 K for 10 h, and then, a MgO-MgAl₂O₄-ZrO₂ composite with a continuous network was successfully obtained by controlling the cooling rate based on the in-situ decomposition reaction of Mg_4.68Al_2.64Zr_1.68O₁₂ at temperatures below 1887 K. The three phases of MgO, MgAl₂O₄ and ZrO₂ are highly dispersed in this continuous network microstructure, with ZrO₂ intertwined by MgO and MgAl₂O₄ and micropores with a size of less than 2 µm. Furthermore, the synthesis mechanism of Mg_4.68Al_2.64Zr_1.68O₁₂ is given as follows: first, MgAl₂O₄ is synthesized using the reaction: MgO(s)+Al₂O₃(s)=MgAl₂O₄(s) at temperatures below 1894 K; and then, Mg_4.68Al_2.64Zr_1.68O₁₂ is further prepared through MgO and ZrO₂ diffusion and dissolution into MgAl₂O₄ at temperatures above 1894 K, for example, at 1923 K or 1993 K in this work.     

Blue pigments based on CoxZn1−xAl2O4 spinels synthesized by the polymeric precursor method

The Co_xZn_1?xAl₂O₄ system (x = 0; 0.1; 0.3; 0.5; 0.7; 0.9 and 1) was synthesized by the polymeric precursor method and characterized by the techniques XRD, TG-DTA, IR, UV–vis and colorimetry. The XRD patterns displayed the characteristic peaks of the spinel structure and a good crystallinity. The DTA curves showed an exothermic peak corresponding to the enthalpy of the transition taking place at about 700 °C. The infrared spectra displayed vibrations at about 650, 550, 540, 520, 500, 490 cm^?1, which were ascribed to the spinel structure. The UV–vis spectra presented three bands at 550, 580 and 620 nm attributed to the Co²⁺ spin transitions in tetrahedral sites. The colorimetric data point out the formation of blue pigments, corresponding to highly negative values of b¹. The lightness, coordinate L¹, increases with the heat treatment temperature. These facts reveal that Co_xZn_1?xAl₂O₄ is a promising system that can be employed to obtain ceramic blue pigments.     

High-temperature thermoelectric properties of polycrystalline Zn1−x−yAlxTiyO ceramics

The as-sintered Zn_1−xAl_xO (0 ≤ x ≤ 0.05) samples crystallized in the ZnO with a wurtzite structure, along with a small amount of the cubic spinel ZnAl₂O₄. The addition of Al₂O₃ to ZnO gave rise to a decrease in grain size, ranging from 7.3 to 2.7 μm and in relative density, ranging from 99.2 to 90.1% of the theoretical density. In the Zn_0.97Al_0.03−yTi_yO samples, as the amount of TiO₂ increased, the grain size of ZnO grains and second phases, such as Zn₂TiO₄ and ZnAl₂O₄, as well as density increased. The co-doping of Al and Ti led to a significant increase in both the electrical conductivity and the absolute value of the Seebeck coefficient, resulting in an increase in the power factor. The highest value of power factor (3.8 × 10⁻⁴ W m⁻¹ K⁻²) was attained for Zn_0.97Al_0.02Ti_0.01O at 800 °C. It is demonstrated that the Al and Ti co-doping is fairly effective for enhancing thermoelectric properties.     

High-temperature conductivity,stability and redox properties of Fe3−xAlxO4 spinel-type materials

Iron-based oxides are considered as promising consumable anode materials for high temperature pyroelectrolysis. Phase relationships, redox stability and electrical conductivity of Fe_3?xAl_xO₄ spinels were studied at 300–1773 K and p(O₂) from 10^?5 to 0.21 atm. Thermogravimetry/XRD analysis revealed metastability of the sintered ceramics at 300–1300 K. Low tolerance against oxidation leads to dimensional changes of ceramics upon thermal cycling. Activation energies of the total conductivity corresponded to the range of 16–26 kJ/mol at 1450–1773 K in Ar atmosphere. At 1573–1773 K and p(O₂) ranging from 10^?5 to 0.03 atm, the total conductivity of Fe_3?xAl_xO₄ is nearly independent of the oxygen partial pressure. The conductivity values of Fe_3?xAl_xO₄ (0.1 ≤ x ≤ 0.4) at 1773 K and p(O₂) ～10^?5 to 10^?4 atm were found to be only 1.1–1.5 times lower than for Fe₃O₄, showing high potential of moderate aluminium additions as a strategy for improvement of refractoriness for magnetite without significant deterioration of electronic transport.     

Synthesis,structure and oxygen thermally programmed desorption spectra of La1−xCaxAlyFe1−yO3−δ perovskites

Perovskites La_1−xCa_xAl_yFe_1−yO_3−δ (x, y = 0 to 1) were prepared by high-temperature solid-state synthesis based on mixtures of oxides produced by colloidal milling. The XRD analysis showed that perovskites La_0.5Ca_0.5Al_yFe_1−yO_3−δ with a high Fe content (1 − y = 0.8–1.0) were of orthorhombic structure, perovskites with a medium Fe content (1 − y = 0.8–0.5) were of rhombohedral structure, and perovskite with the lowest Fe content (1 − y = 0.2) were of cubic structure. Thermally programmed desorption (TPD) of oxygen revealed that chemical desorption of oxygen in the temperature range from 200 to 1000 °C had proceeded in the two desorption peaks. The low-temperature α-peak (in the 200–550 °C temperature range) was brought about by oxygen liberated from oxygen vacancies; the high-temperature β-peak (in the 550–1000 °C temperature range) corresponded to the reduction of Fe⁴⁺ to Fe³⁺. The chemidesorption oxygen capacity increased with increasing Ca content and decreased with increasing Al content in the perovskites. The Al³⁺ ions restricted, probably for kinetic reasons, the reduction of Fe⁴⁺ and the high-temperature oxygen desorption associated with it.     

Catalytic properties in N2O decomposition of mixed cobalt–iron spinels

The effect of introduction of iron in the Co_3 − xFe_xO₄ on catalytic activity in N₂O decomposition was investigated. The spinel catalysts were characterized by XRD, SEM, RS, BET methods, work function measurements and Mössbauer spectroscopy. Introduction of iron in the Co_3 − xFe_xO₄ spinel catalysts at the level of x < 1 leads to preferential substitution of Fe³⁺ in tetrahedral sites, whereas for x > 1 also octahedral ones are substituted. A strong correlation between deN₂O activity (T_50%) and work function was observed showing that electronic factor controls the catalytic reactivity of Co–Fe spinels. The results revealed that the active centers for N₂O decomposition are cobalt ions and thus even a low level of their substitution by iron leads to substantial decrease of the deN₂O activity of the cobalt spinel.