Corrosion mechanism of magnesia-chrome refractory bricks with FetO-SiO2-Cr2O3 copper converter slag

The paper investigates the effect of Cr₂O₃ on the resistance of magnesia-chrome refractory bricks to copper converter slag. The static crucible method was employed to carry out the slag resistance experiment. The corrosion of magnesia-chrome refractory bricks under the action of Fe_tO-SiO₂-xCr₂O₃ (x = 0–5 wt%) slag at 1300 °C was discussed. The microstructure of the corroded sample was analyzed by XRD and SEM-EDS to elucidate the corrosion mechanisms of magnesia-chrome refractory bricks with Fe_tO-SiO₂-Cr₂O₃ slag. The results indicated that the permeability index of the slag-resistant samples gradually decreased with increasing Cr₂O₃ content in the Fe_tO-SiO₂-Cr₂O₃ slag. Combined with SEM and XRD characterization, the MgO in the refractory reacted with FeO and SiO₂ in the molten slag, leading to dissolution and reaction corrosion of the refractories. Meanwhile, forming a (Mg, Fe)O solid solution layer in corroded samples can prevent further chemical reactions and high-temperature dissolution between the Fe_tO-SiO₂-Cr₂O₃ slag and refractories. With the addition of Cr₂O₃ in the Fe_tO-SiO₂-Cr₂O₃ slag, the corrosion effect of slag on refractories was weakened, and the (Mg, Fe)O solid solution layer became thinner. The magnesia-chrome refractory bricks showed excellent slag resistance when the Cr₂O₃ content in the copper converter slag was 5 wt%.     

Corrosion resistance of Al–Cr-slag containing chromium–corundum refractories to slags with different basicity

Al–Cr slag is the solid waste generated by the smelting of Cr metal. It presents a range of environmental hazards. This study addressed the corrosion resistance of Al–Cr slag containing chromium–corundum refractories to slags with different basicity. Herein, we provide suggestions for the use of Cr–corundum of different basicity in kilns. Al–Cr slag, brown fused Al₂O₃, and chrome green were used as the raw materials, with pure calcium aluminate cement being used as a binder. The brick samples, prepared using different blends of chrome green and corundum, were fired at 1600?°C, and subsequently subjected to a slag corrosion test. After corrosion by slag of different basicity, the phase composition and microstructure of the sample were analyzed by X-ray diffraction, energy dispersive spectrometer and scanning electron microscopy. There were two major findings. First, Cr–corundum brick made from Al–Cr slag has a better slag corrosion resistance than that made from Cr₂O₃ and brown fused Al₂O₃. Second, Cr–corundum brick made from Al–Cr slag has superior corrosion resistance to slag with a CaO:SiO₂ ratio of 2:1.     

The microstructures and properties of Fe2O3 and TiO2 co-doped corundum ceramics for solar thermal absorbing materials

Solar thermal absorbing materials are the key components of concentrating solar power. In this study, Fe₂O₃ and TiO₂ co-doped corundum ceramics were prepared by pressureless sintering. The effects of different Fe₂O₃/TiO₂ ratios on the phase composition, microstructure, thermal shock resistance and solar absorptance were investigated via XRD and EPMA testing. The results showed that, with the decrease of Fe₂O₃/TiO₂ ratio, the appropriate amount of FeAlTiO₅ would decompose into ferrite particles, which played a bridging role between the corundum grains making the samples have excellent thermal shock resistance. A6 (90% bauxite, 9.5% Fe₂O₃ and 0.5% TiO₂) sintered at 1460 °C had the optimum comprehensive properties, with a bending strength of 154.80 MPa and an absorptance of 89.20% in the spectral range from 0.3 to 2.5 μm. After 30 thermal shock cycles (1000 °C–25 °C, air-cooled), the bending strength of A6 was 222.05 MPa, and the absorptance was 90.40%, which were 43.44% and 1.35% higher than those before thermal shock, respectively. Therefore, it was suitable as an excellent solar thermal absorbing materials.     

Phase formation,microstructure development,and mechanical properties of kaolin-based mullite ceramics added with Fe2O3

The effects of Fe₂O₃ on phase evolution, density, microstructural development, and mechanical properties of mullite ceramics from kaolin and alumina were systematically studied. X-ray diffraction results suggested that the ceramics consisted of mullite, sillimanite, and corundum, in the sintering range of 1450°C–1580°C. However, as the sintering was raised to 1580°C, mullite is the main phase with a content of 94%, and the corundum phase content is 5.9%. Simultaneously, high-temperature sintering had a positive effect on the densification of the mullite ceramics, where both the bulk density and flexural strength could be optimized by adjusting the content of Fe₂O₃. It was found that 6 wt% Fe₂O₃ was optimal for the formation of rod-shaped mullite after sintering at 1550°C for 3 h. The sample's maximum bulk density was 2.84 g/cm³, with a flexural strength of 112 MPa. Meanwhile, rod-shaped mullite grains with an aspect ratio of ~9 were formed. As a result, a dense network structure was developed, thus leading to mullite ceramics with excellent mechanical properties. The effect of Fe₂O₃ on the properties might be attributed to the fact that Al³⁺ ions in the [AlO₆] octahedron were replaced by Fe³⁺ ions, resulting in lattice distortion.     

Corrosion mechanism of MgAl2O4–CaAl4O7–CaAl12O19 composite by steel ladle slag: Effect of additives

Corrosion behaviors and corroded microstructures of MgAl₂O₄-CaAl₄O₇-CaAl₁₂O₁₉ composites containing various additives (ZrO₂ and TiO₂) against steel ladle slag (containing CaF₂) were investigated using a reaction test method at 1600 °C. Thermodynamic calculation, based on the Al₂O₃–CaO–MgO phase equilibrium diagram was used to further reveal the corrosion mechanism. The attack of the liquid slag on the composite substrate was found to take place through an interdiffusion mechanism, producing the precipitation of spinel in the slag and a continuous layer of calcium dialuminate at the interface. This composite showed a high total corrosion depth due to the high porosity of the substrate and the high fluidity of the slag. Fortunately, the addition of ZrO₂ and TiO₂ can greatly improve the slag corrosion resistance by increasing the viscosity of the slag at an earlier stage. Besides, the highly dense microstructures also improved the corrosion resistance against the liquid slag, and thus suppressed the slag penetration. It was also found that the CA₆ grains with low aspect ratios are more difficult to be wetted and dissolved by the slag.     

Effect of different corundum sources on microstructure and properties of Al2O3–Cr2O3 refractories

Al₂O₃–Cr₂O₃ refractories are completely substitutional solid solutions and exhibit better corrosion and abrasion resistance. To enable the comprehensive utilization of it, the microstructure and properties of Al₂O₃–Cr₂O₃ samples with different corundum sources were investigated in this study. The starting sources of corundum sources included sintered tabular corundum, fused white corundum, or brown corundum with minor impurities of β-Al₂O₃ and TiO₂. The results of mechanical test showed that the introduction of white corundum deteriorates the physical structure, while brown corundum acts in an opposite manner. The optimum bonding strength of the Al₂O₃–Cr₂O₃ brick was reached by combining white and brown corundum, whereby rapid neck growth occurred via surface diffusion during solid-phase sintering.     

Integrated experimental phase equilibria study and thermodynamic modelling of the binary ZnO–Al2O3, ZnO–SiO2, Al2O3–SiO2 and ternary ZnO–Al2O3–SiO2 systems

Phase equilibria of the ZnO–SiO₂, Al₂O₃–SiO₂ and ZnO–Al₂O₃–SiO₂ systems at liquidus were characterized at 1340–1740 °C in air. The ZnO–Al₂O₃ subsolidus phase equilibria were derived from the experiments with the SiO₂- and CaO + SiO₂-containing slags. High-temperature equilibration on silica or platinum substrates, followed by quenching and direct measurement of Zn, Al, Si and Ca concentrations in the phases with the electron probe X-ray microanalysis (EPMA) was used to accurately characterize the system. Special attention was given to zincite phase that was shown to consist of two separate ranges of compositions: round-shaped low-Al zincite (<2 mol.% AlO_1.5) and platy high-Al zincite (4–11 mol.% AlO_1.5). A technique was developed for more accurate measurement of the ZnO solubility in the low-ZnO phases (corundum, mullite, tridymite and cristobalite) surrounded by the ZnO-containing slag, using l-line for Zn instead of K-line, avoiding the interference of secondary X-ray fluorescence. Solubility of ZnO was found to be below 0.03 mol.% in corundum and cristobalite, and below 0.3 mol.% in mullite. Present experimental data were used to obtain a self-consistent set of parameters of the thermodynamic models for all phases in this system using FactSage computer package. The modified quasichemical model with two sublattices (Zn²⁺, Al³⁺, Si⁴⁺) (O^2?) was used for the liquid slag phase; the compound energy formalism was used for the spinel (Zn²⁺,Al³⁺)[Zn²⁺,Al³⁺,Va]₂O^2-₄ and mullite Al³⁺₂(Al³⁺,Si⁴⁺) (O^2?,Va)₅ phases; the Bragg-Williams formalism was used for the zincite (ZnO, Al₂O₃); other solid phases (tridymite and cristobalite SiO₂, corundum Al₂O₃, and willemite Zn₂SiO₄) were described as stoichiometric. Present study is a part of the research program on the characterization of the multicomponent Pb–Zn–Cu–Fe–Ca–Si–O–S–Al–Mg–Cr–As–Sn–Sb–Bi–Ag–Au–Ni system.     

Preparation and characterization of corundum ceramics doped with Fe2O3 and TiO2 for high temperature thermal storage

High-temperature thermal storage materials have received urgent attention for efficient thermal transfer in solar thermal power generation. Corundum ceramics doped with Fe₂O₃ and TiO₂ were prepared via a pressureless sintering. A Fe₂O₃–TiO₂ system with different Fe₂O₃/TiO₂ ratios was applied to corundum ceramics. Phase composition, microstructural evolution, sintering properties, high temperature resistance and thermophysical properties were evaluated. The results indicated that Fe₂O₃ and TiO₂ rendered the grains highly active and enhanced the bonding between grains due to existing stably in the lattice of corundum. In addition, decrease in the Fe₂O₃/TiO₂ ratio led to a new phase of FeAlTiO₅, which refined the grains. These effects gave the samples good sintering properties and thermal shock resistance, but the thermal expansion coefficient mismatch between FeAlTiO₅ and corundum deteriorated the high-temperature (1300 °C) stability. Formula C1 (Fe₂O₃/TiO₂ ratio of 9:1) sintered at 1600 °C had the optimum comprehensive properties, possessing a bending strength loss rate of 1.54% after 30 cycles of thermal shock (1100 °C-room temperature, air cooling) and a constant strength retention rate of approximately 71.34% after 90 h high-temperature cycle. The corresponding thermal conductivity and specific heat capacity were 18.81 W/(m·K) and 1.02 J/(g·K) at 25 °C, which was suitable as a high-temperature thermal storage material.     

Effect of partial substitution of alumina–chromium slag for Al2O3 on microstructures and properties of Al2O3–SiC–C trough castables

Alumina–chromium slag (ACS), a cheap and abundant refractory raw material comprising aluminum–chromium oxides and β-Al₂O₃, is a byproduct of ferrochrome smelting. For this reason, we investigated the relationships between composition and mechanical properties, abrasion resistance, oxidation resistance, and resistance to iron slag erosion for Al₂O₃–SiC–C trough castables in which ACS was substituted for alumina. Due to the presence of β-Al₂O₃ in ACS, the aluminum-chromium slag reacted with SiO₂ to form a low-melting phase of albite and promoted the formation of mullite, which filled the pores at high temperatures and reduced the porosity, thereby promoting densification and strengthening of the sample. The cold mechanical properties of the sample and the normal temperature wear resistance were enhanced, but the high-temperature mechanical properties and the resistance to iron slag corrosion of the sample were impaired. According to the results of the anti-oxidation experiment, the presence of β-Al₂O₃ in the ACS reduced the porosity and made the sample more dense, which remarkably improved oxidation resistance of the sample. For industrial production requirements, ACS substitution should not exceed 48?wt% due to of thermomechanical properties and anti-slag corrosion performance in Al₂O₃–SiC–C trough castables.     

Enhanced performance of low-carbon MgO–C refractories with nano-sized ZrO2–Al2O3 composite powder

Low-carbon MgO–C refractories are facing great challenges with severe thermal shock and slag corrosion in service. Here, a new approach, based on the incorporation of nano-sized ZrO₂–Al₂O₃ composite powder, is proposed to enhance the thermal shock resistance and slag resistance of such refractories in this work. The results showed that addition of ZrO₂–Al₂O₃ composite powder was helpful for improving their comprehensive performances. Particularly, the thermal shock resistance of the specimen containing 0.5 wt% composite powder was enhanced significantly which was related to the transformation toughening of zirconia and in-situ formation of more spinel phases in the matrix; also, the slag resistance of the corresponding specimen was significantly improved, which was attributed to the optimization of pore structure and formation of much thicker MgO dense layer.     

Chemical attack of Al2O3-MgAl2O4 refractory castables in the non-slag-tapping side of refining ladle

In the present work, chemical attacks and corrosion behaviors of a used Al₂O₃-MgAl₂O₄ refractory castable in the non-tapping slag side of a refining ladle were investigated and also compared with that of the counterpart (in the tapping slag side). Corrosion microstructures revealed the stress cracks occurred on the corroded interface and just along the boundary between the infiltration layer and original layer, indicating the thermo-mechanical properties’ mismatch above those two layers was the main reason for the formation of cracks on the corroded interface. Furthermore, the corrosion process of Al₂O₃ aggregates on the interface was studied in detail, and an intergranular mechanism was proposed based on observed microscopic characteristics.     

Slag Resistance Mechanism of Lightweight Microporous Corundum Aggregate

The microstructures of the reaction interfaces between slag and corundum aggregates, microporous corundum produced in the laboratory and tabular corundum were observed after slag resistance experiments, and their associated slag resistance mechanisms were investigated. A continuous isolation layer was observed around the microporous corundum, which showed a significantly better slag resistance than tabular corundum. The formation of columnar crystals of CaAl₁₂O₁₉ (CA₆) and CaAl₄O₇ (CA₂) in the isolation layer was the main reason for the difference in slag resistance. With respect to the nucleation and growth of second phase, the slag resistance mechanism of lightweight microporous corundum was explored by thermodynamic and kinetic analysis. Due to its smaller pore size, the second phase is more likely to achieve supersaturation, and large quantities of crystal nuclei are generated for microporous corundum. The critical dissolved depths of the microporous and tabular corundum in saturated slag were calculated to be 0.14 and 0.27 μm, respectively. Additionally, the small pore sizes lead to an increase in the Ostwald ripening rate of the second phase, and the Ostwald ripening rate of microporous corundum was 12 times that of the tabular corundum based on Ardell's theory.     

Analysis of corrosion of corundum refractory castables in relation to increased MgO content in dendromass ashes

Biomass ash has a significantly lower proportion of Al₂O₃ and higher proportions of K₂O, CaO and SiO₂ than coal ash. Biomass combustion in power plants increases demands on refractory linings and metal fittings in boilers. Grates and linings of combustion chambers in furnaces and boilers are more susceptible to clogging and are degraded by bio-ash slag. The results of this study suggest that the addition of approximately 2% of powder magnesite waste to the wood-chip fuel can significantly mitigate ash slagging and also corrosion of the corundum refractory material. With regard to the resulting increased MgO content in the dendromass ash, the corrosion of corundum refractory material was studied. The MgO content in the ash was increased by adding powder magnesite waste to ash samples. The results of corrosion tests (1450 °C/7 h) showed that ash slag with MgCO₃ addition corroded the corundum material less. Analyses of the post-mortem slag and corrosion interface confirmed: (i) higher K₂O concentration in the ash caused increased corundum material corrosion by both vapours (g-s) and melt (l-s); (ii) K₂O reacted with Al₂O₃ at the corrosion interface and also penetrated intensively into the fine-grain matrix by surface diffusion; (iii) MgO remained in the slag; (iv) increased Al₂O₃ content in the molten slag initiated a liquation of MA-spinel. These results (especially MA spinel liquation from the slag and K₂O diffusion through the matrix followed by micro-grain dissolution) indicate that replacing the mullite binder phase in the matrix with MgO and/or spinel could lead to improved resistance of the refractory material to biomass ash slag.     

Synthesis and Properties of Fusion-Cast Refractories in the MgO – Al2O3 System

Results of a study of fusion-cast refractories in the MgO – Al₂O₃ high-alumina system are reported. A casting technology for spinelide refractories is proposed. The materials synthesized are analyzed for phase composition by x-ray diffractometry and petrography and are shown to consist of corundum, MgAl₂O₄ spinel and their solid solutions. The materials are tested for corrosion resistance in industrial glass melts, and a corundum spinelide material with 5% Mg is recognized as the most promising for practical use.     

Effect of in situ formation of Ti(C,N) on the properties of Al2O3–ZrO2–C slide plate material

Al₂O₃–ZrO₂–C slide plate was ordinarily used in sliding nozzle system because of its excellent mechanical properties and slag corrosion resistance. This study improved the slag corrosion resistance of the slide plate by the carbothermic reduction of TiO₂ and aluminothermic reduction of TiO₂ under high temperature in coke bed to generate Ti(C,N) phase in situ. The result revealed that TiC of the high melting point phase could enter into anorthite (CaAl₂Si₂O₈) of the low melting point phase, forming eutectic phase CaAl₂Si₂O₈–TiC, and improve the viscosity of the slag. Furthermore, TiC and CaAl₂Si₂O₈ captured FeO and MnO from the slag, resulting in the increase of the slag viscosity, inhibiting the penetration corrosion of the slag, and improving the slag corrosion resistance of the materials. In general, compared with the material without TiO₂ powder, the slag corrosion resistance of the material introduced 2 wt.% TiO₂ powder was increased by 24%. Meanwhile, the cold crushing strength of fired specimen at room temperature was increased by 35.6%.     

Effect of atmosphere control on magnetic properties of CaO-Al2O3-SiO2-Fe3O4 glass ceramics

The influences of atmosphere during processes of melting and heat treatment, heat treatment temperature, Fe₃O₄ content and basicity on the magnetic properties of magnetite-based glass ceramics were investigated. For sample containing 20 % Fe₃O₄ melted in different atmospheres, the highest saturation magnetisation was realized in 20vol% air + 80 vol% Ar, due to the fact that ratio of Fe³⁺ to Fe²⁺ in melt obtained in this atmosphere was close to 2. However, it was found that the coercivity of glass ceramics was not affected by the melting atmosphere. A high sintering temperature led to the decrease of saturation magnetisation and the increase of coercivity. As increasing Fe₃O₄ content, the main crystal phase transformed from CaSiO₃ to CaFe_0.6Al_1.3Si_1.08O₆ and finally to magnetite phase, accompanied by the increase of saturation magnetisation and coercivity. In addition, the increase of basicity caused the decrease of saturation magnetisation and the increase of coercivity.     

A comparative study on the slag resistance of dense corundum-spinel refractory and lightweight corundum-spinel refractory with density gradient

Lightweight corundum-spinel refractory with a density gradient structure from exterior to interior was fabricated. Slag resistance of lightweight and dense corundum-spinel refractory is investigated by X-ray diffraction, scanning electron microscopy, energy dispersive analysis, mercury intrusion porosimetry and Factsage. The results show that lightweight corundum-spinel refractory with high apparent porosity exhibits comparable slag resistance to dense corundum-spinel refractory, especially with superior slag penetration resistance. The dense exterior with small pore size in the lightweight corundum-spinel refractory can effectively hinder slag penetration. Corrosion product phases (C₂S, CA₂, CA₆, and C₂M₂A₁₄) with high melting point and inconsistent melting temperature, most of Fe and Mn elements in steel slag solubilizing in spinel, especially strip CA₆ around corundum aggregate, prevent the refractory from further slag penetration and corrosion.     

Effect of applied voltage on wetting and corrosion of corundum refractory by CaO–SiO2–MgO molten slag

The wetting and corrosion behavior of the corundum substrate anode by CaO–SiO₂–MgO molten slag was investigated via the joint application of the sessile drop method with applied voltage and SEM-EDS technique. The slag drop exhibited a good wettability on the corundum substrate. The apparent contact angle at zero voltage slightly exceeded that at a 1 V applied voltage but was lower than those at 1.5 V and 2 V ones. Low applied voltage of 1 V had little effect on the corundum substrate's direct dissolution corrosion processes; high ones of not less than 1.5 V caused the electrode reaction to occur. The stirring effect of O₂ bubbles from the anode reaction aggravated the substrate's direct dissolution and physical stripping. It was found that the applied voltage could inhibit the slag penetration, and the apparent contact angle had no obvious relation with the direct dissolution thickness and penetration depth. A thin but almost continuous MgO?Al₂O₃ (MA) layer could form at the slag/substrate interface at the applied voltage of 1.5 V. These results indicate the positive effect of applied voltage on the distribution of interfacial products and the molten slag penetration in reducing the corrosion of corundum anode under certain conditions. However, when the applied voltage was too high, the vigorous electrode reaction could aggravate the direct dissolution and physical stripping of the corundum anode, and damage the continuation of the formed interface product layer with a high melting point.     

Corrosion resistance and anti-reaction mechanism of Al2O3-based refractory ceramic under weak static magnetic field

A slag resistance experiment of the Al₂O₃-based refractory ceramic with CaO–Al₂O₃–SiO₂ slag at 1600°C under a milli-Tesla static magnetic field was conducted. The magnetic flux density effect on the corrosion at the two- and three-phase interfaces of the Al₂O₃-based refractory ceramic, excluding the ‘electromagnetic damping’, was studied. The slag resistance of the Al₂O₃-based refractory was enhanced and quasi-volcanic corrosion at the three-phase interface was eliminated gradually with an increase in the magnetic flux density. A hypothesis and mechanism for the inhibition effect of the static magnetic field based on the free radical pair reaction model was proposed.     

An approach for matrix densification based on particle packing and its effect on lightweight Al2O3-MgO castables

For lightweight refractory containing lightweight aggregates, the properties of the matrix are decisive to its performance. In the present work, Dinger–Funk equation was adopted to calculate the theoretical packing density of a castables matrix based on Stovall linear packing model and to design its particle size distribution. Four lightweight Al₂O₃-MgO castables with different particle size distribution (represented by q-value) were prepared and examined. Results show that a suitable q-value was needed to ensure acceptable properties including sintering characteristics, strength and slag resistance, which deteriorated distinctly at high q (>=0.31). For the sample with q=0.28, the matrix showed dense and uniform mirostructure, and the properties of castable reached a favourable compromise among sintering characteristics (apparent porosity=14.8%, bulk density=3.02 g cm⁻³, permanent linear change<0.6%), strength (cold modulus of rapture=12.4 MPa, cold crashing strength=155.5 MPa), and resistance against both slag corrosion (I_c=22.4%) and penetration (I_p=11.5%). The sample with q=0.25 showed the highest strength and resistance against slag corrosion (matrix dissolved in slag), but its slag penetration resistance was lower due to the existence of cracks between aggregates and matrix.