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 optimization of the microstructure and phase assemblage of high chromia refractories

The effect of Al₂O₃ and ZrO₂ addition in chromia-based refractories was investigated. The strength of ZrO₂-bearing chromia refractories was greatly enhanced by 4–8 wt% Al₂O₃ additive. In the range of 0–12 wt% ZrO₂ addition, 6 wt% ZrO₂ was most beneficial to the improvement in thermal shock resistance. Corrosion resistance was compared by exposing to three kinds of coal slag with various CaO contents. As the substitution of ZrO₂ for Cr₂O₃ increased, slag penetration increased, particularly in the case of the slag containing ∼16 wt% CaO. Considering the trade-offs between corrosion resistance, thermal shock resistance and mechanical properties, the optimum phase assemblage of high chromia refractories consists of the large granular Cr₂O₃ grains bonded by annular (Cr, Al)₂O₃ grains and well-distributed fine ZrO₂ grains.     

Cast refractories of the Al2O3-Cr2O3-CaO system

Conclusions In order to develop stable materials for glassmaking, we studied the physical and technological properties of the refractories belonging to the Al₂O₃-Cr₂O₃-CaO system that contain 5–20% CaO, 15–35% Cr₂O₃ and 45–80% Al₂O₃.The glass resistance of the refractories of the experimental systems (compositions) exceeds that of the BKCh-33 baddeleyite-corundum products by 3–5 times and their thermal shock resistance is superior to that of the well known chromium-containing refractories at comparable levels of mechanical properties.The developed refractories are recommended for the top or the bottom structures of the glassmaking furnaces depending on their glass resistance and thermal shock resistance and for making the refractory components of ferrous metallurgical units that are in contact with highly basic slags.Translated from Ogneupory, No. 3, pp. 23–26, March, 1989.     

The reaction between the magnesia–chrome brick and the molten slag of MgO–Al2O3–SiO2–CaO–FetO and the resulting microstructure

The reaction and microstructure at the interface of MgO–Cr₂O₃ brick and the molten slag of MgO–Al₂O₃–SiO₂–CaO–Fe_tO after static slag corrosion at 1823–1923 K for various times and the resulting microstructure were investigated and characterized. After the static slag corrosion at 1923 K for 4 h, the XRD results show the major phases of periclase MgO, MgCr₂O₄ spinel, and CaMgSiO₄ as the minor phase. MgCr₂O₄ phase causes MgO to form a discontinuous phase in MgO–Cr₂O₄ brick. After static slag corrosion at 1923 K for 4 h, SEM micrographs show that brick interior cracks, MgO and dissolved MgO. MgO dissolved due to the molten plag penetrated into the brick interior and reaction with it, leading to a localized dissolution of brick slag. TEM micrographs and ED patterns demonstrate that the minor phase of (Mg, Fe)(Al, Cr)₂O₄ precipitates in the MgCr₂O₄ matrix.     

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%.     

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.     

Slag resistance mechanism of CaO·6Al2O3 refractory and its effect on inclusions of aluminum deoxidized steel

In order to verify the advantage of CaO·6Al₂O₃ (CA₆)-based refractories on the inclusions of aluminum deoxidized steel, the five refractories, CA₆, alumina, spinel, and CA₆-alumina and CA₆-spinel composition refractories were prepared into crucibles, and then the laboratory smelting experiments were conducted. After experiment, the slag resistance of the crucible and the variation on inclusions in steel were characterized and discussed. A dense CaO·2Al₂O₃ (CA₂) layer, which was produced by CA₆ reacting with the slag, was distributed between the original bricklayer and the slag layer, improving the slag resistance of refractories. Meanwhile, the 12CaO·7Al₂O₃ (C₁₂A₇), generated by the reaction between CA₂ and refining slag, would release much Ca into the molten steel. The Ca would react with inclusions to produce low melting point substance to float up and remove, contributing to the reduction of the proportion of large size inclusions. In addition, typical inclusions in steel smelted with CA₆ crucible were small-sized MgO·Al₂O₃ inclusions, whereas those of other crucibles are MnS–MgO·Al₂O₃ composite inclusions with MgO·Al₂O₃ as the core, implying CA₆ may absorb sulfur during the smelting process.     

Comparative evaluation investigation of slag corrosion on Al2O3 and MgO-Al2O3 refractories via experiments and thermodynamic simulations

Al₂O₃- and MgO-based refractories are widely used in the steel industry as lining materials for many metallurgical reactors. Due to their direct contact with slag and steel, they suffer corrosion and degradation, especially in the slag-line position, which limits their service performance. The purpose of this article is to obtain a better understanding of the corrosion behavior of the two refractories with different compositions of virtual steelmaking slags (wt%CaO/wt%SiO₂ = 3.0–7.0, Al₂O₃: 18–35 wt%) using laboratory experiments and FactSage thermodynamic modeling. Pure Al₂O₃ and MgO-Al₂O₃ crucibles were adopted to simulate the two refractories, respectively, during the experiment. The results show that the degree of corrosion of both crucibles increases with an increase in slag basicity and a decrease in Al₂O₃ content in the slag. The Al₂O₃ crucible is more susceptible to corrosion than the MgO-Al₂O₃ crucible, which is attributed to the effect of the slag penetrating through the Al₂O₃ crucible matrix and substituting part of its matrix. For the MgO-Al₂O₃ crucible, there was no obvious slag substitution, but a transition layer was found in the contact region between the crucible and the slag. The Al₂O₃ in the crucible matrix reacts with slag to produce calcium alumina (CaAl₁₂O₁₉, CaAl₄O₇) and other complex oxides, while the MgO particles at the MgO-Al₂O₃ crucible-slag interface were only surrounded by liquid slag without an obvious chemical reaction between them. The mechanism of corrosion was studied by experiments combined with thermodynamic calculations and with the establishment of a new corrosion model. This study is expected to provide a guide for the design of related refractories and slags in industrial applications.     

Cr7C3: A potential antioxidant for low carbon MgO–C refractories

Magnesia carbon (MgO–C) refractory, one of the most commonly used refractories in the steelmaking system, relies on graphite to improve the thermal shock resistance and slag corrosion resistance. The oxidation of graphite carbon in a MgO–C brick usually leads to the destruction of the carbon network in the brick, which causes the structure of the brick to become loose and easily eroded. At present, metal powders, carbides, and borides are used as antioxidants to prevent the oxidation of carbon in MgO–C bricks. The metal carbide Cr₇C₃ can be prepared from aluminum chromium slag through a simple synthetic process and at a low cost. In this work, we investigated the oxidation resistance of low carbon MgO–C refractories with different amounts of Cr₇C₃ powder (1, 2, 3, and 4 wt%). The refractories with 3 wt% Cr₇C₃ powder showed optimal resistance to oxidation. The microstructure indicated that oxygen reacts with Cr₇C₃ preferentially over carbon to form chromium oxide and magnesium chromium spinel, blocking the pores and hindering oxygen diffusion. Carbon arising from the reduction of carbon monoxide by Cr₇C₃ can act as a supplementary carbon source. The better oxidation resistance also contributed to the improvements in slag corrosion and thermal shock resistance of the refractories.     

Corrosion of high chromia refractory materials by basic coal slag under simulated coal gasification atmosphere

In this paper, dynamic corrosion experiment of a high chromia refractory interaction with basic coal slag under slagging gasifier conditions was conducted by using rotary drum corrosion test with the FactSage thermodynamic analysis. The microstructures and chemical compositions of the corroded samples were analyzed by scanning electron microscopy (BEI and EDS), and the corrosion mechanism was investigated by combining thermodynamic simulation and SEM analysis. The results show that the simulation results were consistent with the results of corrosion test. Reaction layer and penetration layer are formed from the surface to the interior of the sample after corrosion. The (Mg, Fe) (Al, Cr)₂O₄ spinel solution was formed in the reaction layer, which make the matrix structure become dense and change the overall structure of the particles’ uniformity. Corrosion of Cr₂O₃ aggregate is relatively weak by slag. The Cr₂O₃ dissolves into the slag through the formed spinel solution layer on the surface of aggregates. While, Cr₂O₃ and Al₂O₃ dissolve into molten slag through the spinel solution layer formed in the matrix. ZrO₂ in the matrix directly dissolved into molten slag and penetrates inner the matrix with the penetration of the slag to form a ZrO₂-free region. The liquid sintering of the matrix has happened in the melt, causes the structure of the penetration layer become dense, which is different from that of the original sample.     

Key features of alumina/magnesia/graphite refractories for steel ladle lining

The corrosion resistance of resin bonded alumina/magnesia/graphite refractories containing different kinds of aggregates were investigated when submitted to the action of slags of several CaO/SiO₂ ratios. The laboratory testing was performed by means of the rotary slag attack test. Specifically evaluated was the influence of alumina/carbon ratio and magnesia and silica contents on the refractories corrosion resistance. It was found that this property could be improved by increasing the refractory Al₂O₃/SiO₂ ratio as well as by choosing the appropriate Al₂O₃/C ratio.     

Microstructure and mechanical properties of CaAl12O19 reinforced Al2O3-Cr2O3 composites

Al₂O₃-Cr₂O₃ refractories have excellent slag corrosion resistance and can adapt to the oxidation/reduction atmosphere in the smelting reduction ironmaking furnace. However, Al₂O₃-Cr₂O₃ refractories have poor mechanical properties and sintering properties. In order to improve the mechanical properties of Al₂O₃-Cr₂O₃ materials, the CaAl₁₂O₁₉ reinforced Al₂O₃-Cr₂O₃ composites were prepared by pressureless sintering process, and the influences of CaO content on the sintering properties, mechanical properties, and microstructure evolution of the composites were studied. The results show that a small amount of CaO can significantly improve the compactness of the composites, which is mainly due to the formed sheet-like CA6 fill the gap between the solid solutions, and reduces the porosity of the composites. In addition, the sheet-like CA6 makes the connection between solid solutions closer, and the intergranular fracture gradually transforms into a mixed mode of intergranular and transgranular fracture. The best mechanical propertie is observed at S4 with the CaO content of 2 wt.%. Compared with sample S0 without CaO, the hardness, compressive strength and flexural strength of the S4 were increased by 35.19 %, 49.69 %, and 68.34 %, respectively. The addition of excessive CaO will deteriorate the mechanical properties of the composites, because the formation of a large number of layered CA6 increases the porosity of the composites. Furthermore, a small amount of CaO addition can significantly improve the thermal shock resistance of the composites. After 10 and 20 thermal shock cycles, the strength loss rates of S4 are only 5.83 % and 8.74 %, respectively.     

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.     

Effect of Alumina Reactivity on the Densification and Properties of Al2O3–Cr2O3 Refractories

Alumina‐chrome (Al₂O₃–Cr₂O₃) refractories with Al₂O₃:Cr₂O₃ molar ratio 1:1 were synthesized in the temperature range of 1400–1700°C by conventional solid–oxide reaction route. The effect of different aluminas (viz., hydrated and calcined) on the densification, microstructure, and properties of Al₂O₃–Cr₂O₃ refractories was investigated without changing the Cr₂O₃ source. The starting materials were analyzed to determine the chemical composition, mineralogy, density, surface area, and particle size. Sintered materials were characterized in terms of densification, phase assemblage, and mechanical strength at room temperature and at higher temperatures. Microstructural evolution at different sintering temperature was correlated with sintering characteristics. It can be concluded that the Al₂O₃–Cr₂O₃ refractories prepared with hydrated alumina as Al₂O₃ source show better densification and hot mechanical strength than corresponding calcined variety.     

Effect of fluorine and CaO/Al2O3 mass ratio on the viscosity and structure of CaO–Al2O3-based mold fluxes

The effect of CaO/Al₂O₃ mass ratio (C/A) and fluorine content on the viscosity and structure of CaO–Al₂O₃-based mold fluxes has been researched in this paper. The viscosity results indicated that increasing fluorine only slightly decreases the viscosity of the slag melt, and higher C/A is also observed to decrease the viscosity of molten slag when the C/A changes from 1.3 to 1.7. Structural analysis of the as-quenched fluxes using the Raman spectroscopy showed that the amounts of Al–O⁰ and Si–O–Al structural units all decrease with higher fluorine content and C/A, indicating that a depolymerization of the molten structure is occurring. The results of ²⁷Al and ¹⁹F magic angle spinning nuclear magnetic resonance showed that fluorine tends to participate in the network structure and coordinate with Al³⁺ ions to form complex ionic clusters. The results suggested that the role of fluorine in the CaO–Al₂O₃-based slag system is different from the traditional slag system in which fluorine only acts as a diluent, thus reducing the effect of fluorine on lowering the viscosity. In addition, the coordination environment of Al³⁺ ions can be simplified by higher C/A through promoting the generation of [AlO₄]⁻ tetrahedral structures. Besides, the free O²⁻ ions provided by excess CaO would break the Al–O⁰ bonds and further depolymerize the network structure, thereby decrease the viscosity.     

Comparison study on effect of nano-sized Al2O3 addition on the corrosion resistance of microporous magnesia aggregates against tundish slag

The microporous magnesia aggregates show a promising application prospect as tundish lining, due to the excellent thermal insulation. In this study, the effect of nano-sized Al₂O₃ addition on the corrosion resistance of microporous magnesia aggregates against tundish slag is explored. The results show that the addition of nano-sized Al₂O₃ deteriorates the slag resistance of microporous magnesia aggregates, which is mainly because that the apparent porosity of aggregates increases with the addition of nano-sized Al₂O₃. Furthermore, MgO·Al₂O₃ spinel is formed in situ at the grain boundaries of Al₂O₃-bearing aggregates and the dissolution of MgO·Al₂O₃ spinel into molten slag damages the structure of aggregates. For the Al₂O₃-free microporous magnesia aggregates, as expected, the penetration of high basicity slag (CaO/SiO₂ = 9, mass ratio) into refractory is slighter than that of low basicity slag (CaO/SiO₂ = 4, mass ratio). But, for the Al₂O₃-bearing microporous magnesia aggregates, the corrosion of refractory by high basicity slag is severer. This is mainly because that MgO·Al₂O₃ spinel is more unstable in high basicity slag. Therefore, it is not suitable to add nano-sized Al₂O₃ for the preparation of microporous magnesia as tundish lining.     

Corrosion of phosphate added high-chrome refractory materials in an entrained-flow gasifier

Durability of the refractory liner located in an entrained-flow gasifier is one of the main factors affecting the efficiency and cost of gasification process. This study investigates the corrosion mechanism of phosphate added high-chrome refractories in a commercial entrained-flow gasifier and the effect of phosphate additives on the improvement of service life combining thermodynamic simulation calculations. The microstructures, chemical compositions, and mineral phases of the corroded samples were analyzed by scanning electron microscopy (SEM and EDS) and X-ray powder diffraction (XRD). The results demonstrated that chemical corrosion mainly occurred at the slag-matrix interface and the junction of aggregates and matrix regions. Complex spinel solid solutions were formed at the slag-refractory interface. Phosphate additives decomposed into gaseous products (such as O₂, P₂O₃) and diffused into the interior of refractories at or close to the slag-refractory interface, not only causing an oxidizing environment but also increasing the phosphate contents in the interior of refractories. Phosphate additives in the infiltration layer occupied the gaps between crystal grains of (Cr, Al)₂O₃ solid solutions, reduced the infiltration of silicate phases, and absorbed Ca and Na in the slag, which subsequently increased the viscosity of the slag.     

Modification of interface chemistry and slag structure by transition element Cr

A comparative study on CaO–MgO–Al₂O₃–SiO₂ slag and CaO–MgO–Al₂O₃–SiO₂–Cr₂O₃ slag was conducted to investigate the distribution of the elements at the gas-slag interface. The effect of redox states of chromium on the distribution of sulfur and oxygen at the interface was revealed by gas-slag equilibrium method using X-ray photoelectron spectroscopy at 1873K. From the analysis of the S2p core-level spectra, the negative divalent sulfur(S^2?) was detected at the interface in the Cr-bearing slag, which directly proved that sulfur exists in the form of S^2? in the slag for the first time. However, the S^2? peak is very weak at the interface of Cr-free slag. The reason for the difference between the two slags may be due to chromium changing the interface structure. According to the O1s and Cr2p core-level spectra, non-bridged oxygen(O^?) increased, while bridged oxygen(O⁰) decreased with the etching depth deepened. The increase of NBO/BO and Cr²⁺/Cr³⁺ elucidates that Cr³⁺ can modify the structure of the slag as basicity substance, but its effect is weaker than that of Cr²⁺. Meanwhile, due to the affinity of sulfur and chromium, the addition of chromium may also lead to the enhancement of the S^2? peak at the gas-slag interface. Gradient change of elements at the interface proved the existence of the boundary layer.     

Cordierite ceramics—Spalling-resistant high-melting refractories

Conclusions The production technology of cordierite refractories from fireclay and magnesite differs from other processes in that the components have to be finely ground.The components must be accurately apportioned and the mass thoroughly mixed preferably in batch mixers. Otherwise, the production process of cordierite refractories does not differ from that of chamotte brick.The use of fireclays with a high Al₂O₃ content (38%) and magnesite eliminates the need for commercial alumina.     

Dissolution kinetics of alumina in molten CaO–Al2O3–FetO–MgO–SiO2 oxide representing the RH slag in steelmaking process

In order to effectively remove alumina inclusions suspending in ultra-low C steel during RH process, the dissolution kinetics of alumina in molten CaO–Al₂O₃–Fe_tO–MgO–SiO₂ oxide was investigated. A crucible dissolution technique was used where the alumina crucible was allowed to dissolve in the slag of various conditions ((% CaO)/(% Al₂O₃), (% Fe_tO), temperature). The obtained data were interpreted using a kinetic mass transport equation to obtain the mass transport coefficient (k_m) in each condition. Increasing (% CaO)/(% Al₂O₃), (% Fe_tO), and temperature increased the dissolution rate as well as the k_m provided that the slag composition is not close to its saturation composition by alumina. In order to simulate the dissolution of alumina inclusion in the RH slag, which cannot be measured by a confocal scanning laser microscopy (CSLM) at present due to the opaqueness of the slag, the modified invariant interface approximation was employed. Along with the obtained k_m, the viscosity of slag, and a reference experiment using the CSLM, the dissolution kinetics of alumina inclusion in the Fe_tO-containing RH slag was predicted. The time required for the dissolution of alumina inclusions from liquid steel to RH slag was discussed.