Radical reaction-induced Turing pattern corrosion of alumina refractory ceramics with CaO–Al2O3–SiO2–MgO slags

Quasi-volcanic corrosion occurs at the triple-phase interface of alumina refractory ceramics and MgO-containing CaO–Al₂O₃–SiO₂ slags in the air, causing severe damage to ceramics. To address this limitation, in this study, a slag corrosion experiment is performed on alumina refractory ceramics using CaO–Al₂O₃–SiO₂–MgO slags. Various spectroscopic techniques, including electron paramagnetic resonance spectroscopy, are used to investigate the influence of slag structures with varied MgO contents on the corrosion peaks and mechanism. The results show large quantities of reactive radicals, including superoxide radicals, in the slags. Free-radical reactions between refractory ceramics and slags lead to Turing pattern corrosion. An increase in the amount of non-bridged oxygen in the slag structure decreases the amount of original superoxide radicals. Consequently, the intensity of the free-radical reactions of alumina dissolution increases, thereby increasing the height of the corrosion peaks.     

Al2O3-based binders for corrosion resistance optimization of Al2O3–MgAl2O4 and Al2O3–MgO refractory castables

This work addresses the main aspects related to the use of alternative binders [hydratable (HA) or colloidal alumina (ColAlu)] in castables containing different spinel sources (pre-formed or in situ generated), in order to point out: (i) the features that control the corrosion behavior of these materials, and (ii) the key factors to better select a refractory composition. Thermodynamic calculations, corrosion cup-test and SEM analyses were carried out in order to evaluate the slag attack of the designed refractory compositions. According to the attained results, the alumina-based binders (HA or ColAlu) induced a more effective sintering process due to their high specific surface area, improving the physical properties and the binding level of the generated microstructure. The spinel grain size also played an important role in the corrosion behavior of these refractories, as the finer the particles, the greater their dissolution was into the molten liquid, leading to further precipitation of spinel in the solid–liquid interface as a continuous and thick layer. Among the evaluated compositions and considering the presence of silica fume, the most suitable formulation with optimized corrosion resistance was the one with in situ spinel generation and HA as a binder.     

The corrosion resistance of microsilica-containing Al2O3–MgO and Al2O3–spinel castables

Microsilica addition in Al₂O₃–MgO and Al₂O₃–spinel castables helps to improve their flowability and partially accommodate their residual expansion after firing. Nevertheless, there is a lack of conclusive statements in the literature regarding the effects of microsilica on one of the main requisites for steel ladle refractories: corrosion resistance. In the present work, the performance of alumina–magnesia and alumina–spinel with or without microsilica when in contact with a steel ladle slag was evaluated based on three aspects: the material's physical properties, its chemical composition and the microstructural features before the slag attack. According to the attained results, microsilica induced liquid formation and pore growth during sintering, favoring the physical slag infiltration. Moreover, due to this liquid, CA₆ was formed in the matrix, mainly for the Al₂O₃–spinel composition, which also favored the castable dissolution into the molten slag.     

Post-mortem analysis of MgO–Al2O3–C bricks containing bauxite used in steel ladle walls

A serious problem with integrated masonry linings ladle was that the ladle wall bricks were difficult to be partially replaced. Thus, the service life of the ladle was determined by the properties of ladle wall bricks. In this study, the new generation of MgO–Al₂O₃–C bricks with bauxite aggregates was tested in a ladle lining of an integrated steel ladle for 103 cycles, and the corroded microstructure of the used brick was investigated. A multilayered structure of bauxite aggregates could be observed in the used brick, which inhibited the slag penetration along the boundary of the magnesia aggregates and reduced the degree of the aggregates fall off from the used bricks. Besides, during the process of slag penetration, bauxite aggregates could melt into the slag, which increased the viscosity of the slag and weakened the penetration ability of the slag. The MgO–Al₂O₃–C bricks with bauxite addition could improve the service life of the ladle to a certain extent.     

Effect of varying Al2O3 contents of CaO–Al2O3–SiO2 slags on lumped MgO dissolution

This study utilized the single hot thermocouple technique to examine the dissolution behavior of lumped magnesium oxide (MgO) in CaO–Al₂O₃–SiO₂ ternary slags. The aluminum oxide (Al₂O₃) content in the slag (C/S = 1) varied from 10% to 30%; the MgO sphere with a diameter of 1 mm was placed in molten slags at 1,550 °C. Results showed that the dissolution rate decreased as the Al₂O₃ content increased up to 20%. Over 20% Al₂O₃, MgAl₂O₄ was formed at the interface of MgO and it did not fully melt at 30% Al₂O₃. The dissolution behavior and the formation of MgAl₂O₄ were analyzed by a phase diagram provided by Factsage 7.0 software. In the case of less than 20% Al₂O₃ content, apparent sphere radii were measured; the shrinking core model was then applied to understand the dissolution mechanism. The dissolution rate of both slags was controlled by boundary layer diffusion. The dissolution rate at 20% Al₂O₃ slag appeared to fit the behavior to the boundary layer diffusion, although it deviated during the middle stage of the dissolution because of MgAl₂O₄ formation. The 10% Al₂O₃ slag fitted well to the boundary layer diffusion curve; the obtained diffusion coefficient was 0.94 × 10⁻⁹ m²/s.     

Designing low-carbon MgO–Al2O3–La2O3–C refractories with balanced performance for ladle furnaces

In order to achieve high-quality and stable production of special steel, the performance of low-carbon MgO-C refractories needs to be further optimized. For this purpose, low-carbon MgO–Al₂O₃–La₂O₃–C refractories with enhanced thermal shock resistance and slag resistance were designed and successfully prepared by introducing Al₂O₃ as a reinforcer and La₂O₃ as a modifier. The results showed that the refractory samples with additives show better overall performance than those without additives. When 10 wt% of Al₂O₃ and La₂O₃ were added, the oxidation resistance, thermal shock resistance and slag resistance of the refractory samples coked at 1400 °C are increased by 13.57%, 17.75% and 43.09%, respectively. The analysis found that this can be mainly attributed to the formation of MgAl₂O₄, Mg₂SiO₄, and 2CaO·4La₂O₃·6SiO₂ and the consequent volume expansion effect and intergranular phase enhancement effect. Therefore, a low-cost and enforceable reinforcement strategy for low-carbon MgO-C refractories is proposed, which is expected to be applied in steelmaking.     

Corrosion of spinel clinker by CaO–Al2O3–SiO2 ladle slag

Three different grades of sintered spinel clinker were used containing 47, 69 and 94 wt.% Al₂O₃, respectively, i.e. MgO-rich, stoichiometric and Al₂O₃-rich. Based on these clinkers, the corrosion mechanism of each spinel clinker by CaO–Al₂O₃–SiO₂ slag was investigated and the corrosion and penetration behavior of castables containing powdered spinel clinker examined. A layer of MgO·(Al, Fe)₂O₃ complex spinel formed at the slag-refractory interface was proportional to the MgO content of the spinel clinkers, and it depressed the slag corrosion. The free MgO and spinel minerals in each spinel clinker mainly trapped Fe₂O₃ from the slag. CaO–Al₂O₃ compounds were formed at the slag-clinker interface by the reaction between free Al₂O₃ in the Al₂O₃-spinel clinker and CaO from slag. Slag penetration into the spinel clinkers was retarded by these compounds. As a result of adding fine spinel powder to the matrix of Al₂O₃-based castables, it was observed that higher content of MgO in spinel clinker showed better resistance to slag corrosion but lower resistance to slag penetration.     

Shaped MgO–Al2O3–SiO2 refractory ceramics from recycled materials

Abstract

The aim of the present work is to prepare, characterise and assess MgO–Al₂O₃–SiO₂ refractory ceramics; namely, spinel, mullite and cordierite from chemically recycled precipitates. These precipitates include pure and fine magnesium and aluminium hydroxides as well as water treated fumed silica. Corresponding batches of the aimed oxide ceramics were coprecipitated from these precipitates and subsequently processed up to firing using the proper techniques. The processed bodies were investigated for their chemical and phase composition as well as morphology, microstructure and physical properties. According to the results of these investigations, the processed ceramics could be recommended for the adequate applications. It is concluded that dense, direct bonded and highly refractory spinel and mullite–corundum bodies could be obtained after firing their coprecipitated batches up to 1700°C. On the other side, dense, porous and refractory cordierite–spinel bodies could be processed from its batch after firing up to 1350°C. All of these bodies are refractory oxide ceramics with a very wide range of thermo-chemical, physical and mechanical applications.     

MgO−Al2O3−Cr2O3 refractories of increased corrosion resistance for nonferrous metallurgical furnaces

The paper sums up a study that had as its objective to develop MgO−Al₂O₃−Cr₂O₃ refractories of increased corrosion resistance for harsh service conditions. The refractories thus developed, designated PShKhM-1 and PShKhM-2, have better high-temperature strength and abrasion resistance than PKhS refractories manufactured commercially. The experimental refractories will enhance the durability of furnace and converter linings, extend their campaigns, step up their productivity, and reduce consumption of refractories and repair costs. Translated from Ogneupory i Tekhnicheskaya Keramika, No. 1, pp. 33–37, January, 1998.     

A mechanistic model for pipeline steel corrosion in supercritical CO2–SO2–O2–H2O environments

A mechanistic model was established to predict uniform corrosion rate and investigate the corrosion mechanisms of pipeline steel in supercritical CO₂–SO₂–O₂–H₂O environments. A six-region division (SIWDES: Supercritical CO₂, Interface, Water film, Deposition, Electrodic, and Solid) was applied to mathematically describe the model. The modified three-characteristic-parameter correlation model was used to calculate the ion activity coefficients, which calculates the activity coefficients of ions in thin water film with high ionic strength. The model can reasonably predict the corrosion rate of pipeline steel for the primary variables, determine the concentration distribution of each component in the water and product films, and also reflect the impact of corrosion product film on corrosion rate. A comparative analysis between the model and the experimental results showed that the model reasonably predicted the effects of the main factors on corrosion rate.     

Comprehensive study on corrosion protection properties of Al2O3, Cr2O3 and Al2O3–Cr2O3 ceramic coatings deposited by plasma spraying on carbon steel

In this study, individual Al₂O₃ and Cr₂O₃ coatings and Cr₂O₃-25, 50, 75 wt% Al₂O₃ composite coatings were applied on carbon steel by atmospheric plasma spraying method. Corrosion experiments were performed on as-sprayed and epoxy resin sealed coatings including potentiodynamic polarization, electrochemical impedance spectroscopy and long-term immersion in 3.5 wt% NaCl solution. Phase composition and microstructure of the coatings were investigated by x-ray diffraction, optical microscopy and scanning electron microscopy, before and after the corrosion experiment. The results showed that the Cr₂O₃ coating exhibited the best corrosion resistance, due to the densest microstructure and highest adhesion strength. The Cr₂O₃-25 wt% Al₂O₃ coating had the highest interconnected porosities and thus had the least corrosion resistance compared to other coatings. In general, the as-sprayed coatings induced a maximum increase of 3.93 times the polarization resistance (R_p) in the polarization experiment and a 3.5 times increase in the charge transfer resistance (R_ct) in the EIS experiment, which was not significant. Stresses caused by increased volume of corrosion products in the coating-substrate interface resulted in the spallation of Cr₂O₃-25, 50 wt% Al₂O₃ coatings from the substrate over long-term of immersion. The adhesion strength of the coatings was a determining criterion for the long-term durability of the coatings. The sealing treatment resulted in a significant increase in R_p and R_ct.     

Corrosion of nickel ferrite refractory by Na3AlF6–AlF3–CaF2–Al2O3 bath

Based on research on cermet inert anodes for aluminium production, it has been suggested that nickel ferrite spinel might be suitable for use as a sidewall refractory in Hall-Héroult cells. A corrosion resistant sidewall would allow elimination of the frozen bath ledge, and has potentially huge benefits in terms of energy savings and increased productivity. However, little work has been done to assess nickel ferrite's suitability as a refractory.Dense nickel ferrite samples were prepared and characterized, and corrosion tests in cryolite based baths were conducted. Results confirm that the spinel does have good corrosion resistance. The corrosion mechanism is complex, involving grain boundary attack and formation of a Ni–Fe alloy. This alloy could pose a risk in terms of contamination of the aluminium. The use of additives to restrict penetration of grain boundaries may be the key to development of a successful spinel based refractory.     

Al2O3 loss prediction model of selective laser melting Al2O3–Al composite

The element/phase loss is undesirable but existing during selective laser melting (SLM) of materials with volatile element/phase, which not only changes the material composition but also affects the molten pool flow. In the previous researches, the effect of remelting on the element/phase loss was neglected during the SLM process, instead, laser energy density was thought to be uppermost. In fact, the SLM process fabricates the parts in a manner of line by line and layer by layer, i.e., additive character, and the remelting in the overlap zone occurs during the SLM process. In this paper, three different Al₂O₃ loss prediction models of SLM Al₂O₃–Al composite by considering the additive character of SLM and the distribution of the Al₂O₃ associated with the different molten pool driving forces were developed. By comparing with the experimental results and predicted results, it is found that the Al₂O₃ is distributed on both sides of the molten pool under the combined action of the Marangoni flow and the evaporation recoil pressure. This kind of Al₂O₃ distribution enhances the effect of the remelting on the Al₂O₃ loss, i.e., the remelting brings a logarithmic increase in the Al₂O₃ loss rate. This determines the final Al₂O₃ loss rate of the SLMed 3D samples. During this study, although the Al₂O₃ loss rate of the single-track is only 33%, the loss rate of SLMed 3D samples increases significantly to 97% when the hatching space of 60 μm and scanning speed of 200 mm/s are utilized, i.e., almost no Al₂O₃ in the 3D sample. Thus, it is more important to reduce the remelting, i.e., overlap rate for reducing the element/phase loss. This study is a benefit for understanding and reducing the element/phase loss in SLM.     

Effect of carbon black on corrosion resistance of Al2O3–SiC–C castables to SiO2–MgO slag

Metallurgical solid waste recycling is the shape of things to come in green development of Chinese iron and steel industry. Utilization of ironworks slag for producing mineral wool at high temperature is an important approach. However, refractory lining is seriously corroded by the SiO₂–MgO based slag at 1600 °C during the production process. Different production steps need different atmospheres, the changeable service atmospheres (air and reducing atmosphere) put forward high requirements for slag resistance. The Al₂O₃–SiC–C castables containing carbon black are usually used in iron runner, which faces high-temperature service condition of 1450 °C–1500 °C. Nevertheless, the function of carbon black in the Al₂O₃–SiC–C castables at 1600 °C is till essentially unknown. In the current study, the carbon black was introduced to tabular alumina based Al₂O₃–SiC–C castables to improve corrosion resistance to SiO₂–MgO based slag at 1600 °C. The result showed that 0.4 wt% carbon black was suitable for the castables, which the slag resistance of castables was significantly improved. The carbon black had contributed to block slag by wettability resistance. By comparison with the castables without carbon black, the corrosion index and penetration index had been reduced by 20.2% and 28.0%, respectively, under air atmosphere. And there were little corrosion or penetration under reducing atmosphere for castables with 0.4 wt% carbon black. For the mechanical properties, the Al₂O₃–SiC–C castables with 0.4 wt% carbon black could serve production process although the carbon black impaired the physical properties.     

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.     

Pore formation model for direct laser deposition of Al2O3–ZrO2 ceramic

Pores are some of the most common defects that form during direct laser deposition of ceramic materials. A mathematical model of pore formation for Al₂O₃-ZrO₂ ceramic was developed. The pore formation model, which was developed from the bubble escape factor, reveals the relationship between the movement of the solid-liquid interface of the molten pool and that of the bubbles. In the frontier region of the molten pool, with increasing laser power, the proportion of bubbles that escaped and the area from which bubbles escaped increased. With increasing laser power, the actual and theoretical porosity decreased from 80 % to 40 %. At the central region of the molten pool, the bubble escape factor increased with increasing bubble diameter under the same laser power. The theoretical porosity and the actual porosity decreased with increasing laser power. The pore formation model provides a basis for fabricating high-quality Al₂O₃-ZrO₂ ceramics by direct laser deposition.     

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.