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.     

Corrosion mechanism of cement-bonded Al2O3–MgAl2O4 pre-cast castables in contact with molten steel and slag

In this work, a cement-bonded corundum-spinel (Al₂O₃–MgAl₂O₄) pre-cast refractory brick with two typical Al₂O₃ aggregates was designed as the refractory lining. Corroded microstructure of the used corundum-spinel bricks after industrial trials in a commercial RH refining ladle was analyzed. Degradation processes of two types of alumina aggregates in the same corroded interface also were discussed. Typical corroded microstructure revealed that needle-like calcium hexaaluminate (CA₆) was observed in the matrix of the original layer. The formation of CA₆ was attributed to the reactions with pure calcium aluminate cement and matrix components under a high-temperature gradient during refining. Furthermore, the corrosion process of the used Al₂O₃–MgAl₂O₄ bricks would be discussed based on a post-mortem microstructural characterization, and the corrosion mechanism of the two types of aggregates was also elucidated.     

Thermodynamic evaluation of SiC oxidation in Al2O3–MgAl2O4–SiC–C refractory castables

The literature suggests that MgAl₂O₄ can accelerate SiC oxidation in Al₂O₃–MgAl₂O₄–SiC–C refractory castables. Thus, in this work thermodynamic calculations have been carried out using FactSage^® software in order to explore, search for and understand the role of MgAl₂O₄ on the SiC oxidation. According to the thermodynamic predictions, at 1500 °C and under a reducing atmosphere, there is no evidence that spinel might directly affect SiC oxidation. The increase of SiC content in an Al₂O₃–SiC–C (AL) castable composition was mainly related to the reaction between mullite and carbon. On the other hand, the SiC generation in the Al₂O₃–MgAl₂O₄–SiC–C (SP) composition was a result of the reaction involving liquid SiO₂ and carbon from the refractory. Therefore, the lower SiC content in the SP castable resulted from the refractory's phase transformations. It was also suggested that the samples thermally treated 15 times at 1500 °C did not reach the equilibrium condition, which explains the differences between experimental and thermodynamic results.     

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.     

Effect of TiO2 addition on the sintering densification and mechanical properties of MgAl2O4–CaAl4O7–CaAl12O19 composite

Materials designed in the high-alumina region of Al₂O₃–MgO–CaO system have been widely used in many technological fields. However, their further applications are limited by the high sintering temperatures necessary to achieve densification due to the poor sintering ability of calcium hexaluminate (CaAl₁₂O₁₉) and spinel (MgAl₂O₄). Considering this aspect, the present work investigated the effect of TiO₂ addition on the sintering densification and mechanical properties of MgAl₂O₄–CaAl₄O₇–CaAl₁₂O₁₉ composite by solid state reaction sintering. The results showed that the CA₆ grains presented a more equiaxed morphology instead of platelet structure by incorporating Ti⁴⁺ into its structure, which greatly improved the densification after heating at 1600 °C. The flexural strength was greatly enhanced with increasing addition of TiO₂ due to the significant decrease in porosity and improvement in uniformity of grain size as well as the absence of microcracks in the presence of Al₂TiO₅. The increased content of TiO₂ also played an active role in toughening this composite attributed to the increase in resistance to crack initiation and propagation.     

A post-mortem analysis of the used gel-bonded Al2O3–MgAl2O4 castables in an industrial steelmaking ladle

In this work, a cement-free alumina-spinel (Al₂O₃–MgAl₂O₄) castables with a new aluminum–magnesium gel binder were developed to line the Ruhrstahl Heraeus refining ladle, chemical attacks, and degradation mechanisms of the used alumina-spinel castables after industrial trials were investigated. The results indicated that a reaction product layer of (Mg, Fe)Al₂O₄ was observed between the slag layer and penetration layer (PL), which was mainly derived from the reaction between MgAl₂O₄ spinel in the refractory matrix and FeO_t from slag or an oxidation of steel, and thereby prevented the further penetration of FeO_t. Meanwhile, the in situ spinel could also entrap slight CaO, SiO₂, and FeO_t from the infiltrated slag to form composite spinel in the PL. Moreover, chemical corrosion/penetration and structural spalling dominated the degradation process of the refractory lining in this case. Cracks formed between the deteriorated layer and original layer because of mechanical and thermal stress, which caused spalling from the refractory's hot face.     

Thermal evolution of Al2O3–CaO–Cr2O3 castables in different atmospheres

Al₂O₃–CaO–Cr₂O₃ castables are required for various furnaces linings due to their excellent corrosion resistance. However, toxic and water-soluble Cr(VI) could be generated in these linings during service. In this study Al₂O₃–CaO–Cr₂O₃ castables were prepared and heated at 300–1500 °C in air and coke bed to simulate actual service conditions. The formations of various phases were investigated by XRD and SEM-EDS. The Cr(VI) compounds CaCrO₄ and Ca₄Al₆CrO₁₆ formed in air at 300–900 °C and 900–1300 °C respectively, while C₁₂A₇ and CA₂ were generated rather than forming Cr(VI) compounds in coke bed at 700–1300 °C. However, at 1500 °C, nearly all the chromium existed in the form of (Al_1-xCr_x)₂O₃ solid solution in both atmosphere. As a result, the specimens treated in air contained 185.0–1697.8 mg/kg of Cr(VI) at 500–1300 °C but only 17.2 mg/kg of Cr(VI) at 1500 °C, whereas specimens treated in coke bed exhibited extremely low Cr(VI) concentration in the whole temperature range studied. Moreover, in coke bed, the mutual diffusion between Cr₂O₃ and Al₂O₃ was suppressed and a trace of Cr₂O₃ would even be reduced to form chromium-containing carbides on its surface, which would hindered the sintering process and hence lower the density as well as strength of the castables.     

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.     

Formation mechanism of whiskers in Al–MgAl2O4–MgO refractories at 1400 °C under N2 atmosphere

Al–MgAl₂O₄–MgO refractories were prepared using fused magnesia, metal Al, fused spinel and sintered high purity magnesia as raw materials. The phase composition and microstructure of Al–MgAl₂O₄–MgO refractories treated at 1400 °C under N₂ atmosphere were investigated by means of XRD, SEM and EDS. The results showed that magnesia (MgO) whiskers and MgAlON whiskers were formed on the surface and in the inner area of the Al–MgAl₂O₄–MgO refractories, respectively. The MgO whiskers grew preferentially along the axial direction, forming cylindrical shape MgO whiskers. Then the cylindrical MgO whiskers further absorbed Mg(g) and O₂(g), and grew along the radial direction to form the square columnar shape MgO whiskers. The MgAlON whiskers firstly grew in one-dimensional direction, forming whisker shape MgAlON, then some whisker shape MgAlON gradually developed and grew into two-dimensional flake shape MgAlON. The sintering and thermal shock resistance was significantly improved by the whiskers. The growth process of magnesia whiskers and MgAlON whiskers were dominated by a vapor-solid (VS) mechanism.     

Joining MgAl2O4 ceramics using ZnO–Al2O3–SiO2 glass ceramic with precipitated ZnAl2O4

In this work, crystallization, thermal expansion and wetting behavior of ZnO–Al₂O₃–SiO₂ (ZAS) glass were first investigated. The results showed that ZnAl₂O₄ was precipitated from ZAS glass after crystallization treatment. Crystallization increased the coefficient of thermal expansion (CTE) of ZAS glass ceramic due to the high CTE of ZnAl₂O₄. In addition, ZAS glass exhibited good wettability on the surface of MgAl₂O₄ substrate. On this basis, ZAS glass was used to join MgAl₂O₄ ceramic, and the microstructure and mechanical properties of joints obtained with different cooling methods were investigated. The flexural strength of joints was related to the content of ZnAl₂O₄ crystals in the brazing seams. Additional nucleation and crystallization treatment during cooling process improved the crystallinity of brazing seam, resulting in better matching of the CTE of brazing seam with that of MgAl₂O₄ ceramic. The maximum flexural strength of joints reached 201 MPa, which was equivalent to the strength of MgAl₂O₄ ceramic.     

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.     

In situ formation mechanism of aluminum oxycarbonitride in the unoxidized zone of Al–Al2O3 composites

The Al–Al₂O₃ composites were prepared by fused alumina, α-Al₂O₃ micropowders, and metal aluminum powder. The samples with 3% carbon black (N330), 3% resin powder and α-Al₂O₃ micropowder, 10% α-Al₂O₃ micropowder were named S1, S2, and S3, respectively. They were oxidized at 1500 °C for 3 h in a box-type electric furnace, and then the unoxidized areas were analyzed by X-ray diffraction and scanning electron microscopy. It was found that the aluminum oxycarbonitride formed in situ during the oxidation resistance test inhibited further oxidation of S2. The in situ formation mechanism of aluminum oxycarbonitride in the unoxidized zone is believed to be 7Al + 3Al₃C₄ + 12AlN + 4Al₂O₃ = 12Al₃CON, which is also verified and proven by XRD, SEM and EDS in this work. The oxidation depth of S2 is 46.7% lower than that of S3. Sample S2 hardly has any linear change after fired at 1500 °C × 3 h in coke, which benefits to improve the volume stability and prolongs the service life. Among the three batches, S2 exhibits the minimum creep rate, from 0% to 0.026% at 1500 °C, and the HMOR at 1500 °C in a N₂ atmosphere of S2 is 58 MPa. The Al–Al₂O₃ composites combined with resin strengthened by in situ formed aluminum oxycarbonitride give the composites excellent high-temperature strength owing to the fiber-intersected reinforced microstructure of Al₃CON crystals at high temperature. In the Al–C–N–O system, it was found that the general formula of aluminum oxycarbonitride is expressed by Al_4n+m(C,O,N)_3n+m, and the (n, m) values are (0, 3) for Al₃CON.     

Superplastic deformation of directionally solidified nanofibrillar Al2O3–Y3Al5O12–ZrO2 eutectics

Nanofibrillar Al₂O₃–Y₃Al₅O₁₂–ZrO₂ eutectic rods were manufactured by directional solidification from the melt at high growth rates in an inert atmosphere using the laser-heated floating zone method. Under conditions of cooperative growth, the ternary eutectic presented a homogeneous microstructure, formed by bundles of single-crystal c-oriented Al₂O₃ and Y₃Al₅O₁₂ (YAG) whiskers of ≈100 nm in width with smaller Y₂O₃-doped ZrO₂ (YSZ) whiskers between them. Owing to the anisotropic fibrillar microstructure, Al₂O₃–YAG–YSZ ternary eutectics present high strength and toughness at ambient temperature while they exhibit superplastic behavior at 1600 K and above. Careful examination of the deformed samples by transmission electron microscopy did not show any evidence of dislocation activity and superplastic deformation was attributed to mass-transport by diffusion within the nanometric domains. This combination of high strength and toughness at ambient temperature together with the ability to support large deformations without failure above 1600 K is unique and shows a large potential to develop new structural materials for very high temperature structural applications.     

Fundamentals and applications on in situ spinel formation mechanisms in Al2O3–MgO refractory castables

Although the physical expansion associated with the in situ formation of magnesium–aluminate spinel (MgAl₂O₄) is well-reported, some questions related to this behavior, such as the different volume change values experimentally attained when compared to theoretical one and the pore generation after the reaction, remain open. Thus, the main objective of this work is to shed some light on these questions by evaluating a cement-bonded alumina–magnesia castables, designed using dead-burnt magnesia of different particle size ranges. Microstructural observations suggested that the faster Mg²⁺ migration during the spinel formation led to vacancy accumulation and, consequently, to pore generation, as a direct result of the Kirkendall effect. Additionally, the overall expansion of alumina–magnesia castables seemed to be ruled by two main factors: its sintering efficiency and the different possibilities of the Al₂O₃ and MgO interactions in the mixture. Those consequences, however, do not usually affect the castable corrosion behavior in industrial applications, due to the benefits imposed by the structural constraint.     

A new ternary phase in the system CaO–Al2O3–Cr2O3: Crystal structure and thermal expansion of CaAl2Cr2O7

Polycrystalline material of a novel phase in the system CaO–Al₂O₃–Cr₂O₃ has been obtained by solid-state reactions. Chemical analysis indicated the composition CaAl₂Cr₂O₇. Single-crystal growth of the new compound using borax as a mineralizer was successful. Diffraction experiments at ambient conditions on a crystal with composition CaAl_2.13Cr_1.87O₇ yielded the following basic crystallographic data: space group P 3, a = 7.7690(5) Å, c = 7.6463(5) Å, V = 399.68(6) ų, Z = 3. Structure determination and subsequent least-squares refinements resulted in a residual of R(|F|) = 2.3% for 1440 independent observed reflections and 113 parameters. To the best of our knowledge, the structure of CaAl_2.13Cr_1.87O₇ or CaAl₂Cr₂O₇ represents a new structure type. It belongs to the group of double layer structures where individual double layers contain octahedrally and tetrahedrally coordinated cation positions. Linkage between neighboring sheet packages is provided by additional calcium cations. Furthermore, thermal expansion has been studied in the interval between 29 and 790°C using in situ high-temperature single-crystal diffraction. No indications for a structural phase transition were observed. From the evolution of the lattice parameters the thermal expansion tensor has been obtained. A pronounced anisotropy is evident. The response of structural building units to variable temperature has been discussed.     

The formation mechanism of pores and unbonding in the Al2O3/Al2O3 joints brazed by 50Bi2O3–35B2O3–15ZnO glass

50Bi₂O₃–35B₂O₃–15ZnO (mol. %) glass referred to as Bi50 glass, was used to braze Al₂O₃ ceramics. The phase transformations and wettability of the Bi50 glass on Al₂O₃ substrates at different temperatures were investigated. The results showed that the chemical compatibility of Bi50 glass and Al₂O₃ substrates at 650 °C was excellent. However, Al₂O₃/Al₂O₃ joints having a considerable volume fraction of pores and unbonding were obtained when the joining procedures were carried out by a one-step brazing method. Based on the experiments and simulation results, the prime determinants responsible for the presence of the pores and unbonding within the brazing joints can be divided into two aspects: (i) the intrinsic causes leading to the formation of closed pores (ii) the external factors causing the failure of pores and glass separation. Ultimately, an advanced joining procedure named two-step brazing was proposed, and joints nearly free of defects were acquired.     

Effect of Si3N4 mesophase on the formation of Al2OC-AlNss in resin-bonded Al–Al2O3 composites

In this study, we developed a novel method for synthesising Al₂OC-AlNss using a solid nitrogen source: a Si₃N₄ mesophase. The two-step sintered Al–Al₂O₃ and Si₃N₄–Al–Al₂O₃ samples were prepared under an atmosphere of nitrogen to investigate the effect of Si₃N₄ on the formation of Al₂OC-AlNss in resin-bonded Al–Al₂O₃ composites. The samples were investigated via XRD and SEM. The results indicated that the synthesis of Al₂OC-AlNss with different morphologies was achieved via the Si₃N₄ mesophase, and its morphology was influenced by the source of AlN. Both Al₂OC-AlNss and Al₄O₄C were formed in the two-step sintered Al–Al₂O₃ sample, whereas only Al₂OC-AlNss was formed in the two-step sintered Si₃N₄–Al–Al₂O₃ sample. Induced by the AlN formed by the nitridation of Al, needle-like Al₂OC-AlNss was generated. Compared to that formed by the nitridation of Al, more AlN nuclei were provided by the reaction between Si₃N₄ and Al. Subsequently, columnar and granular Al₂OC-AlNss were formed. Furthermore, fibre-like Al₂OC-AlNss was also generated via the VS and VLS mechanism. The reaction model was established in this study.     

Synthesis mechanism of AlN–SiC solid solution reinforced Al2O3 composite by two-step nitriding of Al–Si3N4–Al2O3 compact at 1500 °C

The in-situ controllable synthesis of AlN–SiC solid solution reinforcement in large-sized Al–Si₃N₄–Al₂O₃ composite refractory by two-steps nitriding sintering was examined. In the first step, a dynamic Al@AlN structure was constructed in the composite by pre-nitriding at 580 °C. During the subsequent sintering process, it cracked above ∼900 °C, and micronized Al cluster (mixture of droplets and vapor) was extracted out gradually. As a result, multiple AlN mesophases were formed through different reaction paths, including i) initial AlN shell formed by solid Al with N₂, ii) reaction of Al cluster with N₂, and iii) reaction of Al cluster with Si₃N₄ from 900 °C to 1500 °C. The Si₃N₄ precursor serves as both a solid nitrogen source and an active Si source, and the controllable reaction between Al and Si₃N₄ leading to uniformly distributed AlN and Si mesophases. AlN–SiC solid solution is significantly formed when liquid Si appears. The shell, granule and whisker SiC–AlN solid solution were observed mainly depending on the dynamic AlN mesophase. The SiC–AlN solid solution reinforced Al₂O₃ materials is a novel promising refractory for large-scale blast furnace lining.     

On the Subsolidus Structure in the CaAl4O7 – Ca7Al6ZrO18 – CaAl2O4 – CaZrO3 – SrZrO3 – SrAl2O4 Region of the CaO – SrO – Al2O3 – ZrO2 System

The subsolidus structure of the CA₂ – C₇A₃Z – CA – CZ – SrZ – SrA region of the CaO – SrO – Al₂O₃ – ZrO₂ system is studied. The occurrence of the solid-phase reaction between strontium aluminate and calcium zirconate is considered from the standpoint of thermodynamics. The conodes, three-component sections, and elementary tetrahedrons are studied in the given region. A promising region for the production of special cements is determined, and rapidly hardening, high-strength, and refractory binding materials are obtained in it.     

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.