Thermodynamic evaluation and properties of refractory materials for steel ladle purging plugs in the system Al2O3-MgO-CaO

The influence of iron oxide in the phase relationships of Al₂O₃-MgO-CaO and Al₂O₃-MgO purging plug refractory material has been studied by the thermodynamic analysis tool FactSage. Results showed that the system without CaO to be advantageous on the onset temperature of liquid phase, and on the liquid content at defined chemical composition and temperature. Therefore, CaO negatively influences the iron-rich slag resistance of the purging plug material. Analysis of used purging plugs proved the thermodynamic results. They showed that spinel solid solution and calcium hexaluminate as stable phases were formed in the reaction with iron oxide slag.Corundum-spinel castables with and without calcium aluminate cement were investigated in the laboratory to compare the relevant technical properties. In the cement bonded castable, the curing and drying strength are increased by increasing the cement content. However high cement addition requires higher water demand, which results in higher open porosity and a lower hot modulus of rupture (HMoR). In the CaO-free, no-cement castable with hydratable alumina binder, the water demand is slightly higher when compared to the ultra-low cement castable. However, the curing and drying strength are still slightly higher for the no-cement castable. As there is no significant difference in HMoR with various hydratable alumina binder additions, low dosage of such binder in the range of two to four percent is normally recommended to avoid excessive water addition. Cement bonded castables (with CaO) show some advantages to the no-cement castable (non-CaO) regarding HMoR, however the no-cement castable could have advantages regarding the iron-rich slag resistance and thermal shock resistance.     

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.     

Improved corrosion resistance of Al2O3-SiC-C castables through in situ carbon containing aluminate cement as binder

Slag corrosion is one of the main damage modes for refractory castables used in iron and steel metallurgy. The matrix plays vital roles for corrosion resistance of refractory castables. In the present paper, the properties of the Al₂O₃-SiC-C-based trough castables with in situ carbon containing calcium aluminate cement (CCAC) and ball pitch as carbon sources, respectively, were comparatively investigated. The microstructures of the trough castables after corrosion were observed by field-emission scanning electron microscopy. The results showed that after being corroded at 1450°C for 3 hours, the corrosion depth of Al₂O₃-SiC-C-castables with CCAC as binder (A2) was 1.2 mm, 65.71% lower than that of the trough castables with ball pitch as carbon source (A1), though the content of carbon materials in the former was much lower than that of the latter. The reasons for these observations were that the in situ carbon materials of CCAC exhibit improved distribution in the matrices of castables and excellent oxidation resistance, resulting in lower porosity within the castables, and hindered the penetration of the molten slag at high temperatures. In addition, the Al₂O₃-SiC-C-castables bonded by CCAC displayed good mechanical properties at room temperature and elevated temperature.     

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.     

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.     

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.     

Preparation and ladle slag resistance mechanism of MgAlON bonded Al2O3 -MgAlON-Zr2Al3C4-(Al2CO)1-x(AlN)x refractories

MgAlON bonded Al₂O₃-MgAlON-Zr₂Al₃C₄-(Al₂CO)_1-x(AlN)_x refractories were prepared at high temperatures from 1300?℃ to 1600?℃ in N₂-flowing based on the design of Al-AlN core-shell. The refractory prepared at 1500?℃ was chosen to conduct the ladle slag resistance test at 1600?℃ in air. All the refractories are composed of MgAlON, Zr₂Al₃C₄, (Al₂CO)_1-x(AlN)_x and Al₂O₃. The ladle slag resistance test for the chosen refractory presents a good result and there exist two different reaction layers —— the reacted slag layer and the spinel solid solution layer. The reacted slag layer consists of spinel solid solution, Ca-ZrO₂ and gehlenite/gehlenite solution, where the formation of those phases has changed the chemical composition and phase composition of the original ladle slag. The compact spinel solid solution layer forms by the decomposition of MgAlON into rich-Al₂O₃ spinel and the incorporation of Mn²⁺ and Fe^2+/3+ into rich-Al₂O₃ spinel, which plays an important role in slag penetration resistance.     

The corrosion and microstructure relationship for cement-bonded spinel refractory castables

Due to the lack of studies addressing the relationship between chemical and microstructural features and the corrosion resistance of castables containing pre-formed and in situ spinel (MgAl₂O₄), the main aspects related to the different wear rates of these compositions when in contact with steel ladle slags have not been properly stated. Considering this scenario, this work presents the slag resistance analysis of castables designed by different spinel incorporation routes (in situ formation, pre-formed spinel addition and both). A high-iron oxide containing industrial slag was used and the results indicated that the role of the distinct CA₆ (CaO·6Al₂O₃) distribution in the castable's microstructure before the slag attack was more relevant than the spinel ability as an ion trapper. The location of CA₆ crystals in the in situ spinel-forming castable led to a suitable physico-chemical protection of both, the tabular alumina aggregates and the matrix, during the experiment. For the pre-formed spinel-containing castable, the former CA₆ presence only in the matrix resulted in a high dissolution of alumina from the aggregates into the liquid during the corrosion test and a great amount of CA₆ crystals was formed. Cracks were then generated and followed by further cycles of penetration and chemical reactions, which spoiled the refractory's performance.     

The development of a thermodynamic model for Al2O3–MgO refractory castable corrosion by secondary metallurgy steel ladle slags

Alumina magnesia in situ spinel castables are used as ladle refractory lining in the steel industry. In contact with slag, they suffer degradations which limits their performance. The purpose of this article is to predict the thermochemical attack of a slag on alumina magnesia refractory using Factsage^® thermodynamic modeling. To evaluate the reliability of the thermodynamic results, a validation step was carried out, which supported that the database was well adapted to the alumina magnesia spinel system. The corrosion phenomenon was then computed for a simple to a complete system to understand the mechanism and the influence of specific oxides. The model was also compared to corroded microstructures from a steel ladle to evaluate the contribution of each constituent in the castable. The aggregates of alumina react with slag to produce monomineral layers of lime aluminates (CA6 and CA2), while complex spinels (Mg, Fe, Mn)O (Fe₂, Al₂)O₃ are formed from the reaction of the slag with the matrix of the castable. Several oxides (MnO, FeO, Fe₂O₃) from the slag contribute to the formation of the spinel structures. The microstructures of refractories used in steel ladles confirm the main conclusions and the thermodynamic approach.     

The impact of bonite aggregate on the properties of lightweight cement-bonded bonite–alumina–spinel refractory castables

The lightweight bonite–alumina–spinel (CA₆–Al₂O₃–MA) refractory castables with bonite aggregate and different spinel sources (pre-formed and in situ formation) were prepared in this study. The phase composition, microstructural features, and mechanical and thermo-mechanical properties of CA₆–Al₂O₃–MA castables treated at various temperatures were investigated by techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS), three-point bending method, and thermal shock test. The results indicated that the incorporation of bonite aggregate had a positive influence on the strength, thermal shock resistance and slag corrosion resistance. It especially decreased the thermal conductivity and had a slightly negative influence on the refractory under load and slag penetration resistance of the castables. For the in situ spinel-containing castable, the formation of in situ spinel with finer particle sizes and acicular CA₆ grains led to higher overall volume expansion, resulting in higher thermal expansion (∆L/L₀), linear change and the apparent porosity of castables. Also, the heat insulation, thermal shock and slag penetration resistance of castables with in situ spinel improved, while the strength, displacement, refractory under load and slag corrosion resistance decreased sharply.     

Revisiting CA6 formation in cement-bonded alumina-spinel refractory castables

This work revisits the proposed mechanisms presented in the literature for CA₆ formation in Al₂O₃-MgO and Al₂O₃-MgAl₂O₄ castables bonded with calcium aluminate cement. New experimental tests, thermodynamic simulations and re-evaluation of the chemical composition and microstructural aspects observed for samples fired in the temperature range of 1150 °C to 1500 °C were carried out. Based on these data, a new interpretation of the CA₆ generation process, as well as the features which influence the location and morphology of this phase were proposed. CA₆ formation via solid and liquid states are suggested to take place in all evaluated compositions, where the former (solid-state) is the main reaction predicted for the silica-free refractories (AM0MS and AS0MS), whereas the liquid-state one prevails in the AM1MS and AS1MS materials. The CA₆ crystal morphology should be affected by these different reaction mechanisms. According to the experimental results, it was also discussed the role of the calcium hexaluminate features in the overall corrosion behavior of the designed refractories when they were placed in contact with molten slag at high temperatures. Such aspects have not been previously reported in published papers related to this subject.     

Preparation of Al2O3@CaCO3 aggregates and its effects on the thermal shock resistance of Al2O3-MgO castables

Al₂O₃@CaCO₃ aggregates were prepared by impregnating corundum aggregates (particle sizes with 3-1 and 5-3 mm) in precursor solutions (Calcium hydrogen citrate, CaHC₆H₅O₇) followed by heat treatment at 430°C. The phase composition and microstructure of the coatings were characterized via X-ray diffraction and scanning electron microscope, respectively. The novel aggregates were used in Al₂O₃-MgO castables. The effects of the Al₂O₃@CaCO₃ aggregates on the physical properties and thermal shock resistance (TSR) of castables were investigated. The results show that uniform CaCO₃ coating of aggregates (C15) with thickness about 10 µm can be attained when the concentration of Ca²⁺ in solution was 0.15 mol L⁻¹. There was a strong bonding between the aggregates and coating that was constituted by particles with size about 0.2 µm. Both improving physical and TSR properties of the castables are related with the unique layer structure, calcium hexaluminate (CA₆) layer in-situ formed at the aggregate-matrix interface, of added Al₂O₃@CaCO₃ aggregates. There is a mass of multi-deflection of cracks along with the CA₆ layer which consumes more fracture surface energy. The castables with C15 exhibit optimal TSR and the residual strength ratio after the thermal shock test is 29.5%, which is 12.8% higher than the castables with corundum aggregates.     

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.     

Preparation and characterization of HA bonded Al2O3–MgO based castables with superior slag resistance for the working lining of Si-killed stainless steel ladles

The study prepared Al₂O₃–MgO based castables bonded by hydratable alumina (HA) instead of calcium aluminate cement (CAC) for the working lining of Si-killed stainless steel ladles. The microstructure, phase composition, mechanical properties, and slag resistance of castables were investigated by SEM, XRD, and thermodynamic software FactSage®. The results indicated that the HA bonded castables showed superior hot flexural strength, thermal shock resistance and slag resistance than the CAC bonded castables, due to the optimized pore characteristics, less liquid content, and higher liquid viscosity of the castable matrix and the formation of a continuous insulating layer.     

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.     

Cement-free spinel-based refractory materials

Channel induction furnaces can operate at temperatures as high as 2000 °C, which requires the use of high-temperature refractory materials resistant to corrosion. CaO, a conventional component of the corundum-containing refractory castables, produces a degrading effect on high-temperature properties; for this reason, low-and ultralow cement materials fail to meet the needed requirements. Therefore a cement-free refractory of the DALCAST series in the Al₂O₃-MgO binary system based on an Al₂O₃ fully hydratable binder has been developed. Physical properties (strength and hardening behavior) of a standard low-cement castable and a newly developed product based on the results of their practical use in channel induction furnaces are compared and discussed. __________ Translated from Novye Ogneupory, No. 6, pp. 95–98, June, 2005.     

Large-scale fabrication of TiC@C powders and its effect on the properties of Al2O3-MgO-C castables

High performance carbon containing castables have always been pursued by researchers and steelmaking producers, unfortunately, poor water-wettability of graphite flakes was greatly limited their application in castables. To respond this, we proposed a large-scale and low-cost modified molten salt shielding synthesis technique for fabricating TiC coated graphite in air atmosphere using graphite flake and Ti powder as raw materials. Microstructure, wettability and oxidation resistance of TiC@C powders, and effect of TiC@C powders on the properties of Al₂O₃-MgO-C castables were investigated. The results demonstrate that TiC coated graphite was synthesized via modified molten salt shielding synthesis route in air atmosphere. A uniform and continuous TiC layer was formed on the surface of graphite, thereby significantly improving the water-wettability and oxidation resistance of graphite flakes. The castables with 5% TiC@C powders possessed lower apparent porosity, higher cold strength, good oxidation resistance, and slag resistance in comparison with the castables with graphite flakes, and slag resistance were also better than Al₂O₃-MgO castables. The as-fabricated TiC@C powders have good water-wettability and oxidation resistance, making them as a prime carbon source for producing carbon containing castables for steel ladle linings.     

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.     

Slag attack evaluation of in situ spinel-containing refractory castables via experimental tests and thermodynamic simulations

Although the in situ spinel formation in alumina-magnesia refractory castables induces an expansive behavior, many investigations highlight its positive role in the corrosion resistance of such materials. Thus, this work addresses the slag attack evaluation of four designed in situ spinel-containing castables (containing hydratable alumina or calcium aluminate cement as a binder source and 0 or 1 wt% of silica fume) when in contact with a Fe_xO rich industrial slag. Corrosion cup-tests, microstructural characterization and a two-step thermodynamic simulation model were used in order to investigate the reactions taking place during the slag-refractory interactions. According to the attained results, hydratable alumina seems to be a suitable binder to improve the corrosion resistance of such castables, as it induces densification and the formation of an alumina-rich spinel phase at the slag-matrix interface. Moreover, the thermodynamic calculations matched to the experimental observations, attesting the efficiency of the proposed simulation model for the evaluation of the in situ spinel-containing castable corrosion behavior.