Corrosion modeling of magnesia aggregates in contact with CaO–MgO–SiO2 slags

Ladle refining is an efficient process for improvement of quality of steel on secondary metallurgy under harsh conditions. Magnesia refractories with high purity are important raw materials for ladle lining in high-quality steel production. However, the penetration by CaO–MgO–SiO₂ slags damages magnesia refractories, which considerably limits their service life. Abundant grain boundaries in magnesia create channels for slag penetration and lead to the destruction of the structure. The effect of the microstructure on the slag corrosion behavior of magnesia aggregates requires further systematic investigation. In this study, a corrosion model was established to describe the slag penetration process of magnesia aggregates. The effects of the grain-boundary size and slag CaO/SiO₂ mass ratio (C/S ratio) on slag penetration were investigated, and the possibility of the microstructure optimization of magnesia aggregates was discussed. The results indicated that magnesia aggregates exhibited excellent slag resistance for slag with a C/S ratio above 1.5 or even 2.0. When the slag C/S ratio was lower than 1.5, the dissolution rate of magnesia decreased more rapidly with the increase in the slag C/S ratio. In addition, the much smaller grain-boundary size increased the slag penetration resistance by promoting the formation of a dense isolation layer and inhibiting further penetration processes. The calculation results agreed well with the experimental results, suggesting that the corrosion model is promising for predicting slag corrosion.     

含ZrO_2添加剂对方镁石-尖晶石耐火材料抗渣性能的影响

采用电熔镁砂、电熔镁铝尖晶石为主要原料,用坩埚法研究了三种含ＺｒＯ２ 添加剂对方镁石－ 尖晶石耐火材料抗渣性能的影响。结果表明：引入的ＺｒＯ２ 能有效吸收渣中的ＣａＯ,形成高熔点的ＣａＺｒＯ３ 固相堵塞在气孔中,阻止了炉渣的进一步渗透,又有效地降低了ＣａＯ 对尖晶石的分解作用及ＣａＯ、ＳｉＯ２ 等对主晶相方镁石的侵蚀作用;同时,ＺｒＯ２ 的引入能促进烧结,提高高温固相直接结合率,对提高抗渣性也有着十分重要的意义。     

添加物对MgO-ZrO2-C材料性能的影响

研究了Al和Si添加物对镁锆炭砖碳化烧成后膨胀性能的影响及机理。结果表明 :Al和Si在高温下氧化成Al2 O3和SiO2 ,继而与CaZrO3或用于稳定氧化锆的稳定剂反应 ,生成铝酸钙、MA、C2 S和M2 S,另外 ,C2 S和ZrO2 还发生了晶型转变。这一系列反应使试样产生很大的体积膨胀 ,从而破坏了制品结构。因此 ,与镁炭砖不同 ,Al和Si不但不能增强镁锆炭砖 ,而且使其结构破坏和耐侵蚀性降低。     

Wear of MgO-C Refractories in EBT Type Furnaces Experienced at Iranian Mobarakeh Steel Plant

Mobarakeh Steel Company produces 3 million tons ofsteel annually with eight 180 tons EBT furnaces. Differ-ent types of magnesia-carbon refractories have been em-ployed at slagline during last 5 years. In the present studythe wear and corrosion of MgO-C refractories of these fur-naces have been studied via post-mortem analysis of usedbricks and the observation of operational effects. Laborato-ry corrosion tests were also arranged to investigate the effectof slag chemistry and the mechanism of chemical corro-sion. Characterization of different magnesia-carbon bricksclarified that the crystal size, type and chemistry of mag-     

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.     

Designing environment-friendly chromium-free Spinel-Periclase-Zirconia refractories for Ruhrstahl Heraeus degasser

Ruhrstahl Heraeus (RH) degassers are globally used to manufacture vacuum-treated steel for automotive and railroad applications. The state-of-the-art environment-friendly chromium-free alternatives for direct-bonded magnesia-chrome refractories used in RH degassers are expensive, and the scientific literature lacks direct correlation between materials chemistry, processing, and functional properties. We have designed a novel spinel-periclase-15 wt% ZrO₂ composition containing 14 wt% in situ spinel which exhibited 7.2 MPa hot modulus of rupture (1500℃), exceeding all reported Cr-free refractories for RH degasser applications. Investigation with scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) attributed this improvement to a reduction in interparticle Ca and Si content which forms low-melting phases, as supported by FactSage thermodynamic simulations. The spinel-periclase composition SP exhibited superior thermal shock resistance because thermal shock-induced cracks were stopped by fracture porosity around MgO particles, formed due to thermal expansion mismatch. SEM-EDS analysis of the SP composition corroded by RH slag at 1650°C revealed that Fe is the most corrosive element followed by Ca and Si. Contradicting the consensus, it was observed that corrosion resistance of fused MgO was better than that of ZrO₂. The cubic ZrO₂ phase reduced FeO_x penetration locally by incorporating CaO from the RH slag into a solid solution and forming a CaZrO₃ phase creating a “slag barrier”. Lastly, pore size was found to greatly exacerbate slag penetration following the Washburn percolation model.     

Effect of coal slag on the wear rate and microstructure of the ZrO2-bearing chromia refractories

The typical properties of slag and refractories for slagging coal gasifier were investigated. In the range of 0–25% CaO/ash, the characteristic ash-fusion temperatures (AFTs) and viscosity of a coal-ash slag decreased with an increase of CaO additive. When the CaO/ash ratio was greater than 25% in the mixture of the coal and limestone, AFTs no longer reduced. The slag viscosity for limestone addition with CaO/ash = 25% was very low and in a narrow range (4–13 Pa.s) at coal gasification temperatures between 1300 °C and 1500 °C. However, corrosion resistance of the ZrO₂-bearing chromia refractories reduced with increasing CaO content in coal slag, especially for a slag with more than 30% CaO content. Increased chromia in three kinds of the ZrO₂-bearing chromia refractories resulted in increased corrosion resistance. The higher the Cr₂O₃ content and the lower the SiO₂ content, the less the deterioration of microstructures in the materials. Thermochemical spalling of the ZrO₂-bearing 80% Cr₂O₃ refractory after 807 operating hours of a coal gasifier was considered as the primary attack mechanism.     

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.     

Effect of electromagnetic field on slag corrosion resistance of low carbon MgO–C refractories

Using MgO–C refractories containing 6% carbon and the slag with a basicity (CaO/SiO₂) of around 0.8, the melting slag resistance experiments of low carbon MgO–C refractories were carried out in induction furnace and resistance furnace, respectively. The microstructure of low carbon MgO–C refractories corroded by slag under the different conditions was analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDAX). The results show that in induction furnace having electromagnetic field (EMF), there are MgFe₂O₄ spinel with a little of Mn ions generated in the interfacial layer. Part of the solid solution is monticellite [CaMgSiO₄] containing a little MnO and FeO. While under the condition of EMF free, there is not MgFe₂O₄ spinel in the interfacial layer and the solid solution is monticellite (CaMgSiO₄). At a high temperature, EMF increases the diffusion coefficient of Fe^2+/3+ ions, which displaces Mg²⁺ and forms MgFe₂O₄ with a little of Mn ions. There are MgAl₂O₄ spinel in the penetration layers under the conditions of both EMF and EMF free. EMF speeds up corrosion of low carbon MgO–C refractories.     

镁锆砖的抗侵蚀性能研究

采用两种不同炉渣,用静态坩埚法对镁锆砖的抗侵蚀性能进行了研究,并通过SEM和XRD等分析手段对镁锆砖的侵蚀机理进行了探索。结果表明：两种炉渣对镁锆砖的侵蚀情况略有不同;抗渣试验过程中未发生ZrO2的晶相转变。镁锆砖的侵蚀机理为：渣中的CaO与砖中的ZrO2发生反应生成高熔点物相CaZrO3,CaZrO3的生成在方镁石晶间形成了致密保护层,从而阻止了渣对镁锆砖的继续侵蚀。     

Comparative study of B4C,Mg2B2O5, and ZrB2 powder additions on the mechanical properties,oxidation, and slag corrosion resistance of MgO–C refractories

Boron-containing additives are used to improve the oxidation resistance of carbon-containing refractories; however, their effects on the mechanical properties and slag corrosion resistance of the refractories have rarely been studied. In this work, B₄C, Mg₂B₂O₅, and ZrB₂ powders were incorporated into low-carbon MgO–C refractories to study their effects on the mechanical properties, oxidation resistance, and slag corrosion resistance of the refractories. The relationships between these properties and the microstructure and phase evolution were also studied. The results show that the flexural strengths of the MgO–C refractories at high temperatures are closely related to the apparent porosity and formation of an Mg₃B₂O₆ phase. The oxidation resistances are greatly improved after the introduction of boron-containing additives into the MgO–C refractories in terms of both thermodynamical aspects and the filling of voids and pores. The most effective antioxidant is B₄C, followed by the ZrB₂ and Mg₂B₂O₅ powders. The mechanisms through which the vanadium-containing slag attacks the MgO–C refractories mainly include the dissolution of magnesia to form melting phases, penetration through pores, and redox reaction with carbon.     

六铝酸钙加入量对MgO-C耐火材料性能的影响

为提高MgO-C耐火材料的寿命,以电熔镁砂(5～3、3～1、≤1、≤0.074 mm)、鳞片石墨(≤0.15 mm)、Si粉(≤0.044 mm)、Al粉(≤0.044 mm)、六铝酸钙(≤0.044 mm)为原料,以热固性酚醛树脂为结合剂,以150 MPa压力机压成型制备了MgO-C砖试样.试样经过1200、1400...     

Role of graphite on the corrosion resistance improvement of MgO–C bricks to MnO-rich slag

In order to clarify the effect of graphite content on the corrosion behavior of MgO–C refractories immersed in MnO-rich slag, the MgO–C refractory samples bearing 5 wt%, 10 wt% and 15 wt% graphite were prepared, and exposed in the slag composed of 40 wt% CaO, 40 wt% SiO₂ and 20 wt% MnO. The results show that metallic Mn particles and (Mg,Mn)O solid solution are formed at the slag/refractories interface. Whereas, no dense layer is formed by (Mg,Mn)O solid solution at the interface. The decrease in MnO content of slag is mainly attributed to the reaction with graphite to form liquid Mn. The graphite is found in the slag, and dissolved in the form of oxidation. The poor wetting limits the contact area of graphite and slag, reducing graphite oxidation and decarburized area. The graphite does not become the passage for slag to penetrate into the refractories due to the oxidation. On the contrary, the dissolution of MgO in slag is faster than graphite, thus is mainly responsible for the degradation of refractories. As a result, MnO and MgO contents change less in the slag contacted with the refractories bearing higher graphite content.     

CaO-MgO-SiO2-H2O体系的热力学基础研究

本文从热力学角度系统研究了CaO-MgO-SiO2-H2O体系及钢渣中钙镁硅矿物在水热条件下的反应特性,结果表明：在CaO-MgO-SiO2-H2O系统中,CaO优先与SiO2反应生成水化硅酸gO只能与剩余的SiO2反应生成水化硅酸镁：MgO固溶时,可促进托勃莫来石向硬硅钙石转化。而对白钙沸石向白钙镁沸石的转化影响不大,不固溶MgO时,低温型水化硅酸钙向高温型转化温度提高,钢渣鲁镁硅矿物中,镁蔷薇辉石活性最大,透辉石活性最差,钙镁橄榄石和镁黄长石介于前两者之间。     

Improving hydration resistance of MgO–CaO ceramics by in situ synthesized CaZrO3 coatings prepared using a non-hydrolytic sol

As refractories, MgO–CaO materials exhibit excellent properties such as high refractoriness and good thermal shock resistance; however, their poor hydration resistance limits their practical applications. In this study, calcium zirconate (CaZrO₃) coatings were deposited on CaO and MgO–CaO ceramics by dipping the ceramics in a non-hydrolytic sol. The optimised coating on the MgO–CaO ceramics was prepared by dipping the ceramics once in a 0.6 mol/L zirconia sol. The CaZrO₃ coating was in situ synthesized after calcination. The multiphase ceramics with different CaO contents were characterised using scanning electron microscopy to determine the grain sizes of MgO and CaO and to analyse the distribution of CaO in the MgO matrix and the surface porosity of the samples. The microstructure and phase analysis results showed that most of the CaO on the surface transformed into CaZrO₃ and was located at the grain boundaries. The MgO–CaO ceramics with the CaZrO₃ coatings, especially the ceramics with 20 wt% CaO, showed significantly improved hydration resistance as compared to the untreated ceramics.     

低炭MgO-C质耐火材料的抗熔渣侵蚀行为

以碱度为 3.0和 1.0的钢渣对石墨含量(w)为 0、2 %、4 %、6 %和 12 %的MgO -C质试样进行了回转抗渣试验 ,并对侵蚀后试样进行了SEM、EDAX和EPMA分析。结果表明 :当石墨含量 (w)≤6 %时 ,试样在两种渣中的侵蚀深度都随石墨含量的增加而减小 ,而当石墨含量达到 12 %时 ,其侵蚀深度又都增加 ;碱度 1.0的渣对石墨含量 (w)≤ 6 %的MgO -C材料的侵蚀严重 ,而碱度 3.0的渣对石墨含量 (w)为 12 %的MgO -C材料的侵蚀严重 ;低碱度渣中Si、Fe对MgO致密层的熔损比高碱度渣中的严重。     

Microstructures and Corrosion Resistance of Al2O3—C Based Refractories to the Melts Containing Titania

The corrosion resisance of the Al2O3-C based refrac-tories in melts containing titania has been studied by quasi-station immersion and rotary immersionThe corrosion rate is decreased with the addition of graphite carbon and ZrO2 in the refractories.The corrosion mehanism of Al2O3-C refractories is the oxidization of graphite carbon by the oxides of the melts and the formation of deteriorate layer,For the Al2O3-C-ZrO2 refractories,the corrosion behavior is due to the interaction between melts and refrac-tories,The new compounds of FeO.SiO2,SiZrO4,Feo.3CaO,2CaO.SiO2 and CaO.SiO2 are formed in the deteriorate layer.     

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.     

Slag resistance mechanism of MgO–Mg2SiO4–SiC–C refractories containing porous multiphase aggregates

The slag resistance of MgO–SiC–C (MSC) refractories should be improved because of the mismatch in the thermal expansion coefficient between the aggregates and matrix, as well as the defects caused by the affinity between periclase and slag. In this study, MgO–Mg₂SiO₄–SiC–C (MMSC) refractories were prepared using porous multiphase MgO–Mg₂SiO₄ (M-M₂S) aggregates to replace dense fused magnesia aggregates. Compared to MSC, the slag penetration index of MMSC decreased by 43.5%. The structure of the porous aggregates increased the surface roughness, and the multiphase composition of the aggregates decreased the mismatch of the thermal expansion coefficient with the matrix, thus reducing debonding between the aggregates and matrix. The aggregates and matrix in the MMSC formed an interlocking structure, which bound them more tightly to improve the slag resistance. The slag viscosity at different depths from the initial slag/refractory interface was calculated using the Ribond model. The M-M₂S aggregates increased Si_xO_y^z− in the slag, which increased the slag polymerization and slag viscosity. The aggregates and matrix in the MMSC reacted with the slag to form high melting point phases, which reduced the channel of the slag. In addition, the penetration depth and velocity derived from the Washburn Equation were modified for the CaO–SiO₂–Al₂O₃–MgO–FeO slag and magnesia based refractory to accurately evaluate slag penetration.     

电磁场作用下高铁渣对MgO-C耐火材料的侵蚀

电磁场会促使熔渣中的铁、锰离子与MgO-C耐火材料反应形成锰掺杂镁铁尖晶石相,为进一步研究锰掺杂镁铁尖晶石的生成形貌及特征,采用Fe2O3质量分数为53.62%、CaO与SiO2质量比为0.8的高铁渣,分别在有、无电磁场环境下,对碳质量分数为14%的MgO-C耐火材料进行渣蚀试验。结果表明:感应炉存在电磁场,使熔渣中部分Fe2+/Fe3+与镁砂中Mg2+发生置换形成镁铁尖晶石,其含有少量Mn2+离子;镁铁尖晶石中铁含量从渣蚀层到渗透层急剧降低,锰含量几乎维持不变;侵蚀后试样渗透层较明显。电阻炉无电磁场,则侵蚀后试样没有形成镁铁尖晶石,熔渣中Si、Ca渗透到方镁石晶格中,形成钙镁榄橄石低熔相,将镁砂溶解到熔渣中;渣蚀层有明显的MgAl2O4生成。