Kinetics of Transformation of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> to MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Spinel Inclusions in Mg-Containing Steel

During ladle furnace refining, initial Al₂O₃ inclusions generally transform into MgO·Al₂O₃ spinel inclusions; these generated spinel inclusions consequently deteriorate the product quality. In this study, the transformation from Al₂O₃ to MgO·Al₂O₃ was investigated by immersing an Al₂O₃ rod into molten steel, which was in equilibrium with both MgO and MgO·Al₂O₃ spinel-saturated slag. A spinel layer, with a thickness of 4 μm, was generated on the Al₂O₃ rod surface just 10 s after its immersion at 1873 K (1600 °C). The thickness of the formed spinel layer increased with the immersion period and temperature. Moreover, the MgO content of the generated spinel layer also increased with the immersion period. In this study, the chemical reaction rate at 1873 K (1600 °C) was assumed to be sufficiently high, and only diffusion was considered as a rate-controlling step for this transformation. By evaluating the activation energy, MgO diffusion in the generated spinel layer was found to be the rate-controlling step. In addition, this estimation was confirmed by observing the Mg and Al concentration gradients in the generated spinel layer. The results of this study suggest that the MgO diffusion in the spinel inclusions plays a substantial role with regard to their formation kinetics.     

Evolution of Al2O3 inclusions by magnesium treatment in H13 hot work die steel

To investigate the evolution mechanism of Al₂O₃ inclusions after Mg treatment in H13 die steel, the determination of inclusions characteristics and thermodynamic calculation were carried out in the present study. The results showed that irregular and cluster Al₂O₃ inclusions in H13 die steel were modified to MgO·Al₂O₃ and MgO after Mg treatment. Two types of MgO·Al₂O₃ were detected after Mg treatment. The long-range gravity between the MgO-containing inclusions is weaker than that of the MgO-free inclusions. The long-range gravity between the inclusions decreases with the increasing of Mg content of the steel. The evolution mechanisms of inclusion in low Mg-containing and high Mg-containing H13 die steel were comprehensive discussed. The different reaction mechanisms result in the different of the core of the MgO·Al₂O₃ inclusion.     

Effects of FeO and CaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ratio in Slag on the Cleanliness of Al-Killed Steel

The slag composition plays a critical role in the formation of inclusions and the cleanliness of steel. In this study, the effects of FeO content and the C/A (CaO/Al₂O₃) ratio in the slag on the formation of inclusions were investigated based on a 10-minute slag–steel reaction in a MgO crucible. The FeO content in the top slag was shown to have a significant effect on the formation of MgO·Al₂O₃ spinel inclusions, and critical content exists; when the initial FeO content in the slag was less than 2 pct, MgO·Al₂O₃ spinel inclusions formed, and the T.O (total oxygen) was 20 ppm; when the initial FeO content in the slag was more than 4 pct, only Al₂O₃ inclusions were observed and the T.O was 50 ppm. It was clarified that the main source of Mg for the MgO·Al₂O₃ spinel inclusion formation was the top slag rather than the MgO crucible. In addition, the cleanliness of the steel increased as the initial FeO content in the top slag decreased. As regards the effects of the C/A ratio, the MgO amount in the observed inclusions gradually increased, whereas the T.O content decreased gradually with the increasing C/A ratio. Slag with a composition close to the CaO-saturated region had the best effect on the inclusion absorption.     

Control of MgO·Al2O3 Spinel Inclusions during Protective Gas Electroslag Remelting of Die Steel

The effect of calcium treatment and/or aluminum-based deoxidant addition on the oxygen control and modification of MgO·Al₂O₃ spinel inclusions during protective gas electroslag remelting (P-ESR) of H13 die steel with low oxygen content was experimentally studied. It is found that all the inclusions in the consumable electrode are MgO·Al₂O₃ spinels, besides a few MgO·Al₂O₃ spinels surrounded by an outer (Ti,V)N or MnS layer. After P-ESR refining combined with proper calcium treatment, all the original MgO·Al₂O₃ spinels in the electrode (except for the original MgO·Al₂O₃ spinels having been removed in the P-ESR process) were modified to mainly CaO-MgO-Al₂O₃ and some CaO-Al₂O₃ inclusions, both of which have a low melting point and homogeneous compositions. In the case of only Al-based deoxidant addition, all the oxide inclusions remaining in ESR ingots are MgO·Al₂O₃ spinels. The operation of Al-based deoxidant addition and/or calcium treatment during P-ESR of electrode steel containing low oxygen content is invalid to further reduce the oxygen content and oxide inclusions amount compared with remelting only under protective gas atmosphere. All the original sulfide inclusions were removed after the P-ESR process. Most of the inclusions in ESR ingots are about 2 μm in size. The mechanisms of non-metallic inclusions evolution and modification of MgO·Al₂O₃ spinels by calcium treatment during the P-ESR process were proposed.     

Evolution of inclusions and change of as-cast microstructure with Mg addition in high carbon and high chromium die steel

The effects of Mg on the inclusions and the as-cast microstructure of high carbon and high chromium die steel, a grade of cold working die steel with high C content of 1.4–1.6% and high Cr content of 11.0–13.0%, were systematically investigated. It is found that inclusions vary with the route as Al₂O₃ (No Mg) to MgO·Al₂O₃ +?Al₂O₃ (5?ppm Mg), and then to MgO+MgO·Al₂O₃ (11 and 15?ppm Mg). The average diameter of the inclusions decreased from 1.91 μm (no Mg) to 1.29 μm (15?ppm Mg), while the number density increased from 2.69?×?10⁴ mm^??3 (no Mg) to ～5.62?×?10⁴ mm^??3 (15?ppm Mg). The changes in the size and the number density were discussed in terms of the effect of inclusions on the nucleation process and the wettability of them with steel melt. The as-cast microstructures were greatly refined with Mg addition that correlated with the evenly dispersed fine Mg containing inclusions.     

Simultaneous Modification of Alumina and MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Inclusions by Calcium Treatment During Electroslag Remelting of Stainless Tool Steel

Calcium modification of both alumina and MgO·Al₂O₃ inclusions during protective gas electroslag remelting (P-ESR) of 8Cr17MoV stainless steel and its effect on nitrides and primary carbides were studied by analyzing the transient evolution of oxide and sulfide inclusions in the P-ESR process. The oxide inclusions that were not removed during P-ESR without calcium treatment were found to retain their original state until in as-cast ingot. Calcium treatment modified all MgO·Al₂O₃ and alumina inclusions that had not been removed in the P-ESR process to liquid/partially liquid CaO-Al₂O₃-(MgO) with uniformly distributed elements, in addition to a small proportion of partially modified inclusions of a CaO-MgO-Al₂O₃ core surrounded by a liquid CaO-Al₂O₃. The modification of low-MgO-containing MgO·Al₂O₃ inclusions involves the preferential reduction of MgO from the MgO·Al₂O₃ inclusion by calcium and the reaction of calcium with Al₂O₃ in the inclusion. It is the incomplete/complete reduction of MgO from the spinel by calcium that contributes to the modification of spinels. Alumina inclusions were liquefied by direct reaction with calcium. Calcium treatment during P-ESR refining also provided an effective approach to prevent the formation of nitrides and primary carbides in stainless steel through modifying their preferred nucleation sites (alumina and MgO·Al₂O₃ inclusions) to calcium aluminates, which made no contribution to improving the steel cleanliness.     

Characteristics analysis of inclusion of 60Si2Mn–Cr spring steel via experiments and thermodynamic calculations

A plant trial of the production of 60Si2Mn–Cr spring steel using silicon–manganese combined with aluminium to deoxidise was performed, and the characteristics of inclusions during ladle furnace refining, calcium treatment and in billets were investigated by scanning electron microscope–energy dispersive spectroscopy and thermodynamic calculations. The formation mechanisms of oxide and CaS inclusions are discussed. The experimental observation and thermodynamic analysis showed that calcium treatment cannot entirely modify large-size MgO·Al₂O₃ spinel inclusions into homogeneous CaO–MgO–Al₂O₃ inclusions, but formed a liquid xCaO·yAl₂O₃ layer on its surface. When the Al content was 0.05 mass%, [Mg], [Ca] and [O] in molten steel could be controlled at 2.7～5 ppm, 2.5～8 ppm and 4.1～5.2 ppm, respectively, to achieve inclusions in the low melting point region. A large amount of CaS was generated in the present process due to a higher sulphur concentration in the molten steel and an excessive amount of Ca–Si wire. To avoid/reduce its formation, the sulphur concentration should be controlled to below 70 ppm.     

Formation and Modification of MgO·Al2O3-Based Inclusions in Alloy Steels

The current study performed thermadynamic calculation, laboratory experiments, and industrial trials for the formation and modification of MgO-Al₂O₃ spinel inclusions in alloy steels. The stability Mg-Al-O diagram was obtained using the thermodymanic study. The resulting MgO-Al₂O₃-CaO inclusions from MgO-Al₂O₃ spinel inclusions after the calcium treatment were spherical, and?>?5???m MgO-Al₂O₃-CaO inclusions have a two-layer structure: an outside CaO-Al₂O₃ layer and a MgO-Al₂O₃ core. The modification of?>?5???m MgO·Al₂O₃ spinel inclusions by calcium treatment includes two steps: (1) reducing MgO in the inclusion into the dissolved magnesium by the dissolved calcium in the steel and (2) generating a liquid xCaO·yAl₂O₃ layer at the outside of the spinel inclusion. For <2???m MgO·Al₂O₃ spinel inclusions, they can possibly be modified into a xCaO·yAl₂O₃ inclusion by reducing all MgO component in the spinel inclusions with the added calcium.     

Thermodynamics on the formation of spinel (MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) inclusion in liquid iron containing chromium

The stability diagram of MgO, spinel solid solution (MgO·(Al _X Cr_1−X )₂O₃), and sesquioxide solid solution ((Al _Y Cr_1−Y )₂O₃) as a function of Mg, Al, and O contents at a constant chromium content (18 mass pct) in liquid iron is drawn at 1873 K. The interaction parameters between Mg and other solutes (Al, Cr, Ni, Ti, Si, and C) are determined by the experimental method, which assures equilibrium between Mg vapor and liquid iron, were applied to calculate the diagram. Titanium deoxidation is not recommended for the prevention of spinel formation, because Ti accelerates Mg dissolution from refractory or slag due to its high affinity for Mg (e _Mg ^Ti = − 0.64). The standard Gibbs free energies of formation for the three inclusions (periclase, spinel, and sesquioxide solid solutions) and the tielines between two solid solutions were calculated with the aid of the regular solution model and the thermochemical F*A*C*T database computing system, respectively. The phase stability regions and oxygen content in steel for the current Fe-Mg-Al-Cr (18 mass pct)-O system are compared with those of the previous non-Cr system. Detailed information on the spinel composition according to Mg and Al contents is also available from the present stability diagram.     

Modification and Minimization of Spinel(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>·<Emphasis Type="Italic">x</Emphasis>MgO) Inclusions Formed in Ti-Added Steel Melts

High-melting-point inclusions such as spinel(Al₂O₃·xMgO) are known to promote clogging of the submerged entry nozzle (SEN) in a continuous caster mold. In particular, Ti-alloyed steels can have severe nozzle clogging problems, which are detrimental to the slab surface quality. In this work, the thermodynamic role of Ti in steels and the effect of Ca and Ti addition to the molten austenitic stainless steel deoxidized with Al on the formation of Al₂O₃·xMgO spinel inclusions were investigated. The sequence of Ca and Ti additions after Al deoxidation was also investigated. The inclusion chemistry and morphology according to the order of Ca and Ti are discussed from the standpoint of spinel formation. The thermodynamic interaction parameter of Mg with respect to the Ti alloying element was determined. The element of Ti in steels could contribute to enhancing the spinel formation, because Ti accelerates Mg dissolution from the MgO containing refractory walls or slags because of its high thermodynamic affinity for Mg ( e_\textMg^\textTi = - 0. 9 3 3). ( {e_{\text{Mg}}^{\text{Ti}} = - 0. 9 3 3}). Even though Ti also induces Ca dissolution from the CaO-containing refractory walls or slags because of its thermodynamic affinity for Ca ( e_\textCa^\textTi = - 0.119 ), \left( {e_{\text{Ca}}^{\text{Ti}} = - 0.119} \right), dissolved Ca plays a role in favoring the formation of calcium aluminate inclusions, which are more stable thermodynamically in an Al-deoxidized steel. The inclusion content of steel samples was analyzed to improve the understanding of fundamentals of Al₂O₃·xMgO spinel inclusion formation. The optimum processing conditions for Ca treatment and Ti addition in austenitic stainless steel melts to achieve the minimized spinel formation and the maximized Ti-alloying yield is discussed.     

Effect of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO slags on the formation of MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> inclusions in ferritic stainless steel

A thermodynamic equilibrium between the Fe-16Cr melts and the CaO-Al₂O₃-MgO slags at 1823 K as well as the morphology of inclusions was investigated to understand the formation behavior of the MgO-Al₂O₃ spinel-type inclusions in ferritic stainless steel. The calculated and observed activities of magnesium in Fe-16Cr melts are qualitatively in good agreement with each other, while those of aluminum in steel melts exhibit some discrepancies with scatters. In the composition of molten steel investigated in this study, the log (X _MgO/X _{Al 2}O₃) of the inclusions linearly increases by increasing the log [a _Mg/a _Al ² ·a _O ² ] with the slope close to unity. In addition, the relationship between the log (X _MgO/X _{Al 2}O₃) of the inclusions and the log (a _MgO/a _{Al 2}O₃) of the slags exhibits the linear correlation with the slope close to unity. The compositions of the inclusions are relatively close to those of the slags, viz. the MgO-rich magnesia-spinel solid solutions were formed in the steel melts equilibrated with the highly basic slags saturated by CaO or MgO. The spinel inclusions nearly saturated by MgO were observed in the steel melts equilibrated with the slags doubly saturated by MgO and MgAl₂O₄. The spinel and the Al₂O₃-rich alumina-spinel solid solutions were formed in the steel melts equilibrated with the slags saturated by MgAl₂O₄ and MgAl₂O₄-CaAl₂O₄ phases, respectively. The apparent modification reaction of MgO to the magnesium aluminate inclusions in steel melts equilibrated with the highly basic slags would be constituted by the following reaction steps: (1) diffusion of aluminum from bulk to the metal/MgO interface, (2) oxidation of the aluminum to the Al³⁺ ions at the metal/intermediate layer interface, (3) diffusion of Al³⁺ ions and electrons through the intermediate layer, and (4) magnesium aluminate (MgAl₂O₄ spinel, for example) formation by the ionic reaction.     

Formation and Evolution Mechanism of the Inclusions of Al2O3·SiO2·CaO and Al2O3·SiO2·CaO·MgO in Seamless Steel Tube Steel

Herein, the formation and evolution mechanism of inclusions of Al₂O₃·SiO₂·CaO and Al₂O₃·SiO₂·CaO·MgO in seamless steel tube steel are investigated. In the long strip defects on the longitudinal cross section of the steel tube after the rolling bar piercing, the defect is mainly formed by Al₂O₃·SiO₂·CaO·MgO inclusions and Al₂O₃·SiO₂·CaO·inclusions dotted with·CaS inclusions after the rolling. The typical inclusions in the different steelmaking stages are mainly composed of CaS, Al₂O₃·(SiO₂), CaO·(SiO₂), MnS·(TiN), Al₂O₃·SiO₂·CaO·(CaS)·(MnS), Al₂O₃·SiO₂·CaO·MgO·(MnO), Al₂O₃·SiO₂·CaO·MgO·(CaS)·(MnS), etc. In the billet, the average sizes of Al₂O₃·SiO₂·CaO-based and Al₂O₃·SiO₂·CaO·MgO-based inclusions are much larger than those of the other types of inclusions. Part of SiO₂ in the deoxidized products SiO₂ can be reduced by [Al], resulting in the formation of the Al₂O₃·SiO₂ composite inclusions. The SiO₂ in Al₂O₃·SiO₂ inclusions can continuously be reduced by the dissolved [Ca] to form the Al₂O₃·SiO₂·CaO composite inclusions. The SiO₂ in the Al₂O₃·SiO₂·CaO inclusions can be reduced by the dissolved [Mg] to form the Al₂O₃·SiO₂·CaO·MgO composite inclusions. Another formation process of Al₂O₃·SiO₂·CaO·MgO inclusions is the entrapment of ladle slag in the vacuum degassing (VD) stage, due to the strong agitation of the rising Ar bubbles in the vacuum condition of the VD stage.     

Control of Non‐metallic Inclusions by Slag‐metal Reactions for High Strength Alloying Steels

A laboratory study was carried out to investigate non‐metallic inclusions in high strength alloying steel refined by high basicity slag. The results indicated that the inclusions were mainly of the CaO? MgO? Al₂O₃ system, Al₂O₃? MgO and MgO‐based inclusions. The steel/slag reaction time and Al₂O₃ content in slag had a great effect on inclusions characteristics. With the reaction time increasing from 30 to 180 minutes, inclusions experienced a transformation process: from mainly Al₂O₃? MgO system and MgO‐based inclusions to spherical CaO? MgO? Al₂O₃ system inclusions surrounded by a lower melting temperature surface layer of CaO? Al₂O₃. Formation and transformation mechanisms of the inclusions were given based on the results. It was also found that with Al₂O₃ content in slag reduced from 40% to 30%, [Mg] contents in steel melts were increased and MgO in slag reached saturation, which contributed to the formation of more MgO‐based inclusions and a more scattered inclusion composition distribution after 90 min reaction.     

Investigation of Oxide Inclusions and Primary Carbonitrides in Inconel 718 Superalloy Refined through Electroslag Remelting Process

The effect of remelting atmosphere and calcium treatment during electroslag remelting (ESR) of Inconel 718 superalloy on the oxide inclusions and primary carbonitrides was investigated. The results show that after ESR refining combined with calcium treatment, the original oxide inclusions in the electrode, mainly MgO·Al₂O₃ spinels and some MgO inclusions, were modified to CaO-Al₂O₃ system inclusions or the inclusions of MgO·Al₂O₃ spinel core surrounded by CaO-MgO-Al₂O₃ system inclusion layer. Without the calcium treatment in ESR process, all the oxide inclusions in superalloy ingots are MgO·Al₂O₃ spinels. All the oxide inclusions in ESR ingots act as the nucleation site for carbonitride (Nb,Ti)CN with two-layer structure precipitation, except for those with a single (Nb,Ti)CN layer containing a small amount of Ti and N in the ingot refined by a proper amount of calcium addition in ESR process. The carbonitrides (Nb,Ti)CN formed directly on the oxide inclusion have a small amount of Nb and C as well as a relatively fixed atomic ratio of Nb/Ti (about 0.6:1). There is a Nb-rich and C-rich (Nb,Ti)CN layer on the pre-existing (Nb,Ti)CN formed on the oxide inclusion. The size of the observed carbonitrides is in the range of 5 ??m to 15 ??m. The calcium treatment in the ESR process has a significant effect on the morphology of carbonitrides in superalloy ingot due to modification of oxide inclusions by Ca-treatment resulting in the change of precipitation and growth conditions for carbonitrides. The morphologies of carbonitrides were changed from clustered block or single octahedral to skeleton-like after calcium treatment.     

Refractory/steel/inclusion interactions in Al-deoxidised valve spring steel treated with Na2CO3

Ca treatment is generally used in the production of Al-deoxidised steel to prevent nozzle blockage by modifying high melting point inclusions such as MgO·Al₂O₃ (Melting point: 2408?K). However, the successful application of Ca treatment can be quite difficult due to the requirements for stringent control of the amount of calcium that is added. In the present paper, a novel and effective method of inclusion modification by Na₂CO₃ treatment is developed and the evolution process of inclusions in Al-deoxidised steel with Na₂CO₃ treated is studied, which is in good agreement with FactSage calculation results. In addition, the relevant refractory/steel/inclusion interaction mechanisms are also discussed. The experimental results show that MgO–Al₂O₃ inclusions can be transformed into Na₂O–MgO–Al₂O₃–SiO₂ inclusions with low-melting points by Na₂CO₃ treatment. After Na₂CO₃ addition, both the dissolved [Na] and [Si] start to reduce MgO and Al₂O₃ in the generated MgO–Al₂O₃ inclusions from outside to inside, accompanied with the reduction of MgO–Al₂O₃ reaction layer at the steel-refractory interface by [Na] and [Si] in the steel.     

Exploration of morphology evolution of the inclusions in Mg-treated 16MnCrS5 steel

To elucidate the morphology evolution of the inclusions in 16MnCrS5 steel with various masses of Mg addition, the experiments and thermodynamics were carried out with a high-temperature tube electric resistance furnace and FactSage software, respectively. The evolutions of the inclusions after the smelting and hot-processing were described. The experimental results show that with Mg addition of 35–42?ppm, many spindle and spherical inclusions with the size below 20?μm appeared, whereas the long-strip inclusions above 20?μm disappeared; after hot-processing, particularly, the h value was above 50%, beneficial to obtaining more spindle inclusions, and most spherical inclusions at 35?ppm were also obtained. The thermodynamics show that with Mg mass between 0.349 and 6.076?ppm, Al₂O₃ was easily converted to MgO·Al₂O₃, whereas above 6.076?ppm, Mg was directly converted to form MgO; above more, MgS coexisted with MgO.     

Characteristics and Modification of Non-metallic Inclusions in Titanium-Stabilized AISI 409 Ferritic Stainless Steel

This study describes an investigation into the improvement of castability, final surface quality and formability of titanium-stabilized AISI 409 ferritic stainless steel on an industrial scale. Non-metallic inclusions found in this industrially produced stainless steel were first characterized using SEM-EDS analyses through the INCA-Steel software platform. Inclusions were found to consist of a MgO·Al₂O₃ spinel core, which acted as heterogeneous nucleation site for titanium solubility products. Plant-scale experiments were conducted to either prevent the formation of spinel, or to modify it by calcium treatment. Modification to spherical dual-phase spinel-liquid matrix inclusions was achieved with calcium addition, which eliminated submerged entry nozzle clogging for this grade. Complete modification to homogeneous liquid calcium aluminates was achieved at high levels of dissolved aluminum. A mechanism was suggested to explain the extent of modification achieved.     

Effect of Al antioxidant in MgO–C refractory on the formation of Al2O3-rich inclusions in high-carbon steel for saw wire under vacuum conditions

Al₂O₃-rich (>70?wt-%) inclusions generally hard and non-deformable are extremely detrimental for saw wire. In order to explore the source of this type of inclusion and provide solutions, experiments on the interaction between Al-containing MgO–C refractory and high-carbon steel for saw wire was conducted on a laboratorial scale using a cold crucible levitation melting furnace under vacuum conditions. [Al]_S (acid-soluble Al), [C] and [Mg] concentrations in steel, Al₂O₃ concentration in inclusions and microstructure of refractory/steel interface, etc. were analysed to clarify the influence of vacuum pressure, refractory addition amount and interaction time. Based on the experimental results and thermodynamic calculations, a presumable impact mechanism of Al antioxidant in MgO–C refractory on the formation of Al₂O₃-rich inclusions in high-carbon steel for saw wire under vacuum conditions was deduced, which in turn provided a reference for the control of Al₂O₃-rich inclusions in high-carbon steel for saw wire.     

Behavior of MgO· Al2O Based Inclusions in Alloy Steel During Refining Process

The transformation of MgO ? Al₂O₃ based inclusions in alloy steel during refining has been studied by industrial trials. Besides Factsage software is used to study the formation and modification of spinel inclusions in alloy steel using calcium treatment during refining process. The results show that the transformation sequence of inclusions is: MgO ? Al₂O₃→CaO-Al₂O₃-MgO complex inclusions→MgO ? Al₂O₃, and under present experimental condition, in order to avoid forming MgO ? Al₂O₃ inclusions the content of dissolved Ca in the molten steel has to reach 1×10^?6. Also the results show that when more calcium was added to molten steel, the content of Al₂O₃ and MgO will be lower. Besides, increasing the content of CaO in the inclusions will increase even if the content of SiO₂ changes little.