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.     

Investigations on the equilibria between Al-Ca-O containing iron melts and CaO-Al2O3-FeOn slags

The equilibria between liquid CaO-Al₂O₃-FeO_n slags and Al-Ca-O-containing iron melts in contact with pure lime (CaO) and pure calcium aluminate (CaO-2Al₂O₃) crucibles were investigated at 1600°C. The iron mass content of the metal phase was varied between 0 and almost 100 %. The results show a strong influence of the miscibility gap in the system Fe-Al-Ca arising from the Fe-Ca binary system on the phase equilibria. By these investigations the conditions of solid alumina reduction by dissolved calcium to liquid calcium aluminate were determined.     

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.     

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.     

Transformation of Alumina Inclusions by Calcium Treatment

The objectives of this study were to investigate reactions of calcium with Al₂O₃ by different model experiments both on the laboratory and on the industrial scale. Experiments with solid Al₂O₃ and CaO were performed between 1350 °C and 1600 °C. Reaction rate constants were determined based on scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) observations of reaction products and weight measurements of the Al₂O₃ reacted via dissolution of the CaO bearing phases from the specimens after the annealing period. The results showed that the formation of calcium aluminate phases proceeded rapidly at temperatures greater than 1405 °C when a liquid calcium aluminate was formed. In the lowest temperature range (1350 °C–1405 °C), when the formation of liquid phase ceased, the reaction rate was several orders of magnitude lower. Industrial trials including Ca-alloy injection into steel, sampling and SEM/EDS analyses, as well as an inclusion rating in the samples show the concept of rapid transformation of the alumina inclusions with Ca treatment.     

Investigation on the removal efficiency of inclusions in Al-killed liquid steel in different refining processes

Industry trials were carried out to study the removal efficiency of inclusions in Al-killed liquid steel in the processes of BOF–LF–RH–CC and BOF–RH–CC. It was found that the removal efficiency of inclusions has a high dependence on inclusion types. Solid inclusions are more easily to be removed than liquid inclusions. The removal efficiency of solid Al₂O₃ inclusions is higher than that of solid CaO–Al₂O₃–MgO inclusions. As liquid CaO–Al₂O₃–MgO inclusions coexisted with solid CaO–Al₂O₃–MgO inclusions in the liquid steel, the low removal efficiency of inclusions in RH degassing process was found in BOF–LF–RH–CC process. However, high removal efficiency and ultra-low total oxygen (T.O) content were obtained in BOF–RH–CC process because the inclusions were mainly composed of solid Al₂O₃ although initial T.O content before RH degassing was relatively high. This is due to the fact that solid Al₂O₃ tends to form cluster-shaped inclusions which have both a higher contact angle and a lower work of adhesion with steel than calcium aluminate, resulting in easier removal by RH degassing. Therefore, it is proposed to weaken steel–slag reaction and calcium treatment before RH degassing to retain solid Al₂O₃ inclusions in the steel.     

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.     

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.     

Dissolution Behavior of Mg from Magnesia-Chromite Refractory into Al-killed Molten Steel

Magnesia-chromite refractory materials are widely employed in steel production, and are considered a potential MgO source for the generation of MgO·Al₂O₃ spinel inclusions in steel melts. In this study, a square magnesia-chromite refractory rod was immersed into molten steel of various compositions held in an Al₂O₃ crucibles. As the immersion time was extended, Mg and Cr gradually dissolved from the magnesia-chromite refractory, and the Mg and Cr contents of the steel melts increased. However, it was found that the inclusions in the steel melts remained as almost pure Al₂O₃ because the Mg content of the steel melts was low, approximately 1 ppm. On the surface of the magnesia-chromite refractory, an MgO·Al₂O₃ spinel layer with a variable composition was formed, and the thickness of the MgO·Al₂O₃ spinel layer increased with the immersion time and the Al content of the steel melts. At the rod interface, the formed layer consisted of MgO-saturated MgO·Al₂O₃ spinel. The MgO content decreased along the thickness direction of the layer, and at the steel melts interface, the formed layer consisted of Al₂O₃-saturated MgO·Al₂O₃ spinel. Therefore, the low content of Mg in steel melts and the unchanged inclusions were because of the equilibrium between Al₂O₃-saturated MgO·Al₂O₃ layer and Al₂O₃. In addition, the effects of the Al and Cr contents of the steel melts on the dissolution of Mg from the magnesia-chromite refractory are insignificant.     

Thermodynamic conditions for inclusions modification in calcium treated steel

The presented paper discussed the fundamental or common thermodynamical relations between calcium-treated aluminium-killed molten steel and non-metallic inclusions. The phase and chemical analyses of inclusions have proven that the correctness of calcium addition can be confirmed and that the analysis of those phenomena can show the effects of previous calcium treatment of aluminium-killed steel. To make the process of manufacturing quality steel successful the factor affecting the necessary calcium addition should be taken into consideration already during the process. Steel, containing too much calcium could have CaS inclusions with a high melting point, while too low contents of calcium cause unsatisfactory modification of solid alumina inclusions to complex liquid calcium-aluminate inclusions. This research included the examination of thermodynamic relations in calcium addition and its reactions with solid Al₂O₃ inclusions. A detailed analysis of the CaO–Al₂O₃ binary system established the modification of solid alumina inclusions via the following intermediate phases: CaO · 6Al₂O₃, CaO · 2Al₂O₃, CaO · Al₂O₃ and liquid phase 12CaO · 7Al₂O₃ and finally again solid CaO, at 1873 K (1600°C). The investigation discusses the further research engaged in consideration of CaO- and Al₂O₃-activities change in each of the quoted intermediate phases. The system as a whole includes details of oxygen activities.     

Inclusion evolution after calcium addition in Ti-bearing Al-kill steel

In current article, experiments with different calcium addition were carried out in an Al₂O₃ crucible at 1873?K to investigate the variation of inclusion in Ti-bearing Al-kill Steel. It was found that calcium significantly influenced the morphology, composition distribution and size of oxide inclusions in Ti-bearing Al-kill Steel. Liquid oxide inclusions were modified promptly after calcium addition. Meanwhile, calcium could also modify solid titanium aluminate inclusions to spherical ones similarly, but there were a number of multilayer inclusions in molten steel at the initial stage. Different calcium treatment level should be adopted in different titanium content steel production process. As for the production practice, to achieve the full liquid inclusions in molten steel, the amount of calcium and titanium should be controlled simultaneously during the production process.     

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.     

Effects of Calcium Addition on Nonmetallic Inclusions in High-Al Steel

To investigate the formation and evolution mechanism of inclusions in high-Al steel, four lab-scaled experiments are carried out with different calcium (Ca) contents. The Al₂O₃ inclusions are modified to (CaO–Al₂O₃)–CaS after Ca addition. With the Ca content increased, the types of CA_x-CaS inclusions are changed from CaS-attached inclusions to CA_x-wrapped inclusions. When the total calcium content (T.Ca) reached 29 ppm, the CA_x–CaS inclusions are primarily distributed within the 50% liquidus in CaO–Al₂O₃–CaS ternary diagram. Some Al₂O₃ inclusions are not completely modified with 7 ppm Ca addition. CaS and CaO–CaS inclusions are observed with a higher Ca addition. The modification of Al₂O₃ by CaS and [Ca] occurs in CaS-attached inclusions with a lower Ca addition. To clarify the formation of CaS, a new modification index for high-Al steel is given based on the T.Ca/T.O index.     

Automated Classification and Analysis of Non-metallic Inclusion Data Sets

The aim of this study is to utilize principal component analysis (PCA), clustering methods, and correlation analysis to condense and examine large, multivariate data sets produced from automated analysis of non-metallic inclusions. Non-metallic inclusions play a major role in defining the properties of steel and their examination has been greatly aided by automated analysis in scanning electron microscopes equipped with energy dispersive X-ray spectroscopy. The methods were applied to analyze inclusions on two sets of samples: two laboratory-scale samples and four industrial samples from a near-finished 4140 alloy steel components with varying machinability. The laboratory samples had well-defined inclusions chemistries, composed of MgO-Al₂O₃-CaO, spinel (MgO-Al₂O₃), and calcium aluminate inclusions. The industrial samples contained MnS inclusions as well as (Ca,Mn)S + calcium aluminate oxide inclusions. PCA could be used to reduce inclusion chemistry variables to a 2D plot, which revealed inclusion chemistry groupings in the samples. Clustering methods were used to automatically classify inclusion chemistry measurements into groups, i.e., no user-defined rules were required.     

Inclusion Characterization in Aluminum-Deoxidized Special Steel with Certain Sulfur Content Under Combined Influences of Slag Refining,Calcium Treatment,and Reoxidation

Inclusions in Al-killed steel with [S] of about 0.0060 to 0.0070 mass pct were characterized and discussed, evaluating the combined effects of basic slag refining and Ca treatment in ladle, together with reoxidation of liquid steel in casting tundish. Inclusions were changed from Al₂O₃ to MgO-Al₂O₃ spinel and then to MgO-Al₂O₃-CaO during basic slag refining. After Ca treatment, many (MgO-Al₂O₃)?+?CaS inclusions were formed, featuring the coexistence of MgO-Al₂O₃ and CaS to form a dual-phased structure. In the following Ar blowing, the number density of (MgO-Al₂O₃)?+?CaS inclusions and pure CaS increased obviously, which implied that [Ca] preferentially reacted with [S] rather than [O] in steel. Reoxidation in casting tundish caused the pickup of oxygen in steel, and the rise of total oxygen (T.O) was 0.0002 mass pct; even 55t steel has been poured. As a result, the content of CaO in inclusions increased and MgO-Al₂O₃-CaO inclusions were formed again. Thermodynamic calculations revealed that the driving force was strong for the formation of CaS-based inclusions. Higher carbon content in steel would help to reduce oxygen content while enhancing the activity of [S] in steel, which further stabilized the existence of CaS-based inclusions. Therefore, inclusions were mostly the solid (MgO-Al₂O₃)?+?CaS dual-phase ones, without the formation of liquid calcium aluminates. Contents of CaS and CaO in inclusions were affected by the [mass pct S]/[mass pct O] ratio, which was calculated as about 4.58 K and 5.34 K at 1873 K and 1823 K, respectively. This finding implied that lower oxygen was not favorable to prevent the solid inclusions in the calcium treatment of high carbon special steel.     

Calcium Modification of Spinel Inclusions in Aluminum-Killed Steel: Reaction Steps

Calcium treatment is a well-established way to modify solid alumina inclusions to liquid or partially liquid calcium aluminates. Spinels (Al₂O₃·xMgO) can also form in liquid steel after aluminum deoxidation. Like alumina, the spinels can be modified readily to liquid inclusions by a calcium treatment. The modification of spinels was studied by observing the transient evolution of inclusions, in laboratory and industrial heats. Spinel modification involves the preferential reduction of MgO from the spinel, with Mg dissolving in the steel, and it proceeds through transient calcium sulfide formation, just like in the case of alumina inclusions. Because magnesium dissolves in steel after the calcium treatment of spinels, the reoxidation of the melt will produce new spinels.     

Experimental Study to Improve the Castability of Aluminum Killed Cold Heading Steel

Experimental study on the LF refining of aluminum killed cold heading steel shows that calcium content in the molten steel increased to about 0.0010% at the end of refining, and the aluminum deoxized products were transformed from Al₂O₃ to the complex inclusions CaO–MgO–Al₂O₃ with lower melting point by the high basicity, high Al₂O₃, and strong deoxidizing slag. The inclusions are in liquid state and can be easily floated up during LF refining and continuous casting. The total oxygen content of the steel falls to about 0.0020%. The experimental technology uses only 50 m calcium wire to the 80‐t heat or even without calcium treatment. As compared to the traditional technology with higher amount of calcium for treatment, which forms CaS and CaO–MgO–Al₂O₃ inclusions with high melting point, the experimental technology improves the castability and reduces the manufacturing cost.     

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.     

Ladle glaze: major source of oxide inclusions during ladle treatment of steel

Abstract

Samples of ladle lining covered by glaze were taken from industrial ladles of different ages at Uddeholm Tooling AB, Hagfors, Sweden. It was found in the samples taken at and below the slag line that a slag infiltrated layer was covered by an outer layer containing many MgO 'islands' of various sizes. The microstructure of the infiltrating slag was the same as the matrix of the outer layer. The slag was found to decompose into the compound 3CaO.Al₂O₃ and a liquid phase during the cooling process. The former phase along with tiny MgO particles from the ladle glaze was found to be one of the major sources of inclusions during the degassing and flotation periods of ladle treatment. Thermodynamic analysis indicated that the reaction between the ladle glaze and the slag from the electric arc furnace resulted in the formation of MgO–Al₂O₃ spinel and an oxide solution, which were also the main inclusions found at the initial stages of ladle treatment. Evidence of this reaction was found in the lining samples taken above the slag line.