钛稳定超纯铁素体不锈钢硅铝复合脱氧的试验研究

 为改进超纯铁素体不锈钢的脱氧工艺,提高夹杂物控制水平,在硅钼高温电阻炉内对钛稳定超纯铁素体不锈钢的精炼过程进行了试验研究。结合热力学计算,研究了不同Si、Al含量(质量分数,下同)比值的硅铝合金的脱氧效果,以及脱氧、钛合金化和钙处理后钢中典型夹杂物的组成和形貌及粒度分布。结果表明：钢中初始氧含量相近的条件下,硅铝合金复合脱氧的钢中酸溶铝、全氧量与纯铝脱氧结果相近。硅铝复合脱氧后钢中夹杂物主要为(MgO-)Al2O3-SiO2复合脱氧产物。钛合金化后夹杂物的类型主要为Al2O3-MgO-(SiO2)-TiOx复合夹杂物和TiN。钙处理后的夹杂物主要为球形的MgO-Al2O3-CaO-SiO2-TiOx类复合氧化物。采用硅铝合金复合脱氧比纯铝脱氧钢的夹杂物的总数量、总面积和平均粒径均要小。     

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.     

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.     

Analysis of various versions of the deoxidation of rail steel at OAO NTMK

The deoxidation of steel melted using various types of deoxidizers during out-of-furnace treatment is studied. The total oxygen and nitrogen content and the oxygen contents in the main types of oxide nonmetallic inclusions are determined by fractional gas analysis of steel samples taken from heats performed by various schedules. The main types of nonmetallic inclusions and their size distributions are found with qualitative and quantitative metallography. The oxygen content in the rail steel is minimal (5 ppm) when calcium carbide CaC₂ is introduced into the metal in tapping of a converter. When the metal is deoxidized using a steel wire filled with calcium or a steel wire filled with silicocalcium, the oxygen content in rail steel is ≈8 and ≈11 ppm, respectively. A comparison of various processes of rail steel deoxidation under the OAO NTMK conditions shows that the limitation of the aluminum content (no more than 30 ppm) or the use of a wire with a calcium or calcium carbide filler is more effective than the use of a wire filled with silicocalcium.     

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 ferrosilicon addition on the composition of inclusions in 16Cr-14Ni-Si stainless steel melts

The silicon deoxidation equilibrium between the 16Cr-14Ni-1.5Mn-Si melts and the CaO-SiO₂-8MgO-5CaF₂ (basicity=1.8) slag at 1743 K was investigated to understand the effect of aluminum and silicon contents on the composition of inclusions. Therefore, the ferrosilicon alloys with different aluminum content were chosen based on the preceding objective. In addition, the phase stability diagram of the inclusions was computed using commercial thermodynamic software based on the Gibbs energy minimization principles. The content of MnO in the inclusions sharply decreases with increasing silicon content when the steel melts were deoxidized by the ferrosilicon alloys containing high aluminum (FeSi-H). The content of SiO₂ in the inclusions slightly increases with increasing silicon content when the FeSi-L is used, while a maximum value is shown at [Si]=1.5 pct when the FeSi-H is used. The content of MgO in the inclusions increases by increasing the content of silicon, regardless of the kinds of ferrosilicon alloys. The use of the FeSi-L as a deoxidizer could suppress the formation of Al₂O₃ in the inclusions, while the content of Al₂O₃ increases with increasing silicon content when the FeSi-H is used. When the FeSi-H is used as a deoxidizer, the inclusions are the glassy type with the composition of Mn-silicates at [Si]≤1.3 pct, while the Mg(Ca)-silicates with the composition of the forsterite phase are observed in the steel composition of [Si]=3.3 pct. When the steel melts were deoxidized by the FeSi-L alloys, the inclusions are the glassy-type Mn-silicates at [Si]=0.8 pct, while the Mn-silicates containing the cristobalite phase are observed at [Si]=1.5 to 2.4 pct. In the composition of [Si]=3.3 pct, the Mg-silicates with the composition of the rhodonite phase are observed. The log(X _SiO2/X _MnO) of the inclusions linearly increases by increasing the log [a _Si · a _O / a _Mn] with the slope close to unity when the FeSi-L is used as a deoxidizer, while the slope of the line is about 2 times greater than that of the expected value when FeSi-H is used. The log (X _MgO/X _MnO) of the inclusions linearly increases by increasing the log [a _Mg/a _Mn] with slopes greater than the expected value of unity.     

超纯铁素体不锈钢夹杂物控制的研究进展

论述了超纯铁素体不锈钢夹杂物控制的热力学,着重于脱氧、TiN析出、尖晶石夹杂物形成及钙处理的热力学研究。介绍了VOD炉内夹杂物行为的数学模拟研究,分析了超纯铁素体不锈钢中夹杂物引起的产品缺陷、夹杂物形成规律及特征,指出TiN或Ti(CN)容易在MgO、Al2O3-MgO、Ti2O3基体上析出,形成包裹型复合夹杂物。最后提出了今后开展超纯铁素体不锈钢夹杂物研究的几点建议。     

Inclusion evolution during refining and continuous casting of 316L stainless steel

The formation and characteristics of non-metallic inclusions in 316L stainless steel produced by the AOD (argon oxygen decarburization)–ladle furnace–continuous casting process were investigated. The morphology and composition of inclusions changed significantly during the refining and casting processes. After de-oxidation with Si/Mn additions, spherical complex inclusions mainly consisting of calcium silicates were observed. The contents of MgO and Al₂O₃ in these inclusions continuously increased as the steel moved from the AOD through ladle processing to the tundish. As the temperature decreased from the tundish through to solidification, harmful crystals of MgO/Al₂O₃ spinel were precipitated within the steel melt as well as within the calcium silicate matrix of existing inclusions. The results obtained from thermodynamic calculations carried out using FactSage? commercial software agreed well with the information derived from evaluation of the industrial samples enabling recommendations to be made for the avoidance of detrimental spinel inclusions.     

Deoxidation equilibria of molten nickel by Mg-Al and Mn-Al

The deoxidation equilibria of aluminum-magnesium and aluminum-manganese in liquid nickel equilibrated with Al₂O₃-saturated MgAl₂O₄ and MnAl₂O₄, respectively, were investigated in the temperature range of 1773 to 1873 K. At 1773 K, the oxygen levels could be reduced to 5.8 to 6.6 ppm with 2.5 to 10 ppm magnesium and 0.05 to 0.9 mass pct aluminum in the Ni-Mg-Al-O system, and to less than 20 ppm with more than 1.5 mass pct manganese and 30 ppm aluminum in the Ni-Mn-Al-O system. With the experimental results mainly obtained in the present work, the interaction parameters, e _Mg ^Al , e _Mn ^Al , e _O ^Mg , e _O ^Mn , and e _O ^Al , and the equilibrium constants, log , log , log K _Mg(Ni), log K _Mn(Ni), and log K _Al(Ni), were estimated using a multiple regression analysis.     

The rate of formation of intermetallic layers between aluminum and steel below 660°C

The rate of formation of intermetallic compounds between aluminum and three ferritic steels, one austenitic steel, and Inconel has been determined by an electrolytic method. The steel was held at zero potential with respect to aluminum in a NaCl-AlCl₃ melt, and the current measured. Comparison of measured thicknesses of intermetallic layers with those calculated from the integrated current gives an average deposition efficiency of 95 pct. For the Type 304 austenitic steel thickness (min), andk is given by logk= −6400/T(⁰K) +4.469. The ferritic steels show a linear rate of growth of Al₅Fe₂, with an initial higher rate such that extrapolation of the linear curve back to zero time gives an intercept of 16±7 μm. The rate constants (mm min⁻¹) may be represented by log (rate)=α/T+β, and the values of α and β are respectively −2650 and−0.788 for a plain carbon steel,−6580 and + 3.469 for a 1.3 pct Cr, 0.4 pct Mo steel, and−5950 and +2.466 for a 2.2 pct Cr, 0.9 pct Mo steel. The more highly alloyed steels are thus attacked, more slowly. Results for Inconel could not be fitted to any simple equation. With the ferritic steels growth is by aluminum diffusing inwards; with Inconel it is by nickel diffusing outward.     

Study of the Effect of Process Parameters in Steel Production on the Content of Corrosion-Active Nonmetallic Inclusions in Corrosion-Resistant Pipes

The main reason for the accelerated local corrosion of tubes is contamination of the steel by corrosion-active nonmetallic inclusions (CANI), which determine the metallurgical properties of tube steel in terms of their corrosion resistance. Studies have shown that there are two main types of corrosion-active nonmetallic inclusions: CANI₁ — inclusions based on calcium aluminates; CANI₂ — complex inclusions that contain calcium sulfide. In order to master to production of tubes of steel 20-PKS at the Volga Pipe Plant (VTZ), a study was made of the effect of the parameters of out-of-furnace treatments on the contamination of steel by CANI. 1. The mechanisms and main sources of formation of CANI in tube steels made by the VTZ were determined. The main reasons for the formation of CANI₁ in furnace slag containing thermodynamically active CaO are mixing of the metallic and slag phases during the argon blow and the simultaneous introduction of additions to correct the chemical composition of the steel. Inclusions of the CANI₂ type may be formed by deoxidation operations carried out with suboptimal proportions of added aluminum and calcium (lime). 2. The following measures are recommended to ensure that steel 20-PKS made by the VTZ is clean with respect to both types of CANI: • optimize the composition of the ladle slag (increase the average content of Al₂O₃, increase the average content of SiO₂ as much as possible, and in any case decrease the average concentration of CaO); • keep the mass ratio of added CaO to added Al within the range 1.5–2; • continue the argon blow done after addition of the last batch of ferroalloys for at least 15–20 min; • ensure that the intensity of the blow is at least 0.5–1.5 m³/min. 3. Vacuum-degassing steel in the ladle after treatment on a ladle-furnace unit makes it possible to distribute the CANI more uniformly over the volume of the steel. __________ Translated from Metallurg, No. 7, pp. 38–42, July, 2005.     

Effect of Sulfur in Steel on Transient Evolution of Inclusions During Calcium Treatment

In the current study, the effect of S content in the molten steel on inclusions during calcium treatment was studied using an induction furnace. The calcium in steel decreased from 48 to 2 ppm, and the sulfur in steel changed a little with time. When sulfur content in steel was as low as 25 ppm during calcium treatment, inclusions shifted from CaO-Al₂O₃-CaS to Al₂O₃-CaO with about 35 pct CaO. When the sulfur increased over 90 ppm, more CaS-CaO formed just after the addition of calcium, and then the CaS content decreased from over 45 pct to lower than 15 pct and inclusions were mostly Al₂O₃-CaO-CaS and Al₂O₃-CaO with a high Al₂O₃ content. Thermodynamic calculation predicted the variation of the composition of inclusions, indicating good agreement with the measurement, while a certain deviation existed, especially for heats with 90 and 180 ppm sulfur. A reaction model was proposed for the formation of CaO and CaS, which considered the reaction between calcium vapor bubbles in the zone and the dissolved oxygen and sulfur in the molten steel, as described by a Langmuir-type adsorption isotherm with a reaction occurring on the remaining vacant sites. The variation of transient CaS inclusions was discussed based on the thermodynamic calculation and the morphology evolution of typical inclusions containing CaS.     

Effect of the conditions of REM microalloying of steel on the corrosion activity of nonmetallic inclusions

Experimental heats of low-alloy steel are performed under various conditions of rare-earth metal microalloying and aluminum and calcium deoxidation. Electron-probe microanalysis of nonmetallic inclusions and a metallographic investigation of a metal are used to show that, when interacting with water, nonmetallic cerium oxide inclusions do not form hydrates and, correspondingly, are not aggressive. When aluminum, calcium, and cerium additions are sequentially introduced into a melt, a continuous cerium oxide shell forms on calcium aluminates, protects corrosive nonmetallic inclusions against interaction with water, and weakens local metal corrosion.     

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.     

钙处理对430不锈钢板坯夹杂物的影响

通过热力学计算分析了430铁素体不锈钢钙处理后在生成液态夹杂物区间内钢中钙质量分数和铝质量分数的关系,并对430铁素体不锈钢未采用钙处理和采用钙处理板坯中夹杂物类型、数量进行了对比,分析了钙处理夹杂物变性过程。结果表明,精炼过程喂入硅钙线可以得到理想的钙处理效果。钙处理后430钢水中高熔点的Al_2O_3和低变性的CaO-SiO_2-Al_2O_3-MgO夹杂物得到良好变性,夹杂物数量比未采用钙处理时明显减少,夹杂物尺寸都小于15μm。CaO和Al_2O_3两者通过发生化学反应变性为低熔点的液态夹杂物。     

Thermodynamic assessment of the Al deoxidation reaction in liquid iron

The deoxidation reaction of aluminum in liquid iron has been investigated thermodynamically using Al₂O₃ crucible at 1873 K under Ar atmosphere as a fundamental study for the accurate control of inclusions in the ladle refining process. In addition to the equilibrium constant log K_A1 for the aluminum deoxidation reaction, the first-order and second-order interaction parameters between aluminum and oxygen were experimentally determined in the concentration range of aluminum up to 1 %. The temperature dependence of the equilibrium constant and the first-order interaction parameter e^A1 was also obtained: log K_A1 = 12.32 - 47400/T, e^A1 = 15.57 - 36500/T. The equilibrium relation between aluminum and oxygen contents in the aluminum deoxidized iron by applying interaction parameters and the equilibrium constant determined in this work satisfies fairly well the equilibrium data over the whole concentration range of aluminum considered.     

Influence of calcium treatment on cleanness and fatigue life of 60Si2MnA spring steel

Contrasting experiments of Al killed 60Si2MnA spring steel were carried out between using and excluding calcium treatment under LF refining slags with low and high basicity ratios (R: CaO/SiO₂?=?3.4, 5.0), respectively. Results showed the high basicity refining slag had a certain effect on controlling inclusions and improving the cleanness of spring steel similarly to calcium treatment. The T.[O] (total oxygen) content of steel without calcium treatment got to below 15?ppm and the fatigue life was long, up to 7.8?×?10⁶?cycles. But in order to reduce the T.[O] below 10?ppm, as well as inclusion number and size in spring steel further, meanwhile, the appropriate calcium treatment should still be used. Besides, as the [Ca] content in the steel with calcium treatment increased, inclusions transformed from Al₂O₃–SiO₂–CaO–MgO to Al₂O₃–SiO₂–CaO–MgO–CaS completely, which reduced the formations of voids between inclusions and steel matrix, and voids decreased with the increase of CaO/Al₂O₃ value and CaS content of inclusions. Finally, the fatigue life of spring steel with high basicity slag and calcium treatment increased to 9.1?×?10⁶ cycles.     

Analysis of the complex deoxidation of carbon steel melts

The joint complex deoxidation of carbon steel melts is analyzed. A procedure is proposed to calculate the equilibrium oxygen concentration in a melt. Rail steel is used as an example to study the joint complex deoxidation of a melt by aluminum and silicon. Mullite (2Al₂O₃ · 3SiO₂) and kyanite (Al₂O₃ · SiO₂) are considered as the reaction products. Thermodynamic calculations demonstrate that the deoxidizing capacity of aluminum is increased in the presence of silicon in a melt. In this case, a substantial increase in the deoxidizing capacity in the concentration range 0.001–0.1 wt % Al is achieved when kyanite (Al₂O₃ · SiO₂) forms in the reaction products. The results of laboratory and industrial experiments on complex deoxidation are shown to agree well with the calculated data. These results demonstrate that the proposed calculation procedure can be recommended to determine the equilibrium oxygen concentration in a melt in the presence of several deoxidizing elements.     

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.