Transient Inclusion Evolution During Modification of Alumina Inclusions by Calcium in Liquid Steel: Part II. Results and Discussion

The formation of intermediate reaction products after calcium addition to aluminum-killed steel was studied. Steel samples were taken from laboratory and industrial heats before and at various times after calcium treatment. Inclusions were characterized by automated and manual scanning electron microscopy and X-ray microanalysis of polished cross sections and inclusions extracted by dissolution of the steel. Industrial and laboratory melts containing more than 40 parts per million (by mass) of dissolved sulfur showed calcium sulfide as the main reaction product after calcium injection, with calcium aluminates appearing later. It is proposed that the calcium aluminates are formed by reaction between the calcium sulfide and the alumina. A laboratory heat containing 7 parts per million of sulfur showed calcium oxide as the main initial calcium reaction product. A simple mechanism is proposed for the modification of alumina inclusions by calcium, considering transient CaO and CaS formation.     

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.     

Interaction of alumina inclusions in steel with calcium-containing materials

Clogging of tundish and submerged entry nozzles (SENs) adversely impacts productivity and quality in the continuous casting of aluminum-killed steels. Clogging results from an accretion layer that develops on the inside surface of the nozzle and restricts steel flow. Current nozzle refractories often react with molten steel to form solid by products that promote clogging. Nozzle materials that are inert with the liquid steel or react with accretions to form liquid reaction products could inhibit or eliminate clogging. Static experiments were conducted to investigate the stability between calcium-based materials and aluminum-killed steel. The results indicate that both calcium titanate and calcium zirconate react with alumina to form calcium aluminates. However, only the reaction between alumina and calcium titanate yielded calcium aluminate chemistries that were molten at steel casting temperatures. Liquid reaction products are preferred since they would be removed from the nozzle by the steel flow, thereby preventing accretion formation and clogging.     

Thermodynamics for Precipitation of CaS Bearing Inclusion and Their Deformation During Rolling Process for Al‐Killed Ca‐Treated Steel

Thermodynamics for CaS bearing inclusions precipitation and their deformative behaviors during compact strip production (CSP) rolling process for Al‐killed calcium treatment steel were researched using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) combined with the results of industrial trials. In addition, thermodynamic software FactSage was applied to calculate component activities of an inclusion and to analyze properties of sulfide‐oxide duplex inclusions. It is possible for CaS bearing inclusion precipitation during secondary refining and continuous casting in two manners: the first is that Ca and S react directly after calcium treatment; the other is as the well modified calcium aluminates react with dissolved sulfur and aluminum in liquid steel. Correspondingly, two types of sulfide‐oxide duplex inclusion were observed in casting slab. For the first type duplex inclusion, nearly no chemical reactions occur between outer CaS layer and solid inclusion core, thus the outer CaS rich layer is easily separated even taken off from the inner core during rolling process, and a crack may be generated correspondingly. The later one performs a better deformation during rolling process.     

钙处理中间产物的形成及其对氧化铝夹杂的改性

通过观测钙处理前后夹杂物形貌和成分的变化,对钙处理效果、中间产物的形成及不同中间产物对氧化铝夹杂的改性路径进行了研究.结果表明,钙处理可将钢液中不规则固态夹杂改性为球形液态夹杂,并且各炉次夹杂物的改性程度不同.热力学分析表明,Als和S含量越高,氧化铝夹杂改性为液态的难度越大.钙处理后的短时间内,Ca S和CaO作为中间产物存在.通过建立中间产物生成的动力学模型,确定了生成不同中间产物的临界硫质量分数为11.1×10-6（钢液中溶解氧质量分数为4×10-6）.由该模型结合结果分析,推断出不同中间产物对氧化铝的改性路径.      

钙处理对20CrMo齿轮钢硫化物夹杂的影响

在热力学计算的基础上,分析了20CrMo含硫齿轮钢钙处理的工艺条件,并对某厂钙处理后的含硫齿轮钢轧材进行了取样研究。结果表明,RH破空后钙处理的钢水中,硫化物和钙铝酸盐能结合生成复合纺锤状和低熔点夹杂;同时,钙处理前钢中w(O)控制在10×10-6以下,可使加入的钙充分对Al2O3、硫化物进行变性,并有利于形成以MnS为核心的氧硫复合夹杂;而且钢水铝脱氧后调整钢中w(AlS)=0.015%～0.025%,并在温度较高时喂Si-Ca线,可减少凝固过程中硫的偏析。该厂通过钙处理工艺生产的含硫齿轮钢夹杂物形貌良好,各项性能均达到客户的要求。     

Model of Inclusion Evolution During Calcium Treatment in the Ladle Furnace

Metallurgical and Materials Transactions B - Calcium treatment of steel is typically employed to modify alumina inclusions to liquid calcium aluminates. However, injected calcium also reacts with...     

Computational Thermodynamics Application on the Calcium Inclusion Treatment of SAE 8620 Steel

A thermodynamic study was carried out to evaluate the contents of Al, Ca, S and O at which liquid or partially liquid inclusions are formed to optimize the castability of SAE 8620 steel. Samples of steel secondary treatment (Ladle) and continuous‐casting billets (Tundish) were obtained from an electric steel mill. Entry data for this study were obtained in heats carried out in the steel plant. Furthermore, analyses were performed with a Scanning Electron Microscope (SEM) and an Energy‐Dispersive Spectrometer (EDS), as well as chemical analysis of both steel and total oxygen. In the Ladle sample, after calcium addition, inclusions had concentrations between 30 and 45% CaO and consisted mainly of calcium‐aluminates with MgO content of 10%. In the Tundish sample, inclusions contained a high percentage of alumina. Combining the characterization of inclusions with a computational thermodynamics model, the obtained results showed that the ideal range of calcium may vary between 10 and 14 ppm to form liquid inclusions with a minimum CaS content for the O, S and Al levels from SAE 8620 in this process stage. An analysis of Mg influence on the formation of calcium‐aluminates was also carried out. For contents of Mg found in aluminium‐killed steels treated with Ca, Mg does not significantly influence the formation of calcium‐aluminates inclusions. Higher calcium contents can be taken into account, depending on both the process type in steel production and the demanded product properties. The present study shows that the combined application of both inclusions characterization techniques and computational thermodynamics can drastically reduce the empiricism regarding the development of processes for the control of non‐metallic inclusions in steels. Thus, this research can contribute to increase the efficiency of manufacturing processes, improve the quality of existent products and make possible the economic development of new ones.     

铝镇静钢钙处理后碰撞行为对Al2O3夹杂物变性的作用

 对铝镇静钢LF精炼钙处理后不同时期取钢样,通过SEM-EDS观察钢样中夹杂物,分析钙处理后铝镇静钢中夹杂物变性机制,并提出了一种夹杂物变性的碰撞机制：在钙处理后,由于钙浓度在钙气泡周围较高形成了CaO类夹杂物, 其与钢液中已有的Al2O3类夹杂物相互碰撞结合在一起,然后二者发生化学反应变性为低熔点的液态夹杂物。通过相图分析从理论上指出：Al2O3类夹杂物可与CaO通过碰撞变性,且其变性机制和控速环节与Al2O3类夹杂物通过与钙发生还原反应的变性不同。夹杂物碰撞使变性速率大大加快,几分钟之内即可良好变性。在本次试验中,约有21%的Al2O3类夹杂物通过与CaO碰撞发生变性。实验室试验和其他研究者的工业试验结果均证明：在二次精炼过程中,通过往钢包中喂入CaO类粉末可以使Al2O3夹杂物变性。     

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.     

钙处理对成品无取向硅钢夹杂物特性的影响

通过取样检测结合热力学计算,分析了钙处理对成品无取向硅钢中夹杂物特征及硫化物夹杂的析出机制的影响。结果表明,钢中尺寸大于3μm的有害夹杂物主要是AlN、MgO-SiO2、CaO-Al2O3-SiO2类复合夹杂物及其与MgS、MnS、CaS的复合析出物。钙处理钢中没有检测到单独的Al2O3、SiO2及铝酸钙类夹杂物。钙处理钢中形成的液态3CaO·Al2O3、MgO·SiO2和Al2O3夹杂物被精炼渣吸收,改性去除了钢中大尺寸Al2O3夹杂物。钙处理钢中尺寸大于3μm的氧化物夹杂主要是含CaO和(或)CaS的Al2O3-SiO2类夹杂。硫化物在MgO-SiO2类氧化物表面的析出有利于其形貌趋于规则。钢中不同形貌的AlN夹杂物呈多尺度分布,钙处理对大尺寸AlN的析出特性影响不大。氧硫化物及其与AlN复合析出并定向长大的过程,与其晶体结构有关。氧化物夹杂的硫容量决定了其与硫复合的难易程度。钙处理钢中CaS在氧化物表面呈局部包裹析出和局部吸附析出。     

Examples of How Fundamental Knowledge can Improve Steelmaking: Desulphurisation Kinetics Calcium and Modification

Sulphur control is an essential part of steel production. This paper summarises two aspects of sulphur in secondary metallurgy. First, it is shown that silicon can contribute to ladle desulphurisation if the ladle slag is low in silica; the effect of silicon is primarily on the equilibrium sulphur level, rather than a specific kinetic effect. Second, sulphur is shown to capture calcium (as calcium sulphide) upon calcium injection to modify inclusions. In steels with less than approximately 100 ppm sulphur, the calcium sulphide subsequently back-reacts with alumina inclusions, to modify the oxide inclusions to calcium aluminates.     

Effect of the CaO-Al2O3-Based Top Slag on the Cleanliness of Stainless Steel During Secondary Metallurgy

The ladle treatment of a 18 pct Cr-9 pct Ni stainless steel, with desulfurization as its main purpose, was simulated on a laboratory scale. The influence of the top slag chemistry on the steel cleanliness was evaluated. A higher steel cleanliness was obtained with an optimized lime-alumina-based slag than with a lime-fluorspar-based slag. The inclusions were found to be mainly in the form of oxysulfide; the alumina content in the inclusions first increased and subsequently showed a slow drop, while the sulfide content decreased during the treatment. The equilibrium between steel and inclusions was found to be more easily reached than that between slag and steel. A slag–steel kinetic model was used to predict the steel chemistry evolution during the treatment. Furthermore, a slag–steel–inclusions interaction kinetic model was developed to calculate the change of alumina content in the inclusions during the ladle treatment. The sulfide content of inclusions was also calculated and compared with the measured values.     

中碳钢钙处理夹杂物变性的“液相窗口”控制模型

 系统研究了国内某钢厂生产的中碳钢Q345B钙处理前后夹杂物类型的变化,从热力学上分析铝脱氧钢中Al2O3夹杂物变性机制及夹杂物中CaS合理控制的条件,确立了夹杂物变性的“液相窗口”模型。热力学计算表明,温度为1873K,w(［Al］)为0.016%时,Al2O3转变为液态钙铝酸盐需要使钢中w(［Ca］)为0.0017%~0.0102%。生产实践表明,钙喂入量在0.0014%~0.0017%时,钙处理可以将钢中高熔点Al2O3的夹杂物转化为低熔点的12CaO·7Al2O3和CaO·Al2O3夹杂物,MnS基本转化为CaS,且无单独CaS析出。     

微小相去除夹杂物的热模拟试验

 采用50 kg真空感应炉进行了碳酸盐诱发微小相去除钢中夹杂物的模拟试验,发现了CaO基颗粒吸附夹杂物的实例,分析了捕获和去除夹杂物的机理。试验结果表明：用净化剂对钢液进行净化后,全氧质量分数、夹杂物面积比率、夹杂物个数分别有所降低。净化前夹杂物主要是簇状或链状的Al2O3夹杂物,净化后形成了低熔点的钙铝酸盐复合物,净化剂释放出的CaO基颗粒与细小非金属夹杂物发生碰撞、反应和吸附,促进了夹杂物的长大和去除。     

X70管线钢铸坯中非金属夹杂物的研究

利用大样电解、金相观测、扫描电镜(SEM)和电子探针(EPMA)等手段,对X70管线钢铸坯中夹杂物的数量、粒径、形貌及组分进行了研究.结果表明:X70管线钢铸坯中夹杂物数量较多,粒径较大,且多为复合夹杂.针对大型夹杂物中硫化物、氧化物、硅铝酸盐和钙铝酸盐复合夹杂的特点,分析了铸坯中夹杂物的主要来源.     

镁处理对45钢中夹杂物的改质效果

采用光学显微镜、扫描电子显微镜、非水溶液原位电解方法对比分析了镁处理(0.0006％ Mg)和钙处理(0.0010％ Ca)45钢中夹杂物类型、尺寸、分布及形态变化.研究表明,相对于传统的钙处理工艺,45钢中加入一定量的镁后,钢中的Al2O3转变为细小弥散的MgO·Al2 O3,MnS在凝固末期以MgO·Al2O3为形...     

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.     

钙处理钢中夹杂物行为的研究

为改善武钢CSP产线钢水的连浇性,通过工业试验对钙处理钢中夹杂物的变化进行了研究,试验结果表明,钙处理后,钢中夹杂由Al2O3和MnS转变为铝酸钙盐或CaO-Al2O3-MgO-CaS复合夹杂,由于钙处理对夹杂物的聚合变性作用,钢中夹杂物直径不小于5μm的比例增加。通过热力学计算,分析了钙处理使夹杂物变性的条件。根据试验结果对工艺进行了优化,钢水结瘤断浇次数由3.6次/月降低到1.5次/月。     

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。