Transient Inclusion Evolution During Modification of Alumina Inclusions by Calcium in Liquid Steel: Part I. Background,Experimental Techniques and Analysis Methods

In aluminum-killed steels, modification of solid alumina inclusions is often carried out by calcium treatment, converting the alumina to liquid calcium aluminates. When calcium treatment is performed, calcium can either react with sulfur in the melt or with solid alumina. Calcium sulfide inclusions are solid at steel casting temperatures and thus would be detrimental to castability if they remained in the steel after calcium treatment. The aim was to study the transient evolution of inclusions after calcium treatment, testing the hypothesis that calcium sulfide may form as an intermediate reaction product, which can subsequently react with alumina to form modified calcium aluminates. The first part gives the project background and describes the experimental and quantification techniques adopted, including the effect of sampler size in laboratory melts. Results of the formation of intermediate calcium reaction products in laboratory and industrial heats are presented in the second part.     

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.     

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。     

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.     

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.     

无缝钢管中非金属夹杂物特性研究

峰位于4869 eV位置,对应于元素锡的四价氧化态。锡泥中含有的主要成分为SnO2。     

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。     

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.      

管线钢铸坯中硫化物特征及形成机理

 对管线钢铸坯中的硫化物特征进行了分析,并对其形成机理进行了讨论。发现从中间包钢液到铸坯,管线钢中夹杂物由低熔点的CaO Al2O3向CaS Al2O3类型转变,且夹杂物尺寸越小,在冷却过程中的转变越充分。根据形貌特征,含硫化物夹杂可分为以下几类,即硫化物在氧化物表面部分析出、硫化物半包裹氧化物、硫化物完全包裹氧化物、纯硫化物和在TiN上析出的硫化物。采用FactSage软件对冷却过程管线钢中的夹杂物转变进行了计算,发现随着温度的降低,液态钙铝酸盐夹杂物逐渐经历CaO·Al2O3→CaO·2Al2O3→CaO·6Al2O3→Al2O3的转变过程,同时CaS和MnS相也在冷却过程中析出,且MnS的析出温度低于CaS,这解释了铸坯中硫化物的特征和形成。     

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.     

超低氧钢中硫化钙夹杂析出的热力学讨论及控制

 对超低氧试验钢中硫化钙夹杂析出的热力学分析表明,在本试验钢成分条件下,钢液在液相线温度以上不会自发生成硫化钙夹杂,硫化钙夹杂是钢液凝固过程中,随着钢液中［Al］、［S］溶解度的降低,［S］与钢液中较低熔点的CaO Al2O3类及CaO MgO Al2O3夹杂物表层的CaO反应析出形成;同时,通过计算得到,本试验钢在凝固过程中不析出硫化钙夹杂的条件为将硫的质量分数控制在0.0004%以下。     

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.     

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...     

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.     

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.     

低碳含碲硫易切削钢的研究与实践

通过合理的化学成分、钢水全氧含量、w(Mn)/w(S)、w(Te)/w(S)及加热温度的设计与控制,成功开发出一种环保型含碲硫1214Te易切削钢,并进行了工艺实践。通过金相显微镜、扫描电镜、能谱仪对1214Te盘圆及1215MS盘圆硫化物夹杂进行观察分析发现,1214Te轧材中硫化物夹杂多数呈纺锤形或椭球形, 1215MS轧材中硫化物夹杂多数呈长条状。在相同切削条件下,1214Te轧材的断屑效果优于1215MS轧材,且切削加工后的1214Te轧材表面粗糙度降低。     

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。     

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.     

轴承钢二次精炼过程夹杂物演变规律

 研究了轴承钢LF精炼和RH真空处理过程各类夹杂物的成分、种类和数量变化,并结合热力学模拟计算了夹杂物与钢液的界面参数,并对试验结果进行分析讨论。夹杂物分析结果表明,精炼25 min后,脱氧产物Al₂O₃消失,钢中夹杂物以纯尖晶石、含少量CaO的尖晶石、CaO·2Al₂O₃和CaO·Al₂O₃为主。继续精炼65 min至LF精炼结束,钢中夹杂物仍以纯尖晶石、含少量CaO的尖晶石、CaO·2Al₂O₃和CaO·Al₂O₃为主。RH真空处理25 min后,钢中夹杂物总数量较LF精炼结束降低75%,其中,纯尖晶石和含少量CaO的尖晶石去除率分别为99.5%和93.2%,CaO·2Al₂O₃去除率为67%。RH破空后钢中夹杂物以液态钙铝酸盐CaO·Al₂O₃和12CaO·7Al₂O₃为主。精炼过程尖晶石类夹杂物尺寸集中在10 μm以下,尺寸大于20 μm夹杂物主要为处于液相区的钙铝酸盐,这些钙铝酸盐在LF精炼前期就已经存在。与钢水接触角大于90°的固态夹杂物纯尖晶石、含少量CaO的尖晶石和CaO·2Al₂O₃在RH真空处理过程容易去除,与钢水接触角小于90°的液态夹杂物CaO·Al₂O₃和12CaO·7Al₂O₃不易去除。因此,将LF精炼结束的夹杂物控制为固态夹杂物有利于RH真空处理过程夹杂物的高效去除。热力学计算结果表明,当钢中w(T[O])为0.001 0%、w([Mg])大于0.000 18%时,脱氧产物Al₂O₃热力学上就不能稳定存在。铝脱氧、高碱度渣精炼条件下很难稳定地获得固态Al₂O₃夹杂物。为获得完全固态尖晶石或高熔点钙铝酸盐夹杂物,钢中w([Ca])需控制在0.000 1%以内。钢中w([Ca])大于0.000 2%,就具备生成液态夹杂物的热力学条件。     

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。