The clustering of alumina inclusions

Factors influencing the tendency of alumina particles in steel to agglomerate and form large clusters during deoxidation and solidification have been investigated by deoxidizing melts of Fe-10 pct Ni alloys with 0.1 pct aluminum under an inert atmosphere. Clusters of alumina inclusions are formed when the melt is stirred by either inductive or mechanical means. Nearly all of the inclusions are found in the clusters if the stirring time is long enough or at moderate stirring rates. Inclusions within the clusters increase in size with time while the size of inclusions in nonclustered regions remains essentially constant. The oxygen content of an ingot solidified soon after deoxidation corresponds well with that calculated from the oxygen content of the charged materials. After most inclusions have migrated to the clusters, the oxygen content in nonclustered regions is found to be as low as 2 ppm. Formerly Graduate Student, M.I.T..     

固态钢加热过程中非金属夹杂物转变研究进展

钢中非金属夹杂物控制是炼钢的关键难题之一,在钢液条件下夹杂物的控制主要是通过夹杂物的改性或聚集长大进而从钢液中去除,在钢的热处理过程中夹杂物的转变机制与液相条件不同,包括新相析出、夹杂物转变和夹杂物结晶。综述了不同钢种热处理过程中夹杂物的转变行为。不同温度下,夹杂物与钢基体之间的热力学平衡发生变化是导致夹杂物成分转变的主要驱动力。不锈钢加热过程中夹杂物由MnO-SiO₂向MnO-Cr₂O₃的转变,铝脱氧钢加热过程中夹杂物由Al₂O₃-MgO-CaO向Al₂O₃-MgO-CaS的转变。硅锰脱氧钢加热过程中SiO₂-MnO夹杂物成分变化不大,夹杂物的变化行为主要是高SiO₂相结晶析出。     

浸入式水口内壁特征对边界层流场结构和氧化铝夹杂物运动行为的影响

铝镇静钢液浇注过程中,浸入式水口耐材内壁特征受到钢液侵蚀和夹杂物聚集影响,从近光滑壁面逐渐向多孔耐火材料壁面和含结瘤物的粗糙结瘤壁面转变,壁面形貌的变化影响边界层流场结构和氧化铝夹杂物的输运。采用物理模拟的方法在浸入式水口模型内壁镶嵌多孔耐火材料结构和含结瘤物耐材壁面结构,结合粒子图像测速技术研究不同特征壁面附近流场边界层。使用MATLAB耦合流场测速结果和氧化铝夹杂物运动数学模型,研究了不同特征壁面的流场边界层中氧化铝夹杂物的运动轨迹。使用象限分析法确定了浸入式水口边界层流场存在上抛和下扫事件。氧化铝夹杂物位于下扫事件区域时,朝向壁面运动,粒径为1 μm的氧化铝夹杂物在下扫事件中运动轨迹更接近壁面,增加了沉积的可能性;氧化铝夹杂物位于上抛事件区域时,远离壁面运动。多孔耐火材料壁面和结瘤壁面边界层内氧化铝夹杂物运动幅度大于光滑壁面边界层流场内氧化铝夹杂物运动幅度。壁面状态由近光滑壁面转变为多孔耐火材料和结瘤壁面时,流场边界层中下扫事件平面占比由10.17%增加到39.77%,上抛事件平面占比由32.96%减小到9.24%;同时,流场边界层中下扫事件发生的概率由25.83%增加到28.24%,这将加速氧化铝夹杂物在多孔耐火材料和结瘤壁面的沉积进程。      

开浇过程二次氧化对铝脱氧不锈钢中夹杂物的影响

为了研究铝脱氧不锈钢开浇过程中二次氧化对钢水洁净度和夹杂物演变的影响,实现钢中夹杂物的有效控制,分别在LF精炼出站、开浇过程中不同时刻取样,采用扫描电镜、ASPEX自动分析仪、热力学计算等不同方法研究了铝脱氧不锈钢中夹杂物的形貌、成分、数量和尺寸分布,确定了铝脱氧不锈钢开浇过程中夹杂物的演变行为和对应机理.研究结果表明,开浇过程钢中氧氮质量分数、夹杂物数密度变化规律类似,20 min时分别增加至7.4×10-5、0.0674%、17.1 mm^-2,此后随着浇铸过程进行逐渐降低;LF精炼出站时钙处理改性夹杂物效果较好,其类型主要为Ca O-Al₂O₃-SiO₂-MnO-(MgO),开浇过程中二次氧化降低了钙处理操作的作用效果,20 min时夹杂物类型转变为MnO-Al₂O3-SiO₂-CaO复合夹杂物,浇铸约60 min时,连铸过程中钢水的洁净度基本达到稳定,此时夹杂物类型重新转变为Ca O-Al₂O₃-SiO     

Separation of Non-metallic Inclusions from Molten Steel Using High Frequency Electromagnetic Fields

The current work is to investigate the removal of non-metallic inclusions from molten steel using electromagnetic separation under high frequency magnetic fields. A certain amount of aluminum nuggets were added to the molten steel to generate alumina inclusions in the current experiments. A layer of alumina clusters close to the wall of the crucible was observed. Models for the entrapment of inclusions by EM fields were developed, indicating that over 91 pct inclusions were captured within the skin depth (2.31 mm from the wall) and the calculation agreed well with the experimental observation. The fluid flow, solidification of the steel and the motion and entrapment of inclusions were studied by three-dimensional mathematical modeling. The separation mechanism of inclusions from molten steel by EM fields was discussed. Both the experiments and the simulation show that EM separation is a feasible and high-efficient method to remove inclusions from the molten steel.     

非钙处理铝脱氧车轮钢夹杂物形成及变形行为

 通过采用扫描电镜对BOF-LF-RH-CC非钙处理工艺生产车轮钢系统取样样品中夹杂物的形貌、尺寸及组成的分析,研究了精炼和凝固过程氧化物夹杂的形成、上浮去除和析出过程,以及轧制过程夹杂物的变形行为。研究发现,在非钙处理条件下,LF精炼过程会形成大量MgO-Al2O3夹杂和CaO-Al2O3夹杂,并且在RH精炼过程中存在MgO-Al2O3夹杂向CaO-Al2O3夹杂的转变过程,最终导致铸坯中出现低变性CaO-Al2O3夹杂;在软吹和镇静过程中,炉渣或空气对钢液的二次氧化与钢液中夹杂物上浮去除存在动态平衡;在钢液凝固过程中,固液界面的Al2O3等氧化物夹杂为MnS的析出提供了异质形核点,形成半包裹状的Al2O3-MnS类复合夹杂物;在轧制过程中,团簇状Al2O3夹杂容易被轧碎在板卷中形成点链状,高熔点半包裹的Al2O3-MnS类复合夹杂物被轧制成小尾巴状,而低熔点的CaO-Al2O3-MnS的复合夹杂形成连续的条状。     

转炉-精炼-连铸过程钢中氧的控制

结合近年来的文献和笔者的研究工作,概要论述了转炉—精炼—连铸过程中钢洁净度(以总氧含量T[O]表示)的控制及夹杂物对产品质量的影响。提高钢的洁净度应从产生夹杂物的源头抓起,尽可能降低转炉终点氧含量。根据生产统计数据,建立了转炉终点氧预报模型。介绍了硅镇静钢、硅铝镇静钢、铝镇静钢三种脱氧模式及脱氧产物的控制方法。采用钢包精炼方法把夹杂物消灭在钢水进入结晶器之前是获得“干净”钢水的关键。介绍了RH、LF、中间包钢水总氧预报模型。介绍了在连铸过程中防止钢水再污染和进一步去除夹杂物的措施。     

A Sulfide Capacity Prediction Model of CaO-SiO2-MgO-FeO-MnO-Al2O3 Slags during the LF Refining Process Based on the Ion and Molecule Coexistence Theory

A sulfide capacity prediction model of CaO-SiO₂-MgO-FeO-MnO-Al₂O₃ ladle furnace (LF) refining slags has been developed based on the ion and molecule coexistence theory (IMCT). The predicted sulfide capacity of the LF refining slags has better accuracy than the measured sulfide capacity of the slags at the middle and final stages during the LF refining process. Increasing slag binary basicity, optical basicity, and the Mannesmann index can lead to an increase of the predicted sulfide capacity for the LF refining slags as well as to an increase of the sulfur distribution ratio between the slags and molten steel at the middle and final stages during the LF refining process. The calculated equilibrium mole numbers, mass action concentrations of structural units or ion couples, rather than mass percentages of components, are recommended to represent the slag composition for correlating with the sulfide capacity of the slags. The developed sulfide capacity IMCT model can calculate not only the total sulfide capacity of the slags but also the respective sulfide capacity of free CaO, MgO, FeO, and MnO in the slags. The comprehensive contribution of the combined ion couples (Ca²⁺ + O²⁻) and (Mn²⁺ + O²⁻) on the desulfurization reactions accounts for 96.23 pct; meanwhile, the average contribution of the ion couple (Fe²⁺ + O²⁻) and (Mg²⁺ + O²⁻) only has a negligible contribution as 3.13 pct and 0.25 pct during the LF refining process, respectively. The oxygen activity of bulk molten steel in LF is controlled by the [Al]–[O] equilibrium, and the oxygen activity of molten steel at the slag–metal interface is controlled by the (FeO)–[O] equilibrium. The ratio of the oxygen activity of molten steel at the slag–metal interface to the oxygen activity of bulk molten steel will decrease from 37 to 5 at the initial stage, and further decrease from 28 to 4 at the middle stage, but will maintain at a reliable constant as 5 to 14 at the final stage during the LF refining process. The proposed high-oxygen potential layer of molten steel beneath the slag–metal interface can be quantitatively verified.     

硅铁合金中金属钙元素对铝脱氧钢中夹杂物的影响

大尺寸CaO?Al₂O₃类夹杂物容易引起轴承钢疲劳失效,大尺寸CaO?Al₂O₃类夹杂物的控制是生产高端GCr15轴承钢的关键因素之一。精炼过程中合金引入杂质元素、渣精炼和精炼过程中卷渣是铝脱氧轴承钢中大尺寸CaO?Al₂O₃类夹杂物的主要潜在来源。硅铁合金通常用来提高轴承钢的淬火和抗回火软化性。本文通过实验室实验、样品分析和热力学计算,研究了硅铁合金中金属钙元素对铝脱氧钢中夹杂物的影响。硅铁合金主要由深色的硅相和浅色的硅铁相组成,钙元素在硅相和硅铁相的界面处以金属化合物形式存在。研究发现,加入硅铁合金后,钢中总钙（T.Ca）含量增加,钢中的Al₂O₃和MgO·Al₂O₃夹杂物被改性为CaO?Al₂O₃类夹杂物,夹杂物尺寸随着夹杂物中CaO含量增加而减小,钢中并未生成大尺寸CaO?Al₂O₃类夹杂物。随着钢中T.Ca含量增加,夹杂物平均尺寸降低,钢中T.O含量增加,表明硅铁合金中金属钙元素不会直接引起钢中大尺寸CaO?Al₂O₃类夹杂物的生成。但是生成的小尺寸固相CaO?Al₂O₃类夹杂物在水口处粘附结瘤,结瘤物脱落后会成为钢中大尺寸CaO?Al₂O₃类夹杂物的来源之一。      

Modification of oxide inclusions in calcium-treated Al-killed high sulphur steels

A study has been carried out to understand the modification of alumina inclusions in Al-killed high sulphur steel with calcium treatment. For calcium treatment to be effective, a general practice is to desulphurise the steel to prevent the formation of solid CaS inclusions that are harmful to steel quality and final properties. To avoid this additional desulphurising step, the authors developed a new approach of calcium treatment of steel at an industrial scale. This approach involves treating the liquid steel with calcium treatment at low aluminium levels which enables formation of liquid calcium aluminate inclusions (C12A7) in the melt and then adding remaining amount of required aluminium. Based on this principle, Al-S diagram has been developed and calcium treatment has been modified accordingly. The inclusion transformation and morphology were studied using scanning electron microscope /energy dispersive spectroscopy analysis and. activity of CaS was calculated.     

Relation between manganese oxide inclusions and microstructure of low-carbon rimmed steel sheet

The influence of manganese oxide inclusions on the microstructure of cold-rolled low-carbon rimmed steel sheet containing 0.30 pct Mn and a high level of oxygen was studied in the laboratory by annealing full-hard samples in the 1200‡ to 1400‡F range. Microprobe results showed that the oxide inclusions deplete the surrounding matrix of its manganese and thereby permit sulfur to remain in solid solution after prior hot rolling. It was found that the dissolved sulfur precipitates during subsequent annealing after cold rolling and produces bands of fine grains in the inclusion area. It was determined that the manganese oxide inclusions, which are generally concentrated toward the center of the sheet cross section, establish a gradient of manganese in solid solution between the surface and center of the steel samples studied. As demonstrated by the electron microprobe and photomicrographic evidence, this manganese gradient caused carbon to diffuse to the sheet surfaces during annealing. The resulting size, shape, and distribution of carbides at the sheet surfaces depended largely on the annealing treatment.     

镧对高碳硬线钢中Al2O3夹杂物改性的晶体学分析

 为了控制与改善高碳硬线钢中氧化铝夹杂物的数量、形状和分布,提高钢的洁净度,细化钢的组织结构,均匀钢的化学成分,在高碳硬线钢中添加稀土镧元素研究其对氧化铝夹杂物的改性问题。通过对高碳硬线钢中添加稀土镧形成的稀土氧(硫)化物,采用扫描电镜和能谱分析进行表征,研究其对氧化铝的改性问题,发现镧的加入可以改变夹杂物的形状,夹杂物从不规则形状转变为较规则的椭圆形,随着夹杂物面间距增大,其逐渐弥散化。利用热力学以及边-边匹配模型计算其与γ-Fe和Al₂O₃之间沿密排晶向的原子间错配度和密排晶面的面间错配度,探究含镧夹杂物作为钢液凝固时初生相异质形核核心的可能性及有效性。结果表明,加入镧后,在1 000～2 000 K温度范围内根据生成夹杂物的吉布斯自由能的大小,得出钢中可能生成夹杂物的顺序为La₂O₃＞La₂O₂S＞LaAlO₃＞LaS＞La₃S₄。利用边-边匹配模型计算稀土氧(硫)化物与γ-Fe和Al₂O₃之间的原子匹配情况,发现了La₂O₃、LaS、La₂O₂S和La₃S₄均可能作为Al₂O₃和γ-Fe异质形核的核心,且La₂O₂S可能优先成为γ-Fe异质形核核心, LaS可能优先成为Al₂O₃异质形核核心,揭示了钢中氧化铝夹杂物的改性机理,为高碳硬线钢中非金属夹杂物的处理提供了理论依据。     

A Reaction Model for Prediction of Inclusion Evolution During Reoxidation of Ca-Treated Al-Killed Steels in Tundish

A reaction model was developed to investigate evolutions of steel chemistry and inclusion compositions during reoxidation of Ca-treated Al-killed steels in a tundish. The evolutions of Al₂O₃, CaO, MgO, and CaO in inclusions were accurately predicted using the current reaction model. The reaction model can widely predict the evolution of inclusions during tundish reoxidation of Ca-treated Al-killed steels with varying concentrations of Al, Ca, and absorbed oxygen.     

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.     

Formation and evolution of macro inclusions in IF steels during continuous casting

The evolution of macro inclusions during continuous casting was investigated by large-area inclusion characterization using ASPEX and analysis of nozzle blockage deposits. Six kinds of inclusions over 5?μm were observed in samples taken from the tundish and the slabs: single alumina particles, alumina dendrites, refractory-related alumina, alumina associated with bubbles, alumina clusters and Al–Ti complex oxides. By examining the morphology of the nozzle blockage deposit, it was concluded that the refractory-related alumina in the slabs came from the decarburization layer washed away by the steel stream. Some of the alumina clusters that came from the nozzle blockage deposit dislodged by the steel flow, were formed by the agglomeration and sintering of 5–20?μm inclusions that were carried over from the tundish. Two kinds of Al–Ti oxides were found in the tundish, and their evolution mechanisms during the casting process were proposed.     

Observation of calcium aluminate inclusions at interfaces between Ca-treated,Al-killed steels and slags

The evolution of Al₂O₃-CaO inclusions on molten steel surfaces and at molten steel/slag interfaces was observed in-situ through a confocal scanning laser microscope (CSLM) equipped with a gold-image furnace. Depending on the slag chemistry, some of the initially liquid inclusions evolved into irregular Al₂O₃ or SiO₂-enriched inclusions during the separation across the interface. Inclusions were found to cluster at specific locations at the steel/slag interface. Unlike capillary-depression-driven clustering, which is observed on molten steel surfaces, a weak repulsive force opposes fluid-flow-driven clustering at the steel/slag interface. After clustering, the irregular solid inclusions were observed to agglomerate to form large aggregates. This article is based on a presentation given in the Mills Symposium entitled “Metals, Slags, Glasses: High Temperature Properties & Phenomena,” which took place at The Institute of Materials in London, England, on August 22–23, 2002.     

Thermodynamics of iron alumino-chromite spinel inclusions in steel

The effect of chromium on the oxygen concentration of iron melts in equilibrium with various spinel reaction products has been determined. Alumina crucibles were used and experiments were performed at 1550, 1600, and 1650°C. Thermodynamic relationships between the equilibrium concentrations of chromium and oxygen in the iron melts have been established for chromium concentrations ranging up to 20 wt pct. Results from X-ray and electron microprobe analyses for the composition of the deoxidation products, together with solute activity relationships, indicate that the composition of the equilibrium spinel phase changes progressively from iron aluminate in the absence of chromium, through a series of aluminate-chromite solid solutions, FeO (Al _x Cr_1−x )₂O₃, (<0.5 pct chromium), to a complex chromite spinel, Fe₂Cr₇O₁₂, (0.5 to 3 pct chromium), and finally chromium oxide, Cr₃O₄ (>3 pct chromium). Deoxidation diagrams have been constructed and the effects of small amounts of alloying elements on the deoxidation behavior of aluminum interpreted in terms of buffered reactions which maintain oxygen concentrations in the melt at levels in excess of those normally associated with aluminum killed steel in equilibrium with alumina alone.     

Simulation of coagulation of non-metallic inclusions in tundish and their trapping into solidified shell in continuous casting mould

Abstract

A mathematical model simulating the coagulation and flotation of non-metallic inclusions in the tundish and continuous casting mould was developed based on turbulence coagulation and Stokes coagulation. From the simulation in the tundish, it was found that Stokes coagulation is dominant in the tundish. In the mould, the simulation result was that argon bubbles become the desirable sites where alumina inclusions are gathered and form large alumina clusters. The influence of the liquid steel flow in the mould applied by an in-mould electromagnetic stirring technique on the trapping rate of non-metallic inclusions into the solidified shell was examined. The horizontal flow in front of the shell was found to be effective for disturbing the trapping and decreasing the population of large non-metallic inclusions in the shallow surface layer of cast slabs. This effect was interpreted by the lift force applied to non-metallic inclusions in the velocity boundary layer formulated.     

钙处理钢中大型球状及棒状夹杂的成因

 大型夹杂物对钢材的加工性能、力学性能和耐腐蚀性能等产生十分有害的影响。用电解萃取法研究了钙处理钢中大型球状/棒状夹杂物的性质,通过对大型球状/棒状夹杂物形貌的扫描电镜观察和元素成分能谱分析,指出钢中的大型球状/棒状夹杂起源于呈团簇状的铝脱氧产物Al₂O₃。大量小颗粒Al₂O₃夹杂组成尺寸较大的夹杂团簇,在钢包内复杂流场作用下形成球状或棒状。钢液在钙处理过程中,变性充分的夹杂物形成了低熔点的铝酸钙,在钢液凝固后形成致密的球状夹杂物;变性不充分的夹杂外形仍然保留Al₂O₃夹杂颗粒形貌。钙处理使Al₂O₃夹杂变性所需的w([Ca])/w([Al])主要受钢液中硫质量分数影响。铝酸钙对钢液中的硫有较强的吸收溶解能力,在浇铸过程中,随着钢液温度下降,铝酸钙吸收的硫以CaS夹杂形式从基体中饱和析出。