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.     

钙处理对涟钢高强机械用钢夹杂物的影响

对涟钢LG600/LG700XL冶炼过程中夹杂物的衍变机理进行分析,分批次试验研究了精炼渣性能和钙处理工艺对钢液洁净度和钢中夹杂物的影响。结果表明,在钙处理工艺下,夹杂物的衍变路线为Al_2O_3→MgO-Al_2O_3→Al_2O_3-CaO,中间包钢液中的夹杂物主要是Al_2O_3-CaO和Al_2O_3-TiO_x复合氧化物。取消钙处理以后,铸坯中氧的质量分数从16×10~(-6)降低到11×10~(-6)。两种工艺下,材样中绝大部分夹杂物都是核心为铝酸盐、外层为TiN的复合夹杂,钙处理工艺下夹杂物核心是Al_2O_3-CaO-CaS,取消钙处理工艺下夹杂物核心是MgO-Al_2O_3尖晶石。两类复合夹杂物尺寸都比较小(10μm),对钢材性能的影响有限。取消钙处理以后,钢液可浇性基本保持不变,没有发生水口堵塞,说明取消精炼过程中的钙处理工艺对涟钢高强机械用钢而言是可行的。     

含硫齿轮钢SAE8620H热轧棒材夹杂物

 以EAF电炉—LF精炼炉—VD真空精炼炉—LF精炼炉—CC连铸工艺流程生产含硫齿轮钢SAE8620H热轧棒材,利用光学显微镜、扫描电镜和能谱仪分别对棒材横纵截面的边缘部位、1/2半径处和中心部位的夹杂物进行了检测,综合分析了夹杂物的尺寸、数量、分布以及形貌和成分。结果表明：含硫齿轮钢SAE8620H热轧棒材中的夹杂物主要有单独硫化锰和核心主要是Al2O3和MgO-Al2O3,外围是MnS或者（Ca、Mn）S的氧硫复合夹杂物;从边缘到中心,夹杂物总数递增,氧硫复合夹杂物比例递减;棒材横截面上夹杂物大部分小于2μm,长宽比小于3;棒材纵截面上夹杂物平均长度为11μm,边缘部位夹杂物平均长度较中心部位短3μm,纺锤状夹杂物的比例占30%。     

铝镇静钢中夹杂物钙处理改性及其影响因素

 钙处理广泛应用于铝镇静钢中非金属夹杂物的改性,但在工业实践中的改性效果差别很大。为了探究钙处理效果差异的原因,通过工业试验和热力学计算研究了铝镇静钢钙处理前后非金属夹杂物的演变,并讨论了钙处理改性夹杂物的影响因素。结果表明,浇铸末期钢液中的T[O]和T[N]质量分数分别为0.002 9%和0.003 9%。精炼前期钢中夹杂物Al₂O₃质量分数达90%以上,钙处理后,钢液中钙质量分数快速增加至0.002 5%,同时夹杂物中CaO质量分数由钙处理前的4%迅速增加到23%,Al₂O₃质量分数由钙处理前的82%降低至70%,夹杂物由团簇状Al₂O₃转变为球形的Al₂O₃-CaO复合夹杂物,夹杂物平均成分靠近液相区。由于二次氧化,浇铸时钢中的T[O]和T[N]含量升高,夹杂物的尺寸和数密度增加,因此,需要加强钢液的保护浇铸。在连铸与轧制过程中,夹杂物中CaO质量分数由中间包中的20%增加至轧材中的37%,Al₂O₃质量分数由中间包内的77%降低至56%,夹杂物的平均成分向液相区移动,但夹杂物类型不发生改变,仍为球形的钙铝酸盐。通过热力学计算得到本研究中试验钢种夹杂物“液态窗口”对应的钙质量分数为0.001 1%～0.002 8%,此外钢液成分对钙处理的“液态窗口”影响很大。随着钢液中T[O]含量升高,“液态窗口”变宽,但所需喂钙量增加;随着钢液中T[S]含量增加,“液态窗口”变窄;钢液中的T[Al]含量对“液态窗口”无明显影响。     

含硫-铝钢GS35C-A硫化钙夹杂热力学分析和工艺改进

针对试验GS35C-A钢（/%:0.34～0.35C,0.20～0.22Si,0.69Mn,0.013～0.016P,0.026～0.045S,0.027～0.046A1,0.000 8～0.001 9Ca）夹杂物变性进行了热力学计算,并对工艺1[BOF-LF（硫合金化）-RH-钙处理-CC]和优化工艺2[BOF-LF-RH-钙处理-硫合金化-CC]对应的钢中夹杂物形貌及数量进行了研究。结果表明:（1）随着钢液中[S]的升高,生成CaS所需的平衡钙含量降低,钙处理变性生成低熔点夹杂物时钢液中的[Al]逐渐降低;（2）优化工艺2后RH离站Ca、S含量分别从优化前（工艺1）的0.001 9%和0.045%降至0.000 8%和0.026%,平均连浇炉数由原2.5炉提高至8炉;（3）优化前（工艺1）中间包典型夹杂物组分为硫化钙包裹的镁铝尖晶石,优化后（工艺2）中间包夹杂物为铝酸钙;RH离站、中间包钢中每mm²夹杂物个数分别从优化前9.09和6.23降至5.06和3.76。     

50t电炉-LF-VD流程生产SAE8620H齿轮钢淬透性的控制

对影响采用50 t电炉-LF-VD工艺生产SAE8620H齿轮钢的淬透性的冶金因素进行分析;重点关注生产过程中化学成分C含量的变化规律,分析工艺过程对化学成分C含量的控制精度的影响因素并进行研究优化。通过实施设计子钢号化学成分、缩窄化学成分控制范围、对工艺关键位置加强全过程控制等措施后,钢中Mn、Cr、Ni均控制在较窄的范围内,w(C)波动控制在0.03%以内,从而较好地控制了SAE8620H齿轮钢淬透性和淬透性带宽。     

车桥管用20Mn2钢的二次氧化行为

本文通过系统取样跟踪分析了BOF→LF→圆坯连铸工艺生产20Mn2钢的洁净度限制环节;结果表明,凤宝20Mn2钢洁净度的限制性环节是二次氧化。明显的二次氧化发生在三个位置：①喂Si-Ca线后;②LF结束到中间包过程;③中间包到结晶器的浇注过程;从入LF到浇注结束整个过程平均增N达40×10-6,累积二次氧化量达到109×10-6,夹杂物总去除量为198×10-6;大型夹杂物在喂Si-Ca线和中间包中均有明显增加,主要为Al-Si-Mn-Ti复合氧化物,是典型的二次氧化产物。因此,目前该厂改善洁净度的关键是保护浇注的控制。     

钙处理对20CrMnTiH齿轮钢中非金属夹杂物的影响

铝脱氧齿轮钢中易生成大量的高熔点Al₂O₃类夹杂物,容易导致水口结瘤及钢材性能恶化,目前较常采用钙处理将钢中高熔点的Al₂O₃类夹杂物改性为低熔点的钙铝酸盐类夹杂物。合理的钙处理可以减轻水口结瘤并提高连铸过程钢液的可浇性,工业试验研究了喂钙前钢液中T.Ca含量、喂钙速度、喂钙量、净空高度及渣厚等参数对齿轮钢中钙收得率的影响,并在1.5 m·s?1的喂钙速度条件下研究了不同喂钙量对钙处理过程中齿轮钢中非金属夹杂物改性的影响。研究结果表明,当喂钙前钢液中T.Ca的质量分数小于10×10?6,喂钙速度为1.5 m·s?1,适当降低喂钙量和净空高度和渣厚,钢液中钙收得率均高于20%。当钢液中T.Ca的质量分数高于17×10?6时,钢中生成大量高熔点CaS型夹杂物,三元相图中夹杂物的平均质量分数远离液相区。随着齿轮钢中T.Ca含量的增加,夹杂物的平均尺寸和数密度逐渐增加。热力学计算结果与工业试验钙处理对钢中非金属夹杂物改性效果具有较好的一致性。      

管线钢连铸坯洁净度研究

针对武钢三炼钢厂“BOF→ Ar→ RH→ L F→ CC”的管线钢生产工艺 ,采取示踪剂示踪、系统取样、综合分析的方法 ,对 RH处理前后、L F处理前后、中间包和铸坯中 T[O]、显微夹杂及宏观夹杂物的变化进行了系统研究。研究表明 ,铸坯中 T[O]平均值为 0 .0 0 14 7%和 0 .0 0 182 % ,显微夹杂物为 2 .78个 / m m2 ,大型夹杂物数量为 1.13mg/ (10 kg) ,各项洁净度指标均达到了很高水平 ,同时夹杂物已基本变性为钙铝酸盐及钙铝酸盐与硫化钙组成的复合夹杂     

Control of inclusions in a resulphurised steel

The formation of non‐metallic endogenous inclusions in ladle‐furnace treatment of a resulphurised C‐Mn Al‐killed steel was investigated. A model based on equilibrium reactions and using as input data compositions and temperatures measured at various stages of secondary steelmaking was developed and applied to different routine and experimental heats. Microstructural analyses were carried out on samples systematically extracted from ladle and from tundish. Detailed characterisation of inclusion morphology and composition was carried out to investigate their properties in the present resulphurised steel and to evaluate reactions taking place during different phases of ladle treatment. The experimental results were also used to validate the theoretical model. A good agreement between predicted concentrations of inclusions and experimentally measured values was obtained.     

Research on Optimum Operation and Structure of Tundish

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Improvement in castability of Al containing resulphurised free machining steel

Abstract

During the continuous casting (CC) of Al containing resulphurised steel, the submerged entry nozzle is often clogged by high melting point inclusions such as MgO.Al₂O₃ spinel and CaS. Casting extended for only one to two heats before optimisation. The main objective of the present study is to improve the castability of this steel. A suitable refining slag composition was sought and designed thermodynamically, and a soft blowing system was improved for reducing the dynamics of steel–slag desulphurisation. An optimisation plant trial was conducted on a sequence with four heats. By adopting the optimised refining slag and improved soft stirring operation, the steel castability was improved and the number of CC heats of a single tundish was increased from 1–2 to more than 4.     

中间包挡墙优化的数值模拟与实践

为了改善首钢三炼钢2号铸机铸坯夹杂物水平,对中间包挡墙结构进行了优化,并对中包内钢水流场进行了三维数值模拟,分析了钢水流场对去除夹杂物的影响.模拟及生产实绩表明：高挡墙方案均具有改善中包冶金效果,V形高挡墙方案安装使用过程结构稳定性更好,采用带导流孔的全挡墙钢水流场分布更加合理,有利于夹杂物的去除.     

帘线钢生产过程中氧化物夹杂的演变规律

 使用ASPEX PSEM explorer研究了帘线钢中氧化物夹杂的成分及形态在炼钢与轧制过程的变化。结果表明,连铸坯夹杂物中SiO2质量分数较中间包有增加趋势,并在铸坯中发现MnO-SiO2-Al2O3和SiO2构成的复合夹杂物,轧制盘条中出现未很好变形的SiO2夹杂物。热力学分析表明：由于连铸过程钢液和夹杂物间的传质作用,导致铸坯夹杂物中SiO2质量分数增加,MnO-SiO2-Al2O3系夹杂在浇铸过程较CaO-SiO2-MnO-Al2O3系夹杂物更易析出SiO2相,形成MnO-SiO2-Al2O3为基体的复合夹杂物。CaO-SiO2-Al2O3-MnO和MnO-SiO2-Al2O3夹杂物在盘条中呈长条状,MnO-SiO2-Al2O3和SiO2析出相构成的复合夹杂在轧制过程将发生相分离,形成“眼睛状”或单颗粒状夹杂。     

去除钢水中非金属夹杂物方法研究

介绍了一种去除钢水中非金属夹杂物的方法,探讨了它对中间包内腔结构改进的作用。经过计算,本方法能够满足10μm以上非金属夹杂物的上浮时间要求。实验证明,通过整流的作用,降低了钢水流动速度,流动更加平稳,可降低注流区的湍流强度,同时使钢液流动路线延长,钢液平均停留时间增加,夹杂物上浮增多,利于提高钢液洁净度。钢水均匀慢速流动减轻了钢水短路流动造成的耐火材料熔损,由耐火材料熔损造成的夹杂物减少。     

Thermodynamic study on calcium treatment of “liquid phase window” and inclusions modification

It is important to study the “liquid phase window” and control non metallic inclusions modification for prevention of submerged entry nozzle blocking during continuous casting. Based on the production practice of medium and high carbon steel in a steel plant, the “liquid phase window” during calcium treatment was studied by combining thermodynamic theoretical calculation and industrial test, which was based on considering the influence of silicon element and temperature on the “liquid phase window”. The results show that the “liquid phase window” varies with T［O］, T［Al］, ［S］ content and temperature, and the low temperature “liquid phase window” must be within the range of high temperature “liquid phase window”, and the silicon content in molten steel has a great influence on the “liquid phase window”. The concepts of “partial liquid phase window” and “complete liquid phase window” are proposed, and the optimum calcium content range of S50C production in a steel plant is determined to be (18-27)×10-6。     

Ca处理“液相窗口”及夹杂物变性热力学研究

摘要：研究“液相窗口”控制钢液中非金属夹杂物变性对于防止连铸过程浸入式水口堵塞具有重要意义。基于某钢厂中高碳钢生产实践,在重点考虑Si元素和温度对“液相窗口”影响的基础上,通过热力学理论计算与工业试验相结合,对Ca处理过程“液相窗口”进行了研究。结果表明：“液相窗口”随钢液中T［O］、T［Al］、［S］含量及温度变化而变化;低温“液相窗口”一定位于高温“液相窗口”范围内;钢液中［Si］含量在某些条件下对“液相窗口”影响较大;并提出了“部分液相窗口”和“完全液相窗口”的概念;确定了某钢厂S50C生产最佳Ca质量分数范围为（18~27）×10-6。     

120t BOF-LF-RH-CC流程GCrl5轴承钢洁净度研究

对“120 t BOF-LF-RH-CC”流程GCrl5轴承钢的洁净度研究结果表明,LF精炼结束以A1₂O₃ • MgO尖 晶石和Al₂O₃-MgO-CaO夹杂为主,RH真空处理后, Al₂O₃- MgO尖晶石几乎全部消失,钢中夹杂物以液态钙铝酸盐为主,T.0含量降至5.3x10^-6;浇注过程中间包重新成Al₂O₃- MgO尖晶石;RH终点和中间包钢水以及连铸坯未发现≥20um钙铝酸盐夹杂。     

石油钻杆钢冶炼过程中夹杂物的析出和衍变

系统分析了国内某钢厂复合脱氧工艺下Cr Mo石油钻杆钢夹杂物在EAF-LF-VD-CC流程中的析晶和衍变规律.由于铝酸盐的上浮,LF冶炼前钢中T[O]含量较低,冶炼过程中氮含量逐渐升高.电镜下钢中大尺寸夹杂物（50μm左右）只出现在LF-VD阶段,主要为低熔点的硅锰酸盐、包含Na₂O的混合物和含有少量CaO的镁铝尖晶石,中间包阶段大尺寸夹杂物完全消失.小尺寸夹杂物（<10μm）出现在精炼全过程中,主要成分是Mg、Al、Si和Ca的复合氧化物、CaS以及二者的复合物,LF冶炼前到中间包阶段小尺寸夹杂物粒径相似,铸坯中其粒径稍微增加.随着精炼过程的进行,钢中小尺寸夹杂物的成分逐渐向复合氧化物的低熔点区域转移,夹杂物中CaO和MgO含量存在竞争关系.铸坯中大型夹杂物（>100μm）包括卷渣引起的复合夹杂,耐材剥落产生的MgO-CaO夹杂和钢液内生的铝酸盐夹杂.内生铝酸盐与精炼过程中小尺寸夹杂物成分相似,外层包覆Ca S,轧制过程中容易破碎成链状引发钻杆钢裂纹.建议适当延长VD处理后钢液的镇静时间,以去除钢中大型铝酸盐夹杂,提高钻杆钢质量.