精炼渣成分与轴承钢夹杂物类型关系热力学分析

针对轴承钢中钙铝酸盐大型夹杂物的控制问题,通过计算GCr15轴承钢中尖晶石MgO·Al2 O3、钙的铝酸盐CaO·6Al2 O3夹杂物生成热力学,分析精炼渣成分与夹杂物类型之间的定量关系.结果表明：当钢水中含有质量分数0.10×10-6的溶解钙[Ca]时,只要溶解镁[Mg]质量分数小于10×10-6,MgO·Al2O3就会被[Ca]还原成 CaO·6Al2O3;当精炼渣碱度为7.04,(MgO)质量分数为1.38%时,钢水中溶解[Mg]质量分数比临界[Mg]质量分数低56%,夹杂物以尺寸大于10μm的CaO-Al2O3系复合夹杂为主;当精炼渣碱度为3.75,(MgO)质量分数3.14%时,钢水中溶解[Mg]质量分数比临界[Mg]质量分数低14%,夹杂物以尺寸小于8μm的MnS包裹MgO·Al2 O3复合夹杂为主;当精炼渣钙铝比C/A为1.8~2.0时,控制精炼渣碱度R为4.5~5.5,(MgO)质量分数为3%~5%,即能使钢中MgO·Al2O3保持稳定而不转变为CaO·6Al2O3.     

Al--Ca复合合金钢水脱氧机理的研究

通过Al-Ca复合合金钢水脱氧的平衡热力学计算,确定了钢液的氧的质量分数在3×10-6~1×10-4条件下,1600℃时的Al-Ca复合合金脱氧产物的稳定区域图.以此为基础,假定钙的收得率为100%,预测了钢液在Al-Ca复合合金Ca/Al质量比为5,加入量为M kg;Al-Ca复合合金Ca/Al质量比为0.2,加入量为M kg;Al-Ca复合合金Ca/Al质量比为0.2,加入量为0.2M kg三种不同脱氧制度下夹杂物的演变历程.结果表明,在Ca/Al=5,复合合金加入量使初始钢液中的[Ca]为0.01%,[Al]为0.002%时,夹杂物在钢液精炼过程中的演变历程为:12CaO·7Al2O3(l)/CaO·Al2O3(l)→CaO(s)→12CaO·7Al2O3(l)/CaO·Al2O3(l)→CaO(s)→12CaO·7Al2O3(l)/CaO·Al2O3(l),并确定了固态和液态脱氧产物在脱氧过程中交替形成为最理想的Al-Ca复合合金脱氧制度,可为钢铁企业脱氧剂的选择和应用提供参考和借鉴.     

Dissolution of Al<Subscript>2</Subscript>TiO<Subscript>5</Subscript> inclusions in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags at 1823 K

Al-Ti-O inclusions always clog submerged nozzles in Ti-bearing Al-killed steel. A typical synthesized Al₂TiO₅ inclusion was immersed in a CaO-SiO₂-Al₂O₃ molten slag for different durations at 1823 K. The Al₂TiO₅ dissolution paths and mechanism were revealed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Decreased amounts of Ti and Al and increased amounts of Si and Ca at the dissolution boundary prove that inclusion dissolution and slag penetration simultaneously occur. SiO₂ diffuses or penetrates the inclusion more quickly than CaO, as indicated by the w(CaO)/w(SiO₂) value in the reaction region. A liquid product (containing 0.7–1.2 w(CaO)/w(SiO₂), 15wt%–20wt% Al₂O₃, and 5wt%–15wt% TiO₂) forms on the inclusion surface when Al₂TiO₅ is dissolved in the slag. Al₂TiO₅ initially dissolves faster than the diffusion rate of the liquid product toward the bulk slag. With increasing reaction time, the boundary reaches its largest distance, the Al₂TiO₅ dissolution rate equals the liquid product diffusion rate, and the dissolution process remains stable until the inclusion is completely dissolved.     

BOF-LF-CC工艺生产50 CrVA弹簧钢洁净度研究

通过对国内某钢厂BOF-LF-CC工艺生产50CrVA弹簧钢进行全流程连续取样,综合分析了冶炼过程中总氧( T. O.)、N含量变化,非金属夹杂物的衍变规律,以及铸坯中大型夹杂物的特征.结果表明,LF精炼前T. O.和N的平均含量分别为106×10-6和13×10-6,铸坯中分别为15×10-6和39×10-6,LF过程脱氧效果明显;运输和浇注过程存在较明显的二次氧化现象,需要加强大包到中间包的保护浇注;铸坯中夹杂物主要为CaO-Al2 O3-MgO和CaO-Al2 O3-SiO2复合氧化物夹杂,其中Al2 O3含量(质量分数)较高,达到60%~70%,未得到低熔点夹杂物,可通过适当提高精炼渣碱度,或喂入适量钙线促使夹杂物充分转变为成分更加均匀的低熔点夹杂物;大型夹杂物以CaO和CaO-Al2 O3-SiO2-( MgO)球状氧化物为主,还存在一定比例的纯Al2 O3夹杂物,需要延长钢包弱搅拌时间使夹杂物充分上浮.     

Formation and thermodynamics of CaS-bearing inclusions during Ca treatment in oil casting steels

Industrial experiments were carried out to investigate the formation of CaS-bearing inclusion during Ca double modification in oil casting steels using polished cross sections and electrolytic extraction. Immediately after Ca addition, the role of newly generated CaS as an intermediate reaction product, which modified the Al_2O_3 inclusion into a liquid calcium aluminate, was confirmed. The formation of transient CaS was attributed to the high surface segregation of S at the liquid steel-calcium vapor interface, where a simple site coverage model based upon the Langmuir adsorption equation was established. Moreover, a CaS outer layer surrounding the liquid calcium aluminate was attained mainly in the tundish, which was distributed unevenly on the surface of liquid particles according to the three-dimensional mapping results. The surface of a well-modified calcium aluminate with higher CaO activity and Al_2O_3 activity under bulk composition conditions in the tundish acted as a favorable site for the generation of CaS. Additionally, CaS could be precipitated directly onto existing inclusions during solidification of the steel, which led to various morphologies of CaS-bearing inclusions in slabs. Furthermore, the phase transformation of inclusions during solidification was strongly influenced both by the S content and the Ca/S ratio in the tundish via thermodynamics.     

高品质GCr15轴承钢二次精炼过程中夹杂物的演变规律

采用FE-SEM/EDS研究了转炉流程生产的GCr15轴承钢LF、RH精炼过程中夹杂物的演变规律,分析了其演变机理。结果表明:钢中复合夹杂物的演变规律可归纳为:Al2O3→MgO·Al2O3→(CaO-MgO-Al2O3-(CaS))复合氧化物夹杂和Al2O3→(Al2O3-MnS)→(Al2O3-MnS-Ti(C,N))复合氧硫碳氮物夹杂2种方式。LF精炼过程脱硫作用明显,钢中的硫化物夹杂数量大幅减少。LF精炼初期钢中主要是MnS、Al2O3、TiN的单相夹杂物。LF精炼结束后钢中的夹杂物演变为Al2O3为核心外包氧化物及MnS、TiN、Ti(C,N)、CaS的复合夹杂物。精炼渣中的CaO和耐火材料中的MgO经还原后与钢中溶解氧反应导致LF精炼结束时D类夹杂物增加。RH及软吹处理进一步强化了去除钢中的硫化物,但D类及其与A、T类复合的夹杂物含量增加。在LF阶段,夹杂物尺寸主要集中在1~3μm范围内,到RH阶段,夹杂物尺寸则主要集中分布在小于1μm的粒度范围。最大夹杂物尺寸由10.79μm降到5.68μm,单位面积夹杂个数由372个/mm2降到258个/mm2。RH及软吹处理有效地降低了钢中大于3μm的夹杂物。     

高级别管线钢钙处理效果评价标准

对X70管线钢进行了六炉钙处理实验.结果表明:钙处理后管线钢生产的后续工序中钢中钙含量显著下降,夹杂物组成和形貌发生显著变化;二次氧化会降低管线钢钙处理效果,但钢中溶解钙和较高CaO含量的CaO-Al2O3复合夹杂可对钢水二次氧化产生的Al2O3发生改性作用;高级别管线钢钙处理效果与钢中钙含量、氧含量、硫含量、钢水二次氧化程度以及钙处理后续时间等有关,采用钢中Ca含量、[%Ca]Tot/[%Al]s、[%Ca]Tot/T[O]、ACR和[%Ca]Tot/[%S]作为钙处理效果的评判标准均存在缺陷.本文建议钙处理效果评判标准为:①铸坯中心部位或轧后板带中心部位不存在单纯的MnS夹杂;②中间包和结晶器中夹杂的nCaO/Al2O3应该与12CaO.7Al2O3相近;③钙处理后夹杂的nCaO/Al2O3应稍高于12CaO.7Al2O3的夹杂.同时还必须注意钙处理应在最后精炼工序的后期进行,尽量防止钢水的二次氧化.     

38CrMoAl高铝钢钢水可浇性控制

38CrMoAl高铝钢由于Al含量较高([Al]=0.7%～1.1%,质量分数),在连铸过程中容易导致水口的堵塞,因此需要对钢中Al2O3夹杂物进行形态控制,保证钢水的可浇性.热力学计算和实验研究结果显示:钢中高含量的Al对渣中即使少量的SiO2都具有较强的还原性;不采用传统的精炼喂钙线工艺,而进行转炉出钢过程渣洗操作,能将高熔点的Al2O3转变为低熔点的球状钙铝酸盐夹杂.同时,采用CaO--Al2O3基中间包覆盖剂,以避免钢渣反应导致钢中夹杂物含量增加.工业性试验结果表明,钢水洁净度较高,可浇性好,连续浇注5炉后,水口内壁基本无结瘤现象.     

18wt%Cr–8wt%Ni不锈钢中增塑性MnO–Al2O3–SiO2基非金属夹杂物的演变及其浸泡性能

The properties of MnO–Al₂O₃–SiO₂-based plasticized inclusion are likely to change during soaking  process due to its low melting point. In this study, the evolution of the MnO–Al₂O₃–SiO₂-based inclusion of 18wt%Cr?8wt%Ni stainless steel under isothermal soaking process at 1250°C for different times was investigated by laboratory-scale experiments and thermodynamic analysis. The results showed that the inclusion population density increased at the first stage and then decreased while their average size first decreased and then increased. In addition, almost no Cr₂O₃-concentrated regions existed within the inclusion before soaking, but more and more Cr₂O₃ precipitates were formed during soaking. Furthermore, the plasticity of the inclusion deteriorated due to a decrease in the amount of liquid phase and an increase in the high-melting-point-phase MnO–Cr₂O₃ spinel after the soaking process. In-situ observations by high-temperature confocal laser scanning microscopy (CLSM) confirmed that liquid phases were produced in the inclusions and the inclusions grew rather quickly during the soaking process. Both the experimental results and thermodynamic analysis conclude that there are three routes for inclusion evolution during the soaking process. In particular, Ostwald ripening plays an important role in the inclusion evolution, i.e., MnO–Al₂O₃–SiO₂-based inclusions grow by absorbing the newly precipitated smaller-size MnO–Cr₂O₃ inclusions.     

Ultrahigh cycle fatigue fracture mechanism of high-quality bearing steel obtained through different deoxidation methods

The mechanism of oxide inclusions in fatigue crack initiation in the very-high cycle fatigue(VHCF)regime was clarified by subjecting bearing steels deoxidized by Al(Al-deoxidized steel)and Si(Si-deoxidized steel)to ultrasonic tension-compression fatigue tests(stress ratio,R=−1)and analyzing the characteristics of the detected inclusions.Results show that the main types of inclusions in Si-and Al-deoxidized steels are silicate and calcium aluminate,respectively.The content of calcium aluminate inclusions larger than 15μm in Si-deoxidized steel is lower than that in Al-deoxidized steel,and the difference observed may be attributed to different inclusion generation processes during melting.Despite differences in their cleanliness and total oxygen contents,the Si-and Al-deoxidized steels show similar VHCF lives.The factors causing fatigue failure in these steels reveal distinct differences.Calcium aluminate inclusions are responsible for the cracks in Al-deoxidized steel.By comparison,most fatigue cracks in Si-deoxidized steel are triggered by the inhomogeneity of a steel matrix,which indicates that the damage mechanisms of the steel matrix can be a critical issue for this type of steel.A minor portion of the cracks in Si-deoxidized steel could be attributed to different types of inclusions.The mechanisms of fatigue fracture caused by calcium aluminate and silicate inclusions were further analyzed.Calcium aluminate inclusions first separate from the steel matrix and then trigger crack generation.Silicate inclusions and the steel matrix are closely combined in a fatigue process;thus,these inclusions have mild effects on the fatigue life of bearing steels.Si/Mn deoxidation is an effective method to produce high-quality bearing steel with a long fatigue life and good liquid steel fluidity.     

无取向硅钢中镁铝尖晶石的变性机理

对无取向硅钢钙处理过程中镁铝尖晶石夹杂的变性机理进行了研究,重点考察了钙处理前期和中期MgO-Al2 O3的变性过程.钙处理前,钢中除了发现单纯的MgO- Al2 O3外,还发现少量被AlN包裹的MgO- Al2 O3.钙处理1.5 min后,在MgO-Al2 O3表面有中间产物CaS或CaO形成;钙处理4.5 min后,生成由内到外依次为MgO-Al2 O3、CaO-MgO-Al2 O3和CaO-Al2 O3的夹杂物;钙处理10 min后,未反应的MgO-Al2 O3消失,CaO-MgO-Al2 O3和CaO-Al2 O3的成分趋于均匀.通过热力学计算得到了Al2 O3/MgO-Al2 O3/MgO和MgO-Al2 O3/xCaO·yAl2 O3的稳定相图,发现在含铝越高的钢中,镁铝尖晶石变性越困难.结合夹杂物的扫描电镜观察、能谱分析和面扫描图分析结果,提出了夹杂物的变性路径：MgO或Al2 O3→MgO- Al2 O3→CaO-MgO-Al2 O3→CaO-Al2 O3;在产物的中间层CaO-MgO-Al2 O3中,Al2 O3含量除了一般情况下的逐渐降低外,偶尔还存在突然升高的情况.     

镁对H13模具钢中夹杂物变性的影响简

本文研究了镁对H13模具钢中夹杂物的影响,对H13钢中夹杂物的变性进行了热力学计算,分析了镁对夹杂物成分、形貌和粒径分布的影响。结果表明,镁处理H13钢后,夹杂物由Al2 O3转变为MgO·Al2 O3,复合型夹杂物的析出位置也发生了改变,夹杂物粒径变小。镁处理使钢中1μm左右的夹杂物增多,2μm以上的夹杂物减少,随着镁含量的升高,粒径的变化更明显。铝质量分数为0．01％～0．03％的H13钢中,微量的镁就可促使MgO·Al2O3夹杂物形成,镁质量分数超过1×10^-4会导致H13钢中MgO·Al2O3完全消失,镁质量分数在3×10^-5～5．5×10^-5时钢液中镁铝尖晶石的数量达到最多。     

Characteristics of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, MnS,and TiN inclusions in the remelting process of bearing steel

The Al₂O₃, MnS, and TiN inclusions in bearing steel will deteriorate the steel's mechanical properties. Therefore, elucidating detailed characteristics of these inclusions in consumable electrode during the electroslag remelting process is important for achieving a subsequently clean ingot. In this study, a confocal scanning violet laser microscope was used to simulate the remelting process and observe, in real time, the behaviors of inclusions. The obtained images show that, after the temperature exceeded the steel solidus temperature, MnS and TiN inclusions in the specimen began to dissolve. Higher temperatures led to faster dissolution, and the inclusions disappeared before the steel was fully liquid. In the case of an observed Al₂O₃ inclusion, its shape changed from angular to a smooth ellipsoid in the region where the solid and liquid coexisted and it began to dissolve as the temperature continued to increase. This dissolution was driven by the difference in oxygen potential between the inclusion and the liquid steel.     

超低碳钢顶渣氧化性对钢液洁净度的影响

为探究降低顶渣氧化性对改善超低碳钢钢液洁净度的影响,在转炉终点至中间包过程中,在多位置取炉渣和钢水试样,分别进行炉渣氧化性、钢液成分和夹杂物分析.实验结果表明:转炉出钢后通过对顶渣改质,渣中T.Fe由转炉终点的19.18％降至RH进站时的4.68％,顶渣氧化性降低明显.渣中T.Fe降低导致钢中[O]的降低,T.Fe较低的炉次平均吹氧量较大,使得铝脱氧前钢中[O]较高.RH结束渣T.Fe与夹杂物数量呈线性关系,T.Fe越低夹杂物数量越少,同时RH结束后夹杂物数量与铝脱氧前钢中[O]无必然关系.顶渣(CaO)/(Al2O3)会影响其吸收Al2O3夹杂物的能力,(CaO)/(Al2 O3)控制不合理的炉次,其夹杂物数量也较多.通过降低顶渣氧化性,热轧板卷缺陷率得到明显降低.     

Dynamic mass variation and multiphase interaction among steel,slag, lining refractory and nonmetallic inclusions: Laboratory experiments and mathematical prediction

The mass transfer among the multiphase interactions among the steel, slag, lining refractory, and nonmetallic inclusions during the refining process of a bearing steel was studied using laboratory experiments and numerical kinetic prediction. Experiments on the system with and without the slag phase were carried out to evaluate the influence of the refractory and the slag on the mass transfer. A mathematical model coupled the ion and molecule coexistence theory, coupled-reaction model, and the surface renewal theory was established to predict the dy-namic mass transfer and composition transformation of the steel, the slag, and nonmetallic inclusions in the steel. During the refining process, Al2O3 inclusions transformed into MgO inclusions owing to the mass transfer of [Mg] at the steel/refractory interface and (MgO) at the slag/re-fractory interface. Most of the aluminum involved in the transport entered the slag and a small part of the aluminum transferred to lining re-fractory, forming the Al2O3 or MgO·Al2O3. The slag had a significant acceleration effect on the mass transfer. The mass transfer rate (or the re-action rate) of the system with the slag was approximately 5 times larger than that of the system without the slag. In the first 20 min of the re-fining, rates of magnesium mass transfer at the steel/inclusion interface, steel/refractory interface, and steel/slag interface were x, 1.1x, and 2.2x, respectively. The composition transformation of inclusions and the mass transfer of magnesium and aluminum in the steel were predicted with an acceptable accuracy using the established kinetic model.     

高品质轴承钢LF--VD过程非金属夹杂物演变规律

对国内一钢厂EAF→LF→VD→CC工艺生产的高品质GCr15轴承钢进行系统取样,针对DS类非金属夹杂物随机性强的特点,利用能够进行大面积试样检测的ASPEX自动扫描电镜分析统计钢中非金属夹杂物的成分、尺寸、数量等信息。研究发现：GCr15轴承钢冶炼过程中非金属夹杂物主要为MgO- Al2 O3- CaO复合夹杂物和MnS,同时有少量的SiO2- Al2 O3和MgO-Al2 O3复合夹杂物;夹杂物尺寸主要集中在3~8μm,并有少量DS类夹杂物出现且尺寸范围波动很大,最大可以达70μm以上,形貌为圆形或近似圆形;VD有较强的去除夹杂物功能,经过VD真空精炼,夹杂物中CaO含量有增加趋势;吊包至铸坯过程,夹杂物成分向Al2 O3含量增多的区域移动,最终轴承钢铸坯中夹杂物成分位于高Al2 O3含量(≥80%),少量MgO (<20%)和低CaO(<5%)的区域;DS夹杂物的生成和去除具有较强的随机性。     

铝、镁脱氧钢中夹杂物的动态演变规律

本研究制备了不同氧、硫含量的实验钢,采用SEM-EDX和CSLM探讨了钢中夹杂物类型及高温演变规律.结果表明,脱氧生成的MgO大多为球形,而MgO·Al2O3呈现不规则形状.单独铝脱氧钢中Al2O3夹杂物通过移动、碰撞、聚合的方式形成大型簇团.铝镁复合脱氧钢中夹杂物形貌和动态演变随着［Al］,［Mg］和［S］含量的变化呈现出不同的现象.当［Mg］,［Al］含量满足MgO生成条件时,夹杂物无明显聚合现象,呈弥散分布的特征;当［Mg］,［Al］含量位于MgO·Al2O3生成区域时,未观察到团簇状夹杂物出现,但夹杂物粒径较MgO大;当夹杂物成分同时满足MgO和MgS生成条件时,夹杂物聚合趋势明显,推测是硫化物的形成促进了夹杂物的聚合现象.     

Modification of MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> spinel inclusions in Al-killed steel by Ca-treatment

The modification of MgO·Al₂O₃ spinel inclusions in Al-killed steel by Ca-treatment has been studied by industrial trials and thermodynamic calculations. In the industrial trials, samples were taken systematically during the refining process in which the molten steel was treated by calcium, and the characters of the inclusions were analyzed using scanning electron microscopy (SEM) and energy dispersive spectra (EDS). The effects of Ca-treatment were evaluated by tracking the compositions of the inclusions. The results show that the modification of MgO·Al₂O₃ spinel inclusions by Ca-treatment is effective and the transformation sequence of the inclusions during the refining is Al₂O₃→MgO·Al₂O₃→liquid complex inclusions. The modification of spinel inclusions by Ca-treatment was calculated by FactSage6.0 utilizing its free-energy minimization routines. The results of thermodynamic calculations indicate that spinel inclusions are easier to be modified than Al₂O₃ inclusions and the spinel inclusions in 30CrMo steel would transform to liquid complex inclusions when the content of dissolved Ca in the molten steel exceeds 1×10⁻⁶. Also, the results show that adding more calcium into the molten steel would lower the contents of Al₂O₃ and MgO and increase the CaO content of the inclusions, while the change in SiO₂ content is little.     

Recovery of iron and calcium aluminate slag from high-ferrous bauxite by high-temperature reduction and smelting process

A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w(CaO)/w(SiO₂) ratio, anthracite ratio, and reduction temperature and time on the recovery and size of iron nuggets and on the Al₂O₃ grade of the calcium aluminate slag were investigated through thermodynamic calculations and experiments. The optimized process conditions were the bauxite/anthracite/slaked lime weight ratio of 100:16.17:59.37, reduction temperature of 1450°C and reduction time of 20 min. Under these conditions, high-quality iron nuggets and calcium aluminate slag were obtained. The largest size and the highest recovery rate of iron nuggets were 11.42 mm and 92.79wt%, respectively. The calcium aluminate slag mainly comprised Ca₂SiO₄ and Ca₁₂Al₁₄O₃₃, with small amounts of FeAl₂O₄, CaAl₂O₄, and Ca₂Al₂SiO₇.     

钙处理过程夹杂物演变及热力学分析

通过检测分析钙处理前后钢中夹杂物的形貌和成分的变化,探讨钢液钙处理过程中夹杂物演变规律.利用热力学计算,优化钙处理工艺.结果表明,钙处理可以将钢液中不规则固态夹杂物改性为球形液态夹杂物;1873 K下,当[ Al ]为0.030%时,[O]控制在5×10-6~17×10-6,[Ca]控制在0.7×10-6~30×10-6,钢中夹杂物变性效果良好;当[Al]为0.030%时,[ S]控制在6×10-6~19×10-6,既能使钢中Al2 O3夹杂生成液态铝酸钙夹杂物,同时又可以减少CaS生成.