SiO2-Al2O3-CaO-MgO系夹杂物低熔点区域优化及控制的热力学计算

为了预测CaO-Al2O3-SiO2-MgO系夹杂物具有良好变形能力的成分控制范围,首次通过热力学软件Fact-Sage对CaO-Al2O3-SiO2-MgO系液相投影图、低熔点区域大小进行了计算分析,并以阀门弹簧钢60Si2CrA为例,对CaO-Al2O3-SiO2-MgO系低熔点夹杂物的生成条件进行了探讨.结果表明...     

Cleanliness of Alloying Structural Steel

 Alloying structural steel used for mechanical structures has a high requirement for cleanliness because its failures are greatly affected by non-metallic inclusions and total oxygen content in steel. It has been reported by some steelmaking plants to have some problems in controlling total oxygen content and inclusions during alloying structural steel production. For this purpose, cleanliness control in 02C-03Si-06Mn-1Cr-02Mo steel was investigated. Firstly, low melting temperature zone (≤1873 K) of CaO-Al2O3-MgO system and formation condition of low melting temperature inclusions were investigated through thermodynamic equilibrium calculation. On this basis, industrial tests were carried out. Through sampling at different stages, transformation of oxide inclusions and change of total oxygen content in steel were studied. The results show that: in order to form CaO-Al2O3-MgO system inclusions with low melting temperature, mass percent of Al2O3, MgO and CaO in inclusions should be controlled from 376% to 708%, 0 to 174% and 255% to 606%; For the condition of 1873 K and 005% (mass percent) dissolved aluminum in steel, the activities of dissolved oxygen, magnesium and calcium should be controlled as 0298×10-4-2×10-4, 01×10-5-40×10-5 and 08×10-8-180×10-8 respectively. With secondary refining proceeding, average total oxygen content and inclusion amount decrease, the type of most inclusions changes from Al2O3 after tapping to Al2O3-MgO after top slag is formed during ladle furnace refining and finally to CaO-Al2O3-MgO after RH treatment. In the final products, average total oxygen content was 127×10-6 and most inclusions were in spherical shape with size less than 5 μm.     

20CrMnTi冶炼过程形成CaO(CaS)-Al2O3-MgO夹杂的分析

 FactSage对钙处理前后钢液的平衡计算以及典型夹杂物在CaO-CaS-Al2O3三元相图中演变规律的研究结果表明：钢中硫含量大于0.01%(质量分数,下同)时,难以得到理想的钙处理效果,主要原因在于钙处理过程中钙主要与硫结合生成CaS夹杂,同时少部分钙将对Al2O3进行变性;钙处理过程中CaO(CaS)-Al2O3演变规律为Al2O3→Al2O3+CaO·6Al2O3+CaS→CaO·2Al2O3+CaS(CaO含量较少)→Al2O3·CaO+CaS(CaO含量较多)。通过对复合夹杂物电镜面分布扫描结果的描边处理能够有效辨别复合夹杂物的成分,发现典型CaO(CaS)-Al2O3-MgO夹杂物成分为xCaO·yAl2O3+xMgO·yAl2O3+Al2O3+CaS,并据此提出了一种新的评价钙处理效果的方法。     

顶渣对帘线钢中夹杂物塑性化的控制

以某钢厂生产的帘线钢铸坯试样为原料,使用硅钼棒炉对其进行顶渣熔炼实验,研究顶渣成分对CaO-Al2O3-SiO2 类夹杂物塑性化的影响。结果表明, 在顶渣碱度为0.8～1.2时,随着顶渣中Al2O3 质量分数的增加夹杂物中的Al2O3 质量分数也随之增加。当顶渣中Al2O3质量分数低于10%时,CaO-Al2O3-SiO2 类夹杂物的成分在塑性区范围,对应的此时钢液中的w［Al］s低于8×10-6。通过控制顶渣的成分可以把CaO-Al2O3-SiO2 类夹杂物的成分控制在塑性区内。     

MgO-Al_2O_3-SiO_2复合夹杂物对430不锈钢凝固组织的影响

通过真空感应炉试验,研究不同Mg含量处理所获得的不同MgO-Al2O3-SiO2复合夹杂物对凝固组织的影响。试验结果表明,随着钢中Mg含量的增加,铸锭等轴晶率呈现先升高后下降的趋势,而等轴晶尺寸和柱状晶宽度呈现先降低后升高趋势,存在一个最佳的Mg的质量分数范围(5~13)×10-6,铸锭的等轴晶率在70%以上。夹杂物观测并结合热力学计算发现,随着钢中Mg含量的增加,MgO-Al2O3-SiO2复合夹杂物外层逐步析出MgO·Al2O3相;然而,Mg的质量分数高于13×10-6时,夹杂物外层开始析出2MgO·SiO2相。晶面错配度计算表明,MgO·Al2O3与δ-Fe的错配度为1.2%,2MgO·SiO2与δ-Fe的错配度为13%。可以判断,MgO·Al2O3相可促进等轴晶形成,抑制晶粒长大,2MgO·SiO2相则起不到促进形核作用。从而解释了铸锭等轴晶率、晶粒尺寸随Mg含量的变化规律。     

超低氧齿轮钢28MnCr5中镁铝尖晶石夹杂物的控制

利用FactSage软件对28MnCr5钢液和镁铝尖晶石夹杂物的平衡反应进行了分析,当w[Al]在0.02%~0.04%之间,w[Mg](0.39~0.42)×10-6的临界范围时开始生成镁铝尖晶石。计算发现:在现有28MnCr5钢精炼工艺条件下,钢液中会不可避免生成镁铝尖晶石夹杂物。当钢液w[Mg]8.5×10-6时,加入钙不能使其转变成低熔点液态夹杂物;而当钢液w[Mg]小于此值时,增加w[Ca]时,夹杂物按照"镁铝尖晶石→CaO-Al2O3-MgO系液态夹杂物→CaO"路径转变,钢液w[Ca]增加至3×10-6左右时均能将其转化为CaO-Al2O3-MgO系液态夹杂物。计算表明,精炼渣还原提供的[Ca]不能使28MnCr5钢中镁铝尖晶石夹杂物完全变性,须采用向钢液中喂钙线等手段来提高钢液中的钙含量。     

Inclusion evolution in 50CrVA spring steel by optimization of refining slag

In order to control the CaO-Al2O3 -SiO 2 -MgO system inclusions in 50CrVA spring steel in a lower melting temperature region, high temperature equilibrium experiments between steel and slag were performed in the laboratory, under the conditions of the initial slag basicity within 3-7 and the con-tent of Al2O3 between 18-35 mass%, to investigate the formation and evolution of this type of in-clusion.The results indicate that the total oxygen content in the steel decreases with the increase of slag basicity and the decrease of Al2O3 content in slags, and CaO-Al2O3 -SiO 2 -MgO inclusions tend to deviate from the low melting point region with the increase of Al2O3 content in slags.The most fa-vorable composition for the refining slag is composed of 51-56 mass% CaO, 9-13 mass% SiO2 , 20-25 mass% Al2O3 and 6 mass% MgO.In this case, the inclusions in 50CrVA spring steel are mostly in the low melting point regions, in which their plasticities are expected to improve during steel roll-ing.The MgO-based inclusions were observed in the steel matrix and the formation mechanism was theoretically and schematically revealed.It is also found that adding around 11 mass% of MgO into the refining slags is beneficial to reducing the refractory corrosion.Further work should be carried out focusing on the evolution rates of MgO-based inclusions.     

Modification of MgO· Al2O3 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 ther-modynamic 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 modifi-Al2O3→MgO.Al2O3→liquid complex inclusions.The modification of spinel inclusions by Ca-treatment was calculated by FactSage6.0 util-izing its free-energy minimization routines.The results of thermodynamic calculations indicate that spinel inclusions are easier to be modi-fied than Al2O3 inclusions and the spinel inclusions in 30CrMo steel would transform to liquid complex inclusions when the content of dis-solved 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.     

高碱度精炼渣对GCr15轴承钢洁净度的影响

 利用实验室渣-钢平衡试验研究了高碱度精炼渣对GCr15轴承钢中[w(T[O])]和夹杂物的影响。结合试验结果和热力学分析,探讨了钢中[w(T[O])、]夹杂物尺寸分布和粒径大小的变化规律,以及氧化物夹杂的转变过程。研究结果表明,碱度为6时,精炼渣(59.4%CaO-24.8%Al2O3-9.8%SiO2-6%MgO)可将钢中[w(T[O])]控制在0.000 6%以内,氧化物夹杂平均尺寸最小为2.26 μm。随着钢中[w([Ca])]和[w([Mg])]的增加,钢中氧化物夹杂转变过程为Al2O3→MgO·Al2O3→MgO→CaO-Al2O3-MgO复合夹杂物(核心为MgO,外围包裹着CaO-Al2O3)。渣-钢反应前期钢中以MgO·Al2O3为主,后期以MgO和CaO-Al2O3-MgO复合夹杂物为主。氧化物夹杂转变的试验结果与热力学分析结果相一致,大多数氧化物夹杂尺寸小于5 μm。     

Characteristics of Deoxidation and Desulfurization during LF Refining Al-killed Steel by Highly Basic and Low Oxidizing Slag简

Steel and slag samples were taken at the start and the end of LF refining for steel plate cold common （SPCC）, in the compact strip production （CSP） process, and at the same time, the temperature and oxygen activity a[o] were measured by using an oxygen sensor. Furthermore, inclusions in steel samples were monitored by scanning electron microscopy （SEM） combined with energy dispersive spectroscopy （EDS）. It was confirmed that a [o] in liq- uid steel was in equilibrium with inclusion rather than with top slag during LF refining. Desulfurization was related to deoxidation since a[o] at slag-steel interface was clarified to be very close to that in liquid steel under the specific con- dition in LF with intense stirring by argon blowing and refined by highly basic low oxidizing slag for Al-killed steel. Sulfur partition ratio （Ls） was very sensitive to a[o]. Since a[o] increased rapidly with temperature rise, it not only offset promotion to desulfurization reaction with temperature rise but decreased Ls. For Al-killed steel, the.modifica- tion of Al2O3 for lowering the activity of Al2O3 in inclusion was believed to be favorable for both deoxidation and desulfurization during LF refining.     

含钛焊丝钢小方坯连铸水口的结瘤机制

 利用扫描电镜对含钛焊丝钢中夹杂物性质及连铸水口结瘤物的物相组成进行了分析,并结合热力学计算研究了水口结瘤的形成机制。结果表明,LF 精炼出站钢液中存在大量Al2O3、TiO2夹杂物,并不断附着沉积在水口内壁形成氧化铝型、氧化钛型或两者结合的结瘤物,连浇炉数仅为4次。通过优化钢中［Al］-［Ti］-［O］关系,控制铝质量分数在钛-铝竞争氧化平衡线之上,即w(［Ti］)/w(［Al］)4/3>84.49 且w(［Ti］)/w(［Al］)>7.46,当钢液中w(［Al］)<0.0068%时,能够降低Al2O3夹杂比例,有效减轻水口结瘤,连浇炉数提升至6炉次。     

小方坯流程高品质轴承钢工艺

相比于电炉冶炼和大方坯流程,采用转炉冶炼加小方坯流程具有更低的生产成本。根据天钢的实际生产情况,对采用“铁水脱硫扒渣→转炉冶炼→LF造渣精炼→VD真空精炼→小方坯连铸”流程生产高品质轴承钢的关键技术进行研究。分析冶炼过程钢水及连铸坯中夹杂物可知：随着LF炉炉渣碱度的升高,钢液中wT［O］大幅降低,控制炉渣碱度R在一个较高范围（7.0~9.0）对于控制钢液中wT［O］很重要;LF精炼初期,夹杂物中Al2O3含量较高,随着精炼的进行夹杂物向着CaO-Al2O3-MgO系和Al2O3-MgO系方向夹杂物发展;VD真空处理促进钢-渣-夹杂物间反应向平衡方向移动,夹杂物接着向CaO-Al2O3-MgO系方向发展,夹杂物中CaO含量增加;在小方坯连铸过程中,采用两级电磁搅拌加低拉速、低比水量的模式获得了较小的碳偏析度。     

CaO-SiO2-Al2O3-MgO夹杂物控制影响因素的多尺度结构

 对CaO-SiO2-Al2O3-MgO夹杂物熔点的影响因素进行了多尺度分析,利用Factsage模拟了CaO质量分数对CaO-SiO2-Al2O3-MgO夹杂物熔点的影响规律。多尺度分析表明,工位操作（101 m）影响夹杂物成分（10-10 m）的最后可控因素为钙线喂入量。其通过影响局部钢液中钙质量分数（100 m）来改善熔池的动力学条件（10-3 m）,改变夹杂物中CaO质量分数（10-10 m）。模拟结果表明,当CaO质量分数为30%时,CaO-SiO2-Al2O3-MgO相图中低熔点区域的比例达到最大。通过实例分析得到了夹杂物控制的工位级效应,表明了对钢液洁净度进行多尺度深入研究的可行性。     

30Cr1Mo1V汽轮机转子钢的精炼渣优化

摘要：为有效控制30Cr1Mo1V汽轮机转子钢中非金属夹杂物和有害杂质元素含量,利用热力学软件FactSage 8.1,计算了1873K下CaO-SiO2-Al2O3-5%MgO系精炼渣与30Cr1Mo1V钢液平衡时的等［O］线、等［S］线,以获得最优精炼渣成分范围。研究了不同精炼渣对钢中氧、硫含量,夹杂物特性的影响,继而揭示了钢中典型MgO·Al2O3夹杂物的热力学形成机制以及夹杂物与精炼渣之间的成分关系,并构建了“钢 渣”界面MgO·Al2O3夹杂物运动模型。实验和模型结果表明,优化渣系50.4%CaO-40-3%Al2O3-4.3%SiO2-5%MgO对钢液脱氧、脱硫和非金属夹杂物控制的效果明显,模型预测结果与夹杂物去除率对应关系良好。     

高端抗硫管线钢非金属夹杂物研究

采用扫描电镜和大样电解等检验方法对抗硫管线钢的冶炼过程试样和连铸坯中夹杂物的数量、尺寸、成分、形貌进行系统分析。结果表明:钢液经过LF精炼后,显微夹杂物的面积比降低了34.7%;中间包钢液的夹杂物面积比较VD出站增加了6.1%。LF进站钢液中的夹杂物主要为Al_2O_3夹杂物,在LF精炼和VD真空处理过程中由于钢渣间的相互作用,形成以CaO、MgO、Al_2O_3为主要组成的复合型夹杂物。钙处理后夹杂物中的CaO和Al_2O_3的物质的量比接近12∶7,并与钢液发生了脱硫反应,形成了含CaS的复合夹杂物。中间包开浇阶段铸坯中的显微夹杂物和大型夹杂物都明显高于稳定浇铸状态;在稳定浇铸状态下,铸坯中的w(T[O])小于15×10~(-6),大型夹杂物的含量小于0.2 mg/kg;大型夹杂物的主要来源是钢包引流砂、结晶器保护渣。     

Study on Transformation of CaO-Al₂O₃-SiO₂-MgO System Inclusions in ZG06Cr13Ni4Mo Stainless Steel

This paper aims at generally studying on the inclusions of ZGG06Cr13Ni4Mo ultra-low carbon stainless steel used for large scale hydraulic turbine sets. On the basis of analysis the industrial test samples, thermodynamic software FactSage is used to study inclusions transformation process in CaO-SiO2-Al2O3-MgO system while stainless steel is been smelting. The results illustrate the inclusions melting points and plasticity variation law. The reasonable inclusions plasticity controlling area is found out in low melting point. The melting point is up to 1280℃ While MgO weight concentration is 10% in CaO-SiO2-Al2O3-MgO system, SiO2, Al2O3 and CaO in inclusions are in weight concentration range of 50-70%, 10-20% and 10-40%, respectively. For purpose of gaining low melting point inclusions, silicon alumina radio in deoxidant should be controlled between 2-5 for ultra-low carbon stainless steel refining in industry.     

RH用低碳深脱硫预熔渣

为实现低碳、超低碳钢在RH中进行深脱硫且钢水不增碳,在200kg真空感应炉上对RH用低碳深脱硫预熔渣进行了脱硫试验研究,结果表明:以CaO-Al2O3-SiO2-MgO为主的低碳深脱硫预熔渣熔点低、脱硫率高,可在真空条件下将钢液中硫的质量分数由30×10-6~50×10-6脱至10×10-6~20×10-6以下,脱硫率达到55%以上,脱硫效果好,脱硫率稳定。该预熔渣中碳的质量分数小于0.05%,在脱硫过程中钢水几乎不增碳,适用于在RH中低碳、超低碳钢深脱硫。研究表明:适当地提高炉渣的光学碱度,可大大地提高其硫容量,增强炉渣的脱硫能力。使用该预熔渣处理钢水有利于钢中夹杂物的去除和细化。     

Ti-IF钢非金属夹杂物形核热力学和演变机理

通过热力学计算与SEM-EDS检测对酒钢BOFLFRHCSP工艺Ti-IF钢夹杂物形核的热力学进行了研究。结果表明,在Ti-IF钢中夹杂物形核主要是非均匀形核,最易形成TiN,其次为CaO,然后为Al_2O_3。温度升高有利于Al_2O_3、CaO的形成;TiN的形成受温度影响较小。Ti-IF钢中w([Als])控制为0.027%~0.055%时,w([Mg])只需大于0.000 015%,就会有镁铝尖晶石MgO·Al_2O_3(MA)析出。Ti-IF钢中夹杂物演变主要有3种途径,分别为尖晶石与硅酸钙的复合夹杂Al_2O_3→MA→MgAlCaSi、低熔点的铝酸钙夹杂Al_2O_3→CaO·6Al_2O_3(CA_6)→CaO·2Al_2O_3(CA_2)→CaO·Al_2O_3(CA)→3CaO·Al_2O_3(C_3A)/12CaO·7Al_2O_3(C_(12)A_7)以及钛的复合物或钛的化合物Al_2O_3→TiOx→Al_2O_3·TiOx和Ti→TiN/Ti(C,N)。     

Investigation on Non-Metallic Inclusions in LCAK Steel Produced by BOF-LF-FTSC Production Route

 The behavior of non-metallic inclusions in LCAK (low carbon aluminum killed) steel produced by BOF (basic oxygen furnace)-LF (ladle furnace) refining-FTSC (flexible thin slab continuous caster) production route was investigated. The results showed that, LF refining for LCAK steel could decrease the wT[O] significantly, and the inclusions were modified by Ca treatment, which prevented nozzle clogging efficiently. However, owing to the unstable casting condition in the earlier stage of casting, a severe reoxidation occurred, accompanied with mold slag entrapment. The transformation of non-metallic inclusions during the steelmaking process was Al2O3→MgO-Al2O3 type inclusion→MgO-Al2O3-CaO type inclusion with a CaS ring, and the mechanism of the transformation was proposed and discussed via thermodynamic and kinetic analysis. Besides, to avoid CaS precipitation, the product of w2[Al]×w3[S] in steel should be less than 2.0×10-10 at 1873 K, which remands higher desulfurization ratio during LF refining.     

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。