A thermodynamic model for deoxidation equilibria in steel

For relattively dilute solutions of oxygen and a deoxidizer M (M=Al, Cr, Ca, Mg, ...) in molten Fe, a thermodynamic model is proposed wherein the dissolved species are M*O associates as well as unassociated M and O atoms. At higher metal concentrations, a small amount of M ₂*O associates also form. Experimental deoxidation equilibria for 15 deoxidizers M are quantitatively reproduced at all temperatures, with only a constant, temperature-independent and composition-independent empirical parameter for the Gibbs energy of formation of each associate. The deoxidation behavior of Mg, Ca, and Ba is elucidated for the first time. The parameters are stored in a database, which can be used to predict complex deoxidation equilibria in multicomponent steels.     

关于KR脱硫工艺脱氧理论问题的研究

 利用脱氧平衡最低值理论公式,计算了1573K下铁水中基于［Al］-［O］平衡和［C］-［O］平衡的氧含量。计算得出［C］-［O］平衡和［Al］-［O］平衡的最低氧质量分数分别为34×10-6和0.015×10-6,但是计算的［C］-［O］平衡控制的最低氧含量相当于由［C］-［O］平衡决定的氧含量的近4倍。因此,在KR铁水脱硫过程中,铝脱氧控制铁水中的氧势。另外,计算结果表明,在铁水预处理过程中,硅的脱氧能力远不及碳和铝,且脱氧平衡最低值理论公式对铁水预处理也具有适用性。铝脱氧结果表明,每吨铁水中加入0.44kg的铝,可使铁水温度升高20℃左右,在一定程度上可弥补KR铁水脱硫过程中因搅拌、脱硫剂的加入所造成的温降。     

On Physico‐Chemical and Technical Limits in Clean Steel Production

Great progresses in steel cleanliness have been attained during the last decades. In the measures of oxygen the lowest levels are approaching 5 ppm in O_tot i.e. close to the thermodynamic limit of Al deoxidation. As the thermodynamics of the reaction system is firmly anchored to the steel chemistry and thus to the properties of steel and the final product, it is useful to examine the thermodynamic constraints for selected steels in the refining and casting processes. In most steels Al‐O equilibrium determines the limit of deoxidation. Calculations by applying thermodynamic software showed that in selected “common” steels the equilibrium oxygen content varied from below 5 ppm up to 30 ppm or higher depending on the aluminium content, interaction effect of other alloying elements and temperature. For lower oxygen content there are several possibilities. The first one is to use stronger deoxidizing additions like Ca, Zr, Ce etc. However, they can be problematic as substitutes as they produce inclusions which influence steel properties. The second way is to intensify the deoxidizing power of certain elements e.g. Si by bringing the steel in intimate contact with a proper slag with low SiO₂ activity in ladle treatment with violent stirring. In the calculation example it was possible to decrease oxygen content from 30 ppm to the level below 10 ppm in C/Mn/Si steel at very low Al level. The third potential but unused process is vacuum deoxidation especially for medium and high carbon steels. Equilibrium oxygen contents below 1 ppm are thermodynamically easily attainable. But in practice the vacuum treatment should be designed to intensify the carbon‐oxygen reaction on the top surface of the stirred steel liquid. Also the eventual reactions with refractory materials should be suppressed.     

VOD炉冶炼20Cr13不锈钢硅脱氧工艺

 以实际工艺流程30 t EAF-VOD-LF-模铸冶炼20Cr13不锈钢为背景,通过热力学计算,对VOD精炼硅脱氧处理后,重新造渣过程中炉渣碱度、合金含量以及钢液温度对钢液中平衡氧含量的影响进行了研究。研究结果表明：钢液中的氧含量随炉渣碱度的增加呈现明显的减小趋势,实际生产中炉渣碱度一般应确保在2以上;为了保证添加合金进行脱氧的冶炼效果,应保证钢液中的硅的质量分数在0.3%以上;降低冶炼温度有利于降低钢液平衡氧含量;炉渣碱度对平衡溶解氧含量和实际生产全氧含量的影响规律基本相同,拟合出平衡溶解氧含量与实际全氧含量之间存在线性关系。     

铁液中Al-C复合脱氧热力学

利用热力学方法,针对铁液中铁水深脱硫条件所需要的低氧含量,研究了Al-C-O平衡时铁溶液中氧含量的变化规律.通过对C、Al及Al-C复合脱氧反应脱氧常数的比较得出,在1573K温度下,铁液中用Al-C复合脱氧,其脱氧能力比单独使用C脱氧能力强.用热力学理论得出1573K温度下铁液中用Al-C复合脱氧的平衡曲线.研究表明:在温度一定时,随着C的活度a_C的增大,Al-C复合脱氧能力逐渐增强;在a_C一定的情况下,随着温度的升高,Al-C复合脱氧能力逐渐减弱.      

Aluminum deoxidation equilibrium in liquid Ni-Fe alloys equilibrated with CaO-Al2O3 slags

The deoxidation equilibrium for Al in Ni-Fe alloys was studied in the equilibrium experiments between CaO-Al₂O₃ slags and Fe-30, 50 and 70 % Ni alloys at 1873 K. By using the values for the first and second order interaction parameters between oxygen and nickel in liquid iron and those between oxygen and iron in liquid nickel, the effect of Ni on the activity coefficient of Al in liquid iron and that of Fe on the activity coefficient of Al in liquid nickel were determined in the whole composition range of Ni-Fe alloys. The oxygen contents in Ni-Fe alloys calculated by the iterative method based on pure iron were in good agreement with those based on pure nickel in the range of [% Al] < 0.03. From this fact, it was found that the Wagner's approximation relating to the multi-component solution was applicable to the deoxidation equilibrium in the whole composition range of Ni-Fe alloys in the restricted concentration of a deoxidizer.     

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.     

含钙钡合金脱氧和非金属夹杂物控制技术研究

采用MoSi2电阻炉在1〖KG-*9〗873 K下开展了含钙钡合金脱氧和非金属夹杂物控制技术研究。结果表明，各组实验终点钢中夹杂物平均长度均小于8 μm，并都有纯三氧化二铝夹杂物存在。采用含钙钡合金的复合脱氧工艺，终点钢中未发现含钡夹杂物，有较多以CaO Al2O3为主要成分的复合夹杂物，w（T.O）＞50×10-6。用AlMnCa脱氧，终点钢样w（T.O）＝37×10-6，含氧化钙夹杂物较少，大于20 μm的夹杂物数量占总夹杂物数量的1.2%。     

钛稳定超纯铁素体不锈钢硅铝复合脱氧的试验研究

 为改进超纯铁素体不锈钢的脱氧工艺,提高夹杂物控制水平,在硅钼高温电阻炉内对钛稳定超纯铁素体不锈钢的精炼过程进行了试验研究。结合热力学计算,研究了不同Si、Al含量(质量分数,下同)比值的硅铝合金的脱氧效果,以及脱氧、钛合金化和钙处理后钢中典型夹杂物的组成和形貌及粒度分布。结果表明：钢中初始氧含量相近的条件下,硅铝合金复合脱氧的钢中酸溶铝、全氧量与纯铝脱氧结果相近。硅铝复合脱氧后钢中夹杂物主要为(MgO-)Al2O3-SiO2复合脱氧产物。钛合金化后夹杂物的类型主要为Al2O3-MgO-(SiO2)-TiOx复合夹杂物和TiN。钙处理后的夹杂物主要为球形的MgO-Al2O3-CaO-SiO2-TiOx类复合氧化物。采用硅铝合金复合脱氧比纯铝脱氧钢的夹杂物的总数量、总面积和平均粒径均要小。     

Thermodynamic assessment of Mg deoxidation reaction of liquid iron and equilibria of [Mg]‐[Al]‐[O] and [Mg]‐[S]‐[O]

The deoxidation reaction of magnesium was investigated thermodynamically employing the equilibrium system between magnesium vapour and liquid iron in the molybdenum chamber sealed with an iron cover at 1873 K as a fundamental study to address the clean steel production technology in the steelmaking process. The previously reported thermodynamic data for magnesium deoxidation reaction are limitedly in good agreement with only their respective specific Mg concentration range, but fail to explain the thermodynamic equilibria generally over the wider range of magnesium concentration beyond the limited range. Therefore, the equilibrium constant, K_Mg for the magnesium deoxidation reaction as well as the first and second‐order interaction parameters between magnesium and oxygen were determined over the extensive magnesium mass content range covering up to 0.04 %. Furthermore, the phase stability diagram based on the equilibria of [Mg]‐[Al]‐[O] in liquid iron for the purpose of controlling the oxide inclusions in the steelmaking process was accomplished using the determined thermodynamic parameters. The equilibria of [Mg]‐[S]‐[O] were also discussed in order to evaluate the utilisation of Mg as a desulphurizing agent as well as deoxidizer in the production process of low carbon steels.     

Thermodynamic Analysis of Desulfurization and Its Connection With Deoxidation and Temperature for SPHC in JISC During LF Refining Process

The thermodynamic characteristics of desulfurization reaction (CaO)+[S]=(CaS)+[O] is analyzed based on the detailed composition of liquid steel and slag of Steel Plate Hot Commercial (SPHC) in Jiuquan Iron & Steel Corporation(JISC), where the activities of CaO, CaS and Al2O3 in molten slag are calculated by thermodynamic software FactSage for a more accurate result. The critical values of [O%]/[S%] for desulfurization at different temperature is are obtained, typically 0.09 at 1873K, which shows directly that it should deoxidize adequately for obtaining a favorable desulfurization condition. In addition, the thermodynamic analysis indicates that the actual dissolved O is much higher than that of equilibrium calculation which shows Al-O reaction in LF is far away from equilibrium, but it is perfect agreement with the computing results when taking the activity of Al2O3 as 1 that due to the inclusion component in LF is mainly Al2O3. Besides, with the temperature rise, the sulfur partition ratio increases softly meanwhile the reaction between Al and O is limited to a great degree resulting in the increase a dissolved oxygen in liquid steel that decreases the sulfur partition ratio seriously. As a result, the sulfur partition ratio appears to decrease with temperature increase in Al killed steel.     

Ce/Mg处理对M50轴承钢洁净度的影响

采用真空感应熔炼工艺冶炼航空轴承钢M50,对比分析了Ce处理、Mg处理和Ce–Mg复合处理对氧、硫含量和夹杂物分布特征的影响,结合热力学计算,阐明了加入Ce、Mg元素对钢液洁净度的影响机理。研究发现,Ce具有很强的脱氧、脱硫能力,加入Ce会优先生成Ce₂O₂S夹杂物,随着钢液中氧含量的降低,Ce还会与As等有害杂质元素结合,起到净化钢液的效果。过量的Ce会加剧其与镁铝尖晶石材质耐火材料的反应,导致钢中夹杂物数量的增加,Ce的质量分数为0.018%时,钢中夹杂物的尺寸和数量最小;添加Mg不仅可以脱氧、脱硫,还可以抑制Ce与镁铝尖晶石耐材的反应,Ce–Mg复合处理可以显著降低钢中的夹杂物的尺寸和数量,将钢中的氧的质量分数降低至0.00075%。      

不同脱氧方式对钢中夹杂物的影响

为控制钢液中氮含量,实验了两种不同脱氧方式:(Ⅰ)出钢过程加Al进行强脱氧;(Ⅱ)出钢时不加Al,加入Si-Mn合金进行弱脱氧,在LF进站再喂入Al线进行强脱氧.借助气体分析仪和扫描电镜对不同脱氧方式下钢中氧氮含量和夹杂物进行了分析.两种不同脱氧方式得到最终产品的全氧含量几乎一致,但方式(Ⅱ)对控制氮含量更为有利,可以使氮的质量分数降低约5×10-6;两种不同脱氧方式对最终产品中夹杂物的类型和尺寸影响不大,均为球状的CaS和CaO-MgO-Al₂O₃夹杂物.文中还推断出了采用Si-Mn弱脱氧时钢中夹杂物的生成过程.      

电渣重熔过程中渣成分变化及钢中氧含量预测

利用XRF和XRD技术分析了电渣重熔过程中不同时间所取渣样的化学成分和物相结构。XRF分析得到电渣重熔过程中渣中Al2O3、CaF2、CaO、SiO2、FeO等成分含量随熔炼时间的动态变化。XRD分析表明:凝固的渣中存在11CaO·7Al2O3·CaF2、12CaO·7Al2O3、CaSiO3等高熔点物质,导致炉渣性质发生变化。根据熔渣化学成分,参考CaF2-CaO-Al2O3渣系的等电导率图和等黏度图,得到了电渣的比电阻和黏度随冶炼时间的变化情况。采用炉渣结构共存理论建立了温度为1 923和1 973K时与渣中Al2O3平衡的钢液中[Al]-[O]平衡关系图。计算结果显示,针对实验研究的钢种,当钢中酸溶铝含量w[Al]s在0.000 1%~1%范围内时,钢液中溶解氧含量随着w[Al]s的增加先减小后增大,当钢中w[Al]s达到0.25%时,钢液中w[O]最小。在实验条件下,因渣成分变化导致的钢中w[O]的波动范围是0.25×10-6~0.48×10-6。     

酒钢SPCC钢的LF精炼脱硫

 通过热力学分析,建立了硫分配比与硫容量的关系,用热力学软件FactSage计算渣中Al2O3活度,用KTH模型计算渣的硫容量,对SPCC(一般用冷轧碳素钢薄板坯钢带)两个浇次10炉钢水在LF进站和出站时取钢、渣样以及测氧和温度,通过分析钢样和渣样成分以及生产检测数据,分析了温度、炉渣成分和钢水成分对LF精炼脱硫的影响规律。定义了硫分配比对钢液中溶解氧活度的急剧变化区(a［O］＜4×10-6),在该区内硫分配比对钢液中溶解氧活度十分敏感,钢液中氧活度的增大导致硫分配比的迅速减小,温度升高,a［O］升高,不仅抵消了升温对脱硫反应轻微的促进作用,反而使硫分配比随温度升高而减小。LF精炼过程Al-O反应未达渣-钢平衡,实际［O］活度介于平衡计算值与Al2O3活度为1的计算值之间,故渣钢硫分配比也介于二者之间。精炼渣二元碱度升高则硫分配比增加,wCaO/wAl2O3在1.6~2.0时脱硫效果较好,硫分配比并不随［Al］s含量的增加而增大,所以用增加w［Al］s来脱硫效果并不明显。钢中夹杂铝(w［Al］t-w［Al］s)降低到10×10-6以下,硫分配比明显升高。     

酒钢CSP流程SPCC钢LF精炼渣-钢平衡及渣成分优化

 利用热力学计算软件FactSage确定了精炼渣中MgO质量分数合理范围为4%~8%,以6%最佳。由工业取样结果结合FactSage分析了1873K时SiO2-CaO-Al2O3-6%MgO准三元系液相区及CaO饱和的固液两相区渣-钢平衡。结果表明:高碱度高w(CaO)/w(Al2O3)(C/A)精炼渣有利于钢液的低氧低硫和低硅控制,但并非造得越“白”越好,相反过高的CaO对脱氧和硅含量控制不利。通过钢渣平衡分析得到了酒钢SPCC精炼渣优化成分范围(质量分数)为：CaO为50%~55%,Al2O3为30%~36%,SiO2为1%~6%,MgO为4%~8%,6%为最佳,碱度为9.0~14.0,w(CaO)/w(Al2O3)为1.5~1.8,实验室渣-钢平衡试验和工业生产结果均验证了优化的渣系较原渣系精炼效果更加优越,能够同时降低钢中总氧、硫和硅含量,也能有效控制钢中夹杂物的成分。     

脱氧方式对高铝钢中非金属夹杂物的影响

摘要：为了研究不同脱氧方式对高铝钢中非金属夹杂物的影响,采用高温试验和热力学计算相结合的方法,对比分析了先SiMn后Al和先Al后SiMn两种脱氧方式下高铝钢中夹杂物形貌、类型、数量和尺寸特征。结果显示：先加入SiMn后,生成大量液态球形的Mn-Si-Al-O系复合夹杂物,再加入Al后夹杂物演变为Al2O3,且夹杂物数量明显减少;采用先Al后SiMn脱氧方式时,高铝钢中夹杂物始终以Al2O3为主,夹杂物最终数量相对较低。2种脱氧方式钢中夹杂物平均等效圆直径和尺寸分布相差不大。此外,采用先SiMn后Al进行脱氧时,发现尺寸较小的AlN颗粒附着在Al2O3夹杂物表面形成Al2O3-AlN复合夹杂物。而采用先Al后SiMn脱氧方式时,高铝钢中发现单一AlN夹杂物和Al2O3-AlN复合夹杂物,AlN夹杂物的形成与钢水中的氧势和合金原料有关。     

AlSiBa 合 金 脱 氧 实 验

 为了研究AlSiBa合金的脱氧效果,在中频感应炉上应用高Ba和低Ba两种合金进行脱氧实验。实验表明Ba合金复合脱氧剂的效果要好于常用的脱氧剂,脱氧快、夹杂物聚集长大上浮容易。与传统脱氧剂相比,当采用低Ba合金脱氧时,效果不明显,起主导作用的还是铝。用高Ba的AlSiBa合金脱氧,钢中SiO2和Al2O3夹杂显著降低,脱氧产物为复合型夹杂,形状多为球状,表明其脱氧效果好。高Ba合金脱氧,当替代比为40%~60%时效果最好,氧达到最低值。