电热法生产铝硅合金的理论研究

本文从理论上系统研究了Al2O3-C系、SiO2-C系、Al2O3-SiO2-C系热力学。结果表明,在Al2O3-SiO2-C系中,硅在很大程度上改善了铝还原的热力学条件,中间产物Al4C3、SiC等碳化物分别与SiO2、Al2O3反应进而生成铝硅合金,使电热法铝硅合金对生产成为现实。动力学研究结果表明,在电热法铝硅合金生产中,Fe的存在使得铝硅合金生成反应的起始温度大大降低,Fe还有助于破坏碳热还原过程中容易生成的碳化物。     

高铝铁矿石球团在预还原过程中的热力学行为

应用物质吉布斯自由能函数法计算高铝铁矿石球团在预还原过程中所发生反应的ΔG,明确球团中物相在该过程中的热力学行为.热力学计算、分析结果表明:还原阶段产生的FeO最易与Al2O3反应生成FeO·Al2O3,其次与SiO2反应生成2FeO·SiO2,最后与SiO2反应生成FeO·SiO2·Al2O3置换2FeO·SiO2和FeO·SiO2中SiO2生成FeO·Al2O3的反应较之SiO2置换FeO·Al2O3中Al2O3的反应要容易得多.FeO.SiO2的还原反应趋势要强于FeO·Al2O3及2FeO.SiO2.     

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...     

CaO-Al2O3基钢液净化剂组成的优化

运用CaO-Al2O3-SiO2三元系的熔点和等αAl2O3相图,分析了CaO-Al2O3渣系净化剂降低钢液中氧化物夹杂的能力与其组成的关系。从热力学角度看,CaO/Al2O3比值高（1.6～2.0）,则αAl2O3低（≤0.02）,有利于钢液中氧化物夹杂的降低;从动力学角度看,CaO/Al2O3低（1.1～1.26）,则熔点低（〈1400℃）,有利于钢液中氧化夹杂的排出。净化剂组成的优化结果表明,适宜的CaO/Al2O3比值为1.41～1.74,净化剂αAl2O3较低（0.02～0.04）,熔点较低（〈1450℃）。工业性试验表明,优化后的净化剂净化钢液效果显著。     

基于20CrMnTi精炼成分的渣钢间氧平衡热力学模拟

基于冶金Si-O平衡反应和冶金熔盐体系存在最小吉布斯自由能原理,运用Factsage热力学软件对20CrMnTi齿轮钢精炼钢液与CaO-Al2O3-SiO2渣系间的氧平衡进行了模拟计算.相图计算结果表明,渣/夹杂物存在2个熔点低于1400℃的区域,其中低SiO2高Al2O3区域的平衡氧含量远远低于高SiO2低Al2O3区域的平衡氧含量.控制炉渣/夹杂物中wCaO/wAl2O3≤2.0且wCaO/wSO=2≥4.7可以实现钢中平衡[O]的质量分数低于5×10-6.     

齿轮钢（8620H）精炼渣优化及工业试验

利用FactSage热力学软件计算了CaO-Al2O3-SiO2-5%MgO四元系的CaO、Al2O3等活度线,通过等活度线图着重探讨精炼渣碱度、w(CaO)/w（Al2O3）、MI指数（曼内斯曼指数）与Al2O3夹杂吸附能力的影响关系,最终得到适用于杭钢生产齿轮钢（8620H）的LF精炼渣系范围为：CaO质量分数为50%~55%,Al2O3质量分数为25%~30%,SiO2质量分数为10%~12%,MgO质量分数为5%~8%。并使用该渣系进行齿轮钢（8620H）工业试验,铸坯中全氧质量分数由0.001 5%降至0.001 0%,且铸坯中显微夹杂物尺寸也明显降低,由2.1降至1.5μm,每10kg铸坯中大型夹杂物质量分数由31.9下降到26.4mg,试验效果良好。     

钙处理对成品无取向硅钢夹杂物特性的影响

通过取样检测结合热力学计算,分析了钙处理对成品无取向硅钢中夹杂物特征及硫化物夹杂的析出机制的影响。结果表明,钢中尺寸大于3μm的有害夹杂物主要是AlN、MgO-SiO2、CaO-Al2O3-SiO2类复合夹杂物及其与MgS、MnS、CaS的复合析出物。钙处理钢中没有检测到单独的Al2O3、SiO2及铝酸钙类夹杂物。钙处理钢中形成的液态3CaO·Al2O3、MgO·SiO2和Al2O3夹杂物被精炼渣吸收,改性去除了钢中大尺寸Al2O3夹杂物。钙处理钢中尺寸大于3μm的氧化物夹杂主要是含CaO和(或)CaS的Al2O3-SiO2类夹杂。硫化物在MgO-SiO2类氧化物表面的析出有利于其形貌趋于规则。钢中不同形貌的AlN夹杂物呈多尺度分布,钙处理对大尺寸AlN的析出特性影响不大。氧硫化物及其与AlN复合析出并定向长大的过程,与其晶体结构有关。氧化物夹杂的硫容量决定了其与硫复合的难易程度。钙处理钢中CaS在氧化物表面呈局部包裹析出和局部吸附析出。     

CaO-Al2O3-SiO2基精炼渣LF脱硫的试验研究

在实验室小型试验炉内,用CaO-Al2O3-SiO2基精炼渣进行了钢水脱硫的试验,主要研究了精炼渣碱度、渣中Al2O3和CaF2对钢水脱硫的影响.结果表明:精炼渣碱度在2.85～3.45时,脱硫率在80％以上;精炼渣中w(Al2O3)=24％时,脱硫率为83.7％;随精炼渣中CaF2含量的增加,脱硫率先增大后降低.最佳精炼渣组成为:w(CaO)/w(SiO2)=3.0、w(CaF2) =7％、w(MgO)=6％、w(Al2O3)=24％.     

铁酸盐粘结相熔化速率及对烧结强度的影响

 考察了添加SiO2和Al2O3对铁酸钙（铁酸一钙CaO·Fe2O3和二铁酸钙CaO·2Fe2O3）熔化速率的影响。同时考察了铁酸盐添加SiO2和Al2O3对以其为粘结相的烧结试样强度的影响。试验结果表明：铁酸一钙中添加SiO2和Al2O3促进了熔体的形成;而二铁酸钙添加SiO2和Al2O3则抑制了其熔体的形成。在CF中添加SiO2和Al2O3对烧结试样强度的影响中,当添加w(SiO2)=2%和w(Al2O3)=4%时获得相对较大的烧结强度;而在CF2中添加SiO2和Al2O3则对烧结试样强度有不利影响。     

坩埚实验中渣组成对合金钢液洁净度的影响

通过Si-Mo高温炉MgO坩埚实验,研究了在1 873 K时,CaO-Al2O3-SiO2渣成分对0.42C-1.15Cr-0.2Mo钢液T[O]以及硫分配比Ls-(S)/[S]的影响.发现渣碱度-(CaO MgO)/SiO2由1增加到3时,T[O]由0.001 4%迅速减少至0.001 0%,此后碱度升高,T[O]变化不明显.(FeO MnO)≤0.50%时,T[O]≤0.001 0%;(FeO MnO)超过0.50%时,T[O]明显升高至0.001 4%.渣碱度、渣中Al2O3活度和[Al]对Ls影响明显:渣中Al2O3,活度升高,Ls减小;渣碱度、[Al]升高,Ls增大.     

CaO-SiO_2-FeO-P_2O_5-Al_2O_3脱磷渣系中组元活度的计算

2CaO·SiO_2-3CaO·P_2O_5含磷固溶体的生成可提高转炉液相渣的脱磷能力,减少渣量.但目前CaO-SiO_2-FeO-P_2O_5-Al_2O_3渣系中各组元活度的变化规律尚不明确,无法为分析含磷固溶体的形成机理提供理论依据.为此,本文依据分子离子共存理论建立了熔渣组元的活度模型,分析了不同条件下组元活度的变化规律.结果表明:随渣中Al_2O_3含量的增加,2CaO·SiO_2、3CaO·P_2O_5、3FeO·P_2O_5的活度逐渐降低;随着碱度的增大,3CaO·P_2O_5的活度升高,2CaO·SiO_2、3FeO·P_2O_5的活度则呈先升高后降低的趋势;随着渣中FeO含量的增加,2CaO·SiO_2、3FeO·P_2O_5及CaO·Al_2O_3的活度逐渐增大,并在w(FeO)为15%时达到最大值,之后逐渐降低;升高温度会导致CaO、3CaO·SiO_2的活度增大,2CaO·SiO_2的活度降低.     

Effect of Oxygen Partial Pressure on Phase Equilibria and Liquidus in CaO-Al2O3-FeOx System

 A high temperature equilibration experiment was carried out to investigate the effect of oxygen partial pressure on the phase equilibria and liquidus in CaO-Al2O3-FeOx system with the intermediate oxygen partial pressures of 10.13 Pa and 1.01×10-3 Pa. The equilibrated phases and their compositions of the quenched samples were analyzed by using SEM/EPMA (Scanning Electron Microscope/Electron Probe Micro-Analysis) and XRD (X-Ray Diffraction). The phase equilibrium results include two cases, the two-phase coexistence and the three-phase coexistence in the high Al2O3 region with oxygen partial pressure of either 10.13 Pa or 1.01×10-3 Pa. Effects of oxygen partial pressure and temperature on the liquidus along the primary phase fields of CaO·Al2O3 and CaO·2Al2O3 were notable. With the decrease of oxygen partial pressure, the liquid area expands and the liquidus of CaO·Al2O3 and CaO·2Al2O3 primary fields moves to the Al2O3-FeOx region. On the other hand, the liquid area of CaO-Al2O3-FeOx system extends extremely to the high Al2O3 region with the temperature increasing from 1400 to 1500 ℃, especially at lower oxygen partial pressure. The present experiment results are in good agreement with the calculated ones by FactSage.     

Phosphorous Enrichment in Molten Adjusted Converter Slag：Part II Enrichment Behavior of Phosphorus in CaO-SiO_2-FeO_x-P_2O_5 Molten Slag

 The enrichment behavior of phosphorus in CaO-SiO2-FeOx-P2O5 slag was studied by making an investigation on the distribution of phosphorous content in the CaO-SiO2-FeOx-P2O5 molten slag. The research results showed that the 2CaO·SiO2 solid particles existing in molten slag were the condensation sites for the phosphorus enrichment. The enrichment process of phosphorus in the molten slag can be recognized as three substeps: mass transfer of phosphorus from bulk slag to the surface of 2CaO·SiO2 particle, superficial solid solution reaction of phosphorus around the 2CaO·SiO2 particle, and diffusion of phosphorus through the product layer of 2CaO·SiO2-3CaO·P2O5 solid solution to the inner of 2CaO·SiO2 particle. Moreover, higher temperature is favorable to the phosphorous enrichment from molten bulk slag to the 2CaO·SiO2 particles.     

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。     

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。     

低碱度低氧化铝精炼渣对帘线钢夹杂物控制

 研究了低碱度、低氧化铝精炼渣对帘线钢夹杂物控制情况。试验采用LD→LF精炼→软吹Ar→连铸工艺生产帘线钢,在碱度1.0、Al2O3质量分数为5%左右的精炼渣成分控制条件下,钢中酸溶铝AlS的质量分数控制在0.000 5%左右,进而控制夹杂物中Al2O3质量分数在22%以内,使得帘线钢中氧化物夹杂MnO-Al2O3-SiO2类、CaO-Al2O3-SiO2类复合夹杂物实现了良好的塑性化控制。根据分析,在帘线钢夹杂物去除方面,软吹氩处理对钢中CaO-Al2O3-SiO2系复合夹杂物去除效果比对MnO-Al2O3-SiO2类夹杂物更加明显;在成分控制方面,钢液中AlS含量随着炉渣碱度、炉渣Al2O3质量分数的升高而升高,而夹杂物中Al2O3质量分数会随着钢液中AlS含量升高而升高。     

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.     

BOF-LF-CSP工艺生产SPHC钢的夹杂物演变

 通过热力学计算及转炉、LF炉、中间包、铸坯的系统取样与SEM、EDS等检测,对BOF-LF-CSP工艺生产的SPHC钢夹杂物在各工序的种类、数量、变性及组成进行了研究。结果表明,在BOF-LF-CSP过程中, 转炉终点夹杂物以Al2O3为主,在LF炉钙处理后钢水Al2O3夹杂的质量分数降低到铝处理后时的50%,出LF炉时钢中剩余的Al2O3夹杂基本完成了球化变性,并以铝酸钙复合物或硅酸盐结合的镁铝钙复合物为主,球化率约为72%;铸坯内夹杂物的平均粒径为5. 4μm、球化率为75. 8%。Al2O3经历了①Al2O3→CaO·6Al2O3→CaO·2Al2O3或CaO·Al2O3→12CaO·7Al2O3或CaO·3Al2O3;②Al2O3→MgO-Al2O3→MgO-Al2O3-CaO→MgO-Al2O3-CaO-SiO2的演变,正确合理的精炼工艺会使夹杂物充分上浮、球化及变形,提高钢水可浇性及钢材性能。     

Inclusion Variations of Hot Working Die Steel H13 in Refining Process

 Inclusion variations of die steel H13, including changes of species, morphologies, compositions, amounts and sizes, in the production of EAF→LF→VD→ingot casting→electro-slag refining (ESR) procedure, were investigated by systematic sampling, and analyzed with scanning electron microscope (SEM), energy dispersive spectrum (EDS), and metallographic microscope. The variation mechanism was studied by comprehensive analysis of total oxygen, nitrogen, and acid soluble aluminum as well as chemical test of refining slag. Based on the investigations, technical measures for cleanness improvement were discussed. The results show that oxide inclusions in H13 steel change from irregular Al2O3→near globular CaO-MgO-Al2O3 and CaO-Al2O3-SiO2 complex inclusions→finer CaO-Al2O3-SiO2 inclusions with higher CaO content→CaO-Al2O3-SiO2 inclusions with higher Al2O3 content and irregular MgO-Al2O3 inclusions→fine irregular MgO-Al2O3-CaS inclusions in various steps of the production; the variations are related with changes of acid soluble aluminum content, reactions between slag and steel, re-oxidation of liquid steel during casting, and refining of ESR. It is also found that Al2O3 inclusions are modified by refining slag in LF and VD refining; and ESR plays a good role in inclusion removal, especially in controlling the large linear VC-CrC-MoC inclusions distributed in grain boundaries. It is suggested that casting protection should be improved, and the basicity of refining slag and acid soluble aluminum content in steel should be raised.