CaO-SiO2-Na2O-CaF2-Al2O3-MgO渣系的结晶温度

通过差热分析仪测定了CaO-SiO2—Na2O-CaF2—Al2O3—MgO系连铸结晶器保护渣的结晶温度。在本实验渣系条件下，连铸保护渣的结晶温度随着渣中CaO／SiO2值、Na2CO3含量、CaF2含量和MgO含量的增加而升高，随着渣中Al2O3含量的增加而降低。化学成分通过改变粘度，来影响晶核形成速度和晶体成长速度，从而决定了连铸保护渣的结晶性能。结晶温度随着保护渣粘度的降低而升高。     

CaO-SiO2-Al2O3-MgO-FeO渣系FeO活度的计算模型

利用熔渣结构共存理论建立了CaO-SiO2-Al2O3-MgO-FeO渣系FeO活度的计算模型,并分析了1400℃时炉渣碱度、MgO和FeO含量对该渣系FeO活度的影响规律。结果表明：当CaO-SiO2-Al2O3-MgO-FeO渣系三元碱度为1.3,Al2O3含量为12wt%,FeO含量为2wt%条件下,随MgO含量的增加,炉渣FeO活度增大;当二元碱度为1.1,Al2O3含量为12wt%,MgO含量为10wt%时,FeO活度随随渣中FeO含量的增加呈线性增加;当渣中Al2O3、MgO和FeO含量分别为12wt%、10wt%和2wt%固定不变时,随着二元碱度的提高,炉渣FeO活度迅速增加。计算得到的上述规律和实测规律一致,说明了本模型用于分析FeO活度的正确性。     

温度和气氛分压对CaO-SiO2-Al2O3-MgO-FetO渣系硫容量的影响

采用气-渣平衡法,用铂坩埚作反应容器,CO-CO2-SO2-N2混合气体提供体系的氧分压和硫分压,测定了一定炉渣成分,不同温度和气氛条件下CaO-SiO2一A12O3一MgO-FetO五元渣系的硫容量.研究得出,对于一定成分组成的CaO-SiO2-A12O3-MgO-FetO五元渣系,当气体流量不变时,硫容量随炉渣温度的升高而减小;当温度一定时,硫容量随体系氧分压增大而增大.     

组分含量对CaO-MgO-SiO2 -Al2O3四元精炼渣系黏度的影响

采用三元二次正交设计方法,利用熔体物性综合测定仪对碱度(CaO/SiO₂)1.2～6.0,MgO 1.9%～10%,Al₂O₃ 6%～29.1%的CaO-MgO-SiO₂-Al₂O₃四元精炼渣系的黏度进行了测试和研究。实验结果表明.该四元渣1500℃的黏度为0.129～4.612 Pa·s,随碱度增加,该精炼渣系的黏度先略有下降后快速增加;随MgO含量增加,该渣系黏度呈现快速降低后略有上升的趋势;随Al₂O₃含量增加,该渣系黏度快速降低。综合来看,碱度为4～5、MgO 4.5%～5.5%、Al₂O₃ 24%～27%时,该精炼渣系黏度(≤1.0 Pa·s)较为适宜,具有较好的流动性,促进渣-金之间的反应,提高吸附夹杂物的能力,并为脱硫创造有利的动力学条件。     

硫容量模型和在五元渣系CaO SiO2 MgO Al2O3 FetO中的应用

 硫容量和硫平衡分配比是衡量炼钢过程中渣系脱硫能力的重要指标。通过光学碱度模型和KTH模型计算了五元渣系CaO SiO2 MgO Al2O3 FetO的硫容量,并与文献的实验测定值进行了比较。结果表明用KTH模型计算的硫容量比用光学碱度模型计算的硫容量更接近实验值,因此KTH模型可用来预测不同组元渣系的硫容量。还详细研究了硫容量和硫平衡分配比的影响因素,结果表明硫容量随炉渣碱度和温度的增加而增加,硫平衡分配比随着钢液中铝、碳、硅含量的增加而增加。     

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In order to accurately control the rare earth content in liquid steel in electroslag remelting (ESR) process, according to the ion and molecule coexistence theory (IMCT) of slag structure and corresponding phase diagrams, a thermodynamic calculating model for the evaluation of mass action concentrations (designated by Ni for structure unit i) for La2O3-Al2O3-CaF2 slag system was formulated. The results show that the calculated values of NLa2O3 are in good agreement with the reported measured values, indicating that this calculating model can wholly embody the characteristics of the slag system. The activity of La2O3 decreases with the increasing of the Al2O3 and CaF2 content, and Al2O3 is stronger than CaF2 in decreasing the activity of La2O3. But the activity of La2O3 increase with the increasing in temperature at the composition range of 30% La2O3, 20% Al2O3, 50% CaF2. Above all, the activity of La2O3 in La2O3-Al2O3-CaF2 slag system can be quantitatively analyzed by this thermodynamic model, and this model can provide a theoretical basis for precisely controlling the lanthanum content in molten steel in ESR process.     

B2O3对CaO-Al2O3-SiO2-MgO-CaF2五元精炼渣系熔化特性的影响

通过半球点法研究了B2O3对40．5％-70．0％CaO-19％～45％Al2O3-SiO2-MgO-CaF2五元渣系熔化温度和完全熔化时间的影响。实验结果表明，当渣中CaO含量为40．5％～60％，CaF2 2％-10％，（B2O3％）／（CaF2％）为0．17—0．33时，渣系的熔化温度较不加B2O3的五元渣平均降低30℃，完全熔化时间平均降低49s。合适的多元脱硫精炼渣系的成分为60％CaO，19％-30％Al2O3，≤10％（MgO＋SiO2），2％～6％CaF2，（B2O3）／（CaF2）=0．17。     

Phosphorus Capacity of CaO-SiO2-Al2O3-MgO-FexO Slag

The CaO-SiO2-Al2O3-MgO-FexO slag occurs in the production process of Corex ironmaking technology.Most of its metallurgical properties,especially the phosphorus property,are different from the slag produced from blast furnace or converter.In order to explore the dephosphorization ability of CaO-SiO2-Al2O3-MgO-FexO slag,its phosphorus capacity was measured at 1 673 Kby gas-slag-metal equilibrium technique.An iron crucible was used as the reaction vessel,Ag alloy with 0.2% P was used as the metal phase which equilibrated with CaO-SiO2-Al2O3-MgO-FexO slag,and a constant flow of CO-CO2-N2 gas was used to provide oxygen partial pressure in the experiment.The effects of MgO,FexO and basicity on slag phosphorus capacity were investigated by single factor test.The results show that the phosphorus capacity rises firstly and then decreases with increasing MgO content under the condition of basicity 1.3,FexO content of 2% and Al2O3 content of 12%.The phosphorus value reaches maximum as the MgO content is 8%.When the basicity of slag is 1.1,MgO content is 10%,and Al2O3 is 12%,the phosphorus capacity increases with the increase of FexO content.The phosphorus capacity rises linearly when the basicity is increased from 1.1to 1.5.     

Effects of B2O3 and CaF2 on Melting Temperatures of CaO-SiO2-Fe2O3 System Fluxes

 Fluorite is widely employed as fluxing agent in metallurgy flux, which inevitably leads to serious fluorine pollution. B2O3 is employed as fluxing agent of CaO-SiO2-Fe2O3 steelmaking fluxes to substitute for CaF2. The effects of B2O3 and CaF2 on the melting properties of this system were investigated. The melting temperatures of fluxes including softening temperature (Ts), hemispherical temperature (Th), and flow temperature (Tf) were measured using the hemisphere method. The results indicate that the fluxing effect of B2O3 is more significant than that of CaF2. When the addition amount of B2O3 (mass percent) exceeds 6%, the melting temperatures of fluxes including Ts, Th and Tf are decreased lower than 1300 ℃. The basicity of fluxes has a significant effect on the melting temperature, and the melting temperatures of the fluxes increase with the increase of fluxes basicity. However, when B2O3 is used as fluxing agent, the melting temperature changes little with the basicity increasing from 2. 5 to 5. 0. These characteristics are suitable for steelmaking process. Moreover, Fe2O3 has an important fluxing effect on this CaO-based steelmaking fluxes. This indicates that the fluxes system is suitable for steelmaking process.     

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.     

MgO含量对CaO-SiO2-Al2O3-MgO熔渣中液态相影响的模拟

运用Factsage软件模拟了MgO含量对CaO-SiO₂-Al₂O₃-MgO熔渣中液相区的影响.结果表明,随着CaO-SiO₂-Al₂O₃-MgO渣中MgO含量增加,渣中低熔点液相区整体向低CaO高SiO₂区移动.相图中1500℃液相区比例由0%MgO（质量分数）时的25.05%上升至9%MgO（质量分数）时的52.69%,而后降至15%MgO时的46.70%.相图中1400℃液相区比例由3%MgO时的14.41%上升至11%MgO时的34.39%,而后降至15%MgO时的31.04%.相图中1300℃液相区比例由5%MgO时的5.57%上升至14%MgO时的11.02%,而后降至15%MgO时的10.50%.相图中1200℃液相区域比例在MgO为0~6%时为零,由7%MgO时的0.88%上升至11%MgO时的1.22%,在MgO为13%~15%时降为零.模拟结果可对以CaO-SiO₂-Al₂O₃-MgO为基本组元配置炼钢渣系的成分选择提供有效指导.     

Viscosity and Structure Changes of CaO-SiO2-Al2 O3-CaF2 Melts with Substituting Al2 O3 for SiO2

During the smelting process of the high Al steels,the reaction between SiO_2 in molten slag and dissolved aluminum in liquid steel always takes place.This aluminathermic reduction reaction will lead to the substitution of 1mol SiO_2 for 2/3mol Al_2O_3.Therefore,the investigations about the influence of the ratio of Al_2O_3 to SiO_2on viscosity and structure changes of mould flux during this process are very necessary.The viscosity variation of CaO-SiO_2-Al_2O_3-CaFv2 melts was studied by changing compositions considering the aluminathermic reduction reaction.It was found that viscosity increased monotonously with gradually increasing the substitution extent.According to the Raman analysis,the substitution of Al_2O_3 for SiO_2 leads to the decrease of non-bridging oxygen but the increase of bridging oxygen.Therefore,degree of polymerization and viscosity increase as the substitution extent increases.By comparing the measured viscosities with the model calculated values,it was found that both the recently developed Zhang′s model and Roboud model could describe the viscosity variation behavior of CaO-SiO_2-Al_2O_3-CaF_2 melts very well.     

CaO-SiO_2-FeO-P_2O_5渣系脱磷影响因素的研究

为了提高转炉渣中CaO的利用率,降低转炉渣的碱度,通过试验研究了CaO粒度、粒状CaO的加入比例、温度和保温时间对含磷富集相的影响。结果表明,适当增大CaO的粒度有利于2CaO·SiO2-3CaO·P2O5固溶体的形成;当渣中粒状CaO的含量较低时,增加粒状CaO的加入比例,可促进渣中大颗粒固溶体的形成并减少渣中磷的含量,但当粒状CaO的含量较高时,2CaO·SiO2-3CaO·P2O5固溶体生成量减少;适当提高温度有利于脱磷反应的进行;随反应时间的延长,2CaO·SiO2-3CaO·P2O5固溶体的粒径增大,而且固溶体中磷的含量也不断增加。     

温度对CaO-SiO2-Al2O3-MgO高炉渣系Al2O3活度的影响

 Al₂O₃作为熔渣中的主要组元之一,其对熔渣的冶金性能的影响尤为突出。对于高炉炼铁而言,高炉渣中Al₂O₃增加会对炼铁及脱硫造成不利影响。然而,随着中国钢铁工业的不断发展,相对低廉的高Al₂O₃进口铁矿石使用量不断攀升,使得高炉渣中Al₂O₃含量明显增加,高炉渣中Al₂O₃质量分数往往大于15%,更高的甚至大于20%。目前关于高Al₂O₃高炉渣系中Al₂O₃组元的热力学性质(例如采用参考渣法测定Al₂O₃的活度)及其对炉渣冶金性能的影响等研究鲜有报道,而温度是影响冶金熔渣冶金性能的重要热力学因素之一,因此探讨温度对冶金熔渣中Al₂O₃组元活度影响的规律不仅具有重要的研究意义,同时也为现场实践提供坚实的理论依据。采用参考渣法对1 773～1 873 K温度条件下CaO-SiO₂-Al₂O₃-MgO高炉渣系Al₂O₃活度进行测定,并采用Raman光谱对熔渣的结构进行检测。考察了温度对CaO-SiO₂-Al₂O₃-MgO高炉渣系Al₂O₃活度的影响。结果表明,随着温度的增加,熔渣中Al₂O₃的化学势降低,熔渣与铜金属熔液之间的反应向右移动来达到新的平衡,因而Al₂O₃的活度随着温度的增加逐渐降低。温度的增加使熔渣中Al₂O₃与碱性金属氧化物发生反应,使钙铝酸盐(CaO·Al₂O₃和CaO·2Al₂O₃)和镁铝酸盐(MgO·Al₂O₃)等复合物生成量增加,此时熔渣的结构由于O2-的增加而逐渐发生解聚,熔渣中的自由Al₂O₃减少,从而导致Al₂O₃活度逐渐降低。     

含Ce2O3锰铁脱磷渣系熔化性质及黏度

 采用立式管式炉制备得到含Ce2O3锰铁脱磷渣系,分别利用HCT-2综合热分析仪和RTW-10型熔体物性仪对渣系的熔化性质和黏度进行测试分析。研究表明,碱度为1.05时,渣系的开始熔化温度和完全熔化温度随[w(Ce2O3)]的增加而升高,其最大值分别为1 121.6和1 282.1 ℃;碱度为0.97时,渣系的开始熔化温度和完全熔化温度随[w(Ce2O3)]的增加出现先降低后升高的趋势,当[w(Ce2O3)]为3时出现最小值,分别为1 008.8和1 148.5 ℃。渣系的黏度值随[w(Ce2O3)]的增加先降低后升高,当[w(Ce2O3)]为3%时,黏度值最小。在碱度为1.05和0.97的脱磷渣系中,黏度最小值分别为0.378和0.308 Pa·s。因此,[w(Ce2O3)]为3%时的锰铁脱磷渣系具有良好的熔化及流动特性。     

二元碱度和Al_2O_3对CaO-SiO_2-FeO-Fe_2O_3-P_2O_5-Al_2O_3-MgO-MnO钢渣中磷酸盐富集的影响

以八元CaO-SiO_2-FeO-Fe_2O_3-P_2O_5-Al_2O_3-MgO-MnO钢渣体系为研究对象,结合热力学计算和实验检测,分析了二元碱度B和Al_2O_3含量对八元钢渣系中磷酸盐富集行为的影响。结果表明:钢渣二元碱度和Al_2O_3含量直接影响钢渣中f-C2S的生成量,进而影响磷酸盐富集相nC_2S-C_3P内P_2O_5的含量。随着二元碱度从1.3提高至2.5,磷酸盐富集率增大,磷酸盐富集相nC2S-C3P中的P_2O_5含量呈现先迅速增大(B从1.3至1.7),然后逐渐减小(B从1.8至2.5)的趋势。当二元碱度和Al_2O_3质量分数分别控制在1.7和12%时,即当满足四元碱度R为1.23时,此八元钢渣体系有较好的磷酸盐富集效果,磷酸盐富集相nC_2S-C_3P内的P_2O_5的质量分数可以达到24.23%。     

MgO和MnO对CaO-SiO2-Fe2O3-P2O5渣的物相影响

转炉渣中的磷主要存在于n2CaO·SiO2-3CaO·P2O5（以下简记为nC2S-C3P）固溶体的富磷相中。为了深入理解转炉渣的物相,便于有效富集钢渣中的磷,研究MgO和MnO含量的变化对CaO-SiO2-Fe2O3-P2O5渣中nC2S-C3P固溶体的磷含量及渣结晶物相的影响,并对其进行热力学分析。结果表明：在CaO-SiO2-Fe2O3-P2O5四元渣系中加入少量MgO或MnO,可以在一定程度上提高nC2S-C3P固溶体中的磷含量;继续提高MgO或MnO含量,固溶体中的磷含量不再发生变化。随着MgO或MnO的加入,富铁相增多,有利于钢渣的磁选分离。