CaO-SiO2-MgO-Al2O3炼铁渣系硫化物容量的热力学模型

基于炉渣离子-分子共存理论(IMCT)建立了CaO-SiO₂-MgO-Al₂O₃炼铁渣系的硫化物容量预报模型,即IMCT-CS₂-模型,比较了该渣系1773 K时实测的硫化物容量、IMCT-CS₂-模型预报的硫化物容量及其他五种硫化物容量模型的计算结果.结果表明,由IMCT-CS₂-模型预报的1773K时CaO-SiO₂-MgO-Al₂O₃炼铁渣系的硫化物容量更精确.本文建立的IMCT-CS₂-模型不仅可计算该渣系的总硫化物容量,而且可计算该渣系中自由CaO和MgO各自的硫化物容量.1 773 K时CaO-SiO₂-MgO-Al₂O₃炼铁渣系中Al₂O₃质量分数由10%增加到17%,CaO质量分数由38%增加到44%,MgO质量分数由12%降低到4%可使自由CaO对该渣系的总硫化物容量贡献率由97%提高到99%,同时使自由MgO的贡献率由3%降低到1%.     

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。     

CaO-Al2O3-Ce2O3渣系的相平衡关系研究

CaO-Al₂O₃-Ce₂O₃渣系是稀土钢新型冶金渣系的基础渣系,其相平衡关系等热力学信息的缺失限制了相关渣系的研究和开发。本文通过高温相平衡实验,结合X射线衍射分析、扫描电镜及能谱分析,研究了CaO-Al₂O₃-Ce₂O₃渣系的相平衡关系。根据1100℃的实验结果,明确了该渣系中十种物相间的共存关系,以Alkemade连线的形式展示,包括：2CaO·Al₂O₃·Ce₂O₃-CaO、2CaO·Al₂O₃·Ce₂O₃-Ce₂O₃、2CaO·Al₂O₃·Ce₂O₃-3CaO·Al₂O_...     

空气气氛条件下CaO-Al2O3-CeO2渣系在1500℃的相平衡关系

采用热力学平衡实验,结合SEM-EDS等检测方法,确定了空气气氛条件下CaO-Al₂O₃-CeO₂渣系在1 500℃的相平衡关系,并绘制出该渣系的等温相图.在空气气氛条件下,CaO-Al₂O₃-CeO₂渣系在1 500℃时存在着三种三相平衡(CA+CA₂+CeO₂,L+CaO+CeO₂,L+CA+CeO₂)和两种两相平衡(L+CeO₂,L+CaO),根据各平衡相关系划分了相应相区,且CeO₂在该渣系中的最大溶解度为28%(质量分数).     

P2O5对CaO-SiO2-FetO-P2O5渣中富磷相的影响

以CaO-SiO₂-Fe_tO-P₂O₅四元渣系为研究对象,结合理论计算和热态实验综合分析 P₂O₅含量变化对该四元渣系物相组成以及富磷相的影响。应用Factsage软件equilib模块计算CaO-SiO₂-Fe_tO-P₂O₅四元渣系在400~1800℃温度区间的多相平衡,再结合SEM+EDS与XRD对热态实验结果进行分析知,随着渣中P₂O₅含量的增加,富磷相中Ca₃(PO₄)₂的含量随之增加。此外,P是以nC₂S-C₃P固溶体的形式存在于富磷相中,但当渣中P₂O₅含量达到18%时,富磷相中的P将以Ca₃(PO₄)₂的形式独立存在。热态实验的分析结果进一步验证了Factsage的理论计算结果。     

Ta2O5及Nb2O5氟含量的控制研究

以钽液和铌液为原料,经过氨气中和沉淀-洗涤-烘干-煅烧等工序制得Ta2O5、Nb2O5粉末,研究了洗水量、煅烧时间对产品氟含量的影响规律。结果表明,钽、铌氧化物与氢氟酸气氛接触一段时间后氟含量增加,由此可将Ta2O5、Nb2O5中的氟含量控制在0.07%～0.12%,满足国外光纤领域对钽铌氧化物的应用要求。     

Ce2O3对CaF2-CaO-Al2O3-MgO电渣重熔渣系熔化行为的影响

目前,采用电渣重熔(ESR,electroslag remelting)还原稀土渣是一种有效的稀土添加工艺,而稀土氧化物的加入势必会改变渣系熔化性质,进而影响ESR工艺顺行及稀土钢质量。基于分子离子共存理论(IMCT)建立了CaF₂-CaO-Al₂O₃-MgO-Ce₂O₃五元渣热力学模型,从热力学角度分析了渣中各组元对Ce₂O₃活度的影响规律。采用半球法测定了不同Ce₂O₃含量和w((CaO))/w((Al₂O₃))(C/A)条件下渣系熔点,结合SEM-EDS和XRD对渣系物相和微观形貌进行测试与分析。研究结果表明,当温度为1 873 K时,C/A、MgO、Ce₂O₃含量增加均增加渣系中Ce₂O₃的活度,且影响顺序为Ce₂O₃     

CaF2-Al2O3-MgO-CaO电渣重熔渣系成分与性质演变行为

电渣重熔过程熔渣成分变化使其性质发生改变,将影响重熔工艺顺行和铸锭质量。针对CaF₂-Al₂O₃-MgO-CaO电渣重熔渣系,研究氟化物挥发导致的熔渣成分变化规律,分析随成分变化熔渣结晶行为及流动性质的演变规律。研究结果表明,在电渣重熔过程因氟化物挥发造成熔渣中CaF₂和Al₂O₃含量下降,CaO含量上升,而MgO含量基本保持不变。随熔渣成分变化,渣层中析出的CaF₂晶体由点状或球状变为块状或条状,MgO·Al₂O₃晶体由球状变为树枝状,作为主要析出相的铝酸钙晶体由CaO·6Al₂O₃变为CaO·2Al₂O₃并最终变为12CaO·7Al₂O₃。生产中结晶器上部的渣皮更易发生分层结晶现象,析出相中靠近熔池侧主要为CaF₂晶体,靠近结晶器侧主要...     

CaO-SiO2-Al2O3-Fe2O3渣系脱磷行为

利用Factsage软件计算了Al2O3含量对CaO-SiO2-Al2O3-Fe2O3四元渣系熔点和黏度的影响,并通过实验研究了在1 400℃时,CaO-SiO2-Al2O3-Fe2O3四元渣系对高磷铁水脱磷行为的影响.结果表明:渣中Al2O3的质量分数在3％～6％之间时,随着A12O3含量的增加,渣系的熔化温度迅速降低,进一步增加渣中的A12O3含量,渣系的熔化温度逐渐增加;Al2O3对CaO-SiO2-Al2O3-Fe2O3渣系的黏度影响不大;渣中Al2O3的质量分数在3％～6％之间变化时,渣系脱磷能力变化不是很大,脱磷率维持在91％左右,进一步增加渣系中A12O3的量,脱磷率逐渐下降;Al2O3对脱磷率产生影响可能是其改变了炉渣中液相所占比例,进而影响磷从铁水中向液相渣的传质过程.     

CaO-SiO2-MgO-Al2O3-FeO-Cr2O3渣系中铬尖晶石析出行为的热力学计算

不锈钢渣中铬赋存在尖晶石相中,可防止Cr⁶⁺浸出。将不锈钢中重金属Cr选择性富集、稳定化,有利于提高不锈钢渣综合利用率。本文基于熔渣非平衡凝固理论,研究了碱度、MgO及FeO含量对CaO-SiO₂-MgO-Al₂O₃-FeO-Cr₂O₃不锈钢渣体系凝固过程中尖晶石相析出温度、析出量及化学组成的影响。计算结果表明：CaO-SiO₂-MgO-Al₂O₃-FeO-Cr₂O₃渣析出相主要有Ca₂SiO₄、Ca₂MgSi₂O₇、Ca₂Al₂SiO₇、尖晶石相等。MgCr₂O₄尖晶石析出量随碱度增加而逐渐增大,提高碱度可抑制FeCr_2...     

低氧分压条件下CaO-SiO_2-P_2O_5(10%)-FeO体系热力学性质的研究

以促进2CaO·SiO_2-3CaO·P_2O_5固溶体生成的非均相脱磷工艺被视为未来实现转炉少渣冶炼的重要手段,但目前相关渣系热力学性质的研究较少,不能为合理解释非均相渣脱磷的机理提供理论依据.为此,本文利用FactSage热力学软件绘制了低氧分压(1mPa)条件下CaO-SiO_2-P_2O_5(10%)-FeO体系及其子体系的热力学相图,分析了不同温度下相平衡关系及液相线的变化规律.研究结果表明:升高温度可使体系中液相区及Ca_3(PO_4)_2初晶区的范围扩大,但会导致α'-Ca_2SiO_4的初晶区缩小以及Ca_2Fe_2O_5等物相的消失;降低氧分压可使体系的液相区缩小,并向高FeO的方向收缩;CaO-SiO_2-P_2O_5(10%)-FeO体系中存在较大的α'-Ca_2SiO_4与Ca_3(PO_4)_2共存区,尤其是α'-Ca_2SiO_4,Ca_3(PO_4)_2与Ca_2Fe_2O_5的三相共存区可极大地促进2CaO·SiO_2-3CaO·P_2O_5固溶体的生成.     

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.     

Study on Electronic Conductivity of CaO-SiO2-Al2O3-FeOx Slag System

Inthepast,becauseoflittleknowledgeoftheinfluenceofelectronictransportintheslag,researchworksaboutconductivityoftheslagweremainlyconcentratedonionicconductivity[1—15],so,thedataofelectronicconductivityarefew.Buttheworks[16—19]completedinrecentyearsshowedthatreactionofmetalmeltwithslagiscontrolledbytheconductionofelectronsintheslagundersomeconditions.Theprocessesthatarebeneficialtoelectronimmigratingthroughtheslagbulkandtheslag/metalfilminterfacewilldrasticallyincreasethereactionrateandtheexte…     

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.     

CaO-SiO_2-B_2O_3熔渣的热力学计算模型

根据CaO-SiO2、CaO-B2O3和SiO2-B2O3二元相图确定了熔渣的结构单元,利用熔渣的分子离子共存理论建立了CaO-SiO2-B2O3三元熔渣活度模型。通过对模型求解,可以计算出熔渣中CaO、SiO2、B2O3、CS、C2S、C3B、C2B、CB和CB2的组分活度。分析了熔渣碱度、B2O3含量及温度对熔渣组分活度的影响,其中熔渣碱度的影响最大,B2O3含量的影响次之,温度的影响最小。     

济钢高炉高Al2O3炉渣渣系优化试验研究

以济钢现场高炉渣样为基准,采用正交设计方法,设计了25组试验方案,研究了w（Al2O3）为15%～23%的高炉炉渣性能,结果表明,济钢高炉炉渣中Al2O3不宜超过20%,MgO不宜超过12.5%。     

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。     

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.