A thermodynamic study of SrO + FexO and BaO + FexO liquid slags by disposable electrochemical oxygen probes

An electrochemical technique involving magnesia-stabilized zirconia as the solid electrolyte and a mixture of Mo + MoO₂ as the reference electrode for the measurements of the activities of Fe_xO in the SrO + Fe_xO and BaO + Fe_xO systems at 1673 K. Measurement of oxygen potentials established at the slag electrode by disposable solid state cells. Expression of the thermodynamic properties of SrO + Fe_xO and BaO + Fe_xO by the binary subregular model.     

Thermodynamics of iron oxide in FexO‐dilute CaO + Al2O3 + SiO2 + FexO slags at 1873 K

The ferrous and ferric ion capacities, and , for the slag of CaO + Al₂O₃ + SiO₂ are determined at 1873 K by means of the distribution equilibrium of iron between Fe_xO dilute slags of the system and Pt + Fe alloys under a controlled atmosphere. Compared with the values of for CaO + Al₂O₃ binary slag at a constant ratio of Al₂O₃ to decreases with an increase in SiO₂ content. Nearly linear relationships are observed between the logarithm of the ferrous and ferric ion capacities and the optical basicity. Applying these capacities, the relationship between (%Fe^T) and PO₂ under iron saturation, as well as the iron redox equilibrium in slag in relation to the optical basicity were discussed.     

Cao—SiO2—CaF2三元渣系的挥发率

通过质量损失法对ＣａＯ－ＳｉＯ２－ＣａＦ２三元渣系挥发率与温度、渣组成的关系进行了研究。结果表明：在渣完全熔化之前有一临界温度，其值大小因渣而异，即酸性渣具有低温临界点；碱性渣具有高温临界点；中性渣则两个临界点均存在；当渣的碱度过高（Ｒ≥１．４）或ＣａＦ２含量减少（≤１０％）时，这两个临界点均不存在。临界温度对渣的挥发率有明显影响；在渣完全熔化之后，挥发率将随碱度的降低及ＣａＦ２含量的增加而提高。     

Chemical potentials of oxygen for three-phase assemblages of CaSiO3(s) + Ca3Si2O7(s) + {CaO + SiO2 + FexO} melt and Ca3Si2O7(s) + Ca2SiO4(s) + {CaO + SiO2 + FexO} melt

By employing an electrochemical technique involving stabilized zirconia as solid electrolyte and Mo + MoO₂ mixture as reference electrode, the equilibrium oxygen partial pressures for three-phase assemblages of CaSiO₃(s) + Ca₃Si₂O₇(s) + {CaO + SiO₂ + Fe_xO} melt and Ca₃Si₂O₇(s) + Ca₂SiO₄(s) + {CaO + SiO₂ + Fe_xO} melt were determined as: - log {P_O2 (CS + C₃S₂ + L)/bar} = - 3.22 13000/(T/K) ± 0.05 - log {P_O2 (C₃S₂ + C₂S + L)/bar} = - 0.92 16400/ (T/K) ± 0.04. respectively, where CS, C₃S₂ and C₂S indicate CaSiO₃(s), Ca₃Si₂O₇(s). and Ca₂SiO₄(s), respectively.     

CaO—Al2O3—CaF2—SiO2—MgO五元精炼渣系的起泡性能

采用二次回归正交试验方法测定了１５３０℃下ＣａＯ－Ａｌ２Ｏ３－ＣａＦ２－ＳｉＯ２－ＭｇＯ五元精炼渣系的起泡性能。得出炉渣起泡指数与炉渣光学碱度、渣中Ａｌ２Ｏ３及ＣａＦ２含量间的回归方程。结果表明：炉渣的光学碱度和ＣａＦ２含量对起泡指数有较大影响,而Ａｌ２Ｏ３含量对起泡指数影响很小。具有最佳发泡性能的炉渣成分中ＣａＯ,Ａｌ２Ｏ３,ＣａＦ２,ＳｉＯ２,ＭｇＯ的质量分数分别为：４４．０６％,３０．００％,７．００％,８．９４％,１０％。研究结果还表明：炉渣起泡指数与炉渣粘度成正比,而与表面张力和密度的平方根成反比。     

CaO基脱硫剂中TCa、CaO、CaF_2、SiO_2、P的联合测定

试样用含有硼酸的混合熔剂熔融,稀盐酸酸化后定容。通过控制测定时各元素的酸度,分别用硅钼蓝光度法测定SiO2,铋磷钼蓝光度法测定P、EGTA滴定法测定TCa;利用CaO易溶解于稀乙酸,而CaF2不溶解于稀乙酸的特性,试样用稀乙酸溶解处理过滤分离后,用EGTA滴定法测定CaO;计算出CaF2量。测定结果满意,方法可行,适合冶金工厂日常生产需要。     

X射线荧光光谱法分析CaO基脱硫剂中总钙、氟化钙、氧化钙、二氧化硅和硫

以不同比例的活性石灰石和萤石混合来制备校正物质,采用熔融法制样成片,分别绘制TCa,CaF2,SiO2,S工作曲线,X射线荧光光谱法测定CaO基脱硫剂中的TCa,CaF2,SiO2,S,CaO含量。分析结果准确,适合工厂日常生产的需要。     

Activity determinations in the CaF2−CaO−SiO2 system at 1450°C

The silica activities of slags in the CaF₂?CaO?SiO₂ system (N_CaO∶N_{SiO 2}>3∶2) have been determined at 1450°C by measuring the equilibrium partial pressure of carbon monoxide for the reaction (SiO₂)+3C _(s) =SiC _(s) +2CO _(g) The results have been correlated with phase diagram determinations and are not consistent with other activity measurements in the literature. Lime activities have been determined using the ternary Gibbs-Duhem relationship.     

A thermodynamic study of the system CaO + Al2O3 + FexO at 1673 K

Electrochemical measurements of the solid-oxide galvanic cell: Mo/Mo + MoO₂/ZrO₂(MgO)/(CaO + Al₂O₃ + Fe_xO) + Fe(s) + Ag/Fe have been conducted at 1673 K in order to obtain the activities of Fe_xO) in CaO + Al₂O₃ + Fe_xO slags. By using the activity data for Fe_xO, the isothermal section of the phase diagram for the system CaO + Al₂O₃ + Fe_xO was derived.     

Chemical potentials of oxygen for mixtures of CaO (s) + Ca4P2O9 (s) + {CaO + P2O5 + FexO} melts and Ca4P2O9 (s) + Ca3P2O8 (s) + {CaO + P2O5 + FexO} melts

Electrochemical measurements involving stabilized zirconia as solid electrode and Mo + MoO₂ as reference electrode were conducted in order to determine the chemical potentials of oxygen for threephase assemblages of CaO (s) + Ca₄P₂O₉ (s) + liquid and Ca₄P₂O₉ + Ca₃P₂O₈ + liquid within the system CaO + Fe_xO + P₂O₅. The results for the former are $$\log (P_{O_2 } /atm) = 6.22 - 27,900 (T/K)$$ while for the latter, $$\log (P_{O_2 } /atm) = 6.35 - 27,600 (T/K)$$      

Chemical potentials of components of the system CaO + P2O5 + FexO at 1673 K

Electromotive force (emf) measurements were conducted with a solid oxide galvanic cell of the type Mo/Mo + MoO₂/ZrO₂ (MgO)/Fe (s) + Fe_xO (in slag)/Ag/Fe at 1673 K in order to obtain the activities of Fe_xO in CaO + P₂O₅ + Fe_xO ternary slags. By using the Gibbs-Duhem integration, the activities of P₂O₅ and CaO were also obtained.     

精炼合成渣中SiO2、CaO、MgO、Al2O3、CaF2的测定

试样用混合熔剂熔融,稀盐酸浸取酸化、定容,移取部分试液,通过控制分析时各组分的酸度,分别用硅钼蓝光度法测定SiO2,EDTA滴定法测定MgO,强碱沉淀分离、氟化盐置换、EDTA滴定法测定Al2O3,EDTA滴定法测定CaO总量。利用CaO易被乙酸溶解,而CaF2不溶解于乙酸的特性,另称取一份试样用稀乙酸处理过滤后,将滤液定容,移取部分滤液,用EDTA滴定法测定CaO量。该方法实现了多成分联合快速测定,SiO2、CaO、MgO、Al2O3、CaF2的相对标准偏差分别<1.21%、0.16%、1.39%、0.61%和1.14%。     

Experimental study of phase equilibria in the PbO-ZnO-“Fe2O3”-CaO-SiO2 system in air for high lead smelting slags (CaO/SiO2=0.35 and PbO/(CaO + SiO2)=5.0 by weight)

Experimental studies on phase equilibria in the multicomponent system PbO-ZnO-CaO-SiO₂-FeO-Fe₂O₃ in air have been conducted to characterize the phase relations of a complex slag system used in commercial lead oxidation smelting. The liquidus in the pseudo-ternary section ZnO-“Fe₂O₃”-(PbO + CaO + SiO₂) with the CaO/SiO₂ weight ratio of 0.35 and the PbO/(CaO + SiO₂) weight ratio of 5.0 has been constructed using results of over 100 high-temperature equilibration and quenching experiments followed by electron probe X-ray microanalysis. The liquidus in this pseudoternary section contains primary phase fields of spinel (zinc ferrite) Zn _x Fe_3−x O_4+y , zincite Zn _u Fe_1−u O, melilite Pb _v Ca_2−v Zn _w Fe_1−w Si₂O₇, hematite Fe₂O₃, magneto-plumbite PbFe₁₀O₁₆, and dicalcium silicate Ca_2−t Pb _t SiO₄. The laboratory results are compared with the slags obtained from an industrial reactor.     

The electrical conductivity of some liquids in the system CaF2+CaO+Al2O3

The conductivity of slags in the binary systems CaF₂+Al₂O₃, CaF₂+CaO and the ternary system CaF₂+CaO+Al₂O₃ has been measured, using a four-lead electrode technique at a frequency of 1 kHz. The cell design used ensured that only molybdenum metal was in contact with the slag at high temperature and that the slag was wholly contained in molybdenum. No frequency dispersion could be detected at frequencies between 0.8 to 10 kHz. It is suggested that the formation of complex ions (e.g. AlO₂F₂ ³⁻ and AlOF ₂ ⁻ ) might account for the observed effects in CaF₂+Al₂O₃, CaF₂+CaO+Al₂O₃ liquids as has been previously suggested. an oxide ion clustering mechanism may explain the conductivities found in CaF₂+CaO.     

A thermodynamic study of the system FexO + AI2O3 + SiO2 at 1673 K

Electrochemical measurements of the solid-oxide galvanic cell Mo/Mo + MoO₂/ZrO₂(MgO)/Fe + (Fe_xO + A1₂O₃ + SiO₂)_slag/Ag/Fe have been made at 1673 K in order to obtain the activities of Fe_xO in Fe_xO + A1₂O₃ + SiO₂ slags. Activities of A1₂O₃ and SiO₂ were also determined by virtue of Gibbs-Duhem integration. By using the activity data, the free energies of formation of hercynite and mullite were also obtained. Leave of absence from the Steelmaking Research Section, Iron and Steel Research Laboratories, Kobe Steel Ltd.     

Experimental liquidus in the PbO-ZnO-“Fe2O3”-(CaO + SiO2) System in Air,with CaO/SiO2 = 0.35 and PbO/(CaO + SiO2) = 3.2

Experimental studies on phase equilibria in the multicomponent system PbO-ZnO-CaO-SiO₂-FeO-Fe₂O₃ in air have been conducted to characterize the phase relations of a complex slag system used in lead and zinc smelting. The liquidus in the pseudoternary section ZnO-“Fe₂O₃”-(PbO + CaO + SiO₂) with a CaO/SiO₂ weight ratio of 0.35 and a PbO/(CaO + SiO₂) weight ratio of 3.2 has been constructed to describe liquidus temperatures as a function of composition in the range of commercial operating conditions employed by the Lead Isasmelt smelting process. The section contains the primary phase fields of spinel (zinc ferrite, Zn _x Fe_3−y O_4+z ), zincite (Zn _u Fe_1−u O), melilite (Pb _v Ca_2−v Zn _w Fe_1−w -Si₂O₇), hematite (Fe₂O₃), magnetoplumbite (PbFe₁₀O₁₆), and wollastonite (CaSiO₃).     

Activities of FexO in complex slags used during the final stages of external dephosphorization of hot metal

Measurements of the activities of Fe_xO in complex slags during the final stages of external dephosphorization by using a disposable electrochemical oxygen probe. Positive deviations of the Fe_xO activities from the Raoult law. Iso-activity curves drawn on the “ternary” diagram, (CaO + MgO + MnO + CaF₂) + Fe_xO + (SiO₂ + P₂O₅) at 1673 K. Calculations of the activities of P₂O₅ in complex slags with an assumption of thermodynamic equilibrium between slags and hot metal. Beneficial effect of CaF₂ in the slags with respect to lowering of the P₂O₅ activity.     

转炉渣中CaO和CaF2的分析

利用氧化钙易溶解于稀醋酸,而氟化钙不溶解于稀醋酸的特性.试样以稀醋酸处理,用滤纸过滤不溶解物残渣,滤液加氢氧化钾溶液调节pH≥12.5,用EGTA滴定法测定CaO含量.过滤的不溶解物残渣在铂金坩埚中灰化、灼烧,加含有硼酸钠的混合熔剂,于950℃左右熔融、酸化浸取定容、分液后,加氢氧化钾溶液调节pH≥12.5,用EGTA滴定法测定CaF2含量.     

The solution rate of alumina in CaF2-Al2 O3 slags

The rate of solution of A1₂O₃ in CaF₂ + 30 wt pct A1₂O₃ (at 1518° and 1509°C) and CaF₂ + 20 wt pct A1₂O₃ (at 1500°C) liquids has been determined. The operative process is diffusion-controlled, with an interdiffusion coefficient,D for the process varying between 8.5 and 8.1 x 10^-5 sq cms ^- 1 in the CaF₂ + 30 wt pct A1₂O₃ slags, and 4.0 × 10^-5 sq cms ^- 1 in the CaF₂ + 20 wt pct A1₂O₃ slag. Estimations of the rate at which alumina inclusions would react with these slag during the electroslag processing of steels, indicate that electrode inclusions approaching 100 μ in diam will be dissolved.