SiO_2-CaO-MgO-Al_2O_3熔渣中铁氧化物的分解电压

电解含有铁氧化物的熔融电解质提铁是一种钢铁冶炼短流程新工艺,该工艺可以减少甚至消除CO2排放。为测定熔渣中铁氧化物的分解电压,采用一端封闭的氧离子传导的氧化锆基固体电解质管内装熔渣,并以烧结在固体电解质管封闭端外侧表面的多孔铂金作为阳极,构建一种阴、阳极相互隔离的新型管状电解池。将该电解池的多孔铂金阳极置于恒定氧分压的气氛下,在熔渣中分别插入铱丝、铁棒作为阴极,利用线性扫描伏安法测定了1 723K下SiO2-CaO-MgO-Al2O3熔渣中FeO的分解电压,研究了熔渣碱度、阴极材料以及阳极气氛氧分压等因素对FeO分解电压的影响。结果表明,增大熔渣碱度、阴极还原合金化以及降低电解产物气体O2的分压,均可降低FeO的分解电压,有利于FeO的电解。测定结果与采用FactSage 6.1热力学软件理论计算的结果一致。证实采用氧离子传导的固体电解质管构建新型管状电解池,测定固体电解质管内熔渣中氧化物的分解电压是可行的。     

Three-Layer Electrorefining of Silicon

To make electrical energy from photovoltaic (PV) silicon (Si) solar cells competitive, the cost in each of the PV manufacturing process steps has to be diminished. Today, high-purity Si is produced by an energy-intensive process exhibiting high irreversible thermodynamic losses. The purity of the product from this process (99,9999999 pct [9 N]) far exceeds what generally is accepted to be the requirements for PV purposes (4 to 6 N). Here we show a novel method for the purification of Si based on the principle of electrochemical refining in a molten high-melting-point fluoride electrolyte at temperatures above the melting point of silicon 1685 K (1412 °C). The method comprised a vertical stack of three molten layers with a metal alloy at the bottom, an intermediate electrolyte layer, and purified metal at the top. The integrity of the layers being secured was through the immiscibility of the liquids and the careful tailoring of the individual densities. Boron (B), exhibiting similar thermodynamic properties to Si, effectively was not removed. A suitable low-B feedstock may be identified in kerf from the sawing of mono- or multicrystalline Si blocks into wafers. To produce purified metal in the 6 N range, practice from electrorefining of aluminum shows that long-term, stable operation in large-scale industrial reactors is needed. The trends and mechanisms observed in the laboratory scale indicate that high purity also can be achieved for Si provided that these criteria can be met.     

基于原子-分子理论的二元合金熔体热力学计算

分别使用Miedema、MIVM、NRTL、Wilson二元合金系热力学模型及FactSage热力学软件计算Bi-Pb、Bi-Sn、Cd-Pb、Pb-Sn 4个二元合金系的活度值,并与实验值进行比较.结果表明:Miedema、MIVM、NRTL、Wilson模型计算不同体系活度的效果不同,每种模型都有其适用的体系.而FactSage热力学软件计算的活度均与实验值吻合较好,文中使用FactSage分别计算Bi-Pb、Bi-Sn、Cd-Pb、Pb-Sn 4个二元系不同温度下的活度值.同时利用原子-分子理论计算Bi-Pb二元系质量作用浓度,给出生成金属间化合物BiPb反应的标准吉布斯自由能的表达式.      

帘线钢凝固过程夹杂物生成热力学及工业实践

 非金属夹杂物是影响帘线钢拉拔性能的重要因素之一,为了研究帘线钢中夹杂物的生成及转变机理,使用ASPEX自动扫描电镜观察分析了帘线钢工业生产过程中不同碱度条件下从钢液到铸坯中非金属夹杂物的转变现象,并使用FactSage7.0热力学计算软件对非金属夹杂物的转变机理进行了讨论。在高碱度条件下,钢液中非金属夹杂物主要类型为低熔点的CaO-SiO₂-Al₂O₃-MnO,铸坯中非金属夹杂物的CaO和MnO含量有所降低,同时SiO₂含量有所增加。在低碱度炉次中,钢液中非金属夹杂物主要为较高熔点的SiO₂-MnO-CaO类型,Al₂O₃含量较低。连铸坯中非金属夹杂物的SiO₂含量与钢液相比有所增加,同时MnO含量降低。热力学计算结果表明,帘线钢凝固和冷却过程中的非金属夹杂物转变由夹杂物自身的相转变和析出、非金属夹杂物和钢液间的化学反应以及溶解氧和钢基体化学成分的反应3方面原因造成。热力学计算结果较好地解释了帘线钢工业生产中钢液和铸坯中非金属夹杂物成分和形貌的转变,为帘线钢中非金属夹杂物的控制提供参考。     

Thermochemical Analysis of Phases Formed at the Interface of a Mg alloy-Ni-plated Steel Joint during Laser Brazing

The thermodynamic stability of precipitated phases at the steel-Ni-Mg alloy interface during laser brazing of Ni-plated steel to AZ31B magnesium sheet using AZ92 magnesium alloy filler wire has been evaluated using FactSage thermochemical software. Assuming local chemical equilibrium at the interface, the chemical activity–temperature–composition relationships of intermetallic compounds that might form in the steel-Ni interlayer-AZ92 magnesium alloy system in the temperature range of 873 K to 1373 K (600 °C to 1100 °C) were estimated using the Equilib module of FactSage. The results provided better understanding of the phases that might form at the interface of the dissimilar metal joints during the laser brazing process. The addition of a Ni interlayer between the steel and the Mg brazing alloy was predicted to result in the formation of the AlNi, Mg₂Ni, and Al₃Ni₂ intermetallic compounds at the interface, depending on the local maximum temperature. This was confirmed experimentally by laser brazing of Ni electro-plated steel to AZ31B-H24 magnesium alloy using AZ92 magnesium alloy filler wire. As predicted, the formation of just AlNi and Mg₂Ni from a monotectic and eutectic reaction, respectively, was observed near the interface.     

调质渣的析晶行为

针对矿渣棉生产时调质渣成纤过程中会有晶体析出的问题,采用FactSage热力学软件、X射线衍射仪(XRD)和场发射扫描电子显微镜(SEM)研究调质渣不同温度下的矿物组成和显微结构;采用熔体物性综合测定仪研究调质渣降温过程中的黏度变化。结果表明,调质渣在冷却过程中,1 240 ℃时开始析出晶体,析出的主晶相为钙铝黄长石（Ca2Al2SiO7）和镁黄长石（Ca2MgSi2O7）。此外,熔融调质渣成纤适宜的温度区间为1 300～1 413 ℃。     

Thermodynamics and kinetics analyses of ZrB2 formation in molten aluminium alloys

Smelter grade aluminium can be used as a source for electrical conductor grade aluminium after the transition metal impurities such as zirconium (Zr), vanadium (V), titanium (Ti) and chromium (Cr) have been removed. Zirconium (Zr), in particular, has a significant effect on the electrical conductivity of aluminium. In practice, the transition metal impurities are removed by adding boron-containing substances into the melt in the casthouse. This step is called boron treatment. The work presented in this paper, which focuses on the thermodynamics and kinetics of Zr removal from molten Al–1?wt-%Zr–0.23?wt-%B alloy, is part of a broader systematic study on the removal of V, Ti, Cr and Zr from Al melt through boron treatment carried out by the authors. The thermodynamic analyses of Zr removal through the formation of ZrB₂ were carried out in the temperature range of 675–900°C using the thermochemical package FactSage. It was predicted that ZrB₂ is stable compared to Al–borides (AlB₁₂, AlB₂) hence would form during boron treatment of molten Al–Zr–B alloys. Al–Zr–B alloys were reacted at 750?±?10°C for 60 minutes, and the change in the chemistry and microstructure were tracked and analysed at particular reaction times. The results showed that the reaction between Zr and AlB₁₂/B was fast as revealed by the formation of boride ring at the early minutes of reaction. The presence of black phase (AlB₁₂), i.e. the original source of B, after holding the melt for 60 minutes advocated that the reaction between Zr and AlB₁₂/B was incomplete, hence still not reached the equilibrium state. The kinetics data suggested a higher reaction rate at the early minutes (2 minutes) of reaction compared to at a later stage (2–60 minutes). Nevertheless, a simple single-stage liquid mass transfer controlled kinetic model can be used to describe the overall process kinetic. The analysis of integrated rate law versus reaction time revealed that the mass transfer coefficient (k_m) of Zr in molten alloy is 9.5?×?10^?4?m?s^?1, which is within a typical range (10^?3 to 10^?4?m?s^?1) observed in other metallurgical solid–liquid reactions. This study suggests that the overall kinetics of reaction was predominantly controlled by the mass transfer of Zr through the liquid aluminium phase.     

The use of computational thermodynamic for yttrium recovery from rare earth elements-bearing residue

The rare earth elements are considered critical metals,due to the risk of supply interruption.The recycling of waste electrical and electronic equipment can be an alternative to supply the rare earth market.Several processes have been developed,and by aqueous media is the most prominent,which makes possible the extraction and separation of elements even in low concentration(traces).As an example of thermal processing,the use of thermodynamic simulations might benefit the metal extraction in hydrometallurgical processing.For this reason,the goal of this work is to evaluate the use of FactSage 7.2 software for the leaching of fluorescent lamp powders by sulfuric acid.The effect of concentration and temperature was evaluated.Results comprise that the thermodynamic software wellpredicted the solid phase formed in all residues of leaching experiments-gypsum was predicted by the software and identified in XRD analyses.It demonstrates that FactSage software can be explored for metals extraction in aqueous media,being important for trace-elements extraction.Yttrium extraction reaches up to 95%at 45℃using H₂SO₄2 mol/L.     

40Cr钢浸入式水口结瘤分层结构的形成机理

  为明确转炉→LF精炼→连铸工艺条件下生产40Cr钢浸入式水口结瘤分层结构的形成机理,采用扫描电镜、阴极发光仪以及FactSage 7.1热力学软件,对40Cr钢水口结瘤形貌及分层结构进行了研究。结果表明,浸入式水口结瘤物分为水口脱碳层、凝钢层、夹杂物堆积层、凝钢层和表面疏松层。分析了40Cr钢在连铸过程中钢中Al2O3、Al2O3 CaO(SiO2)和Al2O3 MgO尖晶石在水口内壁上的分层沉积现象。结合现场工艺,研究了双凝钢层的形成机理,并通过热力学计算解释了结瘤物的形成机理。     

Thermodynamics of lead and bismuth in CaO–CaF2 melts

In order to understand a new refining process for removing tramp elements from alloy steels under strongly reducing conditions, the authors previously reported the thermodynamic behaviour of P, Sn, Sb, As and Cu in CaO–CaF₂ melts. In this investigation, the thermodynamic behaviour of Pb and Bi in CaO–CaF₂ melts under oxygen partial pressures from 10^?16 to 10^?20 atm was studied at temperatures ranging from 1360 to 1550°C, using a similar technique. It was shown that Pb and Bi exist in slag mainly as Ca₂Pb and Ca_1.5Bi, respectively, under very low oxygen partial pressure although a part of Pb is soluble in slags as metal. The obtained results were extrapolated to lower oxygen partial pressures to investigate the possibility of removing these tramp elements from molten iron, causing Bi to be removed from molten iron below an oxygen partial pressure of 10^?23 atm, whereas Pb is removed under higher oxygen partial pressures.     

SPHC钢LF精炼过程钢水增硅分析

硅的控制是CSP工艺生产SPHC钢成分控制的一大难点。通过在国内某厂进行生产试验所获得的相关数据,利用FactSage热力学软件分析了增硅最严重的LF精炼过程钢中[Al]s对硅含量控制的影响。结果发现:LF精炼结束时钢渣间还远未达到平衡,而且整个过程增硅趋势强烈;LF精炼过程增硅严重的主要原因是脱氧喂入了过量的铝,同时顶渣氧化性高也增加了钢中酸溶铝的损耗。     

Experimental Phase Equilibria Studies of the Pb-Fe-O System in Air,in Equilibrium with Metallic Lead and at Intermediate Oxygen Potentials

The phase equilibria information on the Pb-Fe-O system is of practical importance for the improvement of the existing thermodynamic database of lead-containing slag systems (Pb-Zn-Fe-Cu-Si-Ca-Al-Mg-O). Phase equilibria of the Pb-Fe-O system have been investigated: (a) in air at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); (b) in equilibrium with metallic lead at temperatures between 1053 K and 1373 K (780 °C and 1100 °C); and (c) at intermediate oxidation conditions for the liquid slag in equilibrium with two solids (spinel + magnetoplumbite), at temperatures between 1093 K and 1373 K (820 °C and 1100 °C). The high-temperature equilibration/quenching/electron probe X-ray microanalysis technique has been used to accurately determine the compositions of the phases in equilibrium in the system. The Pb and Fe concentrations in the phases were determined directly; preliminary thermodynamic modeling with FactSage was used to estimate the ferrous-to-ferric ratios and to present the results in the ternary diagram.     

不锈钢酸洗污泥用作炼钢造渣剂的试验

 酸洗污泥产量大、污染严重且难处理，常规固化填埋占用土地且浪费资源，将酸洗污泥配入电炉作为造渣剂使用，在生产中回收其中金属铁、铬和镍，并发挥CaO、CaF2等辅料功能，可实现污泥在冶金过程的资源化利用。通过FactSage热力学软件计算发现酸洗污泥中的金属铁、铬和镍绝大部分可回收进入金属液中，且金属液硫质量分数最高为0.014%，不会使金属液增硫。在此基础上，将酸洗污泥制成混合造渣剂，通过静态试验与吹氧熔炼试验发现，当造渣剂与酸洗污泥质量比为1[∶]1时，硫质量分数能够满足钢液要求，铬、镍回收率分别为66.04%和97.90%。     

Electrodeposition of magnesium-yttrium alloys by molten salt electrolysis

Electrodeposition of magnesium-yttrium alloys from molten salts was studied by electrochemical techniques. LiF-YF₃ was electrolyte system with magnesium oxide and Yttrium oxide as raw materials. It was proved that Mg²⁺ and Y³⁺was deposited more prior than other ions during cyclic voltammetry and potential step measurement at 1050 °C. Voltammograms showed Mg²⁺ could be deposited at ?0.5 V, and Y³⁺ could be deposited at ?0.7 V on tungsten electrode compared with platinum electrode. The sedimentation of Mg²⁺ was more positive about 230 mV than that of other ions in electrolyte. The electrolytic codeposition of yttrium and magnesium was 0.58 V on condition that the weight ratio of Y₂O₃/MgO was 4:1. Chronopotentiogram indicated that the process of electrodeposition of magnesium-yttrium alloys on tungsten electrode was controlled by diffusion of ions from electrolyte to electrode interface. It was feasible to prepare Magnesium-Yttrium alloys by controlling content of ions in molten salt electrolyte.     

The separation of zirconium and hafnium in a molten salt-molten zinc system

The commercial separation of zirconium and hafniumvia aqueous/organic extraction procedures is both difficult and expensive. The principal objective of the present work was to study an alternative procedure involving the oxidation-reduction equilibria of zir-conium and hafnium between a molten salt phase and molten zincvia the displacement reaction: Zr(IV)_{molten salt} + Hf_{molten zink} ⇌ Hf(IV)_{molten salt} + Zr_{molten zink} The reaction goes strongly to the right with an equilibrium constant: logK =0.432 ×10⁴/T - 1.565 for Na₂Zr(Hf)F₆ dissolved in NaKCl₂ solvent, thus showing promise as the basis for an anhydrous process for separating zirconium and hafnium. The rate of approach to chemi-cal equilibrium was studied in a baffled stirred reactor. The equilibration rate was found to be controlled by the hafnium mass transfer rate from the molten zinc to the metal-salt interface. The mass transfer rate could be estimated from the physical properties of the molten metal and the salt phases, using the Mayer correlation. Formerly with the Teledyne Wah Chang Cor-poration, Albany, OR.     

Research on determination of the rare-earth content in metal phases of steel

The behavior of the rare-earth dissolved in a-Fe, of the iron-cerium intermetallic compounds and of the rare-earth inclusions in electrolytic separation process has been studied by means of counting measurements of radioactivity, the electron probe, and X-ray analysis. The experimental results show that the rare-earth sulfide and the rare-earth oxide are stable completely in the electrolytic separation process, when the composition of the electrolytic solution is 1 pct 4-methyl ammonium chloride, 5 pct triethanolamine, 5 pct glycerin, and 89 pct methyl alcohol, and the controlling anode current density is ≤100 mA/cm². But Fe-Ce intermetallic compounds and the rare-earth dissolved in a-Fe enter into electrolytic solution as ions. When the cerium ion concentration in electrolytic solution is >7.87 X 10^-5 mol/liter electrolyte, precipitates of cerium hydroxide will be formed. When the inclusions are separated quantitatively, the electrolytic solution must be filtered by using a funnel with filter paper pulp thick up to 6 mm, and not be filtered directly with single filter paper. Samples without rare-earth were remelted and a radioactive isotope¹⁴¹Ce was added to the steel. Inclusions were separated by the electrolytic method in the nonaqueous solution. The counting of 14lCe in the electrolytic solution was measured. Thus the rare-earth content in the metal phases can be calculated. Experimental results show that the rare-earth content in the metal phases increases with the total rare-earth content in steel. The rare-earth content in the metal phases of the steel was also found to increase as the aluminum content in steel was increased. This method for determining the rare-earth content in the metal phases of steel is very sensitive. The sensitivity is 10^-6 pct.     

Modification of MgO· Al2O3 spinel inclusions in Al-killed steel by Ca-treatment

The modification of MgO·Al2O3 spinel inclusions in Al-killed steel by Ca-treatment has been studied by industrial trials and ther-modynamic calculations.In the industrial trials,samples were taken systematically during the refining process in which the molten steel was treated by calcium,and the characters of the inclusions were analyzed using scanning electron microscopy (SEM) and energy dispersive spectra (EDS).The effects of Ca-treatment were evaluated by tracking the compositions of the inclusions.The results show that the modifi-Al2O3→MgO.Al2O3→liquid complex inclusions.The modification of spinel inclusions by Ca-treatment was calculated by FactSage6.0 util-izing its free-energy minimization routines.The results of thermodynamic calculations indicate that spinel inclusions are easier to be modi-fied than Al2O3 inclusions and the spinel inclusions in 30CrMo steel would transform to liquid complex inclusions when the content of dis-solved Ca in the molten steel exceeds 1×10-6.Also,the results show that adding more calcium into the molten steel would lower the contents of Al2O3 and MgO and increase the CaO content of the inclusions,while the change in SiO2 content is little.     

Improving the processing of steelmaking waste. Part 1. Thermodynamic analysis

New approaches are required in the industrial processing of tailings slag from steelmaking. It has been shown in recent years that slag may be processed to obtain not only construction materials but also metal suitable for industrial use. In the present work, we study the expediency of reducing steelmaking slags as to obtain metallic and oxide phases for use in steelmaking and the construction industry. In particular, we consider slag from the tailings at Zlatoust Metallurgical Plant. FactSage software (version 6.4) is used for thermodynamic modeling of high-temperature slag reduction. Three slag compositions are considered, with 5, 10, and 15 wt % FeO. Modeling is undertaken for temperatures at intervals of 5°C in the range 750–1650°C, at a gas pressure of 0.1 MPa. We assume that a known excess of carbon (graphite) is introduced in the system. For convenience of analysis, the basic calculation results are presented as temperature dependences of the masses of the components and the composition of the phases considered. Modeling shows that, beyond 1340°C, practically all the iron is reduced and passes to the melt. Nickel and copper behave analogously. However, the results indicate that complete extraction of manganese in the metallic melt on reduction by carbon should not be expected. Even with maximum manganese extraction in the metallic melt, its presence in the slag and gas phases remains pronounced. The volume of gas phases formed in reduction at different temperatures is estimated. Modeling convincingly shows that, over the whole temperature range considered, carbon monoxide predominates in the gas phase. Information regarding the enthalpy of the system as a function of the temperature permits estimation of the thermal energy that must be expended to bring the system to a state at which the required reduction processes are possible.     

The Thermodynamics of Some Transition Metals in Molten Slags

In the present paper, the thermodynamic behaviour of transition metals, such as Cr, Ti, Nb and V in molten slags is systematically analysed based on a literature survey. These metals exist in molten slags with multi valences. Oxygen partial pressure, slag basicity, total content of each transition metal, content of each component in slag, and temperature are the influential factors on their thermodynamic properties in molten slags. Higher basicity and strong oxidative atmosphere are generally favourable for the stable existence of transition‐metal ions with higher oxidation states. Temperature is a factor that is less influential than the above‐mentioned ones. For a transition metal in molten slag, the concentration ratio of ions of different valences depends on the activity coefficient ratio of their oxides. The present paper summarizes the activity studies regarding the transition metal oxides in various molten slags. For chromium and titanium oxides, information on CaO? SiO₂ based systems is involved. For titanium oxides, its thermodynamic behaviour in MnO? SiO₂ based slags is introduced. For niobium and vanadium, the information in Na₂O? SiO₂, CaO? CaF₂? SiO₂ systems is provided. Thermodynamic studies are described for Nb₂O₅? MnO? SiO₂ molten slag equilibrated with liquid iron at 1828 K.