An Environmentally Friendly Process Involving Refining and Membrane-Based Electrolysis for Magnesium Recovery from Partially Oxidized Scrap Alloy

Magnesium is recovered from partially oxidized scrap alloy by combining refining and solid oxide membrane (SOM) electrolysis. In this combined process, a molten salt eutectic flux (45 wt.% MgF₂–55 wt.% CaF₂) containing 10 wt.% MgO and 2 wt.% YF₃ was used as the medium for magnesium recovery. During refining, magnesium and its oxide are dissolved from the scrap into the molten flux. Forming gas is bubbled through the flux and the dissolved magnesium is removed via the gas phase and condensed in a separate condenser at a lower temperature. The molten flux has a finite solubility for magnesium and acts as a selective medium for magnesium dissolution, but not aluminum or iron, and therefore the magnesium recovered has high purity. After refining, SOM electrolysis is performed in the same reactor to enable electrolysis of the dissolved magnesium oxide in the molten flux producing magnesium at the cathode and oxygen at the SOM anode. During SOM electrolysis, it is necessary to decrease the concentration of the dissolved magnesium in the flux to improve the faradaic current efficiency and prevent degradation of the SOM. Thus, for both refining and SOM electrolysis, it is very important to measure and control the magnesium solubility in the molten flux. High magnesium solubility facilitates refining whereas lower solubility benefits the SOM electrolysis process. Computational fluid dynamics modeling was employed to simulate the flow behavior of the flux stirred by the forming gas. Based on the modeling results, an optimized design of the stirring tubes and its placement in the flux are determined for efficiently removing the dissolved magnesium and also increasing the efficiency of the SOM electrolysis process.     

Mechanism to remove oxide inclusions from molten aluminum by solid fluxes refining method

A novel flux charging method and a crucible quenching method were employed to study the mechanism of solid fluxes refining method regarding the removal of oxide inclusions (Al2O3) from molten aluminum.Electrochemical polishing method was adopted to prepare surfaces of the samples.Through experiments,the morphology of the residual solidified flux in the solidified samples as well as the wetting action of the molten flux during refining were observed for the first time.Three wetting regimes denoted by absorbing regime,engulfing regime and penetration regime correlating with the removal of oxide films (the most typical and common oxide inclusions in molten aluminum) were proposed in terms of different types and distributions of oxide films and different size ratios of the molten flux to oxide films.Particularly,from a thermodynamic point of view,for the first time,the penetration regime provided concrete evidence that the practical oxide inclusions can be wet by molten flux under ambient fluid of molten aluminum.A spreading model was proposed,according to which ingredients and size parameters of practical solid fluxes can be optimized.     

Characteristic reaction products in the AZ91/SiC composite fabricated by pressureless infiltration technique

Since the spontaneous infiltration of molten AZ91 Mg alloy into a powder bed containing SiC particles occurred at 700 °C for 1 h under a nitrogen atmosphere, it was possible to fabricate Mg alloy composites reinforced with SiC particles. Since the fabrication conditions (e.g. temperature, time, and atmosphere) of the composite are different from those of the other fabrication route, reaction products formed during the composite fabrication were investigated in detail using field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HRTEM). From the analysis results, we could identify the formation of MgAl₂O₄ and AlN, as well as MgO in fabricated composite.     

Melting characteristics of magnesium—lithium alloys

Mg-Li-Al alloys containing 4–14 wt% Li and 1.5 wt% Al have been prepared by melting Mg/Mg-Al master alloy and Li separately under MgCl2 + KCl + MgO + CaF₂ and LiCl + LiF flux covers, respectively, and mixing the two together. The observed lithium loss and the pick-up of impurity elements in the melt have been correlated with various physico-chemical phenomena occurring during melting. The effect of holding time on melt composition was also examined. The results indicate that it is possible to control the alloy composition within specified limits by the selection of proper melting fluxes and crucible materials and by restricting the holding time to the minimum possible. These findings suggest that flux-cover melting is a viable route for the production of sound cast ingots of highly reactive magnesium—lithium alloys.     

Reaction mechanism of self-propagating magnesiothermic reduction of ZrB2 powders

Fine zirconium diboride （ZrB2） powders with high purity were successfully prepared by combustion synthesis through magnesiothermic reduction process in Mg-B2O3-ZrO2 system. The reaction mechanism was investigated by differential thermal analysis and quenching experiment. The results show that the whole magnesio-thermic reduction process includes three stages： first, molten B2O3 and Mg formed above the temperature of 650 ℃, and glassy B2O3 and solid ZrO2 particles were coated on the surface of the molten Mg; thus, the hollow balls can be formed when the molten Mg was exuded under capillary function. Second, ZrO2 particles reacted with molten Mg to form Zr and MgO with dissolution-precip-itation mechanism, which released a large amount of heat to induce the diffusion reaction between B203 and Mg to form B and MgO. Last, Zr reacted with B to form ZrB2 grains. The preparation of ZrB2 by self-propagating syn-thesis in Mg-B2O3-ZrO2 system is a solid-liquid-liquid reaction.     

Protective behavior of an SO2/CO2 gas mixture for molten AZ91D alloy

The protective behavior for a molten AZ91D alloy in an open melting furnace was investigated under a protective gas mixture containing 3% SO2 and 97% CO2, and the protection mechanism was discussed. Experimental results show that the gas mixture provides effective protection for AZ91D melt in the temperature range from 680 oC to 730 oC. The microstructure, chemical composition and phase composition of the surface film formed on the molten AZ91D alloy were analyzed using scanning electron microscopy (SEM) with energy dispersive spectrometer (EDS) and X-ray diffraction (XRD). The SEM results demonstrate that the surface films with an average thickness between 0.5 μm and 2 μm are dense and coherent in the protected temperature range. The EDS results reveal that the surface film mainly contains elements S, C, O, Al and Mg. The XRD results show that the surface film consists of MgO, MgS and a small amount of C phase.     

Thermodynamic Calculations for the Dephosphorization of Silicon Using Molten Slag

The dephosphorization of metallurgical-grade Si using molten slags has recently attracted much attention. In the current study, the thermodynamic assessment of an Si-P system was first carried out, and then the dephosphorization reaction equilibria between molten Si and CaO-based slags were calculated using the thermodynamic databases for Si alloy and slags. The thermodynamic calculations show that dephosphorization of Si under oxidizing conditions (in the form of phosphate) merely happens, and the dephosphorization under reducing conditions (in the form of phosphide) can cause the significant dissolution of Ca in molten Si.     

MgO、Li2O对预熔型无氟连铸保护渣熔化温度的影响

实验研究了MgO、Li2O对预熔型无氟连铸保护渣熔化温度的影响规律,测定了实验渣系的熔化温度。结果表明MgO质量分数在7.5%-9%、Li02质量分数在1.2%-2%时,实验保护渣具有较适宜的熔化温度。熔融状态的连铸保护渣,绝大部分呈玻璃透明态,这说明其具有良好的玻璃态,能够提供较好的润滑条件。     

Mechanisms of grain refinement by intensive shearing of AZ91 alloy melt

It has been demonstrated recently that intensive melt shearing can be an effective approach to the grain refinement of both shape casting and continuous casting of Mg alloys. In the present study, the mechanisms of grain refinement by intensive melt shearing were investigated through a combination of both modelling and experimental approaches. The measurement of the cooling curves during solidification, quantification of grain size of the solidified samples, and image analysis of the MgO particle size and size distribution in the pressurized filtration samples were performed for the AZ91 alloy with and without intensive melt shearing. The experimental results were then used as input parameters for the free growth model to investigate the mechanisms of grain refinement by intensive melt shearing. The experimental results showed that, although intensive melt shearing does not change the nucleation starting temperature, it increases the nucleation finishing temperature, giving rise to a reduced nucleation undercooling. The theoretical modelling using the free growth model revealed quantitatively that intensive melt shearing can effectively disperse MgO particles densely populated in the oxide films into more individual particles in the alloy melt, resulting in an increase in the MgO particle density by three orders of magnitude and the density of active nucleating MgO particles by a factor of 20 compared with those of the non-sheared melt. Therefore, the grain refining effect of intensive melt shearing can be confidently attributed to the significantly increased refining efficiency of the naturally occurring MgO particles in the alloy melt as potent nucleation sites.     

ZLSi7Cu2Mg在熔剂中的精炼方法研究

介绍了熔剂精炼ZLSi7Cu2Mg的实验装置以及实验过程。选用5种无机盐混合,对ZLSi7Cu2Mg铝合金进行了精炼实验,通过实验总结出电极熔化速度与电流的变化关系;对比分析了精炼与未精炼试样抗拉强度、伸长率及其金相组织。结果表明:在能够熔化电极的前提下,电流越小,精炼后的铝合金性能越好;熔剂45%KCl+45%MgCl2+10%Na3AlF6对铝熔体的精炼效果最好;精炼后铸件的力学性能相对未精炼时有一定程度的提高。     

An electrochemical method for the preparation of Mg–Li alloys at low temperature molten salt system

Mg–Li alloys have been prepared by electrolysis in a molten salt electrolyte of 50% LiCl–50% KCl (mass%) at low temperature of 420–510 °C. The effects of electrolytic temperature and cathodic current density on alloy formation rate and current efficiency were studied. For the deposition of metallic lithium on the cathode consisting of solid Mg and liquid Mg–Li, both electrolytic temperature and cathodic current density have no obvious influence on current efficiency; while for the deposition of metallic lithium on the solid magnesium cathode, both electrolytic temperature and cathodic current density greatly affect alloy formation rate and current efficiency. The optimum electrolysis condition is—molten salt mixture, LiCl:KCl = 1:1 (mass%), electrolytic temperature: 480 °C, cathode current density: 1.13 A cm⁻². Mg–Li alloys with low lithium content (about 25 wt% Li) were prepared via electrolysis at low temperature following by thermal treatment at higher temperature.     

镁合金真空低压消失模铸造的技术特征与实践

介绍了镁合金在真空低压消失模铸造下的技术特征。研究表明：真空低压消失模铸造的流动性受充型气体的流量与压力、浇注温度、涂层厚度、泡沫密度、真空度等多方面的因素影响；在低充型速度和低真空度的条件下，液态镁合金在真空低压消失模铸造过程中的充型形貌均呈现以内浇道为中心的拱形层状推进流动，如充型速度加快金属液流动前沿拱形形貌更加突出。而真空度增加会出现明显的“附壁效应”；与重力消失模铸造比较，真空低压消失模铸造镁合金铸件凝固更呈现“同时凝固”特征；由于快速充型、压力下凝固，镁合金真空低压消失模铸造零件的铸态抗拉强度（σh=180．8MPa）、屈服强度（σ0.2=113．2MPa）、伸长率（δ=4．4％），高于重力消失模铸造、树脂砂空型铸造的铸态性能，达到了金属型铸造的铸态性能，经热处理达到了压铸镁合金的性能范围。浇注实践表明，真空低压消失模铸造对液态镁合金，具有良好的抗氧化保护能力、优良的浇注充型性能和力学性能，可铸造出高精度的、薄壁复杂的镁合金消失模铸件，是一种极有潜力和优势的镁（铝）合金精密铸造技术。     

氢在合金熔体中的溶解度计算(英文)

基于氢在纯金属中的溶解度数据以及合金之间的相互作用系数,提出氢在合金熔体中溶解度的热力学计算模型。计算结果与文献中的实验数据吻合得很好。结果表明,合金熔体的性质越接近理想溶液,计算结果越准确,合金元素形成化合物的能力及其摩尔混合热对氢在合金熔体中的溶解度有重要影响。     

Dissolution behavior of alumina in mold fluxes for steel continuous casting

Dissolution of alumina in various mold fluxes for steel continuous casting has been investigated by employing the rotating cylinder method. The weight loss of the rod, the dipping area and the immersed time were measured to determine dissolution rate of Al₂O₃. The dissolution rate increased with temperature of molten fluxes, the rotating speed of the rod and the addition of MgO, CaF₂ and Na₂O components in the mold flux. When the Na₂O content exceeded 5%mass, the dissolution rate was found to decrease. Intermediate compounds such as CaO·6Al₂O₃, CaO·2Al₂O₃ and 2CaO·Al₂O·SiO₂ formed at the Al₂O₃/flux interface and formation of three compounds was found to play important roles in the dissolution rate. In conclusion, the dissolution of Al₂O₃ was controlled not only by the mass transfer in the molten flux also by the formation of intermediate compounds on the interface.     

Determination of the Mg-Rich Phase Boundary of the Binary Mg-Nd Phase Diagram by Means of Atom Probe Tomography

The present paper relates the investigation of the Mg-rich side of the binary Mg-Nd phase diagram by means of Atom Probe Tomography (APT). The solid solubility of Nd in Mg at the temperatures 400, 480, 520 °C has been measured. The results of the current investigation demonstrate that the solid solubility of Nd in Mg is much larger than is usually supposed and presented in more recent Mg-Nd phase diagrams. The data presented in this work can be used for further thermodynamic calculations in order to interpolate the phase boundary between temperature points.     

DTA/TG study of tungsten oxide and ammonium tungstate reduction by (Mg + C) combined reducers at non-isothermal conditions

In this work the reaction mechanism in the WO₃–Mg/C systems and ammonium paratungstate (APT)–Mg/C systems are studied. As reducer magnesium, carbon or combinations of both are explored. It is shown that in the WO₃–Mg system the reduction undergoes by solid–solid mechanism before melting Mg, where metallic tungsten and MgO are formed. Unlike this system, in the WO₃–C system mainly WO_x (< 880 °C) and WO₂ (> 960 °C) and small amount W is formed. In the WO₃–Mg–C ternary system reduction temperature shifts to higher temperature range and depends on amount of carbon. Similar to WO₃–Mg system, APT–Mg reaction starts and completes in the solid state. Thus, firstly the APT decomposes, then reduction of formed WO₃ takes place at ~ 600 °C yielding W and MgO. Likewise to WO₃–Mg system adding carbon into APT–Mg mixture shifts reduction temperature to even higher temperature zone which can exceed melting point of Mg and further reduction undergoes with molten magnesium. It is shown that the reduction products are MgO and W.     

Baking treatment effect on materials characteristics and electrochemical behavior of anodic film formed on AZ91D magnesium alloy

The composition and microstructure of the anodic films formed on AZ91D Mg alloy, with or without baking, were investigated. The associated corrosion behavior of the anodized alloy in 3.5 wt% NaCl solution was also examined using electrochemical impedance spectroscopy (EIS). The results show that MgO was the main component in the anodic film which also contained some Mg(OH)₂, Al₂O₃, Al(OH)₃, and MgAl₂O₄. Both the amorphous and crystalline forms of anodic film were identified. The degree of crystallinity depended on baking temperature, which increased with increasing temperature in the range of 50-250 °C. The amounts of MgO and Al₂O₃ increased as a result of a dehydration reaction. The polarization resistance of anodized Mg alloy was improved significantly by increasing the oxide content in the anodic film. An optimum value of polarization resistance of anodic film was obtained for the alloy baked at 150 °C for 2 h followed by air cooling.     

Oxide contributions on arc plasma in tungsten inert gas welding of magnesium alloy

Abstract

To study the effects of oxide activating flux on the arc plasma, the investigation is carried out in tungsten inert gas (TIG) welding on magnesium alloy. In this study, five oxides, ZnO, MnO₂, Cr₂O₃, CeO₂ and CdO, are selected to study the roles of activating flux on the plasma characteristics (shape, electron temperature and electron density) and the arc voltage. The mechanism is also discussed by comparisons between single TIG welding processes with and without fluxes. Results reveal that the electron temperature of arc plasma decreases sharply under the influence of oxide; however, the electron density and the arc voltage get enhanced. The reasons for the increase in arc voltage are the greater electricity resistances that result from the improved welding current density and the constriction of conduction channel.     

Microstructure characterization on the formation of in situ Mg2Si and MgO reinforcements in AZ91D/Flyash composites

5 wt.% and 100 μm in size of fly ash cenosphere particles were incorporated in AZ91D Mg alloy to fabricate in situ Mg₂Si and MgO reinforced AZ91D/Flyash composites by means of compocasting method. The in situ Mg₂Si and MgO were identified using X-ray diffraction (XRD), energy dispersive spectrometer (EDS), and thermodynamic analysis. The results show that the cenosphere particles distributed homogeneously in the matrix alloy. Moreover, most of the cenosphere particles were filled with the matrix alloy. The preliminary discussion was carried out on the growth mechanism of the in situ Mg₂Si.     

ZnCl2和TiO2活性剂对镁合金TIG焊的影响

进行了单侧涂敷活性剂和两侧涂敷活性剂焊接镁合金的研究,分析了不同活性剂对焊缝及电弧的影响.结果表明,在单侧涂覆活性剂和两侧涂敷活性剂试验中,ZnCl2活性剂增加熔深的效果均优于TiO2活性剂.涂敷同样的活性剂,熔深增加的效果随着涂敷活性剂偏移量或间隙量的增大而减小.在单侧涂敷活性剂试验中,ZnCl2活性剂对熔池的偏移作用更明显.热稳定性差的ZnCl2活性剂改变电弧导电通道,使电弧形态发生明显改变.而热稳定性好的TiO2活性剂没有改变电弧导电通道,其电弧形态未发生明显改变.