Removal of aluminum from metallurgical grade silicon using electron beam melting

Small amounts of metallurgical grade silicon were melted in an electron beam furnace in different experimental conditions in order to investigate the aluminum (Al) evaporation behavior during the electron beam melting (EBM) process. Impurity was significantly decreased in the early periods of melting at 9, 15, and 21 kW. These changes slowed down with the extension of the melting time. Moreover, the removal reaction of Al by evaporation from molten silicon during the EBM process occurred in accordance with the first order kinetics. The calculated mass transfer coefficients of Al at 1941, 1964, and 2051 K increased with the increase of melting temperature. The removal rate of Al was controlled by the transportation of Al from the bulk of silicon metal to the molten/vacuum interface within the range of the experimental temperature.     

Research on distribution of aluminum in electron beam melted silicon ingot

The purification of metallurgical grade silicon, especially the removal of aluminum, was investigated by electron beam melting and solidification. Small amounts of silicon raw materials were melted in an electron beam furnace with same melting time and different solidification time to obtain the distribution of Al in silicon ingot. The removal mechanisms in different stages were also discussed. The results show that the removal of Al during melting process only depends on evaporation and that during solidification process depends on both segregation and evaporation. The distribution of Al shows an obvious increasing trend from the bottom to the top of the silicon ingot when solidification time is 600 s. The removal efficiency in most area is close to that in the ingot solidified instantaneously, but the energy consumption is less, which is considered to be an effective way for the purification of silicon.     

冶金法提纯工业硅的研究

以冶金级硅为原料进行了制备高纯多晶硅锭的研究,自行设计了真空感应熔炼与定向凝固设备、电子束熔炼设备.通过酸洗、真空感应熔炼与第一次定向凝固、电子束熔炼、真空感应熔炼与第二次定向凝固等组合步骤对工业硅进行提纯.利用电感耦合等离子体发射光谱仪(ICP-AES)进行成分分析,实验结果表明,定向凝固有效去除了金属杂质,电子束对蒸汽压高的元素,尤其是磷元素的去除作用明显.Al的浓度降低到了0.4×10~(-6),Fe、Ca、Ti、Mn、Cu、Zn等金属杂质的浓度降到了0.1×10~(-6)以下,P含量降低到1.5×10~(-6).     

提纯工业硅除铝的实验研究

为了去除工业硅中的杂质制备太阳能级硅,根据工业硅凝固过程中铝在固相和液相中溶解度的差异,采用定向凝固法去除工业硅中的杂质铝.实验结果表明,铝的去除效率可达98%,说明利用定向凝固法去除工业硅中的铝是可行的.但由于在结晶过程中晶界上会富集部分铝元素,因而定向凝固法并不能除去这一部分杂质.结合金相实验中样品腐蚀前后晶界上的变化,可以知道利用酸浸可以除去晶界上的杂质铝.还研究了先酸浸后定向凝固法相结合除铝,实验结果表明铝的含量可以降到1.6×10-5,铝的去除率达98.6%.     

Evaporated metal aluminium and calcium removal from directionally solidified silicon for solar cell by electron beam candle melting

During the refinement of metallurgical-grade silicon (MG-Si), Al and Ca cannot be reduced to a target level by conducting directional solidification only once. Electron beam candle melting (EBCM) is a new method that can be used to further reduce Al and Ca by directly melting Si ingots after directional solidification. A certain stable molten pool with a maximum surface area and a minimum depth exists and is proven to effectively remove Al and Ca. The energy utilization ratio during EBCM is also compared with that of electron beam melting (EBM).     

电子束熔炼去除冶金级硅中磷、铝、钙的研究

采用电子束熔炼方法提纯了冶金级硅材料。实验结果表明随熔炼时间延长,硅中挥发性杂质元素P、Al、Ca的含量逐渐降低。熔炼40min后,硅中P含量可以降至2.2×10-5%(质量分数);Al、Ca的最低含量为8.5×10-5%和1.5×10-4%(质量分数)。P、Al、Ca的挥发去除为一阶反应过程,反应速率常数分别为0.11、0.12和0.13min-1。     

Study on volatilization rate of silicon in multicrystalline silicon preparation from metallurgical grade silicon

The quantity of silicon lost during evaporation is greater than theoretical expectation during the purification of metallurgical grade silicon by vacuum evaporation. In this paper, silicon volatilization rates were measured for evaporation times of 30, 45 and 60 min at 1723, 1773 and 1823 K, respectively. Results indicate that volatilization rates determined in our experiments are one or two orders of magnitude greater than those from theoretical calculation. The equation for theoretical calculation was revised (ω = (2.23-6.30)× 10⁻¹ p_pa(M/T)^1/2) using silicon evaporation coefficient of 8.5-24. The details of the experimental set-up were found to be important and the mass of silicon evaporated in particular was found to be related to the water-cooling system. The carbon/graphite inserts also and the presence of trace amounts of oxygen in the vacuum furnace could reduce the content of silicon in gaseous phase and support the evaporation of silicon. It was found under certain conditions that there are two principal stages involved: 1) Formation of vapor-liquid equilibrium, 2) Maintenance of the established vapor-liquid equilibrium during the silicon evaporation process. It was found that silicon process losses can be reduced by shortening the time of the first stage.     

精炼法提纯冶金硅至太阳能级硅的研究进展

随着光伏市场需求不断增加,满足光伏电池技术经济指标要求的硅材料出现严重短缺,低成本提纯冶金硅至太阳能级硅工艺技术越来越受到广泛重视,成为研究开发热点.综述了近年来国外有关基于定向凝固原理开发的精炼法提纯冶金硅至太阳能级硅的技术成果,并进行了比较分析,展望了应用前景.     

等离子体刻蚀提纯冶金硅研究

通过自行设计的冷等离子体粉粒纯化系统,将硅粉撒进辉光放电区,以Ar气为反应气体,利用鞘层区域辉光放电的冷等离子体对硅粉料的作用,进行一系列的处理后,硅粉表面形貌平整度明显提高,纯度从98.75 9,6提高到99.56%.在此基础上,设计射频感应放电等离子体的振动倾斜反应室,经实验,将硅粉纯度提高到99.96 9,6,接近太阳级硅的要求,也为该研究未来的发展提供了新的思路和理论参考.     

Reasons for superior mechanical and corrosion properties of 2219 aluminum alloy electron beam welds

Electron beam welds of aluminum alloy 2219 offer much higher strength compared to gas tungsten arc welds of the same alloy and the reasons for this have not been fully explored. In this study both types of welds were made and mechanical properties were evaluated by tensile testing and pitting corrosion resistance by potentio dynamic polarization tests. It is shown that electron beam welds exhibit superior mechanical and corrosion properties. The weld metals have been characterized by scanning electron microscopy; transmission electron microscopy and electron probe micro analysis. Presence of partially disintegrated precipitates in the weld metal, finer micro porosity and uniform distribution of copper in the matrix were found to be the reasons for superior properties of electron beam welds apart from the fine equiaxed grain structure. Transmission electron micrographs of the heat affected zones revealed the precipitate disintegration and over aging in gas tungsten arc welds.     

Surface modification of mild steel with Boron Carbide reinforcement by electron beam melting

We investigated the effect of surface hardening and micro-structural modifications in Mild steel (MS) with the addition of Boron Carbide, melted by thermionic electron beam. Boron Carbide in the form of powder was added by making grooves in MS samples to trap the molten solution for interaction with solid particles. These samples were irradiated by 10 KeV electron beam with variable beam current (50-100 mA). XRD confirmed the addition of Boron Carbide in the matrix and SEM indicated micro-structural changes introduced by the electron beam. Micro-structural modification further revealed that ferrites have been transformed into dendrites and pearlites have been refined as a result of re-solidified melt. This significantly has enhanced the surface hardness greater than 6-times compared to as received Mild steal.     

Refining of metallurgical silicon by directional solidification

The directional solidification of a typical and a previously refined metallurgical silicon was carried out in a vertical Bridgman furnace. The mold velocity out of the hot zone of the furnace changed from one experiment to another in the range between 5 and 110 μm s⁻¹. Samples were extracted from the cylindrical ingots obtained in the experiments to investigate the effects of the mold velocity on the micro and macrostructures and on the concentration profiles of impurities along the ingots. At the lowest mold velocity, the macrostructures consist of columnar grains oriented approximately parallel to the ingot axis. As velocity increases, grains become thinner and more inclined in the radial direction. Precipitated particles containing Si, Fe, Al, and Ti are observed at the top of all ingots and, as the mold velocity increases, they are also seen at the ingot bottom and middle. The concentration profiles of several impurities have been measured along the ingots by inductively coupled plasma atomic emission spectrometry (ICP), indicating an accumulation of impurities at the ingot top. Consequently, the bottom and middle of the ingots are purer than the corresponding metallurgical silicon from which they solidified. Slices from the ingot bottom have also been analyzed by the glow discharge mass spectrometry technique (GDMS), allowing measurement of impurity concentrations that were below the quantification limit of the ICP. The purification effect and the accumulation of impurities at the ingot top are more pronounced as the mold velocity decreases. In the ingots obtained from the typical metallurgical silicon at the lowest mold velocities (5 and 10 μm s⁻¹), except for Al, all impurities are in concentrations below an important maximum limit for the feedstock of solar grade silicon. At the same mold velocities, the concentrations of Fe, Ti, Cu, Mn, and Ni measured at the bottom of the ingots obtained from both types of metallurgical silicon (typical and previously refined) are even below some limits suggested directly for solar grade silicon.     

Microstructure and mechanical properties of nickel based superalloy IN718 produced by rapid prototyping with electron beam melting (EBM)

Abstract

A nickel alloy of a composition similar to that of the nickel based superalloy Inconel alloy 718 (IN718) was produced with the electron beam melting (EBM) process developed by Arcam AB. The microstructures of the as processed and heat treated material are similar to that of conventionally produced IN718, except that the EBM material showed some porosity and the δ phase did not dissolve during the solution heat treatment because the temperature of 1000°C apparently was too low. Mechanical testing of the layer structured material, parallel and perpendicular to the built layers, revealed sufficient strength in both directions. However, it showed only limited elongation when tested perpendicular to the built layers due to local agglomerations of pores. Otherwise, data for the hardness, Young’s modulus, 0·2% yield tensile strength and ultimate tensile strength match those recommended for IN718.     

Electron beam surface treatment. Part II: microstructure evolution of stainless steel and aluminum alloy during electron beam rapid solidification

Surface rapid solidification microstructures of AISI 321 austenitic stainless steel and 2024 aluminum alloy have been investigated by electron beam remelting process and optical microscopy observation. It is indicated that the morphologies of the melted layer of both stainless steel and aluminum alloy change dramatically compared to the original materials. Also, the microstructures were greatly refined after the electron beam irradiation.     

超高真空电子束蒸发在多孔硅上外延单晶硅

采用超高越空电子束蒸发的方法在用阳极氧化制备的多孔硅衬底上外延单晶硅,研究了不同多孔硅衬底对外延质量的影响。采用高能电子衍射表征外延层的晶体结构,截面透射电镜上材料的微结构,原子力镜表征外延层表面的粗糙度,卢瑟福背散射／沟道表征外延层晶体质量,扩展电阻表征材料的电学性能。一系列的测试结果表明对在5mA／cm^2电流密度下阳极氧化10min形成的多孔硅衬底,可用超高真空电子束蒸发的方法外延出质量良好的单晶硅。     

电子束熔炼冶金级硅中杂质钙的蒸发行为

通过双枪电子束熔炼炉熔炼冶金级硅,主要研究了在一定熔炼功率不同熔炼时间下,杂质Ca含量的变化及其蒸发行为,讨论了杂质Ca含量与Si剩余率的关系。实验结果表明,熔炼初期杂质Ca含量显著降低,随着熔炼时间的延长,下降趋势逐渐减缓。在硅熔体表面2133K温度下,杂质Ca的自由蒸发反应遵循一级反应速率方程。杂质Ca的总传质系数为2.64×10-5m/s,并且杂质Ca从熔体内部迁移到硅熔体/气相界面层是其蒸发过程的速率控制步骤。     

电子束熔炼多晶硅对杂质铝去除机制研究

采用电子束熔炼方式,利用铝的蒸发系数较大的特点通过蒸发去除硅中的杂质铝。将实验的实测值与理论计算的蒸发量、损失量等加以比较,得到了铝在电子束下的蒸发去除速率由其在硅中扩散过程所决定的结论,并对铝的去除量与硅的损失量之间关系进行分析。     

Growth of silicon nanowires by electron beam evaporation using indium catalyst

For the first time silicon nanowires have been grown on indium (In) coated Si (100) substrates using e-beam evaporation at a low substrate temperature of 300 °C. Standard spectroscopic and microscopic techniques have been employed for the structural, morphological and compositional properties of as grown Si nanowires. The as grown Si nanowires have randomly oriented with an average length of 600 nm for a deposition time of 15 min. As grown Si nanowires have shown indium nanoparticle (capped) on top of it confirming the Vapor Liquid Solid (VLS) growth mechanism. Transmission Electron Microscope (TEM) measurements have revealed pure and single crystalline nature of Si nanowires. The obtained results have indicated good progress towards finding alternative catalyst to gold for the synthesis of Si nanowires.     

熔析结晶法提纯硅工艺研究进展

随着光伏产业的快速发展,对太阳能级硅原材料的需求不断增加。熔析结晶法作为一种冶金硅提纯的新工艺越来越受到重视。熔析结晶法是利用冶金硅中杂质元素的偏析行为,选择适当的熔析介质,使杂质元素从冶金硅中偏析到熔析介质中,进而获得高纯硅的方法。详细介绍了Al-Si、Sn-Si、Cu-Si、Fe-Si和Ca-Si等熔析体系对冶金硅提纯的研究现状,比较了各种介质体系的优缺点。同时针对熔析结晶法提纯硅存在的问题提出了一些建议。     

Control of the electron beam active zone position in electron beam welding processes

It is known that charged particles emitted from the region of electron beam (EB) interaction with the material being processed, are an important source of information for the understanding of EB welding processes. Measurements for the three largest groups of charged particles, namely, backscattered electrons, true secondary electrons and ions are presented here. It was estimated that only the signals of the direct component amplitude of these particles’ currents, processed by neural networks, could be used to effectively control the EB welding process. Computer simulations of various models of neural networks are described. The best result was obtained for a network that determines an optimal value of focusing current for the weld being made, based on the amplitude of signals measured with a moderately defocused EB.