电子束真空精炼直接定向凝固制备高纯铜的研究

以电子束真空熔炼直接定向凝固技术制备5N高纯铜大铸锭为研究目标,利用电子束熔炼原材料,熔体直接定向凝固后得到高纯铜铸锭.采用GDMS-VG9000辉光放电质谱仪和TCH600氧氢分析仪研究了金属杂质及氧氢元素的去除效果,通过EPMA-1600电子探针研究了提纯后元素的分布情况.结果表明:真空电子束熔炼直接定向凝固技术可将原料为4N(99.9988711％)的电解阴极铜板,制备出纯度5N(99.9997235％)、Φ59 mm大尺寸高纯铜铸锭,杂质元素总量降低了75.506％,中间凝固组织为单晶;五种含量较高的元素Ag、Cu、O、P和S均匀分布,没有出现杂质的偏聚现象;与原材料相比,0、H元素分别降低了86.47％,85.00％.研究表明真空电子束精炼直接定向凝固技术能够制备氧氢含量较低的5N大尺寸高纯铜铸锭.     

多晶硅定向凝固温度场模拟的研究进展

对多晶硅太阳能电池而言,决定其光电转化效率的铸锭晶粒尺寸、晶体缺陷、内应力及杂质的形成与分布等与定向凝固过程的温度场密切相关。因此,为提高多晶硅锭质量必须控制和优化定向凝固过程的温度场。运用数值模拟技术对多晶硅定向凝固温度场进行分析,已被国内外学者广泛应用,获得了有参考价值的模拟结果。结合自身工作,综合分析了多晶硅铸锭缺陷与温度场的关系,总结了多晶硅定向凝固数值模拟中,热导率、加热功率、氩气流动状态、外加磁场及定向凝固系统结构等对温度场的影响,可为多晶硅铸锭的制备及质量改进提供参考。     

定向凝固结合电子束制备高纯铜的研究

对定向凝固结合电子束制备5N高纯铜进行了研究。首先采用真空感应熔炼4N(99.99%)阴极铜并进行定向凝固实验,然后利用电子束对定向凝固后的铸锭进行重熔精炼,利用辉光放电质谱仪进行成分分析。实验结果表明:真空熔炼可以有效去除铜中饱和蒸气压高的杂质;通过定向凝固,杂质元素含量沿铸锭轴向逐渐升高;经过组合工艺提纯后,总杂质含量由13.6×10-6降低至4.0×10-6,铜的纯度提高至99.9996%。     

定向凝固法多晶硅杂质控制数值模拟概述

在传统能源日渐消耗及可再生能源开发利用日趋受到重视的形势下,太阳能光伏发电逐渐成为最具潜力的可再生能源技术之一。多晶硅凭借高效率、低成本的优势成为最主要的光伏材料,其铸锭的品质和成本将直接影响太阳能电池的成本和光电转换效率。定向凝固法是制备多晶硅铸锭的重要方法,该方法晶硅生长过程中存在很多问题,包括熔体流动、杂质传输、固液界面的形状和结构以及缺陷。定向凝固过程中引入的有害杂质严重影响晶硅的机械和电学性能,是限制多晶硅光电转换效率的关键因素。长晶过程中定向凝固炉处于高温环境中,内部的传热传质极其复杂,不具备单一的线性关系和可推断性,且难于进行实验测量,因而数值模拟是研究定向凝固过程中传热传质现象的重要方式。降低长晶过程中杂质的含量可从两方面入手:(1)杂质的来源——原材料本身所携带的杂质和长晶过程中生成的杂质;(2)杂质的输运——找到杂质在熔体和氩气中的输运规律,并利用该规律控制杂质的分凝与输运。近年来,从控制杂质产生和输运的角度考虑,国内外对降低多晶硅中有害杂质的研究主要采用以下手段:(1)控制杂质产生,包括减缓坩埚与挡板之间的化学反应、优化顶部坩埚盖板、增设碳化硅涂层等;(2)优化氩气流动,例如使用导流系统、调整炉膛压力和氩气流量;(3)优化熔体对流形式,包括控制熔体流动方式及分凝、调整加热器功率大小及其排布、采用可旋转坩埚和调整石墨碳毡位置等。为进一步降低定向凝固法多晶硅铸锭成本,坩埚尺寸和投料量不断增大,熔体对流、杂质输运和界面形状也更加难于控制,外加磁场则成为控制熔体对流的一种强有力工具,并能进一步控制杂质输运。目前利用外加磁场控制定向凝固法多晶硅杂质的研究仍刚刚起步,具有很大的研究价值,其中电磁场(EMF)和行波磁场(TMF)在控制搅拌熔体对流方面具有巨大潜力,逐渐被用于多晶硅长晶过程。本文在深入分析杂质来源和输运机理的基础上,综述了国内外对多晶硅定向凝固过程中有害杂质的产生、分布、输运以及排出等问题的研究现状,总结了数值模拟中氩气导流系统、加热器以及外加磁场等因素对杂质的影响。     

高Nb-TiAl合金定向凝固组织的研究EI北大核心

运用区域熔炼定向凝固炉对名义成分为Ti-45Al-8.5Nb-(W,B,Y)(原子分数/%)等离子熔炼铸态合金进行了抽拉速率分别为5,8,10,15,20,30μm/s的定向凝固实验。结果发现:定向凝固后的试棒组织形成四个明显的区段,铸态组织区、定向退火区、熔融结晶区与定向生长区;抽拉速率为5μm/s时,沿拉伸方向生长的柱状晶明显,其内部片层方向与柱状晶生长方向近似成0°,45°或90°夹角关系,随着抽拉速率的增加,柱状晶变细窄;典型组织的BSE图显示,定向凝固能消除普通铸锭冶金过程中的α,β偏析,其组织中无B2相产生,当抽拉速率达到或超过8μm/s时,β相枝晶晶界附近形成了拉长的胞状铝偏析,柱状晶晶界附近有富Ti,Nb,W的析出物出现。     

铸造多晶硅的制备与研究

当今多晶硅已成为最主要的光伏材料,利用定向凝固工艺生产铸造多晶硅铸锭已成为业界广为采用的方法,但目前利用定向凝固工艺生产出来的多晶硅铸锭仍存在较多的缺陷,例如材料利用率低以及组织不均匀等问题.为了进一步优化铸造工艺,采用自行设计的真空电磁感应熔炼炉及定向凝固炉进行了多晶硅定向凝固实验.重点对比研究了石英坩埚和石英陶瓷坩...     

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%.     

6.5%Si高硅钢铸锭凝固组织的CAFE法模拟研究

应用CAFE法对6.5%Si高硅钢铸锭凝固组织进行了模拟研究,确定出了适合高硅钢组织模拟的模型。进一步用该模型研究了过热度及冷却条件对凝固组织的影响,结果表明,随着过热度的降低,凝固组织中柱状晶比例和晶粒平均面积均减小。水冷条件下,高硅钢铸锭凝固组织几乎全是柱状晶,而且晶粒粗大。空冷条件下,等轴晶区扩大,但柱状晶仍占主要部分。缓冷条件下,等轴晶区占主要部分,晶粒平均面积和空冷条件下相当。     

多晶硅铸锭新工艺的研究

多晶硅定向凝固铸锭技术是多晶硅太阳能电池生产的关键技术之一。本文提出多晶硅铸锭新技术-（SRS）法,与传统工艺相比,SRS工艺提纯效果更明显,硅锭中间部分杂质含量更低,硅锭的少子寿命和电阻率更高且分布均匀,大大提高了硅料从硅锭到硅片的利用率。     

高性能轴承钢真空自耗熔炼过程组织演变规律与控制研究

通过Pro-CAST有限元软件模拟了高性能轴承钢真空自耗熔炼过程的温度场、熔池形貌和微观组织,研究了真空自耗铸锭组织演变规律,探究了温度场、熔池形貌对组织生长的影响。熔炼结束后,对真空自耗铸锭进行解剖酸洗以验证模拟结果。研究表明:模拟结果与实验结果吻合,铸锭组织形貌为贯穿铸锭中心的细长柱状晶,真空自耗铸锭的底部、边部和凝固末端有小面积等轴晶。柱状晶的生长带有明显的择优取向,底部柱状晶取向为垂直向上,中上部为斜向上。熔池深度越大,斜向上角度越小;熔池形貌对铸锭组织形貌影响显著,通过控制熔炼参数控制好熔池形貌能有效提高铸锭质量。     

Purifying multicrystalline silicon by directional solidification method with induced electromagnetic field

Abstract

As an improved directional solidification (DS) method, the complex directional solidification (CDS) method is used for purifying and preparing multicrystalline silicon ingot in this experiment. The induced electromagnetic field is imposed to control refining and solidification process. An integral silicon ingot with the diameter of 130 mm, the length of 130 mm and the weight of 4 kg is successfully fabricated in a self-designed CDS furnace. Metallographic analyses reveal that the direction of the most grains is parallel to the axial of silicon ingot. Analyses proved that the distribution of impurities in the cross-section is more homogeneously, the distribution in axial is improved and the effective length of silicon ingot is increased. Theoretical calculations indicate that the effect of solidified rate on the removal of impurities is limited and the impurities can be removed effectively after more than two times directional solidification process.     

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.     

Effect of cooling rate on solidification of electron beam melted silicon ingots

Solidification rate has a significant influence on purification of silicon due to segregation of impurities at a liquid–solid interface of a solidifying silicon ingot. A mathematical model is developed to evaluate time-dependent position of the liquid–solid interface and solidification rate of electron beam melted ingots. A series of solidification experiments with different cooling rates are conducted to measure position of a line which separates directionally grown columnar crystals visible in cross-sections of the solidified ingots. Results show that not the whole ingot solidifies directionally when the reduction rate of the beam current is larger than 1.67 mA/s. The position of the dividing line depends on cooling rate and the experimental trend is consistent with that resulted from theoretical simulations. Modeling shows that the solidification rate changes fast when the beam current reduces linearly that is detrimental for segregation of impurities. It also predicts that an exponential reduction of the beam current leads to a uniform solidification rate which is beneficial to segregation of impurities, though not all exponential current reductions lead to this kind of solidification behavior.     

Silicon purity controlled under electromagnetic levitation (SPYCE): influences on undercooling

The rapid evolution of photovoltaic Si production induced a shortage of high purity silicon raw material. The use of lowest purity silicon has a strong effect on the casting conditions and ingot structure and properties. During solidification, solute rejection at the growth interface leads to an increase of the impurities concentration in the liquid phase and then to the precipitation of silicon nitride and silicon carbide. As a consequence, the grain structure of the ingot changes from columnar to small grains, also known as grits. A new electromagnetic levitation setup which has been developed in order to measure the undercooling versus impurity concentration is presented. The impurity concentration in the levitated Si drop is controlled by the partial pressure of nitrogen or hydrocarbon gas. As nucleation is a random phenomenon, statistical measurements are presented, from samples which showed numerous heating/melting and cooling/solidification phases. The effect of carbon impurities on the undercooling of silicon droplet is discussed.     

太阳能用晶体硅铸锭制备技术

在过去20年中,光伏市场以惊人的速度增长,光伏发电逐步成为世界能源发电的主要来源之一。2016年全球新增装机量超过75GW,较2015年增长34%,其中,又以晶体硅太阳能电池为主,占整个光伏市场的90%以上,而多晶硅又占据了整个晶体硅太阳能电池的70%以上。相比于直拉单晶硅,定向凝固铸造法生产的晶体硅材料具有更好的性价比,但含有较多的杂质、位错等晶体缺陷。更高品质、更低成本的太阳能电池始终是业界追寻的目标。本文以传统铸造法生长多晶硅技术为基础,介绍了目前几种主流的晶体硅铸造工艺方法,包括全熔工艺制备多晶硅锭,半熔工艺生长高效多晶硅锭,以及铸造法制备大尺寸单晶硅锭。另外,本文还从硅锭外观和性能等方面阐述了铸造法晶体硅的发展方向。文中数据部分为笔者进行的实验论证,部分为其他文献的研究成果,希望能为现阶段太阳能晶体硅的生产和研究工作提供参考。     

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).     

A model for distribution of aluminum in silicon refined by vacuum directional solidification

We propose a simple numerical model for distribution of Aluminum (Al) in silicon ingot during vacuum directional solidification, including segregation from silicon crystal to silicon melt as well as evaporation from silicon melt to vacuum atmosphere. According to the model, the effective segregation K_eff and the total evaporation coefficient k_T(Al)of Al under the experimental conditions are 0.0137 and 2.6755 × 10⁻⁶ m·s⁻¹, respectively. In comparison with experimental results, the segregation of Al is dominated at the beginning of solidification, whereas at the last stage of solidification the removal of Al is mainly depended on the evaporation. It is also found that the critical influences on aluminum removal during vacuum directional solidification are temperature and solidification rate.     

铸造多晶硅制备技术的研究进展

近年来,由于低成本、低耗能和少污染的优势,铸造多晶硅成为主要的光伏材料之一,越来越受到人们的广泛关注.系统论述了太阳能级多晶硅制备技术的研究进展,重点介绍了目前铸造多晶硅制备技术,如浇注法(Ingot casting)、定向凝固法及电磁感应加热连续铸造法(EMCP).另外,着重阐述了铸造多晶硅中磷和硼的提纯、多晶硅晶粒组织中晶界和位错的形成与控制以及定向凝固的数值模拟技术,讨论了铸造多晶硅材料的研究现状和存在的问题,展望了今后的发展方向.     

电子束束流密度对冶金硅中杂质磷的影响

采用电子束设备对多晶硅进行熔炼,设计熔炼功率和时间相同、降束时间不同的三组实验,评价硅中杂质磷在熔炼及凝固过程中的去除效果。根据熔炼后硅锭的杂质分布特点推导出表征硅中杂质磷的去除率公式,经计算得到去除率为80%以上,并由磷的蒸发方程计算出在本实验中当电子束熔炼多晶硅锭的束流密度在235mA之上时,硅中的磷都可以被蒸发去除。