Dissolution behaviors of rare earth elements in phosphoric acid solutions

In order to provide practical fundamental data for rare-earth elements (REEs) recovery from phosphoric acid and to better understand REEs behavior during the phosphoric acid evaporation process, the solubilities of REEs in phosphoric acid with various concentrations of phosphorus at different temperatures were measured. A simple linear model between REEs solubility and phosphoric acid concentration is built and the experimental data are found to fit it very well (R²>0.94). Hydrogen-ion concentration is found to be the predominant factor controlling the solubility of REEs in phosphoric acid. In addition, the solubility of REEs in phosphoric acid is found to sharply decrease with increasing temperature, which can be attributed to the increase of the Gibbs energy of the REEPO₄ dissolution reaction or the restraint of the disassociation of phosphoric acid molecules owing to the elevated temperature.     

稀土La和Y在FeCrAl合金中的存在形式

采用真空感应熔炼的方法制备了稀土质量分数为0.15%的FeCr20Al5-La和FeCr20Al5-Y合金, 经由锻造、热轧、冷轧等工序, 最终制得厚度为60μm的合金箔材, 通过TEM和EDAX能谱分析方法研究了稀土元素在合金中的存在形式. 实验结果表明 制备的FeCrAl-RE合金中稀土La主要以单质La和少量固溶的形式存在, 稀土Y则主要有Fe23Y6、单质Y和少量固溶等存在形式.     

Analysis of rare earth elements in high purity europium oxide

Five trace impurities as Ce, Pr, Sm, Gd, and Dy are separated from europium oxide with P507 extraction resin by extraction chromatography. When determined simultaneously by ICP-AES, the impurities show their recovery ratios between 88% and 105%. A lower than 10% relative standard deviation of these elements is obtained when their contents in europium oxide are 5μg/g. The satisfactory results indicate this simple method is sensitive and accurate. It has been employed in the analysis of these five rare earth elements in 99.99% europium oxide.     

稀土系贮氢合金中14种主量元素配分量的测定-X射线荧光光谱法

通过各元素谱线的选择、滤纸片以及测定方法的优化,建立各元素工作曲线。用滤纸片X射线荧光光谱法实现稀土系贮氢合金合金样品中镁、铝、锰、铁、钴、镍、铜、锌、镧、铈、镨、钕、钐、钇14种主量元素配分量的快速测定。点滴方法采用塑料环托法滴加0.1ML,滤纸选择慢速滤纸,溶液总浓度选择40mg/mL,测定方法为样片上覆锡片。对同一样品制备11个样片后测定的14种主量元素配分量的相对标准偏差均在2%以下。回收率为92%~106%。该方法具有较好的精密度和准确性,可用于稀土系贮氢合金中14种主量元素配分量快速测定。     

稀土镧钕对Ti15Cu15Ni钎料硬度及TC4接头抗剪强度的影响

在Ti15Cu15Ni钎料合金基础上添加微量稀土镧钕,以应用普遍的TC4为母材,研究稀土镧钕添加量对钎料合金及钎焊接头性能的影响.结果表明,稀土相分布于α-Ti及金属间化合物的相界,阻碍位错运动,使钎料硬度增加,在稀土含量为1%时达到最大40HRC.稀土镧钕对Ti15Cu15Ni抗剪强度具有较大影响,稀土含量小于0.5%时,抗剪强度随稀土含量增加而增加;稀土含量大于0.5%时,随着稀土含量增加,钎料合金抗剪强度呈下降趋势.当稀土含量等于0.5%时,抗剪强度达到最大为244.55 MPa.     

稀土填充热电材料Bi2Sb3Cex, Bi2Sb3Ndx的制备及电性能研究

在尿素-NaBr-KBr-甲酰胺体系中用脉冲电沉积的方法制备Bi2Sb3Cex及Bi2Sb3Ndx合金薄膜。通过X射线能谱(EDS)及X射线衍射(XRD)分别确定其化学成分、分析其晶型结构。在最佳工艺条件下,稀土元素达到最大填充量,合金薄膜的组成为Bi2Sb3Ce2及Bi2Sb3Nd0.1。合金薄膜是由斜方六面体BiSb和四面立方结构的单质Ce、Nd组成。探索了不同稀土填充的Bi-Sb半导体热电材料的电学性能。     

稀土与碳氮原子共渗及其微合金化创新理论

根据作者的研究成果,在经典化学热处理理论基础上把固体物理学新成就中的缺陷理论与扩散理论及析出相固溶析出理论和晶粒细化超细化理论相融合,首次提出了以稀土、间隙碳、氮原子Cottrell气团为核心的稀土化学热处理创新理论,在该领域开创出一种全新的扩散模式。创建了钢中新的稀土渗碳、稀土渗氮及稀土氮碳共渗工艺体系。新体系不仅显著提高了扩散速度,同时又能显著改善微观组织和大幅度提高使用性能,使齿轮类零件的使用寿命显著提高。     

Effect of rare earth (Ce, La) compounds in the electroless bath on the plating rate, bath stability and microstructure of the nickel-phosphorus deposits

Effects of added rare earth elements (RE) in the acidic hypophosphite plating bath on the plating rate, bath stability and microstructure of the electroless nickel-phosphorus (EN) deposits were studied. The surface appearance and microstructure were examined under a reflection optical microscope and a scanning electron microscope equipped with an in-situ energy dispersive X-ray spectroscopy, which can evaluate the elemental analysis of deposits. It was demonstrated that the rare earth elements can decrease grain size and refine microstructure.The deposition rate of the Ni-P deposits was estimated by gravimetric, polarization and quartz crystal microbalance (QCM) methods. Results revealed that up to an optimum concentration of rare earth elements, the deposition rate increases. The stability test method was used to determine the stabilization effect of RE on the stability of the bath. It was found that the addition of RE significantly improved the Pd stability of the EN bath.     

稀土材料La—Ba—（Mn,Fe）—O的磁电输运特性探讨

研究制备了Ｌａ０．６７Ｂａ０．３３Ｍｎ１－ｘＦｅｘＯ３（ｘ＝０,０．０５,０．１）材料。结果表明：铁替换锰降低了材料的饱和磁化强度及居里温度,主要是因为Ｆｅ离子不参加双交换作用,同时Ｍｎ＾３＋－Ｏ＾３－Ｍｎ＾４＋的作用对随铁离子替代Ｍｎ＾３＋而数量减少,材料的铁磁作用随之减弱。铁替换降低了金属－半导体转换峰温度,相应提高了材料的零场电阻值。值得注意的是铁掺杂提高了大磁阻材料Ｌａ０．６７Ｂａ０．３３Ｍｎ１－ｘＦｅｘＯ３的低温性能,５Ｋ下磁阻比「Ｒ（６Ｔ）－Ｒ（０）」Ｒ（０）从ｘ＝０时的－４０％增加到ｘ＝０．１时的－６０％。本文同时利用迪尼模型对材料大磁阻效应进行了计算分析,发现理论计算曲线可以较好的反映实验上出现的金属－半导体转换峰现象,同时负的大磁阻效应现象也可从理论计算上得到证实。     

Thermal decomposition products of heteronuclear Cu---Re complexes, CuRE(dhbaen)(NO3)·nH2O (RE---La, Eu, Gd, Tb, Dy, Y, Ho, Er, Tm, Yb, and Lu)

To facilitate the preparation of finer and more homogeneous CuREO_x and to achieve a lowering of the formation temperature, heteronuclear CuRE(1:1) complexes, CuRE(dhbaen)(NO₃)·nH₂O were synthesized as precursor. As it was expected for RE=La through Gd, only a mixture of CuO and CuRE₂O₄ was formed even when the complex decomposed at 800 °C since the Cu/RE ratio is 1. For RE=Y and Tb through Lu, Cu₂RE₂O₅ was formed by way of CuO and RE₂O₃. The structure of the decomposed product is controlled by the coordination number and ionic size of RE ion. The minimum radius ratio for eightfold coordination of RE³⁺ ion suggests that preparation of homogeneous Cu:RE(1:1) oxide with Cu₂Ho₂O₅ type structure is difficult for RE=La through Gd.     

青海德合龙洼铜(金)矿成矿物质来源

德合龙洼铜(金)矿床为青藏高原北东端的一个岩浆热液型矿床,成矿作用主要划分为岩浆热液成矿期,包含石英-黄铜矿和毒砂两个成矿阶段。在分析该矿床成矿地质条件的基础上,系统地研究了矿区矿石硫、铅同位素组成,流体包裹体以及稀土元素特征,探讨了成矿物质来源。研究表明:矿区矿石硫样品δ34(SCDT)值分布范围较宽(-3.08×10-3～7.00×10-3),具有岩浆硫性质,可能来源于矿区侵入的中酸性岩体。各类型矿石铅同位素组成稳定,显示正常铅的特征,U和Th放射性成因铅含量较低。对各类型矿石铅同位素进行特征参数示踪、铅构造模式示踪和-β—-γ图解示踪的结果表明:矿区矿石铅主要为地壳与地幔混合的俯冲铅,主要来源于俯冲造山背景下形成的岩浆侵入体。流体包裹体及稀土元素地球化学特征均表明矿区成矿物质可能主要来源于岩浆侵入体,少许成矿物质可能来源于周围地层。总结矿区矿石硫、铅同位素、流体包裹体以及稀土元素分析结果,表明成矿物质主要来源于深部岩浆,这种岩浆的形成可能与板片俯冲造山有关,地壳与地幔组分均可提供成矿物质来源。     

凝胶-燃烧法合成(Y,Gd)Al3(BO3)4:Tb3+荧光材料的结构及其发光性能

采用凝胶-燃烧法合成掺Tb3+和Gd3+的四硼酸铝钇(Y,Gd)Al3(BO3)4:Tb3+荧光粉.分别采用X射线衍射仪(XRD)、扫描电镜(SEM)、发光光谱等测试手段分析不同温度下煅烧所得粉体的物相、形貌与发光性质.XRD和SEM结果表明:(Y,Gd)Al3(BO3)4:Tb3+的最低合成温度为1000 ℃,在该反应过程中,首先形成中间相Al4B2O9、YBO3和Y3Al5O12,而最终形成单相的(Y,Gd)Al3(BO3)4:Tb3+.随煅烧温度的升高,样品结晶程度越来越好,并且颗粒尺寸随温度的升高而增大,在1100 ℃时合成的晶粒尺寸比较均匀,平均粒径在1 μm左右.发光光谱的测试结果表明:在229 nm激发下,(Y,Gd)Al3(BO3)4: Tb3+荧光粉最强发射峰位于542 nm处,属于Tb3+的5D4→7F5的跃迁.在该体系中存在Gd3+→Tb3+的能量传递,使得该荧光粉的发光强度随着Gd3+掺杂浓度的增加而增大.     

微乳液法制备（Y,Gd）2O3：Eu^3＋纳米粒子及光谱特性

采用反相微乳液法制备(Y,Gd)2O3:Eu3 纳米粉体.通过XRD、TG/DSC、SEM、TEM、PL等手段分别对样品的晶化过程、晶粒尺寸、粉体形貌以及发光性能进行分析.结果表明:晶粒尺寸随着晶化温度提高而增加,样品在800℃晶化完全.当乳液浓度为0.37 mol/L时所得粉体颗粒呈近似球形,一次粒径尺寸约20 am.样品在612nm监控光下得到的激发光谱是宽带谱,对应着Eu3 -O2-的电荷迁移带跃迁.发射光谱的特征峰位于612nm处,是由于Eu3 离子的5D0-7F2跃迁造成的.当Eu的原子分数大于10%时发生浓度猝火,导致特征峰强度降低.     

稀土La在纳米晶（W, Ni, Fe, La）复合粉末烧结过程中的作用机理

采用溶胶-喷雾干燥法制备纳米晶(W,Ni,Fe,La)复合粉末,研究了粉末在烧结过程中La对抑制鼓泡和晶粒长大的作用机理,通过XRD与SEM分析了La在烧结过程中的相转变规律和在合金中的存在形式,讨论了稀土La对合金液相烧结过程中扩散的影响。结果表明:稀土La在纳米复合粉末中主要以La2WO6与La4W2O15的形式存在。经液相烧结后,稀土La主要以二次相颗粒的形式分布于粘结相中,生成高温下能稳定存在的La4W2O15相,该相对杂质元素Ca、O具有很好的亲和力,起到晶界净化和晶内净化的作用。同时二次相颗粒存在于粘结相中,抑制了W在粘结相中的扩散,降低了W在粘结相中的溶解度,使得液相烧结溶解-析出过程减慢,从而抑制液相烧结阶段的晶粒长大和鼓泡现象。     

Synergism between protocatechualdehyde and rare earth cerium(IV) ion on the corrosion of cold rolled steel in hydrochloric acid solution

The synergism between protocatechualdehyde (PAL, 3,4‐dihydroxy‐benzaldehye) and rare earth cerium(IV) ion (Ce⁴⁺) on the corrosion of cold rolled steel (CRS) in 1.0 M hydrochloric acid (HCl) solution has been investigated by weight loss and potentiodynamic polarization methods. The results reveal that PAL has a moderate inhibitive effect, while Ce⁴⁺ has a poor effect. Incorporation of PAL with Ce⁴⁺ improves the inhibition performance significantly, and exhibits synergistic inhibition effect. The adsorption of individual PAL obeys the Temkin adsorption isotherm, and the adsorption of the complex of PAL and Ce⁴⁺ accords with the Temkin adsorption isotherm too. The thermodynamic parameters of adsorption heat (ΔH⁰), adsorption free energy (ΔG⁰), and adsorption entropy (ΔS⁰) are calculated and discussed. Polarization curves show that individual PAL acts as a mixed‐type inhibitor, while Ce⁴⁺ slightly inhibits the corrosion reaction. The complex of PAL and Ce⁴⁺ acts as a mixed‐type inhibitor, which drastically inhibits both anodic and cathodic reactions. Depending on the results, the synergism mechanism is proposed from the viewpoint of adsorption theory.     

Corrosion behaviour in salt spray and in 3.5% NaCl solution saturated with Mg(OH)2 of as-cast and solution heat-treated binary Mg–RE alloys: RE = Ce,La, Nd,Y, Gd

Corrosion behaviour was characterised in salt spray and in 3.5% NaCl solution saturated with Mg(OH)₂ of as-cast and solution heat-treated binary Mg–RE alloys. The corrosion rate in the immersion test for the solution heat-treated Mg–RE alloys was substantial, and was greater than that of high-purity Mg. These corrosion rates were probably caused by the particles in the microstructure and/or by Fe rich particles precipitated during the solution heat-treatment. The corrosion rate in the immersion tests for each as-cast Mg–RE alloy was greater than that of high-purity Mg, attributed to micro-galvanic acceleration caused by the second phase. Corrosion rates in salt spray had a general correlation with corrosion rates in the immersion tests, but there were differences. The values of apparent valence were always less than 2 consistent with Mg corrosion being only partly under electrochemical control.     

Effect of deposition processes on residual stress profiles along the thickness in (Ti,Al)N films

The effect of deposition processes on the distribution of residual stresses in the thickness of the (Ti,Al)N films prepared by arc ion plating (AIP) was investigated in the present work, which indicates that the stress distribution exhibits a “bell” shape and the maximum compressive stress appears in the layer near the surface. The residual stress increases with the thickness of a film and the substrate bias voltage, respectively. The stress distribution can be altered, and the adhesion of the film/substrate can be improved by optimizing the deposition parameters. Finally, a film with a thickness of 7.57 μm was successfully directly deposited on the substrate through optimizing the bias voltage.     

我国等温淬火球铁(ADI)生产应用及发展前景

概述了我国等温淬火球铁的生产应用情况,指出我国等淬球铁主要用于三个方面:1)普通抗磨零件,如磨球、衬板、锤头、锤片等;2)承载构件,如斜楔、销套、小型柴油机曲轴等;3)高性能、高精度要求的重要构件,如多缸柴油机曲轴和各类齿轮等。分析了我国等淬球铁扩大应用和工业化生产发展缓慢的主要原因是:1)对等淬球铁的优异性能宣传不够,没有相应的标准提供给设计者;2)大部分球墨铸铁生产厂不能稳定地提供符合等淬球铁要求的球铁铸件;3)缺乏专业的等淬球铁热处理厂和性能先进、稳定的等淬热处理装备。预测了我国等淬球铁的发展前景并对今后工作提出了建议。