熔盐电解精炼铪

用含铪50％左右的熔炼喷溅物制铪氟酸钾电解质,对废铪料进行电解精炼。介绍了半封闭、半连续生产的电解槽。获得的铪粉经电子束提纯,可得符合原子能级标准的铪锭。     

熔盐电解精炼锆的工艺研究

研究了不同配比的NaCl-K2ZrF6熔盐体系的熔点,K2ZrF6:NaCl=3:7的熔点较低为721℃.在此基础上,研究了熔盐配比、阴极电流密度、电解温度等因素对NaCl-K2ZrF6熔盐体系电解精炼电流效率的影响,结果表明阴极电流密度、电解温度均与电流效率成反比.采用XRD及元素含量分析等方法研究了电解精炼产品质量.较佳的工艺条件为K2ZrF6:NaCl为3:7(%,质量分数),温度800℃,阴极电流密度1 A·cm-2,在此条件下,电流效率可达84%以上.阴极锆为合格的工业级锫产品,产品中Fe,Ni,Cr,Mn等杂质分别由2700×10-6,540×10-6,350×10-6,400×10-6降低到30×10-6,10×10-6,18 ×10-6,100×10-6以下,产品纯度达到99%以上.     

粗铋熔盐阳极电解精炼新工艺研究

本文提出了二段电解方案。按此方案在氯化物熔盐电解质中，于３００－５００℃用阳极电解精炼的方法，可将粗铋中的铅、银、锌含量降至一级精铋的要求，同时获得商品铅，金属回收率高。     

熔盐电解精炼金属镧的研究

研究了LiF-LaF3体系下,以La-Ni合金和La金属作可溶性阳极,以Ta为阴极,熔盐电解精炼镧过程中不同工艺条件对槽电压、沉积物形貌、产物杂质含量的影响。采用扫描电镜(SEM)对电解精炼所得La沉积物形貌进行观察,采用电感耦合等离子体质谱法(ICP-MS),辉光放电质谱法(GD-MS),高频燃烧-红外法与惰气脉冲-红外热导法进行最终产品金属La的成分分析。结果表明:槽压与电流之间的线性关系受到接触压降、熔盐性质等因素的影响,控制较高电解温度、使用La-Ni合金代替金属La作阳极时槽压较低;沉积物均为枝晶形貌,电流密度增大导致沉积物的形貌由三维多面体转变为二维片状,电解温度升高导致颗粒几何规则性减弱,低电流密度下沉积物生长机制应为阶梯状生长;金属杂质中W,Ta可由50~100μg·g-1降至2~3μg·g-1,使用La阳极的实验所得精炼产物金属镧纯度为99.867%(分析77个杂质元素)。     

粗铋二段阳极熔盐电解精炼除铅、银第一段工艺研究

本文是在以前工作的基础上进一步研究了在二段阳极电解精炼工艺中第一段电解精炼除铅的各种工艺条件，主要包括电流密度、电解质体系、电解温度、电解时间及极间距等，适当控制这些条件可将粗铋中的大部分的铅除去，得到商品铅和适合第二段电解的中铋．     

钛电解精炼中阳极过程的研究

本文通过测定金属 Ti、Ti-6Al-4V 合金及氢化-脱氢处理后的 Ti-6Al-4V 合金三种不同阳极的极化曲线,分析了合金组分 Al、V 对金属钛极化行为和阴极产品粒度的影响,并探讨了钛及其合金中钛的溶解过程。     

金属热还原K2HfF6制备铪粉的研究

研究了分别以Mg,Al为还原剂,还原K2HfF6制备金属铪粉的可能性。利用X射线衍射(XRD)、扫描电镜(SEM)、能谱分析(EDS)等测试方法分析了产品的物相、形貌,研究了NaCl-KCl熔盐体系对铪粉形貌和杂质含量的影响。实验结果表明:Mg(过量20%)为还原剂,反应温度900℃、时间3 h可以还原铪氟酸钾得到金属铪粉,但产物中含有大量的无法除去的杂质MgF2;Al(过量20%)为还原剂,反应温度900℃、时间3 h制备的铪粉纯度达到98.75%,粒径为3μm左右,杂质含量较低,其中极少量的铝是以铪铝金属间化合物的形式存在的。研究表明,在以铝为还原剂的还原体系中添加NaCl-KCl熔盐由于添加的熔盐使铪和铝更易和杂质形成以氟络盐的形态存在的复杂化合物,导致铪粉中杂质的含量增加,同时由于添加熔盐使体系引入相当数量的电子,有利于铪氟酸钾的还原,在均相反应过程中呈现局部的电中性,使得制取的铪粉尺寸倾向于降低。     

熔盐电解制备碳化钛粉末的研究

在CaCl2熔盐中,以TiO2和炭黑的混合物为阴极,在850℃电解制备得到了碳化钛粉末。研究不同电解时间后所得阴极产物的物相结构,探讨了熔盐电解法制备碳化钛的阴极反应过程及机理。结果表明,氧离子在固相中的传质是阴极反应速度的限制性环节。熔盐电解法制备碳化钛的工艺简单、反应温度低且对环境友好。     

钨电极在稀土钕熔盐电解中的应用研究

根据稀土钕熔盐电解中钼电极所存在的缺点，采用钨代钼作电极，并对钨电极的生产制造过程和连接方式进行了探讨。     

NdF_3-LiF-Nd_2O_3体系熔盐电导率的研究

采用交流阻抗谱技术测定熔盐电阻,并通过CVCC法研究了在1 020～1 120℃的温度范围内NdF3-LiF-Nd2O3熔盐体系的电导率,确定了温度、Nd2O3含量与熔盐电导率之间的关系,分析了温度和Nd2O3含量之间的相互作用以及对熔盐电导率的影响。研究结果表明,温度增加、Nd2O3含量减少,则电导率增大;在温度为1 080℃,Nd2O3含量为1.5%、2%、3.5%时,熔盐电导率变化幅度小,体系较为稳定。     

Electrochemical Behavior of Dissolved Fe2O3 in Molten CaCl2-KF

The electrochemical behavior of dissolved Fe2O2 in 82.5CaCl2-17.5KF （mole percent, %） was studied using cy clic voltammetry, chronoamperometry, and galvanostatic electrolysis at 827 ℃, and the deposits were characterized by XRD and SEM. Pure iron was deposited on a rotating cylinder （210 r/min） with a cell voltage less than -- 1.0 V. Deposition rate was controlled by diffusion on a molybdenum electrode. The diffusion coefficient of iron species Fe（ Ⅲ ） in the melt at 827 ℃ was found to be 9.7×10^-5 cm^2/s.     

Influence of Molten Salt on Luminescent Intensity and Particle Size of Y2O3 ：Eu^3＋ Phosphor

The Y-Eu oxalate precursor was prepared with a homogeneous precipitation method. And the additives, Na2CO3, S, NaCl or their combination, were introduced into the precursor to prepare Y2O3 ：Eu^3＋ red phosphors at 1000 1300 ℃ for 2 h. The effect of molten salts on particle size and luminescent intensity was studied. The experimental results showed that the complex molten salt （Na：CO3 ＋ S ＋ NaCl） was conductive to enhance the luminescent intensity of Y2O3 ：Eu^3＋. The emission intensity of the phosphor prepared with these additives at 1300 ℃ was about 45% higher than that of the one prepared without molten salt, and about 11% higher than that of the corresponding commercial phosphor. Meanwhile, the particle size of Y2O3 ：Eu^3＋ phosphor was controlled effectively with the molten salt.     

Multiferroism in Pr2FeCrO6 perovskite

Pr₂FeCrO₆ perovskite crystallizes in an orthorhombic structure with R3c space group. Magnetic study has revealed that Pr₂FeCrO₆ exhibits room-temperature ferromagnetism with a Curie temperature of about 562 K. Pr₂FeCrO₆ also exhibits weak ferroelectricity. Thus, given its ferroelectric and ferromagnetic nature, the Pr₂FeCrO₆ material can be considered as a multiferroic. In addition, due to its high Curie temperature and multiferroicity, it could be a promising candidate for spintronics applications.     

FeO-MnO-MgO-SiO2渣系和铁液间锰的平衡

利用炉渣结构的共存理论处理FeO-MnO-MgO-SiO₂熔渣和铁液间锰的平衡问题后,证明$K{'_{{\\rm{Mn}}}} = \\frac{{{N_{{\\rm{MnO}}}}}}{{{N_{{\\rm{FeO}}}}[\\% Mn]}}$不因炉渣碱度而改变,是相当守常的。从该规律出发计算得出的[%Mn]_计与实测的[%Mn]_实是符合的,从而证明所推导的计算模型可以反映上述四元渣系的实际情况。     

Hydrothermal synthesis and crystal structure study of two novel 3-D mellitates {Nd2[C6（COO）6] （H2O）6} and {Ho2[C6（COO）6]（H2O）6}

Two novel 3-D coordination compounds, Nd2[C6（COO）6]（H2O）6 （1）and Ho2[C6（COO）6]（H2O）6 （2）, were hydrothermaily synthesized from mellitic acid and neodymium perchlorate （or holmium perchlorate） in the alkaline aqueous solution and characterized with elemental analysis, TG, IR spectrum, and single crystal X-ray diffraction. The two compounds were isostructural and crystallized in the orthorhombic system, space group Pnnm, with a=1.3531 （4） nm, b=0.6687 （2） nm, c=1.0224（3） nm, V=0.92523（5） nm^3, Z=4, D=2.630 g/cm^3, F（000）=696.0, Goof=1.052. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0195, wR2=0.0382 for 1; a=1.3411 （2） nm, b=0.6586（1） nm, c=1.0116（2） nm, V=0.8935（3） nm^3, Z=4, D=2.877 g/cm^3, F（000）=724.0, Goof=1.061. Final R indices [1 〉2∑（Ⅰ）]： R1=0.0200, wR2=0.0479 for 2. In the two compounds 1 and 2, the mellitic acid ligand, in which all the carboxylate groups were deprotonated, had only one kind of coordination mode to bridge metal ions to form four-connected three-dimensional diamondiod networks.     

Synthesis and Crystal Structure of A Bimetallic Terbium Complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3 （THF）3

The reaction of 2, 6-^iPr2CbH3NHSiMe3 with Tb（CH2SiMe3）3（THF）2 in benzene at room temperature afforded a binuclear terbium complex Tb2 {μ-CH2 SiMe2 NC6 H3 ^iPr2 -2, 6}3（THF）3. X-ray diffraction revealed that Tb atoms were bridged by three methylene units. One Tb atom was six-coordinated by two nitrogen atoms, three methylene carbons, and one THF molecule, while the other Tb atom was six-coordinated by one nitrogen atom, three methylene carbons, and two THF molecules. Both Tb atoms adopted a distorted trigonal prism geometry.     

Comparative Study on Thermodynamical and Electrochemical Behavior of Al（88）Ni6La6 and Al（86）Ni6La6Cu2 Amorphous Alloys

Two amorphous ribbons with the compositions of Al88Ni6La6 and Al86Ni6La6Cu2 were made using the melt-spun method,and their thermal response and electrochemical behavior were studied comparatively.Differential scanning calorimetry（DSC）and electrochemical polarization measurements indicated that Al86Ni6La6Cu2 exhibited slightly higher crystallization temperature（Tx）,lower melting point（Tl）and better corrosion resistance in 0.01 mol·L-1 NaCl alkaline solution.These results demonstrated that Cu（2%）addition could slightly promote the glass forming ability,but it could greatly improve the corrosion resistance of Al88Ni6La6 alloy in 0.01 mol·L-1 NaCl alkaline solution.     

CeO2/Bi2MoO6纳米复合材料的制备及 其增强光催化降解性能研究

采用水热法制备了一系列不同的CeO₂/Bi₂MoO₆纳米复合材料,分别考察了pH值（2~9）和Ce/Bi摩尔比（3 %~10 %）等因素对其光催化性能的影响.利用X射线粉末衍射、扫描电镜、红外光谱、紫外-可见漫反射光谱、光致发光光谱、瞬态光电流-时间响应等一系列分析测试手段对催化剂的组成、结构、光电性能等进行表征.结果表明,当pH=6时,所制备的Bi₂MoO₆（BMO）晶体形貌为细针状,复合CeO₂后形貌为厚片状,比表面积减小、晶体颗粒增大.在实验室模拟太阳光条件下（300 W氙灯)进行光催化活性测试,分别以罗丹明B（RhB）、亚甲基蓝（MB）和苯酚为模拟污染物,对复合光催化剂的光催化活性进行考察,结果表明,当CeO₂的含量为5 %时呈现出最高的光催化降解活性. 5 % CeO₂/BMO对RhB、MB和苯酚的光催化反应的速率常数分别为0.037 min-1、0.016 min-1和0.007 min-1,相对于纯的BMO分别提高了3.19倍、1.70倍和4.58倍.其光催化性能增强主要原因是CeO₂与Bi₂MoO₆复合后形成异质结有利于光生电子-空穴的有效分离,从而提高了活性自由基的含量.在自由基捕获实验中,超氧根离子自由基（·O2-）、羟基自由基（·OH）和空穴（h+）参与了光催化降解,其影响顺序为:·O2->·OH>h+.