The vaporization kinetics of Ni3S2

The vaporization of N1₃S₂ was investigated at high temperatures by a lévitation technique. Vaporization was controlled by a mass transfer process within a gas boundary layer around the NI₃S₂ droplet. The vaporizedS ₂ (g) and Ni(g') recombine within the gas bound-ary layer, and this recombination along with the condensation of Ni(g) was found to en-hance the vaporization rate. A model has been developed to account for the experi-mentally-obtained mass transfer coefficients. Y. FUKUNAKA, formerly Research Associate, Department of Metallurgy and Materials Science, University of Toronto.     

Kinetics of galena dissolution in nitric acid solutions with hydrogen peroxide

The extraction of lead from a galena concentrate in nitric acid solutions with additional hydrogen peroxide was studied taking stirring speed, temperature, hydrogen peroxide and nitric acid concentrations, and particle size as dissolution parameters. The dissolution curves followed the surface chemical reaction controlled shrinking core model over the whole range of parameters, except at high nitric acid concentrations where the reaction was diffusion-controlled. The activation energy of 42 kJ mol^− 1 and a linear relationship between rate and inverse particle size support the reaction controlled dissolution mechanism. Hydrogen peroxide addition accelerated the reaction compared with nitric acid alone. It was concluded that the dissolution process is favourable, since the acid consumed for oxidation of galena can easily be regenerated in the same reactor by means of hydrogen peroxide.     

FeTiO3--Fe2 O3固溶体等温碳热还原

基于粉末煅烧技术合成FeTiO₃和FeTiO₃-Fe₂O₃固溶体体系,在热力学分析的基础上,选取1150℃,以固溶体合成物为原料研究FeTiO₃-Fe₂O₃固溶体体系等温碳热还原过程,并采用X射线衍射仪和扫描电镜-能谱仪对还原产物进行系统分析.研究结果表明:合成产物内部成分均匀.钛铁矿的摩尔分数x越小,xFeTiO₃-(1-x) Fe₂O₃固溶体碳热还原反应越易进行,并且反应速率最大值越大.在反应初期,假板钛矿相(FeTi₂O₅-Fe₂TiO₅(Fe₃Ti₃O₁₀))作为过渡相一直存在,至金属Fe和钛铁晶石Fe₂TiO₄生成后逐渐消失.      

正极材料LiNi1/3Co1/3Mn1/3O2的Mg掺杂及电化学性能

为提高正极材料LiNi_1/3Co_1/3Mn_1/3O₂的循环性能, 采用氢氧化物共沉淀法对前驱体进行Mg掺杂, 再经过混锂、球磨、高温煅烧后, 分别对掺杂与未掺杂的正极材料进行了XRD、SEM及电化学性能的比较.研究结果表明:掺杂与未掺杂的正极材料都为标准的α-NaFeO₂型层状结构, 粒度大小无明显变化; 对于掺杂量为0.03与未掺杂的正极材料, 首轮放电比容量分别为138.2 mAh/g和145.3 mAh/g; 而循环50轮的放电比容量则分别为131.1 mAh/g和119.5 mAh/g.由此可见, 通过Mg掺杂, 正极材料的首轮放电比容量虽有少量降低, 而循环性能却有明显增强.      

Kinetics of dissolution of synthetic millerite (β-NiS) in acidic potassium dichromate solutions

The dissolution rate of millerite (β-NiS) in sulphuric acid solutions containing potassium dichromate has been determined by measurement of the rate of nickel ion formation. The effects of temperature, dichromate ion concentration, pH of leaching solution and stirring speed have been investigated. Two distinct regions for dissolution of millerite were observed, below and above 50°C. The activation energy of dissolution is 23.9 and 54.6 kJ mol^?1 in these two regions, respectively. At dichromate concentrations lower than 0.05 M a first order dependence of dissolution rate on Cr₂O₇^2? ion concentration was observed, whereas for higher concentrations a half order dependence was established. The concentration of hydrogen ion affects nickel extraction from β-NiS at pH 1.4, but at lower pH this factor is less important.     

Cr3 C2含量对Cr3 C2/Ni3 Al复合材料摩擦磨损性能的影响

采用热等静压法制备Ni₃Al合金和Cr₃C₂含量不同的Ni₃Al基复合耐磨材料,利用扫描电镜、能谱仪、X射线衍射仪及摩擦磨损试验机,系统地研究Cr₃C₂含量对材料组织特征、硬度及摩擦磨损性能的影响.结果表明:Cr₃C₂/Ni₃Al复合材料中,Cr₃C₂颗粒与Ni₃Al颗粒之间发生互扩散作用,使部分Cr₃C₂颗粒转变为M₇C₃（M=Cr,Fe,Ni）结构;在特定的摩擦磨损条件下,随着Ni₃Al基体中Cr₃C₂比例增大,Cr₃C₂/Ni₃Al复合材料的耐磨性能显著提高,达到了Ni₃Al合金耐磨性能的4~10倍.此外,随着Ni₃Al基体中Cr₃C₂比例的增大,Cr₃C₂/Ni₃Al复合材料对对磨盘的切削、刮擦作用减弱,对磨盘的磨损量减少.      

Morphology of dispersed nickel electrochemically deposited in solutions of the system NiSO4(NiCl2)-(NH4)2SO4-NH3·H2O

Morphology of dispersed nickel obtained by electrolysis in electrolytes (0.1–0.5 M) NiSO₄(NiCl₂)-0.5 M (NH₄)₂SO₄-NH₃·H₂O (to pH 8.0–8.5), which model the leaching solutions of secondary metal, is investigated. It is noted that the sediment of three structural levels is formed on the cathode at the current density 20–100 A/dm². These are (i) spherical particles, (ii) spherical agglomerates, and (iii) conglomerates of the particles of the second structural level. The shape of first-level elemental particles is governed by adsorption of the surface-active NH₃ molecules on the surface of crystalline nuclei. The second and the third levels of structuring emerge due to high surface energies of elemental particles. Spherical agglomerates are mechanically stable and determine the main characteristics of the nickel powder. The sizes of these agglomerates decrease as the cathode current density increases and the nickel concentration in electrolytes decreases, and lie in the limits 2–10 μm. Original Russian Text ? O.I. Kuntyi, 2007, published in Izvestiya VUZ. Tsvetnaya Metallurgiya, 2007, No. 1, pp. 20–23.     

Cr3C2/Ni3Al复合材料耐磨性提高的机制分析

为了探讨Cr₃C₂强化相提高Cr₃C₂/Ni₃Al复合材料耐磨性的机制, 本文采用热等静压技术制备了Ni₃Al合金和Cr₃C₂/Ni₃Al复合材料, 借助纳米压痕仪对Ni₃Al合金和Cr₃C₂/Ni₃Al复合材料中各组成相的力学性能进行了表征, 利用销-盘式摩擦磨损试验机研究了热等静压Ni₃Al合金和Cr₃C₂/Ni₃Al复合材料的耐磨性能, 并结合扫描电子显微镜和纳米压痕仪分析了材料磨损表面形貌和磨损次表面层硬度变化.结果表明, Cr₃C₂的添加提高了复合材料基体的硬度, Cr₃C₂/Ni₃Al复合材料中各组成相的纳米硬度和弹性模量由基体相、扩散相到硬芯相是逐渐增大的, 呈现出梯度变化, 有利于提高Cr₃C₂/Ni₃Al复合材料的耐磨性.在本研究实验条件下, Ni₃Al合金和Cr₃C₂/Ni₃Al复合材料表面的磨损形式主要为磨粒磨损, Cr₃C₂/Ni₃Al复合材料表现出更加优异的耐磨性能.Cr₃C₂/Ni₃Al复合材料耐磨性能的提高主要跟碳化物强化相阻断磨粒切削、减弱摩擦副间相互作用、减小加工硬化层厚度、磨粒尺寸等因素有关.      

Investigation on pumping oxygen characteristics of （Bi2O3）0.73（Y2O3）0.27 solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.     

LiClO4预氧化Ni0.8Co0.17Al0.03(OH)2提升锂离子电池的循环稳定性

层状高镍正极材料（LiNi_0.8Co_0.17Al_0.03O₂）因为具有高的镍含量,相比于LiCoO₂拥有更高的比容量和更低的成本,受到了大众的欢迎。然而,循环过程中容量的快速衰退阻碍了LiNi_0.8Co_0.17Al_0.03O₂的进一步商业化使用。其中,Li+/Ni2+混排现象是造成材料不良循环性能的主要原因之一。本文中,使用具有强氧化性的LiClO₄对Ni_0.8Co_0.17Al_0.03（OH）₂前驱体进行预氧化处理。X射线衍射（XRD）测试和精修结果显示,LiClO₄处理后的LiNi_0.8Co_0.17Al_0.03O₂（LiClO₄-NCA）样品有着更低的Li+/Ni2+混排程度,这与X射线光电子能谱（XPS）测试得到的正极材料中Ni2+/Ni3+结果相一致。电化学测试结果显示,LiClO₄-NCA相比于原始样品LiNi_0.8Co_0.17Al_0.03O₂（NCA）具有更优异的循环性能,1 C倍率循环100圈后,LiClO₄-NCA的容量保持率（94.3%）明显高于NCA（82.4%）。LiClO₄-NCA优异的电化学性能归因于LiClO₄促进了材料中的Ni2+转化为Ni3+,减少了阳离子混排现象,保持了更完整的层状结构。因此,LiClO₄对Ni_0.8Co_0.17Al_0.03（OH）₂前驱体进行预氧化处理可以改善材料中的Li+/Ni2+混排现象,优化层状高镍正极材料的循环稳定性。      

Thermochemical Study on Ternary Solid Complex of La(Gly)2 (Ala)3 Cl3 ·2H2O (s)

The complex of lanthanum chloride with Glycine and Alanine, La(Gly)₂(Ala)₃Cl₃ · 2H₂O, was synthesized and characterized by IR, elementary analysis, thermogravimetric analysis, and chemical analysis. The dissolution enthalpies of LaCl₃ · 7H₂O(s), 2Gly(s) + 3Ala(s) and La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) were determined in 2 mol · L⁻¹ HCl by a solution-reaction isoperibol calorimeter. By designing a thermochemical cycle in terms of Hess' Law and through calculation, the reaction enthalpy of lanthanum chloride seven-hydrate with Glycine and Alanine was obtained: Δ_rH^θ_m(298.15 K) = (29.652 ± 0.504) kJ · mol⁻¹, and the standard enthalpy of formation of La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) Δ_fH^θ_m[La(Gly)₂ (Ala)₃Cl₃ · 2H₂O, s, 298.15 K] = −4467.6 ± 8.3 kJ · mol⁻¹.     

Carbothermic reduction of llmenite (FeTiO3) and rutile (TiO2)

The mechanically activated carbothermic reduction mechanism of ilmenite has been examined by a combination of steady-state and dynamic thermal techniques coupled with X-ray diffraction. The reaction was found to proceed via an initial, rapid reduction to elemental iron and rutile, which was followed by a slow reduction of rutile to a series of oxides of the general formula Ti _n O_2n−1 until Ti₃O₅ was formed, which was found to be relatively stable. Iron was probably incorporated into the Ti _n O_2n−1 lattice only for n>3, forming mixed oxides of uncertain composition. The formation of TiC was evident at temperatures as low as 1100 °C, but the rate of reaction was extremely slow, presumably due to a solid-state diffusion limitation. Increasing the temperature gave increasing conversion of TiO₂ to TiC until it was the only confirmed product. The effect of iron on the later stages of reduction was removed by examining the reduction of pure rutile. It was found that the reduction of Ti₃O₅ was enhanced by the presence of iron. The separation of iron from the titanium product proved to be high, with > 90 pct of iron removed after the initial reduction. The iron removal increased slowly to almost 100 pct when elemental iron and titanium carbide were the products.     

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.     

Silver ion catalysis in nitric acid dissolution of Ni3S2

The dissolution of Ni₃S₂ in nitric acid solutions in the presence of silver ions was investigated. The effect of stirring, particle size, temperature and silver ion concentration were examined. In addition, the reaction residues at various levels of nickel extraction were examined by SEM, X-ray diffraction, electron microprobe and chemical analysis. These observations indicated that the dissolution reaction is topochemical and fits a surface reaction control model. The activation energy was calculated to be 52.6 ± 3.6 kJ/mol, which is reasonable for a rate-limiting surface reaction. The order of the reaction was 0.2 with respect to Ag⁺ concentration. An electrochemical reaction between nitric acid and the intermediate product Ag₂S occurring on the surface of Ni₃S₂ appears to be the rate-determining step.     

Luminescent characteristics of Ba3Y2（BO3）4：Eu^3＋ phosphor for white LED

The Ba3Y2（BO3）4：Eu^3＋ phosphor was synthesized using a high temperature solid-state reaction method and the luminescent characteristics were investigated. The emission spectrum exhibited one strong red emission at 613 nm, corresponding to the electric dipole 5D0-TF2 transition of Eu^3＋, under 365 nm excitation. The excitation spectrum of 613 nm indicated that the Ba3Y2（BO3）n：Eu^3＋ phosphor was effectively excited by ultraviolet （UV） （254, 365 and 400 nm） and blue （470 nm） light. The effect of Eu^3＋ concentration on the 613 nm emission of the Ba3Y2（BO3）n：Eu^3＋ phosphor was measured. The results showed that the emission intensity increased with increasing Eu^3＋ concentration, and then decreased. The CIE color coordinates of Ba3Y2（BO3）4：Eu^3＋ phosphor were x=0.641 and y=0.359 at 15 mol.% Eu^3＋.     

Preparation of La（OH）3 and La2O3 with Rod Morphology by Simple Hydration of La2O3

Lanthanum hydroxide with rod-like morphology was synthesized with simple hydration processing via the hydration of its bulk oxide in normal water solution at boiling temperature. An XRD pattern shows the formation of the hexagonal phase of La（OH）3, indicating that the hydration process is very rapid. The as-prepared La（OH）3 is almost entirely with a needle- or rod-like shape with a width of 2 - 3 μm and a length of 5 - 8 μm. The mechanism of the formation of La（OH）3 with rod-like morphology was preliminarily presented. It is easier to expand the simple hydration process on a large scale than the hydrothermal process.     

Kinetics of reduction of ferric iron in Fe2O3-CaO-SiO2-Al2O3 slags under argon, CO-CO2, or H2-H2O

The rates of reduction of ferric iron in Fe₂O₃-CaO-SiO₂-Al₂O₃ slags containing 3 to 21 wt pct Fe₂O₃ under impinging argon, CO-CO₂, or H₂-H₂O have been studied at 1370 °C under conditions of enhanced mass transfer in the slag using a rotating alumina disc just in contact with the slag surface. For a 6 wt pct Fe slag at a stirring speed of 900 rpm the observed reduction rates by 50 pct H₂-H₂O were a factor of 2 to 3 times higher than those by 50 pct CO-CO₂ and more than one order of magnitude higher than those under pure argon. The observed rates were analyzed to determine the rate-controlling mechanisms for the present conditions. Analysis of the rate data suggests that the rates under 50 pct H₂-H₂O are predominantly controlled by the slag mass transfer. The derived values of the mass-transfer coefficient followed a square-root dependence on the stirring speed for a given slag and, at a given stirring speed, a linear function of the total iron content of the slags. The rates of oxygen evolution during reduction under pure argon were shown to be consistent with a rate-controlling mechanism involving a fast chemical reaction at the interface and relatively slow mass transfer in the gaseous and the slag phases. The rates of reduction by CO-CO₂ (pCO=0.02 to 0.82 atm) were found to be likely of a mixed control by the slag mass transfer and the interfacial reaction. A significant contribution of oxygen evolution to the overall rates was observed for more-oxidized slags and for experiments with relatively low values of pCO. Assuming a parallel reaction mechanism, the estimated net reduction rates due to CO were found to be of the first order in pCO, with the first-order rate constants being approximately a linear function of the ferric concentration. This article is based on a presentation made in the “Geoffrey Belton Memorial Symposium” held in January 2000, in Sydney, Australia, under the joint sponsorship of ISS and TMS. The original symposium appeared in the October 2000 Vol. 31B issue.     

Phase structure and electrochemical properties of non-stoichiometric La0.7Ce0.3(Ni3.65Cu0.75Mn0.35Al0.15(Fe0.43B0.57)0.10)x hydrogen storage alloys

Phase structure and electrochemical characteristics of Co-free La0.7Ce0.3(Ni3.65Cu0.75Mn0.35Al0.15(Fe0.43B0.57)0.10)x (0.90≤x≤1.10) al-loys were investigated. When x was 0.90, the alloy was composed of LaNi5, La3Ni13B2 and Ce2Ni7 phases. The Ce2Ni7 phase disappeared, and the abundant of La3Ni13B2 phase decreased when x increased to 0.95. When x was 1.00 or higher the alloys consisted of LaNi5 phase. The lat-tice parameter a and the cell volume V of the LaNi5 phase decreased, and the c/a ratio of the LaNi5 phase increased with x value increasing. Maximum discharge capacity of the alloy electrodes first increased and then decreased with x value increasing from 0.90 to 1.10, and the highest value was obtained when x was 1.00. High-rate dischargeability at the discharge current density of 1200 mA/g increased from 50.7% (x= 0.90) to 64.1% (x=1.10). Both the charge-transfer reaction at the electrode/electrolyte interface and the hydrogen diffusion in the alloy were responsible for the high-rate dischargeability. Cycling capacity retention rate at 100th cycle (S100) gradually increased from 77.3% (x= 0.90) to 84.6% (x=1.10), which resulted from the increase in Ni content and the c/a ratio of the LaNi5 phase with x value increasing.     

钠源对正极材料Na3V2（PO4）3性能的影响

采用溶胶凝胶-高温固相法,用不同的钠源制备NASICON结构钠离子电池正极材料Na₃V₂（PO₄）₃.借助扫描电子显微镜（SEM）,X射线衍射分析（XRD）,电池测试系统及电化学工作站对制备的Na₃V₂（PO₄）₃结构,形貌,电性能和内阻进行表征.研究结果表明,以Na₂CO₃为钠源合成Na₃V₂（PO₄）₃有更好的颗粒尺寸,形貌结构完整,充放电性能及循环稳定性更好,阻抗也较小;在2.5~4.0 V电压范围内,以0.2 C进行充放电,首次放电比容量达到110.8 mAh/g,50次循环后容量保持率为85.1 %.