Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process

The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The results show that calcium-based additives can react with molybdenum concentrate to form CaSO₄ and CaMoO₄. The initial oxidation temperature of MoS₂ is 450 °C, while the formation of CaMoO₄ and CaSO₄ occurs above 500 °C. The whole calcification reactions are nearly completed between 600 and 650 °C. However, raising the temperature further helps for the formation of CaMoO₄ but is disadvantageous to sulfur fixing rate and molybdenum retention rate. Calcification efficiency of Ca-based additives follows the order: Ca(OH)₂>CaO>CaCO₃. With increasing the dosage of Ca(OH)₂, the molybdenum retention rate and sulfur-fixing rate rise, but excessive dosages would consume more acid during leaching process. The appropriate mass ratio of Ca(OH)₂ to molybdenum concentrate is 1:1. When roasted at 650 °C for 90 min, the molybdenum retention rate and the sulfur-fixing rate of low-grade molybdenum concentrate reach 100% and 92.92%, respectively, and the dissolution rate of molybdenum achieves 99.12% with calcines being leached by sulphuric acid.     

Polymer-assisted sol–gel synthesis and characterization of Zn2SiO4:Eu powders

The synthesis of nanophosphors for various applications and the improvement of their working parameters constitute one of the most topical problems of nowadays technology. Zinc-silicate has been extensively used as host material for phosphors in cathode ray tubes, and nowadays for phosphors in electroluminescent devices. In this work we present novel synthesis procedure for obtaining Zn₂SiO₄:Eu³⁺ powder, based on the combination of standard sol–gel and modified combustion method. Influence of preparation conditions on the structure and morphology are analyzed using X-ray diffraction and scanning electron microscopy. Luminescence properties of Eu³⁺ are investigated with fluorescence emission and lifetime measurements.     

FeTiO3-Fe2O3固溶体合成及其碳热还原研究

为明确Fe₂O₃固溶对FeTiO₃还原过程的影响机理,本文基于粉末煅烧法合成(1-x)FeTiO₃?xFe₂O₃固溶体(0≤x≤1),研究了非等温碳热还原条件下固溶体的还原行为,并采用X射线衍射仪(XRD)和扫描电镜-能谱仪(SEM-EDS)对合成固溶体及还原产物进行表征。结果表明,实验合成固溶体质地均匀,纯度较高,且x越大,FeTiO₃晶格畸变程度越大。固溶体开始还原温度和还原速率(还原度α的增大速率)均随着x值的增加而增加。固溶Fe₂O₃能够促进FeTiO₃还原,且在还原过程中存在过渡相Fe₂TiO₄和Fe₃Ti₃O₁₀。固溶体-石墨交界面首先形成浮士体(FeO)、钛铁尖晶石(Fe₂TiO₄)和TiO₂,进一步还原生成金属Fe和Ti₂O₃。非等温碳热还原过程动力学计算分析,得出表观活化能为295.54 kJ/mol。     

Zn_2SnO_4和Zn_2Sn_(0.8)Ti_(0.2)O_4/C的制备和电化学性能(英文)

以SnCl4.5H2O、TiCl4、ZnCl2和N2H4.H2O为原料,采用水热法制备Zn2Sn0.8Ti0.2O4纳米粉体。在此基础上,以葡萄糖和水热合成的Zn2Sn0.8Ti0.2O4为原料,以碳热还原法制备Zn2Sn0.8Ti0.2O4/C复合材料。利用XRD、XPS、TEM、恒电流充放电等方法分别研究Zn2SnO4和Zn2Sn0.8Ti0.2O4/C复合材料的结构、形貌和电化学性能。同时用非原位XRD、XPS和SEM分析Zn2Sn0.8Ti0.2O4/C复合材料电极在充放电过程中的结构和形貌变化。合成的纯Zn2SnO4的首次放电容量为1670.8mA.h/g,循环40次后放电容量迅速衰减为342.7mA.h/g。而Zn2Sn0.8Ti0.2O4/C复合材料的首次放电容量为1530.0mA.h/g,循环100次后容量还保持为479.1mA.h/g,与纯Zn2SnO4、Zn2Sn0.8Ti0.2O4和Zn2SnO4/C相比,电化学性能有较大的提高。     

Si3N4/Ti/Cu/Ti/Si3N4部分瞬间液相连接界面动力学

采用Ti(5μm)／Cu(70μm)／Ti中间层，通过改变连接时间和连接温度进行Si3N4。陶瓷的部分瞬间液相连接(PTLP连接)，用扫描电镜、电子探针对连接界面区域进行了分析，系统地研究了Si3N4／Ti／Cu／Ti／Si3N4 PTLP连接过程的动力学。结果表明，界面反应层的生长和等温凝固界面的迁移均符合扩散控制的抛物线方程。PTLP连接参数的优化不同于通常的活性钎焊和固相扩散连接的参数优化,反应层生长和液相区等温凝固这两个过程必须协调，才能同时提高室温和高温连接强度。     

高硅硫化锌精矿氧化焙烧中硅酸锌生成反应的动力学

研究了高硅硫化锌精矿氧化焙烧过程中硅酸锌生成反应的动力学。确定了温度、粒度对硅酸锌反应速率的影响,结果指出：硅酸锌生成反应的动力学符合收缩核西式,其过程为固膜扩散控制。测定了各反应条件下的反应速率常数并测得其活化能为406KJ/mol。提出了硅酸锌生成反应的总动力学方程。限制硅酸锌反应速率的有效方法是适当提高精矿粒度和降低焙烧温度至860℃左右。     

浓硫酸焙烧高钛渣的反应动力学（英文）

提出一种新方法,利用浓硫酸焙烧高钛渣提取二氧化钛,并在焙烧工艺的基础上研究焙烧反应动力学。考察焙烧温度、粒度以及酸矿比对反应速率的影响。结果表明,焙烧反应符合未反应核收缩模型。动力学实验数据、SEM和EDAX结果分析表明,用浓硫酸焙烧高钛矿渣的反应受通过固体产物层的内扩散控制。Arrhenius方程得到焙烧反应的表观活化能为18.94 kJ/mol。     

Microwave properties of Ba(Zn1/3Ta2/3)O3 dielectric resonators

Ba(Zn_1/3Ta_2/3)O₃ (BZT) dielectric resonators were prepared by solid-state reaction. The starting materials were BaCO₃, ZnO, and Ta₂O₅ powders with high purity. The double calcined BZT pellets were sintered in air at temperatures of 1575, 1600, 1625, and 1650 °C for 4 h. The X-ray diffraction data allowed the study of the unit cell distortion degree and the presence of the secondary phases. A long-range order with a 2:1 ratio of Ta and Zn cations on the octahedral positions of the perovskite structure was observed with the increase of the sintering temperature. The dielectric constant of BZT resonators measured around 6 GHz was between 26 and 28. High values of Q × f product (120 THz) were obtained for BZT resonators sintered at 1650 °C/4 h. The temperature coefficient of the resonance frequency exhibits positive values less than 6 ppm/°C. The achieved dielectric parameters recommend BZT dielectric resonators for microwave and millimeter wave applications.     

阳极氧化钽酸锂薄膜在NaOH溶液中的腐蚀行为研究

通过阳极氧化法在高纯钽片表面制备了钽酸锂复合薄膜,采用浸泡失重法和电化学测试法考察了镀膜前后样品在10% (质量分数) NaOH溶液中的腐蚀行为。利用X射线衍射仪、扫描电子显微镜及能谱仪分别对薄膜的物相组成、表面及截面形貌、膜层厚度进行了测试分析。结果表明,阳极氧化后得到的复合薄膜由钽酸锂和氧化钽组成;该薄膜与基体之间结合良好,厚度约3 μm;镀膜后样品的质量腐蚀速率至少减少了6倍,腐蚀电流密度下降了2个数量级,腐蚀96 h后样品表面没有明显变化。而对比的纯钽样品却发生了严重的腐蚀反应,生成了很多长条状和多棱柱状的腐蚀产物Na₃TaO₄、Na₂Ta₂O₆和Na₈Ta₆O₁₉。     

Photoluminescence and thermoluminescence studies of Mg2SiO4:Eu nano phosphor

Nanoparticles of Eu³⁺ doped Mg₂SiO₄ are prepared using low temperature solution combustion technique with metal nitrate as precursor and urea as fuel. The synthesized samples are calcined at 800 °C for 3 h. The Powder X-ray diffraction (PXRD) patterns of the sample reveled orthorhombic structure with α-phase. The crystallite size using Scherer's formula is found to be in the range 50-60 nm. The effect of Eu³⁺ on the luminescence characteristics of Mg₂SiO₄ is studied and the results are presented here. These phosphors exhibit bright red color upon excitation by 256 nm light and showed the characteristic emission of the Eu³⁺ ions. The electronic transition corresponding to ⁵D₀ → ⁷F₂ of Eu³⁺ ions (612 nm) is stronger than the magnetic dipole transition corresponding to ⁵D₀ → ⁷F₁ of Eu³⁺ ions (590 nm). Thermoluminescence (TL) characteristics of γ-rayed Mg₂SiO₄:Eu³⁺ phosphors are studied. Two prominent and well-resolved TL glows with peaks at 202 °C and 345 °C besides a shoulder with peak at ∼240 °C are observed. The trapping parameters-activation energy (E), order of kinetics (b) and frequency factor (s) are calculated using glow curve shape method and the results obtained are discussed.     

Thermoelectric properties of semi-conducting compound Zn4Sb3

Hot-pressed samples of the semi-conducting compound Zn₄Sb₃ with the stoichiometric composition were prepared and characterized by X-ray and microprobe analysis. Thermoelectric characterization was done through measurements of the electrical and thermal conductivities as well as the Seebeck coefficient between room temperature and 650 K. All samples had p-type conductivity. High thermoelectric figures of merit (ZT) were obtained between 450 and 650 K and a maximum of about 1.3 were obtained at a temperature of 650 K.     

部分MAX相在NaOH、H2SO4和HCl中的电化学性质

用热压的方法合成了若干MAX相化合物,包括相（Ti₂AlC和Ti₂AlN）和312相（Ti₃SiC₂和Ti3AlC2）;研究了它们在1 mol/L HCl、1 mol/L NaOH和1 mol/L H₂SO₄中的电化学性质及其结构与其稳定性的关系.结果表明:在所有溶液中,312型MAX相比211相更稳定;Ti₃SiC₂ 和Ti₃AlC₂几乎在所有溶液里都发生钝化,而Ti₂AlC和Ti₂AlN在1 mol/L HCl中活跃地溶解,还伴有大量气泡产生;Ti₃SiC₂比Ti₂AlC、Ti₂AlN 和Ti₃AlC₂更稳定.     

Corrosion behavior of select MAX phases in NaOH, HCl and H2SO4

In this paper we report on the electrochemical corrosion of select MAX phases, namely Ti₂AlC, (Ti,Nb)₂AlC, V₂AlC, V₂GeC, Cr₂AlC, Ti₂AlN, Ti₄AlN₃, Ti₃SiC₂ and Ti₃GeC₂ in 1 M NaOH, 1 M HCl and 1 M H₂SO₄ solutions. Polarization characteristics recorded in 1 M NaOH show that V₂AlC, V₂GeC and Cr₂AlC undergo active dissolution at potentials more positive than the corrosion potential, while Ti₂AlC, (Ti,Nb)₂AlC, Ti₃SiC₂ and Ti₃GeC₂ passivate. In the 1 M HCl solutions, Ti₂AlC, V₂AlC and V₂GeC actively dissolve; Ti₃SiC₂ and Ti₃GeC₂ passivate. Depending on potential, (Ti,Nb)₂AlC and Cr₂AlC showed trans-passive behavior. In 1 M H₂SO₄ solutions, Ti₂AlC, (Ti,Nb)₂AlC, Ti₃SiC₂ and Ti₃GeC₂ passivate, V₂AlC and V₂GeC show active dissolution, while Cr₂AlC exhibits trans-passive behavior. Ti₂AlN and Ti₄AlN₃ were passive in all solutions except in 1 M HCl, where Ti₂AlN showed trans-passive behavior. Given that the corrosion behavior of (Ti,Nb)₂AlC is unlike either Ti or Nb, the behavior of the former cannot be predicted from that of the latter.     

熔融NaOH分解橄榄石型硅酸盐的反应机理

采用熔融NaOH分解Mg2SiO4和MgNiSiO4,采用拉曼光谱对碱熔融过程进行在线检测,利用X射线衍射仪和红外光谱仪等分析碱融后的水浸渣,研究硅酸盐在熔融碱中的分解机理。结果表明:NaOH对Mg2SiO4中Mg离子的释放是逐次进行的,其中间产物为Na2MgSiO4;MgNiSiO4在碱熔融分解过程中,Ni离子优先于Mg离子从硅酸盐阵列中释放;镁和镍橄榄石型硅酸盐中的Mg—O和Ni—O最终都可以被Na—O替换,生成Na4SiO4。     

Preparation of Dy-activated strontium orthosilicate (Sr2SiO4:Dy) phosphors and its photoluminescent properties

Dy³⁺-activated β/α′-Sr₂SiO₄ phosphors were successfully prepared by solid-state reaction method with ammonium chloride (NH₄Cl) as the flux. The influences of calcination temperatures, amounts of NH₄Cl and the concentrations of Dy³⁺ on phase composition, morphology and the photoluminescent properties of as-prepared powders were investigated in detail. The β and α′ phases of Sr₂SiO₄ were obtained with 1 wt% and 2-5 wt% NH₄Cl, respectively, as the sintered condition was at 1000 °C for 4 h. With increasing the amount of NH₄Cl, the morphology of phosphors changed from needlelike to regular polyhedron shape and the colors of the Sr₂SiO₄:Dy³⁺ phosphors changed from blue-green to white. The luminescence intensity of ⁴F_9/2 → ⁶H_15/2 transition was slightly higher than that of ⁴F_9/2 → ⁶H_13/2 (ΔL = 2, ΔJ = 2) transition owing to the low-symmetry around Dy³⁺ ions. The optimum concentration of Dy³⁺ was 2.0 mol% and the concentration quenching were caused by the d-d interaction and a cross relaxation. The yellow-to-blue intensity ratio (Y/B) of Dy³⁺ emission did not to change with varying the Dy³⁺ concentration using Li⁺ ions for charge compensation. These indicate that this phosphor can be used as a potential candidate for the phosphor-converted white LEDs with a UV chip.     

Ethanol-assisted synthesis of Zn0.5Fe2.5O4 nanocrystals in thermal solvent of paraffin

In the atmosphere of N₂, low cost paraffin slices were refined and then successfully utilized as a solvent instead of the expensive high-carbon alkanes or alkenes like 1-octadecene to synthesize Zn_0.5Fe_2.5O₄ nanocrystals at 320 °C. In the experiments, the precursor solutions of ferric and zinc oleates were stoichiometrically prepared and injected by two-step operations into the hot solvent, together with controlled amounts of ethanol to tailor their thermal decomposition performances. The synthesized Zn_0.5Fe_2.5O₄ nanocrystals were characterized by XRD and FESEM, having uniform morphology and a quasi-monodisperse size distribution with a mean value 25 nm and a standard deviation of ±12.3%. The formation and structural characteristics of Zn_0.5Fe_2.5O₄ nanocrystals are attributed to the catalysing function of ethanol and the effective separation of nucleation and growth of nanocrystals via the two-step injections of reactive precursors.     

CuO掺杂Ni0.4Zn0.6Fe2O4铁氧体的组织与性能探讨

采用传统球磨法制备了Ni0.4-xCu_xZn0.6Fe₂O₄（x＝0,0.12,0.20,0.28）铁氧体,并通过扫描电镜（SEM）、X-ray衍射（XRD）、综合热分析（TG-DSC）和振动样品磁强计（VSM）等手段研究掺杂CuO对Ni-Zn铁氧体的显微组织、相组成和磁性能。结果表明,随着CuO含量的增加,第二相Ni-Cu-Zn相生成,且 Ni-Cu-Zn铁氧体衍射峰强度逐渐增强;从显微组织形貌和能谱可以看出,Cu ^2＋参与了铁氧体的反应,CuO含量增加得越多,样品烧结性能越好,并促使Ni-Cu-Zn铁氧体的晶化温度降低;磁滞回线显示了Ni0.4-xCu_xZn0.6Fe₂O₄（x＝0,0.12,0.20,0.28）铁氧体的软磁特性,CuO原子分数x为0.2时的铁氧体的饱和磁化强度（Ms）最高,且具有较低的矫顽力（Hc）。     

Fabrication and dry sliding wear behavior of in situ Al–K2ZrF6–KBF4 composites reinforced by Al3Zr and ZrB2 particles

Aluminum matrix composites reinforced by Al₃Zr and ZrB₂ particles were fabricated from Al–x wt.%(K₂ZrF₆–KBF₄) (x = 5, 10, 15, 20, 25) systems via magnetochemistry in situ reaction and the dry sliding wear properties and behavior of the composites were investigated. XRD and SEM analysis show that ZrB₂ and Al₃Zr reinforcement phases have been obtained and been distributed uniformly in the aluminum matrix. Wear test results show that the values of wear weight loss of the composites decrease with the increase of x under all identical wear conditions, and that of the relative wear resistance R_relat. increases under the applied load of 100 N. Especially, when x = 25, the wear weight loss (under a sliding time of 120 min and an applied load of 100 N), which is 0.245 to that of the A356 alloy, and the R_relat. (under the intermediate wear-sliding stage and an applied load of 100 N) is 4.772, which is 1.513 to that of the primary stage, respectively. Two modes of the wear mechanisms of the as-prepared composites were identified.     

Kinetic study on Li2.8(V0.9Ge0.1)2(PO4)3 by EIS measurement

Kinetics for lithium ion transfers in the fast ionic conductor Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ prepared by solid-state reaction method has been studied by electrochemical impedance spectroscopy (EIS) at various temperatures and the results were correlated with observed cathodic behavior. The specific conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ (x = 0.9–2.8) versus temperatures were analyzed from blocking-electrodes by Wagner's polarization method and the activation energy was calculated. It was observed that electronic conductivities of Li_x(V_0.9Ge_0.1)₂(PO₄)₃ increased with lithium contents in the materials. The compounds show a reversible capacity of 131 mAh g⁻¹ at low current density (13 mA g⁻¹). Modeling the EIS data with equivalent circuit approach enabled the determination of charge transfer and surface film resistances. The Li ion diffusion coefficient (D_Li⁺) versus voltage plot shows three valleys during the first charge cycle coinciding with the irreversible plateau of the voltage versus lithium content profiles reflecting the irreversible phase change in the compound. The obtained D_Li⁺ from EIS varies within 10⁻⁸ to 10⁻⁷ cm² s⁻¹, so Li_2.8(V_0.9Ge_0.1)₂(PO₄)₃ shows excellent chemical diffusion performance.