过硫酸铵-硫酸亚铁铵法测定钨精矿中锰量的研究

钨矿试样经磷酸分解,锰进入溶液,加入磷酸氢二钠缓冲溶液控制酸度,在硝酸银存在下,加入过硫酸铵将低价锰氧化为高价锰,加热煮沸破坏过量的过硫酸铵,用标准硫酸亚铁铵溶液滴定样品中的锰量。笔者就溶液酸度、过硫酸铵用量、去除过硫酸铵的煮沸时间、基体元素和杂质元素的影响等进行详细研究探讨,确定了最佳测定条件。实验表明本方法结果准确,精确度高,测定范围为2%～50%。     

Tensile behavior change depending on the varying tungsten content of W–Ni–Fe alloys

Tungsten heavy alloys (WHAs) are metal–metal composites consisting of nearly pure spherical tungsten particles embedded in a Ni–Fe–W or Ni–Co–W or Ni–Cu–W ductile matrix. In this dual phase alloy, there are several complicated relations between the ductile matrix and hard tungsten particles. The aim of this research was to examine the effect of varying tungsten content on the microstructure and mechanical properties of tungsten heavy alloys. The microstructural parameters (grain size, connectivity, contiguity and solid volume fraction) were measured and were found to have a significant effect on the mechanical properties of tungsten-based heavy alloys. The result shows that the binding strength between the W and the matrix phase has a major influence on the ductility of tungsten-based alloys. The larger this binding force is, the better the ductility is.     

WO3 membrane-encapsulated layered LiNi0.6Co0.2Mn0.2O2 cathode material for advanced Li-ion batteries

Despite Nickel-rich materials have all the advantages of high capacity, long cycle life and low cost, there is still a disadvantage that the capacity decreases rapidly as the number of cycles increases. In order to solve this problem, WO₃ was uniformly coated on the surface of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials by wet coating, and its cycling performance was greatly improved with the higher capacity. The coated materials were analyzed by X-ray diffraction(XRD), Scanning electron microscope (SEM), high resolution Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy(XPS). The results showed that the coating thickness was around 3.15?nm, and some tungsten ions were doped into the lattice of the near surface area of the LiNi_0.6Co_0.2Mn_0.2O₂ material. In addition, the results of charge-discharge test showed that 1?wt%WO₃ coating LiNi_0.6Co_0.2Mn_0.2O₂ had the best performance, and delivered a discharge capacity of 140 mAh g^?1 (the capacity retention rate is 84.8%) in the potential interval of 2.8–4.3?V at 1?C (1?C?=?165?mA?g^?1) after 200 cycles, while the bare cathode material only delivered a discharge capacity of 120 mAhg^?1 (the capacity retention rate is 75%). The phenomenon indicates that the WO₃ coating plays a role in inhibiting the harmful side reactions between the cathode material and the electrolyte, improving the electrochemical and structure stability of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials.     

Tungsten oxide in polymer electrolyte fuel cell electrodes—A thin-film model electrode study

Thin films of WO_x and Pt on WO_x were evaporated onto the microporous layer of a gas diffusion layer (GDL) and served as model electrodes in the polymer electrolyte fuel cell (PEFC) as well as in liquid electrolyte measurements. In order to study the effects of introducing WO_x in PEFC electrodes, precise amounts of WO_x (films ranging from 0 to 40 nm) with or without a top layer of Pt (3 nm) were prepared. The structure of the thin-film model electrodes was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy prior to the electrochemical investigations. The electrodes were analyzed by cyclic voltammetry and the electrocatalytic activity for hydrogen oxidation reaction (HOR) and CO oxidation was examined. The impact of Nafion in the electrode structure was examined by comparing samples with and without Nafion solution sprayed onto the electrode. Fuel cell measurements showed an increased amount of hydrogen tungsten bronzes formed for increasing WO_x thicknesses and that Pt affected the intercalation/deintercalation process, but not the total amount of bronzes. The oxidation of pre-adsorbed CO was shifted to lower potentials for WO_x containing electrodes, suggesting that Pt-WO_x is a more CO-tolerant catalyst than Pt. For the HOR, Pt on thicker films of WO_x showed an increased limiting current, most likely originating from the increased electrochemically active surface area due to proton conductivity and hydrogen permeability in the WO_x film. From measurements in liquid electrolyte it was seen that the system behaved very differently compared to the fuel cell measurements. This exemplifies the large differences between the liquid electrolyte and fuel cell systems. The thin-film model electrodes are shown to be a very useful tool to study the effects of introducing new materials in the PEFC catalysts. The fact that a variety of different measurements can be performed with the same electrode structure is a particular strength.     

溶胶-凝胶法制备铯钨青铜粉体的影响因素研究

采用溶胶凝胶法制备铯钨青铜（CsxWO3）粉体。系统研究了分散剂、煅烧温度和反应物铯钨摩尔比对铯钨青铜粉体晶相、形貌、晶粒平均粒径及光学性能的影响。分别采用热重分析仪（TGA）、扫描电子显微镜（SEM）、X射线衍射仪（XRD）、紫外可见近红外分光光度计（UV/VIS/NIR Spectrophotometer）对所制铯钨青铜粉体进行表征。结果表明：分散剂为PEG-600、煅烧温度为600℃和反应物铯钨摩尔比为0.33时,可制得晶型完整,分散性和近红外屏蔽性能均较好的铯钨青铜Cs0.3WO3粉体,其中Cs0.3WO3涂层的可见光透过率在80%以上,近红外阻隔率在70%左右。     

Constraint effect caused by graphene on in situ grown Gr@WO3 -nanobrick hybrid material

This work reported the abnormal constraint effect of graphene on the structural and optical properties of in situ grown Gr@WO₃ nanobrick (NB) hybrid nanomaterials. Stable hybrid Gr@WO₃ nanomaterials were synthesized through a one-step hydrothermal method, in which different graphene contents (0.1, 0.3 and 0.5 wt%) were directly introduced into the precursor solution of tungsten oxide. The existence of graphene in the nucleation phase of tungsten oxide NB decreased the crystallite size from 49.5 nm to 45.3 nm, increased the microstrain from 1.10% to 1.44% and the optical bandgap of the hybrid samples from 2.68 eV to 2.78 eV, and reduced the radiative recombination efficiency of tungsten oxide NB. The hybridization between graphene and tungsten oxide NBs was confirmed by X-ray diffraction and Raman scattering analysis. The optical properties of materials were studied based on the absorbance and diffuse reflectance spectra. In this work, we also proposed a reliable method to estimate the optical bandgap of the sample from the diffuse reflectance spectrum. These findings would introduce an alternative method of fabrication and enhance the understanding of in situ hybrid materials.     

Effect of strontium substitution on the structure and dielectric properties of unfilled tungsten bronze Ba4-xSrxSmFe0.5Nb9.5O30 ceramics

The effects of Sr²⁺ substitution for Ba²⁺ on phase structure, microstructure, dielectric and electric properties for Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2, 3 and 4) ceramics were systematically researched. X-ray diffraction patterns show that Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2 and 3) ceramics are tetragonal tungsten bronze compound with a space group of P4bm, while the sample for x = 4 is an orthorhombic structure compound. The result can be corroborated by the analysis of Raman spectroscopy. As the Sr²⁺ contents increase from 0 to 3, the full width at half maximum of Raman lines of all samples increase gradually, indicating that the degree of lattice distortion increase. All tetragonal tungsten bronze ceramics exhibited a broad permittivity peaks, accompanied by frequency dispersion, indicating all samples are relaxor. The electrical properties of BSSFN ceramics were further studied by complex impedance spectroscopy. XPS spectrum shows that Fe²⁺ and Fe³⁺ coexist in Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ ceramics, and their proportion varies with the concentration of Sr²⁺.     

Synthesis and Characterization of 5-Coordinate Tungsten Hydride Anions: [(tBu3SiNH)(tBu3SiN=)2HWR]M

Treatment of (^tBu₃SiNH)(^tBu₃SiN=)₂WH ( 1 -H) with small alkyl anions (RM) afforded tungsten alkyl hydride anions [(^tBu₃SiNH)(^tBu₃SiN=)₂HWR)]M ( 3 -(R)M: R=CH₃, M=Li; R=ⁿBu, M=Li; R=^neoPe, M=Li; R=CH₂Ph (Bn), M=K (two isomers); R=CCH, M=Na; R=CH=CH₂ (Vy), M=Li). The saturated alkyl anions 3 -(R)M ( 3 -(R)M: R=CH₃, M=Li; R=ⁿBu, M=Li; R=^neoPe, M=Li; R=CH₂Ph (Bn), M=K) degraded via apparent 1,2-RH-elimination to produce the known [(^tBu₃SiN=)₃WH]M ( 2 -HM), but the acetylide ( 3 -(C₂H)Na) and vinyl ( 3 -(Vy)Li) anions converted to their hydrogenated isomers, [(^tBu₃SiN=)₃WVy]Na ( 2 -VyNa) and [(^tBu₃SiN=)₃WEt]Li ( 2 -EtLi), respectively. The structure of 3 -(ⁿBu)Li is reported, and a discussion of tungsten-hydride coupling constants in ^tBu₃SiX-ligated (X=O, NH, N) systems is given.     

Influence of alumina content to mechanical properties and electric discharge machinability of zirconia (1.5Y-1.5Nd-TZP)-tungsten carbide-alumina composites

Composites of yttria neodymia co-stabilized zirconia, 24–32 vol% nanoscale tungsten carbide and 0.5–10 vol% alumina were manufactured by hot pressing and characterized in terms of mechanical properties, phase composition, microstructure and electric discharge machinability. Addition of 10 vol% alumina leads to an increase in hardness and Young’s modulus and an in average slightly higher bending strength. The transformability of the zirconia matrix and thereby fracture toughness is reduced by alumina addition. In EDM alumina reduces the thickness of the re-solidified layer, reduces surface defects and leads to smoother surfaces especially at high discharge currents, the effect on material removal rate is negligible.     

Preparation and characterization of tungsten tailing-based geopolymers

Using tailings to prepare constructive materials is of great significance for sustainable development of mineral processing industry. In this study, the possibility of preparing tungsten tailing-based geopolymers was explored in detail. XRD, FTIR, PLM, SEM and XPS analyses were carried out to characterize the phase composition, chemical bonding, microstructure, chemical state, and interface properties of tungsten tailing-based geopolymers. Results showed tungsten tailings presented little activity using NaOH as activator, while geopolymers with 60% non-pretreatment tungsten tailing and 40% metakaolin presented a 3-day compressive strength of 8.4 MPa and 28-day compressive strength of 9.1 MPa. The geopolymerization products of tungsten tailing-based geopolymers were N-A-S-H gels and aluminosilicate zeolite crystals, while tungsten tailings were wrapped by metakaolin-derived geopolymerization phases as aggregates with interfaces containing Si–O–Si bonding between quartz in tungsten tailings and zeolite and/or gel phase in metakaolin-derived geopolymer in the geopolymerization process. Besides, the leaching test results indicated that the immobilization efficiency of T6M4 geopolymers for Mn and Pb derived from tungsten tailings reached up to 97.28% and 99.95%, respectively. This research results provide a new idea for utilization of tungsten tailings on a large scale.