镧改性的CuHY分子筛中铜离子的分布及其对吸附脱硫性能的影响

在氮气气氛下采用等体积浸渍法制备了载Cu的HY和LaHY分子筛.用x射线衍射(XRD)、N2吸附、氨程序升温脱附和X射线光电子能谱对分子筛进行了表征.通过多晶XRD确定了Cu2+离子在Y型分子筛笼内的结构与分布,并测定了分子筛在含二苯并噻吩(DBT)的模拟柴油中的吸附脱硫性能.结果表明,前驱体CuCl2中的大部分Cu物种与HY和LaHY分子筛进行了离子交换.对于La3+改性的CuHY分子筛(CuLaHY),进入分子筛超笼中的Cu2+离子与骨架氧和水分子配位,牢固地定位于Y型分子筛超笼的SⅡ及SⅢ位;对于CuHY分子筛,超笼中的Cu2+离子只接近于SⅡ及SⅢ位.极少部分CuCl分子高度分散在分子筛笼内,没有定位.处于超笼中SⅡ及SⅢ位的Cu2+离子对模拟柴油中的DBT分子具有吸附作用,是吸附脱硫的活性中心.CuLaHY分子筛的吸附脱硫性能优于CuHY分子筛.当模拟柴油中含有萘时,萘与DBT分子会产生竞争吸附.     

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe₁₂O₁₉) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced alongside ferric chloride among the starting materials. Though all of the Fe²⁺ ions in the starting material were converted to Fe³⁺ ions in the final product, Fe²⁺ was confirmed to participate differently from the Fe³⁺ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe₂O₃ and BaFe₂O₄ were improved when Fe²⁺ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl₂/FeCl₃ when only 2 h of reaction time were needed. It was also found that the role of trivalent Fe³⁺ could be successfully replaced by Al³⁺. Up to 50% of the iron could be replaced by Al³⁺ in the reactants to produce Al-doped products. It was also found that the ratio of Fe²⁺/M³⁺ could be increased in the presence of Al³⁺ to produce high quality barium ferrite.     

The effect of urea-to-nitrates ratio on the morphology and magnetic properties of Mn0.8Mg0.2Fe2O4

Mn_0.8Mg_0.2Fe₂O₄ ferrite was synthesized using flash auto-combustion technique using urea as fuel. The effect of the urea-to-nitrates ratio was examined and found to affect the samples characteristics. The as-burnt powder was crystallized in single-phase spinel structure of cubic symmetry. The lattice parameter was decreased with increase in the urea-to-nitrates ratio (n) while the crystal size increased from 21 to 42 nm with n changing from 6.67 to 10. The coercivity increases while the saturation and remanence magnetization decreases with increase in n. This was attributed to the disturbance of the spin order as a result of the surface effects.     

Preparation and magnetic properties of La-Mn and La-Co doped barium hexaferrites prepared via an improved co-precipitation/molten salt method

La-Mn and La-Co doped barium hexaferrites of formula Ba_(1−x)La_xFe_(12−x)M_xO₁₉ (M=Mn, Co) (x=0.05 to 0.40) were prepared with an improved co-precipitation/molten salt method. For the synthesis, aqueous solutions of the appropriate metal chlorides were prepared in the ratio required except that the initial mole ratio of Fe and dopants to Ba was chosen to be 11:1, and then mixed with excess Na₂CO₃. The solutions were then cooled, filtered off, dried, then mixed with KCl flux, and heated at 450 °C and for 2 h. The temperature was then raised to 950 °C and kept for 4 h, then cooled. This new synthesis method, which employs a lower temperature and shorter reaction time, gives products with improved crystallinity and purity while the saturation magnetization and coercivity values are comparable with those synthesized via the high temperature method.     

Ultra large coercivity in barium ferrite thin films prepared by magnetron sputtering

Hexagonal barium ferrites were deposited onto sapphire substrates by radio frequency magnetron sputtering. The composition, microstructure, and magnetic properties of these isotropic thin films were investigated with Rutherford backscattering spectroscopy, X-ray diffraction, atomic force microscopy, magnetic force microscopy and SQUID magnetometry. The intrinsic coercivity of the films reaches about 11.5 kOe at room temperature. The mechanism of the coercivity is proposed to be nucleation in the decoupled single domain nanometer particles as shown by the characteristics of the magnetic domains and the virgin magnetization curves.     

Thermal hysteresis and domain states in Ni-Zn ferrites synthesized by oxalate precursor method

Nickel zinc ferrites with generic formula, Ni_XZn_1−XFe2O4 (with X=0.28-0.40) were synthesized by an oxalate precursor route starting with acetates to study their magnetic properties. The saturation magnetization versus temperature curves resemble those of R type ferrites. The system shows the presence of Yafet-Kittel type of spin. It is observed that magnetic moment (n_B) values increase with the addition of Ni²⁺. The remanance ratio R tends to increase with the addition of Ni²⁺, which has been attributed to the increase of magnetocrystalline anisotropy constant (K1). The values of R compare well with the theoretical value (0.87). The coercive force (H_c) tends to increase with the addition of Ni²⁺, which has been related to the reverse domain formation. Studies on temperature variation of R and H_c reveal that these parameters are thermally insensitive, which confirms the presence of multi domain grains in the material. These observations have been supported by a.c. susceptibility studies.     

Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method

Nanocrystalline octahedra of cobalt ferrite CoFe₂O₄ powders were synthesized using the organic acid precursor route. The effect of the calcination temperature, Fe³⁺/Co²⁺ molar ratio, calcination time and type of organic acid (oxalic, benzoic and tartaric acids) on the formation, crystallite size, microstructure and magnetic properties was studied systematically. The Fe³⁺/Co²⁺ molar ratio was varied from 2 to 1.739 while the annealing temperature was controlled from 400 to 1000 °C for various periods from 0.5 to 2 h. The resulting powders were investigated using X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD results indicate that a well crystallized, single spinel cobalt ferrite phase was formed for the precursors annealed at 600-800 °C for 2 h, using oxalic and tartaric acids as precursors for Fe³⁺/Co²⁺ molar ratio 1.818. The crystallite size of as-formed powders was in the range of 38.0-92.6 nm at different operating conditions. The calcination temperature and Fe³⁺/Co²⁺ molar ratio have a significant effect on the microstructure of the produced cobalt ferrite. The microstructure of the produced powders was found to be octahedra-shaped. The crystalline, pure cobalt ferrite powders with magnetic properties having a maximum saturation magnetization (76.1 emu/g) was achieved for the single phase at Fe³⁺/Co²⁺ molar ratio 1.818 and annealing temperature of 600 °C for 2 h using tartaric acid precursor.     

Raman tensor elements for multiferroic BiFeO3 with rhombohedral R3c symmetry

A quantitative assessment of the Raman spectrum emitted from a coarse‐grained polycrystal of multiferroic BiFeO₃ has been carried out by means of a polarized Raman microprobe. The dependence of the intensity of Raman phonon modes has been first theoretically modeled as a function of crystal rotation. Then, the Raman tensor elements have been experimentally determined from the analysis of the A_g and E_g vibrational modes. Copyright © 2009 John Wiley & Sons, Ltd.     

Lanthanum-doped Bi4Ti3O12 ceramics prepared by high-pressure technique

We present an effective way in this paper to increase the density of lanthanum doped bismuth titanate ceramics, Bi4-xLaxTi3O12 (BLT), thereby significantly improving the performance of the BLT ceramics. Dense BLT ceramicses, Bi4-xLaxTi3O12 (x = 0.25, 0.5, 0.75, 1.0), are prepared by using nanocrystalline powders fabricated by a-gel method and high-pressure technique. The microstructures of the BLT ceramicses prepared separately by conventional-pressure and high-pressure techniques are investigated by using x-ray diffraction and transmission electron microscope. The influence of La-doping on the densification of bismuth titanate ceramics is investigated. The experimental results indicate that the phase compositions of all samples with various lanthanum dopings sintered at 900°C possess layer-structure of Bi4Ti3O12 . The green compacts are pressed under 2.5 GPa, 3.0 GPa, 3.5 GPa and 4.0 GPa, separately. It is found that the density of BLT ceramics is significantly increased due to the decreasing of porosity in the green compacts by high-pressure process.     

Surface study of fine MgFe2O4 ferrite powder prepared by chemical methods

To study surface behaviors, MgFe₂O₄ ferrite materials having different grain sizes were synthesized by two different chemical methods, i.e., a polymerization method and a reverse coprecipitation method. The single phase of the cubic MgFe₂O₄ was confirmed by the X-ray diffraction method for both the precursors decomposed at 600-1000 °C except for a very small peak of Fe₂O₃ was detected for the samples calcined at 600 and 700 °C by the polymerization method. The crystal size and particle size increased with an increase in the sintering temperature using both methods. The conductance of the MgFe₂O₄ decreased when the atmosphere was changed from ambient air to air containing 10.0 ppm NO₂. The conductance change, C = G(air)/G(10 ppm NO₂), was reduced with an increase in the operating temperature. For the polymerization method, the maximum C-value was ca. 40 at 300 °C for the samples sintered at 900 °C. However, the samples sintered at 1000 °C showed a low conductance change in the 10 ppm NO₂ gas, because the ratio of the O₂ gas adsorption sites on the particle surface is smaller than those of the samples having a high C-value. The low Mg content on the surface affects the low ratio of the gas adsorption sites. For the reverse coprecipitation method, the particle size was smaller than that of the polymerization method. Although a stable conductance was obtained for the sample sintered at 900 and 1000 °C, its conductance change was less than that of the polymerization method.