氧基电解质La_(10-x)V_x(SiO_4)_6O_(3+x)的制备及性能测试(英文)

Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and the influences of V-dopant content on calcining temperature and conductivity were reported.The samples were characterized by thermal analysis(TG-DSC) ,X-ray diffraction(XRD) and scanning electron micrograph(SEM) . The apatite was obtained at 800°C,a relatively low temperature in comparison to 1500°C with the conventional solid-state method.The ceramic pellets sintered at 1200°C for 5 h showed a higher relative density than La9.33Si6O26 pellets sintered at 1400°C for 20 h.The conductivities of samples were measured by electrochemical impedance spectroscopy.The conductivity was improved with the increase of V-dopant content on La site.     

钙钛矿型混合导体透氧膜SrFe0.6Cu0.3Ti0.1O3－δ的制备与表征

Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ （SFCTO） was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5 mm thick SFCTO membrane was 0.35-0.96 ml·min ^-1·cm^-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2 kJ·mol^-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5 ml·min^-1·cm^- 2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.     

Preparation of Nanoporous Thermal Insulating Materials and Their Application as Ladle Linings

The nanoporous thermal insulating material was prepared by using fumed silica,SiC powder and glass fiber as starting materials,the appropriate thickness of the nanoporous thermal insulating material lined in ladle was discussed by the simulation method,and the effect of its application as ladle lining was investigated.The results show that the thermal conductivity of the nanoporous thermal insulating material prepared in composition of fumed silica： SiC powder： glass fiber =75： 20：5 （in mass） is 0.023 W · m^-1 · K^-1 at 1 000 ℃,the appropriate thickness of the nanoporous thermal insulating material lined in ladle is ≤ 5 mm and the average temperature of the ladle outside surface when lined with the nanoporous thermal insulating material is 95 ℃ lower than that with the ordinary thermal insulating material.     

WP/γ-Al2O3催化剂的制备、表征及加氢脱硫和加氢脱氮活性

Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%-37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA, XPS and 31p MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W species was in a high valence state W6 on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31p MAS-NMR results indicated that 31p shift from 85% H3PO4 of 2.55 × 10-4 for WP and 2.57 × 10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activities and lower HDS activities than those prepared by the impregnation method under the same loading of WP.WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.     

Mg2+在胜利褐煤中的负载量对其平衡复吸水含量的影响及其机理分析（英文）

Mg ion-exchanged samples were prepared with acid-washed Shengli lignite. The chemical composition of the ash of the raw sample was determined by X-ray fluorescence. The equilibrium adsorption water contents of sam-ples were determined in a range of relative humidity. The ion-exchange process was characterized by FT-IR, ash content, and pH value. A possible mechanism is proposed for equilibrium adsorption water of ion-exchanged samples at different humidities. The extent of ion-exchange reaction between Mg2+and lignite is control ed by the concentration of Mg2+in MgSO4 solution. The effect of Mg2+on equilibrium adsorption water content varies with relative humidity and content of Mg2+. The factor that controls equilibrium adsorption water content at low relative humidity is water interactions with sorption sites, which are Mg2+–carboxyl group complex. At middle relative humidity capil ary force between Mg2+–water clusters Mg+(H2O)n and capil ary is more impor-tant. At high relative humidity, free water–free water interactions are more significant.     

具有固定硅铝比的Al2O3-2SiO2纳米颗粒制备:过程优化与粉体转化（英文）

Attempts had been made to synthesize Al2O3-2SiO2 nanopowders by sol-gel method with tetraethoxysilane(TEOS) and aluminum nitrate(ANN) as the starting materials.DTS,TEM,SEM and BET were employed to study the effects of process parameters on the size,specific surface area and structure(morphology) of powders.The alkali-activation reactivity of the powders was tested for manufacturing geopolymers and their hydrothermal reactions were performed for fabricating zeolites.The results show that the optimum process parameters and drying method for preparing Al2O3-2SiO2 nanopowders are as follows:the molar ratio of water and ethanol to TEOS are 0:1 and 12:1 respectively at synthetic temperature of 50 ℃ and the drying method is azeotropic distillation with microwave drying.The average particle diameters of the powders were about 70 nm and the largest BET specific surface area was up to 669 m2·g·1.The compressive strength of the geopolymer and the calcium exchange capacity(by CaCO3) of NaA zeolite prepared with the powders reached to 29 MPa and 366 mg·g·1 respectively.     

温度对磷中杂质偏析系数的影响简

The present work is focused on the relationship between effective segregation coefficient keff and tem- perature of melting zone for purification of phosphorus by zone melting method. Values of keff at four temperatures of melting zone are obtained for zone pass n = 1 at travel velocity of molten zone v = 5x 10^-3 m. h^-1 and initial impu- rity concentration C0〈10 μg.g-1, lnkeff is a linear function of 1/T. The keff values of A1, Ca, Cr, Fe, Cd and Sb in- crease with temperatures while that of Mg is almost constant. The purification is acceptable at lower temperature of melting zone such as 323 K. The variations of enthalpy and entropy between impurities and phosphorus in the liq- uid and solid ohases are also 19resented.     

钙钛矿型混合导体透氧膜SrFe0.6Cu0.3Ti0.1O3-δ的制备与表征

Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ (SFCTO) was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5mm thick SFCTO membrane was 0.35-0.96ml·min1·cm-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2kJ·mol-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5ml·min-1·cm2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.     

La_(0.8)Sr_(0.2)MnO_3的燃烧法制备及对HMX热分解的影响(英文)

Perovskite-type La0.8Sr0.2MnO3 was prepared by stearic acid gel combustion method. The obtained powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scaning electron micrograph (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic activity of La0.8Sr0.2MnO3 was investigated on thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by thermal gravity-differential scanning calorimetry (TG-DSC) techniques. The experimental results show that La0.8Sr0.2MnO3 is an effective catalyst for HMX thermal decomposition. The surface-adsorbed species such as H2O, OH&;#61485; and adsorbed oxygen (Oad) could result in an advance in the onset temperature of HMX thermal decompo-sition. The mixture system of Mn3+ and Mn4+ ions and lattice oxygen could play key roles for the increase of the decomposition heat of HMX because these exothermic reactions could be catalyzed by La0.8Sr0.2MnO3 between CO and NOx (from the thermal decom-position of HMX) and the oxidation reaction of CO. According to the previous researches and our results, perovskite-type La0.8Sr0.2MnO3 may be used as a novel catalyst or modifier for nitrate ester plasticized polyether (NEPE) propellant.     

The Effects of Non—Metal Additives on Hydration Reisitance of MgO—C Bricks

The general method of solving the problem of hydration of MgO-C brick is by adding with metal Si,Mg or compround metal additives,but metal additives have bad effect on the MgO-C brick,The test tried adding non-metal additives to matrix material.The results showed that a suitable amount of this kind of additives not only inhibits hydration of MgO-C brick and does not affect corrosion resistance and avoids thermal expansion,but also can improve oxidation resistance.     

Analysis of the conduction mechanisms of the Ni doped apatite-type lanthanum silicate electrolyte ceramics synthesized by the combustion method

In this study, the nickel doped apatite-type lanthanum silicate La_9.33Si_6-xNi_xO_26-x (x = 0, .5, 1.0, 1.5, 2.0) (LSNO) electrolyte powders were successfully generated by using the urea nitrate combustion method at 600°C and 6–8 min. The optimal sintering temperature was determined to be 1500°C on the basis of the linear shrinkage, relative density as a function of temperature, and microcosmic analysis. It was observed that Ni²⁺ successfully replaced Si⁴⁺ in [SiO₄] to form the [Si(Ni)O₄] tetrahedra. LSNO had a typical p6₃/m apatite structure of high purity. A significant change in the cell volume of the doped samples was observed, and the cell volume increased with the doped nickel content. The conductivity reached the peak value at x = 1.0 (1.21 × 10⁻³ S·cm⁻¹, 700°C). Nickel doping introduced the oxygen vacancies and expanded the channels for interstitial oxygen conduction. Further, it also directly reduced the amount of interstitial oxygen in the LSO structure. This led to an enhancement in the conductivity of La_9.33Si_6-xNi_xO_26-x, followed by a decrease on increasing the doped nickel content. The conductivity enhancement in the Ni-doped LSO resulted from the combination of two mechanisms, namely, the oxygen vacancy defect and lattice volume enhancement mechanism.     

掺杂的阳离子缺陷型磷灰石La9.33-2x/3MxSi6O26(M=Mg,Sr,Ca)的合成及离子导电特性

Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33-2x/3 MxSi6O26 (M=Mg, Ca, Sr) is prepared by the sol-gel method with sintering at 1000℃. The powder is characterized by X-ray diffraction (XRD) and scanning electron micrograph (SEM). The apatite can be obtained at relatively low temperature as compared to the conventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33-2x/3 MxSi6O26 (M=Ca, Mg, Sr) indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lattice distortion arising from cation vacancies.     

Effects of La content on the densification,microstructure, and conductivity of doped La10−xGe6O26±δ electrolytes

In this study, the influence of La content on the characteristics of Nb‐, Mo‐, and W‐doped La_xGe₆O_26±δ electrolytes was investigated through sintering study, X‐ray diffraction, scanning electron microscopy, and conductivity measurement. The densification of La_xGe_5.5Nb_0.5O_26±δ and La_xGe_5.5W_0.5O_26±δ was retarded as the x reached 9.75, while that of La_xGe_5.5Mo_0.5O_26±δ improved with increasing La content. The average grain size slightly increased and weight loss due to evaporation of GeO₂ significantly reduced with increasing La content, ranging from 1.39% to 0.26%. Among the systems studied, La_9.33Ge_5.5Nb_0.5O_26.245, La_9.33Ge_5.5Mo_0.5O_26.045, and La_9.50Ge_5.5W_0.5O_26.75 electrolytes revealed great potential for use in SOFC applications.     

Preparation of V doped lanthanum silicate electrolyte ceramics by combustion method and study on conductance mechanism

Vanadium doped La_9.33Si_6−xV_xO_26+0.5x (x = 0.5, 1.0, 1.5) (LSVO) electrolyte powder was prepared by combustion method at 600°C for 5-7 min. The powder was sintered at 1500°C for 3 hours to prepare LSVO ceramics. XPS, IR, XRD, and EIS analysis show that V⁵⁺ doping replaces Si⁴⁺ in [SiO₄] to form [Si(V)O₄] tetrahedron. With the increase in x, the lattice volume increase. When x = 2.0, the LaVO₄ phase was formed, indicating that the limit doping amount of V⁵⁺ replacing Si⁴⁺ is x ≤ 1.5. The conductivity of LSVO increases significantly with the increase in x (x ≤ 1.0), which attributed to the defect reaction caused by V⁵⁺ doping. The addition of the interstitial oxygen Oi* in 6₃ channels and the increase of lattice volume leads to increased conductivity. When x = 1.0, the highest conductivity is 1.46 × 10⁻² S·cm⁻¹ (800°C). The doping enhancement conductivity mechanism is the Interstitial oxygen defect-Lattice volume composite enhancement mechanism.     

Energetic Effects of Substitution of La–Nd and Si–Ge Oxyapatite‐Type Materials

A series of lanthanide oxyapatites, neodymium silicates (Nd_9.33?xM_3x/2(SiO₄)₆O₂; x = 0.0 and 2.0 and M = Ca, Sr, and Ba), and lanthanum germanate (La₁₀(GeO₄)₆O₃) were prepared by a variety of heat treatments and characterized. High‐temperature oxide melt solution calorimetry in molten 2PbO–B₂O₃ solvent at 1078 K was performed to determine their enthalpies of formation from constituent oxides at room temperature. The energetics of these materials is discussed in terms of the effects of doping on two crystallographic sites, the lanthanide and tetrahedral sites. The enthalpy of formation from oxides becomes less exothermic by substituting La with Nd throughout the whole series, in both doped and undoped compositions, reflecting the smaller radius and lower basicity of Nd compared with La. Cation stoichiometric lanthanum germanate apatite (La₁₀(GeO₄)₆O₃) shows a more endothermic enthalpy of formation than the corresponding silicate, reflecting the larger radius and lower acidity of Ge than Si.     

Growth of single-crystals of apatite-type oxide ionic conductor from sintered ceramics by a seeding method

A hexagonal apatite-type La_9.33Si₆O₂₆ single crystal as an oxide ionic conductor has been successfully prepared by a method which is based on the single crystallization of the sintered polycrystalline La_9.33Si₆O₂₆ ceramic on the surface of seed single crystal without their melt. The anisotropy in its conductivity was observed: conductivity component parallel to the c-axis was ca. 100 times higher than the perpendicular component.     

Oxygen Migration in Dense Spark Plasma Sintered Aluminum‐Doped Neodymium Silicate Apatite Electrolytes

Neodymium silicate apatites are promising intermediate temperature (500°C–700°C) electrolytes for solid oxide fuel cells. The introduction of Al promotes isotropic percolation of O^2?, and at low levels (0.83–2.0 wt% Al) enhances bulk conductivity. To better understand the effect of Al‐doping on intrinsic conductivity, and the impact of grain boundaries on the transport, dense Nd_9.33+x/3Al_xSi_6?xO₂₆ (0 ≤ x ≤ 2) pellets were prepared by spark plasma sintering. Phase purity of the products was established by powder X‐ray diffraction and the microstructure examined by scanning electron microscopy. The ionic conductivity measured by AC impedance spectroscopy for the spark plasma sintered ceramics were compared with transport in single crystals of similar composition. Intermediate Al‐doping (0.5 ≤ x ≤ 1.5) delivered superior overall conductivity for both the polycrystalline and single crystal specimens.     

A new family of Cu-doped lanthanum silicate apatites as electrolyte materials for SOFCs: Synthesis,structural and electrical properties

La_9.67Si_6-xCu_xO_26.5-x (LSC, x = 0, 0.1, 0.3 and 0.5) are synthesized by a citric-nitrate method. Substitution Si with Cu promotes the densification process of silicate apatite. Unit cell parameters and volume increase linearly with Cu content. The Rietveld refinement reveals a much more distorted (Si,Cu)O₄ tetrahedra in the oxygen stoichiometric La_9.67Si_5.5Cu_0.5O₂₆ sample. The structural observation from high temperature XRD implies a second-order phase transition in La_9.67Si_5.5Cu_0.5O₂₆. Cu-doping decreases the activation energy of oxygen ion conduction and increases the conductivity of LSC materials in the temperature range of 550–800 °C. La_9.67Si_5.5Cu_0.5O₂₆ shows the conductivity values of 29.3 and 12.3 mS cm⁻¹ at 800 °C and 650 °C, respectively. The oxygen ion transference number of La_9.67Si_5.5Cu_0.5O₂₆ is higher than 0.99. These attractive properties make the La_9.67Si_5.5Cu_0.5O₂₆ a promising oxygen ion conducting electrolyte for applications of solid oxide fuel cells, oxygen sensors, oxygen separation membranes, etc.     

Structural and electrical characterization of Sr- and Al- doped apatite type lanthanum silicates prepared by the pechini method

The subject of this work regards the synthesis of La_9.83−xSr_xSi_6−yAl_yO_26+δ (0≤x,y≤0.5) via a modified Pechini method. The compounds where characterized by XRD and SEM. Pure La_9.83Si₆O_26+δ, La_9.38Sr_0.45Si₆O_26+δ and La_9.38Sr_0.45Si_5.70Al_0.30O_26+δ were prepared after sintering at 1400 °C for 20 h while La_9.38Sr_0.45Si_5.55Al_0.45O_26+δ and La_9.38Sr_0.45Si_5.50Al_0.50O_26+δ contained traces (<8%) of La₂SiO₅ as secondary phase. Rietveld analysis showed that La_9.83−xSr_xSi_6−yAl_yO_26+δ (0≤x,y≤0.5) compounds crystallize in the P6₃/m space group. Al doping on Si site exhibits more pronounced effect upon structural parameters in comparison to Sr doping on La site. Interstitial oxygen accommodates a position at the periphery of the hexagonal channels in the vicinity of the SiO₄ groups. Ion conduction is close related with the size of the hexagonal channels and the interstitial oxygen content. The ion conductivity is promoted when an optimum balance between the aforementioned magnitudes is reached. The LS and LsSa4530 compounds exhibit the highest values of ionic conductivity at 700 °C with 11 and 14 mS/cm and activation energy of 0.47 and 0.46 eV, respectively.     

Electrical conductivity and redox stability of La2Mo2−xWxO9 materials

A series of compounds La₂Mo_2−xW_xO₉ (x = 0-2) were synthesized using a freeze-dried precursor method at relatively low temperatures (673-823 K). These materials were characterised by thermogravimetric and differential thermal analysis (TG/DTA), differential scanning calorimetric (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM) and dilatometric measurements. Oxygen stoichiometry was evaluated by coulometric titration and thermogravimetric analysis at 873-1273 K. The ionic and electronic conductivities of these materials were analysed by impedance spectroscopy and a Hebb-Wagner ion-blocking method under moderately reducing conditions. The presence of W⁶⁺ leads to an increase of the stability range (about 10⁻¹⁶ Pa for La₂Mo_0.5W_1.5O₉ at 1073 K) and prevents oxygen loss and amorphisation. Within the stability range, the electronic conductivity increases gradually as the temperature increases and as the oxygen partial pressure reduces. This indicates that the electronic transport is mainly n-type as a result of the oxygen-content decreasing in the molybdate lattice. Further reduction of the oxygen partial pressure gave rise to the decomposition of La₂Mo_2−xW_xO₉, leading to the formation of new phases with molybdenum in lower oxidation states, which further enhances the electronic conductivity. The results of the coulometric titration and the thermogravimetric studies under a dry 5% H₂/Ar flow suggest that tungsten doped lanthanum molybdate materials can be used as electrolyte only at low temperature and under moderate reducing conditions.