PHASE TRANSITIONS IN Bi2Sr2(Cu1-zFez)O6+δ

We have investigated, by X-ray diffraction, a series of single crystals of Bi-based oxides with the nominal composition Bi₂Sr₂(Cu_1-zFe_z)O_6+δ(0≤z≤0.55). In this system we observed two structural phase transitions with the increase of the doping content. The first transition, from an incommensurate monoclinic phase to an incommensurate orthorhombic phase, occurs at a doping content of iron z_Fe=0.027. The second one corresponds to a phase transition from an incommensurate orthorhombic phase to a commensurate orthorhombic phase at z_Fe=0.34. The comparison of these results with those for more limited substitutions of Zn and Ni indicates the significant role of the insertion of the extra oxygen in the (Bi-O)_∞ double layers.     

Ni/α-Al2O3催化剂作用下苯甲醚的加氢脱氧

Ni-based catalysts supported on di erent supports (α-Al₂O₃,γ-Al₂O₃, SiO2, TiO₂, and ZrO₂) were prepared by impregnation. Effects of supports on catalytic performance were tested using hydrodeoxygenation reaction (HDO) of anisole as model reaction. Ni/α-Al₂O₃ was found to be the highest active catalyst for HDO of anisole. Under the optimal conditions, the anisole conversion is 93.25% and the hydrocarbon yield is 90.47%. Catalyst characteriza-tion using H₂-TPD method demonstrates that Ni/α-Al₂O₃ catalyst possesses more amount of active metal Ni than those of other investigated catalysts, which can enhance the cat-alytic activity for hydrogenation. Furthermore, it is found that the Ni/α-Al₂O₃ catalyst has excellent repeatability, and the carbon deposited on the surface of catalyst is negligible.     

EFFECT OF α-Fe SURFACE LAYER ON THE MAGNETIC REVERSION PROCESS FOR Nd2Fe14B CRYSTAL

The demagnetization process for a Nd₂Fe₁₄B grain covered by an α-Fe layer was studied by use of the finite element technique of micromagnetics. μ_0iH_c decreases with the increase of α-Fe layer thickness t. With the increase of t from 0 to 6nm, μ_0iH_c decreases from ～7 T to ～3.5 T when the angle between the applied field and the c-axis of the Nd₂Fe₁₄B grain is 0.5° and from ～4 T to ～1.5 T when the angle is 30° or 60°. The effect is only slightly affected by the angle between the α-Fe layer and the field direction.     

纯Cr2O3包覆Li4Ti5O12微球的制备及其储锂性能研究

The pure Cr₂O₃ coated Li₄Ti₅O₁₂ microspheres were prepared by a facile and cheap solutionbased method with basic chromium(III) nitrate solution (pH=11.9). And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr₂O₃ works as an adhesive interface to strengthen the connections between Li₄Ti₅O₁₂ particles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, LixCr₂O₃, formed by the lithiation of Cr₂O₃, can further stabilize Li₇Ti₅O₁₂ with high electric conductivity on the surface of particles. While in the acid chromium solution (pH=3.2) modification, besides Cr₂O₃, Li₂CrO₄ and TiO₂ phases were also found in the final product. Li₂CrO₄ is toxic and the presence of TiO₂ is not welcome to improve the electrochemical performance of Li₄Ti₅O₁₂ microspheres. The reversible capacity of 1% Cr₂O₃-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At-20℃, its reversible specific capacity was still as high as 118 mAh/g.     

The effect of anti-hydrogen bond on Fermi resonance: A Raman spectroscopic study of the Fermi doublet ν1—ν12 of liquid pyridine

The effects of anti-hydrogen bond on the ν₁—ν₁₂ Fermi resonance (FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of Fermi coupling coefficient W of the ring breathing mode ν ₁ and triangle mode ν ₁₂ of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the ν₁—ν₁₂ Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν₁—ν₁₂ FR of pyridine. According to the mechanism of the formation of anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν₁—ν₁₂ FR of pyridine is given.     

基于Co3O4修饰SnO2纳米纤维的高响应和高选择性乙醇气体传感器

SnO₂ nanofibers were synthesized by electrospinning and modified with Co₃O₄ via impregnation in this work. Chemical composition and morphology of the nanofibers were systematically characterized, and their gas sensing properties were investigated. Results showed that Co₃O₄ modification significantly enhanced the sensing performance of SnO₂ nanofibers to ethanol gas. For a sample with 1.2 mol% Co₃O₄, the response to 100 ppm ethanol was 38.0 at 300℃, about 6.7 times larger than that of SnO₂ nanofibers. In addition, the response/recovery time was also greatly reduced. A power-law dependence of the sensor response on the ethanol concentration as well as excellent ethanol selectivity was observed for the Co₃O₄/SnO₂ sensor. The enhanced ethanol sensing performance may be attributed to the formation of p-n heterojunctions between the two oxides.     

窄带隙KNb1-xFexO3-δ的室温铁磁性

We have investigated the structure, optical and magnetic properties of ferroelectric KNb_1-xFexO_3-δ (X=0, 0.01, 0.03, 0.05, 0.10, 0.15, 0.20, 0.25) synthesized by a traditional solid-state reaction method. According to the X-ray diffraction and the results of Rietveld refinement, all the samples maintain orthorhombic distorted perovskite structures with Amm2 space group without any secondary phase, suggesting the well incorporation of Fe ions into the KNbO₃ matrix. With the increase of Fe concentration, the band gap of each sample is decreased gradually, which is much smaller than the 3.18 eV band gap of pure KNbO₃. Through X-ray photoelectron spectrum analysis, the increased density of oxygen vacancy and Fe ions may be responsible for the observed decrease in band gap. Compared with the pure KNbO₃, Fe doped samples exhibit room-temperature weak ferromagnetism. The ferromagnetism in KNb_1-xFexO_3-δ with low-concentration dopants (X=0.01-0.10) can be attributed to the bound magnetic polaron mediated exchange. The enhancement of magnetism for the high-concentration (X=0.10-0.20) doped samples may arise from the further increase of magnetic Fe ions.     

LiMn2O4 films grown by pulsed-laser deposition

LiMn₂O₄ films have been deposited onto silicon wafer by pulsed-laser deposition (PLD) technique in order to test their reliability as cathode materials in rechargeable lithium microbatteries. The film formation has been studied as a function of the preparation conditions, i.e., composition of the target, substrate temperature, and oxygen partial pressure in the deposition chamber. Depending on the conditions of deposition, Mn₂O₃ was present as an impurity phase. When deposited onto silicon substrate maintained at 300 °C in an oxygen pressure of 100 mTorr from the target LiMn₂O₄+15 % Li₂O, the PLD films are well-textured with crystallite size of 300 nm. It is found that such a film crystallizes in the spinel structure (Fd3m symmetry) as evidenced by x-ray diffraction and Raman scattering measurements. Surface morphologies of layers were investigated by SEM. The cells Li//LiMn₂O₄ have been tested by cyclic voltammetry and galvanostatic charge-discharge techniques in the range 3.0–4.2 V. The voltage profiles show the two expected steps for Li_xMn₂O₄ with a specific capacity as high as 120 mC/cm² μm. The chemical diffusion coefficients for the Li_xMn₂O₄ thin films appear to be in the range of 10⁻¹¹-10⁻¹² cm²/s. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Preparation techniques and materials for long term stable SOFC - Single cell membranes

Chemical reactions and thermal expansion mismatch between electrodes and electrolyte may reduce the long term stability of SOFC-single cells and can cause undesirable thermomechanical stresses. In solid electrolyte cells the formation of MnAl₂O₄ was detected between the air electrode (La_0.5Ca_0.5MnO₃) and the electrolyte (YSZ/Al₂O₃) in a 5 μm diffusion zone within the electrolyte. The electronically conducting spinel MnAl₂O₄ is thought to be the main factor for delamination of the air electrode under anodic current (electrolysis). The performance and long term stability of the air electrode/electrolyte interface can be improved for electrolysis conditions by an additional intermediate YSZ-layer made by sol-gel technique. The mismatch in thermal expansion between the electrode materials and the electrolyte have been eliminated via optimized doping and by adding small amounts of a silicate-based substituent with a very low thermal expansion co-efficient for the cathode and anode, respectively. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Fabrication of anode supported thick film ceria electrolytes for IT-SOFCs

Anode supported thick film ceria electrolyte unit cells were fabricated using a colloidal dip coating method for IT-SOFCs. Pre-sintering temperature of the anode substrate and the final sintering temperature were found to be the primary parameters determining the density of the film. With Ni-Ce_0.89Gd_0.11 O_2–δ cermet anode, La_0.6Sr_0.4Co_0.2Fe_0.8O₃ cathode and 15 μm Ce_0.89Gd_0.11 O_2–δ electrolyte, the cells were tested in a fuel cell configuration with air at the cathode and moist H₂ at the anode. At 650 °C, the cell indicated a maximum power density of ∼0.27 W/cm² at a current density of 0.62 A/cm². Cell performance was compared with oxygen at the cathode and the cell indicated a maximum power density of ∼0.50 W/cm² at 1.14 A/cm², 650 °C. Activation energy for the area specific resistance (ASR) of the cell suggests that with air at cathode, the cell performance was limited by gaseous diffusion at cathode and with oxygen at cathode, by oxygen ion transport across the electrolyte.     

Preparation and magnetic properties of BaFe12O19/Ni0.8Zn0.2Fe2O4 nanocomposite ferrite

Nanocomposite of hard (BaFe₁₂O₁₉)/soft ferrite (Ni_0.8Zn_0.2Fe₂O₄) have been prepared by the sol–gel process. The nanocomposite ferrite are formed when the calcining temperature is above 800 °C. It is found that the magnetic properties strongly depend on the presintering treatment and calcining temperature. The “bee waist” type hysteresis loops for samples disappear when the presintering temperature is 400 °C and the calcination temperature reaches 1100 °C owing to the exchange-coupling interaction. The remanence of BaFe₁₂O₁₉/Ni_0.8Zn_0.2Fe₂O₄ nanocomposite ferrite with the mass ratio of 5:1 is higher than a single phase ferrite. The specific saturation magnetization, remanence magnetization and coercivity are 63 emu/g, 36 emu/g and 2750 G, respectively. The exchange-coupling interaction in the BaFe₁₂O₁₉/Ni_0.8Zn_0.2Fe₂O₄ nanocomposite ferrite is discussed.     

Synthesis,crystal structure and magnetic properties of Yb8Ag18.5Al47.5, Yb2Pd2Cd and Yb1.35Pd2Cd0.65

We report the synthesis of three new Yb-based compounds, Yb₈Ag_18.5Al_47.5 (Yb₈Cu₁₇Al₄₉-type, tetragonal tI74–I4/mmm), Yb₂Pd₂Cd (Mo₂B₂Fe-type, tetragonal tP10-P4/mbm) and Yb_1.35Pd₂Cd_0.65 (MnCu₂Al-type, cubic cF16–Fm3¯m). The crystal symmetry of these compounds has been determined and the complete structural characterisation carried out by single crystal and powder diffraction techniques. Two symmetry in-equivalent sites are available for the Yb ions in Yb₈Ag_18.5Al_47.5 and Yb_1.35Pd₂Cd_0.65. The 4f levels of the Yb ions are appreciably hybridised in Yb₈Ag_18.5Al_47.5 and to a lesser extent in Yb₂Pd₂Cd as inferred from the magnetisation and heat capacity data. Signatures of heavy fermion behaviour are observed in the heat capacity data of Yb₂Pd₂Cd in which the heat capacity, C/T, increases at low temperatures attaining a value of ≈600 mJ/mol K² at 1.8 K. The electrical resistivity of Yb₂Pd₂Cd follows a linear variation with temperature, T, between 1.4 and 5 K, thus indicating a possible non-Fermi liquid behaviour. In contrast, Yb ions are trivalent in Yb_1.35Pd₂Cd_0.65 and order magnetically near 1.4 K.     

Double-ceramic-layer thermal barrier coatings based on La2(Zr0.7Ce0.3)2O7/La2Ce2O7 deposited by electron beam-physical vapor deposition

Double-ceramic-layer (DCL) thermal barrier coatings (TBCs) of La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) and La₂Ce₂O₇ (LC) were deposited by electron beam-physical vapor deposition (EB-PVD). The composition, interdiffusion, surface and cross-sectional morphologies, cyclic oxidation behavior of DCL coating were studied. Energy dispersive spectroscopy and X-ray diffraction analyses indicate that both LZ7C3 and LC coatings are effectively fabricated by a single LZ7C3 ingot with properly controlling the deposition energy. The chemical compatibility of LC coating and thermally grown oxide (TGO) layer is unstable. LaAlO₃ is formed due to the chemical reaction between LC and Al₂O₃ which is the main composition of TGO layer. Additionally, the thermal cycling behavior of DCL coating is influenced by the interdiffusion of Zr and Ce between LZ7C3 and LC coatings. The failure of DCL coating is a result of the sintering of LZ7C3 coating surface, the chemical incompatibility of LC coating and TGO layer and the abnormal oxidation of bond coat. Since no single material that has been studied so far satisfies all the requirements for high temperature applications, DCL coating is an important development direction of TBCs.     

New FIR laser lines from optically pumped C2H3F, C2H3Cl, C2H3Br, C2H3CN, C2H5F, CH2CF2, HCOOH and CH3Br

Twenty-seven new cw far infrared laser lines with wavelengths between 137 and 988m have been observed from optically pumping C₂H₃F, C₂H₃Cl, C₂H₃Br, C₂H₅F, C₂H₃CN, CH₂CF₂, HCOOH and CH₃Br with a CO₂ laser. The wavelengths of these FIR laser lines were determined together with their optimum pressures and relative intensities.     

Er3+/Yb3+共掺Gd3Sc2Ga3O12晶体的上转换发光

研究了提拉法生长的Er³⁺/Yb³⁺:Gd₃Sc₂Ga₃O₁₂和Er³⁺:Gd₃Sc₂Ga₃O₁₂晶体在室温下320—1700nm范围的吸收光谱和500—750nm范围内的上转换荧光谱,同时对其上转换荧光的可能发生机制、途径以及上转换过程可能对Er^{3+相似文献}   

Chemical quenching of positronium in Fe2O3/Al2O3 catalysts

Fe₂O₃/Al₂O₃ catalysts were prepared by solid state reaction method using α-Fe₂O₃ and γ-Al₂O₃ nano powders. The microstructure and surface properties of the catalyst were studied using positron lifetime and coincidence Doppler broadening annihilation radiation measurements. The positron lifetime spectrum shows four components. The two long lifetimes τ₃ and τ₄ are attributed to positronium annihilation in two types of pores distributed inside Al₂O₃ grain and between the grains, respectively. With increasing Fe₂O₃ content from 3 wt% to 40 wt%, the lifetime τ₃ keeps nearly unchanged, while the longest lifetime τ₄ shows decrease from 96 ns to 64 ns. Its intensity decreases drastically from 24% to less than 8%. The Doppler broadening S parameter shows also a continuous decrease. Further analysis of the Doppler broadening spectra reveals a decrease in the p-Ps intensity with increasing Fe₂O₃ content, which rules out the possibility of spin-conversion of positronium. Therefore the decrease of τ₄ is most probably due to the chemical quenching reaction of positronium with Fe ions on the surface of the large pores.     

SrBi2Ta2O9/Bi4Ti3O12复合铁电薄膜的制备与特性研究

采用溶胶凝胶工艺在p-Si衬底上制备了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合铁电薄膜. 研究了SrBi₂Ta₂O₉/Bi₄Ti₃O₁₂复合薄膜的微观结构与生长行为、铁电性能和疲劳特性. 研究表明: Si衬底Bi₄Ti< 关键词： 2Ta₂O₉')" href="#">SrBi₂Ta₂O₉ 4Ti₃O₁₂')" href="#">Bi₄Ti₃O₁₂ 复合铁电薄膜 溶胶凝胶工艺     

Optical properties of Mn-activated Na2SnF6 and Cs2SnF6 red phosphors

Alkaline hexafluorostantanate red phosphors Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺ are synthesized by chemical reaction in HF/NaMnO₄ (CsMnO₄)/H₂O₂/H₂O mixed solutions immersed with tin metal. X-ray diffraction patterns suggest that the synthesized phosphors have a tetragonal symmetry with the space group D_4h¹⁴ (Na₂SnF₆:Mn⁴⁺) and a trigonal symmetry with the space group D_3d³ (Cs₂SnF₆:Mn⁴⁺). Photoluminescence (PL) analysis, PL excitation (PLE) spectroscopy, and the Raman scattering techniques are used to investigate the optical properties of the phosphors. The Franck-Condon analysis of the PLE data yields the Mn⁴⁺-related optical transitions to occur at ∼2.39 and ∼2.38 eV (⁴A_2g→⁴T_2g) and at ∼2.83 and ∼2.76 eV (⁴A_2g→⁴T_1g) for Na₂SnF₆:Mn⁴⁺ and Cs₂SnF₆:Mn⁴⁺, respectively. The crystal field parameters (Dq) of the Mn⁴⁺ ions in the Na₂SnF₆ and Cs₂SnF₆ hosts are determined to be ∼1930 and ∼1920 cm⁻¹, respectively. Temperature-dependent PL measurements are performed from 20 to 440 K in steps of 10 K, and the obtained results are interpreted by taking into account the Bose-Einstein occupation factor. Comprehensive discussion is given on the phosphorescent properties of a family of Mn⁴⁺-activated alkaline hexafluoride salts.     

Emission features of Ho ion in Nb2O5, Ta2O5 and La2O3 mixed Li2O-ZrO2-SiO2 glasses

Li₂O-ZrO₂-SiO₂: Ho³⁺ glasses mixed with three interesting d-block elemental oxides, viz., Nb₂O₅, Ta₂O₅ and La₂O₃, were prepared. Optical absorption and photoluminescence spectra of these glasses have been recorded at room temperature. The luminescence spectra of Nb₂O₅ and Ta₂O₅ mixed Li₂O-ZrO₂-SiO₂ glasses (free of Ho³⁺ ions) have also exhibited broad emission band in the blue region. This band is attributed to radiative recombination of self-trapped excitons (STEs) localized on substitutionally positioned octahedral Ta⁵⁺ and Nb⁵⁺ ions in the glass network. The Judd-Ofelt theory was successfully applied to characterize Ho³⁺ spectra of all the three glasses. From this theory various radiative properties, like transition probability A, branching ratio β_r and the radiative lifetime τ_r, for ⁵S₂ emission levels in the spectra of these glasses have been evaluated. The radiative lifetime for ⁵S₂ level of Ho³⁺ ions has also been measured and quantum efficiencies were estimated. Among the three glasses studied the La₂O₃ mixed glass exhibited the highest quantum efficiency. The reasons for such higher value have been discussed based on the relationship between the structural modifications taking place around the Ho³⁺ ions.     

XPS investigation of diffusion of two-layer ZrO2/SiO2 and SiO2/ZrO2 sol–gel films

Two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were deposited on K9 glass substrates by sol–gel dip coating method. X-ray photoelectron spectroscopy (XPS) technique was used to investigate the diffusion of ZrO₂/SiO₂ and SiO₂/ZrO₂ films. To explain the difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films, porous ratio and surface morphology of monolayer SiO₂ and ZrO₂ films were analyzed by using ellipsometry and atomic force microscopy (AFM). We found that for the ZrO₂/SiO₂ films there was a diffusion layer with a certain thickness and the atomic concentrations of Si and Zr changed rapidly; for the SiO₂/ZrO₂ films, the atomic concentrations of Si and Zr changed relatively slowly, and the ZrO₂ layer had diffused through the entire SiO₂ layer. The difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films was influenced by the microstructure of SiO₂ and ZrO₂.