La0.7Ca0.3Mn1-xCuxO3的电输运特性

通过固相反应法制备不同掺杂浓度的La_0.7Ca_0.3Mn_1-xCu_xO₃（x=0~0.15）样品, 在77~300 K温度范围内测量了铜掺杂后样品电阻随温度的变化关系. 结果表明, 在未引入铜杂质时, 低温铁磁相的电阻率满足T^2.5关系, 顺磁相符合小极化子近邻跳跃模型; 在低掺杂下, 铁磁区可用T^4.5关系解释; 随着掺杂浓度的增加, 在铁磁区和顺磁区, 任何单一模型均与实验不相符, 表明高掺杂样品的电输运性质存在未知模型.      

三价铁离子掺杂对钛酸锂结构和化学性能的影响

采用溶胶凝胶法制备Li4-x/3FexTi5-2x/3O12(x=0,0.03,0.06,0.09)粉体活性材料,并优化了最佳掺杂量为x=0.03。通过X射线衍射(XRD)、扫描电镜(SEM)、恒流充放电测试对材料进行结构、形貌及电化学性能表征。结果表明:掺杂适量的铁离子不会改变钛酸锂的尖晶石结构和形貌。1C时,Li3.99Fe0.03Ti4.98O12首次放电比容量为145.40 m A·h/g;纯相的首次放电比容量仅为116.95 m A·h/g。     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.     

钙钛矿La0.7CexBa0.3-xMnO3的磁热性能研究

【目的】通过固相反应法制备La_(0.7)Ce_xBa_(0.3-x)MnO_3(x=0,0.05,0.10,0.15,0.20)的钙钛矿锰氧化物,研究Ce元素的不同掺杂量对原体系磁热性能的影响。通过Ce元素的掺杂,来调节原体系过高的居里温度以及改善体系的磁热性能。【方法】通过X射线粉末衍射的方式确定其单相结构,并使用振动样品磁强计对钙钛矿样品进行磁性能的测试。【结果】La0.7CexBa0.3-xMnO3(x=0,0.05,0.10,0.15,0.20)的居里温度分别为342.1K,319.8K,270.0K,244.3K和199.7K。在0~2T的外磁场下,该体系的最大磁熵变分别为2.54J/(kg·K),2.32J/(kg·K),2.51J/(kg·K),2.03J/(kg·K)和1.87J/(kg·K),且最大磁熵变都在居里温度附近。【结论】随着Ce元素掺杂量的增加,化合物居里温度逐渐降低;而最大磁熵变则呈先减小后增大又减小的趋势。同时由Arrott曲线判断这5个样品的相变都是二级相变。当Ce元素的掺杂量为0.05~0.10时,该体系的居里温度在室温附近,且最大磁熵变仍保持较大的值。     

中温SOFC阴极材料La0.7Sr0.3Co1-xCuxO3-δ的制备及性能

采用固相反应法制备了La_0.7Sr_0.3Co_1-xCu_xO_3-δ系列中温固体氧化物燃料电池（SOFC）阴极材料粉体.对其进行晶体结构表征,高温电导率和热膨胀曲线测试,并选取其中性能较好的样品进行了单电池实验.结果表明,Cu的掺杂降低了（La,Sr）CoO La₃体系阴极材料的热膨胀系数,在x=0.05时电导率略高于未掺Cu的样品.以La_0.7Sr_0.3Co_0.95Cu _0.05O _3-δ为阴极、Ce_0.8Sm_0.2O_1.9为电解质组成的SOFC单电池,在850℃最大短路电流密度达511mA/cm²,最大输出功率密度约为0.106W/cm².     

A phase field study for influence of elastic energy on L1<Subscript>0</Subscript>→L1<Subscript>2</Subscript> transient ordering in Ni<Subscript>75</Subscript>Al<Subscript>17</Subscript>Zn<Subscript>8</Subscript>

The influence of the elastic energy on L1₀→L1₂ transient ordering transformation was investigated by microscopic phase field method. It is found that there are three stages experienced in atomic ordering: solute clustering+L10 short range ordering → L1₀ long range ordering → L1₂ long range ordering. Before the formation of the high ordered L1₂ phase, it has firstly taken place the transformation from matrix to L1₀ phase, and then held the L1₀→L1₂ secondary transformation. Elastic energy is proved to take little effect on the stage of short range ordering, but as the elastic energy is multiplied, it obviously shortened the course of the solute clustering, and speeded up the proceeding of the L1₀ long range ordering transition. Accordingly, the increased elastic energy also strengthens the single crystalline directionality of L1₀ phase projecting on 2D plane and makes the ordered degree of Al and Zn atoms enhanced. With the temperature elevation, Al’s and Zn’s ordered degree decreased in L10 phase.     

基于Li2MnO3的富锂类高比容量锂离子电池正极材料的研究进展

综述了近几年来基于Li2MnO3的高比容量二元和三元富锂类锂离子电池正极材料的研究进展.重点讨论了富锂材料zLi2MnO3.(1-z)LiMO2(0相似文献   

纳米Fe2O3-Al2O3复合材料的制备

采用溶胶-凝胶表面包覆法制备了纳米Fe₂O₃-Al₂ O₃复合材料, 利用X射线衍射和透射电镜对样品的物相、 粒度和形貌进行了研 究. 结果表明, α-Fe₂O₃掺杂降低了Al₂O₃相变温度, 在900 ℃可以得到稳定的α-Al₂O₃相.     

烟火药剂中三种常用氧化剂的太赫兹谱研究

为了探索烟火药剂中常用氧化剂的太赫兹谱,利用量子化学模拟计算烟火药剂中常用氧化剂氯酸钾、高氯酸钾和硝酸钾的太赫兹频率吸收范围和特征吸收峰.并用太赫兹时域光谱系统实际测量得到了这些氧化剂以及含高氯酸钾烟火药剂在0.2～2.5THz频谱范围内的吸收光谱峰值位置.氯酸钾在0.2～2.5THz波段的特征吸收峰为2.4THz,纯高氯酸钾和含高氯酸钾混合烟火药剂都在2.0THz和2.2THz处分别具有明显的特征吸收峰,硝酸钾的特征吸收峰位于1.8THz和2.3THz处.理论计算与实验测量结果对比表明,三种氧化剂在0.2～2.5THz波段的特征吸收峰有较好的一致性.     

流动注射分析法测定水样中的NO2--N和NO3--N

采用流动注射技术测定水样中的NO-/2-N和NO-/3-N.以N-(1-萘基)乙烯二胺盐酸盐和对氨基苯磺酸为显色剂,在540nm下比色测定NO-/2-N的含量.水样中的NO-/3-N,在稀醋酸条件下用锌粉将其预还原成NO-/2-N后,也在上述相同的条件下测定其含量.NO-/2-N的检出限为0.005×10-/6,NO-/3-N的检出限为0.05×10-/6,分析速度为65次/小时.     

Bi~(3+)/Yb~(3+)共掺GdVO_4近红外发光性能研究

使用高温固相法制备了一种新的Bi3+,Yb3+共掺杂GdVO4量子裁剪近红外发光材料,该材料在波长为250~400nm的紫外光激发下发射出很强的近红外光(900~1100nm).由于体系中Bi3+离子的引入,相对于Gd0.9Yb0.1VO4,Gd0.87Yb0.1Bi0.03VO4在989nm处的近红外发光强度提高近120%,且其激发峰也从323nm红移至341nm,整个激发谱带更宽,更有利于实际应用.由于Yb3+离子既可以利用基质中的VO3-4电荷迁移态跃迁的能量,也可以同时利用Bi3+的1S0-3P1能级跃迁传递能量,相对于目前报道的理论量子裁剪效率最高的YVO4:Bi3+,Yb3+,GdVO4:Bi3+,Yb3+无论其近红外发光强度还是可见光发光强度强度皆有提升,是一种很有希望的紫外宽带激发近红外发光材料.     

Structure and transport studies on nanometer YBCO/PBCGO multilayers

We have fabricated M doped （M = Al, Co, Fe, Ga, Ni and Zn） PrBa2Cu3O7（PBCO）, i.e. PrBa2（CU1-xMx）3O7. The doping levels x are 0.05, 0.10, 0.15, and 0.20. X-ray data indicated no significant second phase for substituting Cu by Al, Co, Fe and Ga up to 20%. However impurity phases were detected for Ni and Zn substituted samples with doping levels equal to and higher than 15%. At 77 K the electrical resistivity of these compounds is orders in magnitude higher than that of PBCO. We also found that although the lattice parameters in the doped samples differ from PBCO, all samples remain orthorhombic. The lattice parameters of the doped sample are very close to those of YBa2CU3O7-δ （YBCO） and PBCO. For this reason these compounds are better materials to be used as the I-layer for YBCO SIS junctions. Results of structural and transport studies on 2000 A thick PrBa2[Cu0.80G0.2]3O7 （PBCGO） and YBCO/PBCGO multilayers are presented in this paper.     

Preparation and photocatalytic activity of Cu-doped TiO2/SiO2

Cu²⁺-doped nanostructured TiO₂-coated SiO₂ (TiO₂/SiO₂) particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO₂ colloids were synthesized by the sol-gel method using TiOSO₄ as a precursor. The experimental results showed that TiO₂ nanopowders on the surface of SiO₂ particles were well distributed and compact. The amount of TiO₂ increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550°C. The 2-layer coated TiO₂ particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu²⁺-doped TiO₂/SiO₂ was higher than that of undoped TiO₂/SiO₂. The optimum dopant content was about 0.10wt%.     

Surface interactions of MoO3/ α-Fe2O3 system

α-Fe₂O₃ -supported molybdena catalysts have been prepared by heating a mixture of MoO₃ and α-Fe₂O₃. XRD, XPS, LRS, TG-DTA and Mössbauer spectroscopy were used to characterize the interactions between MoO₃ and α-Fe₂O₃. The dispersion capacity of MoO₃ on the surface of α-Fe₂O₃ determined by XRD and XPS was 0.8 mmol/100m² α-Fe₂O₃ in the samples calcined at 420 . For the sample with low MoO₃ loading, LRS and FT-IR results showed that Mo⁶⁺ ions were located in the tetrahedral vacant sites on the surface of α-Fe₂O₃, signed as Mo- . The amount of Mo-II species, formed by Mo6+ ions incorporated into the octahedral vacant sites, increased with the MoO₃ loading. Based on the assumption that the (001) plane of α-Fe₂O₃ is preferentially exposed, almost all the Mo⁶⁺ ions of the dispersed molybdena species existed at the surface octahedral sites for the sample with MoO₃ loading close or beyond the dispersion capacity, and formed the Mo-II species. In this case, the capping O^2- ions linking with the incorporated Mo⁶⁺ ions formed a surface epitaxial structure, which was in good agreement with the results predicted by the incorporation model proposed previously. XRD and Mössbauer spectroscopy of the MoO₃ α-Fe₂O₃ samples calcined at different temperatures showed that the calcination temperature could strongly influence the interaction extent: ( i) at 420 , MoO₃ dispersed on the surface of α-Fe₂O₃ and formed surface Mo species; (ii ) at 500 , MoO₃ reacted with the bulk of α-Fe₂O₃ and formed Fe₂(MoO₄)₃ compound.     

不同形貌LaBO_3型钙钛矿的制备及其催化H_2O_2分解反应性能

采用柠檬酸络合法制备了La BO3(B=Fe,Co,Ni)钙钛矿催化剂,通过X-射线粉末衍射(XRD)、傅立叶-红外光谱(FT-IR)、透射电镜(TEM)、X-射线光电子能谱(XPS)等对催化剂进行了表征,在室温下测定了其对H2O2的催化分解能力.结果表明:催化分解能力依次为La Ni O3>La Co O3>La Fe O3,说明Ni较Co和Fe能更好地分解H2O2.通过改变La Fe O3催化剂的形貌也能提高催化剂性能,如多孔状La Fe O3较负载在SBA-15上的La Fe O3具有更好的催化分解活性.     

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized.Cubic perovskite structures were formed for BaBi0.2CoyFe0.8-yO3-δ (y≤0.4) and BaBixCo0.2Fe0.8-xO3-δ(x=0.1-0.5).The materials exhibited considerable high oxygen permeability at high temperature.The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-δ membrane reached about 0.77×10-6 mol/cm2.s under an air/helium oxygen partial pressure gradient at 900℃, which was much higher than that of other bismuth-contained mixed conducting membranes.The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content.The materials also demonstrated excellent reversibility of oxygen adsorption and desorption.Stable time-related oxygen permeation fluxes were found for BaBi0.2Co0.35Fe0.45O3-δ and BaBi0.3Co0.2Fe0.5O3-δ membranes at 875℃.     

Relationship between luminescence and matrices in the system A12O3-B2O3-Ce2O3

The system Al₂O₃-B₂O₃-Ce₂O₃, with Al/B ratio varying from 4.5 to 2 and Ce/(Al+B) = 0.02, has been prepared at the temperature from 1 200 to 1 400°C. Relationship between luminescence and matrices in the system Al₂O₃-B₂O₃-Ce₂O₃ was investigated. It was found that some changes of the matrices occurred with Al/B ratio varying from 4.5 to 2. These results lead to a great change in luminescence properties, indicating variation of Ce-surroundings of crystal field. With the decrease of the ratio from 3 to 2, the excitation and emission peaks shift to shorter wavelengths. It was also found that a new type of rare earth luminescent materials was obtained with appropriate Al/B ratio.     

ZnGa2Se4:V3+ 光谱的理论研究

应用区分t₂和e轨道共价性的差异(包含静电部分和晶场部分)并考虑了低对称场的能量矩阵, 在考虑和忽略静电参量B₀₀的条件下, 分别研究了t₂和e轨道共价性的差异对三元半导体ZnGa₂Se₄:V ³⁺能级以及低对称分裂的影响; 计算了ZnGa₂Se₄:V ³⁺晶体的能级的低对称分裂, 并与实验值进行比较. 计算结果与实验值符合很好. 研究发现: 在对ZnGa₂Se₄:V ³⁺晶体的光学性质进行理论研究时, 在能量矩阵的静电和晶场部分同时考虑t₂和e轨道共价性的差异是非常有必要的; 晶场参量B₀₀对ZnGa₂Se₂4:V ³⁺的能级有重要影响, 因此不能忽略.     

The concentration quenching characteristics of 5D3-7FJ and 5D4-7FJ (J=0―6) transitions of Tb3+ in YBO3:Tb3+ phosphor

The photoluminescence quenching behaviors of ^5D3-^7Fj and ^5D4-^7Fj （J = 0—6） transitions of Tb^3＋ in YBO3：Tb under 130—290 nm excitation were systematically investigated. The results revealed that the quenching concentrations of both ^5D3-^7Fj and ^5D4-^7Fj transitions of Tb^3＋ in YBO3：Tb were mainly dependent on excitation wavelength. Particularly, the quenching concentrations of ^5D4-^7Fj transitions of Tb^3＋ under 130—290 nm excitation were correlated with excitation bands of YBO3：Tb. The quenching concentrations of ^5D3-^7Fj transitions remained at low concentration （2%） under 186—290 nm excitation and then increased gradually with energy of incoming excitation photon when excited at 130—186 nm. This dependence should be involved in their excitation mechanisms and quenching pathway in particular excitation region.[第一段]     

Effects of minor B additions on tensile strength,fracture toughness and oxidation resistance of Nb–Si based alloys

The effects of minor additions of B on microstructure, ambient tensile strength, fracture toughness and high-temperature oxidation resistance of Nb–Si based alloys were investigated. The added contents were designed as 0.05, 0.10 and 0.20 ?at.%. The results show constituent phases in 0.05B and 0.20B alloys were Nbss, α-Nb₅Si₃; while only 0.10B alloy consisted of γ-Nb₅Si₃. Minor B was prioritized into Nbss and redundant one dissolved into silicide enhanced volume fraction of the silicide. With increasing concentrations of boron, the microstructure was refined at first and then coarsened, while the tensile strength was enhanced remarkably. Compared with other two alloys, the 0.10B alloy containing γ-Nb₅Si₃ shows both the best fracture toughness and oxidation resistance. The important roles of γ-Nb₅Si₃ in balancing overall properties are emphasized.