Density functional study of the L10-αIrV transition in IrV and RhV

Both IrV and RhV crystallize in the αIrV structure, with a transition to the higher symmetry L1₀ structure at high temperature, or with the addition of excess Ir or Rh. Here we present evidence that this transition is driven by the lowering of the electronic density of states at the Fermi level of the αIrV structure. The transition has long been thought to be second order, with a simple doubling of the L1₀ unit cell due to an unstable phonon at the R point (0 1/2 1/2). We use first-principles calculations to show that all phonons at the R point are, in fact, stable, but do find a region of reciprocal space where the L1₀ structure has unstable (imaginary frequency) phonons. We use the frozen phonon method to examine two of these modes, relaxing the structures associated with the unstable phonon modes to obtain new structures which are lower in energy than L1₀ but still above αIrV. We examine the phonon spectra of these structures as well, looking for instabilities, and find further instabilities, and more relaxed structures, all of which have energies above the αIrV phase. In addition, we find that all of the relaxed structures, stable and unstable, have a density comparable to the L1₀ phase (and less than the αIrV phase), so that any transition from one of these structures to the ground state will have a volume change as well as an energy discontinuity. We conclude that the transition from L1₀ to αIrV is probably weakly first order. We also examine the behavior of similar compounds, and show that the αIrV structures of both IrTi and RhTi are lower in energy than the experimentally observed high-temperature L1₀ structure.     

碳化La_2O_3-Mo阴极材料的高温XPS研究

采用高温 X射线光电子能谱 (XPS)对碳化 La2 O3- Mo阴极材料表面 La的价态进行了研究。结果表明 ,材料中的 La2 O3可以被 Mo2 C还原成单质 La。单质 La的结合能高于 La2 O3的结合能。从实验上证实单质 La3d5/2的结合能为 835.96e V,并首次给出单质 La3d3/2结合能实验数值为 852 .2 3e V。     

Thermodynamic functions from lattice dynamic of KMgH3 for hydrogen storage applications

The dynamic and the thermodynamic properties of KMgH₃ have been investigated by density functional theory (DFT). We have found that the calculated lattice parameters differ from the experimental data by less than 0.6% and the electronic density of states (DOS) reveals that the KMgH₃ is an insulator. The formation energy of KMgH₃ from binary hydrides (MgH₂ and KH) has been calculated. Using density-functional perturbation theory, we have calculated the phonon dispersion curves, the phonon density of states, the Born effective charge tensors, the dielectric permittivity tensors and the phonon frequencies at the center of the Brillouin zone of KMgH₃. Also we have assigned the calculated phonon frequencies at the gamma point for Infrared-active and Raman-active modes. For the first time, the thermodynamic functions are computed using the phonon density of states.     

Sm2Ce2O7/YSZ功能梯度热障涂层的残余热应力

目的研究基体材质、厚度及半径对Sm_2Ce_2O_7/YSZ功能梯度热障涂层残余热应力的影响。方法采用ANSYS10.0软件中Plane13单元,通过直接耦合计算,系统分析了不同基体条件下,Sm_2Ce_2O_7/YSZ功能梯度热障涂层的残余热应力。结果在Sm_2Ce_2O_7/YSZ功能梯度热障涂层中存在较大的残余热应力。涂层残余热应力随时间的增加而逐渐降低,900 s后基本维持稳定。涂层径向热应力从中心处到试样边缘逐渐递减。2Cr13对应的涂层应力最小。金属基体厚度在2~10 mm范围内,径向热应力虽然增加,但变化幅度不大。当基体厚度为20 mm时,涂层径向热应力则显著增加。金属基体半径对涂层的最大剪切应力并不产生影响,轴向热应力随基体半径的增加而逐渐降低,径向热应力随半径增加到一定值后趋于稳定。结论 2Cr13钢基体对应的涂层具有最小热应力,基体厚度为10 mm时比较合适,基体半径对涂层轴向热应力的影响最明显。     

Effect of phonon focusing on Knudsen flow of phonon gas in single-crystal nanowires made of spintronics materials

Effect of anisotropy of elastic energy on the phonon propagation in single-crystal nanowires made of Fe, Cu, MgO, InSb, and GaAs materials that are used to fabricate spintronics devices in the regime of the Knudsen flow of phonon gas has been studied. A new method of analyzing the focusing of quasi-transverse modes has been suggested, which made it possible to determine the average values of the densities of phonon states in the regions of focusing and defocusing slow and fast quasi-transverse modes. The effect of phonon focusing on the anisotropy of heat conductivity and lengths of the phonon free paths has been analyzed for all acoustic modes that exist in spintronics nanostructures. It has been shown that for all the nanowires investigated the angular dependences of the free paths of fast and slow transverse modes in the {100} and {110} planes correlate with the angular dependences of the densities of phonon states for these modes. Directions of the heat flux that ensure the maximum and minimum phonon heat conductivity in the nanowires have been determined.     

Influence of phonon focusing on the Knudsen flow of phonon gas in single-crystal nanofilms of spintronic materials

Influence of the anisotropy of elastic energy on the phonon transport has been investigated in single- crystal nanofilms of Fe, Cu, MgO, InSb, and GaAs materials used for spintronic instruments and devices in the Knudsen flow regime of phonon gas. The dependences of the lattice thermal conductivity and lengths of free paths of phonons for all acoustic modes on the geometric parameters of the films have been considered for low temperatures with the dominance of the diffuse scattering of phonons at the boundaries. Physical aspects of the propagation of phonon modes in the films have been analyzed. It has been shown that the anisotropy of phonon transport in single-crystal films is due to the features of the propagation of phonon modes in elastically anisotropic films with a different relationship of the geometric parameters. The directions of heat flow and orientations of the film planes that yield the maximum and minimum thermal conductivity of phonons in film planes have been determined.     

Investigation of the electronic structure of the new quaternary hydride PdSr2LiH5

We have investigated the band structure of the new tetragonal quaternary mixed alkali-alkaline earth transition metal hydride PdSr₂LiH₅ by means of the ab initio augmented plane wave method. We find this material to be metallic. The total density of states as well as its partial wave analysis have been used to investigate the origin of the electronic states. In this hydride, like in superconducting PdH, the palladium d bands are essentially filled and the H-s states have a non-negligible contribution at the Fermi energy. We find the electronic contribution to the electron-optical phonon coupling constant to be sizeable, although smaller than in PdH.     

Preparation and characterization of （metal, nitrogen）-codoped TiO2 by TiCl4 sol-gel auto-igniting synthesis

The nitrogen-doped and （metal, nitrogen）-codoped TiO2 photocatalysts （metal = Ag, Ce, Fe, La） were synthesized by sol-gel auto-igniting synthesis （SAS） with the complex compound sol of TiCl4-NH4NO3-citri acid-metal nitrate- NH3.H20 as a precursor. The products were characterized by means of XRD, XPS, and UV-Vis diffuse reflectance spectra, and their photocatalytic activity was investigated under visible light. It was found that all the synthesized powders showed good absorption for visible light, and that the radius and alterable valence states of doping metallic cations played important roles on their photocatalytic activity. These results were discussed in detail.     

Ab initio energetic study of oxide ceramics with rare-earth elements

Ab initio energetic calculations based on the density functional theory （DFF） and the projector augmented wave method （PAW） for determining the polymorphisms of lanthanide sesquioxides Ln2O3 （where Ln = rare-earth element, Y, and Sc）, LnMO3 perovskites （where M = AI and Ga）, and Ln2B207 pyrochlores （where B = Ti, Zr, and Hf） were reported. The relative lattice stabilities agreed well with the critically assessed results or the experimental results except the C-type Ln2O3 with a cubic structure, for which the calculated total energies were considerably more negative. With the increase of the Ln^3＋-cation radius, the polymorphic structures showed a degenerative tendency. The tendencies and quantities of the enthalpies of formation of the ternary oxide ceramics synthesized from their constituent binary oxides reasonably agreed with the available experimental results, and valuable thermodynamic properties were afforded to the compound, for which no experimental data is available. The enthalpies of formation of both perovskites and pyrochlores tend to become more negative with the increase of the Ln^3＋-cation radius.     

Spectroscopic properties of Er-doped and Er/Yb-codoped PbF2–MOx (M = Te, Ge, B) oxyfluoride glasses

A series of Er³⁺-doped and Er³⁺/Yb³⁺-codoped lead germanate (GP), lead tellurite (TP) and lead borate (BP) transparent oxyfluoride glasses were synthesized. Spectroscopic characteristics of these materials were systemically measured. The Judd–Ofelt parameters were calculated according to absorption spectra. F⁻ ions have a strong effect on refractive index (n) and phonon energy of the host. Intense red and green upconversion is closely related to phonon energy, J–O parameters and sensitizer. The GPEY-2 glass (53GeO₂–43PbF₂–0.5Er₂O₃–2Yb₂O₃) shows good transparency and fairly strong upconversion emissions.     

Interactions of particles with solidifying front in Al_2O_(3P) /Al Si composites

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Chemical stability of La_2O_3 in La_2O_3-Mo cathode materials

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Structure and Raman scattering of Mg-doped ZnO nanoparticles prepared by sol-gel method

Mg-doped ZnO (Mg_xZn_(1-x)O, x=0-0.10)nanoparticles were prepared by sol-gel method. Structural characterization by X-ray diffraction (XRD) indicates that the lattice parameter a increases and c decreases linearly with the increase in Mg content (x) due to the substitution of Mg~(2+) for Zn~(2+) in ZnO lattice. The blueshift of Raman modes is observed, impling the increase in force constant of atom vibration in the Mg_xZn_(1-x)O (MgZnO) nanoparticles. Resonant Raman spectra show longitudinal optical phonon overtones up to fifth order, revealing that the short part of the electron-phonon interaction is enhanced and long-range part is weakened by Mg doping.     

Molecular and electronic properties of β-(BEDT-TTF)2PF6 studied by scanning tunneling microscopy

Two different structures based on one-dimensional molecular rows were observed by scanning tunneling microscopy (STM) in the β-(BEDT-TTF)₂PF₆ crystal surface. The temperature dependence of tunneling current-bias voltage curves showed the property of a metal-insulator phase transition. However, metallic electronic states were observed even at 230K between the energy gap, indicating fluctuation of the charge density wave. The metallic property was recovered when the STM tip was softly brought into contact with the sample surface, where the charge density wave is considered to be formd.     

Size-dependent cohesive energy,melting temperature,and Debye temperature of spherical metallic nanoparticles

It is necessary to theoretically evaluate the thermodynamic properties of metallic nanoparticles due to the lack of experimental data. Considering the surface effects and crystal structures, a simple theoretical model is developed to study the size dependence of thermodynamic properties of spherical metallic nanoparticles. Based on the model, we have considered Co and Cu nanoparticles for the study of size dependence of cohesive energy, Au and Cu nanoparticles for size dependence of melting temperature, and Cu, Co and Au nanoparticles for size dependence of Debye temperature, respectively. The results show that the size effects on melting temperature, cohesive energy and Debye temperature of the spherical metallic nanoparticles are predominant in the sizes ranging from about 3 nm to 20 nm. The present theoretical predictions are in agreement with available corresponding experimental and computer simulation results for the spherical metallic nanoparticles. The model could be used to determine the thermodynamic properties of other metallic nanoparticles to some extent.     

Optical and acoustic phonon modes confined in gallium phosphide nanoparticles

The main aim of this paper is to discuss the confinement effects on the optical and acoustic phonon vibrational modes in gallium phosphide(GaP) nanoparticles(cylindric grain).The Raman scattering from the GaP nanoparticles was investigated.It was found that the red-shifts of the longitudinal optical(LO) mode and transverse optical(TO) mode were 15 cm?1 and 13.8 cm?1,respectively.It is generally accepted that the red-shifts of the optical phonon modes are due to the presence of smaller nanosized particles(～1.2 nm) acting as the nanoclustered building blocks of the GaP nanoparticles.In the low frequency Raman spectrum,a set of Stokes lines with almost the same spacing was clearly observed.The scattering feature originates from the discrete phonon density of states of the nanoclustered building blocks.According to Lamb's vibrational theory,the Raman shift wavenumbers of the spheroidal mode and torsional mode of the lowest energy surface modes for the nanoclustered building blocks were calculated.Good agreement can be achieved between the calculated results and the observed scattering peaks.These results indicate that the corresponding Raman peaks are due to scattering from the localized acoustic phonons in the nanoclustered building blocks in the GaP nanoparticles.     

含Co、Ni、Fe锂铝硅玻璃的析晶机制

以Li2O-Al2O3-SiO2（锂铝硅）微晶玻璃为研究对象,采用DTA、XRD、IR和SEM等测试技术研究含Fe2O3、Co2O3、Ni2O3锂铝硅玻璃的析晶动力学和晶化过程,分析着色剂成分Co2O3、Ni2O3对锂铝硅玻璃晶化过程及结构的影响机制。结果表明：着色剂成分不仅决定锂铝硅微晶玻璃的着色度,而且还影响锂铝硅玻璃的析晶过程和显微结构;着色剂的加入可提高锂铝硅玻璃的析晶温度,但降低析晶动力学参数,且高Co2O3含量的降幅大于高Ni2O3含量的。着色剂对锂铝硅玻璃析晶能力的影响主要与着色离子的离子半径、电场强度及对断裂硅氧四面体联结能力有关。     

Structural,elastic and electronic properties of equiatomic PtTi as potential high-temperature shape memory alloy

We investigated the phase stability from B2 to L1₀/B19/B19′ in equiatomic PtTi alloy using the density functional theory within the generalized gradient approximation. Their structural, energetic, electronic and the mechanical properties were determined to show the stability trend of the shape memory binary alloy. The lattice parameters are well reproduced and agree to within 2% with the available experimental data. We found that the calculated heats of formation and density of states predicted B19 and B19′ PtTi to be the most stable structures compared to B2 and L1₀. On the other hand, their mechanical stability predictions show consistency with regard to the elastic constants and phonon dispersion curves. The elastic instability (negative C_ij) and soft modes were observed in the B2, B19 and B19′ structures and not found in the L1₀ structure.     

反应磁控溅射MgO薄膜溅射模式的分形维表征

用反应磁控溅射的方法制备了MgO薄膜，基于原子力显微镜观测，并借助Fourier变换，计算了薄膜表面形貌的分形维数。发现分形维数变化对应于薄膜溅射模式的变化，二者之间有相关性，氧分压30％的分形维数是一个临界点，分形维数若发生明显跌落，意味着溅射模式发生变化，界于临界值两侧的分形维数，分别对应两种截然不同的溅射模式，与临界值对应的溅射状态则处于金属模式和氧化物模式的混和状态。     

点缺陷对MOX燃料热导率的影响研究

MOX燃料作为快堆燃料重要的候选燃料类型之一，是核燃料闭式循环的关键环节。导热性能是MOX燃料在堆内服役的关键参数，将直接影响快堆的安全性。目前通常只对实测数据进行拟合得到其热导率经验公式，缺乏对不同Pu含量和氧金属比（O/M）的MOX燃料热导率的理论分析。本文基于经典声子热传导理论，通过对MOX燃料在不同Pu含量和O/M下热导率影响因素的分析，研究了不同类型点缺陷对其热导率的影响。研究结果表明，采用声子传导模型可以很好地预测不同成分MOX燃料的热导率。MOX燃料中离子替代型点缺陷造成的质量差和半径差对热导率的影响权重相对较小，而MOX燃料不同O/M比造成的氧空位型点缺陷对热导率的影响权重相对较大。本研究对于不同成分MOX燃料的热导率预测和成分设计具有重要意义。