Studies of tetragonal PbTiO3 subjected to uniaxial stress along the c-axis

Tetragonal PbTiO3 under uniaxial stress along the c-axis is investigated from first-principles. The structural parameters, polarization, and squares of the lowest optical phonon frequencies for E(1TO) and A(1)(1TO) modes at Gamma show abrupt changes near a stress sigma(c) of 1.04 GPa, which is related to the dramatic change of elastic constant c(33) resulting from the uniaxial stress applied along the c-axis. We also find that the uniaxial compressive stress could enhance the piezoelectric stress coefficients, whereas the uniaxial tensile stress could enhance the piezoelectric strain coefficients. It is also found that when the magnitude of uniaxial compressive stress sigma(33) is greater than 12 GPa, PbTiO3 is transformed to the paraelectric tetragonal phase.

Third-order optical nonlinearities of lead-free (Na1-xKx)(0.5)Bi0.5TiO3 thin films

(Na1-xKx)(0.5)Bi0.5TiO3 (NKBT) (x = 0.1, 0.2, and 0.3) thin films with good surface morphology and rhombohedral perovskite structure were fabricated on quartz substrates by a sol-gel process. The fundamental optical constants (the band gaps, linear refractive indices and absorption coefficients) of the films were obtained through optical transmittance measurements. The nonlinear optical properties were investigated by Z-scan technique performed at 532 nm with a picosecond laser. A two-photon absorption effect closely related with potassium-doping content was found in thin films, and the nonlinear refractive index n(2) increases evidently with potassium-doping. The real part of the third-order nonlinear susceptibility chi((3)) is much larger than its imaginary part, indicating that the third-order optical nonlinear response of the NKBT films is dominated by the optical nonlinear refractive behavior. These results show that NKBT thin films have potential applications in nonlinear optics. (C) 2007 Elsevier B.V. All rights reserved.

钙钛矿过渡金属氧化物电、磁性质的理论研究

钙钛矿过渡金属氧化物已有大量实验和理论研究。本论文采用一般梯度近似（GGA）和GGA+U（U表示原位的库仑相互作用）下的第一性原理密度函数方法研究了双层，四层和含氧空位的钙钛矿过渡金属氧化物的晶体结构、电子结构以及电、磁性质。 从对双层钙钛矿Sr2FeMoO6和Sr2CoMoO6的研究，我们发现Sr2FeMoO6的四方相比立方相稳定，而且两种结构下它都显半金属特性；对于Sr2CoMoO6，原位的库仑相互作用决定了它的半导体性质。此外，我们还研究了实验上备受争议的Ba2YIrO6和Ba2LaIrO6在立方 Fm-3m, 菱形 R-3和单斜 P21/n三种结构下的相对稳定性。结果表明第一性原理与半经验的键价模型得到的结论相同，即Ba2YIrO6和Ba2LaIrO6的最稳定结构分别是单斜 P21/n和菱形R-3。 不同Mn-O-Mn角度下YBaMn2O5的电子结构和磁结构的计算结果表明，当Mn-O-Mn 角度处于实验所测的157.8o时，G-型反铁磁结构比A-型稳定，与实验结果相符。随着角度的增加，大约在170出现了磁结构转变。当角度大于170时，A型反铁磁结构比G型稳定，即YBaMn2O5从G型过渡到A型。此外，我们还研究了YBaMn2O5在不同磁结构以及不同角度下的导电性。 通过对四层钙钛矿化合物CaCu3M4O12 （M是3d过渡金属离子：Ti, V, Cr, Mn, Fe, Co）的能带结构计算研究了M离子的电子构型对其磁结构和导电性的影响。结果表明随着M电子数的增加，该系列化合物磁结构为：在CaCu3Ti4O12（Ti4+：d0）中Cu-Cu为反铁磁性耦合，即该物质为反铁磁体；在CaCu3M4O12 (M= V4+：d1, Cr4+：d2, Mn4+：d3, Fe4+：d4；dn，0

层状钙钛矿结构化合物的合成、电性和磁性的研究

近年来，随着金属多层膜，磁隧道结和钙钦矿锰氧化物等材料中磁阻现象的发现，以研究磁阻效应的机理和应用为目的的磁电子学迅速发展。这其中钙钦矿结构的稀土锰氧化物以其超大的磁阻值和丰富的物理内涵而备受瞩目。尽管人们对此已做了大量的工作，但是对这类氧化物的深入认识直至超大磁电阻效应物理机制的合理解释仍需做艰苦细致的努力。本论文选择层状钙钦矿稀土锰氧化物作为研究对象，系统地研究了A位，B位的变化和B位原子之间的相互作用对氧化物的结构、磁性和磁阻性质的影响。希望得到钙钦矿中磁、电性质和磁阻与结构之间的关系，能对该系列化合物中电、磁性质的变化规律和相互作用机理作出合理的解释。基于LaSr2Mn2O7的结构特殊性，我们选择了它作为母体化合物。并通过过渡金属离子Cr，Ti，Ni，Fe对Mn离子取代来研究B位原子的变化对性质的影响。结果发现，Cr3＋因为与Mn4＋具有相同的电子形态而能够参与双交换作用，使掺杂Cr3＋的系列样品的磁化强度随cr含量的增加而增加。而掺杂讨＋，Ni2＋，Fe3＋离子的化合物虽然与Mn离子之间的相互作用各不相同，但引起的磁性变化却是相同的。这四种元素的掺杂都提高了体系的磁阻和电阻率。通过对这几种过渡金属取代的比较，发现在LaS2Mn2O7中对Mn离子进行取代的离子和Mn离子之间的交换作用对磁性质的影响并不起主要作用，掺杂引起的主要作用是致使Mn位的无序度增加和对双交换作用的稀释和阻碍。值得注意的是每个系列样品中都有一个样品的磁阻在高温时出现较大的正值，且随着温度的降低转变为负值。例如，在Fe掺杂的系列样品中，只有x＝0.2的样品表现出正磁阻，且MR在28OK时达到74％。这可能是因为掺杂导致的结构变化引起的。这种正磁阻对材料的应用意义重大。电荷有序对磁阻材料是一种很重要的状态，为了提高LasrZMn2O7的电荷有序温度，我们选择了具有孤对电子的Bi3+来取代Sr2+。结果发现，单相样品只能持续到x≤0.2。样品的电荷有序温度并没有象预想的那样有所提高。这是因为体系的二维结构抑止了Bi3＋离子的作用，同时由于体系中Bi3＋的含量较少没有达到提高电荷有序温度的程度。但Tco降低的程度相对于其它离子的取代效果（如Gd）要低。目前n=3的层状钙钦矿研究较少，但是由于该化合物具有结构可变性和理论上可以解释磁转换机理，我们对（La，ca）4kMn3O10进行了深入的研究。在La3-3xCa1＋3xMn3O10（0.5≤x≤1.0）中随La3＋含量的减少，该系列化合物经历了从铁磁性到顺磁性再到反铁磁性的转变，同时在磁阻上也经历了由负磁阻（x＝0.5～0.7）到正磁阻（x=0.8-1.0）的转变。根据磁性和电性的变化规律，我们认为这种正负磁阻的转变是由于体系中超交换和双交换作用的相互竞争引起的。La3＋含量多时，Mn3十离子含量较多，双交换作用占主导地位，产生负磁阻；随着Mn3+离子含量的减少，双交换作用逐渐减弱，Mn4+离子之间的反铁磁性超交换作用逐渐增强，产生了正磁阻。在低掺杂浓度时LaxCa4-xMn3O10（x＝0-0.9）经历了顺磁性到反铁磁性的转变，为了了解其磁性变化过程，我们进一步研究了富含Mn4＋的这一区间。发现磁化强度在x≤0.2的范围内随x增加而增强，在高于0.2的掺杂范围后随x的增加而逐渐降低。这是因为这一区间的磁结构由基态时的G型-AFM向x＝0.9时的C型-AFM的转变。而且这种转变与载流子浓度密切相关。

Electronic structure of microporous titanosilicate ETS-10

The electronic structure of a microporous titanosilicate framework, ETS-10 is calculated by means of a first-principles self-consistent method. It is shown that without the inclusion of the alkali atoms whose positions in the framework are unknown, ETS-10 is an electron deficient system with 32 electrons per unit cell missing at the top of an otherwise semiconductor-like band structure. The calculated density of slates are resolved into partial components. It is shown that the states of the missing electrons primarily originate from the Ti-O bond. The local density of states of the Ti-3d orbitals in the ETS-10 framework is quite different from the perovskite BaTiO3. The possibilities of ETS-10 crystal being ferroelectric or having other interesting properties are discussed.

Oxidative activation of light alkanes on dense ionic oxygen conducting membranes

The oxidative dehydrogenation of ethane to ethylene (ODHE) has been studied in a catalytic membrane reactor (CMR) using a dense mixed ionic oxygen and electronic conducting perovskite membrane Ba0.5Sr0.5Co0.8Fe0.2O3-&. At 1080K, an ethylene yield of 66% was obtained with the bare membrane. After Pd cluster deposition, the ethylene yield reached 76% at 1050K. Ni cluster deposition led to a decrease of ethane conversion compared to the bare membrane without changing ethylene selectivity.

Novel cobalt-free oxygen permeable membrane

A series of cobalt-free and low cost perovskite oxygen permeable membranes based on BaCexFe1-xO3-delta (BCF) oxides was successfully synthesized and the membrane showed both high oxygen permeability and high stability under reductive atmosphere, which will be most suitable for constructing a membrane reactor for selective oxidation of light hydrocarbons to syngas or high value corresponding oxygenates.

Structure and oxygen permeability of a dual-phase membrane

The dual-phase membrane of La0.15Sr0.85Ga0.3Fe0.7O3-delta-Ba0.5Sr0.5Fe0.2Co0.8O3-delta (LSGF-BSCF) was prepared successfully. This membrane was characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe micro-analyzer (EPMA). This membrane has a dense dual-phase structure: LSGF being the dense body of this membrane and BSCF as another phase running along the LSGF body. This structure is favorable for the oxygen permeation through the membrane. The oxygen permeation test shows that the oxygen permeation flux of LSGF-BSCF membrane (Jo(2) = 0.45 ml/min cm(2), at 915 degreesC) is much higher than that of LSGF membrane (Jo(2) = 0.05 ml/min cm(2)). Thickness dependence of oxygen permeation indicates that the oxygen permeation is controlled by the bulk diffusion. Compared to pure BSCF the dual-phase membrane of LSGF-BSCF is stable in reducing atmosphere. (C) 2003 Elsevier B.V. All rights reserved.

Oxidative dehydrogenation of propane in a dense tubular membrane reactor

Oxidative dehydrogenation of propane (ODP) to propylene was investigated in a dense tubular membrane reactor made of Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCF) at 700degreesC and 750degreesC. The propylene selectivity in the membrane reactor (44.2%) is much higher than that in the fixed-bed reactor (15%) at the similar propane conversion (23-27%). Higher propylene selectivity in the membrane reactor was attributed to the lattice oxygen (O2-) supplied through the membrane.

Structural characterization, stability and electrical properties of strontium niobate ceramic

The double perovskite oxide Sr2CrNbO6 has a cubic structure according to powder X-ray diffraction. After reducing in CO, Sr2CrNbO6 still exhibited a cubic structure refined by Rietveld technique. The TG analysis indicated that Sr2CrNbO6 loses 0.127 oxygen per formula unit from 400 to 700 degrees C in H-2. The morphology and compositions of this ceramic did not significantly change on reduction

Magnetic structure and orbital ordering in tetragonal and monoclinic KCrF3 from first-principles calculations

KCrF3 has been systematically investigated by using the full-potential linearized augmented plane wave plus local orbital method within the generalized gradient approximation and the local spin density approximation plus the on-site Coulomb repulsion approach. The total energies for ferromagnetic and three different antiferromagnetic configurations are calculated in the high-temperature tetragonal and low-temperature monoclinic phases, respectively.

Crystal structure of microwave dielectric ceramics Ba[(Mg1-xCdx)(0.33)Nb-0.67]O-3

A series of complex perovskite solid solutions of Ba[(Mg1-xCdx)(0.33)Nb-0.67]O-3 have been synthesized by the columbite method. Detailed Rietveld refinement of their X-ray diffraction data show that Ba[(Mg1-xCdx)0(.33)Nb(0.67)]O-3 has an order trigonal structure. The ordering degree as determined by the B-site occupancies increases with the partial substitution of Cd for Mg.

Structural stability and electronic properties of Ba2MIrO6 (M = La, Y) by first principles

We investigate the structural stability and electronic properties of ordered perovskite-type compounds Ba2MIrO6 (M = La, Y) by use of density functional theory. Cubic (Fm-3m), rhombohedral (R-3) and monoclinic (P2(1)/n) phases are considered for each compound. It was found that the most energetically stable phase for Ba2YIrO6 and Ba2LaIrO6 is P2(1)/n andR-3, respectively. It is also interesting to find that Ba2YIrO6 in R-3 phase, which was not reported in experiment, has a slightly lower energy than experimentally observed cubic Fm-3m phase.

Near compensated half-metal in Sr2NiOsO6

The electronic and magnetic properties of tetragonal double perovskite Sr2NiOsO6 were studied by use of the density functional theory and including the spin-orbit coupling. Compensated half-metal is found if the spin-orbit coupling is not considered. Spin-orbit coupling induces orbital moments on both Ni and Os, making Sr2NiOsO6 a near compensated half-metal. Ferromagnetic phase is slightly favored over antiferromagnetic phase (by 4 meV). The small energy difference also suggests that both phases are competitive for the ground state. At ferromagnetic phase, the calculated net magnetic moment is 3.53 mu(B), in good agreement with experimental value of 3.44 mu(B). At antiferromagnetic phase, the net magnetic moment is 0.69 mu(B), in which the contribution from the net spin moment is 0.09 mu(B).

Structural stability and magnetic coupling in CaCu3Co4O12 from first principles

The structural, electronic and magnetic properties of CaCu3Co4O12 were studied by use of the full-potential linearized augmented plane wave method. The calculated results indicate that CaCu3Co4O12 is stable both thermodynamically and mechanically. Both GGA (generalized gradient approximation) and GGA + U methods predict that CaCu3Co4O12 is metallic. The ferromagnetic configuration is only slightly more stable in energy compared with the non-magnetic configuration (3.7 meV), suggesting that they are competitive for being the ground state. Co is in the low spin state (S = 1/2).