Electric field gradients in Hf2Fe

Perturbed Angular Correlations (PAC) technique was applied to measure the electric field gradients (EFG) at ¹⁸¹Ta sites in Hf₂Fe. The compound has the cubic structure of the Ti₂Ni prototype with two non‐equivalent crystallographic sites for Hf atoms. EFGs for the two sites were measured as a function of the temperature. In addition, one more EFG was observed, which was assigned to the presence of defects in the lattice. The ratio of the measured EFG at the regular lattice sites has been used to assign charges to the ions through a simple calculation using the point charge model and it is shown that the lattice symmetry can explain the very different EFG at both sites. This revised version was published online in August 2006 with corrections to the Cover Date.     

Iron ions in ZSM-5 zeolite: Fe3+ in framework, Fe2+ in extra-framework positions in catalytic N2O decomposition

Fe-ZSM-5 samples containing a combination of ⁵⁷Fe³⁺ in framework (FW) and regular iron in extra-framework (EFW) sites were prepared by introducing ⁵⁷Fe in hydrothermal synthesis, then exchanging Fe²⁺ of natural isotope composition into the lattice. The stability for one part of Fe²⁺ and Fe²⁺ ? Fe³⁺ reversibility for the other part in catalytic decomposition of N₂O is demonstrated by in situ Mössbaer measurements. Formation of dinuclear Fe_FW–O–Fe_EFW pairs is not prevailing.     

La2Zr2O7:Eu3+纳米棒的合成、表征及其荧光性能

采用传统固相法和水热法成功地制备出棒状La₂Zr₂O₇:Eu³⁺荧光粉. 利用X射线粉末衍射仪、透射电镜和荧光光谱仪等分析了产物的结构、形貌和发光特性. 结果表明红色荧光粉La₂Zr₂O₇:Eu³⁺有良好的晶相,属于立方结构,空间点群为Fd3m; 其形貌主要为纳米棒, 平均直径约47 nm, 长度为50～700 nm. 并对纳米棒的生长机理进行了探讨. 在466 nm蓝光激发下,La₂Zr₂O₇:Eu³⁺荧光粉能发射出Eu³⁺的特征红色荧光,发射主峰位于616 nm处,归属于Eu³⁺的⁵DO_→⁷F2_{超灵敏电偶极跃迁.此外,在产物的发射光谱中能够观察到⁵D}1_→⁷FJ _{(J=0, 1, 2)跃迁和⁵D}1_→⁷FJ _{(J=1, 2, 4)跃迁的劈裂峰,这说明Eu³⁺处在低对称性的晶体场格位中.}     

Characteristics of Fe2O3 Nanoparticles from Doped Low-pressure H2/O2/Ar Flames

A burner stabilized premixed low-pressure flame has been used to generate iron-oxide (Fe₂O₃) nanoparticles with sizes in the range 7–20nm. The H₂/O₂/Ar flames were doped with different amounts of iron-pentacarbonyl (Fe(CO)₅) with concentrations in the range 524–2096ppm. The influence of precursor concentration on composition, structure, morphology, and size have been studied utilizing transmission electron microscopy (TEM), X-ray powder diffraction (XRD), measurements of the specific surface area (BET), and infrared spectroscopy (FT-IR). The product particles consist of both, the - and the -phase of Fe₂O₃. Average particle sizes were measured in the range 7.4–16nm depending on precursor concentration and flame conditions.     

Cu-NQR study of magnetism and superconductivity in Ce1+xCu2+ySi2 under pressure

In order to investigate magnetic properties in the vicinity of the magnetic to superconducting (SC) phase boundary, we have performed Cu-NQR measurements under hydrostatic pressure (P) on two off-stoichiometric Ce_1+xCu_2+ySi₂ polycrystals: Ce_0.99Cu_2.02Si₂ (denoted as Ce 0.99) exhibits the anomalous ground state so-called A phase dominated by critical magnetic correlations and Ce_0.975Cu₂Si₂ (Ce 0.975) shows a static magnetic ordering at ambient P. With increasing P which enhances the Kondo temperature, the fraction of the A phase becomes markedly suppressed, and the SC fraction increases correspondingly, although T_c stays nearly constant in the measured pressure range, P≤14.4 kbar. This shows that the P-induced transition from the A to the SC phases is of a first-order type, without passing through a quantum (T→0) phase transition. However, no superconductivity has been attained in Ce 0.975 up to 19.4 kbar. It is considered that the P-induced superconductivity is sensitive to the sample quality. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of flat milling on vortex matching effect in Bi2Sr2CaCu2O8+y with antidot array

Significant enlargements of antidot diameter by Ar-ion milling were observed in Bi₂Sr₂CaCu₂O_8+y single-crystal films with antidot arrays as well as the thinning of the films. In an original sample with triangular array of antidots, whose diameter is about 200 nm, a few dip structures by the matching effect were observed in the vortex-flow resistance as a function of magnetic field. With increasing the milling time, the number of the dips increases and the appearance of the flow resistance becomes periodic oscillations. These features can be explained mainly by the increase of the antidot diameter.     

Lattice Location Studies of Indium in Cr2O3

The lattice sites of implanted In atoms in Cr₂O₃ were investigated by means of electron emission channeling (EC) measurements using ¹¹¹In probe atoms. EC spectra were recorded for several axes and compared to simulations. Indium atoms are most likely located at near-Cr sites. Small differences in the EC patterns for prompt and delayed electrons may be an indication for displacements of ¹¹¹Cd emitter atoms following the electron capture decay of In. This revised version was published online in September 2006 with corrections to the Cover Date.     

Electron paramagnetic resonance of Mn2+ and Gd3+ in Pr2Zn3(NO3)12.24 H2O single crystals

The electron paramagnetic resonance of Mn²⁺ and Gd³⁺ doped in Pr₂Zn₃(NO₃)₁₂.24H₂O single crystals has been studied at X-band. Mn²⁺ substitutes for two Zn²⁺ sites, while Gd³⁺ substitutes for single type of Pr³⁺ sites. The spin-Hamiltonian analysis of the EPR spectra is presented at 298 K as well as 77 K.     

Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

The study on porosity and thermophysical properties of nanostructured La2Zr2O7 coatings

Lanthanum-zirconium nano-powders were synthesized by molten salts method. Nanostructured lanthanum-zirconium coatings were deposited by air plasma spraying. Scanning electron microscopy and X-ray diffraction were carried out to analyze the as-sprayed coatings and powders. The pore size distribution and buck density of coatings were identified by mercury intrusion porosimetry. The thermophysical properties of the nanostructured coatings were also examined through laser flash technique and differential scanning calorimetry. The results demonstrate that the as-sprayed nanostructured coatings consist of the pyrochlore-type phase. The as-sprayed nanostructured lanthanum-zirconium coatings have a very low porosity. The thermal conductivity of the as-sprayed nanostructured lanthanum-zirconium coating is lower than that of the conventional coating between 200 °C and 950 °C, but when the temperature between 950 °C and 1300 °C, the result is reverse.     

Vortex lattice transitions in YNi2B2C

We have performed extensive small-angle neutron scattering (SANS) diffraction studies of the vortex lattice in single crystal YNi₂B₂C for B‖c. High-resolution SANS, combined with a field-oscillation vortex lattice preparation technique, allows us to separate Bragg scattered intensities from two orthogonal domains and accurately determine the unit cell angle, β. The data suggest that upon increasing field there is a finite transition width where both low- and high-field distorted hexagonal vortex lattice phases, mutually rotated by 45°, coexist. The smooth variation of diffracted intensity from each phase through the transition corresponds to a redistribution of populations between the two types of domains.     

Mössbauer characterization of calcium–ferrite oxides prepared by calcining Fe2O3 and CaO

Calcium ferrite oxides were prepared by calcining a mixture powder of iron- and calcium oxide. The ⁵⁷Fe-Mössbauer spectra of the calcium ferrites oxides were measured, revealing that the products should be Ca₂Fe₂O₅ and CaFe₂O₄, the ratio of which was dependent of the Fe/Ca atomic ratio of the mixture powder.     

Vibrational and dielectric properties of La2Hf2O7 : Experiment and theory

The physical origin of the static dielectric constant and its relationship with lattice dynamics of La₂Hf₂O₇are studied by combining infrared spectroscopy and density functional perturbation theory (DFPT). Both La and Hf show obvious effective charge anomaly which is attributed to the hybridization between 2p states of the oxygen and 5d states of the cations, indicating a mixed covalent-ionic bonding between the cations and the oxygen. The dielectric response is determined by seven infrared phonon modes and the static dielectric constant extracted from infrared reflection spectrum is in close agreement with DFPT calculation. Both experiment and theory reveal that most of the contributions to the static dielectric constant are dominated by three infrared phonon modes at 137, 172 and 297 cm⁻¹. Two of them (172 and 297 cm⁻¹) are from the displacements of oxygen atoms inside HfO₆ octahedra and the other one (137 cm⁻¹) is from the bending of La₂O′ chain. This result indicates that the origin of the static dielectric constant of La₂Hf₂O₇ is directly connected with the two interpenetrating sub-networks of pyrochlore structure (HfO₆ octahedra and La₂O′ chain).     

第一性原理模拟U在Gd2Zr2O7烧绿石中的固溶

采用第一性原理密度泛函理论模拟U在Gd₂Zr₂O₇烧绿石中的固溶,在低浓度U掺杂时,Gd₂Zr₂O₇烧绿石保持烧绿石结构;随着U掺杂浓度增加,Gd₂(Zr_{2-y}U_y)O₇和(Gd_{2-y}U_y)Zr₂O₇体系的晶格常数发生线性变化．计算结果表明,由于总能较低,U原子更偏向于替代无序换位后Gd₂Zr₂O₇晶格中B位的Gd原子．     

Mössbauer study of Fe0.05Ni0.95Cl2

Mössbauer spectra of Fe_0.05Ni_0.95Cl₂ were recorded at temperatures between 4.5 and 50 K and fitted by a sum of two sub-spectra as was done previously for Fe _x Ni_1?x Cl₂ with x?=?0.034, 0.068 or 0.079. We have found that temperature variations of the hyperfine magnetic field H _hf and the quadrupole splitting (1/2)e ² qQ of one of the sub-spectra are similar for the different compositions while some changes are observed for the other sub-spectrum. A particularly interesting result is found for Fe_0.05Ni_0.95Cl₂ which clearly shows the effect of a spin growth when temperature decreases.     

SrAl_2B_2O_7:Dy~(3+)材料的制备及其发光性能

采用高温固相法制备了SrAl2B2O7:Dy3+发光材料.在350nm紫外光激发下,测得SrAl2B2O7:Dy3+材料的发射光谱为一个多峰宽谱,主峰分别为480,573和678nm;分别和Dy3+的4F9/2→6H15/2,4F9/2→6H13/2,4F9/2→6H11/2的跃迁发射相对应;监测573nm的发射峰,得到材料的激发光谱为一个多峰宽谱,主峰分别为295,325,350,365,400nm.研究了Dy3+掺杂浓度对SrAl2B2O7:Dy3+材料发射光谱的影响,随着Dy3+掺杂浓度的增大,SrAl2B2O7:Dy3+材料的Iy/Ib逐渐增大,根据Judd-Ofelt理论解释了其原因.随着Dy3+掺杂浓度的增大,Dy3+的4F9/2→6H13/2跃迁产生的573nm发射峰强度先增大,在4%时达到最大值,之后减小,其自身的浓度猝灭机理为电偶极-电偶极相互作用.不同的电荷补偿剂Li+,Na+,K+的引入均使发光强度得到提高,尤其以Li+最佳,发光强度提高了大约33%.     

Magnetism and superconductivity in ErNi2B2C

We have performed a series of neutron diffraction experiments from the magnetic order and the vortex lattice in single crystal ErNi₂B₂C. The incommensurate magnetic structure develops additional even harmonics below the ‘ferromagnetic’ ordering temperature, T _F of 2.3 K. This feature and the existence of rods of diffuse scattering suggest the development of ferromagnetic microdomain walls. The magnetic structure is very sensitive to the application of a magnetic field with changes in modulation vector and harmonic content. Studies of the vortex lattice show the presence of a 45° reorientation transition and a distorted hexagonal to square transition as a function of applied field. Further distortions of the vortex lattice occur at T _N, but no changes are seen at T _F.     

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.     

Mg2+掺杂Zn2SiO4:Mn2+的溶胶-凝胶法合成及真空紫外发光特性研究

采用溶胶-凝胶法（sol-gel method）于不同气氛条件下成功合成了Zn_1.92-xMg_xSiO₄:0.08Mn²⁺（0≤x≤0.12）系列粉末样品.利用X射线衍射(XRD)、光致发光(PL)谱等分析手段对Zn_1.92-xMg_xSiO₄:0.08Mn²⁺系列     

光沉积Ru和RuO2的锐钛矿TiO2纳米片的光解水产氧

采用水热法以HF作为结构调控剂合成了主要暴露（001）面的锐钛矿TiO₂纳米片,通过光沉积方法分别合成了负载Ru和RuO₂物种的光催化剂。利用X射线衍射、透射电镜和氢气程序升温还原等分析表征了催化剂的结构性质。通过光解水产氧反应来研究催化剂的催化性能,详细考察了Ru含量、负载方式以及氧化和还原处理等因素的影响,光解水产氧速率的差异证明了Ru物种在不同晶面的电荷-空穴分离效应。与负载单一助催化剂的Ru/TiO₂和RuO₂/TiO₂样品相比,活性最优的0.5%Ru-1.0%RuO₂/TiO₂样品由于负载了双助催化剂,其催化活性得到更大的提高,证实了在锐钛矿TiO₂上的晶面电荷-空穴分离效应.