氧化铁掺杂对PMnS-PZN-PZT压电陶瓷性能的影响

通过对晶体结构与压电、介电性能测试,探讨了Fe_2O_3掺杂对PMnS-PZN-PZT陶瓷压电性能的影响.结果表明,PMnS-PZN-PZT陶瓷结构位于三方、四方相共存的MPB区间,Fe_2O_3掺杂导致晶体三方、四方相结构含量发生变化.当Fe_2O_3掺杂含量为0.45 wt;时,晶体结构位于准同型相区间偏四方相结构的位置,压电与介电性能达到最佳:tanδ=0.12;,d_(33)=356 pC · N~(-1),k_p=0.60,Q_m=745,在230 ℃以下的温度范围具有很好的频率温度稳定性.     

Crystallization and stability of different protein crystal modifications: A case study of lysozyme

The crystallization, including both the phase diagram and the phase transition of hen egg white lysozyme (HEWL) was investigated. A tetragonal modification and a needle modification were obtained during crystallization. The phase diagram and stability of two modifications in both acid and basic pH solutions (pH 4.5, 8.0 and 9.0) were determined. Besides in acid solutions, the well‐known tetragonal crystals can also be obtained in basic solutions at low temperature (7 °C) while the needle like modification can only crystallize in a basic solution. Based on the phase diagram, phase transfer behavior was found to exist between the two modifications. In basic solutions, tetragonal modification can transfer to needle shaped crystals. This process can be affected by a changing of pH and temperature. While in acid buffer, the needle shaped crystals dissolve and tetragonal crystals crystallize and remain in solution.     

Morphology and crystal phase evolution of GeO2 in liquid phase deposition process

Morphology and crystal phase evolution of GeO₂ in liquid phase deposition (LPD) process is investigated. Rod-like solid phases precipitate out of solution ahead of truncated cube-like phases. SEM, XRD and TEM analyses reveal that the two sorts of solid phases are tetragonal GeO₂ and hexagonal GeO₂, respectively. The tetragonal GeO₂ phases start to experience a re-dissolving process as soon as the hexagonal phases come into being. The prior precipitation of the rod-like phase arises from a relatively low solute saturation of tetragonal GeO₂. Fast growth of a tetragonal GeO₂ phase along [111] direction leads to development of a rod-like shape. The re-dissolving phenomenon does not agree with the classic growth kinetics of crystals but is strongly favored by our calculations based on thermodynamics. The GeO₂ solutes are released in a fluctuant way by germanate ions, which promotes the occurrence of the re-dissolution phenomenon. The current researches open a door for room-temperature LPD growth of not only the hexagonal GeO₂ particles and film but also the one-dimensional tetragonal GeO₂ product.     

添加不同稳定剂制备的四方氧化锆晶型转变临界尺寸研究

以八水氧氯化锆(ZrOCl2·8H2O)为原料,以氨水(NH3·H2O)、氢氧化钠(NaOH)溶液为沉淀剂,采用溶胶-凝胶法制备纳米级氧化锆粉体,对前驱体加入不同的稳定剂,通过吸滤、干燥、煅烧等工艺,得到以四方氧化锆晶相为主、不同粒度组成、不同四方相含量的样品.利用激光纳米粒度分析仪、X-射线衍射(XRD)等分析手段分别对粉体的粒径、物相组成进行表征,分别采用晶面公式、谢乐公式对四方相含量、晶粒尺寸进行计算.分析了室温下加入不同稳定剂制备的氧化锆纳米粉体中四方相含量和颗粒粒径之间的关系.结果表明:氧化钇稳定的氧化锆纳米粉粒度更细、粒度分布更均匀.经400~1000 ℃×2 h煅烧后,通过氧化锆纳米粉晶粒尺寸累积分布与四方相含量的关系可以得出以氧化镁、氧化钙、氧化钇为稳定剂制备的氧化锆纳米粉相变临界粒径分别为24~28 nm、26~33.6 nm、18~22.6 nm.     

MnGa合金体的电子结构与磁性质的研究

基于密度泛函理论方法系统研究了四方结构MnGa合金体的结构、形成、电子结构和磁性质。结果表明,四方MnGa合金晶胞的生成焓为-4.85 eV,高于一些不含d电子的体系。其呈现导体的能带结构,其中d电子主要形成深能级价带,定域性最强。四方MnGa合金存在着明显的自旋极化,靠近费米能级两侧的s电子和靠近费米能级下方的p电子具有较弱的自旋极化。形成浅能级价带和导带的d电子产生高强度的自旋极化,对磁性质贡献较大。Mn的s电子和Mn的p电子自旋极化作用较弱,Mn的d电子形成浅能级价带和导带,自旋极化作用最强。形成深能级价带的Ga的d电子自旋极化作用较弱,不同位置的Ga原子的自旋极化不同。四方MnGa合金体具有净有效磁矩,呈弱的亚铁磁性。     

Structural phase transition in CuFe2O4 spinel

A structural transition with a reduction in symmetry of the high temperature cubic phase (sp. gr. Fd3m) to the tetragonal phase (sp. gr. I4₁/amd) and the appearance of a ferrimagnetic structure occur in CuFe₂O₄ copper ferrite at T ≈ 440°C. It is established by an experiment on a high-resolution neutron diffractometer that the temperature at which long-range magnetic order occurs is higher than that of tetragonal phase formation. When cooling CuFe₂O₄ spinel from 500°C, the equilibrium coexistence of both phases is observed in a fairly wide temperature range (～40°C). The composition studied is a completely inverse spinel in the cubic phase, and in the tetragonal phase the inversion parameter does not exceed few percent (x = 0.06 ± 0.04). At the same time, the phase formed upon cooling has a classical value of tetragonal distortion (γ ≈ 1.06). The character of temperature changes in the structural parameters during the transition from cubic to tetragonal phase indicates that this transition is based on the Jahn-Teller distortion of (Cu,Fe)O₆ octahedra rather than the mutual migration of copper and iron atoms.     

Effects of purification on the crystallization of lysozyme

We have additionally purified a commercial lysozyme preparation by cation exchange chromatography, followed by recrystallization. This material is 99.96% pure with respect to macromolecular impurities. At basic pH, the purified lysozyme gave only tetragonal crystals at 20°C. Protein used directly from the bottle, prepared by dialysis against distilled water, or which did not bind to the cation exchange column had considerably altered crystallization behavior. Lysozyme which did not bind to the cation exchange column was subsequently purified by size exclusion chromatography. This material gave predominately bundles of rod-shaped crystals with some small tetragonal crystals at lower pHs. The origin of the bundled rod habit was postulated to be a thermally dependent tetragonal ↔ orthorhombic change in the protein structure. This was subsequently ruled out on the basis of crystallization behavior and growth rate experiments. This suggests that heterogeneous forms of lysozyme may be responsible. These results demonstrate three classes of impurities: (1) small molecules, which may be removed by dialysis; (2) macromolecules, which are removable by chromatographic techniques; and (3) heterogeneous forms of the protein, which can be removed in this case by cation exchange chromatography. Of these, heterogeneous forms of the lysozyme apparently have the greatest affect on its crystallization behavior.     

High temperature x‐ray diffraction studies of zirconia thin films prepared by reactive pulsed laser deposition

Zirconium oxide thin films have been deposited on Si (100) substrates at room temperature at an optimized oxygen partial pressure of 3x10^‐2 mbar by reactive pulsed laser deposition. High temperature x‐ray diffraction (HTXRD) studies of the film in the temperature range room temperature‐1473 K revealed that the film contained only monoclinic phase at temperatures ≤ 673 K and both monoclinic and tetragonal phases were present at temperatures ≥ 773 K. The tetragonal phase content was significantly dominating over monoclinic phase with the increase of temperature. The phase evolution was accompanied with the increase in the crystallite size from 20 to 40 nm for the tetragonal phase. The mean thermal expansion coefficients for the tetragonal phase have been found to be 10.58x10^‐6 K^‐1 and 20.92x10^‐6K^‐1 along a and c‐axes, respectively. The mean volume thermal expansion coefficient is 42.34x10^‐6 K^‐1 in the temperature range 773‐1473 K. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Oxidation Kinetics of Amorphous,Polycrystalline, and Nanocrystalline Co33Zr67 Alloys

The oxidation kinetics of amorphous, polycrystalline, and nanocrystalline CoZr₂ alloys have been studied under isothermal conditions in air atmosphere with a microbalance. DSC and X-ray diffraction were used to study the influence of oxidation on crystallization. The three alloys under investigation which have the same composition but differ in the microstructure showed noticeable differences in their oxidation behaviour: the oxidation of the amorphous alloy is characterized by a very fast initial oxygen absorption step, completed in less than 1–2 min, followed by a slow oxide growth obeying a logarithmic time law at 400 °C. The polycrystalline thermodynamically stable tetragonal alloy absorbs small amounts of oxygen and obeys a parabolic rate law in the temperature range 500–800 °C. The activation energy of oxygen diffusion in tetragonal CoZr₂ was determined from the temperature dependence of the parabolic rate constant. The intermediate nano-crystalline phase with a local structure more closely packed and ordered than that of the precursor amorphous phase, shows an oxidation behaviour similar to that of the tetragonal phase, but with a different time exponent.     

Structure and Luminescence of Eu-activated Zirconium Hydroxide and Dioxide at Relatively Low Temperatures

Luminescent materials with composition ZrO₂:0.01 Eu were prepared by co-precipitation of zirconium and europium hydroxides and subsequent thermal decomposition at relatively low temperature. A stabilization of tetragonal ZrO₂ prepared on this way is found. The structure of the prepared samples was investigated. The luminescence spectra of tetragonal and of monoclinic ZrO₂ · 0.01 Eu and of ZrO₂ · n H₂O:0.01 Eu by excitation at 254 nm and at 365 nm are presented.     

Effect of Oxygen Partial Pressure on the Nucleation Kinetics of Orthorhombic YBCO

Effect of oxygen partial pressure on the nucleation kinetics of orthorhombic YBCO from tetragonal phase has been studied using classical nucleation theory. The free energy of formation of orthorhombic YBCO has been evaluated as a function of oxygen partial pressure.     

Precipitates of MnSi cubic phase in tetragonal Mn4Si7 crystal

Higher manganese silicides (HMSs) exhibit interesting thermoelectric and optoelectronic properties. Development of HMS-based thermoelements and microthermopiles of different designs may meet a number of problems, which can be solved only when the real structure of crystals and thin layers on which they are based is established. We have applied scanning and transmission electron microscopy and electron diffraction to investigate HMS crystals of two types: single crystals grown from melt by the Bridgman method and microislands formed by reactive diffusion during manganese vapor deposition on silicon substrates. The exact phase composition of these materials is established: matrix HMS crystal belonging to tetragonal system (Mn₄Si₇ composition) and precipitates of cubic manganese monosilicide MnSi. The shape and sizes of precipitates are determined, the crystallographic relationships between the tetragonal and cubic phases are found, and the interface is investigated.     

Uncertainties in crystallization of hen‐egg white lysozyme: reproducibility issue

The reproducibility of biomacromolecular crystallization (tetragonal and orthorhombic lysozyme crystals) was studied by monitoring the evolution of protein concentration during the crystallization process using Mach‐Zehnder interferometer. It was found that formation of both tetragonal and orthorhombic crystals exhibited poor reproducibility. When the crystallization occurred under isothermal conditions, the protein concentration in the solution varied differently in different experiments under identical conditions (for both types of crystals). Moreover, in the case of orthorhombic lysozyme crystallization (under either isothermal or thermal gradient conditions), it is clear that the crystals could not be always readily formed. When formation of tetragonal lysozyme crystals was conducted at a temperature gradient condition, however, the evolution of concentration was reproducible. The phenomena found in this study revealed that biomacromolecular crystallization can be uncertain, which is probably caused by the process of nucleation. Such uncertainties will be harmful for the efforts of screening crystallization conditions for biomacromolecules. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Orthorhombic — tetragonal phase transition and oxygen index of YBa2Cu3O6+δ

The orthorhombic — tetragonal phase transition of YBa₂Cu₃O_6+δ has been investigated by X-ray powder diffraction methods. The transition is of the second order or very close to second order and no coexistence of tetragonal and orthorhombic phases has been observed. The transition strongly depends on the oxygen index δ which changes with temperature. Typical patterns of the triplet 006, 020, and 002 obtained by precise X-ray powder diffraction measurements have been presented and shown to be useful for identification of YBa₂Cu₃O_6+δ and estimation of oxygen index δ.     

Small-angle X-ray scattering study of conditions for the formation of growth units of protein crystals in lysozyme solutions

The structural composition of lysozyme solutions favorable for the formation of the tetragonal form of protein crystals was studied by synchrotron-based small-angle X-ray scattering depending on the protein concentration and the temperature. Along with lysozyme monomers, dimers and octamers are found in crystallization solutions; the octamer content increases with an increase in the protein concentration.     

Preparation of zirconia aerogel by heating of alcohol–aqueous salt solution

Using zirconyl nitrate dihydrate as starting material, zirconia aerogel with high specific surface area was prepared by heating zirconyl nitrate dihydrate solution with an alcohol–aqueous mixture and supercritical drying method (SCFD). It was characterized by XRD, TEM and BET methods. The specific area of primary ZrO₂ aerogel could reach 675.6 m²/g which was much higher than that of documents so far. While both the specific surface area and pore volume decreased markedly on increasing the calciniation temperature. Contrast with the powder synthesized by ordinary trend, the content of t-ZrO₂ in the aerogel increased when the calcination temperature improved from 500 to 700 °C, the percentage of tetragonal phase was 86% at 700 °C. And it was very interesting that the particle size of the aerogel was bigger than 30 nm after being roasted in 1000 °C, the tetragonal phase still existed.     

Structural Characterization of Y2Pd14B5

Y₂Pd₁₄B₅ is the major phase in as‐cast and annealed multiphase alloys with nominal compositions near YPd₅B₃C_0.3. Its crystal structure determined the first time here by single crystal X‐ray diffraction is body‐centered tetragonal (space group I4₁/amd). Transmission electron microscopy (TEM) reveals that in as‐cast specimens the tetragonal phase has a modulated structure and is oriented intergrown with a face‐centered cubic phase of similar composition, namely YPd₇B₂. According to Rietveld analyses of the multiphase system the structure of this phase can be well‐described by space group Fm m. Annealing the sample for 150 hrs at 973 K results in a coarsening and enrichment of the tetragonal phase as well as a disappearance of the modulations allowing a detailed structure analysis by single crystal diffractometry.     

A Minimal Generating Set of Intermediate-Symmetry Fedorov Groups

Crystallography Reports - Minimization of generating sets (sets of generators) indicated in the International Tables for Crystallography has been performed for tetragonal, trigonal, and hexagonal...     

Effect of the Simulation Box Size and Precipitant Concentration on the Behavior of Tetragonal Lysozyme Dimer

Crystallography Reports - The 10-nanosecond simulation of a lysozyme dimer, which is a fragment of the tetragonal lysozyme crystal structure, has been carried out by the molecular dynamics method...     

Solubility of tetragonal and orthorhombic lysozyme crystals under high pressure

Two-beam interferometry was applied to measure lysozyme solubility under high pressure. This rapid method allowed determination of one data point within 3 h. The solubility of tetragonal lysozyme crystals was determined as a function of temperature at 0.1, 50, and 100 MPa, and that of orthorhombic crystals was measured at 0.1 and 100 MPa. The solubility of tetragonal crystals increased with pressure; however, that of orthorhombic crystals decreased. In both cases, the enthalpy and entropy of dissolution decreased with pressure.