Pressure-Induced Phase Transition in BaTiO3 Nanocrystals

The crystal structure and electric properties of BaTiO3 nanocrystals are studied by in situ high-pressure synchrotron radiation x-ray powder diffraction. The phase transition takes place not only in the samples of BaTiO3 nanocrystals that are tetragonal phase with grain sizes more than 100nm, but also in the samples of BaTiO3 nanocrystals that are cubic phase with grain sizes less than 100nm. The pressures of phase transition are found to increase with decrease of the grain size from about 4 to 10GPa for crystallites ranging from 200 to 10nm in radius. The bulk moduli are calculated according to Birch-Murnaghan state equation before and after the phase transition.     

嵌埋Ni颗粒的BaTiO_3/SrTiO_3薄膜的相变特性

采用高温X射线原位衍射和变温介电谱对SrTiO3基底上外延生长的BaTiO3(嵌埋Ni颗粒)薄膜进行了相变特性分析。从X射线衍射和介电谱的分析结果得出,BaTiO3的相变温度点转变为弥散的温度区间。在这个弥散的相变温度区间内,由于基底和薄膜之间的失配,以及嵌埋Ni颗粒的应力作用,薄膜的介电响应弥散剧烈,并偏离德拜弛豫。分析Cole-Cole图获知,BaTiO3薄膜在四方相转变为立方相的相变过程中同时存在几种极化机制,在高温状态下介电损耗随温度增大而增大。降温过程中,薄膜没有立即恢复四方相,可能是基底和Ni颗粒的共同作用影响了相变弛豫。     

An analysis of the grain growth kinetics in Mn2O3 nanocrystals

The isothermal grain growth of Mn₂O₃ nanocrystals, prepared by the chemical liquid-phase homogeneous precipitation route, was investigated at various temperatures between 200 and 500 °C for different annealing times. X-ray diffraction patterns and transmission electron micrographs show that the average grain sizes are in the range of 4–50 nm. The grain growth data were analyzed using two different models. The first model, assuming normal grain growth as that in conventional polycrystalline materials, yields large grain growth exponent (n) and extremely low activation energy (Q). Although it can describe the evolution of grain sizes, it fails to give satisfactory physical interpretation of n and Q, both beyond the theoretical predictions. The second model is based on the structural relaxation of the interface component in nanocrystalline materials. In this case, the ordering of distorted interfaces by structural relaxation proceeds with grain growth. This structure relaxation model not only describes the evolutions of grain growth well, but also makes reasonable attribution of the low activation energy to the short-range rearrangement of atoms in the interface region as well. PACS 63.50.+x; 78.30.-j; 81.20.-n     

Nanoscale combined reactions: non-equilibrium α-Co formation in nanocrystalline ϶-Co by abnormal grain growth

Electrodeposited nanocrystalline Co offers a relatively unique opportunity to study the interaction of two fundamentally different elementary solid state reactions: grain growth and ε (HCP) to α (FCC) allotropic phase transformation. Samples were isothermally annealed at temperatures above and below the equilibrium transformation temperature (T_εα?=?695?K) and quenched to ambient for subsequent characterization by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Isothermal annealing above 695?K resulted in concurrent grain growth and ε to α transformation. Unexpectedly, however, simultaneous grain growth and ε to α transformation also occurred during isothermal annealing at temperatures as low as 573?K, i.e. 122?K below the expected equilibrium T_εα. It was observed that non-equilibrium α-Co formed within a matrix of nanocrystalline ε-Co via abnormal grain growth, and is therefore fundamentally different from the ε to α transformation typically observed in conventional polycrystalline Co.     

Heterogeneous nucleation and growth of CdSe on magnetite seed nanocrystals: The influence of ligand and morphology

The heterogeneous nucleation and growth of CdSe domains on the Fe₃O₄ seed nanocrystals are hard to be controlled because of significant lattice mismatch between Fe₃O₄ and CdSe nanocrystals. Current study exploits the choice of surface ligand and crystal morphology for Fe₃O₄ seed to investigate ways to overcome the energy barrier imposed by the lattice mismatch for the promotion and control of subsequent growth of CdSe nanocrystals on seeded crystals. Results indicate that the growth of CdSe domains on seed nanocrystals not only depends on the affinity of ligands toward seed nanocrystals, but also is affected by the seed ligands in a similar way to synthesizing individual second-domain nanocrystals. Furthermore, preferential growth of CdSe domains on the corner of cubic seeds are observed, and cubic Fe₃O₄ nanocrystals are favored for the heterogeneous nucleation of CdSe as opposed to spherical ones. A three-stage growth model (heterostructures formation, the adsorption of Se and the heterogeneous nucleation and growth) is proposed, where choice of ligands, geometry features, such as surface curvature and defects are found to have significant impact to overcome energy barrier from lattice mismatch.     

Kinetics of the apparent isothermal and non-isothermal crystallization of the α-Fe phase within the amorphous Fe81B13Si4C2 alloy

Kinetics of the apparent isothermal and the non-isothermal crystallization of α-Fe phase within the amorphous Fe₈₁B₁₃Si₄C₂ alloy were investigated by an X-ray diffraction (XRD) and by a differential scanning calorimetry (DSC). It was established that the apparent isothermal crystallization of α-Fe phase within amorphous Fe₈₁B₁₃Si₄C₂ alloy could be described by the Johnson-Mehl-Avrami (JMA) kinetic model (with parameter n_iso=4.0). The apparent isothermal crystallization process includes a constant rate of nucleation and three-dimensional growth of nuclei. The results of X-ray diffraction (XRD) data of the isothermally crystallized samples confirmed the above established kinetic model. From the kinetic analysis of the non-isothermal crystallization of the α-Fe phase within this amorphous alloy, it was concluded that the autocatalytic two-parameter Šesták-Berggren (SB) reaction model (with kinetic exponents M=0.72 and N=1.02) describes well the studied process under the given conditions. The non-isothermal crystallization process involves the constant nucleation rate of stable nuclei with additional secondary two-dimensional (surface) nucleation and overlapping of the growing nuclei on account of the non-isothermal activation.     

Studies on interdiffusion in Pd/Mg/Si films: Towards improved cyclic stability in hydrogen storage

The paper reports the diffusion coefficients of grain boundary diffusion and grain boundary assisted lattice diffusion of Pd in Mg in Pd/Mg/Si system, a useful material for hydrogen storage, at 473 K in vacuum. The grain boundary diffusivity is measured by Whipple model and grain boundary assisted lattice diffusivity by plateau rise method using Pd depth profiles constructed by Rutherford backscattering spectrometry. It is established that grain boundary diffusivities are about six orders of magnitude faster than lattice diffusivities. Fine grained microstructure of Pd film, high abundance of defects in Mg film and higher stability associated with Pd-Mg intermetallics are responsible for the diffusion of Pd into grain boundaries and subsequently in the interiors of Mg. Besides the indiffusion of Pd, annealing also brings about an outdiffusion of Mg into Pd film. Examination by nuclear reaction analysis involving ²⁴Mg(p,p′γ)²⁴Mg resonance reaction shows the occurrence of Mg outdiffusion. Minimization of surface energy is presumably the driving force of the process. In addition to Pd/Mg interface, diffusion occurs across Mg/Si (substrate) interface as well on increasing the annealing temperature above 473 K. These studies show that dehydrogenation of films accomplished by vacuum annealing should be limited to temperatures less than 473 K to minimize the loss of surface Pd, the catalyst of the hydrogen absorption-desorption process and Mg, the hydrogen storing element, by way of interfacial reactions.     

Large-scale synthesis of single-crystalline MgO with bone-like nanostructures

Uniform bone-like MgO nanocrystals have been prepared via a solvothermal process using commercial Mg powders as the starting material in the absence of any catalyst or surfactant followed by a subsequent calcination. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) measurements indicate that the product consists of a large quantity of bone-like nanocrystals with lengths of 120–200 nm. The widths of these nanocrystals at both ends are in the range of 20–50 nm, which are 3–20 nm wider than those of the middle parts. Explorations of X-ray diffraction (XRD) and selected area electronic diffraction (SAED) exhibit that the product is high-quality cubic single-crystalline nanocrystals. The photoluminescence (PL) measurement suggests that the product has an intensive emission centered at 410 nm, showing that the product has potential application in optical devices. The advantages of our method lie in high yield, the easy availability of the starting materials and permitting large-scale production at low cost. The growth mechanism was proposed to be related with solvent’s oxidation in the precursor formation process and following nucleation and mass-transfer in the decomposition of the precursor.     

旋转磁场对凝固组织形成的影响

研究了旋转磁场作用下Pb-45%Sn亚共晶合金的凝固组织.实验发现,旋转磁场的频率恒定时,凝固组织的晶粒尺寸随着磁场强度的增强而线性减小,同时,初生相的生长形态从枝晶转变为椭球状.X射线测试结果表明,初生相Pb发生了点阵膨胀,并且晶格常数随着磁场强度的增强先变大后减小,磁场强度在此存在一个临界值.能谱分析显示,随着磁场强度的增强,初生相Pb内Sn的含量逐渐降低.根据电磁场理论和扩散定律,对上述现象进行了理论分析,揭示出旋转磁场引起了液相强烈流动,加快了溶质原子的扩散以及对熔体的加热效应,导致了形核率的提高和长大速度的降低. 关键词： 旋转磁场 液相流动 晶格常数 溶质分配     

Surfactants: Perfect heteroepitaxy of Ge on Si(111)

The hetero growth of Ge on Si results in formation of 3D clusters with an uncontrolled defect structure. Introduction of a monolayer of a surfactant completely changes the growth mode to a 2D-layer growth (Frankvan der Merwe) with a continuous and smooth Ge film on Si(111). The surfactant is not incorporated but segregates and floates on the growing Ge film. The saturation of the dangling bonds of the semiconductor reduces the surface free energy and drives the strong segregation. The effect on the growth process is the selective change of activation energies which are important for diffusion and the mobility of the Ge. Up to a thickness of 8 MLs (MonoLayers) the misfit-related strain of the pseudomorphic Ge film is relaxed by formation of a micro rough surface. This allows a partial relaxation of the Ge towards its bulk lattice constant which would not be possible for a flat and continuous film. For thicker Ge films the misfit of 4.2% is relieved by a periodic dislocation network, which is confined to the Si-Ge interface. Ge-films thicker than 20 MLs are free of defects and completely relaxed to the Ge bulk lattice constant: a model system for perfect heteroepitaxial growth.     

Surface exchange reactions and fast grain boundary diffusion in polycrystalline materials: Application of a spherical grain model

Laplace transforms of the solution functions to the diffusion equations for surface exchange reactions and fast grain boundary diffusion in polycrystalline materials of finite thickness have been derived by applying a spherical grain model. Diffusion profiles have been calculated for semi-infinite diffusion systems as well as thin films by application of numerical Laplace inversion. The surface exchange reaction at the surface of the sample (e.g. oxide ceramics) in contact with the constant diffusion source (e.g. gas phase) is assumed to be fairly slow such that the diffusion source is not in equilibrium with the surface during the diffusion anneal. Two limiting cases for the surface conditions are taken into account, viz. fast surface diffusion and a uniform ratio of the surface exchange coefficient/diffusion coefficient. The calculated profiles refer to Harrison's type-A diffusion kinetics. Apart from expressions for the effective diffusion coefficient, analogous relations for the effective surface exchange coefficient are proposed. Relaxation curves for the total amount of diffusant exchanged with the diffusion source are discussed in terms of the diameter of the spherical grains (average grain size), surface exchange coefficient, bulk and grain boundary diffusion coefficient, respectively.     

Repairing Stevenson's step in the 4d Ising model

In a recent paper Stevenson claimed that analysis of the data on the wave function renormalization constant near the critical point of the 4d Ising model is not consistent with analytical expectations. Here we present data with improved statistics and show that the results are indeed consistent with conventional wisdom once one takes into account the uncertainty of lattice artifacts in the analytical computations.     

Anisotropic electrical properties of Bi0.5(Na0.75K0.25)0.5TiO3 ceramics fabricated by reactive templated grain growth (RTGG)

We have fabricated lead-free Bi_0.5(Na_0.75K_0.25)_0.5TiO₃ (BNKT) ceramics by a conventional process (CP) and reactive templated grain growth (RTGG) methods. The effect of grain orientation on structure, dielectric, complex impedance and electrical properties was investigated. The phase formation and grain morphology of BNKT ceramics were examined by X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. High dielectric constant and low dielectric loss was observed for grain oriented (textured) BNKT ceramics. Complex impedance, temperature dependent ac and dc conductivity were performed to explore the conduction behavior of the prepared BNKT ceramics.     

Origin of anomalous lattice expansion in oxide nanoparticles

Anomalous lattice expansions have been measured for the first time in monodisperse CeO2-x nanoparticles and in BaTiO3 single nanoparticles by electron diffraction. X-ray photoelectron spectroscopy studies on CeO2-x nanoparticles and ab initio computer simulation on BaTiO3 clusters show that the origin of expansion is the decrease of electrostatic force caused by valence reduction of Ce ions and the increase in ionicity of Ti ions, respectively. The lattice constant change of oxide (ionic) nanoparticles with the increase in ionicity would depend on the structure of the particles. Hence, first-principles calculations of large ionic clusters are indispensable.     

纳米晶体结构与性能的模拟研究

通过分子动力学方法模拟纳米晶体（1—3nm）的结构．利用模拟的结果，进行了X射线衍射点阵常数、晶粒尺寸及点阵畸变的模拟计算，还计算了结合能及弹性模量等．结果表明纳米晶体无论是晶界和晶粒都与传统的粗晶粒晶体材料没有本质的区别，只是由于晶粒尺寸变小，以及晶界的体积分数等的作用，导致一系列的性能差异 关键词：     

退火诱导机械合金化Fe42.5Al42.5Ti5B10合金的结构演变与晶粒生长动力学

利用XRD和TEM方法研究Fe_42.5Al_42.5Ti₅B₁₀合金在机械合金化及等温热处理过程中的结构演变及晶粒生长动力学,讨论了机械合金化合成机理和热处理过程中的晶粒生长机理.结果表明,球磨过程中Al,Ti,B原子向Fe晶格中扩散,形成Fe(Al,Ti,B)固溶体.机械合金化合成Fe(Al,Ti,B)遵循连续扩散混合机理.球磨50h后,金属Fe,Al,Ti,B已完全合金化,球磨终产物为纳米晶Fe(Al,Ti,B).球 关键词： XRD TEM 42.5Al_42.5Ti₅B₁₀合金')" href="#">Fe_42.5Al_42.5Ti₅B₁₀合金 机械合金化     

Pb_(0.85)Ca_(0.15)TiO_3纳米晶铁电—顺电相变的拉曼光谱研究

采用变温ＦＴ Ｒａｍａｎ技术测定了三种粒径Ｐｂ０．８５Ｃａ０．１５ＴｉＯ３纳米晶的居里温度。１７８９ｎｍ、２５．６９ｎｍ、和３６２５ｎｍ粒子的Ｔｃ分别为２７４℃,２６５℃,２９４℃。认为尺寸效应和掺杂引起的缺陷均对Ｔｃ产生影响。掺杂及焙烧不充分引起的晶体缺陷使居里点弥散。Ｅ（１ＴＯ）软模具有弱阻尼特征     

Dopant induced morphology changes in ZnO nanocrystals

Zinc oxide (ZnO) nanocrystals doped with different groups of impurities, e.g., Li, Na, Cu, Pr and Mg synthesized by solid-state reaction method under similar conditions exhibit different morphology. XRD showed monophasic wurtzite structure but change in lattice parameters and Zn-O bond length indicates incorporation of dopant ion in ZnO lattice. The morphology of ZnO nanocrystals exhibited striking dependence on type of dopant ion with the shape changing from nanorods, spherical to petal like particles. Photoluminescence (PL) shows pronounced UV emission and negligible visible emission for Li, Na and Cu doped ZnO nanocrystals with peak positions coinciding with that of undoped ZnO. Whereas signature emission of Pr³⁺ ion as well as broad visible emission from Mg doped ZnO revealed the role of intra gap metastable states formed by the dopant ion in the emission process.     

显微拉曼研究外延生长的BaTiO_(3-x)薄膜的结构相变与结构动力学(英文)

我们用显微拉曼、卢瑟福背散射谱、X射线散射和非对称摇摆等实验手段研究了在1 0 - 2 到1 0 - 5帕氧气压下用激光分子束外延技术生长的BaTiO3-x薄膜的结构动力学特性。测量结果表明生长氧压越低,晶格常数c和c/a越大,晶格常数a稍微减小,晶胞体积变大。随着生长氧压的减小,薄膜中氧含量减小。在3 0×1 0 - 5帕氧气压下生长的薄膜中氧缺陷可达0 48,但是样品的四方相结构可以很好的维持。显微拉曼研究进一步确定了样品都是四方相结构。另外,在BaTiO2 52 薄膜的拉曼光谱中发现高频段有两个新峰,其可能是由于氧缺陷导致的二级拉曼散射引起的。随着生长氧压的减小,拉曼峰向低频移动,表明薄膜中的应力减小。同时,拉曼峰变宽,这可能是由于氧缺陷导致的结构畸变引起的。由于在薄膜中存在二维张应力,BaTiO3单晶样品中的结构相变特征在我们的样品中从78到5 5 0K的温度范围内不存在。     

Ca改性钛酸铅Pb_(1-x)Ca_xTiO_3纳米晶的拉曼光谱研究

本文在２８８Ｋ和３７８Ｋ温度下测定了不同Ｃａ含量Ｐｂ１－ｘＣａｘＴｉＯ３（ＰＴＣ）纳米晶的拉曼光谱。同时在室温条件下测定了不同晶粒尺寸Ｐｂ０．８５Ｃａ０．１５ＴｉＯ３的拉曼光谱。讨论了Ｃａ掺入量、温度、晶粒尺寸等因素对声子频率的影响。声子频率的变化情况表明,对于ｘ≥０．２的ＰＴＣ纳米晶,与相同Ｃａ含量的陶瓷相比,存在着晶格膨胀的倾向。