Three-dimensional size and orientation of the precipitates in AZ91 magnesium alloys measured by TEM techniques

Knowledge of the microscopic structure, including three-dimensional (3-D) size and orientation of the precipitates, is essential to fully understand the mechanical properties of the magnesium alloys and designing the alloys with better performance. Analytical TEM with high spatial resolution offers the simultaneous measurements of 3-D size, structure, orientation, composition of the precipitates from one typical sample along an established crystallographic axis. Besides popular Burgers orientation relationship (OR), other ORs such as Pitsch--Schrader OR, Crawley OR, Potter OR and a new OR with the form of [0001]_α 1.0° from [311]_γ and (11\bar 20)_α 2.0° from (03\bar 3)_γ between the magnesium matrix and the precipitate γ -Mg₁₇Al₁₂ are identified by TEM imaging and diffraction techniques. As a case study, the thicknesses of the individual precipitates with Burgers OR are further measured to be 100--200~nm through both electron energy-loss spectroscopy and x-ray energy dispersive spectroscopy combining differential x-ray absorption and extrapolation, which are in agreement with the overall 3-D size statistic distribution results obtained through analysing various samples along various directions. Furthermore, the fabricated wedge-shape structure provides a platform on which to study the dependence of the interfacial strain on the variation of the thickness.     

Analysis of Gibbsian Segregation at Heterophase Cu-MnO Interfaces

An alternative methodology to analyze Gibbsian segregation at heterophase interfaces with transmission electron microscopy (TEM) is presented and discussed. In this approach the actual concentration of the segregating element in a monolayer at the interface is obtained. This is in contrast to line scans or maps where the concentrations determined are a convolution of the concentration profiles with the electron probe and where for general interfaces the deconvolution problem can not be solved accurately. This is possible because the present approach uses explicitly the information offered by hetero-interfaces. The method is tested on the possible segregation of indium and gallium dissolved in a Cu matrix to interfaces between MnO precipitates and the Cu matrix. The occurrence of indium segregation is clearly demonstrated and the In concentration in the terminating Cu monolayer at the parallel {111} Cu/MnO interface is determined to be 15 ± 3 at.%, whereas the average In concentration in the Cu matrix is 3.8 ± 0.4 at.%. Further it was found that indium effectively blocks gallium segregation towards the oxide side of the interface. On the other hand, the presence of gallium does not influence the segregation of indium. Explanation for the gallium segregation at the oxide side relies on a thin spinel type Ga _x Mn _y O₄, which reduces the misfit at the metal-oxide interface.     

Morphology and orientation of iron oxide precipitates in epitaxial BiFeO3 thin films grown under two non-optimized oxygen pressures

Microstructures of multiferroic BiFeO₃ thin films epitaxially grown on SrRuO₃-buffered SrTiO₃ (001) substrates by laser molecular-beam epitaxy under two non-optimized oxygen pressures were characterized by means of transmission electron microscopy. The results showed that the films grown under oxygen pressures of 1 Pa and 0.3 Pa contain a secondary phase embedded in the BiFeO₃ matrix. High-angle annular dark-field imaging, elemental mapping and composition analysis in combination with selected area electron diffraction revealed that the parasitic phase is mainly antiferromagnetic α-Fe₂O₃. The α-Fe₂O₃ particles are semi-coherently embedded in the BiFeO₃ films, as confirmed by high-resolution transmission electron microscopy. In addition to the α-Fe₂O₃ phase, ferromagnetic Fe₃O₄ precipitates were found in the BiFeO₃ films grown under 0.3 Pa and shown to accumulate in areas near the film/substrate interfaces. In our heteroepitaxy systems, very low density misfit dislocations were observed at the interfaces between the BiFeO₃ and SrRuO₃ layers implying that their misfit strains may be relieved by the formation of the secondary phases. Using X-ray photoelectron spectroscopy it was found that Fe exists in the +3 oxidation state in these films. The possible formation mechanisms of the secondary phases are discussed in terms of film growth conditions.     

A TEM study of the stability of intermetallic precipitates in Zircaloy nuclear reactor components

Transmission electron microscopy (TEM) has been used to characterise the radiation-induced changes in Zr(Cr,Fe)₂ intermetallic precipitates present in Zircaloy-2 and -4 nuclear reactor components. The results show that the precipitates become completely amorphous at low fluences (<1 × 10²⁴ n·m⁻²) during low temperature neutron irradiation (about 330 K) with no associated chemical composition change. At higher temperatures (about 573 K), a duplex amorphous-crystalline structure is produced. The precipitates retain a crystalline core surrounded by a peripheral amorphous layer that advances inwards with increasing fluence. The amorphous outer layer is coincident with a depletion of Fe that is dispersed into the surrounding hcp -phase matrix. Subsequent post-irradiation heat-treatment below the amorphous phase recrystallisation temperature results in the back-diffusion of Fe into the precipitates.     

High-resolution electron microscopy observations of continuous precipitates with Pitsch-Schrader orientation relationship in an Mg–Al based alloy and interpretation with the O-lattice theory

High-resolution electron microscopy was applied to analyze the continuous precipitated particles of the γ-Mg₁₇Al₁₂ phase with Pitsch-Schrader OR in the heat-treated AZ91 alloy at 473 K for 8 h. The existence of a continuous precipitated particle with the Pitsch-Schrader OR including the selection of the habit plane and the growth direction in Mg–Al system is rationalized by the constrained coincidence site lattice/constrained complete pattern shift lattice (CCSL/CDSCL) model and the O-lattice theory.     

高分辨扫描透射电子显微镜原理及其应用

扫描透射电子显微术是目前应用最广泛的电子显微表征手段之一,具有分辨率高、对化学成分敏感和图像直观易解释等特点。其中高分辨扫描电子显微镜可以直接获得原子分辨率的Z 衬度像,结合X射线能谱(EDS)和电子能量损失谱(EELS),可在亚埃尺度上对材料的原子和电子结构进行分析。文章简述了扫描透射电子显微镜的基本原理及其应用现状,重点论述了高角环形暗场(HAADF)和环形明场(ABF)像的成像原理、特征和应用。此外,文中还对原子尺度分辨率的X射线能谱及电子能量损失谱元素分析方法进行了简述。     

Structure and orientation of an intermetallic phase in a W-Ni-Co alloy

The aim of this investigation is crystal structure determination of an intermetallic phase formed in a W-Ni-Co alloy during a heat-treatment carried out at a temperature of 800°C. This intermetallic phase is expected to play a critical role on the final microstructure (fine tungsten particles in an FCC matrix that is present in between large tungsten grains) and thereby, on the properties of the alloy. 92W-5.3Ni-2.7Co alloy was prepared through powder metallurgy route (liquid phase sintering) followed by heat-treatment at 800°C for 5?h. The intermetallic phase formed at this temperature was characterised using transmission and scanning electron microscopes. The intermetallic phase was found to have orthorhombic crystal structure with Pnam (62) space group as determined using automated diffraction tomography along with precession electron diffraction. Chemical analysis in TEM suggested that the intermetallic phase is based on stoichiometry (Co,Ni)₂W. Orientation imaging of the phase was also carried out in TEM and EBSD to understand its evolution. Equiaxed or lath morphology of the intermetallic phase was found to depend on the crystallographic orientation relationship of the phase with the tungsten grains and the matrix phase.     

Surface chemistry and catalysis of oxide model catalysts from single crystals to nanocrystals

Fundamental understandings of surface chemistry and catalysis of solid catalysts are of great importance for the developments of efficient catalysts and corresponding catalytic processes, but have been remaining as a challenge due to the complex nature of heterogeneous catalysis. Model catalysts approach based on catalytic materials with uniform and well-defined surface structures is an effective strategy. Single crystals-based model catalysts have been successfully used for surface chemistry studies of solid catalysts, but encounter the so-called “materials gap” and “pressure gap” when applied for catalysis studies of solid catalysts. Recently catalytic nanocrystals with uniform and well-defined surface structures have emerged as a novel type of model catalysts whose surface chemistry and catalysis can be studied under the same operational reaction condition as working powder catalysts, and they are recognized as a novel type of model catalysts that can bridge the “materials gap” and “pressure gap” between single crystals-based model catalysts and powder catalysts. Herein we review recent progress of surface chemistry and catalysis of important oxide catalysts including CeO₂, TiO₂ and Cu₂O acquired by model catalysts from single crystals to nanocrystals with an aim at summarizing the commonalities and discussing the differences among model catalysts with complexities at different levels. Firstly, the complex nature of surface chemistry and catalysis of solid catalysts is briefly introduced. In the following sections, the model catalysts approach is described and surface chemistry and catalysis of CeO₂, TiO₂ and Cu₂O single crystal and nanocrystal model catalysts are reviewed. Finally, concluding remarks and future prospects are given on a comprehensive approach of model catalysts from single crystals to nanocrystals for the investigations of surface chemistry and catalysis of powder catalysts approaching the working conditions as closely as possible.     

Interface and grain boundary structures in YBa2Cu3O7-x and YBa2Cu4O8 materials

Y₂BaCuO₅YBa₂Cu₃O_7-x (Y211/Y123) interfaces in melt-processed YBa₂Cu₃O_7-x were studied by high-resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Yttrium enrichment and barium depletion were observed locally at the Y211/Y123 interfaces where Y123 (001) facets were present. This effect may be interpreted as the result of lattice substitution of Ba by Y near these interfaces. Cation nonstoichiometry was found near Y211/Y123 interfaces where liquid phases (Cu-Ba-O) were present. This chemical disorder introduces numerous point defects in the Y123, and these defects may act as additional pinning sites alongwith stacking faults. A comparison of grain boundary (GB) chemical composition in polycrystalline YBa₂Cu₃O_7-x and YBa₂Cu₄O₈(Y124), studied using nanoprobe parallel-detection electron energy-loss spectroscopy (EELS), is presented. The studies of Y124 show that stoichiometric grain boundaries can also form weak links between superconducting grains. It is suggested that weak-link behavior is determined largely by misorientation at grain boundaries.     

Passivation of the surface of aluminum nanopowders by protective coatings of the different chemical origin

The results of investigation and analysis of electro-exploded aluminum nanopowders, whose surface were passivated with the following substances: liquids - nitrocellulose (NC), oleic acid (C₁₇H₃₃COOH) and stearic acid (C₁₇H₃₅COOH), suspended in kerosene and ethanol, fluoropolymer; solids - boron and nickel; gases - N₂, CO₂ and air (for a comparison) are discussed. The surface protection for the aluminum nanopowders by coatings of different chemical origins leads to the some advantages of the powders properties for an application in energetic systems, e.g. solid propellants and “green” propellants (Al-H₂O). Aluminum nanopowders with a protected surface showed the increased stability to oxidation in air during the storage period and higher reactivity by heating. The TEM-visual diagram of the formation and stabilization of the coatings on the particles has been proposed on the basis of experimental results. The kinetics of the interaction of aluminum nanopowders with air has been discussed. The recommendations concerning an efficiency of the protective “non-Al₂O₃” layers on aluminum nanoparticles were proposed.