Abstract: This paper aims to give an overview of the technique of energy-filtered transmission electron microscopy (EFTEM). It explains the basic principles of the technique and points to the relevant literature for more detailed issues. Experimental examples are given to show the power of EFTEM to study the chemical composition of nanoscale samples in materials science. Advanced EFTEM applications like imaging spectroscopy and EFTEM tomography are briefly discussed. (C) 2004 Elsevier B.V. All rights reserved.

Abstract: In this paper the luminescence of the scheelite-based CaGd2(1-x)Eu2x(WO4)4 solid solutions is investigated as a function of the Eu content and temperature. All phosphors show intense red luminescence due to the 5D0 7F2 transition in Eu3+, along with other transitions from the 5D1 and 5D0 excited states. For high Eu3+ concentrations the intensity ratio of the emission originating from the 5D1 and 5D0 levels has a non-conventional temperature dependence, which could be explained by a phonon-assisted cross-relaxation process. It is demonstrated that this intensity ratio can be used as a measure of temperature with high spatial resolution, allowing the use of these scheelites as thermographic phosphor. The main disadvantage of many thermographic phosphors, a decreasing signal for increasing temperature, is absent.

Abstract: Well shaped single crystalline Mn3O4 nano-octahedra with exposed highly active {011} facets at different particle sizes have been synthesized and used as anode materials for lithium ion batteries. The electrochemical results show that the smallest sized Mn3O4 nano-octahedra show the best cycling performance with a high initial charge capacity of 907 mA h g−1 and a 50th charge capacity of 500 mA h g−1 at a current density of 50 mA g−1 and the best rate capability with a charge capacity of 350 mA h g−1 when cycled at 500 mA g−1. In particular, the nano-octahedra samples demonstrate a much better electrochemical performance in comparison with irregular shaped Mn3O4 nanoparticles. The best electrochemical properties of the smallest Mn3O4 nano-octahedra are ascribed to the lower charge transfer resistance due to the exposed highly active {011} facets, which can facilitate the conversion reaction of Mn3O4 and Li owing to the alternating Mn and O atom layers, resulting in easy formation and decomposition of the amorphous Li2O and the multi-electron reaction. On the other hand, the best electrochemical properties of the smallest Mn3O4 nano-octahedra can also be attributed to the smallest size resulting in the highest specific surface area, which provides maximum contact with the electrolyte and facilitates the rapid Li-ion diffusion at the electrode/electrolyte interface and fast lithium-ion transportation within the particles. The synergy of the exposed {011} facets and the smallest size (and/or the highest surface area) led to the best performance for the Mn3O4 nano-octahedra. Furthermore, HRTEM observations verify the oxidation of MnO to Mn3O4 during the charging process and confirm that the Mn3O4 octahedral structure can still be partly maintained after 50 dischargecharge cycles. The high Li-ion storage capacity and excellent cycling performance suggest that Mn3O4 nano-octahedra with exposed highly active {011} facets could be excellent anode materials for high-performance lithium-ion batteries.

Abstract: Sunlight-driven hydrogen production via photoreforming of aqueous solutions containing renewable compounds is an attractive option for sustainable energy generation with reduced carbon footprint. Nevertheless, the absence of photocatalysts combining high efficiency and stability upon solar light activation has up to date strongly hindered the development of this technology. Herein, two scarcely investigated iron(III) oxide polymorphs, β- and ε-Fe2O3, possessing a remarkable activity in sunlight-activated H2 generation from aqueous solutions of renewable oxygenates (i.e., ethanol, glycerol, glucose) are reported. For β-Fe2O3 and ε-Fe2O3, H2 production rates up to 225 and 125 mmol h−1 m−2 are obtained, with significantly superior performances with respect to the commonly investigated α-Fe2O3.

Abstract: Glass ceramic composites were prepared by bulk crystallization of NaNbO3 in sodium niobium borate glasses. A homogeneous bulk crystallization of the NaNbO3 phase takes place during heat treatments that produces visible-near infrared transparent materials with similar to 30 nm NaNbO3 nanocrystallites. Upon thermal poling, a strong Na+ depleted nonlinear optical thin layer is observed at the anode side that should induce a large internal static electric field. In addition, the chi((2)) response of the poled glass ceramic composites increases from 0.2 up to 1.9 pm/V with the rate of crystallization. Two mechanisms may be considered: a pure structural chi((2)) process connected with the occurrence of a spontaneous ferroelectric polarization or an increase of the chi((3)) response of the nanocrystallites that enhances the electric field induced second harmonic generation process. (c) 2006 American Institute of Physics.

Abstract: ITEM specimens of a LaAlO3/SrTiO3 multilayer are prepared by FIB with internal lift out. Using a Ga+1 beam of 5 kV, a final cleaning step yielding top, top-angle, side, and bottom-angle cleaning is performed. Different cleaning procedures, which can be easily implemented in a dual beam FIB system, are described and compared; all cleaning types produce thin lamellae, useful for HRTEM and HAADF-STEM work up to atomic resolution. However, the top cleaned lamellae are strongly affected by the curtain effect. Top-angle cleaned specimens show an amorphous layer of around 5 nm at the specimen surfaces, due to damage and redeposition. Furthermore, it is observed that the LaAlO3 layers are preferentially destroyed and transformed into amorphous material, during the thinning process.

Abstract: Gold nanoparticles have been efficiently photodeposited onto titanate-loaded SBA-15 (Ti(x)/SBA-15) with different titania coordination. Transmission electron microscopy shows that relatively large Au nanoparticles are photodeposited on the outer surface of the Ti(x)/SBA-15 materials and that TiOx tends to form agglomerates in close proximity to the Au nanoparticles, often forming coreshell Au/TiOx structures. This behavior resembles typical processes observed due to strong-metal support interactions. In the presence of gold, the formation of hydrogen on Ti(x)/SBA-15 during the photodeposition process and the performance in the hydroxylation of terephthalic acid is greatly enhanced. The activity of the Au/Ti(x)/SBA-15 materials is found to depend on the TiOx loading, increasing with a larger amount of initially isolated TiO4 tetrahedra. Samples with initially clustered TiOx species show lower photocatalytic activities. When isolated zinc oxide (ZnOx) species are present on Ti(x)/SBA-15, gold nanoparticles are smaller and well dispersed within the pores. Agglomeration of TiOx species and the formation of Au/TiOx structures is negligible. The dispersion of gold and the formation of Au/TiOx in the SBA-15 matrix seem to depend on the mobility of the TiOx species. The mobility is determined by the initial degree of agglomeration of TiOx. Effective hydrogen evolution requires Au/TiOx coreshell composites as in Au/Ti(x)/SBA-15, whereas hydroxylation of terephthalic acid can also be performed with Au/ZnOx/TiOx/SBA-15 materials. However, isolated TiOx species have to be grafted onto the support prior to the zinc oxide species, providing strong evidence for the necessity of TiOSi bridges for high photocatalytic activity in terephthalic acid hydroxylation.

Abstract: Neodymium nickelate thin films have been prepared on NdGaO3 substrates by RF magnetron sputtering and post-annealing treatment under oxygen pressure. Transport properties are found to depend strongly on film thickness. Thick films show transport properties close to bulk ceramics, while very thin films exhibit a large transition from metal to insulator which occurs over a wide temperature range with high resistivity. Structure and surface morphology of the films have been investigated by Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM). Thin films (approximate to17 nm) grow heteroepitaxially, while thicker films (approximate to73 nm) show a granular structure. The thinnest sample suggests a symmetry change induced by the epitaxial strain of the substrate. This paper discusses the relationship between microstructure and transport properties.

Abstract: Grains of K-feldspar are commonly seen as heterogeneous mixtures of mineral species and varieties with random microstructures. Most consider that observable features arise from incomplete re-equilibrations owing to slow kinetic and localized effects of aqueous fluids (catalyst), with geological environment and chemical impurities playing only a secondary role. Here, an alternative approach is explored by studying well-preserved regularities in the twin patterns of K-feldspars formed in the subsolidus stage from a historical perspective. Selected samples from granitic pegmatites were studied by polarized light optical microscopy (PLOM), electron-probe micro-analysis (EPMA), scanning (SEM) and transmission electron microscopy (TEM), cathodoluminescence imaging (CL), micro-Raman spectroscopy (MRS) and 31P nuclear magnetic resonance (NMR). We have found that the essential feature of this crystalline medium is the astounding capability to recrystallize in self-organized twin patterns. The mechanism involves coupling between short-range atomic motion, and long-range displacive correlations propagated as ideal and non-ideal Albite and Pericline orientations. We suggest a general evolutionary process to explain the development of macroscopic twin patterns in microcline, based on three twin generations as microtwins, macrotwins and cryptotwins. Evolutionary variants also were identified; they depend on both internal crystallochemical features and an external geological stimulus. We suggest a continuous monoclinictriclinic transformation for impure K-feldspar, whereas a discontinuous inversion occurs where the starting composition is close to the ideal chemical formula. Twin patterns can evolve by twin coarsening to single-orientation microcline if the system releases energy, or by twin fragmentation to finely twinned microcline if the system stores energy. Hence, K-feldspar is seen here as a very sensitive medium in which precious geological information is recorded in the form of twin patterns, and thus useful for general geological challenges.