Abstract: Microstructural deformation mechanisms in adiabatic shear bands in Ti6Al4V are studied using traditional TEM and selected area diffraction, and more advanced microstructural characterisation techniques such as energy dispersive X-ray spectroscopy, high angle annular dark field STEM and conical dark field TEM. The shear bands under investigation are induced in Ti6Al4V samples by high strain rate compression of cylindrical and hat-shaped specimens in a split Hopkinson pressure bar setup. Samples from experiments interrupted at different levels of deformation are used to study the evolution of the microstructure in and nearby the shear bands. From the early stages of adiabatic shear band formation, TEM revealed strongly elongated equiaxed grains in the shear band. These band-like grains become narrower towards the centre of the band and start to fraction even further along their elongated direction to finally result in a nano-crystalline region in the core. In fully developed shear bands, twins and a needle-like martensite morphology are observed near the shear band.

Abstract: Microstructural investigations with transmission electron microscopy were carried out on quenched Ni-Ti alloys with 52 and 54.5 at% Ni. For the Ni52Ti48 specimen long time exposed diffraction patterns of a single grain show besides the expected reflections of the B2-phase, two sets of extra reflections in different zones. The first type of spots is explained by lattice displacement waves, which are regarded as precursors of the martensitic Ni-Ti phases, B 19' and R-phase, respectively. The second set of reflection with more diffuse intensity than the other reflections is related to Ni4Ti3 precipitates in an early state of formation. For the Ni-richer Ni54.5Ti45.5 alloy only Ni4Ti3 precipitates in an early state of formation are found but no precursors of the B 19'- and R-phase.

Abstract: The Ni3-xGaTe2 series of compounds (0 x 0.65) was synthesized by a high-temperature ceramic technique at 750 °C. Crystal structures of three compounds in the series were determined by X-ray powder diffraction: Ni2.98(1)GaTe2 (RI = 0.042, Rp = 0.023, Rwp = 0.035), Ni2.79(1)GaTe2 (RI = 0.053, Rp = 0.028, Rwp = 0.039), Ni2.58(1)GaTe2 (RI = 0.081, Rp = 0.037, Rwp = 0.056); the structures were verified by electron diffraction and, for the former compound, high-resolution electron microscopy. The compounds crystallize in a hexagonal lattice with P63/mmc, and the structures can be regarded as a hexagonal close-packed array with a -Ga-Te-Te- stacking sequence. The octahedral and trigonal bipyramidal voids in the hcp structure are selectively filled with Ni atoms to form one entirely occupied and two partially occupied sites, thus allowing variations in the nickel content in the series of compounds Ni3-xGaTe2 (0 x 0.65). A superstructure with asup = 2asub (P63/mmc) has been identified for Ni3-xGaTe2 (0.5 x 0.65) by electron diffraction. Real-space, high-resolution images confirm an ordering of Ni atoms and vacancies inthe ab plane. Quantum-chemical calculations performed forNi3-xGaTe2 (x = 0, 0.25, 0.75, 1) suggest anisotropic metallic conductivity and Pauli paramagnetic behavior that are experimentally confirmed for Ni3GaTe2.

Abstract: A novel series of mixed-valent, heteroleptic transition metal diketonates that can be utilized as prospective single-source precursors for the low-temperature preparation of oxide materials are reported. The first mixed-valent iron beta-diketonates with different Fe-III/Fe-II ratios have been synthesized by applying the mixed-ligand approach. Based on nearly quantitative reaction yields and analysis of iron-oxygen bonds, these compounds were formulated as [Fe-III(acac)(3)][Fe-II(hfac)(2)] (1) and [Fe-II(hfac)(2)][Fe-III(acac)(3)][Fe-II(hfac)(2)] (2). In the above heteroleptic complexes, the Lewis acidic, coordinatively unsaturated Fe-II centers chelated by two hfac (hexafluoroacetylacetonate) ligands with electron-withdrawing substituents maintain bridging interactions with oxygen atoms of electron-donating acac (acetylacetonate) groups that chelate the neighboring Fe-III atoms. Switching the ligands on Fe-III and Fe-II atoms in starting reagents resulted in the instant ligand exchange between iron centers and in yet another polynuclear homometallic diketonate [Fe-II(hfac)(2)][Fe-III(acac)(2)(hfac)][Fe-II(hfac)(2)] (3) that adheres to the same bonding pattern as in complexes 1 and 2. The proposed synthetic methodology has been extended to design heterometallic diketonates with different M : M' ratios. Homometallic parent molecules have been used as templates to obtain heterometallic mixed-valent [Fe-III(acac)(3)][Mn-II(hfac)(2)] (4) and [Ni-II(hfac)(2)] – [Fe-III(acac)(3)][Ni-II(hfac)(2)] (5) complexes. The combination of two different diketonate ligands with electron-donating and electron-withdrawing substituents was found to be crucial for maintaining the above mixed-valent heterometallic assemblies. Theoretical investigation of two possible “isomers”, [Fe-III(acac)(3)][Mn-II(hfac)(2)] (4) and [Mn-III(acac)(3)][Fe-II(hfac)(2)] (40) provided an additional support for the metal site assignment giving a preference of 9.78 kcal mol(-1) for the molecule 4. Heterometallic complexes obtained in the course of this study have been found to act as effective single-source precursors for the synthesis of mixed-transition metal oxide materials MxM2-xO3 and MxMi-xO. The title highly volatile precursors can be used for the low-temperature preparation of both amorphous and crystalline heterometallic oxides in the form of thin films or nanosized particles that are known to operate as efficient catalysts in oxygen evolution reaction.

Abstract: Reduction of La1xCaxMnO3 (0.6 ≤ x ≤ 1) perovskite phases with sodium hydride yields materials of composition La1xCaxMnO2+δ. The calcium-rich phases (x = 0.9, 1) adopt (La0.9Ca0.1)0.5Mn0.5O disordered rocksalt structures. However local structure analysis using reverse Monte Carlo refinement of models against pair distribution functions obtained from neutron total scattering data reveals lanthanum-rich La1xCaxMnO2+δ (x = 0.6, 0.67, 0.7) phases adopt disordered structures consisting of an intergrowth of sheets of MnO6 octahedra and sheets of MnO4 tetrahedra. X-ray absorption data confirm the presence of Mn(I) centers in La1xCaxMnO2+δ phases with x < 1. Low-temperature neutron diffraction data reveal La1xCaxMnO2+δ (x = 0.6, 0.67, 0.7) phases become antiferromagnetically ordered at low temperature.

Abstract: Electron energy loss spectroscopy (EELS) is an ideal tool to obtain chemical information from nanoscale volumes. Quantification of the experimental spectra however has prevented for a long time access to the available information in a reliable and reproducible way. We present recent advances in model-based quantification of EELS spectra and show that we obtain the best possible precision for a given dataset, as well as remarkably good accuracies when applied to three different materials. The results are shown to be far superior over conventional quantification techniques and could hold a promise for standardless quantification of EELS spectra.

Abstract: An extension to model-based electron energy loss spectroscopy (EELS) quantification is reported to improve the possibility of modelling fine structure changes in electron energy loss spectra. An equalisation function is used in the energy loss near edge structure (ELNES) region to model the differences between a single atom differential cross section and the cross section for an atom in a crystal. The equalisation function can be shown to approximate the relative density of unoccupied states for the given excitation edge. On a set of 200 experimental h-BN spectra, this technique leads to statistically acceptable models resulting into unbiased estimates of relative concentrations and making the estimated precisions come very close to the Cramer-Rao lower bound (CRLB). The method greatly expands the useability of model-based EELS quantification to spectra with pronounced fine structure. Another benefit of this model is that one also gets an estimate of the unoccupied density of states for a given excitation edge, without having to do background removal and deconvolution, making the outcome intrinsically more reliable and less noisy. (c) 2006 Elsevier B.V. All rights reserved.

Abstract: Synchrotron small angle X-ray scattering (SAXS) was used to characterize silicalite-1 zeolite crystallization from TEOS/TPAOH/water clear sol. SAXS patterns were recorded over a broad range of length scales, enabling the simultaneous monitoring of nanoparticles and crystals occurring at various stages of the synthesis. A simple two-population model accurately described the patterns. Nanoparticles were modeled by polydisperse coreshell spheres and crystals by monodisperse oblate ellipsoids. These models were consistent with TEM images. The SAXS results, in conjunction with in situ light scattering, showed that nucleation of crystals occurred in a short period of time. Crystals were uniform in size and shape and became increasingly anisotropic during growth. In the presence of nanoparticles, crystal growth was fast. During crystal growth, the number of nanoparticles decreased gradually but their size was constant. These observations suggested that the nanoparticles were growth units in an aggregative crystal growth mechanism. Crystals grown in the presence of nanoparticles developed a faceted habit and intergrowths. In the final stages of growth, nanoparticles were depleted. Concurrently, the crystal growth rate decreased significantly.

Abstract: The modified atomic scattering amplitudes (MASAs) of mixed Ga_1-xIn_xAs, GaAs_1-xN_x, and InAs_1-xN_x are calculated using the density functional theory approach and the results are compared with those of the binary counterparts. The MASAs of N, Ga, As, and In for various scattering vectors in various chemical environments and in the zinc-blende structure are compared with the frequently used Doyle and Turner values. Deviation from the Doyle and Turner results is found for small scattering vectors (s<0.3 Å^-1) and for these scattering vectors the MASAs are found to be sensitive to the orientation of the scattering vector and on the chemical environment. The chemical environment sensitive MASAs are used within zero pressure classical Metropolis Monte Carlo, finite temperature calculations to investigate the effect of well size on the electron 002 and 220 structure factors (SFs). The implications of the use of the 002 (200) spot for the quantification of nanostructured Ga_1-xIn_xAs systems are examined while the 220 SF across the well is evaluated and is found to be very sensitive to the in-plane static displacements.