A plethora of technological applications justify why titanium dioxide is probably the most studied oxide, and an optimal exploitation of its properties quite frequently requires a controlled modification of the surface. Low-energy ion bombardment is one of the most extended techniques for this purpose and has been recently used in titanium oxides, among other applications, to favour resistive switching mechanisms or to form transparent conductive layers. Surfaces modified in this way are frequently described as reduced and defective, with a high density of oxygen vacancies. Here we show, at variance with this view, that high ion doses on rutile titanium dioxide (110) induce its transformation into a nanometric and single-crystalline titanium monoxide (001) thin film with rocksalt structure. The discovery of this ability may pave the way to new technical applications of ion bombardment not previously reported, which can be used to fabricate heterostructures and interfaces.
The mechanisms of growth of a circular void by plastic deformation were studied by means of molecular dynamics in two dimensions (2D). While previous molecular dynamics (MD) simulations in three dimensions (3D) have been limited to small voids (up to s«10nm in radius), this strategy allows us to study the behavior of voids of up to 100 nm in radius. MD simulations showed that plastic deformation was triggered by the nucleation of dislocations at the atomic steps of the void surface in the whole range of void sizes studied. The yield stress, defined as stress necessary to nucleate stable dislocations, decreased with temperature, but the void growth rate was not very sensitive to this parameter. Simulations under uniaxial tension, uniaxial deformation and biaxial deformation showed that the void growth rate increased very rapidly with multiaxiality but it did not depend on the initial void radius. These results were compared with previous 3D MD and 2D dislocation dynamics simulations to establish a map of mechanisms and size effects for plastic void growth in crystalline solids.
Surface defects have a profound influence on many attributes of materials, therefore experimental techniques and specific studies focused on their controlled generation and properties are mandatory. We have carried out a thorough study of the role of surface defects on a variety of physico-chemical properties of metals and oxides, using different experimental techniques and molecular dynamics simulations. In particular, we have studied the defects formed upon bombardment with Ar+ ions in a reconstructed Au(100) surface at very low ion doses. At room temperature, the pristine defects are mainly single vacancies, which diffuse by collective atomic motions, then cluster and collapse, resulting in 2D dislocation dipoles. These dislocations exhibit an enhanced chemical reactivity due to the elastic stress of their cores. We have also performed indentation tests of flat and stepped Au(111) samples with an atomic force microscope, revealing noticeable differences in their mechanical behavior when probed at the nanoscale. Thus, the stepped sample has a 20% smaller Young's modulus, 40% smaller yield point and 50% smaller shear stress. These differences, as well as reversible, quasiplastic behavior of the stepped sample up to a critical load, are due to the active role of steps as dislocation nucleation centers. In contrast, a TiO2(110) surface, modified with ion bombardment, does not show noticeable changes in its nanomechanical properties, which is an indication of the very different mechanical responses of oxides compared to simple metals at the nanoscale. Finally, we show how surface defects affect the chemical activity of a Pt(111) surface when exposed to methanol. The nature of the adsorbed species and the dynamics of the surface reactions are modified in the presence of surface defects, rendering the defective surface into a more robust state against catalytic poisoning.
We have imaged the rearrangement of the magnetic domains on magnetite (001) when crossing the spinreorientation transition and the Verwey transition with nanometer resolution. By means of spin-polarized lowenergy electron microscopy we have monitored the change in the easy axes lowering the temperature through both transitions in remanence. The spin-reorientation transition occurs in two steps: initial nucleation and growth of domains with a new surface magnetic orientation is followed by a smooth evolution.
In this work, the electronic properties of the metal sites in cubic and monoclinic ZrO2 supported Pd and PdCu catalysts have been investigated using CO as probe molecule in in-situ IR studies, and the surface composition of the outermost layers has been studied by APXPS (Ambient Pressure X-ray Photoemission Spectroscopy). The reaction products were followed by mass spectrometry, making it possible to relate the chemical properties of the catalysts under reaction conditions with their selectivity. Combining these techniques, it has been shown that the structure of the support (monoclinic or cubic ZrO2) affects the metal dispersion, mobility, and reorganization of metal sites under methanol steam reforming (MSR) conditions, influencing the oxidation state of surface metal species, with important consequences in the catalytic activity. Correlating the mass spectra of the reaction products with these spectroscopic studies, it was possible to conclude that electropositive metal species play an imperative role for high CO2 and H2 selectivity in the MSR reaction (less CO formation).
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