Robust nonadiabatic molecular dynamics for metals and insulators

We present a new formulation of the correlated electron-ion dynamics (CEID) scheme, which systematically improves Ehrenfest dynamics by including quantum fluctuations around the mean-field atomic trajectories. We show that the method can simulate models of nonadiabatic electronic transitions and test it against exact integration of the time-dependent Schrodinger equation. Unlike previous formulations of CEID, the accuracy of this scheme depends on a single tunable parameter which sets the level of atomic fluctuations included. The convergence to the exact dynamics by increasing the tunable parameter is demonstrated for a model two level system. This algorithm provides a smooth description of the nonadiabatic electronic transitions which satisfies the kinematic constraints (energy and momentum conservation) and preserves quantum coherence. The applicability of this algorithm to more complex atomic systems is discussed.

Influence of strain and polycrystalline ordering on magnetic properties of high moment rare earth metals and alloys

Despite being the most suitable candidates for solenoid pole pieces in state-of-the-art superconductor- based electromagnets, the intrinsic magnetic properties of heavy rare earth metals and their alloys have gained comparatively little attention. With the potential of integration in micro- and nanoscale devices, thin films of Gd, Dy, Tb, DyGd and DyTb were plasma-sputtered and investigated for their in-plane magnetic properties, with an emphasis on magnetisation vs. temperature profiles. Based on crystal structure analysis of the polycrystalline rare earth films, which consist of a low magnetic moment FCC layer at the seed interface topped with a higher moment HCP layer, an experimental protocol is introduced which allows the direct magnetic analysis of the individual layers. In line with the general trend of heavy lanthanides, the saturation magnetisation was found to drop with increasing unit cell size. In-situ annealed rare earth films exceeded the saturation magnetisation of a high-moment Fe65Co35 reference film in the cryogenic temperature regime, proving their potential for pole piece applications; however as-deposited rare earth films were found completely unsuitable. In agreement with theoretical predictions, sufficiently strained crystal phases of Tb and Dy did not exhibit an incommensurate magnetic order, unlike their single-crystal counterparts which have a helical phase. DyGd and DyTb alloys followed the trends of the elemental rare earth metals in terms of crystal structure and magnetic properties. Inter-rare-earth alloys hence present a desirable blend of saturation magnetisation and operating temperature.

Experimental and Modelling Studies of the Thermodynamics and Kinetics of Phase and Structural Transformations in a Gamma TiAl-based Alloy

This work combines microscopy, synchrotron radiation X-ray diffraction, differential scanning calorimetry and thermodynamic calculations in the characterisation of phase transformation behaviour of a Ti–46Al–1.9Cr–3Nb alloy upon continuous heating at constant rates. It has been found that the Ti–46Al–1.9Cr–3Nb alloy after being forged at 1200 °C without further treatment has a duplex microstructure consisting of fine equiaxed and lamellar ? grains with a small amount of a2 plates and particles and about 1 wt.% B2 phase. Differential scanning calorimetry revealed reproducibly several thermal effects upon heating of the as-forged alloy. These thermal effects are related to the equilibration and homogenisation of the sample, change of phase ratios between a2, ? and B2 phases in particular the increase of B2 in respect to a2 and ?, and the following five phase transformations: a2 + ? + B2 a + ? + B2, a + ? + B2 a + ?, ? + a a, a a + ß, a + ß a + ß + L. The observation of these transformations by differential scanning calorimetry is largely in agreement with literature phase diagrams and thermodynamic calculations, though care is needed to consider the different alloy compositions. Kinetics of the ? + a a phase transformation in the Ti–46Al–1.9Cr–3Nb alloy has been quantitatively derived from the calorimetry data, giving phase compositions at any point during the transformation upon continuous heating.

Delamination Fracture Related to Tempering in a High-Strength Low-Alloy Steel

The delamination or splitting of mechanical test specimens of rolled steel plate is a phenomenon that has been studied for many years. In the present study, splitting during fracture of tensile and Charpy V-notch (CVN) test specimens is examined in a high-strength low-alloy plate steel. It is shown that delamination did not occur in test specimens from plate in the as-rolled condition, but was severe in material tempered in the temperature range 500 °C to 650 °C. Minor splitting was seen after heating to 200 °C, 400 °C, and 700 °C. Samples that had been triple quenched and tempered to produce a fine equiaxed grain size also did not exhibit splitting. Microstructural and preferred orientation studies are presented and are discussed as they relate to the splitting phenomenon. It is concluded that the elongated as-rolled grains and grain boundary embrittlement resulting from precipitates (carbides and nitrides) formed during reheating were responsible for the delamination.

Relationship between microstructure and deformation behaviour during dynamic compression in Ti-3Al-5Mo-5V alloy

The relationship between microstructure and deformation and damage behaviour during dynamic compression in Ti-3Al-5Mo-5V alloy has been studied using several experimental techniques, including optical microscopy, scanning electron microscopy and microhardness measurements. It was found that the deformation behaviour during dynamic compression was closely related to deformation parameters. After dynamic deformation, the deformation shear band that formed in the titanium alloy had microhardness similar to that of the matrix. However, the microhardness of the white shear band was much higher than the matrix microhardness. The effects of deformation parameters, including deformation rate and deformation degree, on deformation localisation were investigated. Based on the results from the present work, the microstructure and deformation processing parameters can be optimised. In addition, treatment methods after dynamic compression were explored to restore alloy properties. Using post-deformation heat treatment, the microstructure and property inhomogeneity caused by shear bands could be largely removed.

UV-activated photocatalyst films and inks for cleaning tarnished metals

A simple UV-activated, TiO2-based film or ink for removing thin oxide or sulfide layers from metal surfaces by reductive photocatalysis is described.

Promotion of Ceria Catalysts by Precious Metals: Changes in Nature of the Interaction under Reducing and Oxidizing Conditions

By depositing ceria over supported precious metal (PM) catalysts and characterizing them with in situ diffuse reflectance UV (DR UV) and in situ Raman spectroscopy, we have been able to prove a direct correlation between a decrease in ceria band gap and the work function of the metal under reducing conditions. The PM ceria interaction results in changes on the ceria side of the metal ceria interface, such that the degree of oxygen vacancy formation on the ceria surface also correlates with the precious metal work function. Nevertheless, conclusive evidence for a purely electronic interaction could not be provided by X-ray photoelectron spectroscopy (XPS) analysis. On the contrary, the results highlight the complexity of the PM ceria interaction by supporting a spillover mechanism resulting from the electronic interaction under reducing conditions. Under oxidizing conditions, another effect has been observed; namely, a structural modification of ceria induced by the presence of PM cations. In particular, we have been able to demonstrate by in situ Raman spectroscopy that, depending on the PM ionic radius, it is possible to create PM ceria solid solutions. We observed that this structural modification prevails under an oxidizing atmosphere, whereas electronic and chemical interactions take place under reducing conditions.