A Stabilization Mechanism of Zirconia Based on Oxygen Vacancies Only

The microscopic mechanism leading to stabilization of cubic and tetragonal forms of zirconia (ZrO$_2$) is analyzed by means of a self-consistent tight-binding model. Using this model, energies and structures of zirconia containing different vacancy concentrations are calculated, equivalent in concentration to the charge compensating vacancies associated with dissolved yttria (Y$_2$O$_3$) in the tetragonal and cubic phase fields (3.2 and 14.4% mol respectively). The model is shown to predict the large relaxations around an oxygen vacancy, and the clustering of vacancies along the $$ directions, in good agreement with experiments and first principles calculations. The vacancies alone are shown to explain the stabilization of cubic zirconia, and the mechanism is analyzed.Comment: 19 pages, 6 figures. To be published in J. Am. Ceram. So

Un nuovo approccio per la calibrazione dell'equazione generale del moto nella modellazione stocastica della circolazione ferroviaria

2009/2010La circolazione ferroviaria è interessata da una serie di fenomeni stocastici che determinano una notevole differenza tra gli orari pianificati e l’esercizio reale. Negli ultimi anni sono state proposte numerose metodologie di analisi della circolazione ferroviaria con lo scopo di individuarne le origini a livello di orario o di infrastruttura. In particolare le ricerche precedenti si sono concentrate sull’analisi delle partenze e dei tempi di fermata dei treni. Non si riscontrano invece in letteratura dei lavori focalizzati sull’intera marcia del treno e volti quindi all’individuazione della variabilità della marcia rispetto a quella calcolata con l’equazione generale del moto né sul comportamento dei treni all’interno dei grandi impianti che spesso rappresentano i punti critici delle reti. Per superare queste carenze vengono proposti due nuovi approcci per l’analisi della circolazione dei treni, rispettivamente sulle linee e nelle grandi stazioni di testa. Viene presentata una metodologia di ottimizzazione per ricavare, a partire dal tracciato gps rilevato a bordo treno, una serie di parametri di prestazione che compensino le differenze tra il profilo di velocità reale e quello teorico. Tali parametri, inseriti nell’equazione generale del moto per le diverse fasi, ne permettono quindi la calibrazione. Una volta ricavati tali parametri per un certo numero di corse, le loro distribuzioni possono essere utilizzate nell’ambito della microsimulazione stocastica o a supporto della pianificazione dell’orario. Quest’ultima possibilità è stata implementata nell’ambito di questo lavoro, sviluppando un approccio che supera i tempi deterministici convenzionalmente utilizzati introducendo tempi di percorrenza ed occupazione probabilistici. Si tiene in questo modo conto delle variabilità riscontrate nella circolazione dei treni in modo esplicito già in fase di pianificazione dell’orario ottenendo una stima realistica della stabilità della circolazione. Il secondo approccio è focalizzato sull’analisi delle dinamiche di funzionamento di una grande stazione di testa. Contrariamente da quanto affermato in ricerche precedenti, l’esperienza suggerisce l’esistenza di stazioni di grande rilevanza in cui i piazzamenti dei treni sui binari non seguono rigorosamente la pianificazione, ma subiscono delle alterazioni seguendo dinamiche probabilistiche. Tale analisi è stata condotta su Roma Termini, la più complessa stazione di testa al mondo, dimostrando una notevole variabilità nell’uso dei binari di stazione e consentendo di creare una relazione tra la variabilità dei piazzamenti ed una serie di fenomeni quali i ritardi e la densità dell’orario pianificato.XXIII Ciclo198

The prismatic Sigma 3 (10-10) twin bounday in alpha-Al2O3 investigated by density functional theory and transmission electron microscopy

The microscopic structure of a prismatic $\Sigma 3$ $(10\bar{1}0)$ twin boundary in \aal2o3 is characterized theoretically by ab-initio local-density-functional theory, and experimentally by spatial-resolution electron energy-loss spectroscopy in a scanning transmission electron microscope (STEM), measuring energy-loss near-edge structures (ELNES) of the oxygen $K$-ionization edge. Theoretically, two distinct microscopic variants for this twin interface with low interface energies are derived and analysed. Experimentally, it is demonstrated that the spatial and energetical resolutions of present high-performance STEM instruments are insufficient to discriminate the subtle differences of the two proposed interface variants. It is predicted that for the currently developed next generation of analytical electron microscopes the prismatic twin interface will provide a promising benchmark case to demonstrate the achievement of ELNES with spatial resolution of individual atom columns

PixFEL: development of an X-ray diffraction imager for future FEL applications

A readout chip for diffraction imaging applications at new generation X-ray FELs (Free Electron Lasers) has been designed in a 65 nm CMOS technology. It consists of a 32 × 32 matrix, with square pixels and a pixel pitch of 110 µm. Each cell includes a low-noise charge sensitive amplifier (CSA) with dynamic signal compression, covering an input dynamic range from 1 to 104 photons and featuring single photon resolution at small signals at energies from 1 to 10 keV. The CSA output is processed by a time-variant shaper performing gated integration and correlated double sampling. Each pixel includes also a small area, low power 10-bit time-interleaved Successive Approximation Register (SAR) ADC for in-pixel digitization of the amplitude measurement. The channel can be operated at rates up to 4.5 MHz, to be compliant with the rates foreseen for future X-ray FEL machines. The ASIC has been designed in order to be bump bonded to a slim/active edge pixel sensor, in order to build the first demonstrator for the PixFEL (advanced X-ray PIXel cameras at FELs) imager

The Sigma 13 (10-14) twin in alpha-Al2O3: A model for a general grain boundary

The atomistic structure and energetics of the Sigma 13 (10-14)[1-210] symmetrical tilt grain boundary in alpha-Al2O3 are studied by first-principles calculations based on the local-density-functional theory with a mixed-basis pseudopotential method. Three configurations, stable with respect to intergranular cleavage, are identified: one Al-terminated glide-mirror twin boundary, and two O-terminated twin boundaries, with glide-mirror and two-fold screw-rotation symmetries, respectively. Their relative energetics as a function of axial grain separation are described, and the local electronic structure and bonding are analysed. The Al-terminated variant is predicted to be the most stable one, confirming previous empirical calculations, but in contrast with high-resolution transmission electron microscopy observations on high-purity diffusion-bonded bicrystals, which resulted in an O-terminated structure. An explanation of this discrepancy is proposed, based on the different relative energetics of the internal interfaces with respect to the free surfaces

Two different mechanisms of stabilization of regular pi-stacks of radicals in switchable dithiazolyl-based materials

Materials based on regular π-stacks of planar organic radicals are intensively pursued by virtue of their technologically relevant properties. Yet, these π-stacks are commonly unstable against π-dimerization. In this computational study, we reveal that regular π-stacks of planar dithiazolyl radicals can be rendered stable, in some range of temperatures, via two different mechanisms. When the radicals of a π-stack are both longitudinally and latitudinally slipped with respect to each other, the corresponding regular π-stacked configuration is associated with a locally stable minimum in the potential energy surface of the system. Conversely, those regular π-stacks in which radicals are latitudinally slipped with respect to each other are stable as a result of a dynamic interconversion between two degenerate dimerized configurations. The existence of two stabilization mechanisms, which can be traced back to the bonding properties of isolated π-dimers, translates into two different ways of exploiting spin-Peierls-like transitions in switchable dithiazolyl-based materials

Bouncing pre-big bang on the brane

A regular bouncing universe is obtained in the context of a dilaton-gravity brane world scenario. The scale factor starts in a contracting inflationary phase both in the Einstein and in the string frame, it then undergoes a bounce (due to interaction with the bulk Weyl tensor), and subsequently enters into a decelerated expanding era. This graceful exit is obtained at low curvature and low coupling, and without violating the Null Energy Condition.Comment: 16 pages, 3 figures; final version to be published on PRD. General improvement of section II (better specification of the matter content on the brane and discussion about the late time behavior), main results unchanged; 2 references adde

Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials

Quantum ESPRESSO is an integrated suite of computer codes for electronic-structure calculations and materials modeling, based on density-functional theory, plane waves, and pseudopotentials (norm-conserving, ultrasoft, and projector-augmented wave). Quantum ESPRESSO stands for "opEn Source Package for Research in Electronic Structure, Simulation, and Optimization". It is freely available to researchers around the world under the terms of the GNU General Public License. Quantum ESPRESSO builds upon newly-restructured electronic-structure codes that have been developed and tested by some of the original authors of novel electronic-structure algorithms and applied in the last twenty years by some of the leading materials modeling groups worldwide. Innovation and efficiency are still its main focus, with special attention paid to massively-parallel architectures, and a great effort being devoted to user friendliness. Quantum ESPRESSO is evolving towards a distribution of independent and inter-operable codes in the spirit of an open-source project, where researchers active in the field of electronic-structure calculations are encouraged to participate in the project by contributing their own codes or by implementing their own ideas into existing codes.Comment: 36 pages, 5 figures, resubmitted to J.Phys.: Condens. Matte

Free energy and molecular dynamics calculations for the cubic-tetragonal phase transition in zirconia

The high-temperature cubic-tetragonal phase transition of pure stoichiometric zirconia is studied by molecular dynamics (MD) simulations and within the framework of the Landau theory of phase transformations. The interatomic forces are calculated using an empirical, self-consistent, orthogonal tight-binding (SC-TB) model, which includes atomic polarizabilities up to the quadrupolar level. A first set of standard MD calculations shows that, on increasing temperature, one particular vibrational frequency softens. The temperature evolution of the free energy surfaces around the phase transition is then studied with a second set of calculations. These combine the thermodynamic integration technique with constrained MD simulations. The results seem to support the thesis of a second-order phase transition but with unusual, very anharmonic behaviour above the transition temperature