First-principles investigation of Ag-Cu alloy surfaces in an oxidizing environment

In this paper we investigate by means of first-principles density functional theory calculations the (111) surface of the Ag-Cu alloy under varying conditions of pressure of the surrounding oxygen atmosphere and temperature. This alloy has been recently proposed as a catalyst with improved selectivity for ethylene epoxidation with respect to pure silver, the catalyst commonly used in industrial applications. Here we show that the presence of oxygen leads to copper segregation to the surface. Considering the surface free energy as a function of the surface composition, we construct the convex hull to investigate the stability of various surface structures. By including the dependence of the free surface energy on the oxygen chemical potential, we are able compute the phase diagram of the alloy as a function of temperature, pressure and surface composition. We find that, at temperature and pressure typically used in ethylene epoxidation, a number of structures can be present on the surface of the alloy, including clean Ag(111), thin layers of copper oxide and thick oxide-like structures. These results are consistent with, and help explain, recent experimental results.Comment: 10 pages, 6 figure

Fragmentation pathways of nanofractal structures on surface

We present a detailed systematical theoretical analysis of the post-growth processes occurring in nanofractals grown on surface. For this study we developed a method which accounts for the internal dynamics of particles in a fractal. We demonstrate that particle diffusion and detachment controls the shape of the emerging stable islands on surface. We consider different scenarios of fractal post-growth relaxation and analyze the time evolution of the island's morphology. The results of our calculations are compared with available experimental observations, and experiments in which the post-growth relaxation of deposited nanostructures can be probed are suggested.Comment: 34 pages, 11 figure

Alloy surface segregation in reactive environments: A first-principles atomistic thermodynamics study of Ag3Pd(111) in oxygen atmospheres

We present a first-principles atomistic thermodynamics framework to describe the structure, composition and segregation profile of an alloy surface in contact with a (reactive) environment. The method is illustrated with the application to a Ag3Pd(111) surface in an oxygen atmosphere, and we analyze trends in segregation, adsorption and surface free energies. We observe a wide range of oxygen adsorption energies on the various alloy surface configurations, including binding that is stronger than on a Pd(111) surface and weaker than that on a Ag(111) surface. This and the consideration of even small amounts of non-stoichiometries in the ordered bulk alloy are found to be crucial to accurately model the Pd surface segregation occurring in increasingly O-rich gas phases.Comment: 13 pages including 6 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Fibrous Monolithic Ceramics: III, Mechanical Properties and Oxidation Behavior of the Silicon Carbide/Boron Nitride System

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/66176/1/j.1151-2916.1994.tb05399.x.pd

Dust-particle transport in tokamak edge plasmas

Dust particulates in the size range of 10nm-100{micro}m are found in all fusion devices. Such dust can be generated during tokamak operation due to strong plasma/material-surface interactions. Some recent experiments and theoretical estimates indicate that dust particles can provide an important source of impurities in the tokamak plasma. Moreover, dust can be a serious threat to the safety of next-step fusion devices. In this paper, recent experimental observations on dust in fusion devices are reviewed. A physical model for dust transport simulation, and a newly developed code DUSTT, are discussed. The DUSTT code incorporates both dust dynamics due to comprehensive dust-plasma interactions as well as the effects of dust heating, charging, and evaporation. The code tracks test dust particles in realistic plasma backgrounds as provided by edge-plasma transport codes. Results are presented for dust transport in current and next-step tokamaks. The effect of dust on divertor plasma profiles and core plasma contamination is examined

Divergent compensatory responses to high-fat diet between C57BL6/J and C57BLKS/J inbred mouse strains

Impaired glucose tolerance (IGT) and type 2 diabetes (T2DM) are polygenic disorders with complex pathophysiologies; recapitulating them with mouse models is challenging. Despite 70% genetic homology, C57BL/6J (BL6) and C57BLKS/J (BLKS) inbred mouse strains differ in response to diet- and genetic-induced obesity. We hypothesized these differences would yield insight into IGT and T2DM susceptibility and response to pharmacological therapies. To this end, male 8-wk-old BL6 and BLKS mice were fed normal chow (18% kcal from fat), high-fat diet (HFD; 42% kcal from fat), or HFD supplemented with the PPARγ agonist pioglitazone (PIO; 140 mg PIO/kg diet) for 16 wk. Assessments of body composition, glucose homeostasis, insulin production, and energy metabolism, as well as histological analyses of pancreata were undertaken. BL6 mice gained weight and adiposity in response to HFD, leading to peripheral insulin resistance that was met with increased β-cell proliferation and insulin production. By contrast, BLKS mice responded to HFD by restricting food intake and increasing activity. These behavioral responses limited weight gain and protected against HFD-induced glucose intolerance, which in this strain was primarily due to β-cell dysfunction. PIO treatment did not affect HFD-induced weight gain in BL6 mice, and decreased visceral fat mass, whereas in BLKS mice PIO increased total fat mass without improving visceral fat mass. Differences in these responses to HFD and effects of PIO reflect divergent human responses to a Western lifestyle and underscore the careful consideration needed when choosing mouse models of diet-induced obesity and diabetes treatment

Amblyopia and quality of life: a systematic review

Background/Aims Amblyopia is a common condition which can affect up to 5% of the general population. The health-related quality of life (HRQoL) implications of amblyopia and/or its treatment have been explored in the literature. Methods A systematic literature search was undertaken (16th-30th January 2007) to identify the HRQoL implications of amblyopia and/or its treatment. Results A total of 25 papers were included in the literature review. The HRQoL implications of amblyopia related specifically to amblyopia treatment, rather than the condition itself. These included the impact upon family life; social interactions; difficulties undertaking daily activities; and feelings and behaviour. The identified studies adopted a number of methodologies. The study populations included; children with the condition; parents of children with amblyopia; and adults who had undertaken amblyopia treatment as a child. Some studies developed their own measures of HRQoL, and others determined HRQoL through proxy measures. Conclusions The reported findings of the HRQoL implications are of importance when considering the management of cases of amblyopia. Further research is required to assess the immediate and long-term effects of amblyopia and/or its treatment upon HRQoL using a more standardised approach

Is facet joint distraction a cause of postoperative axial neck pain after ACDF surgery?

Introduction: Intervertebral distraction in anterior cervical discectomy and fusion (ACDF) has been postulated to injure the degenerative facet joints posteriorly and increase postoperative pain and disability. This study aims to determine if there is a correlation between the amount of facet distraction and postoperative patient reported outcomes. Methods: A retrospective cohort analysis of patients undergoing ACDF for degenerative pathologies was performed. Each patient received lateral cervical spine x-rays at the immediate postoperative time point and were split into groups based on the amount of facet distraction measured on these films: Group A: \u3c 1.5 mm; Group B: 1.5-2.0 mm; and Group C: \u3e 2.0 mm. Patients reported outcome measures were obtained preoperatively and at 1-year postoperatively. Univariate and multivariate analyses were performed to compare outcomes between groups. Results: A total of 229 patients were included with an average follow-up of 19.8 [19.0, 20.7] months with a mean facet joint distraction of 1.7mm. There were 87 patients in Group A, 76 patients in Group B, and 66 patients in Group C. Patients significantly improved across all outcome measures from baseline to postoperatively (p \u3c 0.05). There was no difference between groups at any time point with respect to outcome scores (p \u3e 0.05). Multiple regression analysis did not identify increasing distraction as a predictor of patient outcomes. Conclusions: There were no significant differences between patient outcomes and the amount of facet distraction after ACDF surgery. Multivariate analysis did not find a correlation between facet distraction and overall HRQOL outcome

Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions

Previous and present "academic" research aiming at atomic scale understanding is mainly concerned with the study of individual molecular processes possibly underlying materials science applications. Appealing properties of an individual process are then frequently discussed in terms of their direct importance for the envisioned material function, or reciprocally, the function of materials is somehow believed to be understandable by essentially one prominent elementary process only. What is often overlooked in this approach is that in macroscopic systems of technological relevance typically a large number of distinct atomic scale processes take place. Which of them are decisive for observable system properties and functions is then not only determined by the detailed individual properties of each process alone, but in many, if not most cases also the interplay of all processes, i.e. how they act together, plays a crucial role. For a "predictive materials science modeling with microscopic understanding", a description that treats the statistical interplay of a large number of microscopically well-described elementary processes must therefore be applied. Modern electronic structure theory methods such as DFT have become a standard tool for the accurate description of individual molecular processes. Here, we discuss the present status of emerging methodologies which attempt to achieve a (hopefully seamless) match of DFT with concepts from statistical mechanics or thermodynamics, in order to also address the interplay of the various molecular processes. The new quality of, and the novel insights that can be gained by, such techniques is illustrated by how they allow the description of crystal surfaces in contact with realistic gas-phase environments.Comment: 24 pages including 17 figures, related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.htm