Quantitative optical determination of the shape of Cu nanocrystals in a composite film

5 pages, 4 figures, 1 table.We demonstrate that optical extinction spectroscopy can be used to determine the effective shape of Cu nanocrystals (NCs) embedded in a transparent amorphous Al2O3 host both produced by pulsed laser deposition. The axial ratio of the NCs was extracted from the positions of the surface plasmon modes of the optical extinction spectra of the nanocomposite film. Comparison to the results obtained by grazing incidence small angle x-ray scattering shows excellent agreement. Thus, optical spectroscopy can be used as a simple, easily accessible, and versatile tool for the characterization of the NCs that form nanocomposite films.This work was supported by the European Union (BRITE Project No. 98-0616).Peer reviewe

Insights into the fabrication and structure of plutonium pyrochlores

Rare earth zirconates, such as Nd2Zr2O7, crystallise with the pyrochlore structure and are a group of materials which have been suggested as potential nuclear waste forms for actinide immobilisation. In this work, a new hydroxide co-precipitation route is presented to investigate the incorporation of Pu into Nd2Zr2O7. The plutonium content was varied between 5 and 10 mol% and the structural uptake and Pu oxidation state were probed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS). The experimental findings were complemented by DFT ab initio calculations. For all the incorporation mechanisms studied PuO2 was used as the reference reactant state to allow for a direct comparison between the possible Pu uptake scenarios. Analysis of the experimental data suggests that Pu(IV) cations substitute for Nd(III) cations leading to structural distortion of the pyrochlore A-sites. The computed solution energies and bond-distances corroborate the experimental findings and indicate that the excess charge is balanced via the introduction of oxygen at formerly vacant sites

A thermodynamic adsorption/entrapment model for selenium(IV) coprecipitation with calcite

Selenium is an environmentally relevant trace element, while the radioisotope 79Se is of particular concern in the context of nuclear waste disposal safety. Oxidized selenium species are relatively soluble and show only weak adsorption at common mineral surfaces. However, a possible sorption mechanism for selenium in the geosphere is the structural incorporation of selenium(IV) (selenite, SeO3 2) into calcite (CaCO3). In this study we investigate the interactions between selenite and calcite by a series of experimental and computational methods with the aim to quantify selenite incorporation into calcite at standard conditions. We further seek to describe the thermodynamics of selenite-doped calcite, and selenite coprecipitation with calcite. The structure of the incorporated species is investigated using Se K-edge EXAFS (isotropic and polarization dependent) and results are compared to density functional theory (DFT) calculations. These investigations confirm structural incorporation of selenite into calcite by the substitution of carbonate for selenite, leading to the formation of a Ca(SeO3)X(CO3)(1-X)solid solution.Coprecipitation experiments at low supersaturation indicate a linear increase of the selenite to carbonate ratio in the solid with the increase of the selenite to carbonate ratio in the contact solution. This relationship can be described under the assumption of an ideal mixing between calcite and a virtual CaSeO3 endmember, whose standard Gibbs free energy (G0(CaSeO3_exp) = 953 ± 6 kJ/mol, log10(KSP(CaSeO3_exp)) = 6.7 ± 1.0) is defined by linear extrapolation of the excess free energy from the dilute Henry’s law domain to X(CaSeO3) = 1. In contrast to this experimental result, DFT and force field calculations predict the virtual bulk CaSeO3 endmember to be significantly less stable and more soluble: G0(CaSeO3 bulk) = 912 ± 10 kJ/mol and log10(KSP(CaSeO3_bulk)) = 0.5 ± 1.7. To explain this discrepancy we introduce a thermodynamic adsorption/entrapment concept. This concept is based on the idea that the experimental value of 953 ± 6 kJ/mol reflects the Gibbs free energy of CaSeO3 within the surface layer, while the value obtained from atomistic calculations reflects bulk thermodynamic properties. In coprecipitation experiments performed at steady-state conditions the difference between these values is compensated by the supersaturation. Thus, if the Gibbs free energies of the bulk CaCO3 and CaSeO3 endmembers are substituted with the Gibbs free energies of the surface endmembers, the coprecipitation experiment can still be treated within the formalism of equilibrium thermodynamics. This concept leads to a number of important consequences, which can be tested both experimentally and theoretically.We show that selenite adsorption at the calcite surface and selenite coprecipitation with calcite under supersaturated conditions can be described with the same partition coefficient. This implies that the coprecipitation can be viewed as a sequence of adsorption and entrapment events. On the other hand, our aragonite recrystallization experiments show that at near equilibrium conditions the calcite growth is inhibited in the presence of selenite. Consistent with these observations, our DFT calculations show that the substitution of carbonate for selenite is energetically more favorable at the surface than inside the bulk. The whole set of the experimental and atomistic simulation results leads to the conclusion that the calcite–CaSeO3 solid solution can only grow continuously if the aqueous solution is supersaturated with respect to the bulk solid solution. Under these conditions selenite coprecipitates with calcite at a partition coefficient of D = 0.02 ± 0.01. If the solution is undersaturated with respect to the bulk solid solution, only surface ion-exchange occurs. Elevated selenite concentrations in bulk calcite therefore reflect non-equilibrium conditions

Mathematics in Medical Diagnostics - 2022 Proceedings of the 4th International Conference on Trauma Surgery Technology

The 4th event of the Giessen International Conference Series on Trauma Surgery Technology took place on April, the 23rd 2022 in Warsaw, Poland. It aims to bring together practical application research, with a focus on medical imaging, and the TDA experts from Warsaw. This publication contains details of our presentations and discussions

Strong asymptotics for Jacobi polynomials with varying nonstandard parameters

Strong asymptotics on the whole complex plane of a sequence of monic Jacobi polynomials $P_n^{(\alpha_n, \beta_n)}$ is studied, assuming that $$\lim_{n\to\infty} \frac{\alpha_n}{n}=A, \qquad \lim_{n\to\infty} \frac{\beta _n}{n}=B,$$ with $A$ and $B$ satisfying $A > -1$, $B>-1$, $A+B < -1$. The asymptotic analysis is based on the non-Hermitian orthogonality of these polynomials, and uses the Deift/Zhou steepest descent analysis for matrix Riemann-Hilbert problems. As a corollary, asymptotic zero behavior is derived. We show that in a generic case the zeros distribute on the set of critical trajectories $\Gamma$ of a certain quadratic differential according to the equilibrium measure on $\Gamma$ in an external field. However, when either $\alpha_n$, $\beta_n$ or $\alpha_n+\beta_n$ are geometrically close to $\Z$, part of the zeros accumulate along a different trajectory of the same quadratic differential.Comment: 31 pages, 12 figures. Some references added. To appear in Journal D'Analyse Mathematiqu

Motor expertise modulates the unconscious processing of human body postures

Little is known about the cognitive background of unconscious visuomotor control of complex sports movements. Therefore, we investigated the extent to which novices and skilled high-jump athletes are able to identify visually presented body postures of the high jump unconsciously. We also asked whether or not the manner of processing differs (qualitatively or quantitatively) between these groups as a function of their motor expertise. A priming experiment with not consciously perceivable stimuli was designed to determine whether subliminal priming of movement phases (same vs. different movement phases) or temporal order (i.e. natural vs. reversed movement order) affects target processing. Participants had to decide which phase of the high jump (approach vs. flight phase) a target photograph was taken from. We found a main effect of temporal order for skilled athletes, that is, faster reaction times for prime-target pairs that reflected the natural movement order as opposed to the reversed movement order. This result indicates that temporal-order information pertaining to the domain of expertise plays a critical role in athletes’ perceptual capacities. For novices, data analyses revealed an interaction between temporal order and movement phases. That is, only the reversed movement order of flight-approach pictures increased processing time. Taken together, the results suggest that the structure of cognitive movement representation modulates unconscious processing of movement pictures and points to a functional role of motor representations in visual perception

The impact of the Great Exhibition of 1851 on the development of technical education during the second half of the nineteenth century

This paper examines the contribution made by the mechanics’ institute movement in Britain just prior to, and following, the opening of the Great Exhibition of 1851 in London. It argues that far from making little contribution to education, as often portrayed by historians, the movement was ideally positioned to respond to the findings of the Exhibition, which were that foreign goods on display were often more advanced than those produced in Britain. The paper highlights, through a regional study, how well suited mechanics’ institutes were in organising their own exhibitions, providing the idea of this first international exhibition. Subsequently, many offered nationally recognised technical subject examinations through relevant education as well as informing government commissions, prior to the passing of the Technical Instruction Acts in 1889 and the Local Taxation Act of 1890. These acts effectively put mechanics’ institutes into state ownership as the first step in developing further education for all in Britai