On‐site analysis of Limoges enamels from sixteenth to nineteenth centuries: an attempt to differentiate between genuine artefacts and copies

A selection of 15 painted enamels, most of which belong to Limoges productions, from 1500 to 1900 A.D. , has been studied on‐site in the storage rooms of musée des Arts décoratifs in Paris. The Raman signatures of the transparent and/or opacified glass matrix are discussed and compared with those which were previously recorded on glazed pottery, enamelled and stained glasses as well as Chinese cloisonné enamels. Analysed enamels mostly belong to soda‐lime‐based glass. Three types of compositions such as soda‐lime (fifteenth to sixteenth century), soda‐rich (fifteenth, sixteenth/nineteenth centuries) and lead‐potash‐lime (sixteenth and nineteenth centuries) are identified on the basis of the Raman signature of the glaze according to the wavenumber maxima of the Si O stretching and bending multiplets. The pigment signatures are similar to those recorded on ceramic glazes and glass enamels, which proves the similarity of the technologies. Cassiterite as an opacifier and hematite red and Naples yellow pigment variations give characteristic Raman signatures. The presence of lead arsenate as a pigment opacifier in nineteenth‐century samples is confirmed. Attempts are made to establish tools for the differentiation between genuine artefacts and nineteenth‐century restoration or fakes. Copyright © 2010 John Wiley & Sons, Ltd.     

Thulium environment in a silica doped optical fibre

Thulium-doped optical fibre amplifiers (TDFA) are developed to extend the optical telecommunication wavelength division multiplexing (WDM) bandwidth in the so-called S-band (1460–1530 nm). The radiative transition at 1.47 μm (³H₄ → ³F₄) competes with a non-radiative multi-phonon de-excitation (³H₄ → ³H₅). The quantum efficiency of the transition of interest is then highly affected by the phonon energy (E_p) of the material. For reliability reasons, oxide glasses are preferred but suffer from high phonon energy. In the case of silica glass, E_p is around 1100 cm^?1 and quantum efficiency is as low as 2%. To improve it, phonon energy in the thulium environment must be lowered. For that reason, aluminium is added and we explore three different core compositions: pure silica, and silica slightly modified with germanium or phosphorus. The role of aluminium is studied through fluorescence decay curves, fitted according to the continuous function decay analysis. From this analysis, modification of the thulium local environment due to aluminium is evidenced.     

Steric effects on reaction rates II: Rate and equilibrium constants for oxidation of bicyclic alcohols

Equilibrium constants for oxidation of a series of bicyclic alcohols with cyclohexanone have been determined under Meerwein-Ponndorf conditions. The data provide the thermodynamic background for interpretation of the mechanism of alcohol oxidation and ketone reductions. Free energies of the equilibrium (ΔG_ox) are compared with values calculated by molecular mechanics.     

Simultaneous off-shell excitation of He 23 S by an electron and one or more photons

We report data on the excitation of the 2³ S metastable state in helium by electrons in the presence of an intense laser field. The metastable signal is detected when the electron energy is insufficient to excite this state by itself. The additional energy comes from a pulsed CO₂ laser developing peak intensities in the interaction region in the 10⁸ W× cm^?2 range and requires the absorption of one or more photons. This process involves the active participation of all three bodies: the electron, the photon and the target atom. These data represent the first observation of this process when more than one photon is required.     

Better characterization of surface organometallic catalysts through resolution enhancement in proton solid state NMR spectra

Delayed-acquisition methods, namely, echo and constant-time-acquisition approaches, allow a significant improvement in resolution in the proton solid state NMR spectra of surface organometallic catalysts such as [syn-(SiO)Mo(=NAr)(=CH(t)Bu)(CH2(t)Bu)] and [(SiO)Re(C(t)Bu)(=CH(t)Bu)(CH2(t)Bu)] (syn/anti ratio = 1:1). This enables the observation of all of the proton resonances, which is not possible with the simple proton single-pulse technique under magic-angle spinning. For example, the methylene protons of the neopentyl ligands, buried in the large peak associated with all of the methyls in the 1H MAS spectrum, can easily be identified by recording a delayed-acquisition spectrum (resolution enhancement of a factor of 3 is obtained). Moreover, combining constant-time acquisition with heteronuclear carbon-proton correlation spectroscopy also improves the resolution of the 2D HETCOR spectra.     

Wavefront sensing issues in MCAO

The problematic of wavefront sensing in Multiconjugate Adaptive Optics (MCAO) is addressed in this article. We first focus on the sky coverage estimation which drives, in particular, the choice between natural and laser guide stars and therefore has a major impact on wavefront sensor design. Then a comparison between star oriented and layer oriented concepts is proposed. Analytical developments and optimization of the concepts are derived in the simplest MCAO case: the ground layer AO system. From this study, advantages and drawbacks of each concept are highlighted. To cite this article: T. Fusco et al., C. R. Physique 6 (2005).     

Smectic shells

Confining a smectic liquid crystal between two spherical surfaces results in the formation of a complex defect structure characterized by a set of curvature walls that divide the sphere into crescent domains, causing the undulation of the smectic layers. In this paper, we examine in detail these smectic textures and discuss the various possible origins of the observed patterns.     

Deformation properties of the neutron-deficient odd-A Pt and Hg nuclei

Nuclear and atomic spectroscopy measurements have provided a great number of data on the neutron-deficient Pt and Hg nuclei. The odd-A Pt and Hg with A<186 have a prolate shape, and the even-even isotopes have a triaxial shape, while the nuclear shape of the odd-A Pt and Hg with A>186 is still an open question. The energy of the low-lying levels and the nuclear moments have been calculated in the framework of a semimicroscopic “axial-rotor + 1 quasiparticle” coupling model. The predictions are compared with the experimental data and discussed. The results strongly suggest a prolate shape for the negative-parity low-lying states of the odd-A ^187–191Pt and ^187–193Hg isotopes.     

Approximation locale précisée dans des problèmes multi-échelles avec défauts localisés

We proceed here with our systematic study, initiated in [3], of multiscale problems with defects, within the context of homogenization theory. The case under consideration here is that of a diffusion equation with a diffusion coefficient of the form of a periodic function perturbed by an $L^r({\mathbb{R}}^d)$, $1<r<+\infty$, function modelling a localized defect. We outline the proof of the following approximation result: the corrector function, the existence of which has been established in [3], [4], allows us to approximate the solution to the original multiscale equation with essentially the same accuracy as in the purely periodic case. The rates of convergence may however vary, and are made precise, depending upon the $L^r$ integrability of the defect. The generalization to an abstract setting is mentioned. Our proof exactly follows, step by step, the pattern of the original proof of Avellaneda and Lin in [1] in the periodic case, extended in the works of Kenig and collaborators [12], and borrows a lot from it. The details of the results announced in this Note are given in our publications [2], [11].