The use of micro-XRD for the study of glaze color decorations

The compounds responsible for the colors and decorations in glass and glazed ceramics include: coloring agents (transition-metal ions), pigments (micro- and nanoprecipitates of compounds that either do not dissolve or recrystallize in the glassy matrix) and opacifiers (microcrystalline compounds with high light scattering capability). Their composition, structure and range of stability are highly dependent not only on the composition but also on the procedures followed to obtain them. Chemical composition of the colorants and crystallites may be obtained by means of SEM-EDX and WDX. Synchrotron radiation micro-X-ray diffraction (SR-micro-XRD) has a small beam size adequate (10 to 50 microns footprint size) to obtain the structural information of crystalline compounds and high brilliance, optimal for determining the crystallites even when present in low amounts. In addition, in glass decorations the crystallites often appear forming thin layers (from 10 to 100 micrometers thick) and they show a depth-dependent composition and crystal structure. Their nature and distribution across the glass/glaze decorations gives direct information on the technology of production and stability and may be related to the color and appearance. A selection of glass and glaze coloring agents and decorations are studied by means of SR-micro-XRD and SEM-EDX including: manganese brown, antimony yellow, red copper lusters and cobalt blue. The selection includes Medieval (Islamic, and Hispano Moresque) and Renaissance tin-glazed ceramics from the 10th to the 17th century AD.     

Diagrammatic structure of the general coupled cluster equations

The general formula for the number of diagrammatic terms occurring in the T_n equation within a particular coupled cluster model is derived. Both the antisymmetrized and Goldstone diagrams are considered. In addition to the full coupled cluster equation approximate approaches are discussed, and for each the general formula for the number of terms is given. Analogous expressions are presented for the number of diagrammatic terms contributing to the elements of the transformed Hamiltonian [Hbar] = e^?T He^T .     

Capabilities of through‐the‐substrate microdiffraction: application of Patterson‐function direct methods to synchrotron data from polished thin sections

Some theoretical and practical aspects of the application of transmission microdiffraction (µXRD) to thin sections (≤30 µm thickness) of samples fixed or deposited on substrates are discussed. The principal characteristic of this technique is that the analysed micro‐sized region of the thin section is illuminated through the substrate (tts‐µXRD). Fields that can benefit from this are mineralogy, petrology and materials sciences since they often require in situ lateral studies to follow the evolution of crystalline phases or to determine new crystal structures in the case of phase transitions. The capability of tts‐µXRD for performing structural studies with synchrotron radiation is shown by two examples. The first example is a test case in which tts‐µXRD intensity data of pure aerinite are processed using Patterson‐function direct methods to directly solve the crystal structure. In the second example, tts‐µXRD is used to study the transformation of laumonite into a new aluminosilicate for which a crystal structure model is proposed.     

Plane Sources of Waves in the Presence of Magnetic Field

In this paper the generation of harmonic waves in an elastic magneticmaterial, which is a perfect conductor of electricity, isconsidered. It has been assumed that an infinite body is subjected tothe action of an initially constant magnetic fieldH = (H,0,0) and in the plane ax+by=0 acts a source ofdistortion. It has been shown that this source may produce bothtransverse and longitudinal waves and each of them consists of two parts,which propagate with different speeds. The amplitudes and speeds in dependence on theangle between the direction of wave propagation and the magnetic fieldintensity H have been discussed.     

Almost sure convergence of the kT-occupation time density estimator

In this Note, we introduce an extension of the k-nearest neighbor estimator in continuous time, the $k_T$-occupation time estimator, and we give sufficient conditions for its existence. Then, we show the almost sure convergence for α-mixing and bounded processes in two cases, the superoptimal case (when parametric rates are reached) and the optimal case (when i.i.d. rates of density estimation are reached). To cite this article: B. Labrador, C. R. Acad. Sci. Paris, Ser. I 343 (2006).     

Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far‐Red (Polarized) Luminescence

The physicochemical properties of cationic dioxa ( 1 ), azaoxa ( 2 ), and diaza ( 3 ) [6]helicenes demonstrate a much higher chemical stability of the diaza adduct 3 (pK_R+=20.4, =?0.72 V) compared to its azaoxa 2 (pK_R+=15.2, =?0.45 V) and dioxa 1 (pK_R+=8.8, =?0.12 V) analogues. The fluorescence of these cationic chromophores is established, and ranges from the orange to the far‐red regions. From 1 to 3 , a bathochromic shift of the lowest energy transitions (up to 614 nm in acetonitrile) and an enhancement of the fluorescence quantum yields and lifetimes (up to 31 % and 9.8 ns, respectively, at 658 nm) are observed. The triplet quantum yields and circularly polarized luminescence are also reported. Finally, fine tuning of the optical properties of the diaza [6]helicene core is achieved through selective and orthogonal post‐functionalization reactions (12 examples, compounds 4 – 15 ). The electronic absorption is modulated from the orange to the far‐red spectral range (560–731 nm), and fluorescence is observed from 591 to 755 nm with enhanced quantum efficiency up to 70 % (619 nm). The influence of the peripheral auxochrome substituents is rationalized by first‐principles calculations.