Phase transitions in the H+-conducting perovskite ceramics by the quasi-elastic neutron and high-pressure Raman scattering

H⁺-containing lanthanide-doped perovskites A(Ba, Sr etc.)B(Zr, Ce, Ti etc.)O₃ are potential ceramic membranes for fuel cell and medium temperature water electrolysis (300–800 °C). The comparison studies of the hydrated and non-hydrated Yb-doped BaZrO₃ and SrZrO₃ were performed by thermal expansion, medium–high temperature neutron and room-temperature high-pressure Raman scattering. Neutron diffraction and elastic/quasi-elastic studies carried out for BaZrO₃ ceramic show the presence of the protons, their successive diffusion above ∼600 °C, and then their departure above 750 °C (under vacuum). Phase transitions and their modification by proton insertion are discussed. A high-pressure Raman study of SrZrO₃ performed at room temperature in the diamond anvil cell reveals the presence of two pressure-induced phase transitions at about 5 and 22 GPa and confirms that proton insertion modifies the phase transition sequences. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Optimization conditions for the separation of rare earth elements,americium, curium and cesium with HPLC technique

In order to validate the neutronic code calculations used in the nuclear field, it is necessary to quantify the isotopic composition of the nuclear irradiated fuels with high precision and accuracy. A separation step whose objective is to isolate the elements of interest in a fraction as pure as possible, is performed before mass spectrometry detection (MC-ICP-MS, TIMS), in order to eliminate isobaric interferences. In a first step, uranium and plutonium are separated from the fission products by ion exchange chromatography. Then, fission products are separated by high performance liquid chromatography (HPLC). A gradient separation with a silica sulphonated support as stationary phase and hydroxy-methyl butyric acid (HMB) as eluent solution provides a good degree of separation of the rare earth elements, Am, Cm and Cs. But, for a same manufacturer, the rate of sulphonated groups is variable from one column to another for a given production batch. For every replacement of column, it is necessary to adjust the separation conditions. Furthermore, the high radioactivity of the samples injected damages the stationary phase, dragging a regular renewal of the columns. The goal of this study is to determine the optimal separation conditions with a minimum of tests in order to limit the time assigned to this operation. A first Doehlert experimental design with pH and HMB concentration as variables has been implemented to optimize Gd, Eu separation, in isocratic initial conditions. A second one has been tested in order to separate the higher lanthanides and to fix the final conditions of the gradient separation. A last set of tests has been performed to characterize the cesium behaviour. Finally, the gradient conditions have been adjusted in order to perform the full separation of lanthanides, Cs, Am and Cm with nuclear facilities.     

Two-dimensional organization of a large number of stationary optical filaments by adaptive wave front control

We present an adaptive technique for the formation of multiple co-propagating and stationary filaments in a gaseous medium. Wavefront shaping of the initial beam is performed using a deformable mirror to achieve a complete two-dimensional control of the multi-spot intensity pattern in the laser focus. The spatial organization of these intensity spots yields reliable formation of up to five stable and stationary filaments providing a test bed for fundamental studies on multiple filamentation. PACS 42.65.Jx; 52.38.Hb; 42.65.Sf     

Acoustic emission potentialities for characterization of Mullins effect in natural rubber materials filled with carbon black

Acoustic Emission (AE) was investigated in order to monitor in real time the Mullins effect. Cyclic uniaxial tensile tests were carried out on two different natural rubbers. Different behaviour is revealed depending on whether or not the material undergoes the Mullins effect. The acoustic emission activity is very important during the first cycle, but decreases gradually with increasing number of cycles, when the Mullins effect is observed. On the contrary, when there is no Mullins effect no significant AE activity is recorded.     

Synthesis of 6-amino-5-cyano-1,4-disubstituted-2(1H)-pyrimidinones via copper-(I)-catalyzed alkyne-azide 'click chemistry' and their reactivity

In this paper we present the room temperature synthesis of a novel serie of 1,4-disubstituted-1,2,3-triazoles 4a-l by employing the (3+2) cycloaddition reaction of pyrimidinones containing alkyne functions with different model azides in the presence of copper sulphate and sodium ascorbate. To obtain the final triazoles, we also synthesized the major precursors 6-amino-5-cyano-1,4-disubstituted-2(1H)-pyrimidinones 3a-r from ethyl 2,2-dicyanovinylcarbamate derivatives 2a-c and various primary aromatic amines containing an alkyne group. The triazoles were prepared in good to very good yields.     

Π‐Stacking Functionalization of Carbon Nanotubes through Micelle Swelling

We report on a new, original and efficient method for π‐stacking functionalization of single‐wall carbon nanotubes. This method is applied to the synthesis of a high‐yield light‐harvesting system combining single‐wall carbon nanotubes and porphyrin molecules. We developed a micelle‐swelling technique that leads to controlled and stable complexes presenting an efficient energy transfer. We demonstrate the key role of the organic solvent in the functionalization mechanism. By swelling the micelles, the solvent helps the non‐water‐soluble porphyrins to reach the micelle core and allows a strong enhancement of the interaction between porphyrins and nanotubes. This technique opens new avenues for the functionalization of carbon nanostructures.