Stability and Physical Properties of Metastable Ba-Si Clathrates.

In the present study, we have investigated the stability of different Ba-Si clathrates with pressure and temperature using DFT calculations and studied the stability of type I Ba8Si46 and type IX Ba24Si100 clathrates using high pressure─high temperature synthesis technique, calorimetry, and diffraction experiments. When increasing pressure, the type I Ba8Si46 clathrate and BaSi6 become more stable. In good qualitative agreement with experiments, the type IX Ba24Si100 clathrate becomes stable at a pressure of 1-2 GPa thanks to the pressure and thermal effect of both electronic and vibrational contributions. One can notice that the presence of Ba in the cages of type IX clathrate increases significantly the stability and the mechanical properties of type IX clathrate. We have determined the P-T existence domain of type IX Ba24Si100 clathrate from ex situ experiments, which was confirmed by in situ synchrotron X-ray experiments. At room pressure and under an oxidizing atmosphere, the type I Ba8Si46 and the type IX Ba24Si100 clathrates are stable up to about 560 °C and up to about 600 °C, respectively. The thermoelectric properties of type IX Ba24Si100 are also reported.

Towards the Prediction of Sandwich Composites Durability in Severe Condition of Temperature: A New Numerical Model Describing the Influence of Material Water Content during a Fire Scenario.

An advanced fire thermal model was developed to predict the evolution of the temperature and decomposition gradient across a sandwich composite structure when exposed to high temperatures (fire). This model allows the prediction of a large numbers of parameters, such as thermal expansion, gas mass storage, porosity, permeability, density, and internal pressure. The highlight of this model is that we consider, in the sandwich constituents (core and skins), additional parameters, such as changing volume porosities, other coupled constituents (as infused resin in the balsa core), and what make the main originality of the present approach: moisture content (free and bounded water). The time dependence of many parameters, i.e., among others, the combustion advancing front and mechanical properties, can be predicted in a large number of material and fire scenarios. The proposed approach was validated in the case of sandwich panels, with glass/polyester or glass/vinyl ester skins and balsa core, exposed to high temperatures up to 750 °C. The influence of water on the thermal and mechanical responses is also highlighted.

Synergy between polymorphism, pressure, spin-crossover and temperature in [Fe(PM-BiA)2(NCS)2]: a neutron powder diffraction investigation.

The pressure dependencies of the lattice parameters of the spin transition compound [Fe(PM-BiA)2(NCS)2] have been derived from neutron powder diffraction measurements at low temperature. The study of the compound [Fe(PM-BiA)2(NCS)2]-pI has first confirmed the atypical spin crossover behaviour under pressure of this compound that shows a pressure induced structural transition inducing the transformation into a different polymorph, [Fe(PM-BiA)2(NCS)2]-pII. This phenomenon avoids a first-order spin transition in favour of continuous transition around 0.75 GPa at ambient temperature. Low temperature measurements under pressure up to 1.07 GPa allowed us not only to describe the spin-crossover for both polymorphs but also to reach phase-diagram regions where both polymorphs co-exist in different spin-states. Finally, the reversibility of the structural variations has been demonstrated.

Bolaamphiphiles derived from alkenyl L-rhamnosides and alkenyl D-xylosides: importance of the hydrophilic head.

The two step synthesis of a new bolaamphiphile derived from alkenyl L-rhamnosides was described. The general synthetic strategy of bolaamphiphiles derived from L-rhamnose was based on a previous work describing the synthesis of bolaamphiphiles derived from D-xylose. The conformational properties of this new compound were investigated by FTIR spectroscopy in an aqueous film in order to obtain a reference for further studies about the membrane-interacting properties. Moreover, the surface activity of this new bolaamphiphile was analyzed by Langmuir balance technology and was compared with that of the analogous bolaamphiphile derived from alkenyl D-xylosides. The findings indicate that the rhamnoside-based bolaform has an increased surface activity and a better ability to form aggregates than xyloside-based one.

Nano-scaled TiO(OD)2: a time resolved 1H/2D isotope exchange study observed in situ with neutron scattering at 20 °C and 40 °C.

In situ neutron diffraction measurements of the nanocrystalline deuterated oxyhydroxide TiO(OD)(2) compound were performed as a function of time and temperature under NH(3) gas flow in order to study the hydrogen-deuterium exchange mechanism. Data were collected on the instrument D20 at the ILL (France) and the analysis of the kinetics was directly based on the contrast variation of the incoherent neutron cross section of hydrogen and deuterium. The time evolution of the hydrogenated phase fraction was described using the well-known Kolmogorov-Johnson-Mehl-Avrami (KJMA) expression. The H/D exchange reaction is complete within 140 s at 20 °C and within 120 s at 40 °C. The activation energy for the H/D exchange reaction is estimated to be 37 kJ mol(-1).

Study of the thermal nitridation of nanocrystalline Ti(OH)4 by X-ray and in situ neutron powder diffraction.

In situ neutron diffraction measurements of nanocrystalline titanium oxynitrides were performed, as a function of temperature and time, to explore the nitrogen/oxygen substitution mechanism occurring during their synthesis by reaction of gaseous ammonia with nanocrystalline Ti(OH)(4). These neutron diffraction experiments are supported by chemical analysis and X-ray diffraction, allowing the description of the structural variations and ordering process between the Ti(O/N)(2) anatase and the Ti(O/N) rock-salt phases. Our results show that the formation of the Ti(O/N) rock-salt phase goes along with the creation of vacancies on the Ti sites and that the N/O substitution proceeds but without N/O ordering.

Tricaesium tris-(pyridine-2,6-dicarboxyl-ato-κO,N,O)lutetium(III) octa-hydrate.

Colourless block crystals of the title compound, Cs(3)[Lu(dipic)(3)]·8H(2)O [dipic is dipicolinate or pyridine-2,6-dicarboxyl-ate, C(7)H(3)NO(4)] were synthesized by slow evaporation of the solvent. The crystal structure of this Lu(III)-complex, isostructural with the Dy(III) and Eu(III) complexes, was determined from a crystal twinned by inversion and consists of discrete [Lu(dipic)(3)](3-) anions, Cs(+) cations and water mol-ecules involving hydrogen bonding. The Lu atom lies on a twofold rotation axis and is coordinated by six O atoms and three N atoms of three dipicolinate ligands. One Cs atom is also on a twofold axis. The unit cell can be regarded as successive layers along the crystallographic c-axis formed by [Lu(dipic)(3)](3-) anionic planes and [Cs(+), H(2)O] cationic planes. In the crystal structure, although the H atoms attached to water mol-ecules could not be located, short O-O contacts clearly indicate the occurrence of an intricate hydrogen-bonded network through contacts with other water mol-ecules, Cs cations or with the O atoms of the dipicolinate ligands.

Extension of the experimental electron density analysis to metastable states: a case example of the spin crossover complex Fe(btr)2(NCS)2.H2O.

An experimental electron density (ED) analysis of the spin crossover coordination complex Fe(btr)(2)(NCS)(2).H(2)O has been performed in the ground low-spin (LS) state and in the metastable thermally quenched high-spin (HS) state at 15 K by fitting a multipolar model to high-resolution X-ray diffraction measurements. The ED has been quantitatively analyzed using the quantum theory of atoms in molecules. This is the first time the ED distribution of a molecular metastable state has been experimentally investigated. The electron deformation densities and derived Fe 3d orbital populations are characteristic of LS (t(2g)(6) e(g)(0)) and HS (t(2g)(4) e(g)(2)) electron configurations and indicate significant sigma donation to the Fe d(x)2(-)(y)2 and d(z)2 atomic orbitals. The Fe-N(NCS) and Fe-N(btr) coordination interactions are characterized using the laplacian distribution of the ED, the molecular electrostatic potential, and the fragment charges obtained by integration over the topological atomic basins. A combination of electrostatic and covalent contributions to these interactions is pointed out. Interlayer interactions are evidenced by the presence of bond critical points in N...H hydrogen bonds involving the non-coordinated water molecule. Systematic differences in the atomic displacement parameters between the LS and HS states have been described and rationalized in terms of modifications of bond force constants.