Vibration analysis of hydrogen, deuterium and tritium in metals: consequences on the isotope effect.

The present study focuses on the impact of the vibrational frequencies on the thermodynamic behavior of hydrides, deuterides and tritides, using high scale harmonic phonon calculations based on first-principle calculations. 115 MH y hydrides were considered, for [Formula: see text] with M among 30 metallic elements. The results were found to be in good agreement with the available experimental data and pointed out trends on the evolution of the hydride zero point energy as a function of the crystal structure and the host metal nature. Based on this information, the vibration contribution to the formation enthalpy was deduced. This contribution is responsible for the differences between the enthalpies and therefore pressures of formation of the hydride, deuteride and tritide compounds. This so-called 'isotope effect' is experimentally observed but has never been studied by large scale calculations. A straightforward method has been developed allowing to quantify the isotope effect at non zero temperature. It explains the experimentally observed relative stability of hydride, deuteride and tritide compounds. As a major achievement, a new phenomenon was highlighted, which has never been anticipated, consisting in an inversion of the isotope effect when the temperature increases.

Systematic First-Principles Study of Binary Metal Hydrides.

First-principles calculations were systematically performed for 31 binary metal-hydrogen (M-H) systems on a set of 30 potential crystal structures selected on the basis of experimental data and possible interstitial sites. For each M-H system, the calculated enthalpies of formation were represented as functions of H composition. The zero-point energy correction was considered for the most stable hydrides via additional harmonic phonon calculations. The sequence of stable hydrides (ground-state) given by the convex hull was found in satisfactory agreement with the experimental data. In addition, new high pressure dihydrides and trihydrides were predicted, providing orientations for new materials synthesis. The overall results provide a global overview of hydride relative stabilities and relevant input data for thermodynamic modeling methods.

Antibacterial properties of nanostructured Cu-TiO2 surfaces for dental implants.

The influence of copper derived TiO2 surfaces (nCu-nT-TiO2) on the death of nosocomial Staphylococcus aureus (Sa) and Escherichia coli (Ec), was investigated. TiO2 nanotube (nT-TiO2) arrays were fabricated by anodic oxidation of pure titanium sheets in fluorhydric solutions, leading to surface nanostructuration and creation of specific reactive sites. Copper nanocubes with a mean size of 20 nm have been synthesized and deposited on the nT-TiO2 surface by pulsed electrodeposition from a copper sulphate solution. Scanning Electron Microscopy (SEM) reveals that Cu nanocubes are both inserted into the TiO2 nanotubes and on the nanotube edges. X-ray Photoemission Spectroscopy (XPS) and SEM-EDX confirm the metallic nature of copper nanoparticles, covered with a thin mixed CuO-Cu2O thin layer. As the adsorption of proteins is one of the early stages of biomaterial surface interactions with body fluids before bacterial colonization, Infrared Spectroscopy (IR) in reflection-absorption mode, SEM and XPS have been used to follow the evolution of nCu-nT-TiO2 surfaces when exposed to a simulated plasma solution containing Bovine Serum Albumin (BSA). Finally bacterial tests have revealed a high biocide potential of the nCu-nT-TiO2 surface, which leads to the entire death of SA and EC.

Two steps bulk-surface functionalization of nanoporous alumina by methyl and vinyl-silane adsorption. Evidence for oxide surface highly reactive sites creation.

Functionalization of a novel nanoporous monolithic alumina synthesized from amalgam is investigated. The structure is studied by X-ray diffraction, BET, MEB and IR spectroscopy, before and after chemical functionalization by trimethylethoxy silane adsorption and annealing at high temperature. These treatments retain both monolith microstructure and nanostructure while strongly improving material mechanical properties. Allyldimethoxysilane and alcohol adsorption on the annealed samples, proves that highly reactive sites are available for further polymer grafting, as demonstrated by a significant shift of allyldimethoxysilane ν(SiH) to 2,215 cm(-1) and adsorbed acetate formation. Simple quantum computations on model systems support this conclusion. Chemical processes reported in this paper, allow a nanostructured alumina monoliths functionalization to optimize ceramics-polymer bonds, and to tune new hybrid biomaterial properties.

Structure and surface reactivity of novel nanoporous alumina fillers.

Recent studies have shown that the particle size of fillers used for the reinforcement of dental resin composites should be multimodally distributed, in which micron-sized fillers are mixed with nanoparticles so as to achieve a higher filler level in the resin, and should be kept well dispersed so as to be functionalized by a silane. In this study, porous alumina monoliths with high specific surface area, measured by the Brunauer-Emmett-Teller (BET) method, were obtained using a novel preparation method. Structure and surface reactivity have been investigated as functions of temperature and chemical treatments. The impregnation of the as-prepared material by triméthyletoxysilane (TMES) stabilized alumina with high specific surface area at higher temperature. FTIR study has described the effect of TMES treatment and temperature on the structure of the material. The use of allyldimethoxysilane (ADMS), as a probe molecule for measuring the surface reactivity, has allowed us to show that the treatment of samples with TMES and their reheating at 1300 degrees C results in adsorption sites which give stronger chemical bonds. This preliminary study has, therefore, allowed us to optimize the structural and surface treatment of experimental fillers before their use in the reinforcement of resin composites or resin-modified glass ionomer cements.

Physical properties of gamma alumina surface hydroxyls revisited through a large scale periodic quantum-chemistry approach.

We have studied surface hydroxyls adsorbed onto (001), (011), and (111) gamma alumina surfaces using a quantum-chemistry approach in order to compare with empirical models proposed in the literature. Local electronic structures and geometries in the low OH coverage limit have been evaluated for both ideal and relaxed surfaces with the help of a large scale periodic quantum-chemical code. Hydroxyl groups are adsorbed onto surfaces, and a study of their local electronic structure, vibrational frequencies, charges, and adsorption energies is performed and analyzed as a function of their adsorption site geometry. Our results show that, even on ideal (nonrelaxed) surfaces, OH local environments are more complicated than those stated by empirical models and strongly influence the hydroxyl stretching vibrational mode. Large scale simulation shows that disorder takes place even at 0 K, and the analysis of the vibrational frequencies leads to a revision of Knözinger's empirical model. Cationic vacancies in the first surface layers have also been taken into account; they have a significant influence on the surface atomic and electronic structures, modifying the physical properties of adsorbed OH entities. This work emphasizes the necessity to perform an electronic structure calculation to better understand adsorbed OH properties on gamma alumina surfaces and reveals the difficulty to make a one-to-one correspondence between OH stretching frequencies and their other physical properties. Finally, we show that these results agree with some available experimental studies.