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Mixed phase materials in the quasi binary diopside (CaMgSi2O6) – molybdite (MoO3) system were synthesized by a precipitation method. Materials were fabricated with diopside to molybdite ratios of 1:0, 10:1, 5:1, 2:1 and 1:1. XRD, SEM and EDS results show that alongside the initial diopside phase, phases such as calcium molybdate CaMoO4, rod-like enstatite MgSiO3 and cristobalite SiO2 formed as the molybdite content increased, and diopside was entirely absent at the highest molybdite content. At lower Mo content, mixed phase materials showed higher hardness and slower biodegradation in SBF relative to pristine diopside, while maintaining reasonable hydroxyapatite (HAp) formation capability. In contrast, materials with higher molybdite content exhibited lower hardness and bioactivity. The variation in the mechanical and bioactive performance could be attributed to the presence of bulk CaMoO4, acting as a reinforcement, and rod-like MgSiO3 with a highly porous and fragile structure. The trend of hardness is not consistent to the proportion of the component phases could be attributed to morphologies, interfaces, and densities of the samples. Both of secondary phases had poorer HAp deposition compared to pure diopside, indicating the MoO3 addition lowered mixed phase CaMgSi2O6 – MoO3 bioceramics’ ability to form Hap. The results suggest that moderate addition of molybdite to diopside would be an effective pathway towards crystalline bioceramics with enhanced performance.

International audience; Here we introduce a versatile stereolithographic route to produce three different kinds of Si-containing thermosets that yield high performance ceramics upon thermal treatment. Our approach is based on a fast and inexpensive thiol-ene free radical addition that can be applied for different classes of preceramic polymers with carbon-carbon double bonds. Due to the rapidity and efficiency of the thiol-ene click reactions, this additive manufacturing process can be effectively carried out using conventional light sources on benchtop printers. Through light initiated cross-linking, the liquid preceramic polymers transform into stable infusible thermosets that preserve their shape during the polymer-to-ceramic transformation. Through pyrolysis the thermosets transform into glassy ceramics with uniform shrinkage and high density. The obtained ceramic structures are nearly fully dense, have smooth surfaces, and are free from macroscopic voids and defects. A fabricated SiOC honeycomb was shown to exhibit a significantly higher compressive strength to weight ratio in comparison to other porous ceramics.

To develop high emissivity coatings on fibrous ceramic substrates with improved thermal resistance for reusable space systems, WSi2-MoSi2-Si-SiB6-borosilicate glass coatings were prepared on fibrous ZrO2 by slurry dipping and subsequent high temperature rapid sintering. A coating with 50 wt% WSi2 and 50 wt% MoSi2 presents optimal thermal stability with only 10.06 mg/cm2 mass loss and 4.0 % emissivity decrease in the wavelength regime of 1.27 to 1.73 microns after 50 h oxidation at 1773 K. The advantages of double phase metal silicide coatings combining WSi2 and MoSi2 include improved thermal compatibility with the substrate and an enhanced glass mediated self healing ability.

In this paper, we study the contact stiffness of a fractal rough surface compressed by a rigid flat plane. A numerical model based on the analysis of flat punch indentation is proposed for simulated hierarchical surfaces, which are generated using statistical and fractal descriptors collected by surface profilometry. The contact stiffness of surfaces under increasing normal load is determined on the basis of the total truncated area at varying heights. The results are compared with experimental data from nanoindentation on four types of treated rough surfaces, showing good agreement with experimental observations below a certain truncation depth. Furthermore, the limits of the model's validity are discussed by focusing on surface geometries and deformation of contacting asperities. With this proposed truncation method, we present a parametric analysis to establish a correlation between contact stiffness and surface roughness descriptors. The contact stiffness shows a unified power-law scaling with respect to the applied load over a wide range for simulated surfaces with distinct sets of roughness descriptors. The exponent of the power-law relationship is found to correlate positively to the fractal dimension while its amplitude is inversely correlated to the surface roughness amplitude. This study provides an easily implemented and computationally efficient method to connect mechanical behaviour with multi-scale surface structure, which can be utilized in design and optimization of engineering applications involving rough contacts.

Lithium ceramics have been considered as tritium breeder materials in many proposed designs of fusion breeding blankets. Heat generated in breeder pebble beds due to nuclear breeding reaction must be removed by means of actively cooled plates while generated tritiums is recovered by purge gas slowly flowing through beds. Therefore, the effective thermal conductivity of pebble beds that is one of the governing parameters determining heat transport phenomenon needs to be addressed with respect to mechanical status of beds and purge gas pressure. In this study, a numerical framework combining finite element simulation and a semi-empirical correlation of gas gap conduction is proposed to predict the effective thermal conductivity. The purge gas pressure is found to vary the effective thermal conductivity, in particular with the presence of various sized gaps in pebble beds. Random packing of pebble beds is taken into account by an approximated correlation considering the packing factor and coordination number of pebble beds. The model prediction is compared with experimental observation from different sources showing a quantitative agreement with the measurement.

International audience; Copper dopants are varyingly reported to enhance photocatalytic activity at titanium dioxide surfaces through uncertain mechanisms. In order to interpret how copper doping might alter the performance of titanium dioxide photocatalysts in aqueous media we applied density functional theory methods to simulate surface units of doped anatase (101) planes. By including van der Waals interactions, we consider the energetics of adsorbed water at anatase surfaces in pristine and copper doped systems. Simulation results indicate that copper dopant at anatase (101) surfaces is most stable in a 2+ oxidation state and a disperse configuration, suggesting the formation of secondary CuO phases is energetically unfavourable. In agreement with previous reports, water at the studied surface is predicted to exhibit molecular adsorption with this tendency slightly enhanced by copper. Results imply that the enhancement of photoactivity at anatase surfaces through Cu doping is more likely to arise from electronic interactions mediated by charge transfer and inter-bandgap states increasing photoexcitation and extending surface-hole lifetimes rather than through the increased density of adsorbed hydroxyl groups.https://doi.org/10.1016/j.apsusc.2016.06.178; Il a été rapporté que les dopants au cuivre amélioraient l'activité photocatalytique à la surface du dioxyde de titane par le biais de mécanismes incertains. Afin d’interpréter la façon dont le dopage au cuivre pourrait altérer les performances des photocatalyseurs en dioxyde de titane en milieu aqueux, nous avons appliqué des méthodes de théorie de la densité fonctionnelle pour simuler des unités de surface de plans anatase (101) dopés. En incluant les interactions de van der Waals, nous considérons l’énergétique de l’eau adsorbée aux surfaces anatases dans les systèmes vierges et dopés au cuivre. Les résultats de la simulation indiquent que le dopant au cuivre à la surface de l'anatase (101) est le plus stable dans un état d'oxydation 2+ et dans une configuration dispersée, ce qui suggère que la formation de phases secondaires de CuO est énergétiquement défavorable. En accord avec les rapports précédents, il est prévu que l'eau présente à la surface étudiée présente une adsorption moléculaire avec cette tendance légèrement renforcée par le cuivre. Les résultats impliquent que l'amélioration de la photoactivité sur les surfaces de l'anatase par le dopage au Cu est plus susceptible de résulter d'interactions électroniques induites par le transfert de charge et les états inter-bandes interdites augmentant la photoexcitation et allongeant la durée de vie des trous de surface plutôt que par la densité accrue de groupes hydroxyles adsorbés.https://doi.org/10.1016/j.apsusc.2016.06.178

Thick anatase films were fabricated on graphite substrates using a method of anodic aqueous electrophoretic-deposition using oxalic acid as a dispersant. Thick films were subsequently fired in air and in nitrogen at a range of temperatures. The morphology and phase composition were assessed and the photocatalytic performance was examined by the inactivation of Escherichia coli in water. It was found that the transformation of anatase to rutile is enhanced by the presence of a graphite substrate through reduction effects. The use of a nitrogen atmosphere allows higher firing temperatures, results in less cracking of the films and yields superior bactericidal performance in comparison with firing in air. The beneficial effects of a nitrogen firing atmosphere on the photocatalytic performance of the material are likely to be a result of the diffusion of nitrogen and carbon into the TiO2 lattice and the consequent creation of new valence band states.

International audience; Thin TiO 2 films on quartz substrates were prepared by spin coating of undoped and metal-ion-doped Sol-Gel precursors. These films were characterised by Scanning Electron Microscopy, Laser Raman Microspectroscopy, X-ray Diffraction and UV-Vis Transmission. The photocatalytic performances of the films were assessed by the photo-degradation of methylene-blue in aqueous solution under UV irradiation. Films exhibited a high degree of orientation and a thermal stabilization of the anatase phase as a result of substrate effects. In the absence of dopants, the rutile phase formed as parallel bands in the anatase which broadened as the transformation progressed. TiO 2 films doped or co-doped with transition metals exhibited the formation of rutile in segregated clusters at temperatures under ~800°C as a result of increased levels of oxygen vacancies. Photocatalytic activity of the films synthesised in this work was low as likely result of poor TiO 2 surface contact with dye molecules in solution. The presence of transition metal dopants appears detrimental to photocatalytic activity while the performance of mixed phase films was not observed to differ significantly from single phase material.