Phase-separated Ca and Mg-based nanoparticles in SiO[Formula: see text] glass investigated by molecular dynamics simulations.

The development of new applications based on glass doped with nanoparticles is growing in interest during the last years. The structure and properties of Ca-based silicate nanoparticles formed in situ in a silica matrix through a phase separation mechanism were investigated by using Molecular Dynamics simulations and compared to nanoparticles formed from MgO-codoping. We showed that such nanoparticles have non-spherical shape, are amorphous and inhomogeneously distributed in the host glass. In this modeled structure, a release of non-bridging oxygen atoms, due to a depolymerization phenomenon of the nanoparticles' silica network, was observed. Besides, we demonstrated that nanoparticles' composition is size-dependent. Compared to Mg-silicate nanoparticles, Ca-based nanoparticles are larger, less concentrated in Ca, and we observed a steeper concentration change during the phase separation process. Those differences are related to the diffusion coefficients of Ca and Mg. This numerical analysis informs on the alkaline-earth nanoparticles' properties within a host silica glass, which can be a relevant guide for the development of new materials for applications such as nanoparticle-doped optical fibers.

The Effect of Size and Thermal Treatment on the Photoluminescent Properties of Europium-Doped SiO2 Nanoparticles Prepared in One Pot by Sol-Gel.

Europium (Eu)-doped silica nanoparticles have attracted great interest for different applications, in particular in biomedicine as biosensors or for tissue regeneration. Sol-gel is the most common process used to prepare those particles, with size varying from tens to hundreds of nanometers. In this article, we focus our attention on the comparison between two commonly used sol-gel derived methods: reverse microemulsion (for particles smaller than 100 nm) and Stöber method (for particles larger than 100 nm). Europium concentration was varied between 0.2 and 1 mol%, and the nanoparticle diameters were 10, 50 and 100 nm. The link between the local environment of europium ions and their optical properties was investigated and discussed. Using Transmission Electron Microscopy, nitrogen sorption, X-ray diffraction, Fourier-Transform Infra-Red and pulsed doubled Nd:YAG laser, we confirmed that fluorescence lifetime was improved by thermal treatment at 900 °C due to the elimination of aqueous environment and modification of structure disorder. The size of nanoparticles, the amount of europium and the thermal treatment of obtained materials influence the emission spectra and the decay curves of Eu3+.

Europium-Doped Sol-Gel SiO2-Based Glasses: Effect of the Europium Source and Content, Magnesium Addition and Thermal Treatment on Their Photoluminescence Properties.

Rare-earth doped silica-based glasses lead the optical materials due to their tailorable spectroscopic and optical properties. In this context, we took advantage of the sol-gel process to prepare various Eu-doped silica glasses to study their luminescent properties before and after annealing at 900 °C. The effect of magnesium on these properties was studied in comparison with Mg-free-glass. Using TEM, nitrogen sorption, XRD and FT-IR, we confirmed that the magnesium modifies the glass structure and the thermal treatment eliminates the aqueous environment, modifying the structure ordering. The emission spectra and the decay time curves show the advantages of the Mg addition and the annealing on the photoluminescent properties.

A simple transferable adaptive potential to study phase separation in large-scale xMgO-(1-x)SiO2 binary glasses.

A simple transferable adaptive model is developed and it allows for the first time to simulate by molecular dynamics the separation of large phases in the MgO-SiO2 binary system, as experimentally observed and as predicted by the phase diagram, meaning that separated phases have various compositions. This is a real improvement over fixed-charge models, which are often limited to an interpretation involving the formation of pure clusters, or involving the modified random network model. Our adaptive model, efficient to reproduce known crystalline and glassy structures, allows us to track the formation of large amorphous Mg-rich Si-poor nanoparticles in an Mg-poor Si-rich matrix from a 0.1MgO-0.9SiO2 melt.

Effect of compositional variation on optical and structure properties of europium-doped SiO(2)-HfO(2) glasses.

Glasses with compositions (100-x)SiO(2)-xHfO(2):0.3Eu(3+) (molar ratio, x=0,10,20,30) for optical applications were prepared using the sol-gel route. The introduction of hafnium into the glass matrix induced the energy splitting of the F27 state of Eu(3+) ions. Furthermore, fluorescence line narrowing (FLN) spectra indicated that Eu(3+) clustering occurred in glasses containing no hafnium. The addition of hafnium promoted better dispersion of Eu(3+) ions in the glass matrix. The role of hafnium on modifying the properties of glasses was discussed with respect to x-ray diffraction and FLN analysis.

Molecular dynamics simulation study of erbium induced devitrification in vitreous PbF2.

Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er(3+) ions were carried out. This technique appears to be a relevant way to perform systematic analysis of the system structure and to study the influence of defects on PbF2 crystallization. We modeled the total enthalpy, the radial distribution functions, and the diffracted intensities of systems containing different amounts of Er(3+) ions. We demonstrated by means of different simulations that Er(3+) ions lowered the devitrification temperature of PbF2, in good agreement with the experimental results. The genuine role of Er(3+) ions in the devitrification process of PbF2 has been investigated. Er(3+) ions have an unquestionable influence of the crystallization of PbF2. Although the latter does not start in the nearest neighborhood of Er(3+) ions, the presence of Er(3+) ions in a close environment may favor the lead fluoride crystallization.