Structure of chalcogenide glasses by neutron diffraction

5 pages. Proceedings International Workshop Non-crystalline Solids, Gijon (Spain).International audienceThe purpose of this work is to study the change in the structure of the Ge-Se network upon doping with Ag. The total structure factor S(Q) for two samples has been measured by neutron diffraction using the two-axis diffractometer dedicated to structural studies of amorphous materials, D4, at the Institut Laue Langevin. We have derived the corresponding radial distribution functions for each sample and each temperature, which gives us an insight about the composition and temperature dependence of the correlation distances and coordination numbers in the short-range. Our results are compatible with the presence of both GeSe4/2 tetrahedra and Se-Se bonds. The Ag atoms are linked to Se in a triangular environment. Numerical simulations allowing the identification of the main peaks in the total pair correlation functions have complemented the neutron diffraction measurements

Functional relationships between wood structure and vulnerability to xylem cavitation in races of Eucalyptus globulus differing in wood density

Wood density can be considered as a measure of the internal wood structure, and it is usually used as a proxy measure of other mechanical and functional traits. Eucalyptus is one of the most important commercial forestry genera worldwide, but the relationship between wood density and vulnerability to cavitation in this genus has been little studied. The analysis is hampered by, among other things, its anatomical complexity, so it becomes necessary to address more complex techniques and analyses to elucidate the way in which the different anatomical elements are functionally integrated. In this study, vulnerability to cavitation in two races of Eucalyptus globulus Labill. with different wood density was evaluated through Path analysis, a multivariate method that allows evaluation of descriptive models of causal relationship between variables. A model relating anatomical variables with wood properties and functional parameters was proposed and tested. We found significant differences in wood basic density and vulnerability to cavitation between races. The main exogenous variables predicting vulnerability to cavitation were vessel hydraulic diameter and fibre wall fraction. Fibre wall fraction showed a direct impact on wood basic density and the slope of vulnerability curve, and an indirect and negative effect over the pressure imposing 50% of conductivity loss (P50) through them. Hydraulic diameter showed a direct negative effect on P50, but an indirect and positive influence over this variable through wood density on one hand, and through maximum hydraulic conductivity (ks max) and slope on the other. Our results highlight the complexity of the relationship between xylem efficiency and safety in species with solitary vessels such as Eucalyptus spp., with no evident compromise at the intraspecific level.Estación Experimental Agropecuaria BarilocheFil: Barotto, Antonio José. Universidad Nacional de La Plata. Facultad de Ciencias Agrarias y Forestales. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Monteoliva, Silvia Estela. Universidad Nacional de La Plata. Facultad de Ciencias Agrarias y Forestales. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Gyenge, Javier. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Balcarce. Agencia de Extensión Rural Tandil. Consejo Nacional de Investigaciones Cientificas y Técnicas; ArgentinaFil: Martinez Meier, Alejandro. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Bariloche. Área de Recursos Forestales. Grupo de Ecología Forestal; ArgentinaFil: Fernandez, Maria Elena. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Balcarce. Agencia de Extensión Rural Tandil. Consejo Nacional de Investigaciones Cientificas y Técnicas; Argentin

“On demand” triggered crystallization of CaCO3 from solute precursor species stabilized by the water-in-oil microemulsion

Can we control the crystallization of solid CaCO3 from supersaturated aqueous solutions and thus mimic a natural process predicted to occur in living organisms that produce biominerals? Here we show how we achieved this by confining the reaction between Ca2+ and CO32- ions to the environment of nanosized water cores of water-in-oil microemulsions, in which the reaction between the ions is controlled by the intermicellar exchange processes. Using a combination of in situ small-angle X-ray scattering, high-energy X-ray diffraction, and low-dose liquid-cell scanning transmission electron microscopy, we elucidate how the presence of micellar interfaces leads to the formation of a solute CaCO3 phase/species that can be stabilized for extended periods of time inside micellar water nano-droplets. The nucleation and growth of any solid CaCO3 polymorph, including the amorphous phase, from such nano-droplets is prevented despite the fact that the water cores in the used microemulsion are highly supersaturated with respect to all known calcium carbonate solid phases. On the other hand the presence of the solute CaCO3 phase inside of the water cores decreases the rigidity of the micellar surfactant/water interface, which promotes the aggregation of micelles and the formation of large (>2 μm in diameter) globules. The actual precipitation and crystallization of solid CaCO3 could be triggered “on-demand” through the targeted removal of the organic-inorganic interface and hence the destabilization of globules carrying the CaCO3 solute

Cryptomelane formation from nanocrystalline vernadite precursor: a high energy X-ray scattering and transmission electron microscopy perspective on reaction mechanisms

International audienceBackground:Vernadite is a nanocrystalline and turbostratic phyllomanganate which is ubiquitous in the environ‑ment. Its layers are built of (MnO6)8− octahedra connected through their edges and frequently contain vacancies and(or) isomorphic substitutions. Both create a layer charge deficit that can exceed 1 valence unit per layer octahedron and thus induces a strong chemical reactivity. In addition, vernadite has a high affinity for many trace elements (e.g., Co, Ni, and Zn) and possesses a redox potential that allows for the oxidation of redox sensitive elements (e.g., As, Cr, Tl). As a result, vernadite acts as a sink for many trace metal elements. In the environment, vernadite is often found associated with tectomanganates (e.g., todorokite and cryptomelane) of which it is thought to be the precursor. The transformation mechanism is not yet fully understood however and the fate of metals initially contained in vernadite structure during this transformation is still debated. In the present work, the transformation of synthetic vernadite (δ‑MnO2) to synthetic cryptomelane under conditions analogous to those prevailing in soils (dry state, room tempera‑ture and ambient pressure, in the dark) and over a time scale of ~10years was monitored using high‑energy X‑ray scattering (with both Bragg‑rod and pair distribution function formalisms) and transmission electron microscopy

Smart Vehicle to Grid Interface Project: Electromobility Management System Architecture and Field Test Results

This paper presents and discusses the electromobility management system developed in the context of the SMARTV2G project, enabling the automatic control of plug-in electric vehicles' (PEVs') charging processes. The paper describes the architecture and the software/hardware components of the electromobility management system. The focus is put in particular on the implementation of a centralized demand side management control algorithm, which allows remote real time control of the charging stations in the field, according to preferences and constraints expressed by all the actors involved (in particular the distribution system operator and the PEV users). The results of the field tests are reported and discussed, highlighting critical issues raised from the field experience.Comment: To appear in IEEE International Electric Vehicle Conference (IEEE IEVC 2014

Mechanisms and kinetics of C-S-H nucleation approaching the spinodal line: Insights into the role of organics additives

Wet chemistry C-S-H precipitation experiments were performed under controlled conditions of solution supersaturation in the presence and absence of gluconate and three hexitol molecules. Characterization of the precipitates with SAXS and cryo-TEM experiments confirmed the presence of a multi-step nucleation pathway. Induction times for the formation of the amorphous C-S-H spheroids were determined from light transmittance. Analysis of those data with the classical nucleation theory revealed a significant increase of the kinetic prefactor in the same order as the complexation constants of calcium and silicate with each of the organics. Finally, two distinct precipitation regimes of the C-S-H amorphous precursor were identified: i) a nucleation regime at low saturation indexes (SI) and ii) a spinodal nucleation regime at high SI where the free energy barrier to the phase transition is found to be of the order of the kinetic energy or less.Comment: Accepted in Cement and Concrete Research. 30 pages plus supplementary materials. arXiv admin note: substantial text overlap with arXiv:2111.0274

Arsenate Incorporation in Gypsum Probed by Neutron, X-ray Scattering and Density Functional Theory Modeling

International audienceThe ability of gypsum, a common sulfate mineral, to host arsenic atoms in its crystalline structure, is demonstrated through experimental structural studies of the solid solutions formed upon synthetic coprecipitation of gypsum (CaSO4 ·2H2O) and arsenic. Neutron and X-ray diffraction methods show an enlargement of the gypsum unit cell proportional to the concentration of arsenic in the solids and to the pH solution value. The substitution of sulfate ions (SO42-) by arsenate ions is shown to be more likely under alkaline conditions, where the HAsO42- species predominates. A theoretical Density Functional Theory model of the arsenicdoped gypsum structure reproduces the experimental volume expansion. Extended X-ray Absorption Fine Structure (EXAFS) measurements of the local structure around the arsenic atom in the coprecipitated solids confirm solid state substitution and allow some refinement of the local structure, corroborating the theoretical structure found in the simulations. The charge redistribution within the structure upon substitutions of either the protonated or the unprotonated arsenate species studied by means of Mulliken Population Analyses demonstrates an increase in the covalency in the interaction between Ca2+ and AsO4 3-, whereas the interaction between Ca2+ and HAsO4 2- remains predominantly ionic

Sources of phenotypic variation of wood density and relationships with mean growth in two eucalyptus species in Argentina

Aims of the study: To describe the radial patterns of wood density, and to identify their main sources of variation, and the potential tradeoffs with mean tree growth, in two Eucalyptus species. Area of study: Mesopotamian (Corrientes and Entre Ríos provinces) and Pampean region (Buenos Aires province) of Argentina. Materials and methods: Eucalyptus grandis and Eucalyptus viminalis, growing in genetic trials installed in two sites per species were studied. X-ray wood microdensity profiles were developed from core samples. Each profile was proportionally divided in 10 sections. Mean, maximum, minimum and the standard deviation of wood density, for each section were computed. Mean annual growth was used to study the relationships with wood microdensity variables. A linear mixed-effects model computed the significance of different sources of phenotypic variation. Pearson´s correlation computed the relationships between variables. Main results: The pattern of radial variation in E. grandis showed a decrease in wood density from pith to bark, mainly due to the decrease in minimum wood density, while in E. viminalis, wood density increased towards the outer wood. In both species, the standard deviation of the wood density increased along the radial profile from pith to bark. Significant variation in wood density was explained by site, provenance and clone/family effects. In E. grandis mean, maximum and minimum wood density were negatively correlated with mean growth, whereas in E. viminalis correlations were positive but close to zero. Research highlights: Both the pattern of radial variation of wood density and the relationship between wood density and mean growth were different in the studied Eucalyptus species, and they varied within species depending on the site they were growing and genetic provenance.Fil: Alarcón, Pamela Cecilia. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Concordia; Argentina.Fil: Alarcón, Pamela Cecilia. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina.Fil: Fernández, María Elena. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina.Fil: Fernández, María Elena. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Balcarce. Agencia de Extensión Rural Tandil; Argentina.Fil: Oberschelp, Gustavo Pedro Javier. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Concordia; Argentina.Fil: Pathauer, Pablo Santiago. Instituto Nacional de Tecnología Agropecuaria (INTA). Instituto de Recursos Biológicos; Argentina.Fil: Martínez Meier, Alejandro. Instituto Nacional de Tecnología Agropecuaria (INTA). Estación Experimental Agropecuaria Bariloche; Argentina.Fil: Martínez Meier, Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina

Arsenic uptake by gypsum and calcite: Modeling and probing by neutron and x-ray scattering

Here we report on two structural studies performed on As-doped gypsum (CaSO4 2H2O) and calcite (CaCO3), using neutron (D20-ILL) and x-ray (ID11-ESRF) diffraction data and EXAFS (BM8-ESRF). The aim of this study is to determine whether As gets into the bulk of gypsum and calcite structures or is simply adsorbed on the surface. Different mechanisms of substitution are used as hypotheses. The combined Rietveld analysis of neutron and x-ray diffraction data shows an expansion of the unit cell volume proportional to the As concentration within the samples. DFT-based simulations confirm the increase of the unit cell volume proportional to the amount of carbonate or sulphate groups substituted. Interpolation of the experimental Rietveld data allows us to distinguish As substituted within the structure from that adsorbed on the surface of both minerals.Comment: Proceedings of the Eighth International Conference on Neutron Scatterin

Electron transfer at the mineral/water interface: Selenium reduction by ferrous iron sorbed on clay

International audienceThe mobility and availability of the toxic metalloid selenium in the environment is largely controlled by sorption and redox reactions, which may proceed at temporal scales similar to that of subsurface water movement under saturated or unsaturated conditions. Since such waters are often anaerobic and rich in Fe2+, we investigated the long-term (≤ 1 month) kinetics of selenite (Se(IV)O3 -) sorption to montmorillonite in the presence of Fe2+ under anoxic conditions. A synthetic montmorillonite was used to eliminate the influence of structural Fe. In the absence of aqueous Fe2+, selenite was sorbed as outer-sphere sorption complex, covering only part of the positive edge sites, as verified by a structure-based MUSIC model and Se K-edge XAS (X-ray absorption spectroscopy). When selenite was added to montmorillonite previously equilibrated with Fe2+ solution however, slow reduction of Se and formation of a solid phase was observed with Se K-edge XANES (x-ray absorption near-edge spectroscopy) and EXAFS (extended x-ray absorption finestructure) spectroscopy. Iterative transformation factor analysis of XANES and EXAFS spectra suggested that only one Se reaction product formed, which was identified as nano-particulate Se(0). Even after one month, only 75% of the initially sorbed Se(IV) was reduced to this solid species. Mössbauer spectrometry revealed that before and after addition and reduction of Se, 5% of total sorbed Fe occurred as Fe(III) species on edge sites of montmorillonite (≈ 2 mmol kg-1). The only change observed after addition of Se was the formation of a new Fe(II) species (15%) attributed to the formation of an outer-sphere Fe(II)-Se sorption complex. The combined Mössbauer and XAS results hence clearly suggest that the Se and Fe redox reactions are not directly coupled. Based on the results of a companion paper, we hypothesize that the electrons produced in the absence of Se by oxidation of sorbed Fe(II) are stored, for example by formation of surface H2 species, and are then 3 available for the later Se(IV) reduction. The slow reaction rate indicates a diffusion controlled process. Homogeneous precipitation of an iron selenite was thermodynamically predicted and experimentally observed only in the absence of clay. Interestingly, half of Fe was oxidized in this precipitate (Mössbauer). Since DFT calculations predicted the oxidation of Fe at the water-FeSe solid interface only and not in the bulk phase, the average particle size of this precipitate does not exceed 2 nm. A comparison with the Mössbauer and XAS spectra of the clay samples demonstrates that such homogenous precipitation can be excluded as a mechanism for the observed slow Se reduction, emphasizing the role of abiotic, heterogeneous precipitation and reduction for the removal of Se from subsurface waters