Guillaume Wille

Thermophysical Properties of Containerless Liquid Iron up to 2500 K

AbstractThermophysical properties of high temperature liquid iron heated with a CO2 laser have been determined in an aerodynamic levitation device equipped with a high-speed camera and a three-wavelength pyrometer. Characteristic curves of the free cooling and heating of the drop can be used to determine the same apparent emissivity of solid and liquid iron and to calibrate pyrometers based on the known value of the melting point of iron, i.e., 1808 K. Examination of the recalescence of undercooled liquid iron and further solidification are used to obtain the ratio of the melting enthalpy versus the heat capacity of liquid iron as

Characterization of alunite supergroup minerals by Raman spectroscopy

\frac{{\Delta H_m }}{{c_P^l }} = 306 \pm 2.5{\text{ K}}

MINERALOGICAL AND ISOTOPIC RECORD OF DIAGENESIS FROM THE OPALINUS CLAY FORMATION AT BENKEN, SWITZERLAND: IMPLICATIONS FOR THE MODELING OF PORE-WATER CHEMISTRY IN A CLAY FORMATION

. The surface tension σ was determined from an analysis of the vibrations of liquid drops. Results are accurately described by σ (mJ⋅m−2)=(1888±31)−(0.285±0.015) (T−Tm) between 1750 K (undercooled liquid) and 2500 K. The density of liquid iron has been deduced from the image size and the mass of the liquid iron drops.

A Deep Alteration and Oxidation Profile in a Shallow Clay Aquitard: Example of the Tégulines Clay, East Paris Basin, France

The density, surface tension, and spectral and total hemispherical emissivities of liquid boron obtained with contactless diagnostics are reported for temperatures between 2360 and 3100 K. It is shown that, contrary to previous expectations, liquid boron is denser than the solid at its melting point. It is also shown that the high total emissivity of 0.36 is not consistent with that of a liquid metal as recently claimed. Finally, good agreement is found with previously reported surface tensions and spectral emissivities of liquid boron.

Do natural biofilm impact nZVI mobility and interactions with porous media? A column study

Raman spectroscopy has been used to study the molecular structure of different natural minerals of the alunite supergroup (AB(3)(XO(4))(2)(OH)(6)), with A=K(+), Na(+), Ca(2+), Sr(2+), Ba(2+), B=Al(3+), Fe(3+) and X=S(6+), P(5+). The influence of the ions, in A-, B- and X-sites, is highlighted in the Raman spectra by variations in the position of certain vibrations and is discussed in association with published crystallographic data in order to describe the observed differences. It was found that A-site substitutions are characterized by wavenumber shifts of the vibrations involving hydroxyl groups. The positions of these vibrational bands vary linearly with the ionic radius of the ions in this site. B-site substitutions induce shifts of all bands due to structural modifications that lead to differences in the chemical environment around the hydroxyl and XO(4) groups and changes in B-O bond lengths. A correlation showed that these shifts correlate well with the ionic radii of the B-ions. The spectra of compounds containing both sulfate and phosphate groups are described by numerous vibration bands caused by a complex elemental composition and a symmetry change of the XO(4) groups. This study has also made it possible to generalize substitution effects on the wavenumbers of several vibrations and show that Raman spectroscopy could be a powerful tool for identifying and distinguishing minerals of the alunite supergroup.

RISE: Correlative Confocal Raman and Scanning Electron Microscopy

The availability of Raman spectroscopy in a powerful analytical scanning electron microscope (SEM) allows morphological, elemental, chemical, physical and electronic analysis without moving the sample between instruments. This paper documents the metrological performance of the SEMSCA commercial Raman interface operated in a low vacuum SEM. It provides multiscale and multimodal analyses as Raman/EDS, Raman/cathodoluminescence or Raman/STEM (STEM: scanning transmission electron microscopy) as well as Raman spectroscopy on nanomaterials. Since Raman spectroscopy in a SEM can be influenced by several SEM-related phenomena, this paper firstly presents a comparison of this new tool with a conventional micro-Raman spectrometer. Then, some possible artefacts are documented, which are due to the impact of electron beam-induced contamination or cathodoluminescence contribution to the Raman spectra, especially with geological samples. These effects are easily overcome by changing or adapting the Raman spectrometer and the SEM settings and methodology. The deletion of the adverse effect of cathodoluminescence is solved by using a SEM beam shutter during Raman acquisition. In contrast, this interface provides the ability to record the cathodoluminescence (CL) spectrum of a phase. In a second part, this study highlights the interest and efficiency of the coupling in characterizing micrometric phases at the same point. This multimodal approach is illustrated with various issues encountered in geosciences.

Natural attenuation of TiO2 nanoparticles in a fractured hard-rock

Argillaceous rocks are considered to be a suitable geological barrier for the long-term containment of wastes. Their efficiency at retarding contaminant migration is assessed using reactive-transport experiments and modeling, the latter requiring a sound understanding of pore-water chemistry. The building of a pore-water model, which is mandatory for laboratory experiments mimicking in situ conditions, requires a detailed knowledge of the rock mineralogy and of minerals at equilibrium with present-day pore waters. Using a combination of petrological, mineralogical, and isotopic studies, the present study focused on the reduced Opalinus Clay formation (Fm) of the Benken borehole (30 km north of Zurich) which is intended for nuclear-waste disposal in Switzerland. A diagenetic sequence is proposed, which serves as a basis for determining the minerals stable in the formation and their textural relationships. Early cementation of dominant calcite, rare dolomite, and pyrite formed by bacterial sulfate reduction, was followed by formation of iron-rich calcite, ankerite, siderite, glauconite, (Ba, Sr) sulfates, and traces of sphalerite and galena. The distribution and abundance of siderite depends heavily on the depositional environment (and consequently on the water column). Benken sediment deposition during Aalenian times corresponds to an offshore environment with the early formation of siderite concretions at the water/sediment interface at the fluctuating boundary between the suboxic iron reduction and the sulfate reduction zones. Diagenetic minerals (carbonates except dolomite, sulfates, silicates) remained stable from their formation to the present. Based on these mineralogical and geochemical data, the mineral assemblage previously used for the geochemical model of the pore waters at Mont Terri may be applied to Benken without significant changes. These further investigations demonstrate the need for detailed mineralogical and geochemical study to refine the model of pore-water chemistry in a clay formation.

TEM and FESEM characterization of asbestiform and non-asbestiform actinolite fibers in hydrothermally altered dolerites (France)

The oxidation profile of a surficial clay aquitard was studied on a 35-meter borecore from the Albian Tegulines Clay near Brienne-le-Château (Paris Basin, France). Mineralogical, geochemical, and petrophysical data showed evidences of gradual oxidation taking place down to a depth of 20 m. Below 20 m, the clay material was nonplastic and nonfractured, and it inherited reduced redox conditions from bacterial sulfate reduction that occurred after sediment deposition. Above 20 m, the clay material was plastic. Up to a depth of 10-11 m, only rare yellowish aggregates of glauconite attested to limited oxidation, and pore water chemistry was unmodified. The 5–11 m depth interval was characterized by intensive pyrite oxidation, calcite dissolution, and formation of sulfate and iron hydroxide minerals. The upper 2-3 m was ochrous and entirely oxidized. These mineralogical changes were mirrored with pore water chemistry modifications such as an increase of alkalinity and sulfate concentration in the upper part of the profile. The presence of siderite at ∼11 m evinced the reactivity of Fe(II) in the structure of clay minerals with dioxygen from meteoric waters that infiltrated into the Tegulines Clay through vertical fractures.