Éditeur(s) : HAL CCSD Springer/Terra Scientific Publishing Company
Résumé : International audience
We report oil the discovery of magnetite nanoparticles ranging in size from 2 to 14 full in the mineralized zones of the Pena Colorada iron-ore deposit, southern Mexico. Micrometric scale magnetite was magnetically reduced and divided into distinct size ranges: 85-56 mu m, 56-30 mu m, 30-22 mu m, 22-15 mu m, 15-10 mu m, 10-7 mu m and 7-2 mu m. Nanometric-scale magnetite in the size range 2-14 nm was identified. The magnetite was characterized by X-ray diffraction, transmitted and reflected light microscope, high-resolution transmission electron microscopy (TEM), high angle annular dark field, Mossbauer spectroscopy and its magnetic properties. Crystallographic identification of nanostructures Was performed using high-resolution TEM. Characteristic changes were observed when the particles make the size transition from micro- to nanometric sizes, as follows: (1) frequency-dependent magnetic Susceptibility percentage (chi FD%) measurements Show high Values (13%) for the 2-14 nm fractions attributed to dominant fractions of superparamagnetic particles; (2) variations of chi FD% < 4.5% in fractions of 56-0.2 mu m occur in association with the presence of microparticles formed by magnetite aggregates of nanoparticles (< 15 nm) embedded in berthierine; (3) Mossbauer spectroscopy results identified a superparamagnetic fraction; (4) nanometric and 0.2-3 mu m grain size magnetite particles require a magnetic field up to 152 mT to reach saturation during the isothermal remanent magnetization experiment; (5) coercivity and remanent magnetization of the magnetite increase when the particle size decreases, probably due to parallel Coupling effects; (6) two-magnetic Susceptibility versus temperature experiments of the same 2-14 nm sample show that the reversibility during the second heating is due to the formation of new magnetite nanoparticles and growth of those already present. during the first heating process.
ISSN: 1343-8832

hal-00413053
https://hal.archives-ouvertes.fr/hal-00413053

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The nucleation and growth processes of spherulitic alkali feldspar have been investigated in this study through X-ray microtomography and electron backscatter diffraction (EBSD) data. Here we present the first data on Shape Preferred Orientation (SPO) and Crystal Preferred Orientation (CPO) of alkali feldspar within spherulites. The analysis of synchrotron X-ray microtomography and EBSD datasets allowed us to study the morphometric characteristics of spherulites in trachytic melts in quantitative fashion, highlighting the three-dimensional shape, preferred orientation, branching of lamellae and crystal twinning, providing insights about the nucleation mechanism involved in the crystallization of the spherulites. The nucleation starts with a heterogeneous nucleus (pre-existing crystal or bubble) and subsequently it evolves forming “bow tie” morphologies, reaching radially spherulitic shapes in few hours. Since each lamella within spherulite is also twinned, these synthetic spherulites cannot be considered as single nuclei but crystal aggregates originated by heterogeneous nucleation. A twin boundary may have a lower energy than general crystal–crystal boundaries and many of the twinned grains show evidence of strong local bending which, combined with twin plane, creates local sites for heterogeneous nucleation.This study shows that the growth rates of the lamellae (10− 6–10− 7 cm/s) in spherulites are either similar or slightly higher than that for single crystals by up to one order of magnitude. Furthermore, the highest volumetric growth rates (10− 11–10− 12 cm3/s) show that the alkali feldspar within spherulites can grow fast reaching a volumetric size of ~ 10 μm3 in 1 s.
ISSN: 0024-4937

hal-01172356
https://hal.archives-ouvertes.fr/hal-01172356
DOI : 10.1016/j.lithos.2014.12.003

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Experimentally Assisted Molecular Modelling (EAMM) is an original approach for predicting the structure of organic micro-crystals and deducing their habit in the presence of various solvents and additives. It is applied here in the case of n-octylamino-nitrobenzoxadiazole (nOA-NBD), a fluorescent compound. This general approach is first of all described and validated by its blind application to three known and closely-related crystals. Then, the whole process is applied to predict the molecular crystal generated by n-octylamino-NBD, including the molecule conformation, its structure (cell parameters, molecular packing, X-ray powder diagrams) and its theoretical plus actual habits in the presence of a solvent (p-xylene) and two additives (acetic acid and n-dodecane). The conformation of the predicted molecule is validated by comparison with two similar molecules embedded in observable crystals. Then, the choice between two proposed structures (with the same energy and two equiprobable packings) is based on the comparison between experimental and re-computed X-ray powder diffraction diagrams, and also on the interpretation of an actual TEM image in the light of the proposed cell parameters. This choice is confirmed by the comparison between the vapour-grown face development (proposed by the BFDH or the attachment energy models) and the actual face development in a pure solvent. Finally, the actual habit deduced from comparing the crystal attachment energy with the adsorption energy of solvent or additive molecules is validated by SEM images of NBD micro-crystals in presence of the solvent alone or in presence of both additives. In conclusion, the EAMM approach appears to be a decisive tool for quickly simulating structural and habit properties of the molecular crystals, accessible or not by experimentation. Thus, a numerical selection of molecules becomes possible in view of deriving organic materials with predetermined properties, such as the fluorescence properties of the compound considered in the present study.
ISSN: 0022-0248

hal-00857894
https://hal.archives-ouvertes.fr/hal-00857894
DOI : 10.1016/j.jcrysgro.2011.07.035

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Wood has a hierarchical structure involving several levels of organisation. The stiffness of wood relies on its capacity to transfer mechanical stress to its stiffest element at the lowest scale, namely crystalline cellulose. This study aims at quantifying to what extend crystalline cellulose contributes to wood stiffness depending on its moisture content. The crystal strains of cellulose were measured using X-ray diffraction on wet and dry specimens of spruce, based on a previously published methodology. The comparison between crystal strain and macroscopic strain shows that, during elastic loading, cellulose strain is lower than macroscopic strain. The means ratio of crystal/macroscopic strain amounts 0.85 for dry specimens and 0.64 for wet specimens. This strain ratio cannot be explained just by the projection effect due to the difference in orientation between cellulose microfibrils and cell wall, but results from deformation mechanisms in series with cellulose. Analysis shows that this series contribution represents a non-negligible contribution to wood compliance and is strongly moisture-dependent. This contribution amounts 9% for dry specimens and 33% for wet specimens, corresponding to a 4-fold increase in compliance for the series contribution. The origin of these strains is ascribed to mechanisms involving bending or shear strain at different scales, due to the fact that reinforcing element are neither perfectly straight nor infinitely long.
ISSN: 0266-3538

hal-01425031
https://hal.archives-ouvertes.fr/hal-01425031
https://hal.archives-ouvertes.fr/hal-01425031/document
https://hal.archives-ouvertes.fr/hal-01425031/file/Art_Almeras_al_Contribution_cellulose_moisture-dependent_elastic_behavior_2017.pdf
DOI : 10.1016/j.compscitech.2016.11.025

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We analyzed twelve fault gouge samples from the Bogd fault in south-western Mongolia to understand the origin and behavior of clay minerals. The investigation relies on x-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high energy synchrotron x-ray diffraction methods to investigate microstructure and preferred orientation. Smectite (montmorillonite), illite-smectite mixed layers, illite-mica and kaolinite are the major clay components, in addition to quartz and feldspars, which are present in all samples. The observations suggest that the protoliths and the fault rocks were highly altered by fluids. The fluid-rock interactions allow clay minerals to form, as well as alter feldspars to precipitate kaolinite and montmorillonite. Thus, newly formed clay minerals are heterogeneously distributed in the fault zone. The decrease of montmorillonite component of some of the highly deformed samples also suggests that dehydration processes during deformation were leading to illite precipitation. Based on synchrotron x-ray diffraction data, the degree of preferred orientation of constituent clay minerals is weak, with maxima for (001) ranging from 1.3 to 2.6 multiples of a random distribution (m.r.d). Co-existing quartz and feldspars have random orientation distributions. Microstructure and texture observations of the gouges from the foliated microscopic zone, alternating with micrometric isotropic clay-rich area, also indicate that the Bogd fault experienced brittle and ductile deformation episodes. The clay minerals may contribute to a slip weakening behavior of the fault.
ISSN: 0191-8141

insu-00667194
https://hal-insu.archives-ouvertes.fr/insu-00667194
DOI : 10.1016/j.jsg.2011.10.006

Éditeur(s) : HAL CCSD
Résumé : We present an experimental study of relations between hydraulic properties of clayey rocks and their deformation at bulk and micro scale. The experimentation is based on triaxial deformation of kaolinitic core samples, on permeability measurements, and on several methods of analysis of the microstructure. To produce the samples, remoulded kaolinite material is consolidated by axial loading up to 20 MPa in an oedometric cell. Then, in a triaxial cell, an undrained stress path is applied in order to induce shearing damage in the sample. The permeability of the sample is measured by fluid flow across the sample. Before and after these hydro-mechanical tests, the evolution and the homogeneity of the pore space and moreover the texture of the material are analysed by X-ray tomography, environmental scanning electron microscopy and thermic neutron diffraction. Contrary to expectations, the permeability at the sample scale does not vary significantly, although quite large deformation is reached. The final deformation is heterogeneous, with well-developed shear bands. It appears that the development of compacting and dilating zones generates a heterogeneous permeability field, which results in a negligible variation of the bulk permeability at the sample scale.
International Journal of Rock Mechanics and Mining Science

hal-00496407
https://hal.archives-ouvertes.fr/hal-00496407
DOI : 10.1016/j.ijrmms.2010.04.007

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The structural parameters of fluorinated nanocarbons presenting different shapes, i.e. spherical, tubular and discotic are investigated and correlated to their tribological properties. Different fluorination rates of graphitized carbon blacks (0D), carbon nanofibres (1D) and a mixture of carbon nanodiscs and nanocones (2D) were achieved under pure molecular fluorine gas flow (direct fluorination). Raman spectrometry, X-ray diffraction and 19F solid state nuclear magnetic resonance underline similar structure and nature of the C-F bonds (covalent) for equivalent fluorine contents. In spite of the similarities of physical-chemical properties at equivalent fluorine contents, the tribological properties of the fluorinated nanocarbons differ. Those properties are discussed taking into account the role of the fluorine content and location of the fluorine atoms in the decrease of the interparticle interactions and in the cleavage of the external fluorocarbon layers to form the tribofilm. Finally, the effect of the shape is discussed.
ISSN: 0022-1139

hal-00787267
https://hal.archives-ouvertes.fr/hal-00787267

Éditeur(s) : HAL CCSD Taylor & Francis
Résumé : The diamond anvil cell (DAC) is a fundamental device used to explore the properties of materials under extreme pressure and temperature (P/T) conditions. In the past years, simultaneous high P/T DAC experiments using the resistively heated DAC (RH-DAC) techniques have been developed for studying materials properties in a wide P/T range. However, the mechanical instability of metallic gaskets used for sample confinement at high P/T conditions remains a limiting factor for exploiting the accessible P/T range of the RH-DAC. In this study, we present a new gasket configuration that overcomes these limitations. It is based on an amorphous boron-epoxy mixture inserted in a rhenium gasket. We show how these gasket inserts stabilize the sample chamber over a wide P/T range, allowing monitoring sample properties using X-ray diffraction and absorption spectroscopy up to 50GPa and 1620K.
ISSN: 0895-7959

hal-01608425
https://hal.archives-ouvertes.fr/hal-01608425
DOI : 10.1080/08957959.2016.1245297
PRODINRA : 387347

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Despite many studies, our understanding of silica precipitation from natural waters remains limited, in particular for geothermal waters. Here we present a detailed study on the kinetics of silica polymerization as a function of fluid temperature and pH using high-temperature (250-260 °C) seawater-derived geothermal fluids as those discharged from the Bouillante geothermal site.We monitored the on-site decrease in monomeric silica concentration(initial SiO2 concentration of about 600 mg/l)with time using the molybdenum blue spectrophotometric method on samples of separated water collected from the high-pressure separator at 167 °C and cooled to 25, 50, 75, and 90 °C and for pH values ranging from 5 to 8. During all these experiments, only silica polymerization was observed, with the formation of colloidal particles in suspension in the solutions. No scaling of amorphous silica was formed. The collected data were after modeled in order to determine the useful kinetic parameters for predicting and preventing amorphous silica precipitation in the production wells during fluid exploitation in the specific context of Bouillante. Results under the investigated experimental conditions show that the kinetics of silica precipitation is affected more strongly by pH than by temperature change. The reaction in the acidic Bouillante solution begins with a transition period that significantly decreases the kinetics of silica polymerization. Modeling the experimental data indicates that the silica polymerization up to the state of equilibrium is characterized by a 2nd-order kinetic law relative to dissolved silica; this could indicate that the polymerization is controlled mainly by the formation of dimers. However, the first hour of the experiments is better characterized by a 4th-order kinetic law, suggesting more complex polymerization reactions in the initial stage with the formation of nanocolloidal particles containing 3 to 4 monomers. In both cases, the corresponding kinetics rate constant k is linearly dependent on pH for pH between 5 and 7. The activation energy Ea for the overall reaction, calculated using the Arrhenius equation under the considered pH and temperature conditions, ranges between 41±9.8 and 54±9.6 kJ/mol. To complete this work, the colloid particles formed at the end of the kinetics experiments were extracted and analyzed by SEM and TEM microscopy, X-ray Diffraction and the BET method. Results show that the size of the colloids increase and their specific surface decrease with increasing pH and are thus dependent on pH. Globally, our work provides a reliable database for understanding silica polymerization kinetics in natural geothermal brines or geologic waters characterized by a near neutral pH and moderate dissolved silica concentrations.
ISSN: 0009-2541

hal-01403092
https://hal-brgm.archives-ouvertes.fr/hal-01403092
DOI : 10.1016/j.chemgeo.2016.08.031

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Prediction of ice mass flow and associated dynamics is pivotal at a time of climate change. Ice flow is dominantly accommodated by the motion of crystal defects – the dislocations. In the specific case of ice, their observation is not always accessible by means of the classical tools such as X-ray diffraction or transmission electron microscopy (TEM). Part of the dislocation population, the geometrically necessary dislocations (GNDs) can nevertheless be constrained using crystal orientation measurements via electron backscattering diffraction (EBSD) associated with appropriate analyses based on the Nye (1950) approach. The present study uses the Weighted Burgers Vectors, a reduced formulation of the Nye theory that enables the characterization of GNDs. Applied to ice, this method documents, for the first time, the presence of dislocations with non-basal or Burgers vectors. These or dislocations represent up to of the GNDs observed in laboratory-deformed ice samples. Our findings offer a more complex and comprehensive picture of the key plasticity processes responsible for polycrystalline ice creep and provide better constraints on the constitutive mechanical laws implemented in ice sheet flow models used to predict the response of Earth ice masses to climate change.
ISSN: 0012-821X

hal-01685565
https://hal.archives-ouvertes.fr/hal-01685565
DOI : 10.1016/j.epsl.2017.06.020

Éditeur(s) : HAL CCSD North Carolina State University
Résumé : Few studies have been conducted about relation between cellulose parameters and biomechanical properties of wood in tropical angiosperms species. For this purpose, on 13 trees from 3 species of French Guyana tropical rainforest in a clear active process of restoring verticality, i) growth strains were measured in situ in order to determine the occurrence of tension wood within samples and ii) cellulose structural parameters were estimated on all the samples using X-ray diffraction method. Crystallite size was estimated from the full-width at half-maximum of the Miller index (002) arc diffraction and angle T was measured following Cave's method. Relationships between these parameters and growth stresses were good and the variations between normal and tension wood were significant, i.e. a lower angle T and a larger crystallite size in tension wood. In order to have a good estimation of the microfibril angle in the main layer of the secondary wall for each species, an experimental calibration was done between angle T and microfibril angle observed with scanning electron microscopy.
ISSN: 19302126

hal-01031799
https://hal.archives-ouvertes.fr/hal-01031799
https://hal.archives-ouvertes.fr/hal-01031799/document
https://hal.archives-ouvertes.fr/hal-01031799/file/42-575-1-PB.pdf

Éditeur(s) : HAL CCSD Springer Verlag/ASM International
Résumé : The use of zinc sheets has largely increased in the last years, fundamentally because of new tendencies in architecture and, at the same time, due to its excellent properties, as corrosion resistance under aggressive climatic conditions, malleability, recyclability, and surface finishing aspect. In the present work, the X-ray diffraction technique is used to characterize the crystallographic texture evolution of a strongly anisotropic Zn20 zinc sheet (Zn-Cu-Ti) subjected to uniaxial tension, plane strain, and equibiaxial tension, for specimens cut at 0, 45, and 90 deg with respect to the rolling direction. The crystallographic texture evolution is evaluated by means of pole figures, orientation distribution function, and Kearns factors. For all tested strain paths, deformation produces a decrease in the intensity of the crystallographic textures, due to a dispersion of the orientations of the different axes around the initial maxima.
ISSN: 1073-5623

hal-01583268
https://hal.archives-ouvertes.fr/hal-01583268
DOI : 10.1007/s11661-017-4069-y

Éditeur(s) : HAL CCSD MDPI
Résumé : International audience
This work investigates the structural formation and analyses of titania membranes (TM) prepared using different vacuum exposure times for molecular weight (MW) cut-off performance and oil/water separation. Titania membranes were synthesized via a sol-gel method and coated on macroporous alumina tubes followed by exposure to a vacuum between 30 and 1200 s and then calcined at 400 °C. X-ray diffraction and nitrogen adsorption analyses showed that the crystallite size and particle size of titania increased as a function of vacuum time. All the TM membranes were mesoporous with an average pore diameter of ~3.6 nm with an anatase crystal morphology. Water, glucose, sucrose, and polyvinylpyrrolidone with 40 and 360 kDa (PVP-40 kDa and PVP-360 kDa) were used as feed solutions for MW cut-off and hexadecane solution for oil filtration investigation. The TM membranes were not able to separate glucose and sucrose, thus indicating the membrane pore sizes are larger than the kinetic diameter of sucrose of 0.9 nm, irrespective of vacuum exposure time. They also showed only moderate rejection (20%) of the smaller PVP-40 kDa, however, all the membranes were able to obtain an excellent rejection of near 100% for the larger PVP-360 kDa molecule. Furthermore, the TM membranes were tested for the separation of oil emulsions with a high concentration of oil (3000 ppm), reaching high oil rejections of more than 90% of oil. In general, the water fluxes increased with the vacuum exposure time indicating a pore structural tailoring effect. It is therefore proposed that a mechanism of pore size tailoring was formed by an interconnected network of Ti-O-Ti nanoparticles with inter-particle voids, which increased as TiO2 nanoparticle size increased as a function of vacuum exposure time, and thus reduced the water transport resistance through the TM membranes. © 2016 by the authors.
ISSN: 1996-1944

hal-01683214
https://hal.univ-antilles.fr/hal-01683214
DOI : 10.3390/ma9110938

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
Radial trends of vibrational properties, including the specific dynamic modulus (E'/r) and damping coefficient (tand), were investigated for 3 tropical rainforest hardwood species, Simarouba amara, Carapa procera and Symphonia globulifera by free-free flexural vibration test. The microfibril angle (MFA) was estimated through X-Ray diffraction. Consistent patterns of radial variations were observed for all studied properties. E'/r was found to decrease from pith to bark, which is strongly related to the increasing pith-bark trend of MFA. The variation of tand along the radius can be partly explained by MFA, and partly by the gradient of extractives due to heartwood formation. The coupling effect of MFA and extractives could be separated through the analysis of log(tand) - log(E'/r) diagram. For the studied species, the extractive content putatively associated to heartwood formation generally tends to decrease the wood damping coefficient. However, this weakening effect of extractives was not observed for inner part of the heartwood, suggesting the mechanical action of extractives was reduced during their chemical ageing.
ISSN: 1435-0211

hal-00797055
https://hal.archives-ouvertes.fr/hal-00797055
https://hal.archives-ouvertes.fr/hal-00797055/document
https://hal.archives-ouvertes.fr/hal-00797055/file/Radial_variations_vibrational_Zhang_al.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
In fold-and-thrust belts, shortening is mainly accommodated by thrust faults which are preferential zones for recrystallisation and mass transfer. This study focuses on a detachment fault related to the emplacement of the Monte Perdido thrust unit in the southern Pyrenees. The studied fault zone consists of a 10 m thick intensively foliated phyllonite developed within the Millaris marls, of Eocene age. The lithological homogeneity of the hanging wall and footwall allows us to compare the Millaris marls outside the fault zone with the highly deformed marls located in the fault zone and to quantify the chemical, mineralogical and volumetric changes related to deformation processes along the fault. The Millaris marls are composed of detrital quartz, illite, chlorite, minor albite and pyrite, in a micritic calcite matrix. In the fault zone, the cleavage planes are marked by clay minerals and calcite ± chlorite veins attest to fluid-mineral interactions during deformation. The mineral proportions in all samples from both the fault zone and Millaris marls have been quantified by two methods: (1) X-ray diffraction and Rietveld refinement, and (2) bulk chemical analyses as well as microprobe analyses to calculate modal composition. The excellent agreement between the results of these two methods allows us to estimate mineralogical variations using a modification of the Gresens' equation. During fault activation, up to 45 wt% of calcite was lost while the amounts of quartz and chlorite remained unchanged. Illite content remained constant to slightly enriched. The mineralogical variations were coupled with a significant volume loss (up to 45%) mostly due to the dissolution of micritic calcite grains. Deformation was accompanied by pressure solution and phyllosilicates recrystallisation. These processes accommodated slip along the fault. They required fluids as catalyst, but they did not necessitate major chemical transfers.
ISSN: 0264-8172

hal-00976361
https://hal.archives-ouvertes.fr/hal-00976361
DOI : 10.1016/j.marpetgeo.2013.12.016

Éditeur(s) : HAL CCSD Geological Society of London
Résumé : International audience
The mylonitic Cambrian quartzites, Moine Thrust Zone, NW Scotland, have long been used to study microstructural and petrofabric evolution and to develop understanding of grain-scale processes accommodating large-scale displacements. Today, structural geology is entering a new age of understanding of the basic processes involved in microstructural evolution due to the emergence of novel instrumental techniques and theoretical models. It seems apposite therefore to re-evaluate the microstructure of one example of this classic quartz mylonite from the Stack of Glencoul, Assynt, using arguably the most important of these new techniques, electron backscattered diffraction (EBSD). The three-dimensional (3D) microstructure and petrofabric of this rock was analysed using EBSD, to: 1) corroborate previous optical and X-ray texture goniometry measurements; 2) investigate the potential for sampling and/or tectonic sectioning bias that may be introduced inadvertently into any petrofabric analysis; and 3) predict its seismic properties. It is found that microstructures do differ between orthogonal structural sections, leading to variations in strengths of different components in the overall petrofabric that might impact on seismic properties. The results emphasize the true 3D nature of microstructures and petrofabrics, which can be recognized and accommodated more readily by this new generation of analytical techniques.
Continental Tectonics and Mountain Building: The Legacy of Peach and Horne

hal-00565749
https://hal.archives-ouvertes.fr/hal-00565749