Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Predicting the impact of underground engineering on the environment requires the knowledge of natural media at different scales. In particular, understanding basic phenomena controlling the properties of rocks in the presence of complex fluids necessitates a detailed atomic description of the solid/fluid/solid contacts, the subject of Part I of the present study. First, building the solid interspace between two different crystals in a non-periodic situation is achieved using the ab initio and molecular mechanics code GenMol (TM). A description of the fluid confined within the interspace is then derived from the original genetic iterative multi-species (GIMS) algorithm implemented in the same code. This approach consists of equilibrating chemical potentials, cycle after cycle and species after species, between the confined fluid and the free natural fluid. An elementary iteration for a species k consists of different steps incrementing the number N-k of particles k, with other numbers N-k remaining constant. At each step, an optimum fluid composition is obtained by a genetic process distributing the fluid particles on a grid by stochastic shots, followed in fine by a refining process. The effectiveness of the GIMS approach is demonstrated in the case study of a fluid confined between two (0 0 1) kaolinite faces, with apertures h varying between 4 and 10 A. connected to a 9-species external solution [H2O, Cl-, Na+ CO2(aq), NaCl(aq), Ca2+, Mg2+, HCO3-, H3O+] where concentrations are ranging from 55 to 10(-4) mol/L. The results show a drastic variation in the solute/solvent and cations/ions ratios in the confined fluid when aperture h is lowered to less than 1 nm. These results obtained with a very rapid convergence of the iterative algorithm combined with a very competitive genetic optimizer are validated with high precision on a free solution. This description of contacts between crystals is original and unattainable by standard crystal interface approaches. It opens the way to understanding and/or predicting phenomena between crystals in a complex natural environment, such as adhesion or repulsion investigated in the Part II of this study.
ISSN: 0022-0248

hal-00544569
https://hal.archives-ouvertes.fr/hal-00544569
DOI : 10.1016/j.jcrysgro.2010.08.009

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
This work deals with the problem of finding for a given industrial target the molecule conformation leading to the most efficient crystal polymorph and/or designing unknown crystal packing of new molecules. The originality of the method relies first on constraining the domain of the most probable crystals, before converging towards the predicted packing by a double genetic-refining optimization algorithm. Validation of this approach is discussed on the case study of 46 energetic crystal compounds, using the semi Ab Initio and Molecular Mechanics code GenMol™. This validation shows that all observed structures are retrieved in any circumstances with a relatively high number of good rankings.
ISSN: 0022-0248

hal-00857875
https://hal.archives-ouvertes.fr/hal-00857875
DOI : 10.1016/j.jcrysgro.2009.04.002

Éditeur(s) : HAL CCSD CRC Press Taylor & Francis Group
Résumé : In the chapter : Role of water-rock-gas interaction in sequestration of CO2
Water-Rock Interaction XIII

ISBN : 978-0415604260
hal-00855782
https://hal.archives-ouvertes.fr/hal-00855782

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
We report on microstructural data obtained by optical microscopy and transmission electron microscopy concerning the crystallographic relationships of serpentine minerals with their host olivine in two contrasting situations. In the first case, mesh-textured lizardite (liz) is developed in a standard 60% serpentinized oceanic harzburgite from the Oman ophiolite where olivine converts to columnar lizardite. The joined columns are perpendicular to the basal plane (001)(liz), corresponding to the pseudofibres observed optically. The plane (001)(liz) is locally parallel to the narrow boundary ol-liz; thus column orientations register the interface of serpentinization. The ol-liz relationships are not strictly topotactic, but reflect preferred cracking orientations in olivine, parallel to (010)(ol). In the second case, antigorite (atg) develops in a rare sample of antigorite schist in a kimberlite from Moses Rock (Colorado Plateau), representative of a suprasubduction-zone mantle wedge. High-resolution transmission electron microscopy (HRTEM) images along [010](atg) show domains of very regular modulation with a 43 center dot 5 A wavelength (m = 17, where m is the number of silicate tetrahedra along the wave), with few defects, indicative of HP-HT antigorite, and also heavily kinked regions as fingerprints of strong tectonic shear. TEM imaging and electron diffraction patterns reveal two topotactic relationships between antigorite and olivine: [100](atg)//[010](ol) and < 100 >(atg)//< 100 >(ol); the planes in contact are (001)(atg)//(100)(ol) and (001)(atg)//(010)(ol), respectively. The [010](atg)//[001](ol) and antigorite lamellae are parallel to the forsterite b-axis. In both cases, the topography of olivine-serpentine interfaces is controlled by open fluid pathways along microcracks oriented according to the anisotropy of the olivine aggregate. In the cases studied, the serpentine aggregate exhibits a preferred orientation inherited from that of the peridotite. These results have some relevance to the seismic anisotropy of serpentinized mantle. Anisotropy of propagation of seismic waves as a result of the olivine fabric is maintained and reinforced with the development of lizardite. Conversely, the development of antigorite produces a trench-parallel fast S-wave polarization and an anisotropy that is lowered at low degrees of serpentinization and then increased with increasing serpentinization.
ISSN: 0022-3530

hal-00456061
https://hal.archives-ouvertes.fr/hal-00456061
DOI : 10.1093/petrology/egp049

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
GenMol (TM) code is used to simulate Atomic Force Microscopy (AFM) tests at a kaolinite/brine/kaolinite contact, the confined fluid in sub-nanometre interspaces being in equilibrium with an external multi-species solution. The attraction/repulsion effort, i.e. the derivative versus the interspace aperture h of the interaction energy between both kaolinite faces, is computed versus the variable composition of the confined fluid (see for the method Part I of this work). Two external solutions are tested. Solution Si is a neutral brine (pH=7.5) leading to a possible attraction for apertures lower than 7 angstrom. Solution S2 is an acidified brine (pH=3.2) leading to repulsion whatever may be the aperture h. These two AFM simulations prove the existence of a critical pH value (3.2 < pH(crit) < 7.5) of the external solution, below which the acidification of a natural brine in a CO2 confinement inhibits adhesion between kaolinite aggregates.
ISSN: 0022-0248

hal-00544678
https://hal.archives-ouvertes.fr/hal-00544678
DOI : 10.1016/j.jcrysgro.2010.08.012

Éditeur(s) : HAL CCSD Société géologique de France
Résumé : International audience
EISSN: 1777-5817

hal-01672822
https://hal-amu.archives-ouvertes.fr/hal-01672822
DOI : 10.1051/bsgf/2017183