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 American Chemical Society
Résumé : The distribution of water and ions in nanoporous membranes, in particular close to their surfaces with external reservoirs, is investigated by means of molecular dynamics (MD) simulations using classical polarizable force fields. A sodium iodide (NaI) aqueous solution is considered in uncharged weakly hydrophilic (WH) and highly hydrophilic (HH) nanoporous materials modeled by a single truncated nanopore in contact with two reservoirs. In the inner part of the nanopore, the spatial distribution of water and ions is obtained by coupling semi-infinitesimal longitudinal and semi-infinitesimal radial descriptions. In the HH material, in contrast with the WH material, species are no longer uniformly distributed in the inner nanopore and water molecules are distributed in a nearly frozen axially periodic corona-like structure which leads to the formation of ionic tunnels. In the reservoirs, water molecules and ions attracted by the membrane surface create a necking of the confined solution which acts as a barrier at the entrance of the nanopore. In the WH nanopore subsurface, close to the surface of the membrane, the species distribution is analogous to the interface distribution between an aqueous electrolyte solution and air. In the HH nanopore subsurface, this distribution is modulated by the water corona-like structure. These results provide useful information for predicting properties of nanoporous membranes, in particular the drastic reduction of diffusion coefficients in HH materials, and give a guide to designing synthetic membranes for applications in nanofiltration, etc.
ISSN: 1932-7447

hal-00682155
https://hal.archives-ouvertes.fr/hal-00682155
DOI : 10.1021/jp2078924

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 Elsevier
Résumé : International audience
We study diffusion in a heterogeneous medium that is characterized by spatially varying diffusion properties from a random walk point of view. We show that an inhomogeneous continuous time random walk (CTRW) with a spatially variable exponential transition time distribution solves the spatially discretized heterogeneous diffusion equation. This demonstrates the equivalence of the widely used time-domain random walk (TDRW) scheme and spatially inhomogeneous CTRW and at the same time provides a demonstration of the formal equivalence of the TDRW particle formulation and the heterogeneous diffusion equation. Based on this equivalence, we develop a TDRW method for heterogeneous diffusion under spatially variable multirate mass transfer properties. We discuss the implementation of these schemes and study the diffusion behavior in the presence of traps that are characterized by a truncated power-law trapping time distribution.
ISSN: 0309-1708

hal-00767566
https://hal.archives-ouvertes.fr/hal-00767566
DOI : 10.1016/j.advwatres.2012.07.015