Chemically Enhanced Convective Dissolution of CO_{2}.

Convective dissolution, one of the main mechanisms for geological storage of CO_{2}, occurs when supercritical or gas CO_{2} dissolves partially into an aqueous solution, thus triggering downward convection of the denser CO_{2}-enriched liquid. Chemical reaction in the liquid can greatly enhance the process. Here, experimental measurements of convective flow inside a cylinder filled with a sodium hydroxide (NaOH) solution show that the plume's velocity can be increased tenfold as compared to a situation with no NaOH. This tremendous effect is predicted by a model with no adjusting parameters.

Space-Group Symmetries Generate Chaotic Fluid Advection in Crystalline Granular Media.

The classical connection between symmetry breaking and the onset of chaos in dynamical systems harks back to the seminal theory of Noether [Transp. Theory Statist. Phys. 1, 186 (1918)10.1080/00411457108231446]. We study the Lagrangian kinematics of steady 3D Stokes flow through simple cubic and body-centered cubic (bcc) crystalline lattices of close-packed spheres, and uncover an important exception. While breaking of point-group symmetries is a necessary condition for chaotic mixing in both lattices, a further space-group (glide) symmetry of the bcc lattice generates a transition from globally regular to globally chaotic dynamics. This finding provides new insights into chaotic mixing in porous media and has significant implications for understanding the impact of symmetries upon generic dynamical systems.

Horizontal pre-asymptotic solute transport in a plane fracture with significant density contrasts.

We investigate the dispersion of a finite amount of solute after it has been injected into the laminar flow occurring in a horizontal smooth fracture of constant aperture. When solute buoyancy is negligible, the dispersion process eventually leads to the well-known asymptotic Taylor-Aris dispersion regime, in which the solute progresses along the fracture at the average fluid velocity, according to a one-dimensional longitudinal advection-dispersion process. This paper addresses more realistic configurations for which the solute-induced density contrasts within the fluid play an important role on solute transport, in particular at small and moderate times. Flow and transport are coupled, since the solute distribution impacts the variations in time of the advecting velocity field. Transport is simulated using (i) a mathematical description based on the Boussinesq approximation and (ii) a numerical scheme based on a finite element analysis. This enables complete characterization of the process, in particular at moderate times for which existing analytical models are not valid. At very short times as well as very long times, the overall downward advective solute mass flow is observed to scale as the square of the injected concentration. The asymptotic Taylor-Aris effective dispersion coefficient is reached eventually, but vertical density currents, which are significant at short and moderate times, are responsible for a systematic retardation of the asymptotic mean solute position with respect to the frame moving at the mean fluid velocity, as well as for a time shift in the establishment of the asymptotic dispersion regime. These delays are characterized as functions of the Péclet number and another non-dimensional number which we call advective Archimedes number, and which quantifies the ratio of buoyancy to viscous forces. Depending on the Péclet number, the asymptotic dispersion is measured to be either larger or smaller than what it would be in the absence of buoyancy effects. Breakthrough curves measured at distances larger than the typical distance needed to reach the asymptotic dispersion regime are impacted accordingly. These findings suggest that, under certain conditions, density/buoyancy effects may have to be taken into consideration when interpreting field measurement of solute transport in fractured media. They also allow an estimate of the conditions under which density effects related to fracture wall roughness are likely to be significant.

X-ray studies of interlayer water absorption and mesoporous water transport in a weakly hydrated clay.

The swelling of layered smectite clay particles consists of a change in the interlayer repetition distance ( d -spacing) as a function of temperature and humidity. For the synthetic clay sodium fluorohectorite, hydrodynamically stable hydration states with zero, one and two intercalated monolayers of water have previously been reported, with discrete jumps in d -spacing at the transitions between the hydration states. Keeping the temperature fixed and varying the ambient relative humidity, we find small reproducible d -spacing changes also within the hydration states. These changes are monotonous as a function of relative humidity, and one order of magnitude smaller than the shift in d -spacing that is typical of the transition between two hydration states. The reproducibility and reliability of this relative humidity controlled d -shift enables us to use the interlayer repetition distance d as a measure of the local humidity surrounding the clay particles. We provide an example of application of this observation: imposing a humidity gradient over a quasi-one-dimensional temperature-controlled sample, and using x-ray diffraction to record the d -spacing, we are able to extract profiles of the relative humidity along the sample length. Their time evolution describes the transport of water through the mesoporous space inside the clay. An analysis of the measured humidity profiles based on the Boltzmann transformation, under certain simplifying assumptions, yields a diffusive behavior that is either normal or possibly weakly anomalous.

Electric field induced structuring in clay-oil suspensions: new insights from WAXS, SEM, leak current, dielectric permittivity, and rheometry.

The electric field induced structuring in clay-oil suspensions has been studied by means of wide angle x-ray scattering (WAXS), rheometry, scanning electron microscopy (SEM), as well as leak current density and dielectric constant measurements. The clay particles' orientation distribution was inferred from the azimuthal changes of the clay diffraction peak intensity. The angular width of that distribution was quantified through an orientational order parameter. Chain and column formation processes were distinguished by comparison of the time evolution of the diffraction peak amplitude with that of the current density. Leak current density was measured for different electric field strengths E and clay particle concentrations Φ. The following scaling relation was found: [Formula: see text]. In addition, the dependence of the yield stress on the electric field and on the particle concentration was measured and shown to scale as: [Formula: see text].

Phase diagram of polydisperse Na-fluorohectorite-water suspensions: a synchrotron small-angle x-ray scattering study.

Systems of platelet-shaped nanostacks of the synthetic clay Na-fluorohectorite, suspended in saline solutions of various salt concentrations, exhibit a rich phase behavior with up to four phases coexisting in a single sample tube. They are studied here using small-angle x-ray scattering: the anisotropy of the obtained images is quantified, and, together with x-ray absorption measurements, this provides a precise determination of the phase boundaries, as well as a measure of the orientational ordering of the clay colloids in the various gel phases. The coexistence of different phases results from a sedimentation-induced vertical gradient in particle fraction. Quantitative relation of the vertical coordinate to the clay particle fraction in these samples allows determination of a phase diagram for these Na-fluorohectorite systems, as a function of the particle fraction and salt concentration.

Electrorheological suspensions of laponite in oil: rheometry studies.

We have studied the effect of an external direct current (DC) electric field ( approximately 1 kV/mm) on the rheological properties of colloidal suspensions consisting of aggregates of laponite particles in a silicone oil. Microscopy observations show that, under application of an electric field greater than a triggering electric field Ec approximately 0.6 kV/mm, laponite aggregates assemble into chain- and/or columnlike structures in the oil. Without an applied electric field, the steady-state shear behavior of such suspensions is Newtonian-like. Under application of an electric field larger than Ec, it changes dramatically as a result of the changes in the microstructure: a significant yield stress is measured, and under continuous shear the fluid is shear-thinning. The rheological properties, in particular the dynamic and static shear stress, were studied as a function of particle volume fraction for various strengths (including null) of the applied electric field. The flow curves at constant shear rate can be scaled with respect to both the particle fraction and electric field strength onto a master curve. This scaling is consistent with simple scaling arguments. The shape of the master curve accounts for the system's complexity; it approaches a standard power-law model at high Mason numbers. Both dynamic and static yield stresses are observed to depend on the particle fraction Phi and electric field E as PhibetaEalpha, with alpha approximately 1.85 and beta approximately 1 and 1.70 for the dynamic and static yield stresses, respectively. The yield stress was also determined as the critical stress at which there occurs a bifurcation in the rheological behavior of suspensions that are submitted to a constant shear stress; a scaling law with alpha approximately 1.84 and beta approximately 1.70 was obtained. The effectiveness of the latter technique confirms that such electrorheological (ER) fluids can be studied in the framework of thixotropic fluids. The method is very reproducible; we suggest that it could be used routinely for studying ER fluids. The measured overall yield stress behavior of the suspensions may be explained in terms of standard conduction models for electrorheological systems. Interesting prospects include using such systems for guided self-assembly of clay nanoparticles.