No abstract

The adsorption of silica nanoparticles onto representative mineral surfaces and at the decane/water interface was studied. The effects of particle size (the mean diameters from 5 to 75 nm), concentration and surface type on the adsorption were studied in detail. Silica nanoparticles with four different surfaces [unmodified, surface modified with anionic (sulfonate), cationic (quaternary ammonium (quat)) or nonionic (polyethylene glycol (PEG)) surfactant] were used. The zeta potential of these silica nanoparticles ranges from −79.8 to 15.3 mV. The shape of silica particles examined by a Hitachi-S5500 scanning transmission electron microscope (STEM) is quite spherical. The adsorption of all the nanoparticles (unmodified or surface modified) on quartz and calcite surfaces was found to be insignificant. We used interfacial tension (IFT) measurements to investigate the adsorption of silica nanoparticles at the decane/water interface. Unmodified nanoparticles or surface modified ones with sulfonate or quat do not significantly affect the IFT of the decane/water interface. It also does not appear that the particle size or concentration influences the IFT. However, the presence of PEG as a surface modifying material significantly reduces the IFT. The PEG surface modifier alone in an aqueous solution, without the nanoparticles, yields the same IFT reduction for an equivalent PEG concentration as that used for modifying the surface of nanoparticles. Contact angle measurements of a decane droplet on quartz or calcite plate immersed in water (or aqueous nanoparticle dispersion) showed a slight change in the contact angle in the presence of the studied nanoparticles. The results of contact angle measurements are in good agreement with experiments of adsorption of nanoparticles on mineral surfaces or decane/water interface. This study brings new insights into the understanding and modeling of the adsorption of surface-modified silica nanoparticles onto mineral surfaces and water/decane interface.

The kinetics of aggregation of silica nanoparticle solutions as a function of NaCl and silica concentrations is studied experimentally and theoretically. Silica nanoparticles form fractal aggregates due to the collapse of the electrical double layer at high salt concentrations and resulting reduction in stabilizing repulsive force. We propose a convenient model to describe the aggregation of silica nanoparticles and the growth of their aggregate size that depends on particle size and concentration and salt concentration. The model agrees well with experimental data. The aggregation of silica nanoparticles also affects the rheology of the suspension. We propose an equilibrium approach for sediment volume fraction to determine the maximum effective packing fraction. The results for the relative viscosity of silica aggregates agree well with the proposed viscosity model, which also collapses onto a single master curve.

In this work, we study the adsorption of hydrocarbon molecules on carbonate surfaces by means of first-principles calculations based on Density Functional Theory (DFT) with and without van der Waals (vdW) corrections. Energetic, electronic, and structural properties have been determined for the adsorption of the representative hydrocarbons (hexane and benzene) on calcite (CaCO 3 ) and dolomite [CaMg(CO 3 ) 2 ] (10−14) dry surfaces. Those hydrocarbons were selected to represent aromatics and alkanes on surfaces, and for each molecule the evaluated properties are similar for both surfaces. Due to the obtained similarities in both surfaces, we have evaluated the vdW corrections only for calcite. Our results suggest that Ca sites are the most energetically favorable for hydrocarbon adsorption on both minerals. This effect is mostly due to the electronic level ordering that leads to charge differences in the possible adsorbed sites (Ca, Mg, and CO 3 ) in the carbonate surfaces. The vdW corrections strengthen the hydrocarbon−surface bond with a corresponding reduction in the bond distance between the benzene and the surface. However, this reduction is not even for all atoms in the molecule, and the angle between the benzene aromatic ring and the surface increases. The energy barrier, for the displacement of the hydrocarbons along the calcite surface, was determined for representative surface direction, using the Nudged Elastic Band method, and adsorption energies for the most stable sites show the same order of magnitude.

We have used molecular dynamics simulations to calculate the interfacial tension of hydroxylated SiO(2) nanoparticles under different temperatures and solutions (helium and brine with monovalent and divalent salts). In order to benchmark the atomistic model, quartz SiO(2) interfacial tension was measured based on inverse gas chromatography under He atmosphere. The experimental interfacial tension values for quartz were found between 0.512 and 0.617 N/m. Our calculated results for the interfacial tension of silica nanoparticles within helium atmosphere was 0.676 N/m, which is higher than the value found for the system containing He∕α-quartz (0.478 N/m), but it is similar to the one found for amorphous silica surface. We have also studied the interfacial tension of the nanoparticles in electrolyte aqueous solution for different types and salts concentrations (NaCl, CaCl(2), and MgCl(2)). Our calculations indicate that adsorption properties and salt solutions greatly influence the interfacial tension in an order of CaCl(2) > MgCl(2) > NaCl. This effect is due to the difference in distribution of ions in solution, which modifies the hydration and electrostatic potential of those ions near the nanoparticle.