Molecular dynamics studies of aqueous silica nanoparticle dispersions: salt effects on the double layer formation.

The ion distribution around hydroxylated silica nanoparticles (NP-H) dispersed in brine was investigated by fully atomistic molecular dynamics. The NP-H dispersions in aqueous electrolyte media are simulated in solutions of varying salinity (NaCl, CaCl2, and MgCl2), salt concentration (0.06 × 10(-3) to 3.00 × 10(-3) mole fraction [Formula: see text]), and temperature (300 and 350 K) at 1 atm. The NP-H models reproduce the observed experimental concentration of silanol and geminal surface sites, which are responsible for local charge variations on the nanoparticles' surface. Interestingly, under certain salt concentration conditions, the formation of an electrical double layer (DL) around the overall neutral NP-H occurs. The resulting DLs are attenuated with increasing temperature for all evaluated salts. With increasing salt concentration, a sign inversion of the effective charge at the first ion layer is observed, which modifies the electrostatic environment around the nanoparticle. The minimum salt concentration that leads to a DL formation at 300 K is 1.05 × 10(-3), 0.37 × 10(-3), and 0.06 × 10(-3) χs for NaCl, CaCl2, and MgCl2, respectively. The width of the DL decreases sequentially in ionic strength from NaCl to CaCl2 to MgCl2, which is similar to that found for highly charged surfaces. These results are in line with our previous experimental data for negative charged NP-H. All together, these observations suggest an interplay mechanism between the formation and narrowing of electric double layers on the stability of NP dispersions in both neutral and negatively charged NP-H.

Adsorption of surface functionalized silica nanoparticles onto mineral surfaces and decane/water interface.

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.

Interface tension of silica hydroxylated nanoparticle with brine: a combined experimental and molecular dynamics study.

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.