A surface force apparatus for nanorheology under large shear strain

We describe a surface force apparatus designed to probe the rheology of a nanoconfined medium under large shear amplitudes (up to 500 $\mu$m). The instrument can be operated in closed-loop, controlling either the applied normal load or the thickness of the medium during shear experiments. Feedback control allows to greatly extend the range of confinement/shear strain attainable with the surface force apparatus. The performances of the instrument are illustrated using hexadecane as the confined medium

Phase Diagram for Self-assembly of Amphiphilic Molecule C12E6 by Dissipative Particle Dynamics Simulation

In a previous study, dissipative particle dynamics simulation was used to qualitatively clarify the phase diagram of the amphiphilic molecule hexaethylene glycol dodecyl ether (C12E6). In the present study, the hydrophilicity dependence of the phase structure was clarified qualitatively by varying the interaction potential between hydrophilic molecules and water molecules in a dissipative particle dynamics (DPD) simulation using the Jury model. By varying the coefficient of the interaction potential $x$ between hydrophilic beads and water molecules as x=-20, 0, 10, and 20, at a dimensionless temperature of T=0.5 and a concentration of amphiphilic molecules in water of phi=50% the phase structures grew to lamellar (x=-20), hexagonal (x=0), and micellar (x=10) phases. For x=20, phase separation occurs between hydrophilic beads and water molecules

Colloidal aggregation and critical Casimir forces

A recent Letter [Phys. Rev. Lett. 103, 156101 (2009)] reports the experimental observation of aggregation of colloidal particles dispersed in a liquid mixture of heavy water and 3-methylpyridine. The experimental data are interpreted in terms of a model which accounts solely for the competing effects of the interparticle electrostatic repulsion and of the attractive critical Casimir force. Here we show, however, that the reported aggregation actually occurs within ranges of values of the correlation length and of the Debye screening length ruled out by the proposed model and that a significant part of the experimental data presented in the Letter cannot be consistently interpreted in terms of such a model.Comment: 1 page, 1 figure; For the reply see arXiv:1007.077

Layering Transitions and Solvation Forces in an Asymmetrically Confined Fluid

We consider a simple fluid confined between two parallel walls (substrates), separated by a distance L. The walls exert competing surface fields so that one wall is attractive and may be completely wet by liquid (it is solvophilic) while the other is solvophobic. Such asymmetric confinement is sometimes termed a `Janus Interface'. The second wall is: (i) purely repulsive and therefore completely dry (contact angle 180 degrees) or (ii) weakly attractive and partially dry (the contact angle is typically in the range 160-170 degrees). At low temperatures, but above the bulk triple point, we find using classical density functional theory (DFT) that the fluid is highly structured in the liquid part of the density profile. In case (i) a sequence of layering transitions occurs: as L is increased at fixed chemical potential (mu) close to bulk gas--liquid coexistence, new layers of liquid-like density develop discontinuously. In contrast to confinement between identical walls, the solvation force is repulsive for all wall separations and jumps discontinuously at each layering transition and the excess grand potential exhibits many metastable minima as a function of the adsorption. For a fixed temperature T=0.56Tc, where Tc is the bulk critical temperature, we determine the transition lines in the L, mu plane. In case (ii) we do not find layering transitions and the solvation force oscillates about zero. We discuss how our mean-field DFT results might be altered by including effects of fluctuations and comment on how the phenomenology we have revealed might be relevant for experimental and simulation studies of water confined between hydrophilic and hydrophobic substrates, emphasizing it is important to distinguish between cases (i) and (ii).Comment: 16 pages, 13 figure

Heterogeneous critical nucleation on a completely-wettable substrate

Heterogeneous nucleation of a new bulk phase on a flat substrate can be associated with the surface phase transition called wetting transition. When this bulk heterogeneous nucleation occurs on a completely-wettable flat substrate with a zero contact angle, the classical nucleation theory predicts that the free energy barrier of nucleation vanishes. In fact, there always exist a critical nucleus and a free energy barrier as the first-order pre-wetting transition will occur even when the contact angle is zero. Furthermore, the critical nucleus changes its character from the critical nucleus of surface phase transition below bulk coexistence (undersaturation) to the critical nucleus of bulk heterogeneous nucleation above the coexistence (oversaturation) when it crosses the coexistence. Recently, Sear [J.Chem.Phys {\bf 129}, 164510 (2008)] has shown by a direct numerical calculation of nucleation rate that the nucleus does not notice this change when it crosses the coexistence. In our work the morphology and the work of formation of critical nucleus on a completely-wettable substrate are re-examined across the coexistence using the interface-displacement model. Indeed, the morphology and the work of formation changes continuously at the coexistence. Our results support the prediction of Sear and will rekindle the interest on heterogeneous nucleation on a completely-wettable substrate.Comment: 11pages, 9 figures, Journal of Chemical Physics to be publishe

Premicellar aggregation of amphiphilic molecules: Aggregate lifetime and polydispersity

A recently introduced thermodynamic model of amphiphilic molecules in solution has yielded, under certain realistic conditions, a significant presence of metastable aggregates well below the critical micelle concentration -- a phenomenon that has been reported also experimentally. The theory is extended in two directions pertaining to the experimental and technological relevance of such premicellar aggregates. (a) Combining the thermodynamic model with reaction rate theory, we calculate the lifetime of the metastable aggregates. (b) Aggregation number fluctuations are examined. We demonstrate that, over most of the metastable concentration range, the premicellar aggregates should have macroscopic lifetimes and small polydispersity.Comment: 7 pages, 2 figure

Liquid transport generated by a flashing field-induced wettability ratchet

We develop and analyze a model for ratchet-driven macroscopic transport of a continuous phase. The transport relies on a field-induced dewetting-spreading cycle of a liquid film with a free surface based on a switchable, spatially asymmetric, periodic interaction of the liquid-gas interface and the substrate. The concept is exemplified using an evolution equation for a dielectric liquid film under an inhomogeneous voltage. We analyse the influence of the various phases of the ratchet cycle on the transport properties. Conditions for maximal transport and the efficiency of transport under load are discussed.Comment: 10 pages, 5 figure

Solvent-mediated interactions between nanoparticles at fluid interfaces

We investigate the solvent mediated interactions between nanoparticles adsorbed at a liquid-vapor interface in comparison to the solvent mediated interactions in the bulk liquid and vapor phases of a Lennard-Jones solvent. Molecular dynamics simulation data for the latter are in good agreement with results from integral equations in the reference functional approximation and a simple geometric approximation. Simulation results for the solvent mediated interactions at the interface differ markedly from the interactions of the particles in the corresponding bulk phases. We find that at short interparticle distances the interactions are considerably more repulsive than those in either bulk phase. At long interparticle distances we find evidence for a long-ranged attraction. We discuss these observations in terms of interfacial interactions, namely, the three-phase line tension that would operate at short distances, and capillary wave interactions for longer interparticle distances.Comment: 22 pages, 6 figure

Drivers of Wettability Alteration for Oil/Brine/Kaolinite System: Implications for Hydraulic Fracturing Fluids Uptake in Shale Rocks

Hydraulic fracturing technique is of vital importance to effectively develop unconventional shale resources. However, the low recovery of hydraulic fracturing fluids appears to be the main challenge from both technical and environmental perspectives in the last decade. While capillary forces account for the low recovery of hydraulic fracturing fluids, the controlling factor(s) of contact angle, thus wettability, has yet to be clearly defined. We hypothesized that the interaction of oil/brine and brine/rock interfaces governs the wettability of system, which can be interpreted using Derjaguin–Landau–Verwey–Overbeek (DLVO) and surface complexation modelling. To test our hypothesis, we measured a suit of zeta potential of oil/brines and brine/minerals, and tested the effect of ion type (NaCl, MgCl2 and CaCl2) and concentrations (0.1, 1, and 5 wt %). Moreover, we calculated the disjoining pressure of the oil/brine/mineral systems and compared with geochemical modelling predictions. Our results show that cation type and salinity governed oil/brine/minerals wettability. Divalent cations (Ca2+ and Mg2+) compressed the electrical double layer, and electrostatically linked oil and clays, thus increasing the adhesion between oil and minerals, triggering an oil-wet system. Increasing salinity also compressed the double layer, and increased the site density of oppositely charged surface species which made oil and clay link more strongly. Our results suggest that increasing salinity and divalent cations concentration likely decrease water uptake in shale oil reservoirs, thus de-risking the hydraulic fracturing induced formation damage. Combining DLVO and surface complexation modelling can delineate the interaction of oil/brine/minerals, thus wettability. Therefore, the relative contribution of capillary forces with respect to water uptake into shale reservoirs, and the possible impairment of hydrocarbon production from conventional reservoirs can be quantified

Manning condensation in two dimensions

We consider a macroion confined to a cylindrical cell and neutralized by oppositely charged counterions. Exact results are obtained for the two-dimensional version of this problem, in which ion-ion and ion-macroion interactions are logarithmic. In particular, the threshold for counterion condensation is found to be the same as predicted by mean-field theory. With further increase of the macroion charge, a series of single-ion condensation transitions takes place. Our analytical results are expected to be exact in the vicinity of these transitions and are in very good agreement with recent Monte-Carlo simulation data.Comment: 4 pages, 4 figure