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

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

Reply to "Comment on 'Precision measurement of the Casimir-Lifshitz force in a fluid'"

We have reviewed the Comment of Geyer et al. [arXiv:0708.1548] concerning our recent work [Phys. Rev. A 75, 060102 (R) (2007)], and while we disagree with their criticisms, we acknowledge them for giving us the opportunity to add interesting addition material and a more detailed description of our experiment. We describe further our calculation and explain why a more sophisticated model is not warranted. We also present detailed experiments on the effects of electrostatic forces in our measurements and show that the contribution due to work function differences is small and that the residual electrostatic force is dominated by trapped charges and external fields. Finally, we estimate the effect of double layer interactions. These additional calculations and measurements support our original conclusion that the experimental results are consistent with the Lifshitz theory

Impact of molecular structure on the lubricant squeeze-out between curved surfaces with long range elasticity

The properties of butane (C4H10) lubricants confined between two approaching solids are investigated by a model that accounts for the curvature and elastic properties of the solid surfaces. We consider the linear n-butane and the branched iso-butane. For the linear molecule, well defined molecular layers develop in the lubricant film when the width is of the order of a few atomic diameters. The branched iso-butane forms more disordered structures which permit it to stay liquid-like at smaller surface separations. During squeezing the solvation forces show oscillations corresponding to the width of a molecule. At low speeds (< 0.1 m/s) the last layers of iso-butane are squeezed out before those of n-butane. Since the (interfacial) squeezing velocity in most practical applications is very low when the lubricant layer has molecular thickness, one expects n-butane to be a better boundary lubricant than iso-butane. N-butane possessing a slightly lower viscosity at high pressures, our result refutes the view that squeeze out should be harder for higher viscosities, on the other hand our results are consistent with wear experiments in which n-butane were shown to protect steel surfaces better than iso-butane.Comment: 7 pages, 10 figures, format revtex. Submitted to J. Chem. Phy

Myelin figures: the buckling and flow of wet soap

Myelin figures are interfacial structures formed when certain surfactants swell in excess water. Here, I present data and model calculations suggesting myelin formation and growth is due to the fluid flow of surfactant, driven by the hydration gradient at the dry surfactant/water interface; a simple model based on this idea qualitatively reproduces the various myelin growth behaviors observed in different experiments. From a detailed experimental observation of how myelins develop from a planar precursor structure, I identify a mechanical instability that may underlie myelin formation. These results indicate the mixed mechanical character of the surfactant lamellar structure, where fluid and elastic properties coexist, is what enables the formation and growth of myelins.Comment: 11 pages, 10 figures, to appear in Phys. Rev. E. Corrected figures/typo

Contact mechanics with adhesion: Interfacial separation and contact area

We study the adhesive contact between elastic solids with randomly rough, self affine fractal surfaces. We present molecular dynamics (MD) simulation results for the interfacial stress distribution and the wall-wall separation. We compare the MD results for the relative contact area and the average interfacial separation, with the prediction of the contact mechanics theory of Persson. We find good agreement between theory and the simulation results. We apply the theory to the system studied by Benz et al. involving polymer in contact with polymer, but in this case the adhesion gives only a small modification of the interfacial separation as a function of the squeezing pressure.Comment: 5 pages, 4 figure

Theory of adhesion: role of surface roughness

We discuss how surface roughness influence the adhesion between elastic solids. We introduce a Tabor number which depends on the length scale or magnification, and which gives information about the nature of the adhesion at different length scales. We consider two limiting cases relevant for (a) elastically hard solids with weak adhesive interaction (DMT-limit) and (b) elastically soft solids or strong adhesive interaction (JKR-limit). For the former cases we study the nature of the adhesion using different adhesive force laws ($F\sim u^{-n}$, $n=1.5-4$, where $u$ is the wall-wall separation). In general, adhesion may switch from DMT-like at short length scales to JKR-like at large (macroscopic) length scale. We compare the theory predictions to the results of exact numerical simulations and find good agreement between theory and the simulation results