Freezing of fluids confined between mica surfaces

Using grand ensemble simulations, we show that octamethyl-cyclo-tetra-siloxane (OMCTS) confined between two mica surfaces can form a variety of frozen phases which undergo solid-solid transitions as a function of the separation between the surfaces. For atomically smooth mica surfaces, the following sequence of transitions 1[triangle up] --> 1[triangle up]b --> 2B --> 2 square --> 2[triangle up] are observed in the one- and two-layered regimes, where n[triangle up], n[square], and nB denote triangular, square, and buckled phases, respectively, with the prefix n denoting the number of confined layers. The presence of potassium on mica is seen to have a strong influence on the degree of order induced in the fluid. The sequence of solid-solid transitions that occurs with the smooth mica surface is no longer observed. When equilibrated with a state point near the liquid-solid transition, a counterintuitive freezing scenario is observed in the presence of potassium. Potassium disrupts in-plane ordering in the fluid in contact with the mica surface, and freezing is observed only in the inner confined layers. The largest mica separations at which frozen phases were observed ranged from separations that could accommodate six to seven fluid layers. The extent of freezing and the square-to-triangular lattice transition was found to be sensitive to the presence of potassium as well as the thermodynamic conditions of the bulk fluid. The implications of our results on interpretation of surface force experiments as well as the generic phase behavior of confined soft spheres is discussed.     

Hydration structure of water confined between mica surfaces

We report further molecular dynamics simulations on the structure of bound hydration layers under extreme confinement between mica surfaces. We find that the liquid phase of water is maintained down to 2 monolayer (ML) thick, whereas the structure of the K(+) ion hydration shell is close to the bulk structure even under D = 0.92 nm confinement. Unexpectedly, the density of confined water remains approximately the bulk value or less, whereas the diffusion of water molecules decreases dramatically. Further increase in confinement leads to a transition to a bilayer ice, whose density is much less than that of ice Ih due to the formation of a specific hydrogen-bonding network.     

Hydration forces between mica surfaces in electrolyte solutions

The forces between two molecularly smooth mica surfaces were measured over a range of concentrations in aqueous Li⁺, Na⁺, K⁺ and Cs⁺ chloride solutions. Deviations from DLVO forces in the form of additional short-range repulsive “Hydration” forces were observed only above some critical bulk concentration, which was different for each electrolyte. These observations are interpreted in terms of the corresponding ion exchange properties at the mica surface. “hydration” forces apparently arise when hydrated cations adsorbed on mica are prevented from desorbing as two interacting surfaces approach. dehydration of the cations leads to a repulsive hydration force. A simple site-binding model was successfully applied to describe the charging behavior of interacting mica surfaces . By subtraction of the DLVO-regulation theory from the total measured force the net hydration force was obtained for mica surfaces apparently fully covered with adsorbed cations. The magnitude of this extra force followed the series Na⁺ > Li⁺ > K⁺ > Cs⁺ and, in each case, could be described by a double-exponential decay.     

Hydration force between mica surfaces in aqueous KCl electrolyte solution

Liquid-vapor molecular dynamics simulations are performed to study the interaction forces between two mica surfaces in an aqueous KCl electrolyte solution. Strong repulsive hydration force is obtained within a distance of ~2 nm between the two mica surfaces, which cannot be explained by the continuum theory of double-layer repulsion. We find that this short-range repulsive hydration force is much stronger than the double-layer force between mica surfaces. Whereas the simulation system is much smaller than the surface force measurement system, fundamental mechanisms of repulsive hydration force are revealed. In particular, important features of the step-like force oscillatory behavior during normal compression and force hysteresis during retraction are observed. Detailed analysis of the ionic density distributions shows that the "forced adsorption" of diffusive K(+) ions onto mica surfaces during compression and the subsequent "slow desorption" of the absorbed K(+) ions from mica surfaces upon retraction are responsible for the hysteresis phenomenon. From a mechanics point of view, we attribute the load bearing capacity of the dense electrolyte to the very hard hydration shells of K(+) metal ions under confinement. We find that the hydrated K(+) ions and Cl(-) co-ions remain very diffusive in the aqueous film. Water molecules in the hydration layer are also very fluidic, in the sense that the diffusion constant of water molecules is less than its bulk value by at most 3 orders of magnitude under the extreme confinement.     

Nanoscale repulsive forces between mica and silica surfaces in aqueous solutions

Nanoscale repulsive forces between mineral surfaces in aqueous solutions were measured for the asymmetric mica-silica system. The force measured with an atomic force microscope (AFM) has universal character in the short range, less than ～1 nm or about 3-4 water molecules, independent of solution conditions, that is, electrolyte ion (Na, Ca, Al), concentration (10(-6)-10(-2)M), and pH (3.9-8.2). Notably, the force is essentially the same as for the glass-silica system. Single force curves for a mica-silica system in a 10(-4)M aqueous NaCl solution at pH ～ 5.1 show oscillations with a period of about 0.25 nm, roughly the diameter of a water molecule, a consequence of a layer-by-layer dehydration of the surfaces when pushed together. This result provides additional support to the idea that nanoscale repulsive forces between mineral surfaces in aqueous solutions arise from a surface-induced water effect; the water between two mineral plates that are pushed together becomes structured and increasingly anchored to the surface of the plates by the creation of a hydrogen-bonding network that prevents dehydration of the surfaces.     

Quasistatic computer simulations of shear behavior of water nanoconfined between mica surfaces

We combine the grand canonical Monte Carlo and molecular dynamics techniques to simulate the shear response of water under a 9.2 ? confinement between two parallel sheets of muscovite mica. The shear deformation is modeled in the quasistatic regime corresponding to an infinitely small shear rate. It is found that the confined water film is capable of sustaining shear stress, as is characteristic of solids, while remaining fluid-like in respect of molecular mobility and lateral order. An important information is obtained by splitting the stress tensor components into contributions arising from the interaction of the opposing mica sheets between themselves and their interaction with water. The mica-mica contributions to shear stress show a strong anisotropy dictated by the alignment of the surface K(+) ions in chains along the x axis. On shearing in this direction, the mica-mica contribution to shear stress is negligible, so that the shear resistance is determined by the water interlayer. By contrast, in the y direction, the mica-mica contribution to shear resistance is dominant. The water-mica contribution is slightly less in magnitude but opposite in sign. As a consequence, the mica-mica contribution is largely canceled out. The physics behind this cancellation is the screening of the electrostatic interactions of the opposing surface K(+) ions by water molecules.     

Interfacial friction between semiflexible polymers and crystalline surfaces

The results obtained from molecular dynamics simulations of the friction at an interface between polymer melts and weakly attractive crystalline surfaces are reported. We consider a coarse-grained bead-spring model of linear chains with adjustable intrinsic stiffness. The structure and relaxation dynamics of polymer chains near interfaces are quantified by the radius of gyration and decay of the time autocorrelation function of the first normal mode. We found that the friction coefficient at small slip velocities exhibits a distinct maximum which appears due to shear-induced alignment of semiflexible chain segments in contact with solid walls. At large slip velocities, the friction coefficient is independent of the chain stiffness. The data for the friction coefficient and shear viscosity are used to elucidate main trends in the nonlinear shear rate dependence of the slip length. The influence of chain stiffness on the relationship between the friction coefficient and the structure factor in the first fluid layer is discussed.     

Effect of nanobubbles on friction forces between hydrophobic surfaces in water

Micro- and nanoscale combined hierarchical polymer structures were fabricated by UV-assisted capillary force lithography. The method is based on the sequential application of engraved polymer molds with a UV-curable resin of polyurethane acrylate (PUA) followed by surface treatment with a trichloro(1H,1H,2H,2H-perfluorooctyl) silane in vapor phase. Two distinct wetting states were observed on these dual-roughness structures. One is “Cassie–Wenzel state” where a water droplet forms heterogeneous contact with microstructures and homogeneous contact with nanostructures. The other is “Cassie–Cassie state” where a droplet makes heterogeneous contact both with micro- and nanostructures. A simple thermodynamic model was developed to explain static contact angle, hysteresis, and wetting transition on dual-roughness structures.     

Epitaxially guided assembly of collagen layers on mica surfaces

Ordered assembly of collagen molecules on flat substrates has potential for various applications and serves as a model system for studying the assembly process. While previous studies demonstrated self-assembly of collagen on muscovite mica into highly ordered layers, the mechanism by which different conditions affect the resulting morphology remains to be elucidated. Using atomic force microscopy, we follow the assembly of collagen on muscovite mica at a concentration lower than the critical fibrillogenesis concentration in bulk. Initially, individual collagen molecules adsorb to mica and subsequently nucleate into fibrils possessing the 67 nm D-periodic bands. Emergence of fibrils aligned in parallel despite large interfibril distances agrees with an alignment mechanism guided by the underlying mica. The epitaxial growth was further confirmed by the formation of novel triangular networks of collagen fibrils on phlogopite mica, whose surface lattice is known to have a hexagonal symmetry, whereas the more widely used muscovite does not. Comparing collagen assembly on the two types of mica at different potassium concentrations revealed that potassium binds to the negatively charged mica surface and neutralizes it, thereby reducing the binding affinity of collagen and enhancing surface diffusion. These results suggest that collagen assembly on mica follows the surface adsorption, diffusion, nucleation, and growth pathway, where the growth direction is determined at the nucleation step. Comparison with other molecules that assemble similarly on mica supports generality of the proposed assembly mechanism, the knowledge of which will be useful for controlling the resulting surface morphologies.     

Sliding friction between polymer surfaces: a molecular interpretation

For two contacting rigid bodies, the friction force F is proportional to the normal load and independent of the macroscopic contact area and relative velocity V (Amonton's law). With two mutually sliding polymer samples, the surface irregularities transmit deformation to the underlying material. Energy loss along the deformation cycles is responsible for the friction force, which now appears to depend strongly on V [see, e.g., N. Maeda et al., Science 297, 379 (2002)]. We base our theoretical interpretation on the assumption that polymer chains are mainly subjected to oscillatory "reptation" along their "tubes." At high deformation frequencies-i.e., with a large sliding velocity V-the internal viscosity due to the rotational energy barriers around chain bonds hinders intramolecular mobility. As a result, energy dissipation and the correlated friction force strongly diminish at large V. Derived from a linear differential equation for chain dynamics, our results are basically consistent with the experimental data by Maeda et al. [Science 297, 379 (2002)] on modified polystyrene. Although the bulk polymer is below T(g), we regard the first few chain layers below the surface to be in the liquid state. In particular, the observed maximum of F vs V is consistent with physically reasonable values of the molecular parameters. As a general result, the ratio FV is a steadily decreasing function of V, tending to V(-2) for large velocities. We evaluate a much smaller friction for a cross-linked polymer under the assumption that the junctions are effectively immobile, also in agreement with the experimental results of Maeda et al. [Science 297, 379 (2002)].     

Restructuring of hydrophobic surfaces created by surfactant adsorption to mica surfaces

Hydrophobic surfaces created by the adsorption of a monolayer of surfactants, such as CTAB or DODAB, to mica display long-range mutual attraction when placed in water. Initially, this attraction was considered to be due to hydrophobic interaction, but more careful measurements using AFM showed that the surfactant monolayer undergoes rearrangements to produce charged patches on the surface; therefore, the nature of the long-range interaction is due to the electrostatic interaction between patches. The monolayer rearrangement depends on the nature of the surfactant and its counterion. To study possible monolayer rearrangements in molecular detail, we performed detailed molecular dynamics computer simulations on systems containing a monolayer of surfactants RN(CH(3))(3)(+)Cl(-) (R indicates a saturated hydrocarbon chain) adsorbed on a mica surface and immersed in water. We observe that when chain R is 18 carbons long the monolayer rearranges into a micelle but it remains a monolayer when the chain contains 24 carbons.     

An atomic force microscopy study of asphaltenes on mica surfaces. Influence of added resins and demulsifiers

 Monolayers of asphaltene and resins on the water surface have been transferred at a surface pressure of 10 mN/m onto mica substrates using the Langmuir–Blodgett technique. Atomic force microscopy (AFM) has been used to examine the topography of these layers. Monolayers consisting of pure asphaltene fractions provide a rigid film with a close-packed structure, while the resins build up a continuous open network. Mixed films of these two fractions show that a gradual increase in resin concentration leads to an opening of the rigid asphaltene structure towards a more resin like configuration. Increased aggregation when the two heavy functions are present in one film is seen as larger individual units in the AFM pictures. Addition of high-molecular-weight demulsifiers/inhibitors results in the same kind of influence on the asphaltene film as seen with the resins. Received: 30 April 1999 Accepted: 29 November 1999     

pH dependence of friction forces between silica surfaces in solutions

The pH dependence of the friction between a silica particle and a silica wafer was investigated using lateral force microscopy. Measurements were done in the range of 3.6 < or = pH < or = 10.6 and the effect of high loading force was also examined. It is found that the friction is independent of the pH of solutions and increases linearly with the applied load, when the pH is between 3.6 and 8.6. On the other hand, once the pH is above 9.0, the friction becomes extremely small and the dependence on the applied load becomes nonlinear. It is postulated that this transition is due to the development of a gel layer composed of polymer-like segments of silicilic acid anchored on the surface; at the lower applied load, this layer acts as a boundary lubricant between the surfaces, but, at the higher applied load, the entanglements of these segments and more direct contact between two solid surfaces leads to the increase of the friction. The effects found here are expected to play an important role in elucidating the basic mechanism of the planarization process of silica wafers.     

Molecular simulation studies of nanoscale friction between phosphorylcholine self-assembled monolayer surfaces: correlation between surface hydration and friction

We performed all-atom molecular dynamics simulations to study the friction between surfaces covered with two phosphorylcholine self-assembled monolayers (PC-SAM) under shear. PC-SAM surfaces with a sqrt7 X sqrt7R19 degrees lattice structure and a parallel arrangement of the head groups were used as model zwitterionic surfaces. They provide a full representation of the zwitterionic nature of phospholipid surfaces, which are believed to play an important role in the lubrication of biological joints such as knees and hips. The surfaces were immersed in aqueous solutions and kept in contact with two regions of bulk water. Sodium chloride and potassium chloride solutions at various concentrations were employed to study the effects of the presence of ions on friction. The results show a strong relationship between surface hydration and friction. Higher ionic concentrations or ions with shorter Debye lengths cause a larger disruption to the hydration around the zwitterionic surfaces, leading to larger friction forces. In addition, the results show that under nanoscale confinement, the friction coefficients of PC-SAM surfaces in pure water are directly proportional to both shear velocity and surface separation distance. These results are comparable to previously published experimental studies.     

Nonlinear friction characteristics between silica surfaces in high pH solution

Molecular-scale characteristics of friction forces between silica particles and silica wafers in aqueous solutions of the normal (pH 5.6) and high pH (pH 10.6) are investigated, using the lateral force measuring procedure of the atomic force microscope (AFM). Various significant differences of friction characteristics between solutions of normal and high pH's are found. In the case of solutions of normal pH, the friction force increases linearly with increasing loading force, as the Amonton's law for solid bodies indicates. However, in the case of high pH solutions, the increasing rate with the loading force is considerably reduced in the low loading region, but the value increases abruptly above a critical loading force to overcome the magnitude of friction force of normal pH above the region of very high loading. It is very interesting to know that this nonlinear force curve at high pH is independent of the atomic-scale roughness of surfaces, although the magnitude of friction is greatly influenced by the roughness in the case of normal pH. The reason why the friction at high pH is independent of the surface roughness is postulated to be due to the hairy-like layer formed on the silica surface. The existence of hairy-like layers at high pH is proven directly by the dynamic method of normal force measurements with AFM and the thickness is estimated to be at least ca. 1.3 nm.     

The formation of hetero-epitaxial deposits of strontium sulfate on mica surfaces

As a continuation of an investigation concerning the fate of²²⁶Ra during uranium ore milling and long-term tailings storage we have grown hetero-epitaxial deposits of strontium sulfate on mica surfaces. The deposits formed readily on the substrate from supersaturated aqueous solutions of the parent ions and appear to be strongly adherent.     

Stability of silanols and grafted alkylsilane monolayers on plasma-activated mica surfaces

We investigated the effect of physical and chemical modifications of mica surfaces induced by water vapor-based plasma treatments on the stability of silanols and grafted alkylsilane monolayers. The plasma-activated substrates were characterized using XPS, TOF-SIMS, and contact angle measurements. They revealed a large surface coverage of silanol groups (Si-OH) and a loss of aluminum atoms compared to freshly cleaved mica surfaces. The stability of plasma-induced silanol groups was investigated by contact angle measurements using ethylene glycol as a probe liquid. The Si-OH surface coverage decreased rapidly under vacuum or thermal treatment to give rise to hydrophobic dehydrated surfaces. The stability of end-grafted monofunctionalized n-alkylsilanes was investigated in different solvents and at different pH using water contact angle measurements. The degrafting of alkylsilanes from the activated mica was promoted in acidic aqueous solutions. This detachment was associated with the hydrolysis of covalent bonds between the alkylsilanes and the mica surface. The monolayer stability was enhanced by increasing the length of the alkyl chains that probably act as a hydrophobic protective layer against hydrolysis reactions. Stable alkylsilane monolayers in water with pH greater than 5.5 were obtained on mica surfaces activated at low plasma pressure. We attributed this stability to the loss of surface Al atoms induced by the plasma treatment.