Abstract:
We have investigated the effect of humidity on surface deformation and adhesion of mica surfaces coated with n-octadecyltriethoxysilane self-assembled monolayers using a surface forces apparatus. The Maugis model of contact elasticity based on linear elastic fracture mechanics is used to analyze the results. The Laplace pressure is assumed to act in the "Dugdale" zone outside the contact area to account for capillary condensation. We measure the radius of the contact area as a function of applied load and use the model to obtain the surface energy and elastic constant of these surfaces for humidities ranging from 0 to 99%. The limiting values in dry and near-saturated conditions are as expected from well-known theories. A significant result is that we also obtain the surface energy for intermediate humidities. Increasing humidity modifies the deformed shape of the surfaces in contact due to capillary condensation. The sharp bifurcation at the edge of the contact zone for low humidities (JKR-type contact) is replaced by rounded edges (DMT-type contact) with increasing humidity. This is predicted by the Maugis model and is experimentally observed using optical interference fringes of equal chromatic order. We are able to separate the capillary condensation and solid-solid contributions to the adhesive force because the Maugis model allows a direct calculation of the area on which the Laplace pressure acts. At humidities approaching saturation the forces due to capillary condensation dominate monolayer-monolayer adhesion. At lower humidities both capillary condensation and direct monolayer-monolayer interaction contribute to the overall adhesion. © 2003 American Chemical Society.
PMID: 16114933;Abstract:
The surface forces apparatus technique and the Johnson-Kendall-Roberts theory were used to study the elastic properties of an n- octadecyltriethoxysilane self-assembled monolayer (OTE-SAM) on both untreated and plasma-treated mica. Our aim was to measure the thickness compressibilities of OTE monolayers on untreated and plasma-treated mica and to estimate their surface densities and phase-states from the film compressibility. The compressibility moduli of OTE are (0.96 ± 0.02) × 10 8 N/m 2 on untreated mica and (1.24 ± 0.06) × 108 N/m 2 on plasma-treated mica. This work suggests that the OTE phase-state is pseudocrystalline. In addition, the results from the compressibility measurements in water vapor suggest that the OTE-SAM on both untreated and plasma-treated mica is not homogeneous but rather contains both crystalline polymerized OTE domains and somewhat hydrophilic gaseous regions. © 2005 American Chemical Society.
Abstract:
In this article we extend our previous thermodynamic analysis of films confined to slit pores with smooth walls (i.e., plane-parallel solid surfaces without molecular structure) to the situation in which the walls themselves possess structure. Structured-wall models are frequently employed to interpret experiments performed with the surface forces apparatus (SFA), in which thin films (1-10 molecular diameters thick) are subjected to shear stress by moving the walls laterally over one another at constant temperature, chemical potential, and normal stress or load. The periodic structure of the walls is reflected in a periodic variation of the shear stress with the lateral alignment (i.e., shear strain) of the walls. We demonstrate by means of a solvable two-dimensional model that the molecular length scale imposed by the structure of the walls precludes the derivation of a simple mechanical expression for the grand potential analogous to that which holds in the smooth-wall case. This conclusion is borne out by the results of a grand-canonical Monte Carlo simulation of the three-dimensional prototypal model consisting of a Leonard-Jones (12,6) fluid confined between fcc (100) walls. Criteria for the thermodynamic stability of thin films confined by structured walls are derived and applied to the SFA. © 1994 American Institute of Physics.
Abstract:
Grand canonical ensemble Monte Carlo computer simulations have been used to study monolayer octamethylcyclotetrasiloxane (OMCTS) and cyclohexane films confined between mica-like surfaces to determine the effect of the mica surfaces on the orientation and distortion of the films at different surface alignments. The film molecules are packed as a highly ordered lattice. The orientation of the lattice is fixed relative to the mica surfaces and depends on the size of the film molecule. Registry shifts distort the film lattice by effectively stretching it along a particular direction that depends on the size of the film molecule. For a particular registry, OMCTS and cyclohexane monolayers are stretched in perpendicular directions. Coupling between the monolayers and the mica surfaces generates a nonzero shear stress when the surfaces are out of alignment, but the film does not become disordered or melt. It is possible that precisely controlled solid surfaces could be used to create packed arrays of film molecules with desired orientation and degree of distortion that may be useful in nanotechnological applications.
Abstract:
The grand canonical Monte Carlo method is used to study a binary mixture of Lennard-Jones atoms confined to various corrugated slit-micropores which are in thermodynamic equilibrium with their bulk phase counterpart. The micropore walls have the structure of the (100) face of an fcc lattice. In addition to this atomic scale structure, one wall possesses nanoscale structure in the form of rectilinear grooves (corrugation). The grooved surface divides the confined fluid film into two strip shaped regions. The confined film is studied in each region as a function of groove width, bulk phase composition, and the size of the wall atoms.
