Investigating the interface of superhydrophobic surfaces in contact with water.

Neutron reflectivity (NR) is used to probe the solid, liquid, vapor interface of a porous superhydrophobic (SH) surface submerged in water. A low-temperature, low-pressure technique was used to prepare a rough, highly porous organosilica aerogel-like film. UV/ozone treatments were used to control the surface coverage of hydrophobic organic ligands on the silica framework, allowing the contact angle with water to be continuously varied over the range of 160 degrees (superhydrophobic) to <10 degrees (hydrophilic). NR shows that the superhydrophobic nature of the surface prevents infiltration of water into the porous film. Atomic force microscopy and density functional theory simulations are used in combination to interpret the NR results and help establish the location, width, and nature of the SH film-water interface.

Reduced water density at hydrophobic surfaces: effect of dissolved gases.

Here, direct noninvasive neutron reflectivity measurements reveal the presence of a reduced (deuterated) water density region, with a sigmoidal density profile at the hydrophobic silane-water interface that depends on the type and concentration of dissolved gases in the water. Removal of dissolved gases decreases the width of the reduced water density region, and their reintroduction leads to its increase. When compared with recent computer simulations, a locally fluctuating density profile is proposed, whereas preexisting nanobubbles are excluded. The presence of a fluctuating reduced water density region between two hydrophobic surfaces and the attractive "depletion force" to which it leads may help explain the hydrophobic force and its reported diminution in deaerated water. Our results are also quantitatively consistent with recent dynamic surface force apparatus results that drastically revise previous estimates of the slip length of water flowing past hydrophobic surfaces from microns to approximately 20 nm. Our observations, therefore, go a long way toward reconciling three quite different types of experiments and phenomena: water depletion at hydrophobic surfaces, water slip at hydrophobic surfaces, and the hydrophobic interaction.

Neutron reflectivity study of lipid membranes assembled on ordered nanocomposite and nanoporous silica thin films.

Single bilayer membranes of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) were formed on ordered nanocomposite and nanoporous silica thin films by fusion of small unilamellar vesicles. The structure of these membranes was investigated using neutron reflectivity. The underlying thin films were formed by evaporation induced self-assembly to obtain periodic arrangements of silica and surfactant molecules in the nanocomposite thin films, followed by photocalcination to oxidatively remove the organics and render the films nanoporous. We show that this platform affords homogeneous and continuous bilayer membranes that have promising applications as model membranes and sensors.

Peering into the self-assembly of surfactant templated thin-film silica mesophases.

It is now recognized that self-assembly is a powerful synthetic approach to the fabrication of nanostructures with feature sizes smaller than achievable with state of the art lithography and with a complexity approaching that of biological systems. For example, recent research has shown that silica/surfactant self-assembly combined with evaporation (so-called evaporation induced self-assembly EISA) can direct the formation of porous and composite thin-film mesostructures characterized by precise periodic arrangements of inorganic and organic constituents on the 1-50-nm scale. Despite the potential utility of these films for a diverse range of applications such as sensors, membranes, catalysts, waveguides, lasers, nano-fluidic systems, and low dielectric constant (so-called low k) insulators, the mechanism of EISA is not yet completely understood. Here, using time-resolved grazing incidence small-angle X-ray scattering (GISAXS) combined with gravimetric analysis and infrared spectroscopy, we structurally and compositionally characterize in situ the evaporation induced self-assembly of a homogeneous silica/surfactant/solvent solution into a highly ordered surfactant-templated mesostructure. Using CTAB (cetyltrimethylammonium bromide) as the structure-directing surfactant, a two-dimensional (2-D) hexagonal thin-film mesophase (p6mm) with cylinder axes oriented parallel to the substrate surface forms from an incipient lamellar mesophase through a correlated micellar intermediate. Comparison with the corresponding CTAB/water/alcohol system (prepared without silica) shows that, for acidic conditions in which the siloxane condensation rate is minimized, the hydrophilic and nonvolatile silicic acid components replace water maintaining a fluidlike state that avoids kinetic barriers to self-assembly.