Anne M. Ruminski

Effect of surface interactions on the hysteresis of capillary condensation in nanopores

Gas adsorption and liquid desorption of a number of organic vapors in anodized nanoporous alumina, with controlled geometry (cylindrical pore diameters from 10 to 60 nm), are studied using optical interferometry. The narrow-diameter distribution of disconnected pores allows checking the validity of the (long-predicted but not experimentally verified) Kelvin equation without any adjustable parameters, modeling or other assumptions. Evaporation occurs at liquid-vapor equilibrium according to this equation, whereas condensation occurs from metastable states of the vapor phase by nucleation, enhanced by surface defects inside the nanopores. This produces hysteresis, in qualitative agreement with theoretical models and simulations that use Van der Waals interactions between the fluid and the pore surface. The reproducibility of the hysteresis depends on the strength of these interactions, which play an important role in the dynamics of capillary condensation.

Controlling the Role of Nanopore Morphology in Capillary Condensation

The effect of pore morphology on capillary condensation and evaporation in nanoporous silicon is studied experimentally. A variety of cooperative and local effects are observed in tailored nanopores with well-defined regions by directly probing gas adsorption in each region using optical interferometry. All observations are ascribed to the ability of the nanopore region to access the gas reservoir directly and the nucleation of liquid bridges at local heterogeneities within the nanopore region. These assumptions, consistent with recent simulations, can be extended to any real nanoporous system.

Preparation and characterization of pore-wall modification gradients generated on porous silicon photonic crystals using diazonium salts.

One-dimensional photonic crystals (rugate filters) constructed from porous silicon were modified by the chemical hydrosilylation of terminal alkenes (decyl, 10-carboxydecyl, and 10-hydroxydecyl) in the presence of a concentration gradient of diazonium salt initiators. The concentration gradient was generated by vertically orienting the Si wafer containing the porous Si layer in an alkene solution and then introducing the diazonium salt at the bottom edge of the wafer. Slow diffusion of the salt led to a varying density of grafted alkene across the surface of the porous layer. The modified surfaces were end-capped with methyl groups by electrochemical grafting to impart improved stability and greater hydrophobicity. The surface modified with 10-carboxydecyl species was ionized by deprotonation of the carboxy groups to increase the hydrophilicity of this porous silicon surface. The pore-wall modification gradients were characterized using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS). The more hydrophilic portion of the gradient changes color when water infiltrates the porous nanostructure because of a shift in the stop band of the photonic crystal. The more hydrophobic portion of the gradient excludes water, although mixtures of water and ethanol will infiltrate this region, depending on the concentration of ethanol in the mixture. A simple visual sensor for small quantities of ethanol in water, capable of detecting ethanol concentrations of between 0 and 8% with a resolution of 1% is demonstrated.