Electrohydrodynamic flow and colloidal patterning near inhomogeneities on electrodes.

Current density inhomogeneities on electrodes (of physical, chemical, or optical origin) induce long-range electrohydrodynamic fluid motion directed toward the regions of higher current density. Here, we analyze the flow and its implications for the orderly arrangement of colloidal particles as effected by this flow on patterned electrodes. A scaling analysis indicates that the flow velocity is proportional to the product of the applied voltage and the difference in current density between adjacent regions on the electrode. Exact analytical solutions for the streamlines are derived for the case of a spatially periodic perturbation in current density along the electrode. Particularly simple asymptotic expressions are obtained in the limits of thin double layers and either large or small perturbation wavelengths. Calculations of the streamlines are in good agreement with particle velocimetry experiments near a mechanically generated inhomogeneity (a "scratch") that generates a current density larger than that of the unmodified electrode. We demonstrate that proper placement of scratches on an electrode yields desired patterns of colloidal particles.

Enhancement of surface activity in CO oxidation on Pt(110) through spatiotemporal laser actuation.

We explore the effect of spatiotemporally varying substrate temperature profiles on the dynamics and the resulting reaction rate enhancement of the catalytic oxidation of CO on Pt(110). The catalytic surface is "addressed" by a focused laser beam whose motion is computer controlled. The averaged reaction rate is observed to undergo a characteristic maximum as a function of the speed of this moving laser spot. Experiments as well as modeling are used to explore and rationalize the existence of such an optimal laser speed.

Geometry-induced pulse instability in microdesigned catalysts: the effect of boundary curvature.

We explore the effect of boundary curvature on the instability of reactive pulses in the catalytic oxidation of on microdesigned Pt catalysts. Using ring-shaped domains of various radii, we find that the pulses disappear (decollate from the inert boundary) at a turning point bifurcation, and we trace this boundary in both physical and geometrical parameter space. These computations corroborate experimental observations of pulse decollation.

Guiding chemical pulses through geometry: Y junctions.

We study computationally and experimentally the propagation of chemical pulses in complex geometries. The reaction of interest, CO oxidation, takes place on single crystal Pt(110) surfaces that are microlithographically patterned; they are also addressable through a focused laser beam, manipulated through galvanometer mirrors, capable of locally altering the crystal temperature and thus affecting pulse propagation. We focus on sudden changes in the domain shape (corners in a Y-junction geometry) that can affect the pulse dynamics; we also show how brief, localized temperature perturbations can be used to control reactive pulse propagation. The computational results are corroborated through experimental studies in which the pulses are visualized using reflection anisotropy microscopy.

Sudden onset of pitting corrosion on stainless steel as a critical phenomenon.

Stainless steels undergo a sharp rise in pitting corrosion rate as the potential, solution concentration, or temperature is changed only slightly. We report experiments using real-time microscopic in situ visualizations that resolve the nucleation and evolution of individual pits during the transition. They suggest that the sudden onset of corrosion is explained by an explosive autocatalytic growth in the number of metastable pits and that stabilization of individual pits takes place only later. This finding agrees with a theoretical approach treating the onset of pitting corrosion as a cooperative critical phenomenon resulting from interactions among metastable pits, and it extends perspectives on the control and prevention of corrosion onset.