Patterning of colloidal particles in the galvanic microreactor

A Cu-Au galvanic microreactor is used to demonstrate the autonomous patterning of two-dimensional colloidal crystals with spatial and orientational order which are adherent to the electrode substrate. The microreactor is comprised of a patterned array of copper and gold microelectrodes in a coplanar arrangement that is immersed in a dilute hydrochloric acid solution in which colloidal polystyrene microspheres are suspended. During the electrochemical dissolution of copper, polystyrene colloids are transported to the copper electrodes. The spatial arrangement of the electrodes determines whether the colloids initiate aggregation at the edges or centers of the copper electrodes. Depending on the microreactor parameters, two-dimensional colloidal crystals can form and adhere to the electrode. This thesis investigates the mechanisms governing the autonomous particle motion, the directed particle trajectory (inner- versus edge-aggregation) as affected by the spatial patterning of the electrodes, and the adherence of the colloidal particles onto the substrate. Using in situ current density measurements, particle velocimetry, and order-of-magnitude arguments, it is shown that particle motion is governed by bulk fluid motion and electrophoresis induced by the electrochemical reactions. Bulk electrolyte flow is most likely driven by electrochemical potential gradients of reaction products formed during the inhomogeneous copper dissolution, particularly due to localized high current density at the electrode junction. Preferential aggregation of the colloidal particles resulting in inner- and edge-aggregation is influenced by changes to the flow pattern in response to difference in current density profiles as affected by the spatial patterning of the electrode. Finally, by determining the onset of particle cementation through particle tracking analysis, and by monitoring the deposition of reaction products through the observation of color changes of the galvanic electrodes in situ, it is shown that particle cementation coincides with the precipitation and deposition of reaction products. The precipitation process is caused by shifts in the chemical equilibria of the microreactor due to changes in the composition of the electrolyte during the reactions, which can be used to control particle cementation. The corrosion driven transport, deposition and adherence of colloidal particles at corrosion sites have implications for the development of autonomous self-healing materials.