We have analyzed the emerging precipitate pattern of calcium-oxalate in a flow system. The circular symmetry is broken because of the hydrodynamic instability at the tip of the underlying gravity current. The presence of a concentration gradient maintained by the flow leads to the enrichment of the thermodynamically unstable calcium oxalate dihydrate form.

We have produced hollow copper-containing precipitate tubes using a flow-injection technique, and characterized their linear and volume growth. It is shown that the ratio of the volume increase rate to that of pumping is constant independent of the chemical composition. It is also found that osmosis significantly contributes to the tube growth, since the inward flux of chemical species dominates during the precipitate pattern formation. The asymmetric hydrodynamic field coupled with the inherent concentration and pH gradients results in different particle morphology on the two sides of the precipitate membrane. While the tubes have a smooth outer surface, the inner walls are covered with nanoflowers for copper phosphate and with nanoballs for copper silicate.

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In this work we present that aggregation of charged and pH sensitive nanoparticles can be spatiotemporally controlled by an autonomous way using the chlorite-tetrathionate autocatalytic front, where the front regulates the electrostatic interaction between nanoparticles due to protonation of the capping (carboxylate-terminated) ligand. We found that the aggregation and sedimentation of nanoparticles in liquid phase with the effect of reversible binding of the autocatalyst (H(+)) play important roles in changing the front stability (mixing length) and the velocity of the front in both cases when the fronts propagate upward and downward. Calculation of interparticle interactions (electrostatic and van der Waals) with the measurement of front velocity revealed that the aggregation process occurs fast (within a few seconds) at the front position.

The precipitation reaction of calcium oxalate is studied experimentally in the presence of spatial gradients by controlled flow of calcium into oxalate solution. The density difference between the reactants leads to strong convection in the form of a gravity current that drives the spatiotemporal pattern formation. The phase diagram of the system is constructed, the evolving precipitate patterns are analyzed and quantitatively characterized by their diameters and the average height of the gravity flow. The compact structures of calcium oxalate monohydrate produced at low flow rates are replaced by the thermodynamically unstable calcium oxalate dihydrate favored in the presence of a strong gravity current.