Nonclassical Crystallization Causes Dendritic and Band‐Like Microscale Patterns in Inorganic Precipitates

Abstract

The self‐organization of complex solids can create patterns extending hierarchically from the atomic to the macroscopic scale. A frequently studied model is the chemical garden system which consists of life‐like precipitate shapes. In this study, we examine the thin walls of chemical gardens using microfluidic devices that yield linear Ni(OH)2 precipitate membranes. We observe distinct light‐scattering patterns within the compositionally pure membranes, including disorganized spots, dendrites, and parallel bands. The bands are tilted with respect to the membrane axis and their spacing (20–100 μm) increases with increasing flow rates. Scanning electron microscopy reveals that the bands consist of submicron particles embedded in a denser material and these particles are also found in the reactant stream. We propose that dendrites and bands arise from the attachment of solution‐borne nanoparticles. The bands are generated by particle‐aggregation zones moving upstream along the slowly advancing membrane surface. The speed of the aggregation zones is proportional to the band distance and defines the system's dispersion relation. This speed‐wavelength dependence and the flow‐opposing motion of the aggregation zones are likely caused by low particle concentrations in the wake of the zones that only slowly recover due to Brownian motion and particle nucleation.