Volume 62, Issue 36 e202306885
Research Article

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

Dr. Jéssica A. Nogueira

Dr. Jéssica A. Nogueira

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390 USA

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Dr. Bruno C. Batista

Dr. Bruno C. Batista

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390 USA

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Maggie A. Cooper

Maggie A. Cooper

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390 USA

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Prof. Dr. Oliver Steinbock

Corresponding Author

Prof. Dr. Oliver Steinbock

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390 USA

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First published: 18 July 2023

Graphical Abstract

Microfluidic experiments yield compositionally pure Ni(OH)2 membranes that show internal microscale structures such as parallel bands, dendritic trees, and disorganized spots. These light-scattering patterns result from nonclassical crystallization and nanoparticle aggregation. The particles form in the flowing NiCl2 solution and self-organize aggregation zones—that for band patterns—move over the membrane surface in the upstream direction.

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.

Conflict of interest

The authors declare no conflict of interest.

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.

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