Biomineralization on the wavy substrate: Shape transition of nacreous tablets from pyramids of amorphous nanoparticles to dome-capped prisms of single crystals

Abstract

Nacre has long served as a model for understanding the biomineralization process and designing bio-inspired materials. However, our current knowledge about nacre is essentially based on the investigation of the flat nacre, where its building blocks, the aragonite tablets, grow on the flat substrate. Here, using field-emission scanning (SEM) and transmission electron microscopy (TEM), we investigate a new type of nacre, where the tablets grow on the wavy substrate. We first show that: (1) with growth, the tablet undergoes a shape transition from a pyramid to a frustum and finally to a dome-capped prism; (2) the shape transition occurs earlier at the downslope side of the tablet than at the upslope due to the slope effect; and (3) the shape of the top and base facet of the mature tablet depends on that of the substrate surface. In addition, we report that the tablet initially consists of amorphous calcium carbonate (ACC) nanoparticles, which gradually transforms into a single crystal of aragonite with time. Finally, we propose that the shape transition is induced by the crystal lattice mismatch between the tablet and substrate. We conclude that the topography and strain of the substrate play key roles in the biomineralization process of nacre.

Statement of significance: Nacre is the iridescent inner lining of many mollusk shells, consisting of more than 95wt% aragonite tablets and minor biopolymers. Owing to its superior mechanical properties, nacre has been extensively studied. However, nearly all previous works focused on the flat tablets. Here, we focus on the curved tablets grown on the wavy substrate. The main finding is that the topography and strain of the substrate play key roles in the growth process of the tablets. They not only induce the shape transition of the tablets from pyramids to dome-capped prisms, but also control the final shape of the tablets. The finding advances our understanding of the biomineralization process of nacre.

Keywords: Amorphous calcium carbonate; Aragonite tablet; Biomineralization; Shape transition; Wavy substrate.