Total morphosynthesis of biomimetic prismatic-type CaCO3 thin films

Abstract

Biomimetic mineralization can lead to advanced crystalline composites with common chemicals under ambient conditions. An exceptional example is biomimetic nacre with its superior fracture toughness. The synthesis of the prismatic layer with stiffness and wear resistance nonetheless remains an elusive goal. Herein, we apply a biomimetic mineralization method to grow prismatic-type CaCO3 thin films, mimicking their biogenic counterparts found in mollusk shells with a three-step pathway: coating a polymer substrate, deposition of a granular transition layer, and mineralization of a prismatic overlayer. The synthetic prismatic overlayers exhibit structural similarity and comparable hardness and Young’s modulus to their biogenic counterparts. Furthermore, employment of a biomacromolecular soluble additive, silk fibroin, in fabrication of the prismatic thin films leads to micro-/nano-textures with enhanced toughness and emerging under-water superoleophobicity. This study highlights the crucial role of the granular transition layer in promoting competition growth of the prismatic layer.

Amorphous Phase Mediated Crystallization: Fundamentals of Biomineralization

“…Cantaert et al [125] reported the oriented crystallization of calcium phosphate in nano-cylindrical pores that mimic collagen fibrils. Xiao et al [126] morphosynthesized a biomimetic prismatic-type calcium carbonate layer on substrates with a granular transition layer through competing growths on films. The granular transition layer was formed on substrates using (NH 4 ) 2 CO 3 gas diffusion into calcium solutions in the presence of poly-aspartic acid or poly-acrylic acid, in which amorphous precursors were formed as reported by Gower et al [127].…”

Role of Interface Interactions in the Construction of GO‐Based Artificial Nacres

“…Recently, inspired by the abundant interfacial architecture of nacre, numerous high-performance nanocomposites have been successfully fabricated based on various building blocks, such as aluminum oxide (Al 2 O 3 ) flake, [26] CaCO 3 platelet, [27][28][29][30] brushite platelet, [31] montmorillonite (MMT), [32][33][34][35][36][37][38][39][40][41] hydroxyapatite (HA), [42,43] layered double hydroxides, [44,45] and carbon nanotubes (CNTs). [46,47] The bioinspired strategy affords these materials with well alignment, high loading of building blocks, and strong interface interactions, thereby causing excellent mechanical properties.…”

Seeded Mineralization in Silk Fibroin Hydrogel Matrices Leads to Continuous Rhombohedral CaCO3 Films

“…The granular nature of the nanodomains was next confirmed by AFM imaging (Figure 1e). The rough topography of the seed layers deposited on SF matrices is in contrast with the flat counterparts disclosed on PVA [31] and chitosan [32], respectively. We assume that the appearance of raspberry-shaped nanodomains is Calcium cations and other reacting agents are required to transport through the SF hydrogels for mineralization.…”

“…Moreover, it is worth noting that seeded growth is accompanied by competition between adjacent growing structural units, leading to crystalline films with a structural gradient and orientational preference [30]. For instance, seeded mineralization opens the door for obtaining prismatic-type CaCO 3 films with a vertical orientational preference [31][32][33]. Owing to the high packing density and uniform alignment of prisms, these films can exhibit comparable mechanical performance to their biogenic counterparts [31].…”

“…For instance, seeded mineralization opens the door for obtaining prismatic-type CaCO 3 films with a vertical orientational preference [31][32][33]. Owing to the high packing density and uniform alignment of prisms, these films can exhibit comparable mechanical performance to their biogenic counterparts [31]. In principle, the application of underlying granular seeds can effectively promote heterogenous nucleation in hydrogel matrices, so that mineralization in proper conditions can give rise to the delivery of uniform films.…”