Abstract
Crystallization via particle attachment was used in a unified model for both classical and non-classical crystallization pathways, which have been widely observed in biomimetic mineralization and geological fields. However, much remains unknown about the detailed processes and driving mechanisms for the attachment. Here, we take calcite crystal as a model mineral to investigate the detailed attachment process using in situ Atomic Force Microscopy (AFM) force measurements and molecular dynamics simulations. The results show that hydration layers hinder the attachment; however, in supersaturated solutions, ionic bridges are formed between crystal gaps as a result of capillary condensation, which might enhance the aggregation of calcite crystals. These findings provide a more detailed understanding of the crystal attachment, which is of vital importance for a better understanding of mineral formation under biological and geological environments with a wide range of chemical and physical conditions.
Highlights
Crystallization is a pathway of condensation or organization of materials by their components from a dispersed state or a different form, which is an important process in biological, geological, industrial, and ecological systems
One biomineralization system demonstrated a pathway for fabricating a single calcite crystal via amorphous precursor phase-mediated crystallization, which was revealed in sea urchin embryonic spicules [5]
Materials with elevated dopant ratios [10]; occlusions of organic polymers, which induce defects and enhance mechanical properties [11,12]; and complex and hierarchical morphologies with rich interfaces and textured patterns [13,14] have been widely observed by “non-classical” Crystallization by particle attachment (CPA) pathways; these features are difficult to understand in terms of the classical crystallization (CC) pathway because materials with these structures are in a high energy state, and are thermodynamically unfavorable
Summary
Crystallization is a pathway of condensation or organization of materials by their components from a dispersed state or a different form, which is an important process in biological, geological, industrial, and ecological systems. Materials with elevated dopant ratios [10]; occlusions of organic polymers, which induce defects and enhance mechanical properties [11,12]; and complex and hierarchical morphologies with rich interfaces and textured patterns [13,14] have been widely observed by “non-classical” CPA pathways; these features are difficult to understand in terms of the CC pathway because materials with these structures are in a high energy state, and are thermodynamically unfavorable. We found that the capillary gap formed during attachment can facilitate ionic bridge formation, enriching the understanding of the CPA process of mineral formation in geological environments, as well as in biomineralization
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