Calcium phosphates are the main minerals in human bone, enamel, atherosclerosis, and dental calculus. Amorphous precursors may play a key role in biomineralization. We studied the formation and transformation of calcium phosphate particles of amorphous phase by stopped-flow spectrophotometry, simultaneous measurements of particle size and solution pH, and high-resolution transmission electron microscopy. Ion pairs and clusters formed in the first few seconds. They then constituted initial amorphous phase containing protonated phosphates and hydrated calcium ions, which was different from that containing Ca 9 (PO 4 ) 6 . Crystalline domains developed at multiple sites inside the primary particles of the amorphous phase. With the consuming of interdomain constituents, these particles partially collapsed, liberating crystallites and inducing rapid precipitation. This study sheds new light on the understanding of crystallization in amorphous phase, as well as the induction period in precipitation kinetics.
A new and simple method for preparation of hollow calcium carbonate nanospheres under mild conditions is developed. Hollow vaterite nanospheres are achieved by water-induced phase transformation of poly(4-sodium styrene sulfonate)-stabilized amorphous calcium carbonate (PSS−ACC) in water−ethanol solution at room temperature. It is found that the sizes of the resulting hollow-structured nanospheres can be easily regulated by the content of PSS and the phase transformation can be greatly affected by the ratio of water to ethanol in the mixed solvent. A combination effect of PSS and water is emphasized in this formation process. It is important to control the amounts of PSS and water in the experiments so that a large scale of hollow vaterite nanospheres with different sizes can be achieved. We suggest that the PSS−ACC particles use themselves as the templates to form the new crystallized shells, and its mechanism is also discussed.
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