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Polymorph Selection and Structure Evolution of CaCO3 Mesocrystals under Control of Poly(sodium 4‑styrenesulfonate): Synergetic Effect of Temperature and Mixed Solvent
journal contribution
posted on 2014-11-05, 00:00 authored by Lei Liu, Jun Jiang, Shu-Hong YuThe
synergetic effects of water/ethanol mixed solvent and crystallization
temperature upon CaCO3 polymorph discrimination and structural
assembly under control of poly(sodium 4-styrenesulfonate)
(PSS) were examined. CaCO3 mesocrystals of all three anhydrous
polymorphs (calcite, aragonite, and vaterite) with progressively developed
morphologies can be selectively realized in one system by consecutively
decreasing the water/ethanol volume ratio (R) at
the proper temperature. At a lower crystallization temperature (10
°C), decreasing the R value resulted in a polymorph
transition of CaCO3 from pure calcite to pure vaterite,
which was mainly attributed to the increased ethanol content and the
resulting conformation change of PSS molecules. In contrast, CaCO3 polymorphs changed from pure calcite to almost pure aragonite
at higher crystallization temperature (40 °C), where the temperature
effect was more obvious and became the dominant parameter for CaCO3 polymorph selection. In addition, a dipole effect was employed
to explain the formation of calcite and vaterite mesocrystals with
continuously and increasingly developed superstructures. This study
could have important implications in the design and preparation of
a great deal of inorganic materials with well-defined morphologies,
polymorphs, and ordered arrangement that can be controlled by simply
adjusting the reaction media and temperature.
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conformation changetemperature effectcalciteCaCO 3 mesocrystalsethanol contentStructure EvolutionCaCO 3CaCO 3 MesocrystalsCaCO 3 polymorph discriminationR valuecrystallization temperatureMixed SolventThe synergetic effectsCaCO 3 polymorphsPSS moleculespolymorph transitionPolymorph Selectionvaterite mesocrystalsreaction mediaCaCO 3 polymorph selection
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