title: Continuous structural evolution of calcium carbonate particles: a unifying model of copolymer-mediated crystallization.
abstract: Two double-hydrophilic block copolymers, each comprising a nonionic block and an anionic block comprising pendent aromatic sulfonate groups, were used as additives to modify the crystallization of CaCO3. Marked morphological changes in the CaCO3 particles were observed depending on the reaction conditions used. A poly(ethylene oxide)-b-poly(sodium 4-styrenesulfonate) diblock copolymer was particularly versatile in effecting a morphological change in calcite particles, and a continuous structural transition in the product particles from polycrystalline to mesocrystal to single crystal was observed with variation in the calcium concentration. The existence of this structural sequence provides unique insight into the mechanism of polymer-mediated crystallization. We propose that it reflects continuity in the crystallization mechanism itself, spanning the limits from nonoriented aggregation of nanoparticles to classical ion-by-ion growth. The various pathways to polycrystalline, mesocrystal, and single-crystal particles, which had previously been considered to be distinct, therefore all form part of a unifying crystallization framework based on the aggregation of precursor subunits.
authors.affiliation: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, United Kingdom.
authors.forename: Alex N
authors.initials: AN
authors.lastname: Kulak
authors.forename: Peter
authors.initials: P
authors.lastname: Iddon
authors.forename: Yuting
authors.initials: Y
authors.lastname: Li
authors.forename: Steven P
authors.initials: SP
authors.lastname: Armes
authors.forename: Helmut
authors.initials: H
authors.lastname: Cölfen
authors.forename: Oskar
authors.initials: O
authors.lastname: Paris
authors.forename: Rory M
authors.initials: RM
authors.lastname: Wilson
authors.forename: Fiona C
authors.initials: FC
authors.lastname: Meldrum
mesh_terms: D002119:Calcium Carbonate / Q000737:chemistry*; D003460:Crystallization; D008855:Microscopy, Electron, Scanning; D008956:Models, Chemical; D015394:Molecular Structure; D010316:Particle Size; D011108:Polymers / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D011108:Polymers; D002119:Calcium Carbonate