title: In situ platelets formation into aqueous polymer colloids: The topochemical transformation from single to double layered hydroxide (LSH-LDH) uncovered.
abstract: Layered Single Hydroxide (LSH) of chemical composition Zn5(OH)8(acetate)2·nH2O is synthesized under in situ condition in an aqueous dispersion of an amphiphilic, carboxylate bearing polyester via a modified polyol route. The one-pot LSH generation yields agglomerates of well intercalated platelets, 9-10nm separated from each other. However the corresponding Layered Double Hydroxide (LDH) of formal composition Zn2Al(OH)6 (acetate)·nH2O is found to proceed via the formation of crystallized, similarly spaced LSH sheets in the neighborhood of amorphous Al rich domains as evidenced by X-ray diffraction and transmission electron micrographs. The initial phase segregation effaces over time while LSH platelets convert into the LDH phase. Fingerprinted by the change of in-plane cation accommodation, the associated topochemical reaction of the edge-sharing octahedral LSH platelets involves the transformation of metal lacunae, adjacently covered by one tetrahedral coordinated cation on each side to balance the negative surcharge, into fully occupied and monolayered platelets of edge-sharing octahedral LDH, the former voids being occupied by trivalent cations. This replenishing process of empty sites, coupled with the dissolution of tetrahedral sites is likely to be observed for the first time due to the presence of well separated, polymer intercalated platelets. TEM pictures vision crystal growth arising from the zone of the LSH edge-slab and by using solid state kinetics formalism the associated high activation energy of the first-order reaction agrees well with a plausible dissolution re-precipitation mechanism. The conversion of LSH into LDH platelets may be extended to others cations as Co(2+), Cu(2+), as well as the aluminum source (AlCl3) and the water-soluble polymer (NVP), thus indicating it is a new prevalent facet of LDH.
authors.affiliation: Université Clermont Auvergne, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand - ICCF, UMR-CNRS n°6296, BP 80026, F-63171 Aubière, France.
authors.forename: Thomas
authors.initials: T
authors.lastname: Stimpfling
authors.affiliation: Université Clermont Auvergne, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand - ICCF, UMR-CNRS n°6296, BP 80026, F-63171 Aubière, France.
authors.forename: Arthur
authors.initials: A
authors.lastname: Langry
authors.affiliation: BASF Coatings GmbH, Glasuritstrasse 1, 48165 Muenster, Germany.
authors.forename: Horst
authors.initials: H
authors.lastname: Hintze-Bruening
authors.affiliation: Université Clermont Auvergne, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand - ICCF, UMR-CNRS n°6296, BP 80026, F-63171 Aubière, France. Electronic address: Fabrice.Leroux@univ-bpclermont.fr.
authors.forename: Fabrice
authors.initials: F
authors.lastname: Leroux
mesh_terms: D003102:Colloids / Q000737:chemistry; D006878:Hydroxides / Q000737:chemistry*; D010316:Particle Size; D011091:Polyesters / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013499:Surface Properties; D014867:Water / Q000737:chemistry
chemical_list: D003102:Colloids; D006878:Hydroxides; D011091:Polyesters; D011108:Polymers; C024617:polyol; D014867:Water; C031356:hydroxide ion
keywords: Layered structure; Platelets intercalation versus exfoliation; Polymer nanocomposite; Solid state kinetics; Topochemical transformation