title: The gap between crystalline and osmotic swelling of Na-montmorillonite: a Monte Carlo study.
abstract: Although the swelling of clay during moistening is a broadly experienced occurrence, the mechanisms driving it and especially the reason for the existence of a peculiar gap between crystalline and osmotic swelling of Na-montmorillonite are not yet fully understood. We obtained a deeper insight by means of Monte Carlo simulations of Na-montmorillonite swelling, which yield the swelling curve, interaction energies between and characteristic positions of structural atoms and water molecules. We find that a chainlike structure consisting of Na cations, water molecules, and oxygens of substituted tetrahedrons of neighboring mineral layers is formed in the interlayer space of Na-montmorillonite at a layer spacing of approximately 19 A, where experimental investigations show termination of crystalline swelling. Such a persistent structure may lock the interlayer space, until excess water is able to break this chain by osmotic forces. We suggest that its formation is the reason for the existence of a gap in layer spacings between approximately 19 and approximately 40 A, which have been named "forbidden" layer spacings in experimental studies.
authors.affiliation: Center for Radiation Protection and Radioecology (ZSR), University of Hannover, Herrenhäuser Strasse 2, 30419 Hannover, Germany.
authors.forename: Artur
authors.initials: A
authors.lastname: Meleshyn
authors.forename: Claus
authors.initials: C
authors.lastname: Bunnenberg
mesh_terms: D001546:Bentonite / Q000737:chemistry*; D002414:Cations, Monovalent; D003198:Computer Simulation; D003460:Crystallization; D008956:Models, Chemical; D009010:Monte Carlo Method; D009995:Osmosis; D012964:Sodium / Q000737:chemistry*
chemical_list: D002414:Cations, Monovalent; D001546:Bentonite; D012964:Sodium