The effect of the relative permittivity on the tactoid formation in nanoplatelet systems. A combined computer simulation, SAXS, and osmotic pressure study

Maria Jansson; Axel Thuresson; Tomás S Plivelic; Jan Forsman; Marie Skepö

doi:10.1016/j.jcis.2017.11.051

The effect of the relative permittivity on the tactoid formation in nanoplatelet systems. A combined computer simulation, SAXS, and osmotic pressure study

J Colloid Interface Sci. 2018 Mar 1:513:575-584. doi: 10.1016/j.jcis.2017.11.051. Epub 2017 Nov 20.

Authors

Maria Jansson¹, Axel Thuresson², Tomás S Plivelic³, Jan Forsman², Marie Skepö⁴

Affiliations

¹ Theoretical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden. Electronic address: maria.jansson@teokem.lu.se.
² Theoretical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden.
³ MAX IV Laboratory, Lund University, P.O. Box 118, SE-221 00 Lund, Sweden.
⁴ Theoretical Chemistry, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden. Electronic address: marie.skepo@teokem.lu.se.

PMID: 29190569
DOI: 10.1016/j.jcis.2017.11.051

Abstract

The structural properties, and the intracrystalline swelling of Na⁺-, and Ca²⁺-montmorillonite (Na-, and Ca-mmt) have been investigated as an effect of decreasing the relative permittivity of the solvent, i.e. from water to ethanol (EtOH), utilizing the experimental techniques; small angle X-ray scattering (SAXS) and osmotic pressure measurements. The experimental data were compared with the continuum model, utilizing coarse-grained molecular dynamics bulk simulations, Monte Carlo simulations of two infinite parallel surfaces corresponding to two clay platelets, and the strong coupling theory. It was found that it is possible to tune the electrostatic interactions to obtain a transition from a repulsive to an attractive system for the Na-mmt by increasing the EtOH concentration, i.e. the Bjerrum length increases, and hence, the attractive ion-ion correlation forces are enhanced. A qualitative agreement was observed between the simulations and the experimental results. Moreover, a non-monotonic behavior of the intracrystalline swelling of Ca-mmt as a function of EtOH concentration was captured experimentally, where an increase in the osmotic pressure, and hence, an increase in the d-spacing was found at low concentrations, indicating that repulsive short-ranged interactions dominate in the system. Theoretically, the non-monotonic behavior could not be captured with the continuum model, probably due to the limitation that the electrostatic interactions solely enters the Hamiltonian via the Bjerrum length.

Keywords: Clay; Electrostatic interactions; Ethanol; Ion-ion correlations; Molecular dynamics simulations; Monte Carlo simulations; Montmorillonite; Nanoplatelets; Relative permittivity; Small angle X-ray scattering.