Thermodynamics, kinetics, and mechanics of cesium sorption in cement paste: A multiscale assessment

Abstract

Cesium-137 is a common radioactive byproduct found in nuclear spent fuel. Given its 30 year half life, its interactions with potential storage materials—such as cement paste—is of crucial importance. In this paper, simulations are used to establish the interaction of calcium silicate hydrates (C-S-H)—the main binding phase of cement paste—with Cs at the nano- and mesoscale. Different C-S-H compositions are explored, including a range of Ca/Si ratios from 1.0 to 2.0. These calculations are based on a set of 150 atomistic models, which qualitatively and quantitatively reproduce a number of experimentally measured features of C-S-H—within limits intrinsic to the approximations imposed by classical molecular dynamics and the steps followed when building the models. A procedure where hydrated Ca[superscript 2+] ions are swapped for Cs[superscript 1+] ions shows that Cs adsorption in the C-S-H interlayer is preferred to Cs adsorption at the nanopore surface when Cs concentrations are lower than 0.19 Mol/kg. Interlayer sorption decreases as the Ca/Si ratio increases. The activation relaxation technique nouveau is used to access timescales out of the reach of traditional molecular dynamics (MD). It indicates that characteristic diffusion time for Cs[superscript 1+] in the C-S-H interlayer is on the order of a few hours. Cs uptake in the interlayer has little impact on the elastic response of C-S-H. It leads to swelling of the C-S-H grains, but mesoscale calculations that access length scales out of the range of MD indicate that this leads to practically negligible expansive pressures for Cs concentrations relevant to nuclear waste repositories.