Nanoscale Prediction of the Thermal, Mechanical, and Transport Properties of Hydrated Clay on 10⁶- and 10¹⁵-Fold Larger Length and Time Scales

Coupled thermal, hydraulic, mechanical, and chemical (THMC) processes, such as desiccation-driven cracking or chemically driven fluid flow, significantly impact the performance of composite materials formed by fluid-mediated nanoparticle assembly, including energy storage materials, ordinary Portland cement, bioinorganic nanocomposites, liquid crystals, and engineered clay barriers used in the isolation of hazardous wastes. These couplings are particularly important in the isolation of high-level radioactive waste (HLRW), where heat generated by radioactive decay can drive the temperature up to at least 373 K in the engineered barrier. Here, we use large-scale all-atom molecular dynamics simulations of hydrated smectite clay nanoparticle assemblages to predict the fundamental THMC properties of hydrated compacted clay over a wide range of temperatures (up to 373 K) and dry densities relevant to HLRW management. Equilibrium simulations of clay-water mixtures at different hydration levels are analyzed to quantify material properties, including thermal conductivity, heat capacity, thermal expansion, suction, water and ion self-diffusivity, and hydraulic conductivity. Predictions are validated against experimental results for the properties of compacted bentonite clay. Our results demonstrate the feasibility of using atomistic-level simulations of assemblages of clay nanoparticles on scales of tens of nanometers and nanoseconds to infer the properties of compacted bentonite on scales of centimeters and days, a direct upscaling over 6 orders of magnitude in space and 15 orders of magnitude in time.