Atomistic origin of montmorillonite clay subjected to freeze-thaw hysteresis

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The freeze-thaw cycles of frozen soil could significantly affect its thermo-hydro-mechanical-chemical (THMC) properties, causing the frost heaving and thawing settlement. The microscale essence is the water-ice phase transition, but the microscale details are still poorly understood, especially at ultra-low temperatures. Nuclear magnetic resonance (NMR) technology and molecular dynamics (MD) simulation methods were performed to explore the freeze-thaw behaviors of montmorillonite clay under temperature of 210 - 293 K. Then, the water-ice phase transition, freeze-thaw hysteresis, ice nucleation mechanism, and surface effect of clay at an atomistic level were discussed. A classification method of different types of unfrozen water through NMR experiment was proposed, including bulk, capillary, and bound water. Here, it is found that: (1) the freeze-thaw process of frozen soil at the macroscale was essentially the occurrence of ice-water phase transition at the microscale. (2) The freeze-thaw hysteresis was caused by different growth and melting rates of ice crystals, where the ice growth/nucleation on clay surface was more difficult to develop. (3) The surface effect of clay was essential for the ice nucleation and the existence of bound water. For example, little unfrozen water still existed in unfrozen soil even at 213 K. (4) For unsaturated frozen soil, the quasi-liquid water was an essential component of unfrozen water that cannot be ignored. This work could provide an atomistic insight to unravel the atomistic origin of the freeze-thaw mechanism of montmorillonite clay and complement relevant experimental evidence.