Mohammad Mirzadeh

Freezing in charged porous media can induce significant pressure and cause damage to tissues and functional materials. We formulate a thermodynamically consistent theory to model freezing phenomena inside charged heterogeneous porous space. Two regimes are distinguished: free ions in open pore space lead to negligible effects of freezing point depression and pressure. On the other hand, if nano-fluidic salt trapping happens, subsequent ice formation is suppressed due to the high concentration of ions in the electrolyte. In this case, our theory predicts that freezing starts at a significantly lower temperature compared to pure water. In 1D, as the temperature goes even lower, ice continuously grows, until the salt concentration reaches saturation, all ions precipitate to form salt crystals, and freezing completes. Enormous pressure can be generated if initial salt concentration is high before salt entrapment. We show modifications to the classical nucleation theory, due to the trapped salt ions. Interestingly, although the freezing process is enormously changed by trapped salts, our analysis shows that the Gibbs-Thompson equation on confined melting point shift is not affected by the presence of the electrolyte.

A remarkable variety of organisms and wet materials are able to endure temperatures far below the freezing point of bulk water. Cryo-tolerance in biology is usually attributed to "anti-freeze" proteins, and yet massive supercooling ($< -40^\circ$C) is also possible in porous media containing only simple aqueous electrolytes. For concrete pavements, the common wisdom is that freeze-thaw damage results from the expansion of water upon freezing, but this cannot explain the large pressures ($> 10$~MPa) required to damage concrete, the observed correlation between pavement damage and de-icing salts, or the damage of cement paste loaded with benzene (which contracts upon freezing). In this Letter, we propose a different mechanism -- nanofluidic salt trapping -- which can explain the observations, using simple mathematical models of dissolved ions confined to thin liquid films between growing ice and charged surfaces. Although trapped salt lowers the freezing point, ice nucleation in charged pores causes enormous disjoining pressures via the rejected ions, until their removal by precipitation or surface adsorption at a lower temperatures releases the pressure and allows complete freezing. The theory is able to predict the non-monotonic salt-concentration dependence of freeze-thaw damage in concreter and provides a general framework to understand the origins of cryo-tolerance.