Freezing point depression and freeze-thaw damage by nanofluidic salt trapping

Abstract

A remarkable variety of organisms and wet materials are able to endure temperatures far below the freezing point of bulk water. Cryotolerance in biology is usually attributed to "antifreeze" proteins, and yet massive supercooling (<−40∘C) is also possible in porous media containing only simple aqueous electrolytes. For concrete pavements, the common wisdom is that freeze-thaw (FT) damage results from the expansion of water upon freezing, but this cannot explain the high pressures (>10 MPa) required to damage concrete, the observed correlation between pavement damage and deicing salts, or the FT damage of cement paste loaded with benzene (which contracts upon freezing). In this work, we propose a different mechanism—nanofluidic salt trapping—which can explain the observations, using simple mathematical models of dissolved ions confined between growing ice and charged pore surfaces. When the transport time scale for ions through charged pore space is prolonged, ice formation in confined pores causes enormous disjoining pressures via the ions rejected from the ice core, until their removal by precipitation or surface adsorption at lower temperatures releases the pressure and allows complete freezing. The theory is able to predict the nonmonotonic salt-concentration dependence of FT damage in concrete and provides some hint to better understand the origins of cryotolerance from a physical chemistry perspective.

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