Reversible uptake of water on NaCl nanoparticles at relative humidity below deliquescence point observed by non-contact environmental AFM. Bruzewicz, D. A., Checco A., Ocko B. M., Lewis E. R., McGraw R. and Schwartz S. E. J. Chem. Phys. Accepted, November 2010.

The behavior of NaCl nanoparticles as a function of relative humidity (RH) has been characterized using non-contact environmental atomic force microscopy (e-AFM) to measure the heights of particles deposited on a prepared hydrophobic surface. Cubic NaCl nanoparticles with sides of 35 and 80 nm were found to take up water reversibly with increasing RH well below the bulk deliquescence relative humidity (DRH) of 75% at 23° C, and to form a liquid-like surface layer of thickness 2 to 5 nm, with measurable uptake (>2 nm increase in particle height) beginning at 70% RH. The maximum thickness of the layer increased with increasing RH and increasing particle size over the range studied. The liquid-like behavior of the layer was indicated by a reversible rounding at the upper surface of the particles, fit to a parabolic cross section, where the ratio of particle height to maximum radius of curvature increases from zero (flat top) at 68% RH to 0.7 ± 0.3 at 74% RH. These observations, which are consistent with a reorganization of mass on the solid NaCl nanocrystal at RH below the DRH, suggest that the deliquescence of NaCl nanoparticles is more complex than an abrupt first-order phase transition. The height measurements are consistent with a phenomenological model that assumes favorable contributions to the free energy of formation of a liquid layer on solid NaCl due both to van der Waals interactions, which depend partly upon the Hamaker constant, Afilm, of the interaction between the thin liquid film and the solid NaCl, and to a longer-range electrostatic interaction over a characteristic length of persistence, ξ; the best fit to the data corresponded to Afilm = 1 kT and ξ = 2.33 nm.


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