Probing Anisotropic Surface Properties and Surface Forces of Fluorite Crystals

Fluorite is the most important mineral source for producing fluorine-based chemicals and materials in a wide range of engineering and technological applications. In this work, atomic force microscopy was employed, for the first time, to probe the surface interactions and adhesion energy of model oleic acid (a commonly used surface modification organics for fluorite) molecules on fluorite surfaces with different orientations in both air and aqueous solutions at different pH conditions. Fitted with the Derjaguin-Landau-Verwey-Overbeek theory, the force results during surface approaching demonstrate the anisotropy in the surface charge of different orientations, with the {111} surface exhibiting a higher magnitude of surface charge, which could be attributed to the difference in the atomic composition. The adhesion measured during surface retraction shows that model oleic acid molecules have a stronger adhesion with the {100} surface than with the {111} surface in both air and aqueous solutions. The anisotropic adhesion energy was analyzed in relation to the surface atom (especially calcium) activity, which was supported by the surface free energy results calculated based on a three-probe-liquid method. Each calcium atom on the {100} surface with four dangling bonds is more active than the calcium atom on the {111} surface with only one dangling bond, supported by a larger value of the Lewis acid component for the {100} surface. The model oleic acid molecules present in the ionic form at pH 9 exhibit a higher adhesion energy with fluorite surfaces as compared to their molecular form at pH 6, which was related to the surface activity of different forms. The adhesion energy measured in solution is much lower than that in air, indicating that the solvent exerts an important influence on the interactions of organic molecules with mineral surfaces. The results provide useful information on the fundamental understanding of surface interactions and adhesion energy of organic molecules on mineral surfaces with different orientations, and the methodology can be extended to many other crystal surfaces in various interfacial processes.