Surface charge heterogeneity of kaolinite in aqueous suspension in comparison with montmorillonite

Abstract

An analogous study to 2:1 type montmorillonite [Tombácz, E., Szekeres, M., 2004. Colloidal behavior of aqueous montmorillonite suspensions: the specific role of pH in the presence of indifferent electrolytes. Appl. Clay Sci. 27, 75–94.] was performed on 1:1 type kaolinite obtained from Zettlitz kaolin. Clay minerals are built up from silica tetrahedral (T) and alumina octahedral (O) layers. These lamellar particles have patch-wise surface heterogeneity, since different sites are localized on definite parts of particle surface. pH-dependent charges develop on the surface hydroxyls mainly at edges besides the permanent negative charges on silica basal plane due to isomorphic substitutions. Electric double layers (edl) with either constant charge density on T faces (silica basal planes) or constant potential at constant pH on edges and O faces (hydroxyl-terminated planes) form on patches. The local electrostatic field is determined by the crystal structure of clay particles, and influenced by the pH and dissolved electrolytes. The acid–base titration of Na-kaolinite suspensions showed analogous feature to montmorillonite. The initial pH of suspensions and the net proton surface excess vs. pH functions shifted to the lower pH with increasing ionic strength indicating the presence of permanent charges in both cases, but these shifts were smaller for kaolinite in accordance with its much lower layer charge density. The pH-dependent charge formation was similar, positive charges in the protonation reaction of (Si–O) Al–OH sites formed only at pHs below ∼ 6–6.5, considered as point of zero net proton charge (PZNPC) of kaolinite particles. So, oppositely charged surface parts on both clay particles are only below this pH, therefore patch-wise charge heterogeneity exists under acidic conditions. Electrophoretic mobility measurements, however, showed negative values for both clays over the whole range of pH showing the dominance of permanent charges, and only certain decrease in absolute values, much larger for kaolinite was observed with decreasing pH below pH ∼ 6. The charge heterogeneity was supported by the pH-dependent properties of dilute and dense clay suspensions with different NaCl concentrations. Huge aggregates were able to form only below pH ∼ 7 in kaolinite suspensions. Coagulation kinetics measurements at different pHs provided undisputable proofs for heterocoagulation of kaolinite particles. Similarly to montmorillonite, heterocoagulation at pH ∼ 4 occurs only above a threshold electrolyte concentration, which was much smaller, only ∼ 1 mmol l − 1 NaCl for kaolinite, than that for montmorillonite due to the substantial difference in particle geometry. The electrolyte tolerance of both clay suspensions increased with increasing pH, pH ∼ 6–6.5 range was sensitive, and even a sudden change occurred above pH ∼ 6 in kaolinite. There was practically no difference in the critical coagulation concentration of kaolinite and montmorillonite (c.c.c.∼ 100 mmol l − 1 NaCl) measured in alkaline region, where homocoagulation of negatively charged lamellae takes place. Rheological measurements showed shear thinning flow character and small thixotropy of suspensions at and above pH ∼ 6.7 proving the existence of repulsive interaction between uniformly charged particles in 0.01 M NaCl for both clays. The appearance of antithixotropy, the sudden increase in yield values, and also the formation of viscoelastic systems only at and below pH ∼ 6 verify the network formation due to attraction between oppositely charged parts of kaolinite particles. Under similar conditions the montmorillonite gels were thixotropic with significant elastic response.