Search

Aggregation kinetics and surface charging properties of rod-like sulfated cellulose nanocrystals (CNCs) have been investigated in aqueous suspensions containing monovalent, divalent, or trivalent inorganic salts. Electrophoresis and time-resolved dynamic light scattering (DLS) were used to characterize the surface charge and colloidal stability of the CNCs, respectively. The surface charge and aggregation kinetics of the sulfated CNCs were found to be independent of solution pH (pH range 2–10). For the monovalent salts (CsCl, KCl, NaCl, and LiCl), the critical coagulation concentration (CCC) followed the order of Cs+ < K+ < Na+ < Li+, which follows the direct Hofmeister series, indicating specific interaction of the cations with the CNCs surface. The experimental aggregation kinetics of CNCs were in very good agreement with predictions based on the classic Derjaguin–Landau–Verwey–Overbeek (DLVO) theory. A Hamaker constant of 3.6 × 10−20 J for the CNCs in aqueous medium was derived, for the first time, from the colloidal stability curves with monovalent salts. This value is consistent with a previous value determined by direct force measurements for cellulose surfaces in aqueous solutions. For the divalent salts (MgCl 2 , CaCl 2 , and BaCl 2), the CCC values followed the order Mg2+ > Ca2+ > Ba2+, which is in the reverse order of the counterion ionic size. For the trivalent salts (LaCl 3 , AlCl 3 , and FeCl 3), the CNCs suspension was destabilized much more effectively. The observed complex stability curves with AlCl 3 and FeCl 3 are attributed to charge neutralization and charge reversal imparted by the adsorption of aluminum and ferric hydrolysis species on the CNC surface. The significant charge reversal induced by the ferric hydrolysis species led to the restabilization of suspensions. Our results on the colloidal stability of CNCs are of central importance to the nanotechnology and materials science communities working on various applications of CNCs. [ABSTRACT FROM AUTHOR]

Electrophoretic mobility and time resolved light scattering are used to measure the effect on charging and aggregation of amidine and sulfate latex particles of different oxyanions namely, phosphate, arsenate, sulfate, and selenate. In the case of negatively charged sulfate latex particles oxyanions represent the coions, while they represent counterions in the case of the positively charged amidine latex. Repulsive interaction between the sulfate latex surface and the coions results in weak ion specific effects on the charging and aggregation. On the other hand the interaction of oxyanions with the amidine latex surface is highly specific. The monovalent dihydrogen phosphate ion strongly adsorbs to the positively charged surface and reverses the charge of the particle. This charge reversal leads also to the restabilization of the amidine latex suspension at the intermediate phosphate concentrations. In the case of dihydrogen arsenate the adsorption to amidine latex surface is weaker and no charge reversal and restabilization occurs. Similar differences are seen between the sulfate and selenate analogues, where selenate adsorbs more strongly to the surface as compared to the sulfate ion and invokes charge reversal. The present results indicate that ion specificity is much more pronounced in the case of counterions. [ABSTRACT FROM AUTHOR]