Effect Of Structure-Making And Structure-Breaking Ions On Adsorption Of Guar Gum Onto Quartz

Introduction Guar gum is a natural nonionic polysaccharide. Guaran, the functional polysaccharide in guar gum is a chain of (1?4)-linked ß-D-mannopyranose units with a-D-galactopyranose units connected to the mannose backbone through (1?6) glycosidic linkages. The poly-mannose chain is randomly substituted with galactose units at a mannose-to-galactose ratio of 1.8-1.0 [1]. Cheng et al. reported that the molecular weight of natural guar gum is 1.935 • 106 [2]. Robinson et al. found that the molecular weights of five grades of commercial guar gums ranged from 4.4 • 105 to 16.5 • 105 [3]. Guar gum is frequently used as a depressant of naturally hydrophobic gangue minerals (e.g. talc) in the flotation of PGM-bearing ores, and according to Harris et al. a wide variety of modified guar gums are available for this application [4]. The Canadian potash industry utilizes natural guar gum as a blinder of water-insoluble slimes in the flotation of potash (sylvinite) ores, a process that is carried out in a saturated KCl/NaCl brine. The role of the polysaccharide is to prevent a primary amine collector from adsorbing onto these unwanted fine minerals. Hydrophobic interactions between basal cleavage planes and the polymer appear to be involved in guar gum adsorption on talc [5,6]. Liu and Laskowski stressed the importance of metal impurities on mineral surfaces that can serve as the active sites for polysaccharide adsorption [7]. This postulate was consistent with the later observation that, in addition to hydrogen bonding, the adsorption of guar gum onto talc was strongly dependent on the surface concentration of magnesium sites [8,9]. In this case the adsorption process was visualized as metal-polysaccharide complexation facilitated by the cis-configuration of the hydroxyl groups of mannose monomers. Hydrogen bonding and chemical interactions with metal sites were also suggested by Rath and Subramanian in their studies on guar gum adsorption on biotite mica [10]. In a recent study, Wang et al. demonstrated that hydrogen bonding is the main driving force behind guar gum adsorption onto talc [11]. Their data also show that the adsorption density of guar gum on alumina is about five times lower than the adsorption density on talc. Pawlik and Laskowski reported that the amount of guar gum adsorbed on illite was independent of ionic strength over a wide range of salt concentrations [12]. The adsorption density of the polysaccharide on illite did not measurably change with ionic strength from that of distilled water to about 50%-saturated KCl/NaCl potash brine (~3N KCl/NaCl). However, guar gum adsorption on dolomite dramatically decreased over the same range of ionic strengths, and no reliable explanation of that phenomenon was proposed [12]. The water structure-breaking or structure-making capabilities of background ions are usually ignored when discussing adsorption mechanisms of polymers. The concept of “structure breakers” and “structure makers” was first introduced by Gurney, and Frank and Wen who postulated that each ion is surrounded by three distinct regions of water structure [13,14]. In the first layer, water molecules are tightly bound to the ion. The second region extends farther away from the ion and is referred to as the region of structure breaking. Only at larger distances, where the ionic field is weak, water molecules form the “normal” ice-like structure. It is also now recognized that the first layer can be further divided into the primary and secondary hydration shells. Small, strongly hydrated ions reinforce the “normal” structure of water and the region of structure breaking disappears. In contrast, large less-hydrated ions disturb the ice-like structure and generate an extensive region of structure breaking. Experimentally, these two effects can readily be distinguished through viscosity measurements. Increasing concentrations of structure-breaking ions result in a decrease of the viscosity of aqueous solutions. On the other hand, increasing amounts of structure-makers significantly reduce the viscosity of water. Alkali metal cations form a sequence known as the Hofmeister series. The Hofmeister series - Cs+, K+, Na+, Li+ - orders the cations from the least hydrated to the most hydrated. Based on literature viscosity data for aqueous