Some anomalous effects of sodium ions on the electrophoretic mobility and heteroaggregation of microgel particles

J Colloid Interface Sci. 2004 May 15;273(2):435-41. doi: 10.1016/j.jcis.2004.02.049.


Experiments on the kinetics of heteroaggregation between oppositely charged particles, using both dynamic light scattering and turbidity methods, are reported. The negatively charged particles were cross-linked poly( [Formula: see text] -isopropylacrylamide) [PNIPAM] microgel particles, prepared using a carboxylic-acid-based initiator; these particles are swollen at room temperature. The positive particles were poly(4-vinylpyridine) [P4VP] particles, prepared using an amidinium-based initiator; such particles do not respond to temperature changes but do swell below pH approximately 4, where the pyridine moieties become protonated. As expected, the rate of heteroaggregation was shown to be largely independent of added salt concentration (up to approximately 20 mM), for a variety of alkali metal chlorides (MCl, where M = Li, Na, K, or Rb). However, an unexpected, significant decrease in the aggregation rate was observed at certain specific sodium chloride concentrations (typically at approximately 1 and also approximately 4 mM). Similar effects were not seen with the other alkali metal chloride salts. This strange effect was eventually attributed to the fact that the net charge on the positively charged P4VP particles had been reduced by the adsorption of (anionic) silicate species leached from the glassware container. Sodium silicates are known to be significantly more soluble than those of the other alkali metal ions, particularly at high pH. Moreover, P4VP particles dispersed in water, ostensibly at neutral pH, do buffer the aqueous medium to pH values around 9 or higher. This mechanism was confirmed by determining the electrophoretic mobility of the P4VP particles as a function of pH in the presence of the various alkali metal chloride salts. The mobility remained positive in 1 mM salt solutions over the pH range 3 to 11 for all the salts, except for sodium chloride; in that case the mobility reversed sign at alkaline pH values. A similar effect was observed for a cationic polystyrene latex sample, prepared with the same amidinium-based initiator. These experiments demonstrate the importance of soluble silicates, leached from glass storage vessels, particularly in the presence of sodium ions. Needless to say, the "anomalous" effects disappeared when plastic storage vessels were used in place of the glass ones.