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Langmuir. 2004 Apr 27;20(9):3536-42.

Flocculation of microgel particles with sodium chloride and sodium polystyrene sulfonate as a function of temperature.

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School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, United Kingdom.


The flocculation behavior of poly(N-isopropylacrylamide) (PNIPAM) microgel particles, containing surface sulfate groups, has been studied as a function of sodium chloride [NaCl] concentration, between 0.1 and 800 mM NaCl and over the temperature range 25-60 degrees C. The critical flocculation temperature (CFT) of the particles was determined as a function of NaCl concentration. Three regions of NaCl concentration were established. First, at very low values of [NaCl] (< approximately 25 mM), no CFT value could be determined; this implies that the interparticle electrostatic repulsion is sufficient to prevent any flocculation occurring. This remains the case even at temperatures well in excess of the lower critical solution temperature for PNIPAM in solution, where the particles are essentially deswollen. Second, at intermediate [NaCl] (approximately 25-100 mM), the CFT decreased strongly with increasing [NaCl]. In this region, the electostatic forces are weakened sufficiently for the van der Waals forces to cause flocculation. Third, at higher [NaCl] (> approximately 100 mM), the electrostatic repulsion is screened out, and the CFT decreases linearly with [NaCl]. The reason for this decrease is the fact that aqueous solutions of NaCl become increasingly poorer solvent environments for PNIPAM with increasing [NaCl]. These trends are apparent also in the values determined for the hydrodynamic size of the stable PNIPAM particles as a function of [NaCl] and temperature. It is shown that the flocculation of the PNIPAM particles is consistent with a weak, reversible flocculation model. This is apparent, for example, from the fractal dimensions of the flocs (approximately 2.0), determined from the power law used to fit the time evolution of the hydrodynamic size of the flocs, and also from the estimated depth of the mimimum in the interparticle pair potential, based on the critical size of the primary particles where flocculation just begins to occur. The effect of adding sodium poly(styrene sulfonate) [PSS] to the PNIPAM dispersions, in the absence of NaCl, was also investigated. The minimum amount of PSS required to induce flocculation was found to decrease with increasing temperature.


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