Repeptization (redispersion) from an aggregated state is usually only possible in charge-stabilized colloidal systems if the system is either coagulated in the secondary minimum of the interaction potential or if the system cannot settle completely into the primary minimum. In this work, we analyze the zeta potential, conductivity, and long-term stability of colloidal systems of iron(III) pyrophosphate and surprisingly find that the system seems to defy conventional wisdom as it can be repeptized from its coagulated state regardless of aging time and background ions. Moreover, after having been stored for up to a month in 2 M NaCl, dialysis of iron pyrophosphate will yield a colloidal dispersion that is actually stable for a longer period of time than a fresh system with background electrolyte removed.
■ INTRODUCTIONDestabilization and coagulation in the primary minimum of the interaction potential occurs when colliding particles overcome the repulsion and cross the stabilizing barrier; see Figure 1. Once trapped, lowering the ionic strength will only repeptize (redisperse) the particles if there is a distance of closest approach (or cutoff distance) between the particles, otherwise repeptization from the deep primary minimum will be impossible. 1 A possible cause for such a cutoff distance in an electrocratic (charge-stabilized) system arises if interparticle interactions during a Brownian collision occur under constant surface charge instead of constant surface potential, as the reequilibration needed for a constant potential takes place in a timespan orders of magnitude larger than that of the collisions. This implies that the cutoff distance will vanish over time with equilibration, explaining why aged systems cannot be repeptized as is indeed often observed. 2,3 Other possible causes for a cutoff distance include surface roughness and the presence of the hydration layer itself, but these will also vanish over time by re-equilibration or sintering. 1,4−6 Note that we are working with a system that contains no stabilizing agents such as surfactants or polymers, making steric stabilization (another common cause for a distance of closest approach) highly unlikely.While repeptization is important from a practical viewpoint as it governs the ability for colloidal dispersions to be dried, stored, and redispersed, it is almost exclusively studied when going from the dried to the dispersed state, 4,7 comprising only a minor part of the phenomenon. However, current literature agrees that while repeptization from the primary minimum can be experimentally realized when coagulation is induced by monovalent background ions and short aging times, the repeptization of systems aggregated by polyvalent ions is not possible by simply lowering the ionic strength of the medium: it needs additional means such as addition of surfactants 8 or Received: September 12, 2012 Revised: November 13, 2012 Published: November 14, 2012 Figure 1. Schematic representations of interparticle interaction potentials in an electrocratic ...