The behavior of mixtures of polymer and surfactant as peptizing agents for
controlling Ostwald ripening and solvent-mediated phase transformations of
amorphous colloidal particles is studied by equilibrium dialysis and electr
on spin resonance (ESR) spectroscopy using nitroxide spin-labeled compounds
. It is found that amorphous phase stability is dependent on the interplay
between polymer-surfactant complexation in the bulk fluid and the conformat
ion of adsorbed molecules at the particle-fluid interface. Optimum stabilit
y is obtained over a range of compositions in which both polymer and surfac
tant are strongly bound to the surface of the particles. The conformation o
f the adsorbed polymer is characterized by a high fraction of train segment
s and relatively few loops. The shorter chain surfactant functions as a fil
ler to fill vacancies on the surface. The results suggest that the combinat
ion of polymer and surfactant may provide a defect-free monolayer that offe
rs better protection against solvent-mediated transformations than either p
olymer or surfactant alone.