Colloid
aggregation and retention in the presence of macromolecular
coatings (e.g., adsorbed polymers, surfactants, proteins, biological
exudates, and humic materials) have previously been correlated with
electric double layer interactions or repulsive steric interactions,
but the underlying causes are not fully resolved. An interaction energy
model that accounts for double layer, van der Waals, Born, and steric
interactions as well as nanoscale roughness and charge heterogeneity
on both surfaces was extended, and theoretical calculations were conducted
to address this gap in knowledge. Macromolecular coatings may produce
steric interactions in the model, but non-uniform or incomplete surface
coverage may also create compressible nanoscale roughness with a charge
that is different from the underlying surface. Model results reveal
that compressible nanoscale roughness reduces the energy barrier height
and the magnitude of the primary minimum at separation distances exterior
to the adsorbed organic layer. The depth of the primary minimum initially
alters (e.g., increases or decreases) at separation distances smaller
than the adsorbed organic coating because of a decrease in the compressible
roughness height and an increase in the roughness fraction. However,
further decreases in the separation distance create strong steric
repulsion that dominates the interaction energy profile and limits
the colloid approach distance. Consequently, adsorbed organic coatings
on colloids can create shallow primary minimum interactions adjacent
to organic coatings that can explain enhanced stability and limited
amounts of aggregation and retention that have commonly been observed.
The approach outlined in this manuscript provides an improved tool
that can be used to design adsorbed organic coatings for specific
colloid applications or interpret experimental observations.