Scaling Relationships for Spherical Polymer Brushes Revisited.
In this short paper, we revisit the scaling relationships for spherical polymer brushes (SPBs) i.e. polymer brushes grafted to rigid, spherical particles. Considering that the brushes can be described to be encased in a series of hypothetical spherical blobs, we identify significant physical discrepancies in the model of Daoud and Cotton (Journal of Physics, 1982) which is considered to be the state of the art in scaling modeling of SPBs. We establish that the "brush" configuration of the polymer molecules forming the SPBs is possible only if the swelling ratio (which is the ratio of the end to end length of the blob encased polymer segment to the corresponding coil like polymer segment) is always less than unity a notion that has been erroneously overlooked in the model of Daoud and Cotton. We also provide new scaling arguments that (a) establish this swelling (or more appropriately shrinking) ratio as a constant (less than unity) for the case of "good" solvent, (b) recover the scaling predictions for blob dimension and monomer number and monomer concentration distributions within the blob, and
The journal of physical chemistry. B