An Investigative Study of Polymer Adsorption Onto Montmorillonite Clay

Date of Award


Degree Type


Degree Name

Doctor of Philosophy (PhD)


Polymers and High Performance Materials

First Advisor

Robert Y. Lochhead

Advisor Department

Polymers and High Performance Materials


For colloidal systems with adsorbed polymer, the mechanisms governing stabilization and flocculation are defined by the critical overlap concentration, c*. Below c*, steric stabilization or bridging flocculation are viable mechanisms of adsorption, while above c* associative thickening stabilization, depletion stabilization or depletion flocculation may occur. While these types of systems have been described by their mechanism of interaction, few studies have been geared towards evaluating and actually defining these interactions. This research focuses on elucidating the mechanisms of interaction for a series of polyacrylamide copolymers adsorbed onto montmorillonite clay. The well-defined copolymers synthesized and characterized for these studies include: nonionic polyacrylamide, (PAm); cationic poly(acrylamide-co-[3-(methacryloylamino) propyl] trimethylammonium chloride), (PAmMaap Quat); nonionic/anionic poly(acrylamide-co-acrylic acid), (PAmAA); and anionic poly(acrylamide-co-[2-acrylamido-2-methylpropane sulfonic acid]), (PAmAmps). By combining the results from the following experiments it was possible to determine the mechanisms of interaction for each of the clay/polymer systems at pH 3, 7 and 10. The adsorption capacity of each of the copolymers was determined from constructing adsorption isotherms while the polymer conformation was determined from 13 C NMR line-broadening experiments. FTIR spectroscopy verified which surface of the clay was involved in adsorption along with the polymer moiety bound to the surface. Finally, the stabilization behavior was evaluated from statistically designed phase diagrams as a function of polymer and clay concentrations. By evaluating the phase behavior as well as c* for the polymer/solvent systems, it was determined that there was no direct correlation between c* for a polymer/solvent system and the mechanism of interaction for colloid/polymer/solvent systems previously defined by Vincent, Sato and Napper. In general, the nonionic polymers act as H-bond acceptors (amide and acid moieties) and donators (acid groups) which result in associatively stabilized homogeneous montmorillonite clay dispersions. The cationic copolymers exhibit strong, irreversible interactions with the clay resulting in heterogeneous bridging flocculation, which was shown to be dependent on the charge density of the copolymer. Furthermore, the anionic copolymers show no signs of adsorption, but create a network of repulsive forces with the montmorillonite clay, which ultimately results in depletion stabilization with some degree of depletion flocculation.