Neutron and light scattering studies of polymers adsorbed on laponite

The adsorption of poly(ethylene oxide) (PEO) and various poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronic) copolymers onto the synthetic clay Laponite, was investigated using Small Angle Neutron Scattering (SANS) and Dynamic Light Scattering (DLS). The Laponite particles are anisotropic, with a relatively high aspect ratio; but are the same order of magnitude in size as the polymer radius of gyration. Consequently, the particles present a radically different adsorption geometry compared to a locally planar interface, that is assumed by the majority of adsorption studies. The PEO homo-polymer formed thin layers, with the layer thickness being much smaller on the face than on the edge of the particle. Furthermore, the face thickness remained constant with increasing molecular weight, unlike the edge thickness, which grew with a small power law dependence on the molecular weight. Although the hydrodynamic thicknesses (DLS) were larger than those observed with SANS, the layer thicknesses were much smaller than that expected for polymer adsorption on spherical particles. Experimentally determined inter-particle structure factors suggested that the adsorbed PEO layers provided a steric repulsion term to the inter-particle interactions. The autocorrelation functions for aggregating Laponite dispersions were followed with DLS. It was found that the stabilisation provided by the adsorbed layer reduced the aggregation rate, with lower molecular weights being most effective. SANS and DLS measurements on Laponite/Pluronic systems revealed that the thickness of the Pluronic layer was the same on the edge and face of the particle. As the Pluronic anchor fraction decreased, and the PEO block molecular weight increased, a growth in the layer size and adsorbed amount was observed. The low anchor fraction Pluronics had higher adsorbed amounts and thicker layers, than the highest Mw homo-polymers, demonstrating the importance of the PPO block in the adsorption process. In all cases, monolayer plateau adsorption occurred below the critical micelle concentration. (author)