Abstract
The forces and viscosity between calcium benzene sulfonate surfactant-coated mica surfaces in various hydrocarbon liquids containing a polyamine-functionalized hydrocarbon polymer (MW≈8000) have been measured using the surface forces apparatus technique. The polymer is found to adsorb to the substrate surfaces by displacing the surfactant layer, and to produce forces that are monotonically repulsive. The forces have a maximum range of 50–100 nm (>3RH), indicating that tails play a particularly important role in the interaction of this relatively low molecular weight polymer. The forces become steeply repulsive below about 10 nm (∼0.6RH), at which point a “hard-wall” repulsion comes in that can sustain pressures greater than 100 atm. Thin-film viscosity measurements indicate that the far-field positions of the slipping planes ΔH depend on the shear rate, showing that significant shear thinning/thickening effects occur within the outermost tail regions of the adsorbed layers during shear. The position of the slipping plane, or hydrodynamic layer thickness ΔH, varies from 0.6RH to 2RH away from each surface (mica and surfactant-coated mica surfaces). Beyond the hydrodynamic layer the far-field fluid viscosity is the same as that of the bulk polymer solution. At separations below D = 2ΔH the viscosity increases as each polymer layer is compressed. The static forces exhibited various time- and history-dependent effects, which further indicate that a number of different relaxation/equilibration processes are operating simultaneously in this complex multicomponent system. The results reveal that the interactions of tails of functionally adsorbed polymers play a more important role than previously thought. This is especially true in this study where the adsorbed polymers are of low molecular weight and where the tails may represent the largest fraction of interacting segments.
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