Dynamic interactions of interfacial polymers
Abstract: The relationship between the amount and conformation of apolymer at the solid-liquid interface, and the resultinginteraction forces between two such surfaces has beeninvestigated. With a degree of control of the polymerconformation, by varying the temperature, solvent quality,polymer charge density etc, it has been possible to measure andinterpret the resulting changes in the surface interactions.The recurring themes of dynamics and hydrodynamics have beencontinually considered due to the large range and viscoelasticnature of the polymeric systems.The polymeric systems investigated in this thesis are, poly(N-isopropylacrylamide), poly (12-hydroxystearate) and a seriesof AM-MAPTAC polyelectrolytes with variable chargedensities.Adsorption and conformation of polymers have beeninvestigated by the novel QCM instrument. By comparison tosimultaneously measured energy loss information, a greaterunderstanding of the conformation of the polymer has beengained, both as a function of layer build-up during initialadsorption, and as a result of induced conformational changes.Comparing the results toin situsurface plasmon resonance and subsequent x-rayphotoelectron spectroscopy measurements, the relativeconcentration of polymer within the layer is determined. Inaddition, efforts have been made to extend the scope of thetechnique, in such ways as measuring with QCM as a function oftemperature and deriving viscoelastic properties. The later isstill to be achieved in absolute terms for polymer layers inliquid environments, yet both the principle and experimentalcapabilities have been shown.Normal interaction forces have been measured as a functionof solvation of the polymer layer, for both adsorbed andgrafted polymer layers. For fully solvated (steric) polymerlayers, which can act as colloidal stabilisers, the dynamics ofthe repulsive force, including hydrodynamics have beeninvestigated. The same has been achieved for collapsed polymerlayers, in which the dynamic adhesion has also beeninvestigated. The effect on the adhesion of three differentdynamic mechanisms has been determined (which, like the surfaceforces, depend on the polymer conformation andviscoelasticity). These dynamic mechanisms are based onbridging forces, polymer entanglement and a viscoelastic?bulk?response from the surface layers.Lateral or friction measurements have also been completed.The effect of load and rate have been investigated as afunction of both the polymer charge density and the underlyingsubstrate, which result in a variable conformation and bindingstrength to the substrate. This has resulted in a complexaddition of numerous mechanisms, the dominant mechanism beingdetermined by the binding strength to the surface, polymerconformation and viscoelasticity. The results have shown thatadsorbed polymer layers can be used to both increase anddecrease friction, and to change the direction of the ratedependence.
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