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Title: Polymer adsorption to titania surfaces studied by adsorption isotherm, rheology and atomic force microscopy
Author: Naden, Benjamin John
ISNI:       0000 0001 3438 8590
Awarding Body: Imperial College London
Current Institution: Imperial College London
Date of Award: 2008
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This Ph.D. study investigates the adsorption of monomeric (isostearic acid, ISA) and oligomeric fatty acids (poly(hydroxystearic acid), PHS 1400 and PHS 3500) to nanoparticles of industrial interest in carriers with different solvent properties. It was found that it was necessary to apply a number of methods to study the adsorption and subsequent stabilisation of the particles by the dispersing molecules, namely adsorption isotherm methods, rheological techniques, atomic force microscopy and UV/vis spectroscopy. The particles (surface) studied consist of uncoated titania and a commercially available titania coated with a combination of alumina and silica. The use of gel permeation chromatography (GPC) to study the adsorption behaviour of polydisperse dispersants provided information not only about the amount of the dispersant adsorbed to the surface, but also the preferential adsorption of low molecular weight components. The displacement of large molecules by smaller ones could be monitored in order to gain insight into the types of adsorption mechanisms at work. It was found that small molecules were unable to fully displace their larger counterparts, suggesting that there was more than one adsorption mechanism in effect. This was supported by the adsorption study of one of the fatty acid dispersants which was esterified with methanol to remove the acid functionality. Adsorption at the particle surface still occurred, but at a much reduced rate. The preferential adsorption of the smaller molecules was also found to be largely eliminated. Adsorption isotherms showed Langmuir-like adsorption behaviour of the molecules to the surface, probably through a combination of acid-base interaction and other specific interactions between surfactant molecule and surface. Adsorption of the dispersant molecules at the particle surface was found to vary with solvent properties reflecting the equilibrium which is established between solubility of the dispersant in solution (χ) and that adsorbed on the surface (г) as a result of adsorption affinity (χs). Steric layer thickness δ could be varied by altering dispersion medium (and hence solvency of the stabilising chain) and by altering molecular weight of the surfactant. This had a significant effect upon the bulk properties of the suspended particles measured by rheological methods. For optimised dispersion performance with high solids load at low viscosity whilst maintaining descrete dispersed particles, as determined by assessing the optical properties of the suspension, the stabilising layer required is dependent upon the particle type and size: small particles require small steric layers. It was found that some degree of polydispersity was important for the oligomeric fatty acid dispersants. Although good adsorption characteristics were observed for the monodisperse monomeric dispersant, adsorption appeared to be optimum for the 1400 Mw oligomeric which had a high proportion of low molecular weight components as well as larger molecules present. Removal of the low molecular weight components from PHS 3500 resulted in interactions measured by AFM that appeared to indicate bridging behaviour due to reduced packing efficiency.
Supervisor: Bismarck, Alexander ; Kessell, L. ; Luckham, Paul Sponsor: Uniqema Ltd
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral