Volumetric Properties and Viscosity of Fluid Mixtures at High Pressures: Lubricants and Ionic Liquids
Dickmann, James Scott
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The present thesis explores the volumetric and transport properties of complex fluid mixtures under pressure in order to develop a better, more holistic understanding of the relationship between the volumetric properties, derived thermodynamic properties, and viscosity. To accomplish this broad objective, two different categories of fluid mixtures were examined using a combination of experimental data and models. These included base oils and their mixtures with polymeric additives, used in lubricants and ionic liquids, with cosolvent addition, for use in biomass and polymer processing. Experimental density data were collected using a variable-volume view-cell at pressures up to 40 MPa and temperatures up to 398 K. A unique high pressure rotational viscometer was developed to study the effect of pressure, temperature, and shear rate on viscosity while also allowing for the simultaneous examination of phase behavior. Viscosity data were collected at pressures up to 40 MPa, temperatures up to 373 K, and shear rates up to 1270 s-1. Experimental density and viscosity data were fit to a pair of coupled model equations, the Sanchez-Lacombe equation of state and the free volume theory respectively. From density, derived thermodynamic properties, namely isothermal compressibility, isobaric thermal expansion coefficient, and internal pressure, were calculated. By generating these models, viscosity could be viewed in terms of density, allowing for a direct link with thermodynamic properties. In the first part of the study, the effect of composition on density, thermodynamic properties, and viscosity was examined for base oils used in automotive lubricants. Six different base oils, four mineral oils and two synthetic oils, were studied to develop a better understanding on how the thermodynamic properties, particularly isothermal compressibility and internal pressure, vary with the concentration of cyclic molecules in the oil stock. Isothermal compressibility was found to decrease with cycloalkane content, while internal pressure increased. Additionally, the effect of two different polymeric additives on the volumetric properties and viscosity of a base oil composed of poly(α olefins) was examined. Both additives are polymethacrylate based, one with amine functionality, and are used as viscosity index modifiers in engine oils and automatic transmission fluids. The polymer with amine functionality was found to have a significant effect on internal pressure, seen as a large drop at high polymer concentration (7 mass percent), due to the addition of repulsive intermolecular interactions. In the second part of the study, six ionic liquids with the 1-alkyl-3-methylimidazolium cation and their mixtures with ethanol were examined. Two anions were used, chloride and acetate. The effect of ethanol addition on the derived thermodynamic properties and viscosity was studied in terms of chain length of the alkyl group on the cation. In addition, a method of estimating Hildebrand solubility parameter was employed, allowing for solubility parameter to be put in terms of pressure, temperature, and composition. The effect of cosolvent addition on the thermodynamic properties was changed by the length of the alkyl group on the cation. As the cation became bulkier, anion-cation interactions weakened, allowing for an increase in the anion-cosolvent interactions.
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