High-temperature, high-pressure (HTHP) conditions are exemplified in ultra-deep petroleum reservoirs and can be exhibited within diesel engines. Accurate pure component hydrocarbon data is essential in understanding the overall behavior of petroleum and diesel fuel at these conditions. The present study focuses on the HTHP properties of toluene since this hydrocarbon is frequently used to increase the octane rating of gasoline and toluene occurs naturally in crude oil. In this thesis experimental densities and viscosity are presented to 535 K and 300 MPa extending the database of toluene viscosity data to higher temperature than previous studies. The data is correlated to a Tait-like equation and a Padѐ approximate in conjunction with a single mapping of the isotherms. Free-volume theory and a superposition of the viscosity in relation to the Leonnard-Jones repulsive force are both used to model the toluene viscosity data. It was found that the data are in good agreement with the available literature data.

Modern automotive applications such as transmission clutch plates, combustion chambers, diesel fuel injector tips, and axle gears and friction plates operate at temperatures that can exceed 250°C and pressures of 40,000 psia. Industrial practice is to add homopolymers and copolymers to base oils to modify bulk fluid viscosity and frictional properties for these demanding applications. However, designing polymeric additives for lubricants and predicting their performance is limited by the lack of available high-temperature high-pressure (HTHP) viscosity and density data needed to test contemporary lubricity models. Thus, a major objective of this thesis is the design, development, and commissioning of a rolling ball viscometer/densitometer (RBVD) capable of simultaneously determining fluid densities and viscosities at temperatures in excess of 250°C and pressures of 40,000 psia. Resulting data may then be generated to directly address the fundamental need for lubricant property data at these HTHP conditions. The design and development of the RBVD is described in detail to highlight the design iterations and modifications utilized to ensure robust operation at extreme conditions. Three significant and novel features of this RBVD apparatus that distinguish and differentiate it from other apparatus of this type are: (1) specially designed metal-to-metal and sapphire-to-metal seated surfaces capable of eliminating temperature- and chemically-sensitive elastomeric seals; (2) use of a bellows piston to eliminate significant temperature and operational constraints; and (3) incorporation of a linear variable differential transducer (LVDT) to simultaneously permit determination of solution density and viscosity. A detailed analysis of initial accumulated uncertainty for the experimental viscosity and density techniques revealed the need for key RBVD modifications. Final data are presented showing that the RBVD is capable of measuring viscosities with an accuracy of ± 2 to 3 percent and densities to ± 0.7 percent, including at the extreme operating conditions targeted. A second objective of this thesis is the measurement of HTHP viscosities of star polymer-solvent mixtures to determine the impact of star polymer architecture on solution viscosity at extreme conditions similar to those that might be experienced in automotive applications. This objective is motivated by current challenges facing industry to identify polymeric additives that can be added to base oils to improve fuel economy and allow for the implementation of novel hardware technology that relies on enhanced lubricant properties. Relative to linear polymers, the unique architecture of star polymers enhances polymer solubility in base oils while having a more favorable impact on viscosity and density properties over a wide range of temperatures and pressures. Data are presented for an industrially-relevant star polymer in octane to assess the impact of the star configuration on solvent viscosity at extreme conditions. The star polymer used in this instance consists of an ethylene glycol dimethacrylate (EGDMA) core with poly(lauryl methacrylate-co-methyl methacrylate) (LMA-MMA) arms. The star polymer has a total weight averaged molecular weight (Mw) and Mw of each arm of 575,000, and 45,000, respectively. The copolymer arms of the star polymer have an LMA-to-MMA mole ratio of 0.6. The results of further viscosity studies are presented for a model system of well-characterized commercially available narrow polydispersity index (PDI) star polystyrenes (PS) in toluene. Each PS is evaluated at a two percent by weight concentration in toluene to evaluate the effect of arm molecular weigh on viscosity. Each three-arm star polymer has arm and total molecular weights ([arm Mw] total star Mw) of ([15,400] 41,200), ([36,000] 97,600), and ([108,000] 305,000). In this instance, the viscosity of toluene increased by more than a factor of three for the star with the highest Mw arms.