Abstract:

To help understand the fuel oxidation process in practical combustion environments, laminar flame speeds and high temperature chemical kinetic models were studied for several practical fuels and "surrogate" fuels, such as propane, dimethyl ether (DME), and primary reference fuel (PRF) mixtures, gasoline and n-decane. The PIV system developed for the present work is described. The general principles for PIV measurements are outlined and the specific considerations are also reported.

Laminar flame speeds were determined for propane/air over a range of equivalence ratios at initial temperature of 298 K, 500 K and 650 K and atmospheric pressure. Several data sets for propane/air laminar flame speeds with N 2 dilution are also reported. These results are compared to the literature data collected at the same conditions. The propane flame speed is also numerically calculated with a detailed kinetic model and multi component diffusion, including Soret effects.

This thesis also presents experimentally determined laminar flame speeds for primary reference fuel (PRF) mixtures of n-heptane/iso-octane and real gasoline fuel at different initial temperature and at atmospheric pressure. Nitrogen dilution effects on the laminar flame speed are also studied for selected equivalence ratios at the same conditions. A minimization of detailed kinetic model for PRF mixtures on laminar flame speed conditions was performed and the measured flame speeds were compared with numerical predictions using this model.

The measured laminar flame speeds of n-decane/air mixtures at 500 K and at atmospheric pressure with and without dilution were determined. The measured flame speeds are significantly different that those predicted using existing published kinetic models, including a model validated previously against high temperature data from flow reactor, jet-stirred reactor, shock tube ignition delay, and burner stabilized flame experiments. A significant update of this model is described which continues to predict the earlier validation experiments as well as the newly acquired laminar flame speed data and other recently published shock tube ignition delay measurements.

A high temperature decomposition and oxidation model based on a hierarchical nature of reacting systems to reflect the new development in the small molecule and radical kinetics and thermochemistry and to evaluate recent measurements of DME laminar flame speeds is developed. The, thermal decomposition of DME was studied theoretically by using the RRKM/master equation approach and the high temperature model was then compared with the literature experimental data. The new model predicts well high temperature flow reactor data, high temperature shock tube ignition delays, and the species profiles from the burner-stabilized flames. Predictions of laminar flame speed and jet-stirred reactor data also reasonably agree with the available experimental data. The remaining uncertainties that need to be addressed for further model improvement will also be discussed.

This thesis also presents a novel temperature-dependent feature sensitivity analysis methodology for combustion modeling. The obtained information is demonstrated to be of critical relevance in optimizing complex reaction schemes against multiple experimental targets. Applications of the presented approach are not limited to sensitivities with respect to reaction rate coefficients; the method can also be used to investigate any temperature-dependent property of interest (such as binary diffusion coefficients). This application is also demonstrated in this thesis.