Estimation of the flammability zone boundaries with thermodynamic and empirical equations

The flammability zone boundaries are very important properties to prevent explosions in the process industries. Within the boundaries, a flame or explosion can occur so it is important to understand these boundaries to prevent fires and explosions. Very little work has been reported in the literature to model the flammability zone boundaries. Two boundaries are defined and studied: the upper flammability zone boundary and the lower flammability zone boundary. Three methods are presented to predict the upper and lower flammability zone boundaries: The linear model The extended linear model, and An empirical model The linear model is a thermodynamic model that uses the upper flammability limit (UFL) and lower flammability limit (LFL) to calculate two adiabatic flame temperatures. When the proper assumptions are applied, the linear model can be reduced to the well-known equation yLOC = zyLFL for estimation of the limiting oxygen concentration. The extended linear model attempts to account for the changes in the reactions along the UFL boundary. Finally, the empirical method fits the boundaries with linear equations between the UFL or LFL and the intercept with the oxygen axis. xx Comparison of the models to experimental data of the flammability zone shows that the best model for estimating the flammability zone boundaries is the empirical method. It is shown that is fits the limiting oxygen concentration (LOC), upper oxygen limit (UOL), and the lower oxygen limit (LOL) quite well. The regression coefficient values for the fits to the LOC, UOL, and LOL are 0.672, 0.968, and 0.959, respectively. This is better than the fit of the "zyLFL" method for the LOC in which the regression coefficient’s value is 0.416.

Investigation into the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film gadolinium-doped ceria

The research reported in this dissertation investigates the impact of grain boundaries, film interface, and crystallographic orientation on the ionic conductivity of thin film Gd-doped CeO2 (GDC). Chapter 2 of this work addresses claims in the literature that submicron grain boundaries have the potential to dramatically increase the ionic conductivity of GDC films. Unambiguous testing of this claim requires directly comparing the ionic conductivity of single-crystal GDC films to films that are identical except for the presence of submicron grain boundaries. In this work techniques have been developed to grow GDC films by RF magnetron sputtering from a GDC target on single crystal r plane sapphire substrates. These techniques allow the growth of films that are single crystals or polycrystalline with 80 nm diameter grains. The ionic conductivities of these films have been measured and the data shows that the ionic conductivity of single crystal GDC is greater than that of the polycrystalline films by more than a factor of 4 over the 400-700°C temperature range. Chapter 3 of this work investigates the ionic conductivity of surface and interface regions of thin film Gd-doped CeO2. In this study, single crystal GDC films have been grown to thicknesses varying from 20 to 500 nm and their conductivities have been measured in the 500-700°C temperature range. Decreasing conductivity with decreasing film thickness was observed. Analysis of the conductivity data is consistent with the presence of an approximately 50 nm layer of less conductive material in every film. This study concludes that the surface and interface regions of thin film GDC are less conductive than the bulk single crystal regions, rather than being highly conductive paths. Chapter 4 of this work investigates the ionic conductivity of thin film Gd-doped CeO2 (GDC) as a function of crystallographic orientation. A theoretical expression has been developed for the ionic conductivity of the [100] and [110] directions in single crystal GDC. This relationship is compared to experimental data collected from a single crystal GDC film. The film was grown to a thickness of _300 nm and its conductivity measured along the [100] and [110] orientations in the 500-700°C temperature range. The experimental data shows no statistically significant difference in the conductivities of the [100] and [110] directions in single crystal GDC. This result agrees with the theoretical model which predicts no difference between the conductivities of the two directions.