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.

Investigation into the enhancement of polycarbonate with conductive nanomaterials

Polymers are typically electrically and thermally insulating materials. The electrical and thermal conductivities of polymers can be increased by the addition conductive fillers such as carbons. Once the polymer composites have been made electrically and thermally conductive, they can be used in applications where these conductivities are desired such as electromagnetic shielding and static dissipation. In this project, three carbon nanomaterials are added to polycarbonate to enhance the electrical and thermal conductivity of the resulting composite. Hyperion Catalysis FIBRILs carbon nanotubes were added to a maximum loading of 8 wt%. Ketjenblack EC-600 JD carbon black was added to a maximum loading of 10 wt%. XG Sciences xGnP™ graphene nanoplatelets were added to a maximum loading of 15 wt%. These three materials have drastically different morphologies and will have varying effects on the various properties of polycarbonate composites. It was determined that carbon nanotubes have the largest effect on electrical conductivity with an 8 wt% carbon nanotube in polycarbonate composite having an electrical conductivity of 0.128 S/cm (from a pure polycarbonate value of 10-17 S/cm). Carbon black has the next largest effect with an 8 wt% carbon black in polycarbonate composite having an electrical conductivity of 0.008 S/cm. Graphene nanoplatelets have the least effect with an 8 wt% graphene nanoplatelet in polycarbonate having an electrical conductivity of 2.53 x 10-8 S/cm. Graphene nanoplatelets show a significantly higher effect on increasing thermal conductivity than either carbon nanotubes or carbon black. Mechanically, all three materials have similar effects with graphene nanoplatelets being somewhat more effective at increasing the tensile modulus of the composite than the other fillers. Carbon black and graphene nanoplatelets show standard carbon-filler rheology where the addition of filler increases the viscosity of the resulting composite. Carbon nanotubes, on the other hand, show an unexpected rheology. As carbon nanotubes are added to polycarbonate the viscosity of the composite is reduced below that of the original polycarbonate. It was seen that the addition of carbon nanotubes offsets the increased viscosity from a second filler, such as carbon black or graphene nanoplatelets.

AN EXPERIMENTAL INVESTIGATION INTO THE EFFECTS OF BIODIESEL BLENDS ON PARTICULATE MATTER OXIDATION IN A CATALYZED PARTICULATE FILTER DURING ACTIVE REGENERATION

Active regeneration experiments were carried out on a production 2007 Cummins 8.9L ISL engine and associated DOC and CPF aftertreatment system. The effects of SME biodiesel blends were investigated in this study in order to determine the PM oxidation kinetics associated with active regeneration, and to determine the effect of biodiesel on them. The experimental data from this study will also be used to calibrate the MTU-1D CPF model. Accurately predicting the PM mass retained in the CPF and the oxidation characteristics will provide the basis for computation in the ECU that will minimize the fuel penalty associated with active regeneration. An active regeneration test procedure was developed based on previous experimentation at MTU. During each experiment, the PM mass in the CPF is determined by weighing the filter at various phases. In addition, DOC and CPF pressure drop, particle size distribution, gaseous emissions, temperature, and PM concentration data are collected and recorded throughout each experiment. The experiments covered a range of CPF inlet temperatures using ULSD, B10, and B20 blends of biodiesel. The majority of the tests were performed at CPF PM loading of 2.2 g/L with in-cylinder dosing, although 4.1 g/L and a post-turbo dosing injector were also used. The PM oxidation characteristics at different test conditions were studied in order to determine the effects of biodiesel on PM oxidation during active regeneration. A PM reaction rate calculation method was developed to determine the global activation energy and the corresponding pre-exponential factor for all test fuels. The changing sum of the total flow resistance of the wall, cake, and channels was also determined as part of the data analysis process in order to check on the integrity of the data and to correct input data to be consistent with the expected trends of the resistance based on the engine conditions used in the test procedure. It was determined that increasing the percent biodiesel content in the test fuel tends to increase the PM reaction rate and the regeneration efficiency of fuel dosing, i.e., at a constant CPF inlet temperature, B20 test fuel resulted in the highest PM reaction rate and regeneration efficiency of fuel dosing. Increasing the CPF inlet temperature also increases PM reaction rate and regeneration efficiency of fuel dosing. Performing active regeneration with B20 as opposed to ULSD allows for a lower CPF temperature to be used to reach the same level of regeneration efficiency, or it allows for a shorter regeneration time at a constant CPF temperature, resulting in decreased fuel consumption for the engine during active regeneration in either scenario.

EXPERIMENTAL INVESTIGATION INTO PARTICULATE MATTER DISTRIBUTION IN CATALYZED PARTICULATE FILTERS USING A 3D TERAHERTZ WAVE SCANNER

The particulate matter distribution (PM) trends that exist in catalyzed particulate filters (CPFs) after loading, passive oxidation, active regeneration, and post loading conditions are not clearly understood. These data are required to optimize the operation of CPFs, prevent damage to the CPFs caused by non-uniform distributions, and develop accurate CPF models. To develop an understanding of PM distribution trends, multiple tests were conducted and the PM distribution was measured in three dimensions using a terahertz wave scanner. The results of this work indicate that loading, passive oxidation, active regeneration, and post loading can all cause non-uniform PM distributions. The density of the PM in the substrate after loading and the amount of PM that is oxidized during passive oxidations and active regenerations affect the uniformity of the distribution. Post loading that occurs after active regenerations result in distributions that are less uniform than post loading that occurs after passive oxidations.