NOx produced during combustion can persist in the exhaust gases of a gas turbine engine in quantities significant to induce regulatory concerns. There has been much research which has led to important insights into NOx chemistry. One method of NOx reduction is exhaust gas recirculation. In exhaust gas recirculation, a portion of the exhaust gases that exit are redirected to the inlet air stream that enters the combustion chamber, along with fuel. Due to the presence of NOx in the exhaust gases which are subsequently introduced into the burner, knowledge of the effects of NOx on combustion is advantageous. Contrary to general NOx research, little has been conducted to investigate the sensitizing effects of NO2 and N2O addition to methane/oxygen combustion. Experiments were made with dilute and real fuel air mixtures of CH4/O2/Ar with the addition of NO2 and N2O. The real fuel air concentrations were made with the addition of NO2 only. The equivalence ratios of mixtures made were 0.5, 1 and 2. The experimental pressure range was 1 - 44 atm and the temperature range tested was 1177 – 2095 K. The additives NO2 and N2O were added in concentrations from 831 ppm to 3539 ppm. The results of the mixtures with NO2 have a reduction in ignition delay time across the pressure ranges tested, and the mixtures with N2O show a similar trend. At 1.3 atm, the NO2 831 ppm mixture shows a 65% reduction and shows a 75% reduction at 30 atm. The NO2 mixtures showed a higher decrease in ignition time than the N2O mixtures. The real fuel air mixture also showed a reduction. Sensitivity Analyses were performed. The two most dominant reactions in the NO2 mixtures are the reaction O+H2 = O+OH and the reaction CH3+NO2 = CH3O+NO. The presence of this second reaction is the means by which NO2 decreases ignition delay time, which is indicated in the experimental results. The reaction produces CH3O which is reactive and can participate in chain propagating reactions, speeding up ignition. The two dominant reactions for the N2O mixture are the reaction O+H2 = O+OH and, interestingly, the other dominant reaction is the reverse of the initiation reaction in the N2O-mechanism: O+N2+M = N2O+M. The reverse of this reaction is the direct oxidation of nitrous oxide. The O produced in this reaction can then speed up ignition by partaking in propagation reactions, which was experimentally observed.

Increasingly stringent legislations call for more efficient and cleaner combustion technology as well as sustainable fuels. Chemical kinetic models are required in designing and optimizing novel engine concepts as well as selecting appropriate renewable fuels. Among the many reactions controlling fuel reactivity, OH + Fuel elementary reaction is one of the most important reactions that plays a critical role from low to high temperatures. In this thesis, OH + Fuel elementary reactions are studied for a wide spectrum of conventional and renewable fuels. The overall rate coefficients are measured in a shock tube using OH time-history profiles recorded with a UV laser diagnostic. Alkanes constitute important components of gasoline and diesel. Overall rate coefficients are measured for a series of large branched alkanes and the rate rules are derived based on the next-nearest-neighbor classification method. The strength of this method lies in the ability to predict the rate coefficients for large and/or highly-branched alkanes, where both experiments and theoretical calculations are hard to reach. Next, OH reactions with bio-derived fuels, methanol and cyclic-ketones, are studied. For OH + methanol reaction, site-specific contributions from different C-H bonds are quantified using deuterium kinetic isotopic effect, and the measured rate coefficients are found to improve the general behavior of a detailed methanol kinetic model. Reactions of cyclic ketones with OH radicals are found to exhibit similar reactivity as those of similar carbon length acyclic ketones + OH reactions. Acetaldehyde is one of the most abundant hazardous byproducts in the combustion of various fuels. Similar to methanol, OH + acetaldehyde reaction is 4 studied at the site-specific level and the importance of competing reaction channels are quantified at high temperatures. Finally, reactions of OH + cyclohexadienes and OH + trimethylbenzenes, relevant for the fate of polycyclic aromatics hydrocarbons, are investigated. A highly complex temperature dependence is observed for these molecules, a six-parameter Arrhenius expression is needed to describe the overall reactivity. The work reported in this thesis provides elementary reaction data that are highly valuable for increasing the fidelity and accuracy of predictive chemical kinetic models.

The Navy is interested in comparing multi-thermocouple probes, tested in the field, with scanned laser absorption thermometry. This comparison aims to understand the effects of excess Carbon Monoxide (CO) and carbon (soot) resulting from rich nitromethane (CH3NO2) combustion events interacting with the outside air, as well as aluminum catalysts, on the temperature of the ensuing fireball. These interactions create mixing zones with varying gas temperature and composition. Currently, research at the UCF shock tube involves taking preliminary CO-scanned thermometry data with the goal of comparing thermocouple insert results in the future. The thermocouple insert is securely positioned within a specially designed end wall and protected by a heat shield. By comparing the temperature measurements obtained by one-dimensional shock relations with those obtained through scanned laser thermometry, based on CO characterization experiments conducted previously on the same shock tube, we aim to analyze temperature measurements and evaluate how the presence of the thermocouple insert affects the incident shockwave geometry, as well as the resulting reflected wave and temperature conditions. The goal is to observe any discrepancies in temperature measurements between the one-dimensional shock relations and the scanned laser method. This will enable researchers to assess the impact of the thermocouple insert in testing environments. Experiments were conducted using a mixture of 3% carbon monoxide (CO), 20% helium (He), and 77% argon (Ar), with an expected temperature range of 950 – 1950K, at pressures of 0.7 – 1 atmosphere (atm).

High-fidelity chemical kinetic models for low-temperature combustion processes require high-fidelity data from fundamental experiments conducted in idealized transient reactors, such as shock tubes and rapid compression machines (RCM). Non-intrusive laser absorption diagnostics, in particular quantum cascade lasers (QCL) in the mid-infrared wavelength region, provide a unique opportunity to obtain quantitative, time-resolved species concentration and temperature from these reactive systems. In this work, three novel laser absorption diagnostics in the mid-infrared wavelength region are presented for three different experimental applications. The first diagnostic was developed for measuring CO2 concentration using an external cavity QCL centered in the ν3 fundamental vibrational band of CO2. Absorption cross-sections were measured in a shock tube, at a fixed wavelength for the R(32) line centered at 2371.42 cm-1 (4.217 µm) over 700 – 2900 K and nominal pressures of 1, 5 and 10 bar. The diagnostic was used to measure rate coefficients for the reaction between carbon monoxide and hydroxyl radical over 700 – 1230 K and 1.2 – 9.8 bar using highly dilute mixtures. The second diagnostic was developed for measuring CO concentration using a pulsed QCL centered at 2046.28 cm-1 (4.887 µm) and an off-axis cavity implemented on the RCM. The duty cycle and pulse repetition rate of the laser were optimized for increased tuning range, high chirp rate and increased line-width to achieve effective laser-cavity coupling. A gain factor of 133 and time resolution of 10 μs were demonstrated. CO concentration-time profiles during the oxidation of highly dilute n-heptane/air mixtures were recorded and compared with chemical kinetic models. This represents the first application of a cavity-enhanced absorption diagnostic in an RCM. Finally, a calibration-free temperature diagnostic based on a pair of pulsed QCLs centered at 2196.66 cm-1 and 2046.28 cm-1 was implemented on the RCM. The down-chirp phenomenon resulted in large spectral tuning (∆v ~ 2.8 cm-1) within a single pulse of each laser at a high pulse repetition frequency (100 kHz). The diagnostic for was used to measure the temperature rise during first-stage ignition of n-pentane at nominal pressures of 10 and 15 bar for the first time.

A new shock tube targeting low temperature, high pressure, and long test times was designed and installed at the Turbomachinery Laboratory in December of 2008. The single-pulse shock tube uses either lexan diaphragms or die-scored aluminum disks of up to 4 mm in thickness. The modular design of the tube allows for optimum operation over a large range of thermodynamic conditions from 1 to 100 atm and between 600-4000 K behind the reflected shock wave. The new facility allows for ignition delay time, chemical kinetics, high-temperature spectroscopy, vaporization, atomization, and solid particulate experiments. An example series of ignition delay time experiments was made on mixtures of CH4/C2H6/O2/Ar at pressures from 1 to 30.7 atm, intermediate temperatures from 1082 to 2248 K, varying dilutions (between 75 and 98% diluent), and equivalence ratios ranging from fuel lean (0.5) to fuel rich (2.0) in this new facility. The percentage by volume variation and equivalence ratios for the mixtures studied were chosen to cover a wide parameter space not previously well studied. Results are then used to validate and improve a detailed kinetics mechanism which models the oxidation and ignition of methane and other higher order hydrocarbons, through C4, with interest in further developing reactions important to methane- and ethane-related chemistry.

A system for recording the trajectories of non-planar shocks and particle tracers within a shock tube flow has been developed. The optics consists of a double-pass schlieren system with a multiply pulsed ruby laser as light source. The laser is synchronized with a high speed framing camera. A grid of ammonium chloride tracers is injected into the flow field, and the motion of the tracers behind the Mach reflection of intermediate strength shocks has been recorded. Analysis of the trajectories has yielded the space and time variation of the physical properties within the flow field. / Graduate / 0605

A 30.5 cm diameter, detonation driven shock tube facility has been designed, constructed and tested. The design goals of the shock tube were to reproduce free field blast wave profiles on a laboratory scale using atmospheric gaseous detonation as the energy source. Numerical simulations were utilized to explore the gas dynamic evolution inside detonation driven shock tubes and to select the optimal design parameters for the shock tube.The Friedlander profile was used to evaluate the generated pressure profiles as an approximation of free field blast waves. It has been found that the detonation driver length should be kept below 20% of the total length of the tube in order to produce Friedlander waves. Additionally, it has been found that an annular vent can be added to the shock tube to enhance the negative phase of the blast profile, more accurately reproducing real free field blast waves. The shock tube has been constructed in a modular fashion from 2.54 cm thick steel tubing. An adjustable bag type diaphragm has been employed to allow for a variable driver size and a high voltage ignition system is used to initiate detonation in the driver section. Due to the available location for the shock tube, tests using the vented configuration could not be accomplished for safety reasons. Conducted experiments produced results that agree well with corresponding numerical simulations. Overall, the shock tube design was successful in creating Friedlander blast waves. At the time of writing, a manufacturer error in correctly reporting the specifications of the clamps used on the shock tube resulted in a lower maximum pressure of operation.

Recent attacks and accidental explosions have demonstrated the necessity of ensuring the blast resistance of critical buildings and infrastructure in Canada such as federal and provincial offices, military buildings and embassies. Of particular importance is the blast resistance of ground-story columns in buildings which must be properly detailed to provide the necessary strength and ductility to prevent progressive collapse. There exists a need to explore the use of innovative materials that can simultaneously improve the performance of such columns, while also allowing for a relaxation of required detailing to ease construction. Advancements in concrete material science have led to the development of ultra-high performance fiber reinforced concretes (UHPFRC) which show superior mechanical properties when compared to conventional concrete, such as increased compressive strength, tensile resistance and toughness. These enhanced properties make UHPFRC an attractive material for use in the blast design of reinforced concrete columns. This thesis presents the results of a research program examining the performance of UHPFRC columns under simulated blast loads. As part of the experimental program twelve half-scale UHPFRC specimens, six built with regular grade steel reinforcement and six built with steel high-strength steel reinforcement, are tested under blast loading using the University of Ottawa shock tube. The specimens were designed according to CSA A23.3 standard requirements for both seismic and non-seismic regions, using various fibre types, fibre amounts and longitudinal reinforcement ratios, allowing for an investigation of various design parameters on blast behaviour. The results demonstrate that the use of UHPFRC improves the blast performance of columns by reducing displacements, increasing resistance and enhancing damage tolerance. The results also indicate that fiber content, fiber properties, seismic detailing, longitudinal reinforcement ratio and longitudinal reinforcement strength are factors which can affect the behaviour and failure mode of UHPFRC columns. As part of the analytical study the response of the UHPFRC columns is predicted using dynamic inelastic analysis. The dynamic responses of the columns are predicted by generating dynamic load-deformation resistance functions for UHPFRC and conducting single-degree-of-freedom (SDOF) analysis using software RC-Blast.

Despite the on-going intensity of research in the field of protective structural design, one topic that has been largely ignored in the literature is the effect of high strain rates on the bond between reinforcing steel and the surrounding concrete. Therefore, a comprehensive research program was undertaken to establish the effect of high strain rates on reinforced concrete bond. The experimental research consisted of the construction and testing of fourteen flexural beam-end bond specimens and twenty-five lap-spliced reinforced concrete beams. The physical and material properties of the specimens were selected based on a range of design parameters known to significantly influence bond strength. In order to establish a baseline for comparison, approximately half of the total number of specimens were subjected to static testing, while the remainder were subjected to dynamic loading generated using a shock tube. The strain rates generated using the shock tube were consistent with those obtained for mid- and far-field explosive detonation. Results of the beam-end and lap splice beam tests showed that the flexural behaviour of reinforced concrete was significantly stronger and stiffer when subjected to dynamic loading. Furthermore, the high strain rate bond strength was always greater than the corresponding low strain rate values, yielding an average dynamic increase factor (DIF) applied to ultimate bond strength of 1.28. Analysis of the low and high strain rate test results led to the development of empirical expressions describing the observed strain rate sensitivity of reinforced concrete bond for spliced and developed bars with and without transverse reinforcement. The predictive accuracy of the proposed DIF expressions was assessed against the experimental results and data from the literature. It was found that the dynamic bond strength of reinforced concrete can be predicted with reasonably good accuracy and that the proposed DIF expressions can be used for analysis and design of protective structures. An analytical method was also developed to predict the flexural load-deformation behaviour of reinforced concrete members containing tension lap splices. The analysis incorporated the effect of reinforcement slip through the use of pseudo-material stress-strain relationships, in addition to giving consideration to the effect of high strain rates on bond-slip characteristics and on the material properties of concrete and steel. A comparison of the analytical predictions with experimental data demonstrated that the proposed analysis technique can reasonably predict the flexural response of beams with tension lap splices. The results also demonstrated that the model is equally applicable for use at low- and high-strain rates, such as those generated during blast and impact.

Titanium dioxide and aluminum oxide are conventional materials used in heterogeneous catalysis as catalyst support. The widely used crystalline phase of both supports is the metastable phase (anatase and γ-Al$_2$O$_3$) in which they possess a higher specific surface area compared to the thermodynamically stable phase (rutile and α-Al$_2$O$_3$). However, these phases have better thermal and mechanical stability than anatase and γ-Al$_2$O$_3$. A novel method to induce phase transformation and structural modification of crystalline materials is by applying shock waves. This study aims to experimentally investigate the effects of shock wave treatment on titania and alumina. A pressure-driven shock tube was used in this work to generate the shock waves. Two sets of experiments were carried out for TiO$_2$ and one for Al$_2$O$_3$. Titania samples were prepared in the form of pellets for the first set. Titania and alumina samples were maintained as powder for the second set of experiments. For titania, twenty shocks were applied at nominal temperature and pressure of ~ 1772 K and 23.3 bar in the first set of experiments, while thirty shocks of ~ 1572 K and 66 bar were applied in the second set of experiments. For alumina, twenty shock loadings were applied at the same conditions used for the second set of titania. Characterization techniques, such as XRD, Raman spectroscopy, TEM, SEM, XPS, and N$_2$ physisorption were employed on treated samples in order to understand the effects of shock wave treatment. Partial phase transformation was observed in shock treated TiO2 from Raman spectra and TEM images. Crystallite size reduction was observed in the first set of experiments, while increase in defects was observed by the enhanced Ti$^{+3}$ in XPS spectra in both sets of experiments. Partial phase transformation was also observed in shock treated Al$_2$O$_3$, when mixed with CNF (carbon nanofibers), from XRD patterns and confirmed with XPS. For alumina, TEM and SEM images showed the smallest particles in contact with carbon fibers, while the biggest particles exhibited agglomeration. Physisorption experiments showed a decrease of 40% in surface area and pore collapse.