After the restriction of different halogenated fire suppressants by the Montreal Protocol, there is an urgent need to identify environmentally friendlier alternatives. In particular, several efforts have been conducted to find substitutes of Halon 1301 (CF_(3)Br) which was considered the best in its class, not only because of its superior extinguishing performance, but also due to its relatively low toxicity. Different options have been proposed over the last decade. However, no single compound has been found to meet all of the exigent criteria. Further progress in this research requires fundamental combustion knowledge that can help us understand the unique performance of Halon 1301, to prevent this search from becoming a tedious trial-and-error process. To this end, the present work aids in the search of fire suppressants alternatives by improving the flame inhibition mechanism understanding, starting with CF_(3)Br, which serves as a benchmark for new fire suppressants. Then, a case study of two of the most currently used fire suppressants, C_(2)HF_(5) (HFC-125) and C_(2)HF_(7) (HFC-227), is presented and compared with CF_(3)Br performance. For these analyses, a systematic analytical methodology was used to examine the effect of fire suppressants on ignition and laminar flame propagation of C_(1)-C_(3) alkanes premixed mixtures, as good representatives of flammable gas fires (Class B fires). This methodology integrates model formulations and experimental designs in order to examine both chemical kinetics and thermal effects on fire suppressants at different stoichiometric conditions. Modeling predictions were based on a detailed chemical kinetics mechanism which was assembled from a new, well-studied H_(2), C_(0)–C_(5) hydrocarbon mechanism from NUI Galway and recent CF_(3)Br and HFC fire suppressant chemistry from NIST. Experimental study involved the use of a shock tube (for ignition analysis) and a freely expanding flame speed bomb (for laminar flame speed analysis). Most of the experimental data provided in this work are the first measurements of their kind for the compounds and mixtures explored in this thesis. These measurements are extremely valuable since they can be used as a metric for model validation which represents one of the objectives of this work. Current analyses indicate that the combustion properties of halogenated compounds cannot be generalized and depends on different factors. On one hand, the presented results showed that all the tested fire suppressants can decrease the laminar flame speed of the examined C_(1)-C_(3)alkanes premixed flames; however, in some cases they can act as ignition promoters. In order to understand these behaviors, sensitivity analyses were conducted showing that halogenated species, resulting from the fire suppressants decomposition, can participate in both promoting and inhibiting reactions that compete to give a net effect. Identification of the key reaction responsible for such effects was conducted. Then, improvements on the fire suppressant chemistry can be done by modifying the corresponding Arrhenius parameters of such important reactions. This work not only provides fundamental knowledge of halogenated flame inhibition mechanisms, but also serves as the basis for more accurate chemical kinetics mechanisms that can be used for better predictions over a wide range of conditions.

This thesis focuses on ignition of diisopropyl ketone (DIPK), a new biofuel candidate that is produced by endophytic conversion. The ignition delay times behind reflected shockwaves were modeled in a high-pressure shock tube. The ignition delay times were compared to other biofuels and gasoline surrogates. Parametric studies of the ignition delay experiments were performed between 1-10 atm and 900 -1200K. An OH optical sensor was developed in conjunction for the ignition delay experiments. The OH optical sensor uses a microwave discharge lamp to generate light at 308 nm that will then be shined through the combustion reaction. Using Beer-Lambert law the concentration of OH can be obtained during ignition and oxidation of hydrocarbon fuels in a shock tube. DIPK ignition delay time experiments are planned in two shock tubes (located at UCF and UF) to provide ignition and OH time-histories data for model validation.

An axi-symmetric shock-tube model has been developed to simulate the shock-wave propagation and reflection in both non-reactive and reactive flows. Simulations were performed for the full shock-tube geometry of the high-pressure shock tube facility at Texas A&M University. Computations were carried out in the CFD solver FLUENT based on the finite volume approach and the AUSM+ flux differencing scheme. Adaptive mesh refinement (AMR) algorithm was applied to the time-dependent flow fields to accurately capture and resolve the shock and contact discontinuities as well as the very fine scales associated with the viscous and reactive effects. A conjugate heat transfer model has been incorporated which enhanced the credibility of the simulations. The multi-dimensional, time-dependent numerical simulations resolved all of the relevant scales, ranging from the size of the system to the reaction zone scale. The robustness of the numerical model and the accuracy of the simulations were assessed through validation with the analytical ideal shock-tube theory and experimental data. The numerical method is first applied to the problem of axi-symmetric inviscid flow then viscous effects are incorporated through viscous modeling. The non-idealities in the shock tube have been investigated and quantified, notably the non-ideal transient behavior in the shock tube nozzle section, heat transfer effects from the hot gas to the shock tube side walls, the reflected shock/boundary layer interactions or what is known as bifurcation, and the contact surface/bifurcation interaction resulting into driver gas contamination. The non-reactive model is shown to be capable of accurately simulating the shock and expansion wave propagations and reflections as well as the flow non-uniformities behind the reflected shock wave. Both the inviscid and the viscous non-reactive models provided a baseline for the combustion model iii which involves elementary chemical reactions and requires the coupling of the chemistry with the flow fields adding to the complexity of the problem and thereby requiring tremendous computational resources. Combustion modeling focuses on the ignition process behind the reflected shock wave in undiluted and diluted Hydrogen test gas mixtures. Accurate representation of the Shock - tube reactive flow fields is more likely to be achieved by the means of the LES model in conjunction with the EDC model. The shock-tube CFD model developed herein provides valuable information to the interpretation of the shock-tube experimental data and to the understanding of the impact the facility-dependent non-idealities can have on the ignition delay time measurements.