Call number: LD2668 .T4 1985 S562 / Master of Science

The purpose of this research was to determine if it is feasible to apply Lorentz mixing to supersonic diffusion flames, such as those found in SCRAMjet engines. The combustion rate in supersonic diffusion flames is limited by the rate at which air and fuel mix. Lorentz mixing increases turbulence within a flow, which increases the rate at which species mix and thus increases the rate of combustion. In order to determine the feasibility of Lorentz mixing for this application, a two-dimensional model of supersonic reacting flow with the application of a Lorentz force has been examined numerically. The flow model includes the complete Navier-Stokes equations, the ideal gas law, and terms to account for diffusion of chemical species, heat release due to chemical reaction, change in species density due to chemical reaction, and the Lorentz forces applied during Lorentz mixing. In addition, the Baldwin-Lomax turbulence model is used to approximate turbulent transport properties. A FORTRAN program using the MacCormack method, a commonly used computational fluid dynamics algorithm, was used to solve the governing equations. The accuracy of the program was verified by using the program to model flows with known solutions. Results were obtained for flows with Lorentz forces applied over a series of power levels and frequencies. The results show significant increases in the rate of combustion when Lorentz mixing is applied. The amount of power required to drive Lorentz mixing is small relative to the rate at which energy is released in the chemical reaction. An optimum frequency at which to apply Lorentz mixing was also found for the flow being considered. The results of the current study show that Lorentz mixing looks promising for increasing combustion rates in supersonic reacting flows, and that future study is warranted. In particular, researchers attempting to improve combustion in SCRAMjet engines may want to consider Lorentz mixing as a way to improve combustion. / Graduation date: 1997

The importance of two sources of NO formation, nitrogen in combustion air and nitrogen in the fuel, during black liquor combustion was studied using a laminar entrained flow reactor. Pyrolysis and combustion experiments were conducted in nitrogen atmosphere and in a mixture of argon and helium in the composition 99% argon, 1% helium. The experiments were performed at three different temperatures: 700, 900, and 1100��C and at two residence times: 0.6 and 1.6 seconds. The results indicated that there was NO formation from the combustion air which was found to be prompt NO. There was NO formation from combustion air at all temperatures, and it decreased as temperature increased. Depending on conditions, prompt NO formation accounted for 6-80% of the total NO formation. NO reduction experiments were conducted to investigate the effect of molten sodium carbonate on NO reduction. The experiments were performed at two different temperatures, 800��C which is lower than the melting point of sodium carbonate and 900��C which is higher than the melting point of sodium carbonate. The rate constant for NO reduction was calculated and was found to agree well with that obtained in a previous study. The effect of the molten sodium carbonate on NO reduction was found to be negligible during black liquor pyrolysis. The rate in absence of any reducing gas components could explain NO reduction during black liquor combustion only to a limited extent. Models for nitrogen evolution during pyrolysis and combustion were developed by using data from previous studies. A model for nitrogen release during pyrolysis was developed as a function of residence time and temperature. Nitrogen release during pyrolysis was also found to be directly proportional to carbon release and the rate of nitrogen evolution with respect to the rate of carbon evolution decreased as temperature increased. / Graduation date: 1997

Includes bibliographical references. / [210] leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / This thesis presents two advanced modelling studies which address some unresolved fluidized bed combustion (FBC) issues. In the first study, finite element methods are used to solve a transient continuum/percolation model of a single porous char and its surrounding boundary layer so as to generate temperature, O2,CO2, CO pressure and porosity distributions for over 100 different FBC conditions. In the second study, a new discrete approach for the determination of the diffusion coefficients of the fluid-solid system is described and used, based on moecular dynamics and percolation concepts. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemical Engineering, 1996

Energetic materials (i.e., explosives, propellants, and pyrotechnics) have been used for centuries in a wide variety of applications that include celebratory firework displays, the demolition of ‘immovable’ structures, mining resources from the earth’s crust, launching humans into outer space, and propelling munitions across the battlefield. Many different scientific and engineering domains have found unique value in their characteristic release of significant heat and pressure. While the rate at which energetic materials react is often dependent on the source of initiation, surrounding thermodynamic conditions, and formulation sensitivity, many applications aim for a controlled combustion process to produce large amounts of work output – solid and liquid rocket motors and gun-launched projectiles are a few key examples. Other energetic material systems are often inadvertently exposed to thermal insults, which can result in similar combustion behavior. To accurately model these systems, it is important to have a fundamental understanding of the chemical kinetics that control various aspects of the combustion process (e.g., changes in temperature (T), pressure (P), and species mole fractions (X)). Detailed chemical kinetic models are often used to understand and subsequently predict such behavior. Understanding the gas-phase reaction kinetics of energetic materials is essential when trying to predict critical performance parameters such as flame speeds, temperature and pressure profiles, and heat flux between material phases. These parameters can have significant impact on predictions of system-level performance (e.g., the specific impulse of solid rocket motors, propellant burn rates in projectile systems, and munition responses to thermal insult and extended temperature cycling). While the gas-phase reaction kinetics of energetic material combustion were heavily studied from the late 1970’s to the early 2000’s, research efforts beyond this time frame have primarily focused on condensed-phase chemistry as it is thought to be less understood. Over the past two decades, however, there have been significant advances in our understanding of small molecule reactions that have not yet been accounted for in many energetic material models. One such example are chemically termolecular reactions – a new class of phenomenological reactions that have not yet been considered for inclusion in any energetic material kinetic models. Recent studies have indicated that chemically termolecular reactions, mediated through ephemeral collision complexes, have significant impact on the global kinetics of certain combustion systems. This discovery has since prompted the question of which systems are significantly influenced by chemically termolecular reactions and should therefore account for their presence in gas-phase phenomenological models. Although a select number of systems have already been investigated, such as flame speed and ignition delay predictions in common hydrocarbon combustion scenarios, the influence of chemically termolecular reactions on the kinetics of energetic materials has not yet been explored. As an initial investigation into energetic materials, a case study for RDX was performed, for which abundant computational and experimental data are available. To aid in assessing the impact of chemically termolecular reactions, for which almost no data are available, this study leveraged an automated procedure to identify and estimate rate constants for potential chemically termolecular reactions based exclusively on data available for related reactions. Four detailed kinetics models for RDX were independently screened for potential chemically termolecular reactions. Model predictions including these chemically termolecular reactions revealed that they have significant potential impact on profiles of major species, radicals, and temperatures. T he analysis pinpointed ∼20-40 chemically termolecular reactions, out of the thousands of possibilities, estimated to have the largest impact. These reactions, including many mediated by ephemeral HNO** and NNH** complexes, are therefore worthwhile candidates for more accurate quantification via master equation calculations. More generally, just as the importance of including chemically termolecular reactions in hydrocarbon combustion models is becoming recognized, the present results show compelling evidence for the need for their inclusion in energetic material models as well. The investigation into chemically termolecular reactions yielded a secondary conclusion based on the observed influence of the small molecule C/H/N/O chemistry on overall predictions of energetic material combustion – updating the small molecule chemistry in RDX models produced significant changes to predictions of major species and temperature, suggesting that the development of a comprehensive gas-phase energetic material combustion model would be of great value and have broad utility as a foundational model for a great variety of C/H/N/O energetic materials. To begin developing such a model, all small molecule chemistry in current kinetic models was reviewed with the intent of identifying a sub-model in need of revisions and subsequently addressing its uncertainties using targeted experiments to improve overall predictions. The ammonia sub-model was selected as it is both highly uncertain and highly influential in many energetic material models. Ammonia (NH₃) has garnered substantial attention in recent years due to its importance across many scientific domains – including its potential use as a carbon-free fuel and long-term energy storage option, its use in reducing combustion-generated nitrogen oxide emissions, its role as a decomposition fragment of many energetic materials, and its presence as an important impurity during biofuel and biomass combustion that can affect overall system kinetics, among others. Yet, it is generally recognized that there are still significant gaps in the present understanding of ammonia kinetics -– in both experimental data sets and sub-models within the overall ammonia kinetic mechanism. For example, most experimental studies of ammonia oxidation have used molecular oxygen as the primary or sole oxidizer. While large mole fractions of molecular oxygen are encountered in many combustion scenarios, there are select systems where ammonia is more likely to be oxidized via nitrogen-containing species (e.g. N₂O and NO₂) and, more generally, there are relatively untested reaction sets that would be accentuated in such conditions. To address these gaps in available experimental data needed for the validation of ammonia kinetics models, jet-stirred reactor experiments were performed for mixtures of NH₃/N₂O/N₂ over an intermediate temperature range (850-1180 K). In these experiments, the mole fractions of NH₃, N₂O, and NO were measured using a combination of gas chromatography, chemiluminescence, electrochemical detection, and infrared absorption – where agreement among the different diagnostics (within 3% for N₂O and 7% for NO) ensured high confidence in the experimental measurements. Comparison of the experimental results and model predictions suggested deficiencies in commonly used models for nitrogen kinetics. Various modeling analyses pointed to the central role of the N₂O + NH₂ = N₂H₂ + NO reaction, on which recent kinetic models all rely on the same rate constant estimate that appears to have not been tested in previous validation data sets for NH₃ kinetics. A second set of jet-stirred reactor experiments were performed for mixtures of NH₃/NO₂/O₂/N₂ over a slightly different temperature range (700–1100 K). Agreement among different diagnostics (≤7% for NO₂ and ≤4% for NH₃) and excellent experimental repeatability confirmed high confidence in all species measurements. Measured mole fractions were compared to predictions from five recently developed kinetic models using flux analysis and uncertainty-weighted kinetic sensitivity analysis, both of which pointed to the importance of reactions involving H₂NO that are both influential in this system and highly uncertain. The measurements from the jet-stirred reactor experiments presented here were combined with comprehensive sets of experimental data and high-level theoretical kinetics calculations using the MultiScale Informatics (MSI) approach to unravel the large uncertainties present in current NH3 oxidation kinetic sub-models. Emphasis was placed on NH₃ oxidation via nitrogen-containing species as this chemistry has been shown to accentuate influential reactions (e.g., the NO₂+NH₂ and NH₂+NO reactions) that are known to be important during the combustion of many energetic materials (e.g., AN, ADN, and AP). The resulting MSI model accurately predicted nearly all of the experimental and theoretical target data within estimated or reported uncertainties. Additional predictions of two NH₃/NO₂ validation data sets, which were not included in the MSI framework, demonstrated its ability to accurately extrapolate predictions to untested T/P/X conditions, indicating that the converged MSI model demonstrates truly predictive behavior. The MSI NH₃ oxidation model presented here should be considered for inclusion in many energetic material models as the NH₃/NOₓ kinetic system is known to be important to the combustion of various propellant and explosive formulations. This sub-model will help to form a foundational gas-phase kinetic model relevant to many different energetic materials, including those that contain inorganic additives for increased energy density and blast effects.

We investigate several aspects of the numerical solution of the radiative transfer equation in the context of coal combustion: the parallel efficiency of two commonly used opacity models, the sensitivity of turbulent radiation interaction (TRI) effects to the presence of coal particulate, and an improvement of the order of temporal convergence using the coarse mesh finite difference (CMFD) method. There are four opacity models commonly employed to evaluate the radiative transfer equation in combustion applications; line-by-line (LBL), multigroup, band, and global. Most of these models have been rigorously evaluated for serial computations of a spectrum of problem types [1]. Studies of these models for parallel computations [2] are limited. We assessed the performance of the Spectral-Line- Based weighted sum of gray gasses (SLW) model, a global method related to K-distribution methods [1], and the LBL model. The LBL model directly interpolates opacity information from large data tables. The LBL model outperforms the SLW model in almost all cases, as suggested by Wang et al. [3]. The SLW model, however, shows superior parallel scaling performance and a decreased sensitivity to load imbalancing, suggesting that for some problems, global methods such as the SLW model, could outperform the LBL model. Turbulent radiation interaction (TRI) effects are associated with the differences in the time scales of the fluid dynamic equations and the radiative transfer equations. Solving on the fluid dynamic time step size produces large changes in the radiation field over the time step. We have modifed the statistically homogeneous, non-premixed flame problem of Deshmukh et al. [4] to include coal-type particulate. The addition of low mass loadings of particulate minimally impacts the TRI effects. Observed differences in the TRI effects from variations in the packing fractions and Stokes numbers are difficult to analyze because of the significant effect of variations in problem initialization. The TRI effects are very sensitive to the initialization of the turbulence in the system. The TRI parameters are somewhat sensitive to the treatment of particulate temperature and the particulate optical thickness, and this effect are amplified by increased particulate loading. Monte Carlo radiative heat transfer simulations of time-dependent combustion processes generally involve an explicit evaluation of emission source because of the expense of the transport solver. Recently, Park et al. [5] have applied quasidiffusion with Monte Carlo in high energy density radiative transfer applications. We employ a Crank-Nicholson temporal integration scheme in conjunction with the coarse mesh finite difference (CMFD) method, in an effort to improve the temporal accuracy of the Monte Carlo solver. Our results show that this CMFD-CN method is an improvement over Monte Carlo with CMFD time-differenced via Backward Euler, and Implicit Monte Carlo [6] (IMC). The increase in accuracy involves very little increase in computational cost, and the figure of merit for the CMFD-CN scheme is greater than IMC. / Graduation date: 2012

Liquid fragmentation phenomenon is explored from both a fundamental (fully resolved) and an engineering (modeled) perspective. The dual objectives compliment each other by providing an avenue to gain further understanding into fundamental processes of atomization as well as to use the newly acquired knowledge to address practical concerns. A compressible five-equation interface model based on a Roe-type scheme for the simulation of material boundaries between immiscible fluids with arbitrary equation of state is developed and validated. The detailed simulation model accounts for surface-tension, viscous, and body-force effects, in addition to acoustic and convective transport. The material interfaces are considered as diffused zones and a mixture model is given for this transition region. The simulation methodology combines a high-resolution discontinuity capturing method with a low-dissipation central scheme resulting in a hybrid approach for the solution of time- and space-accurate interface problems. Several multi-dimensional test cases are considered over a wide range of physical situations involving capillary, viscosity, and gravity effects with simultaneous presence of large viscosity and density ratios. The model is shown to accurately capture interface dynamics as well as to deal with dynamic appearance and disappearance of material boundaries. Simulation of atomization processes and its interaction with the flow field in practical devices is the secondary objective of this study. Three modeling requirements are identified to perform Large-Eddy Simulation (LES) of spray combustion in engineering devices. In concurrence with these requirements, LES of an experimental liquid-fueled Lean Direct Injection (LDI) combustor is performed using a subgrid mixing and combustion model. This approach has no adjustable parameters and the entire flow-path through the inlet swirl vanes is resolved. The inclusion of the atomization aspects within LES eliminates the need to specify dispersed-phase size-velocity correlations at the inflow boundary. Kelvin-Helmholtz (or aerodynamic) breakup model by Reitz is adopted for the combustor simulation. Two simulations (with and without breakup) are performed and compared with measurements of Cai et al. Time-averaged velocity prediction comparison for both gas- and liquid-phase with available data show reasonable agreement. The major impact of breakup is on the fuel evaporation in the vicinity of the injector. Further downstream, a wide range of drop sizes are recovered by the breakup simulation and produces similar spray quality as in the no-breakup case.