O presente trabalho procura estudar e compreender os processos reativos de chama, tentando identificá-los através de uma abordagem químico termodinâmica, em contraposição às análises clássicas, puramente cinético-químicas. Estas são justificadas por se considerar este tipo de fenômeno como existindo em condições distantes da condição de equilíbrio termodinâmico e não passíveis de análise termodinâmica, coisa que, através desta investigação, pretende-se questionar. Neste estudo, considerou-se a chama como ocorrendo em um escoamento unidimensional ideal, em regime permanente, em fluido perfeito, i.e. não há viscosidade e dividiu-se a chama em fatias, em que a exergia química era transformada em exergia térmica, em se adaptando \"o problema do tijolo aquecido\" (ou \"hot brick problem\"). O processo reativo global de chama adiabática foi, por evidência experimental, considerado como sendo bi-variante i.e. completamente determinado com a definição da pressão e da temperatura dos reagentes, conhecidos a priori, em espécie e em quantidade. O teorema de Duhem1 nos garante, portanto, que caso se estabeleça o equilíbrio, este estaria determinado. Aqui se procurou reunir subsídios para sua identificação. Investigaram-se a modelagem de chamas adiabáticas e reversíveis de duas fatias, consideradas como meio efetivo, em se igualando a exergia química à exergia térmica, bem como o que se considerou como sendo chamas adiabáticas de duas fatias de máxima irreversibilidade interna. Para a chama adiabática irreversível obteve-se temperaturas de ignição próximas à temperatura de autoignição para 4 de 6 combustíveis. Por fim, conclui-se que a chama contínua não é o limite da chama irreversível de infinitas fatias. Enquanto que aquela tem irreversibilidade máxima, segundo o modelo apresentado, a irreversibilidade desta é um máximo relativo. / The present study attempts at an understanding of the reactive processes within a flame. A chemical thermodynamics approach is employed in juxtaposition to the classical analysis which are purely chemical kinetic. These are justified because this phenomenum is considered to take place far from equilibrium conditions and not subject to thermodynamic analysis. This fact will be questioned in this study. A one-dimensional, ideal and steady flow flame was considered. The reactive process of an adiabatic flame was, by experimental evidence, considered to possess two degrees of freedom, i.e it would be completely determined by defining the reactants\' pressure and temperature, whose species and quantities were a priori known. Duhem\'s theorem2 tells us that if equilibrium is estabilished, it would be fully determined. An adiabatic and reversible two-sliced flame (the effective medium) was determined by equating the chemical exergy of the flame to the physical exergy of the two slices relative to the ignition point. Also, the constrained extremum of the difference between the chemical and physical exergies allowed the relative maximum of an internally irreversible adiabatic flame to be determined. For the irreversible flame, close simulation of the autoignition temperature for 4 of 6 fuels was obtained. Finally, the conclusion that a continuous flame is not the limit of an irreversible flame with infinite slices is demonstrated. Whilst that flame is the flame with maximum irreversibility, this flame has a relative maximum of internal irreversibility.

Moderate or Intense Low-oxygen Dilution (MILD) combustion is a combustion technology that can simultaneously improve the energy efficiency and reduce the pollutant emissions of combustion devices. It is characterised by highly preheated reactants and a small temperature rise during combustion due to the large dilution of the reactant mixture with products of combustion. These conditions are generally achieved using exhaust gas recirculation. However, the physical understanding of MILD combustion remains limited which prevents its more widely spread use. In this thesis, Direct Numerical Simulation (DNS) is used to study turbulence, premixed flames and MILD combustion to obtain these additional physical insights. In a first stage, the scale-locality of the energy cascade is analysed by applying a multiscale analysis methodology, called the bandpass filter method, on DNS of homogeneous isotropic turbulence. Evidence supporting this scale-locality were obtained and the results were found to be similar for Reynolds numbers ranging from 37 to 1131. Using the same method in turbulent premixed flames, the scale-locality of the energy cascade was still observed despite the presence of intense reactions. In addition, it was found that eddies of scales larger than the laminar flame thickness were imparting the most strain on the flame. In a second part, a methodology was developed to conduct the DNS of MILD combustion with mixture fraction variations. This methodology included the effect of mixing of exhaust gases with fuel and oxidiser in unburnt, burnt and reacting states. In addition, a specific chemical mechanism that includes the chemistry of ${\rm OH^*}$ was developed. From these DNS, the role of radicals on the inception of MILD combustion was studied. In particular, due to the reactions initiated by these radicals, the initial temperature rise in MILD combustion was occurring concurrently with an increase in the scalar dissipation rate of mixture fraction which is contrasting to conventional combustion. The reaction zones in MILD combustion were also analysed and extremely convoluted reaction zones were observed with frequent interactions among them. These interactions yielded the appearance of volumetrically distributed reactions. Furthermore, the adequacy of some species to identify these reaction zones was assessed and ${\rm OH}$ showed a poor correlation with regions of heat release. On the other hand, ${\rm OH^*}$, ${\rm HCO}$ or ${\rm OH} \times {\rm CH_2O}$ were found to be well correlated. Through the study of the flame index, the existence of non-premixed and premixed modes of combustion were also highlighted. The premixed mode was observed to be dominant but the contribution of the non-premixed mode to the total heat release was non negligible. Because of the presence of radicals and high reactant temperatures, auto-igniting regions and propagating reaction zones are both observed locally. The balance between these phenomena was investigated and it was found that this was strongly influenced by the typical lengthscale of the mixture fraction field, with a smaller lengthscale favouring sequential autoignition. Finally, using the bandpass filtering method, the effect of heat release rate in MILD combustion on the energy cascade was studied and this showed that the energy cascade was not unduly affected.

This Thesis considers peculiarities of nanoparticle formation from the gas in different systems. The main role of the surface condensation in the nanoparticle growth in metal flames was established through a series of experiments and was described by the developed model. The stagnation of the post-nucleation nanoparticle growth was experimentally revealed and theoretically explained. The influence of generation conditions on the post-processing nanoparticle properties was examined. The non-isothermal approach to correct the homogeneous nucleation theory was developed. The results of this work can be summarized in 3 categories: (1) Nanoparticle formation in metal flames. In this work, it was demonstrated that the surface condensation is a main process responsible for nanooxides growth during metal combustion. It was shown that the rate of this condensation growth is consistent with the exponential law, which could lead to the formation of the lognormal particle size distribution in the system, where the Brownian coagulation is suppressed. The post-nucleation stagnation of the nanoparticle growth was found. The particle overheating was suggested as a cause of the growth stagnation. The found stagnation leads to the accumulation of the supercritical clusters in the system generating nanoparticles. The role of these supercritical clusters in the nanoparticle agglomeration was considered. (2) Study of properties of nanoparticles generated in different metal flames. The light absorption, photoluminescence and magnetic properties of nanoparticles produced in different metal flames were examined. The significant broadening of the absorption edge was found in nanooxides produced by direct metal combustion. This broadening allowed one to excite the unforeseen photoluminescence from these nanoparticles. The significant light absorption in the visible light found in the titania particles produced by metal combustion allows one to consider these particles as a prospective photocatalyst. The unusual optical properties revealed were related to the extreme conditions of the nanoparticle formation, namely, to high energy release (about 5 eV per condensing molecule). The stabilization of spinel structure was found in iron oxide particles synthesized by iron combustion. It allowed one to produce nanoparticles with magnetization close to the high-limit value of the bulk. (3) Approach to correct the homogeneous nucleation theory. The existing homogeneous nucleation theory implies that nucleation occurs at isothermal conditions, i.e. subcritical clusters have the same temperature as the ambient gas does. However, the theory overestimates the actual nucleation rate and underestimates the critical cluster size. It is understandable that due to release of the latent heat of condensation, the cluster temperature in the nucleating system should be higher than the environment temperature. In this work, it was suggested the method to account for the cluster overheating during nucleation. It was demonstrated that the consistent description of the detailed balance in the nucleating system may allow one to evaluate magnitudes of overestimation of the actual nucleation rate and underestimation of the number of molecules in the critical cluster, usually obtained by the isothermal nucleation theory. The numerical estimates are in good agreement with the wellknown experimental results. The implications of the results to generation of atmospheric aerosols were discussed.

State-of-the-art reacting-flow computations have to compromise either on the detail of chemical reactions or on the dimensionality of the solution, while experiments in flames are limited by the flow accessibility and provide at best a limited number of observables. In the present work, the partially premixed laminar flame structure is examined using a detailed-chemistry, one-dimensional simulation. The computational results are compared to unpublished single-point multiscalar measurements obtained at Sandia National Labs in 2001. The study is focused on axisymmetric laminar partially-premixed methane/air flames with varying premixture strength values of 1.8, 2.2, and 3.17. The combination of computational and experimental results is used to analyze the spatial and scalar flame structure under the overarching concept of flamelets. The computations are based on the Cantera open-source software package developed at CalTech by D. Goodwin, and incorporating the GRI 3.0 chemical kinetic mechanism utilizing 325 chemical reactions and 53 species for methane combustion. Cross-transport effects as well as an optically-thin radiation model are included in the calculations. Radiation changes the flame profiles due to its effect on temperature, and the attendant effects on a number of species. Using the detailed analysis of different reaction rates, the adiabatic and radiative nitric oxide concentrations are compared. The cross-transport effects, i.e. Soret and Dufour, were studied in detail. The Soret term has a small but important effect on the flame structure through a reduction of the hydrogen mass fraction, which changes the conserved scalar values. Based on the flamelet approach and a unique formulation of the conserved scalar, the flame thermochemistry can be analyzed and understood. A number of interesting effects on the flame thermochemistry can be discerned in both experiments and computations when the premixture strength is varied. An increase in premixing results in a counterintuitive decrease in intermediate species such as carbon monoxide and hydrogen, as well as an expected increase in nitric oxide concentrations. Good agreement is found between experiments and calculations in scalar space, while the difference in dimensionality between axisymmetric measurements and opposed jet computations makes comparison in physical space tentative.

Emissions of oxides of nitrogen (NOx) from combustion devices is a topic of tremendous current importance. The bulk of the review of NOx emissions has been in the field of turbulent jet flames. However laminar jet flames have provided much insight into the relative importance of NOx reaction pathways in non premixed combustion for various flame conditions. The existing models include detailed chemistry kinetics for various species involved in the flame. These detailed models involve very complex integration of hundreds of chemical reactions of various species and their intermediates. Hence such models are highly time consuming and also normally involve heavy computational costs. This work proposes a numerical model to compute the total production of NOx in a non-premixed isolated circular laminar jet flame. The jet consists of the fuel rich inner region and the O2 rich outer region. The model estimates both thermal NOx and prompt NOx assuming single step kinetics for NOx formation and a thin flame model. Further the amount of air entrainment by jet depends upon the Sc number of fuel. The higher the Sc number, the higher is the air entrained which lowers the flame temperature and hence NOx formation. With increasing Sc number, flame volume increases which leads to an increase in the NOx formation. The effect of the Sc number variation on the net production of NOx and flame structure is also investigated. The effect of equilibrium chemistry for CO2 <-> CO + 1/2 O2 and H2O <-> H2 +1/2 O2 on total NOx emission is studied. Also the effect of both CO2 and H2O equilibrium is considered simultaneously and the net x NO formation for propane is 45 ppm. The split between pre-flame and post-flame regions is also investigated. For Propane, 96% of NO emissions occur in the pre-flame region and about 4% in the post-flame region. The model predictions are compared with experimental values of NOx missions reported elsewhere.

High speed chemically reacting flows are important in a variety of aerospace applications, namely ramjets, scramjets, afterburners, and rocket exhausts. To study flame extinction under similar high Mach number conditions, we need access to thermochemistry measurements in supersonic environments. In the current work a two-stage miniaturized combustor has been designed that can produce open supersonic methane-air flames amenable to laser diagnostics. The first stage is a vitiation burner, and was inspired by well-known principles of jet combustors. We explored the salient parameters of operation experimentally, and verified flame holding computationally using a well-stirred reactor model. The second stage of the burner generates an external supersonic flame, operating in premixed and partially premixed modes. The very high Mach numbers present in the supersonic flames should provide a useful test bed for the examination of flame suppression and extinction using laser diagnostics. We also present the development of new line imaging diagnostics for thermochemistry measurements in high speed flows. A novel combination of vibrational and rotational Raman scattering is used to measure major species densities (O_2, N_2, CH_4, H_2O,CO_2, CO, & H_2) and temperature. Temperature is determined by the rotational Raman technique by comparing measured rotational spectra to simulated spectra based on the measured chemical composition. Pressure is calculated from density and temperature measurements through the ideal gas law. The independent assessment of density and temperature allows for measurements in environments where the pressure is not known a priori. In the present study we applied the diagnostics to laboratory scale supersonic air and vitiation jets, and examine the feasibility of such measurements in reacting supersonic flames. Results of full thermochemistry were obtained for the air and vitiation jets that reveal the expected structure of an under-expanded jet. Centerline traces of density, temperature, and pressure of the air jet agree well with computations, while measurements of chemical composition for the vitiation flow also agree well with predicted equilibrium values. Finally, we apply the new diagnostics to the exhaust of the developed burner, and show the first ever results for density, temperature, and pressure, as well as chemical composition in a supersonic flame.

A new parallel implicit adaptive mesh refinement (AMR) algorithm is developed for the prediction of unsteady behaviour of laminar flames. The scheme is applied to the solution of the system of partial-differential equations governing time-dependent, two- and three-dimensional, compressible laminar flows for reactive thermally perfect gaseous mixtures. A high-resolution finite-volume spatial discretization procedure is used to solve the conservation form of these equations on body-fitted multi-block hexahedral meshes. A local preconditioning technique is used to remove numerical stiffness and maintain solution accuracy for low-Mach-number, nearly incompressible flows. A flexible block-based octree data structure has been developed and is used to facilitate automatic solution-directed mesh adaptation according to physics-based refinement criteria. The data structure also enables an efficient and scalable parallel implementation via domain decomposition. The parallel implicit formulation makes use of a dual-time-stepping like approach with an implicit second-order backward discretization of the physical time, in which a Jacobian-free inexact Newton method with a preconditioned generalized minimal residual (GMRES) algorithm is used to solve the system of nonlinear algebraic equations arising from the temporal and spatial discretization procedures. An additive Schwarz global preconditioner is used in conjunction with block incomplete LU type local preconditioners for each sub-domain. The Schwarz preconditioning and block-based data structure readily allow efficient and scalable parallel implementations of the implicit AMR approach on distributed-memory multi-processor architectures. The scheme was applied to solutions of steady and unsteady laminar diffusion and premixed methane-air combustion and was found to accurately predict key flame characteristics. For a premixed flame under terrestrial gravity, the scheme accurately predicted the frequency of the natural buoyancy induced oscillations. The performance of the proposed parallel implicit algorithm was assessed by comparisons to more conventional solution procedures and was found to significantly reduce the computational time required to achieve a solution in all cases investigated.

Thesis (M.S.)--University of Texas at El Paso, 2009. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

This thesis describes an experimental investigation of the response of lean turbulent swirling flames with different degrees of premixedness (i.e. different mixture patterns) to acoustic forcing using the same burner configuration and varying only the fuel injection strategy. Special emphasis was placed on the amplitude dependence of their response. Also, the behaviour of self-excited fully premixed flames was examined. kHz OH* chemiluminescence was used to study qualitatively the heat release response of the flames, while kHz OH Planar Laser Induced Fluorescence (PLIF) was employed to understand the response of the flame structure and the behaviour of the various parts of the flame. The Proper Orthogonal Decomposition (POD) method was used to extract the dominant structures of the flame and their periodicity. In the first part of the thesis, self-excited oscillations were induced by extending the length of the duct downstream of the bluff body. It was found that the longer the duct length and the higher the equivalence ratio, the stronger the self-excited oscillations were, with the effect of duct length being much stronger. The dominant frequencies of the system were found to increase with equivalence ratio and bulk velocity and decrease with duct length. For some conditions, three simultaneous periodic motions were observed, where the third motion oscillated at a frequency equal to the difference of the other two frequencies. A novel application of the POD method was proposed to estimate the convection velocity from the most dominant reaction zone structures detected by OH* chemiluminescence imaging. For a range of conditions, the convection velocity was found to be in the range of 1.4-1.7 bulk flow velocities at the inlet of the combustor. In the second part, the response of fully premixed, non-premixed with radial fuel injection (NPR) and axial fuel injection (NPA) flames was investigated and compared. All systems exhibited a nonlinear response to acoustic forcing. The highest response was observed by the NPR flame, followed by the fully premixed and the non-premixed with axial fuel injection flame. The proximity of forced flames to blow-off was found to be critical in their heat release response, as close to blow-off the flame response was significantly lower than that farther from blow-off. In the NPR and NPA systems, it was shown that the acoustic forcing reduced the stability of the flame and the stability decreased with the increase in forcing amplitude. In the fully premixed system, the flame area modulations constituted an important mechanism of the system, while in the NPR system both flame area and equivalence ratio modulations were important mechanisms of the heat release modulations. The quantification of the local response of the various parts of the flame at the forcing frequency showed that the ratio RL (OH fluctuation at 160 Hz to the total variance of OH) was greater in the inner shear layer region than in the other parts in the case of NPR and NPA flames. In fully premixed flames, greater RL values were observed in large regions on the downstream side of the flame than those in the ISL region close to the bluff body. The ratio of the convection velocity to the bulk velocity was estimated to be 0.54 for the NPR flame, while it was found to be unity for the respective fully premixed flame. In the last part of the thesis, the response of ethanol spray flames to acoustic oscillations was investigated. The nonlinear response was very low, which was reduced closer to blow-off. The ratio RL was the highest in the spray outer cone region, downstream of the annular air passage, while RL values were very low in the inner cone region, downstream of the bluff body. Unlike NPR and fully premixed flames, in case of spray and NPA systems, it was found that forcing did not affect greatly the flame structure. The understanding of the nonlinear response of flames with different degrees of premixedness in a configuration relevant to industrial systems contributes to the development of reliable flame response models and lean-burn devices, because the degree of premixedness affects greatly the flame response. Also, the understanding of the behaviour of forced spray flames is of great interest for industrial applications, contributing to the development of thermoacoustic models for liquid fuelled combustors. Finally, the estimation of the convection velocity is of importance in the modelling of self-excited flames and flame response models, since the convection velocity affects the flame response significantly.

O presente trabalho procura estudar e compreender os processos reativos de chama, tentando identificá-los através de uma abordagem químico termodinâmica, em contraposição às análises clássicas, puramente cinético-químicas. Estas são justificadas por se considerar este tipo de fenômeno como existindo em condições distantes da condição de equilíbrio termodinâmico e não passíveis de análise termodinâmica, coisa que, através desta investigação, pretende-se questionar. Neste estudo, considerou-se a chama como ocorrendo em um escoamento unidimensional ideal, em regime permanente, em fluido perfeito, i.e. não há viscosidade e dividiu-se a chama em fatias, em que a exergia química era transformada em exergia térmica, em se adaptando \"o problema do tijolo aquecido\" (ou \"hot brick problem\"). O processo reativo global de chama adiabática foi, por evidência experimental, considerado como sendo bi-variante i.e. completamente determinado com a definição da pressão e da temperatura dos reagentes, conhecidos a priori, em espécie e em quantidade. O teorema de Duhem1 nos garante, portanto, que caso se estabeleça o equilíbrio, este estaria determinado. Aqui se procurou reunir subsídios para sua identificação. Investigaram-se a modelagem de chamas adiabáticas e reversíveis de duas fatias, consideradas como meio efetivo, em se igualando a exergia química à exergia térmica, bem como o que se considerou como sendo chamas adiabáticas de duas fatias de máxima irreversibilidade interna. Para a chama adiabática irreversível obteve-se temperaturas de ignição próximas à temperatura de autoignição para 4 de 6 combustíveis. Por fim, conclui-se que a chama contínua não é o limite da chama irreversível de infinitas fatias. Enquanto que aquela tem irreversibilidade máxima, segundo o modelo apresentado, a irreversibilidade desta é um máximo relativo. / The present study attempts at an understanding of the reactive processes within a flame. A chemical thermodynamics approach is employed in juxtaposition to the classical analysis which are purely chemical kinetic. These are justified because this phenomenum is considered to take place far from equilibrium conditions and not subject to thermodynamic analysis. This fact will be questioned in this study. A one-dimensional, ideal and steady flow flame was considered. The reactive process of an adiabatic flame was, by experimental evidence, considered to possess two degrees of freedom, i.e it would be completely determined by defining the reactants\' pressure and temperature, whose species and quantities were a priori known. Duhem\'s theorem2 tells us that if equilibrium is estabilished, it would be fully determined. An adiabatic and reversible two-sliced flame (the effective medium) was determined by equating the chemical exergy of the flame to the physical exergy of the two slices relative to the ignition point. Also, the constrained extremum of the difference between the chemical and physical exergies allowed the relative maximum of an internally irreversible adiabatic flame to be determined. For the irreversible flame, close simulation of the autoignition temperature for 4 of 6 fuels was obtained. Finally, the conclusion that a continuous flame is not the limit of an irreversible flame with infinite slices is demonstrated. Whilst that flame is the flame with maximum irreversibility, this flame has a relative maximum of internal irreversibility.