Dynamics of thermal ignition of spray flames in mixing layers

Conditions are identified under which analyses of laminar mixing layers can shed light on aspects of turbulent spray combustion. With this in mind, laminar spray-combustion models are formulated for both non-premixed and partially premixed systems. The laminar mixing layer separating a hot-air stream from a monodisperse spray carried by either an inert gas or air is investigated numerically and analytically in an effort to increase understanding of the ignition process leading to stabilization of high-speed spray combustion. The problem is formulated in an Eulerian framework, with the conservation equations written in the boundary-layer approximation and with a one-step Arrhenius model adopted for the chemistry description. The numerical integrations unveil two different types of ignition behaviour depending on the fuel availability in the reaction kernel, which in turn depends on the rates of droplet vaporization and fuel-vapour diffusion. When sufficient fuel is available near the hot boundary, as occurs when the thermochemical properties of heptane are employed for the fuel in the integrations, combustion is established through a precipitous temperature increase at a well-defined thermal-runaway location, a phenomenon that is amenable to a theoretical analysis based on activation-energy asymptotics, presented here, following earlier ideas developed in describing unsteady gaseous ignition in mixing layers. By way of contrast, when the amount of fuel vapour reaching the hot boundary is small, as is observed in the computations employing the thermochemical properties of methanol, the incipient chemical reaction gives rise to a slowly developing lean deflagration that consumes the available fuel as it propagates across the mixing layer towards the spray. The flame structure that develops downstream from the ignition point depends on the fuel considered and also on the spray carrier gas, with fuel sprays carried by air displaying either a lean deflagration bounding a region of distributed reaction or a distinct double-flame structure with a rich premixed flame on the spray side and a diffusion flame on the air side. Results are calculated for the distributions of mixture fraction and scalar dissipation rate across the mixing layer that reveal complexities that serve to identify differences between spray-flamelet and gaseous-flamelet problems.

The structure of lean hydrogen-air flame balls

An analysis of the structure of flame balls encountered under microgravity conditions, which are stable due to radiant energy losses from H₂O, is carried out for fuel-lean hydrogen-air mixtures. It is seen that, because of radiation losses, in stable flame balls the maximum flame temperature remains close to the crossover temperature, at which the rate of the branching step H + O₂ -> OH + O equals that of the recombination step H + O₂ + M -> HO₂ + M. Under those conditions, all chemical intermediates have very small concentrations and follow the steady-state approximation, while the main species react according to the overall step 2H₂ + O₂-> 2H₂O; so that a one-step chemical-kinetic description, recently derived by asymptotic analysis for near-limit fuel-lean deflagrations, can be used with excellent accuracy to describe the whole branch of stable flame balls. Besides molecular diffusion in a binary-diffusion approximation, Soret diffusion is included, since this exerts a nonnegligible effect to extend the flammability range. When the large value of the activation energy of the overall reaction is taken into account, the leading-order analysis in the reaction-sheet approximation is seen to determine the flame ball radius as that required for radiant heat losses to remove enough of the heat released by chemical reaction at the flame to keep the flame temperature at a value close to crossover. The results are relevant to burning velocities at lean equivalent ratios and may influence fire-safety issues associated with hydrogen utilization.

Real time monitoring of click chemistry self-healing in polymer composites

A photo-healable rubber composite based on effective and fast thiol-alkyne click chemistry as a selfhealing agent prestored in glass capillaries is reported. The click reaction and its effect on the mechanical properties of the composite are monitored in real time by dynamic mechanical analysis, showing that the successful bleeding of healing agents to the crack areas and the effective photoinitiated click reaction result in a 30% storage modulus increase after only 5 min of UV light exposure. X-ray tomography confirms capillary-driven bleeding of reactants to the damaged areas. The effect of storing the click chemistry reactants in separate capillaries is also studied, and results show the importance of stoichiometry in achieving a significant level of repair of the composite. No reactant degradation or premature chemical reaction is observed over time in samples stored in the absence of UV radiation; they are able to undergo the self-healing reaction even one month after preparation.

Flamelet structures in spray ignition

In typical liquid-fueled burners the fuel is injected as a high-velocity liquid jet that breaks up to form the spray. The initial heating and vaporization of the liquid fuel rely on the relatively large temperatures of the sourrounding gas, which may include hot combustion products and preheated air. The heat exchange between the liquid and the gas phases is enhanced by droplet dispersion arising from the turbulent motion. Chemical reaction takes place once molecular mixing between the fuel vapor and the oxidizer has occurred in mixing layers separating the spray flow from the hot air stream. Since in most applications the injection velocities are much larger than the premixed-flame propagation velocity, combustion stabilization relies on autoignition of the fuel-oxygen mixture, with the combustion stand-off distance being controlled by the interaction of turbulent transport, droplet heating and vaporization, and gas-phase chemical reactions. In this study, conditions are identified under which analyses of laminar flamelets canshed light on aspects of turbulent spray ignition. This study extends earlier fundamental work by Liñan & Crespo (1976) on ignition in gaseous mixing layers to ignition of sprays. Studies of laminar mixing layers have been found to be instrumental in developing un-derstanding of turbulent combustion (Peters 2000), including the ignition of turbulent gaseous diffusion flames (Mastorakos 2009). For the spray problem at hand, the configuration selected, shown in Figure 1, involves a coflow mixing layer formed between a stream of hot air moving at velocity UA and a monodisperse spray moving at velocity USUA. The boundary-layer approximation will be used below to describe the resulting sl ender flow, which exhibits different igniting behaviors depending on the characteristics of t he fuel. In this approximation, consideration of the case U A = U S enables laminar ignition distances to be related to ignition times of unstrained spray flamelets, thereby pro viding quantitative information of direct applicability in regions of low scala r dissipation-rate in turbulent reactive flows (see the discussion in pp. 181–186 of Peters (2000)) . This report is organized as follows. Effects of droplet dispersion dynamics on ignition of sprays in turbulent mixing layers are discussed in Section 2. The formulation f or ignition in laminar mixing layers is outlined in Sections 3 and 4. The results are presented in Section 5. In Section 6, the mixture-fraction field and associated scalar dissipat ion rates for spray ignition are discussed. Finally, some brief conclusions are drawn in Section 7.

Effects of radiation losses on very lean methane/air flames propagating upward in a vertical tube

The stationary upward propagation of a very lean methane/air flame in a long vertical tube open at the bottom and closed at the top is simulated numerically using a single overall chemical reaction to model combustion and assuming an optically thin gas and a transparent or non-reflecting tube wall to approximately account for radiation losses from CO2CO2 and H2OH2O. Buoyancy plays a dominant role in the propagation of these flames and causes a large region of low velocity of the burnt gas relative to the flame to appear below the flame front when the equivalence ratio is decreased. The size of this region scales with the radius of the tube, and its presence enhances the effect of radiation losses, which would be otherwise negligible for a standard flammability tube, given the small concentration of radiating species. Heat conduction is found to be important in the low velocity region and to lead to a conduction flux from the flame to the burnt gas that causes extinction at the flame tip for a value of the equivalence ratio near the flammability limit experimentally measured in the standard tube. The effect of radiation losses decreases with the radius of the tube. Numerical results and order-of-magnitude estimates show that, in the absence of radiation, a very lean flame front fails to propagate only after recirculation of the burnt gas extends to its reaction region and drastically changes its structure. This condition is not realized for the standard flammability tube, but it seems to account for the flammability limit measured in a tube of about half the radius of the standard tube.

Twist grain boundaries in three-dimensional lamellar Turing structures

Steady spatial self-organization of three-dimensional chemical reaction-diffusion systems is discussed with the emphasis put on the possible defects that may alter the Turing patterns. It is shown that one of the stable defects of a three-dimensional lamellar Turing structure is a twist grain boundary embedding a Scherk minimal surface.

Constraints on nebular dynamics and chemistry based on observations of annealed magnesium silicate grains in comets and in disks surrounding Herbig Ae/Be stars

Understanding dynamic conditions in the Solar Nebula is the key to prediction of the material to be found in comets. We suggest that a dynamic, large-scale circulation pattern brings processed dust and gas from the inner nebula back out into the region of cometesimal formation—extending possibly hundreds of astronomical units (AU) from the sun—and that the composition of comets is determined by a chemical reaction network closely coupled to the dynamic transport of dust and gas in the system. This scenario is supported by laboratory studies of Mg silicates and the astronomical data for comets and for protoplanetary disks associated with young stars, which demonstrate that annealing of nebular silicates must occur in conjunction with a large-scale circulation. Mass recycling of dust should have a significant effect on the chemical kinetics of the outer nebula by introducing reduced, gas-phase species produced in the higher temperature and pressure environment of the inner nebula, along with freshly processed grains with “clean” catalytic surfaces to the region of cometesimal formation. Because comets probably form throughout the lifetime of the Solar Nebula and processed (crystalline) grains are not immediately available for incorporation into the first generation of comets, an increasing fraction of dust incorporated into a growing comet should be crystalline olivine and this fraction can serve as a crude chronometer of the relative ages of comets. The formation and evolution of key organic and biogenic molecules in comets are potentially of great consequence to astrobiology.

Desenvolvimento de procedimento analítico para determinação de iodato em sal de mesa utilizando sistema com multicomutação e detecção espectrofotométrica

A iodação do sal de mesa é considerada o caminho mais eficiente para controlar os Distúrbios por Deficiência de Iodo. Em países tropicais, o elemento pode ser adicionado na forma de KIO3. Para garantir que os níveis ideais do ânion estejam disponíveis ao consumidor, o controle de qualidade do sal consiste numa estratégia fundamental. Sistemas em fluxo com multicomutação representam uma alternativa versátil para o desenvolvimento de procedimentos simples, rápidos e limpos, minimizando o consumo de reagentes e a geração de resíduos. Nesse contexto, um procedimento analítico utilizando sistema com multicomutação e detecção espectrofotométrica foi desenvolvido para a determinação de iodato em sal de mesa. A reação empregada foi baseada na formação de um composto roxo (540 nm) entre iodato (IO3-) e p-aminofenol (PAP) em meio ácido. O tempo de residência da zona de amostra no percurso analítico foi explorado a fim de favorecer a reação lenta e a frequência de amostragem para a melhoria do desempenho analítico. Foram selecionados 2 pulsos para inserção de amostra, 3 pulsos para reagente (PAP 0,25% (m/v) em HCl 0,025 mol L-1), 7 ciclos de amostragem, 200 pulsos de carregador (água), bolha de ar de 1 s (40 µL), reator de 70 cm (3 mm d.i.) e parada de fluxo de 480 s. Resposta linear foi observada entre 2,28x10-5 e 3,65x10-4 mol L-1, descrita pela equação A = 0,2443 + 2030 C, r = 0,997. Limite de detecção (99,7% de confiança), coeficiente de variação (n = 20) e frequência de amostragem foram estimados em 8,2x10-6 mol L-1, 0,42% e 70 determinações por hora, respectivamente. Houve consumo de 1,05 mg de PAP e geração de 0,70 mL de resíduos por determinação. As principais espécies concomitantes presentes na amostra não interferiram na determinação de iodato em concentrações até 8 vezes maiores que as usualmente encontradas. Estudos de adição e recuperação de iodato foram realizados pelo procedimento proposto, obtendo porcentagens de recuperação entre 88 e 104%. O procedimento analítico desenvolvido apresenta sensibilidade adequada para a determinação de iodato em amostra de sal de mesa e elevada frequência de amostragem quando comparado com procedimentos descritos na literatura

Reciclagem de resíduos eletroeletrônicos: um estudo cinético da lixiviação ácida de ferro de placas de circuito impresso de microcomputadores.

O aumento no consumo mundial de novos aparelhos eletroeletrônicos aliado à redução no tempo de vida útil destes equipamentos tem como principal consequência ao meio ambiente a geração de resíduos. No Brasil, com a instituição da Política Nacional de Resíduos Sólidos, criou-se a obrigatoriedade legal da responsabilidade dos fabricantes pela logística reversa dos equipamentos eletroeletrônicos, incentivando pesquisas para o desenvolvimento dos métodos de reciclagem e tratamento dos materiais descartados. O processo de lixiviação foi avaliado como alternativa à etapa de separação magnética presente nas atuais rotas hidrometalúrgicas para recuperação de metais valiosos de placas de circuito impresso. Para avaliar a composição das placas, foi realizado ensaio de dissolução em água régia. As amostras foram moídas e submetidas a ensaios de lixiviação com ácido sulfúrico nas concentrações de 1 e 2mol/L, às temperaturas de 75ºC, 85ºC e 95ºC, durante 24 horas. Com ácido sulfúrico 2mol/L a 95ºC, o tempo necessário para se obter 100% de extração do ferro foi de 2 horas. Nestas condições, não foi detectada a presença de cobre dissolvido. A cinética da reação é controlada por reação química e obedece a equação .=1(1)3. A energia de ativação aparente do processo equivale a 90kJ/mol.

Estudo do processo de absorção e dessorção de CO2 na solução aquosa de metildietanolamina e piperazina.

Estudou-se o processo de absorção e dessorção de CO2 em solução aquosa da mistura de metildietanolamina (MDEA) e piperazina (PZ). Os ensaios de absorção foram realizados numa coluna de parede molhada com promotor de película, e, os ensaios de dessorção num sistema de semibatelada, ambos em escala de laboratório. Os testes experimentais de absorção foram realizados a 298 K e pressão atmosférica, com vazão de gás (CO2 e ar atmosférico) de 2,2.10-4 m3 s-1 e as seguintes vazões de líquido: 1,0.10-6; 1,3.10-6 e 1,7.10-6 m3 s-1. O sistema de absorção foi caracterizado através da determinação da área interfacial, a, o coeficiente volumétrico de transferência de massa, kGa, e o coeficiente volumétrico global médio de transferência de massa, KGa. No caso dos ensaios de dessorção, estes foram realizados nas temperaturas de 353, 363 e 368 K, onde empregou-se uma solução carbonatada de 10% PZ-20% MDEA e uma corrente de ar atmosférico nas vazões de 1,1.10-5 m3 s-1 e 2,7.10-5 m3 s-1. Este sistema foi caracterizado através da determinação do coeficiente volumétrico global de transferência de massa, KLa. Os resultados experimentais da área interfacial mostram que este é função da vazão do líquido, sugerindo uma maior área de irrigação como o aumento desta, onde teve-se uma maior área de transferência de massa. O resultado do parâmetro, KGa, indica uma dependência da vazão de líquido, a qual está associada à variação da área interfacial e à dependência do parâmetro KG com o perfil das concentrações da MDEA e PZ ao longo da coluna. A partir da teoria do duplo filme e pelo conhecimento dos parâmetros KGa, a e kGa, estimou-se um parâmetro cinético-difusivo associado à fase líquida, (( ) ) . Os resultados experimentais mostram que esse parâmetro varia pouco com a vazão de líquido, indicando tratar-se de um processo independente da hidrodinâmica do líquido, característico de sistemas com reação rápida. A concentração das aminas e carbamatos, nos ensaios de absorção e dessorção, foi determinada através dos modelos de calibração obtidas pela técnica de espectroscopia no infravermelho. Nos ensaios de absorção, foram observados que a concentração de PZ teve uma variação considerável (4 a 5% massa massa-1), entanto que a de MDEA variou pouco (0,3 a 0,5% massa massa-1), sugerindo que o processo de absorção de CO2 na mistura MDEA-PZ é controlado principalmente pela PZ, e supõe-se que a MDEA tem um papel de receptor de prótons procedentes da reação entre a PZ e o CO2. Nos ensaios de dessorção, observou-se que esse processo é afetado pela temperatura, sendo que, em temperaturas perto da ebulição (372 K), a taxa de dessorção de CO2 é maior do que em temperaturas menores, em certa forma é devido à dependência da velocidade de reação química com a temperatura. Os resultados do parâmetro KLa indicam que este diminui em função da concentração de carbamato de PZ (por exemplo, na temperatura de 368 K, de 7,5.10-4 a 1,0.10-4 s-1), devido a que este componente é decomposto em altas temperaturas gerando o CO2 e as aminas, sugerindo uma diminuição na velocidade de dessorção de CO2. Assim também, os resultados experimentais do parâmetro KLa indicam que este aumenta ligeiramente com a vazão do gás.

NaOH and KOH for preparing activated carbons used in energy and environmental applications

Alkaline hydroxides, especially sodium and potassium hydroxides, are multi-million-ton per annum commodities and strong chemical bases that have large scale applications. Some of them are related with their consequent ability to degrade most materials, depending on the temperature used. As an example, these chemicals are involved in the manufacture of pulp and paper, textiles, biodiesels, soaps and detergents, acid gases removal (e.g., SO2) and others, as well as in many organic synthesis processes. Sodium and potassium hydroxides are strong and corrosive bases, but they are also very stable chemicals that can melt without decomposition, NaOH at 318ºC, and KOH at 360ºC. Hence, they can react with most materials, even with relatively inert ones such as carbon materials. Thus, at temperatures higher than 360ºC these melted hydroxides easily react with most types of carbon-containing raw materials (coals, lignocellulosic materials, pitches, etc.), as well as with most pure carbon materials (carbon fibers, carbon nanofibers and carbon nanotubes). This reaction occurs via a solid-liquid redox reaction in which both hydroxides (NaOH or KOH) are converted to the following main products: hydrogen, alkaline metals and alkaline carbonates, as a result of the carbon precursor oxidation. By controlling this reaction, and after a suitable washing process, good quality activated carbons (ACs), a classical type of porous materials, can be prepared. Such carbon activation by hydroxides, known since long time ago, continues to be under research due to the unique properties of the resulting activated carbons. They have promising high porosity developments and interesting pore size distributions. These two properties are important for new applications such as gas storage (e.g., natural gas or hydrogen), capture, storage and transport of carbon dioxide, electricity storage demands (EDLC-supercapacitors-) or pollution control. Because these applications require new and superior quality activated carbons, there is no doubt that among the different existing activating processes, the one based on the chemical reaction between the carbon precursor and the alkaline hydroxide (NaOH or KOH) gives the best activation results. The present article covers different aspects of the activation by hydroxides, including the characteristics of the resulting activated carbons and their performance in some environment-related applications. The following topics are discussed: i) variables of the preparation method, such as the nature of the hydroxide, the type of carbon precursor, the hydroxide/carbon precursor ratio, the mixing procedure of carbon precursor and hydroxide (impregnation of the precursor with a hydroxide solution or mixing both, hydroxide and carbon precursor, as solids), or the temperature and time of the reaction are discussed, analyzing their effect on the resulting porosity; ii) analysis of the main reactions occurring during the activation process, iii) comparative analysis of the porosity development obtained from different activation processes (e.g., CO2, steam, phosphoric acid and hydroxides activation); and iv) performance of the prepared activated carbon materials on a few applications, such as VOC removal, electricity and gas storages.

Algerian natural montmorillonites for arsenic(III) removal in aqueous solution

The adsorption of As(III) from aqueous solutions using naturally occurring and modified Algerian montmorillonites has been investigated as a function of contact time, pH, and temperature. Kinetic studies reveal that uptake of As(III) ions is rapid within the first 3 h, and it slows down thereafter. Equilibrium studies show that As(III) shows the highest affinity toward acidic montmorillonite even at very low concentration of arsenic. The kinetics of As(III) adsorption on all montmorillonites used is well described by a pseudo-second-order chemical reaction model, which indicates that the adsorption process of these species is likely to be chemisorption. Adsorption isotherms of As(III) fitted the Langmuir and Freundlich isotherm models well. The adsorption of As(III) is pH-dependent obtaining an optimal adsorption at pH 5. From the thermodynamic parameters, it is concluded that the process is exothermic, spontaneous, and favorable. The results suggest that M1, M2, and acidic-M2 could be used as low-cost and effective filtering materials for removal of arsenic from water.

Surface growth for molten silicon infiltration into carbon millimeter-sized channels: Lattice–Boltzmann simulations, experiments and models

The process of liquid silicon infiltration is investigated for channels with radii from 0.25 to 0.75 [mm] drilled in compact carbon preforms. The advantage of this setup is that the study of the phenomenon results to be simplified. For comparison purposes, attempts are made in order to work out a framework for evaluating the accuracy of simulations. The approach relies on dimensionless numbers involving the properties of the surface reaction. It turns out that complex hydrodynamic behavior derived from second Newton law can be made consistent with Lattice-Boltzmann simulations. The experiments give clear evidence that the growth of silicon carbide proceeds in two different stages and basic mechanisms are highlighted. Lattice-Boltzmann simulations prove to be an effective tool for the description of the growing phase. Namely, essential experimental constraints can be implemented. As a result, the existing models are useful to gain more insight on the process of reactive infiltration into porous media in the first stage of penetration, i.e. up to pore closure because of surface growth. A way allowing to implement the resistance from chemical reaction in Darcy law is also proposed.

Avaliação do efeito de escala no cálculo da perigosidade de incêndio florestal

Dissertação apresentada à Escola Superior Agrária do Instituto Politécnico de Castelo Branco para cumprimento dos requisitos necessários à obtenção do grau de Mestre em Sistemas de Informação Geográfica - Recursos Agro-Florestais e Ambientais.

Symmetry contaminations in reactive scattering through long-lived collision complexes

We extend our Lanczos subspace time-independent wave packet method [J. Chem. Phys. 116 (2002) 2354] to investigate the issue of symmetry contaminations for the challenging deep-well H + O-2 reaction. Our central objective is to address the issue of whether significant symmetry contamination can occur if a wavepacket initially possessing the correct O-O exchange symmetry is propagated over tens of thousands of recursive steps using a basis which does not explicitly enforce the correct symmetry, and if so how seriously this affects the results. We find that symmetry contamination does exist where the symmetry constraint is not explicitly enforced in the basis. While it affects individual resonances and the associated peak amplitudes, the overall shape of the more averaged quantities such as total reaction probabilities and vibrational branching ratios are not seriously affected. (C) 2004 Elsevier B.V. All rights reserved.