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.

Preignition is an ignition event that happens before it is expected to happen and, many times, where it is not expected to happen. Understanding this phenomenon is of great importance as it influences the design and operation of modern downsized boosted internal combustion engines. To gain a fundamental understanding of preignition, homogeneous reactors like shock tubes and rapid compression machines may be used to decipher the influence of fuel chemical structure, temperature, pressure, equivalence ratio and bath gas on preignition. In this thesis, a comprehensive study of the preignition tendency of various chemical systems is presented. Firstly, renewable fuels like ethanol, methanol and a surrogate of conventional fuels, n-hexane, are characterized by traditional shock tube techniques, such as the measurements of ignition delay times and pressure-time histories, to identify thermodynamic conditions which promote non-ideal ignition behavior. Preignition pressure rise and the expedition of measured ignition delay times are identified as the indicators of non-homogeneous combustion. It is shown that preignition effects are more likely to be observed in mixtures containing higher fuel concentration and that preignition energy release is more pronounced at lower temperatures. High-speed imaging was implemented to visualize the combustion process taking place inside the shock tube. End-wall imaging showed that low-temperature ignition may be initiated from an individual hot spot that grows gradually, while high-temperatures ignition starts from many spots simultaneously which consume the reactive mixture almost homogeneously. Simultaneous lateral and endwall imaging was implemented in both low- and high-pressure shock tube facilities. All tested fuels exhibited localized ignition at low temperatures, and methanol showed a higher propensity than ethanol to ignite far from the endwall. Imaging experiments were also performed in a rapid compression machine to understand preignition at lower temperatures. Herein, ethanol showed non-homogeneous ignition while iso-octane and diethyl ether exhibited homogeneous ignition at the low-temperature conditions. Various criteria for the onset of preignition were tested against experimental observations to propose an adequate predictor of non-ideal ignition phenomena in practical applications. A non-dimensional number, relating the ignition delay sensitivity and laminar flame speed of the mixtures, was found to be the best criterion to elucidate ignition regimes.

Energy demand is rapidly increasing due to the increase in population and rising living standards. Petroleum-based fuels account for the main source of energy consumed in the world. However, they are also considered to be the main source of the unwanted emissions to the atmosphere. In this context, chemical kinetic studies of combustion processes are essential for a better understanding of the underlying reactions and to achieve increased combustion efficiency and reduced pollutant emissions. In this study, ignition delay times, a global indicator of fuel reactivity, were measured for promising fuels for use in advanced combustion engines. Also, rate coefficients were measured for promising oxygenated hydrocarbons that can be used as additives to conventional fuels. Ignition delay time measurements of four primary reference fuel (PRF) blends, mixtures considered to be some of the simplest gasoline surrogates, were measured behind reflected shock waves to provide a large experimental dataset to validate PRF chemical kinetic models. The kinetic modeling predictions from four chemical kinetic models were compared with the experimental data. Ignition delay correlations were also developed to reduce the simulation cost of complicated models. Recently, naphtha, a low-octane distillate fuel, has been proposed as a low-cost refinery fuel. Likewise, a mid-octane blend which consists of low-octane (light and heavy naphtha) and high-octane (reformate) distillate fuels has been proposed to power gasoline compression ignition (GCI) engines. In this work, experimental and modeling studies were conducted on low and mid-octane distillate fuels (naphtha and GCI blend) and surrogate candidates to assess their autoignition characteristics for use in advanced internal combustion engines. Oxygenated molecules are considered to be promising additives to conventional fuels. Thermal decomposition of three esters (ethyl levulinate, ethyl propionate and diethyl carbonate ) and a five-member cyclic ketone (cyclopentanone) was investigated in this work. Laser absorption technique was employed to follow the reaction progress by measuring ethylene (C2H4) near 10.532 µm using a CO2 gas laser for the decomposition process of the three esters. The reaction progress of the decomposition of cyclopentanone was followed by monitoring CO formation using a quantum cascade laser at a wavelength near 4.556 µm.

Population growth and increasing standards of living have resulted in a rapid demand for energy. Our primary energy production is still dominated by fossil fuels. This extensive usage of fossil fuels has led to global warming, environmental pollution, as well as the depletion of hydrocarbon resources. The prevailing difficult situation offers not only a challenge but also an opportunity to search for alternatives to fossil fuels. Hence, there is an urgent need to explore environmentally friendly and cost-effective renewable energy sources. Oxygenates (alcohols, ethers) and ammonia are among the potential renewable alternative fuels of the future. This thesis investigates the combustion characteristics of promising alternative fuels and their blends using a combination of experimental and modelling methodologies. The studied fuels include ethanol, diethyl ether, dimethyl ether, dimethoxy methane, γ-valerolactone, cyclopentanone, and ammonia. For the results presented in this thesis, the studies may be classified into three main categories: 1. Ignition delay time measurements of ethanol and its blends by using a rapid compression machine and a shock tube. The blends studied include binary mixtures of ethanol/diethyl ether and ternary mixtures of ethanol/diethyl ether/ethyl levulinate. A chemical kinetic model has been constructed and validated over a wide range of experimental conditions. The results showed that a high-reactivity fuel, diethyl ether, may be blended with a low-reactivity fuel, ethanol, in varying concentrations to achieve the desired combustion characteristics. A ternary blend of ethanol/diethyl ether/ethyl levulinate may be formulated from a single production stream, and this blend is shown to behave similarly to a conventional gasoline. 2. Ignition delay time and flame speed measurements of ammonia blended with combustion promoters by utilizing a rapid compression machine and a constant volume spherical reactor. The extremely low reactivity of ammonia makes it unsuitable for direct use in many combustion systems. One of the potential strategies to utilize ammonia is to blend it with a combustion promoter. In this work, dimethyl ether, diethyl ether, and dimethoxy methane are explored as potential promoters of ammonia combustion. Chemical kinetic models were developed and validated in the high temperature regime by using flame speed data and in the low-to-intermediate temperature regime by using ignition delay time data. The results showed that even a small addition (~ 5 – 10%) of combustion promoters can significantly alter ammonia combustion, and diethyl ether was found to have the highest propensity to enhance ammonia ignition and flame propagation. Blends of combustion promoters with ammonia can thus be utilized in modern downsized turbo-charged engines. 3. Octane boosting and emissions minimization effects of next generation oxygenated biofuels. These studies were carried out using a cooperative fuel research engine operating in a homogenous charge compression ignition (HCCI) mode. The oxygenated fuels considered here include γ-valerolactone and cyclopentanone. The results showed that γ-valerolactone and cyclopentanone can be effective additives for octane boosting and emission reduction of conventional fuels. Overall, the results and outcomes of this thesis will be highly useful in choosing and optimizing alternative fuels for future transportation systems.

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Wastes have a real potential as being players in the energy mix of tomorrow. They can have a high heating value depending on their composition, which makes them good candidates to be converted into liquid fuel via pyrolysis. Among the different types of wastes, automotive residues are expected to rocket due to the increasing number of cars and the tendency to build cars with more and more polymers. Moreover, the existing regulations concerning the recycling of end-of-life vehicles become more and more stringent. Unconventional fuels such as those derived from automotive shredder residues (ASR) have a particular composition which tends to increase the amount of pollutants comparing with conventional fuels. Relying on alternative combustion modes, such as reactivity controlled compression ignition (RCCI), is a solution to cope with these pollutants. In RCCI, two types of fuels are burned simultaneously, namely a light fraction with a low reactivity, and a heavy fraction with a high reactivity. The heavy fraction governs the ignition as it is injected directly in the cylinder close to the end of compression. A variation of its ignition delay could impact the quality of the combustion. Nevertheless, this issue can be tackled by adjusting the injection timing. As long as the low reactivity fuel is concerned, such a solution cannot be adopted as its reactivity depends on the initial parameters (equivalence ratio, inlet temperature, exhaust gas recirculation ratio). However, if the fuel is too reactive, it could create knock that have a dramatic impact on the engine, leading to damages. Thus, being able to predict its features is a key aspect for a safe usage. Predicting methods exist but had never been tested yet with fuels derived from automotive residues. With petroleum products, usual prediction methods stand at three different levels: the chemical composition, the properties, and the reactivity in an appliance. The fuel is studied at these three levels. First, the structure gives a good overview of the fuel auto-ignition. For instance, aromatics tend to have higher ignition delay time (IDT) than paraffins. Second, the octane numbers are good indicators of the fuel IDT and of the resistance toward knock. Precisely, the octane numbers depict the resistance of a fuel towards an end-gas auto-ignition. Last, the IDT was studied in a rapid compression machine and a surrogate fuel was formulated. Surrogate fuels substitute real fuels during simulations because real fuels cannot be modelled by kinetic mechanisms due to their complexity.The existing methods to estimate the composition were updated to predict the n-paraffin, iso-paraffin, olefin, napthene, aromatic and oxygenate(PIONAOx) fractions. A good accuracy was achieved compared with the literature. This new method requires the measurement of the specific gravity, of the distillation cut points, of the CHO atom fractions, of the kinematic viscosity and of the refractive index.Two methods to predict the octane numbers were developed based on Bayesian inference, principal component analysis (PCA) and artificial neural network (ANN). The first is a Bayesian method which modifies the pseudocomponent (PC) method. It introduces a correcting factor which corrects the existing formulation of the PC method to increase its accuracy. A precision of more than 2% is achieved. The second method is based on PCA and ANN. 41 properties are studied among which reduced set of principal variables are selected to predict the octane numbers. 10 properties calculated only with the distillation cut points, the CHO atom fraction and the specific gravity were selected to accurately predict the octane numbers.Measurements of the IDT in a rapid compression machine (RCM) of a fuel produced from ASR were realized. They are the first measurements insuch a machine ever made. This provide experimental data to the literature. Moreover, these experimental data were used to formulate a surrogate fuel. Surrogate fuels can be used to realize simulations under specific conditions. The current thesis investigates fuels derived from ASR. It was showed that this fuel can be burnt in engines as long as their properties are carefully monitored. Among others, the IDT is particularly important. Nevertheless, additional experimental campaigns and simulations in engine are required in order to correctly assess all of the combustion features of such a fuel in an engine. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Dans un contexte de recherche de nouveaux modes de combustion propres, la combustionhomogène à allumage par compression HCCI s’inscrit comme une stratégie prometteuse.Cependant, cette combustion est limitée par un niveau élevé de bruit. La recherche descarburants permettant de relaxer cette contrainte constitue l’objectif global de cette étude.Particulièrement, on s’intéresse ici à l’influence de l’Indice de Cétane, de la volatilité et de lacomposition chimique des carburants sur les Délais d’Auto-Inflammation et sur les vitesses decombustion globales évaluées par les taux maximaux d’accroissement de la pression et dudégagement d’énergie apparente. L’étude se base dans un premier temps sur l’analyse d’essaissur banc moteur dans lesquels on a testé plusieurs carburants de synthèse à l’état pur et enmélange avec un Gazole conventionnel. Dans un deuxième temps des essais ont été préparés etréalisés sur Machine à Compression Rapide avec deux configurations en injection directe et enmélange homogène. Les essais Moteur ont permis d’orienter les paramètres expérimentauxciblés sur ce dispositif. D’autre part, pour étudier les régimes de combustion, des mesures dechamps de température locale ont été réalisées en mélange inerte (N2, CO2, Ar) par FluorescenceInduite par Laser avec un traceur Toluène. L’étude montre les limites des paramètres habituelspour caractériser l’adéquation carburant combustion HCCI et propose un nouveau critère basésur la dépendance des délais d’auto-inflammation à la température et à la richesse. / Advanced combustion strategies such as Homogeneous Charge Compression Ignition (HCCI)usually enable cleaner combustion with less NOx and Particulate Matter emissions comparedto conventional Diesel combustion. However, these strategies are difficult to implement due todifficulties related to combustion timing and burn rate control. Lately various studies have beenfocusing on extending advanced combustion functioning with new technologies and withsearching fuels properties to enable such combustion modes. This study is focused on theimpact of fuel Cetane Number, volatility and chemical composition on Ignition Delay, HeatRelease Rate and Pressure Rise Rate. The study is based on three complementary experiments.First, several synthetic fuel was tested on a research engine and analysis was focused on theHeat Release Rate. Secondly, experiments on a Rapid Compression Machine were performedto study the auto-ignition phenomena at homogeneous conditions with surrogate fuels (blendsof n-Heptane and Methyl-Cyclohexane). Analysis of the combustion regimes was supported bya study of the temperature field based on a Toluene Laser Induced Fluorescence experiment ininert (N2, CO2, Ar) mixture. Finally, the RCM was adapted to allow direct injection of fuel tostudy the auto-ignition at less homogeneous conditions. Results showed the limits of theconventional fuels properties to describe an adequate fuel formulation for the HCCI combustionmode. A new criterion based on the dependency of ignition delays to temperature and air fuelratio variations is proposed.

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