Tesi sul tema "Oxydation kinetics"
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Nengovhela, Nkhangweleni Ryneth. "Kinetics of the chemical and biological iron (II) oxydation". Diss., University of Pretoria, 2003. http://hdl.handle.net/2263/30337.
Testo completoBernardie, Raphaelle. "Oxydation du nickel dans le dioxyde de carbone et son revêtement par l'alumine sous plasma thermique". Thesis, Limoges, 2017. http://www.theses.fr/2017LIMO0037/document.
Testo completoA surface treatment process, developed for C40E steel substrates before alumina plasma spraying, has been extended to nickel substrates. As an alternative to sand blasting, nickel substrates were pre-oxidized under CO2, to create a protoxide nickel layer of controlled thickness. This oxide layer significantly increases the alumina coating adherence on nickel substrates. A kinetic study of nickel oxidation under CO2has been realized, in order to better control the nickel preoxidation. TEM investigations of alumina/nickel interfaces showed a heteroepitaxial growth of alumina on nickel monoxide, which justify the strong alumina coatings adhesion. This high adherence (around 105 MPa) has been measured using a modified tensile test (ASTM C633-13), specifically set up for pre-oxidized steel C40E substrates
Sanviemvongsak, Tom. "Oxydation et corrosion à haute température de superalliages à base de nickel issus de la fabrication additive". Thesis, Toulouse, INPT, 2020. http://www.theses.fr/2020INPT0066.
Testo completoThe resistance to isothermal and cyclic oxidation of alloy 718 produced by laser beam melting (LBM) and electron beam melting (EBM) was compared to that of wrought alloy 718 (AMS5662). Isothermal oxidation tests at 850 °C in air showed similar oxidation behaviour in terms of weight gain and intergranular oxidation for all three alloys. The effect of roughness on oxidation kinetics was quantified and it was shown that the intergranular oxidation kinetics follow Wagner's model of internal oxidation partially controlled by the volume diffusion of Al. Cyclic oxidation tests at 900 °C showed a much more adherent oxide layer for the wrought sample than for the LBM and EBM samples. This could be due to a higher amount of sulphur in solution in the AM samples. The resistance to cyclic hot corrosion and cyclic oxidation at 900 °C and 1100 °C of superalloys from AM (Alloy A, IN738, C1023 and Hastelloy X) were compared. The tests carried out on CIRIMAT’s cyclic oxidation rig and on Safran Helicopter Engine’s burner rig showed similar mass variation kinetics on the two rigs despite the very different atmospheres, except for alloys strongly affected by hot corrosion at 900 °C on the burner rig. The alloys most susceptible to cyclic hot corrosion have a lower Cr content (Alloy A) and/or a high Mo content (C1023), and exhibit intergranular oxidation (Alloy A, C1023 and 738). Overall, for the densest materials, the results do not show significant differences between the samples made by AM and the cast samples. These results validate the use of these AM Ni-based superalloys, as far as high temperature oxidation-corrosion is concerned
Ayadi, Hana. "Catalyseurs performants pour le traitement de la pollution organique azotée par Oxydation en Voie Humide Catalytique". Thesis, Lyon, 2017. http://www.theses.fr/2017LYSE1273/document.
Testo completoManganese oxide-based catalysts have been synthesized through different routes and evaluated in the Catalytic Wet Air Oxidation of ammonia. Such catalysts are active, selective towards molecular nitrogen and stable under the applied reaction conditions. Molecular nitrogen and nitrite are primary products. A detailed study of the impact of the operating conditions (manganese content, oxygen partial pressure, ammonia concentration, initial pH, and charge at the catalyst surface) on the catalytic performances was carried out. The selectivity in molecular nitrogen is optimum when i) the amount of catalyst is low, ii) the ratio nO2:nNH4+ is close to stoichiometry (˜ 0.75) and ii) the pH at the point of zero charge of the catalyst is neutral. Although strongly basic conditions (pH 13) improve the catalytic activity, the conversion nitrite to nitrate is inhibited and the selectivity in molecular nitrogen is degraded. From a kinetic point of view, the reaction order with respect to oxygen and ammonia are 0 and 1, respectively. The influence of the oxidation state of manganese (+II, +III and +IV) in the presence of bulk manganese oxides or ceria-supported manganese oxides indicated that the active site would consist of a pair of Mn(+III) and Mn(+IV). The reaction makes the active site and the oxides where manganese is initially present at a low oxidation state are markedly modified upon reaction. A synergy between manganese and cerium is also confirmed, involving the two Mn(+III)/Mn(+IV) and Ce(+III)/Ce(+IV) redox couples in a concerted way
Glikman, Jean-François. "Oxydation photo-thermique des copolymeres ethylene-acetate de vinyle, ethylene-acrylate d'ethyle, ethylene-acide acrylique". Clermont-Ferrand 2, 1987. http://www.theses.fr/1987CLF21050.
Testo completoKeller, Michel. "Development of a multi-scale approach using chemical kinetics and reactive force field molecular dynamics to model soot formation and oxidation". Thesis, Institut polytechnique de Paris, 2019. http://www.theses.fr/2019IPPAE005.
Testo completoIn the present study bond formation reactions between soot precursors and their role in the soot inception process is investigated. The soot precursors were generated in macroscopic detailed gas-phase kinetic calculations and according to certain criteria introduced in simulation boxes to model bond formation between soot precursor molecules with reactive force field molecular dynam-ics modeling. The impacts of temperature, fuel mixture and equivalence ratio have been investigated on the rate and structure of the newly formed molecules. The resulting structures compare well to previously reported experimental results. Furthermore, the bond formation rate between PAH is found to be linearly correlated with the temperature at which the PAH precursors are generated, while fuel and equivalence ratio do not have a direct impact on the reaction rate. The generated growth structures are lumped in: 1) directly linked, 2) aliphatically linked and 3) pericondensed polycyclic hydrocarbons. It is found that the amount of aliphatically linked PAH increases with the amount of aliphatic content of fuel mixture. Finally, a reaction scheme is presented displaying the most representative reaction pathways to form growth structures in each lumping class and their eventual intercon-version. The present work – that applies a combined approach of macroscopic gas-phase kinetic calculations and atomistic reactive force field simulations – offers a good alternative to obtain structural differences of nascent soot for a broad range of thermodynamic conditions and detailed reaction mechanisms for soot inception process
Wouters, Yves. "Oxydation thermique des métaux dans la vapeur d'eau : cas du nickel et du titane". Grenoble INPG, 1996. http://www.theses.fr/1996INPG0056.
Testo completoLailliau, Maxence. "Étude expérimentale et modélisation cinétique de la combustion de composés modèles de biocarburants : Détermination d'intermédiaires par spectrométrie de masse à photo-ionisation par rayonnement synchrotron". Thesis, Orléans, 2019. http://www.theses.fr/2019ORLE3096.
Testo completoWith the depletion of fossil fuel resources, the search for new alternatives such as biofuels produced from biomass has intensified. A wide variety of compounds can be produced by treating this biomass. Ethers are one of them and can be used as additives to conventional fuels or as fuel. To this end, it is necessary to have a better knowledge of the kinetics of the oxidation of these compounds which differ from conventional fuels by the presence of oxygen atoms in their structure, making the chemistry more complex. This thesis aims to develop kinetic mechanisms of the oxidation of simple ethers based on experimental data obtained in jet stirred reactor. The oxidation of four ethers at atmospheric pressure and high pressure (10 atm) was studied over a wide range of temperatures (450 - 1250 K) under different equivalence ratios (0.5 to 4). The mole fraction profiles of the reactants, products of combustion and main stable intermediates were measured by gas chromatography, infra-red spectrometry or photoionization mass spectrometry using synchrotron radiation. The results thus obtained then served as a basis for validating kinetic mechanisms modeling the oxidation of these species whose agreement with the measurements is globally satisfactory for compounds for which few studies are available
Hun, Nicolas. "Mécanismes et cinétiques d'oxydation du SiC à hautes températures et faibles pressions d'oxygène : application au gainage des réacteurs rapides à gaz". Thesis, Bordeaux 1, 2011. http://www.theses.fr/2011BOR14453/document.
Testo completoGas Fast Reactor (GFR) is one of the different Generation IV concepts under investigation for energy production. SiC/SiC composites are candidates of primary interest for a GFR fuel cladding use, thanks to good corrosion resistance among other properties. The mechanisms and kinetics of SiC oxidation under operating conditions have to be identified and quantified as the corrosion can decrease the mechanical properties of the composite. An experimental device has been developed to study the oxidation of silicon carbide under high temperature and low oxygen partial pressure. The results pointed out that not only parabolic oxidation, but also interfacial reactions and volatilization occur under such conditions. After determining the kinetics of each mechanism, as functions of oxygen partial pressure and temperature, the data are used for the modeling of the composites oxidation. The model will be used to predict the lifetime of the composite in operating conditions
Martinet, Christine. "Oxydation du silicium par plasma d'oxygène : Cinétiques de croissance et analyses physiques des couches". Université Joseph Fourier (Grenoble ; 1971-2015), 1995. http://www.theses.fr/1995GRE10162.
Testo completoMorajkar, Pranay P. "Application of laser photolysis coupled to time resolved optical detection methods to study the kinetics and spectroscopy of atmospherically relevant species". Thesis, Lille 1, 2012. http://www.theses.fr/2012LIL10063/document.
Testo completoOH and HO2 radicals play a vital role in many oxidation processes in the atmosphere. Thedegradation of volatile organic compounds under tropospheric conditions is induced by reaction withhydroxyl radicals followed by the subsequent chemistry of the initial OH oxidation products with O2.This thesis deals with the kinetic study of some of these atmospherically relevant reactions to betterunderstand their oxidation mechanisms using experimental techniques such as laser photolysiscoupled to detection by Laser Induced Fluorescence (LIF, for OH), continuous wave- Cavity RingdownSpectroscopy (cw-CRDS, for HO2) and time resolved UV spectroscopy (UV, forHexamethylbenzene-OH adduct). Different chemical systems have been studied using the above techniques: 1) the reaction ofHO2 radicals with formaldehyde, 2) the 248 nm photolysis of acetaldehyde and 3) the OH initiatedoxidation of Hexamethyl benzene. In addition to this, the spectroscopic application of cw-CRDStechnique and UV spectroscopy has been used for the measurement of absorption cross section ofselected absorption lines of formaldehyde in the near infrared region and Hexamethylbenzene-OHadduct in the UV region respectively
Malki, Abdelhafid. "Transformation électrocatalytique de produits issus de la biomasse : oxydation du fructose sur électrodes d'or et de platine". Poitiers, 1988. http://www.theses.fr/1988POIT2274.
Testo completoRidany, Manal. "Radicaux phénoxy impliqués dans la biosynthèse de la lignine : photo-génération en conditions de chimie en flux, formation et piégeage par la peroxydase de raifort". Electronic Thesis or Diss., Université de Lille (2022-....), 2023. http://www.theses.fr/2023ULILR084.
Testo completoLignin is the second most abundant biopolymer on the planet, although its creation mechanism and structures remain unknown. In this study, lignin and lignification were investigated using three different approaches. The first technique was developed to study the different linkages constitute lignin by radical coupling to form a dimer in presence of riboflavin as a photosensitizer under UV-light (395 nm), using continuous-flow photochemistry in micro-reactors. The second technique was devised to investigate the lignin interunit connections created by a simple lignin monomeric molecule, meaning immobilized enzymes that allowed for the simulation of the hydrophobic environment for lignin production. The third technique, which involved the use of alkyne-containing monolignols, allowed researchers to investigate the behavior of peroxidases during the oxidation of lignin monomers. It also enabled researchers to investigate lignification by analyzing the deactivation or identification of lignification peroxidases via click-chemistry processes.The first strategy consisted of the dimerization of different monomers of natural lignin. High dimerization yield of all coupled dimers was achieved including C-C, C-O or β-β' linkages. Immobilized enzymes were employed in the second strategy to investigate vanillin polymerization as a lignin template. After derivatization in either acidic or basic solution, the oxidation reaction of vanillin catalyzed by immobilized HRP resulted in the synthesis of polyvanillin with up to 15 units, primarily linked by carbon-oxygen bonds, as demonstrated by MALDI-FT-ICR studies. In the third strategy the modulation of HRP activity during oxidation of its substrates was explored utilizing modified monolignols bearing alkyne tags. In the presence of H2O2, HRP creates phenoxyl radicals during phenol oxidation. These radicals react with HRP, changing its heme or apoprotein via several routes. Coumaric acid-derived compounds inhibited HRP with varying effectiveness and specificity across the lignification probes utilized in this work. A kinetic analysis demonstrated that two probes, propargyl coumarate and methyl coumarate, were responsible for the full loss of HRP activity
Bataillou, Léa. "Modélisation de l'oxydation à haute température des alliages Ni-Cr". Thesis, Toulouse, INPT, 2019. http://www.theses.fr/2019INPT0104/document.
Testo completoThis thesis aims to better understand the kinetics and mechanisms of growth of chromia scales. This work is articulated in two complementary parts, on the one hand a modeling part which studies the kinetic aspects, and on the other hand an experimental part centered on the characterization of chromia growth understanding of the mechanisms. The purpose of the modeling part is to take into account the effect of diffusion short circuits in chromia the growth kinetics. The aim is to understand how a dual diffusion by both volume and grain boundaries can impact oxidation kinetics. This approach helps to define "good practices" for experimental oxidation kinetics interpretation. This modeling work was done using analytical models EKINOX numerical model. Several grain growth laws have been studied (parabolic growth, cubic growth, and grain size gradient). In addition, a parametric study was carried out to study the influence of grain growth rate on the growth kinetics of chromia. Calculations of oxidation kinetics for the various cases treated made it possible to conclude that the taking into account diffusion short circuits and their proportion evolution in time generates a deviation of the oxidation kinetics from a simple parabolic law. The rate of oxidation kinetics calculated varies with the growth rate of the oxide grains chosen as input data of the modelling. When kinetics are treated using a kinetic law involving a growth rate that changes over time, it is possible to determine the time range for which the evolution of oxide grain size significantly influences the oxidation kinetics. The oxidation kinetics modeled for the different cases were extrapolated using the methods conventionally used in high temperature oxidation, the log-log method and the local kp method. To extrapolate experimental kinetics, it is recommended to use the local kp method beforehand in order to know if the steady state has been reached. For the second experimental part, oxidation tests of the model alloy Ni-30Cr at 700°C in technical argon atmosphere were carried out. The chromia layer formed at the end of these tests was finely characterized in order to determine the oxidation mechanism as well as the kinetically limiting step. Under the conditions of the study, the nature of the oxide layer was identified as chromia. The oxidation kinetics follows a parabolic law after a transient stage that lasts about 3 hours. The stationary kp value has been determined. The mechanism of chromia growth has been identified as the diffusion of oxygen by the grain boundaries and the volume of the oxide. The morphology of the oxide layer indicates a faster oxidation over the grain boundaries of the metal. Finally, the chromine grains adopt a preferential orientation in the <0001> direction of the corundum structure. Chromium depletion profiles have been determined in the metal substrate and indicate a more pronounced chromium depletion at the grain boundaries of the metal. The type of semiconduction was determined in chromine and reveals an n-type semiconduction for an oxidation time of 7 h and an n-type and insulating semiconduction for an oxidation time of 50 h
Khidour, Lhoussaine. "Dégradation par oxydation catalytique, en milieu aqueux, d'effluents industriels soufrés volatils : étude de leur devenir dans des conditions atmosphériques simulées". Université Joseph Fourier (Grenoble ; 1971-2015), 1994. http://www.theses.fr/1994GRE10061.
Testo completoBrisebourg, Mathieu. "Corrosion active/passive de matériaux en présence de mélanges réactifs à très haute température". Thesis, Bordeaux 1, 2012. http://www.theses.fr/2012BOR14325/document.
Testo completoExperimental and theoretical studies have been carried out in order to obtain further knowledge and understanding of the corrosion behavior of silicon carbide under complex gas mixtures at very high temperatures. To that purpose, two original experimental methods based on Joule-heating have been designed for the in-situ following of SiC oxidation kinetics, and a model accounting for both heterogeneous kinetics and gas-phase transport phenomena has been developed thanks to a finite volume method. At high temperatures and low oxidant partial pressure, oxidation of SiC is « active » and associated with the formation of gaseous products and high degradation rates of the original materials, the reaction being rate-determined by species transport through a gaseous boundary layer. At low temperatures and high oxidant partial pressures, oxidation is « passive » and associated with the growth of a condensed oxide scale acting as a protecting diffusion barrier. An analytical study has been conducted in order to try and isolate the effects of the various physical and chemical phenomena involved during this passive oxidation, such as different growth mechanisms, volatilization or bubble formation, and quantify how temperature and gas composition influence them.An experimental study of the active/passive transition in the oxidation of SiC has been conducted under gas mixtures including one or two different oxidant species. Numerical simulation tools as well as new insights on oxidation mechanisms were used to analyze different predictive models of the active/passive transition and evaluate and understand the differences between these theoretical results and the ones obtained experimentally
Galant, françois Magda. "Étude cinétique de la réaction exothermique d'oxydation du sulfure de zinc". Vandoeuvre-les-Nancy, INPL, 1995. http://www.theses.fr/1995INPL037N.
Testo completoThion, Sébastien. "Etude expérimentale et numérique de la cinétique d'oxydation de biocarburants lignocellulosiques : cétones, éthers et lévulinates". Thesis, Orléans, 2016. http://www.theses.fr/2016ORLE2036/document.
Testo completoFuels produced from biomass are an interesting alternative to conventional fuels. Lignocellulosic biomass is indeed highly available and a wide variety of compounds can be obtained through its physico-chemical conversion. However, the structure of the fuels obtained from such processes involves oxygenated groups that make complicated the understanding of the oxidation chemistry. The work presented here is part of the 2G-CSAFE project, which aims at exploring the oxidation kinetics of these fuels. Chemical functions studied in this work include ketones, ethers and esters. The combination of two functions (as for levulinates) is also investigated. After a literature review aiming at collecting the information reported on the simplest compound of each group (acetone, dimethylether and methylformate), available studies on butanone, cyclopentanone, cyclohexanone, dibutyl-ether, butyl-formate and methyl levulinate are considered. The oxidation of these compounds is thereafter studied by numerical and experimental approaches. Ab initio calculations are performed to study the impact of the oxygenated groups on the structure and to derive rate constants for the major chemical pathways. Experiments are then carried out in a jet-stirred reactor for temperatures ranging from 450 to 1250 K, pressures of 1 or 10 atm and equivalence ratios from 0.5 to 2. The data obtained through these two approaches are finally used to develop and validate kinetic mechanisms. The overall agreement between experiments and simulations is satisfactory and results presented here can be used as a source of analogy for the future modeling of other similar oxygenated fuels
Legras, Laurent. "Etude en microscopie électronique à transmission des mécanismes d'oxydation interne d'aimants Fe-Nd-B". Rouen, 1994. http://www.theses.fr/1994ROUES052.
Testo completoMaunier-Morin, Marie-Christine. "Oxydation électrocatalytique de l'éthanol sur le platine et l'or : effets de structure, étude des mécanismes sur le platine par voltammétrie à potentiel programme et par spectroscopie infrarouge de réflexion". Poitiers, 1988. http://www.theses.fr/1988POIT2308.
Testo completoLebrun, Jean-Marie. "Etude des mécanismes d'oxydation et de frittage de poudres de silicium en vue d'applications photovoltaïques". Thesis, Grenoble, 2012. http://www.theses.fr/2012GRENI054/document.
Testo completoPhotovoltaic conversion is a promising energy resource. Bulk crystalline silicon technologies currentlydominate the market but suffer from high material losses that are highly detrimental to solar cellproduction costs. The challenge is then the elaboration of low cost silicon materials through a powdermetallurgy route. However, silicon sintering is dominated by grain coarsening mechanisms thatpreclude densification. Identification of these mechanisms is controversial in the literature. Especially,the role of the native oxide layer (SiO2) at the powder particle surfaces has remained unexplored yet.In this manuscript, the influence of the atmosphere on the reduction of this silica layer is studied usingthermogravimetric analysis. Reduction kinetics is consistent with a thermochemical model taking intoaccount the powder oxygen content, the partial pressure of oxidizing species and the pore morphologyof the sintered material. For the first time, experimental evidences support the idea that the silica layerinhibits grain coarsening. New sintering processes, involving a control of the silicon monoxideatmosphere (SiO(g)) surrounding the sample are then proposed and investigated in order to monitorthe stability of this layer. Stabilization of the silica layer at temperatures as high as 1300 – 1400 °C isshown to enhance densification although it retards lattice diffusion kinetics. In these conditions, thesintering behavior can be divided into two sequential stages marked by two shrinkage peaks on thedilatometric curves. This result is unusual for the sintering of single-phase materials. However, it canbe explained with help of a kinetic model using appropriate geometrical simplifications andobservations of the sample microstructures
Sbiai, Adil. "Matériaux composites à matrice époxyde chargée par des fibres de palmier dattier : effet de l’oxydation au tempo sur les fibres". Thesis, Lyon, INSA, 2011. http://www.theses.fr/2011ISAL0043/document.
Testo completoTo increase in value the agricultural waste products of the date palm tree -phoenix dactylifera l-, especially the fibers from the leaflets, their use as filler in polyepoxide matrix (dgeba / ipd) was investigated to prepare new bio-based composites. Our goal in the first part is to study the chemical modification of palm fiber by oxidation mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl (tempo). The kinetic and the topology of the reaction, as well as the characterization of fibres in rough and oxidized state, were also studied. An original kinetic model was proposed taking into account the heterogeneous character of this chemical reaction. The second part was devoted to study the kinetics and rheokinetic of the polymerization of dgeba / ipd with and without modified and unmodified fibers. This enabled to show the effect of the introduction of the date palm tree fibers (oxidized and non oxidized) on the composite formation. The thermal properties of the prepared composites were also investigated in this part of work. In the last part of this work, the mechanical properties of these composites were investigated and enabled to highlight the effect of the fibers oxidation on these properties. In addition, the effect of oxidation on the course of the injection during the rtm process (moulding by transfer of resin) was investigated. A positive effect of the oxidation of the fibers on the course of the injection was obtained and was attributed to the higher wettability of oxidized fibres by the resin
Okamba, Diogo Octavie. "Thermo-oxydation des polyamides". Thesis, Paris, ENSAM, 2015. http://www.theses.fr/2015ENAM0002/document.
Testo completoSome metal components of automotive engine are bound to be replaced by polyamide parts. However, despite their thermal resistance polyamides are sensitive to oxygen leading to thermal oxidation chain reactions responsible for their long-term properties. While durability is critical for polyamide users, only a few studies deal with the elaboration of a kinetic model capable of predicting polyamide lifetime (time to embrittlement) in contrary to polyolefins (especially polyethylene). This PhD thesis is a contribution to the understanding of aliphatic polyamide thermal degradation by considering chemical and physical aspects of oxidation process in order to build a kinetic model. Our approach is based on a multi-scale physicochemical characterization of oxidized PA11 film samples under air between 90 and 165 °C but also under oxygen pressure. The proposed kinetic model coupling oxidation and solid state polymerization is able to simulate the whole experimental data (hydroperoxides, carbonyls and molar mass changes). In a same time, an intrinsic criterion for embrittlement is assessed to predict lifetime whatever the exposure conditions. Finally, the influence of phenols and copper salts on the oxidation kinetic is investigated. A first kinetic model including the phenol stabilizing effect is capable of simulating the main observed trends for stabilized PA11 such as the appearance of the pseudo induction period which contributes to the significant improvement of PA11 durability
Wang, Bin. "Comportement à l'oxydation des verres métalliques massifs à base de zirconium". Phd thesis, Université Paris Sud - Paris XI, 2011. http://tel.archives-ouvertes.fr/tel-00769926.
Testo completoHiault, Florence. "Biocatalyse : aldolisation, acylation et oxydation - Applications synthétiques". Thesis, Paris 6, 2017. http://www.theses.fr/2017PA066515.
Testo completoThe research work presented in this manuscript pertains to the field of biocatalysis and some applications in organic synthesis. The main subject is the development of stereoselective synthetic methods allowing access to substituted alpha-amino beta-hydroxy acids. The use of a biocatalyst enabling the preparation of optically enriched alpha-amino beta-hydroxy acids in a single step from glycine by an aldol reaction, in the presence of pyridoxal phosphate, was investigated. Aliphatic, aromatic and heteroaromatic aldehydes could be successfully used as electrophilic partners in such reactions that allow an excellent control of the stereocenter created at the alpha position of the carbonyl group whereas moderate levels of diastereoselectivity were generally observed. The enzymatic kinetic resolution of acyclic or cyclic alpha,beta-dihydroxy esters, which are precursors of alpha-substituted alpha-amino beta-hydroxy acids, was also achieved by monoacylation in the presence of a lipase and an acyl donor. Independently, a one-pot sequence involving a biocatalytic oxidation was developed to access highly functionalized nitrogen containing compounds
De, Pauw Virginie. "Mécanismes de nitruration et d'oxydation du composé intermétallique Sm2 (Fe, Co)1#7 pour aimants permanents". Rouen, 1996. http://www.theses.fr/1996ROUES053.
Testo completoTogbe, Casimir. "Etude cinétique de l'oxydation de constituants de biocarburants et composés modèles : formation de polluants". Phd thesis, Université d'Orléans, 2010. http://tel.archives-ouvertes.fr/tel-00585394.
Testo completoErnault, Estève. "Thermo-oxydation de résines époxy/amine". Thesis, Paris, ENSAM, 2016. http://www.theses.fr/2016ENAM0060/document.
Testo completoEpoxy/amine resins are thermoset materials made of epoxy prepolymer and amine hardener. Those materials are used in several industrial applications, such as paint or to encapsulate electronics. The main goal of this work is to predict lifetime of three resins: DGEBA or DGEBU/cycloaliphatic diamine, DGEBA/aliphatic diamine, in thermo-oxidative environment. In order to achieve this, a multi scale study of the oxidation is done, at several temperatures (from 110°C to 200°C) and oxygen partial pressures (0,2 bars et 50 bars). At molecular scale, the formation of amides and carbonyls has been noticed. At macromolecular scale, chain scission has been observed in epoxy/cycloaliphatic diamine but in DGEBA/aliphatic diamine cross linking seems to be predominant. Those properties are directly related to functional properties: mechanical and dielectric break down appear later in DGEBA/aliphatic diamine than in epoxy/cycloaliphatic diamine. The extrapolation of life is possible thank to kinetic modelling, based on chemical mechanistic scheme. The resolution of this kinetic scheme allowed us to model all experimental data (concentration of oxidation products, chain scission and cross linking), either in homogenous oxidation and in thick samples (3 mm). Stresses induced by oxidation in a thick sample of DGEBA/cycloaliphatic diamine have been simulated thanks to Matlab ® and finite elements by Abaqus ®
Ramirez, Lancheros Helena. "Etude expérimentale et modélisation cinétique de l'oxydation, l'auto-inflammation et la combustion de carburants Diesel et bio-Diesel". Phd thesis, Université d'Orléans, 2012. http://tel.archives-ouvertes.fr/tel-00717701.
Testo completoSouchet, Raphaële. "Etude du rôle du fer et du manganèse lors de l'oxydation d'alliages cuivre-nickel industriels". Rouen, 1994. http://www.theses.fr/1994ROUES020.
Testo completoBennadji, Hayat. "Biodiesel : combustion des esthers éthyliques d'huiles végétales comme additifs au pétrodiesel". Thesis, Vandoeuvre-les-Nancy, INPL, 2010. http://www.theses.fr/2010INPL044N/document.
Testo completoAn increasingly popular biofuel is biodiesel, composed of a mixture of saturated and unsaturated fatty acid methyl or ethyl esters, with a long aliphatic main chain. This PhD dissertation provides a literature review concerning the origin of biodiesel, its manufacturing process, performance and emissions of diesel engines fueled with biodiesel, and the kinetics of oxidation of biodiesel. Efforts were made to highlight the main differences between methyl and ethyl esters while showing where further research needs to be developed or pursued. For these reasons, the autoignition of five esters were measured behind reflected shock tube: ethyl acrylate, methyl acrylate, ethyl crotonate, methyl crotonate, and ethyl butanoate. Detailed mechanisms for the oxidation of the five studied esters were automatically generated using the version of EXGAS software. In addition, the oxidation of ethyl butanoate as a model compound for Fatty Acid Ethyl Esters (FAEE) has been investigated in tubular plug flow reactor at atmospheric pressure over wide range of temperature (500-1200 K). The results consist of concentration profiles of the reactants, stable intermediates, and final products. The model was again validated satisfactorily by comparison between computed results and the generated experimental data
Contri, Boris. "Procédés d’assemblages céramique – métal : étude des couples Inconel®625 – Alumine et Titane Zirconium Molybdène (TZM) – Carbure de silicium". Electronic Thesis or Diss., Limoges, 2023. http://www.theses.fr/2023LIMO0093.
Testo completoThis work has for objective to present the results obtained for the ceramic-metal bonding by hot-pressing in two cases: Inconel®625 / Alumina and TZM / Silicon carbide. All the thesis take place according to the last results obtained for similar bonding, in the laboratory IRCER, by studying the feasibility of direct bonding and bonding after pre-oxidising the metal part. A part of this study is then dedicated to the oxidation behaviour of inconel®625 under CO2 using a thermobalance with a sample hot introduction. Using the oxidation kinetics obtained, the reaction mechanism is proposed and the conditions for the metal pre-oxidation determined.Then during the manuscript are presented the processes and the results obtained after variations of parameters such as temperature and the heat treatment time for the two couples of materials. The absence of inter-phase formation in the couple Inconel®625 / Alumina and the formation of a complex inter-phase in the couple TZM / Silicon carbide allow us to propose two studies with different metal-ceramic bonding.A last part is dedicated to the characterization and the understanding of the bonding obtained in each case. To explain the properties of the samples obtained we used scaning electron microscopy but also numerical simulation for the first couple Inconel®625 / Alumina and tensile test for the second couple TZM / Silicon carbide
Hamdani, Fethi. "Improvement of the corrosion and oxidation resistance of Ni-based alloys by optimizing the chromium content". Thesis, Lyon, INSA, 2015. http://www.theses.fr/2015ISAL0012/document.
Testo completoThis fundamental study is focused on the understanding of the influence of the chemical composition of Ni-based alloys on their corrosion and oxidation mechanisms. This work is not dedicated for a particular application. It is well known for instance that Ni-based alloys are susceptible to intergranular stress corrosion cracking (IGSCC) in primary water. Thus, Alloy600 (Ni-16Cr-9Fe), used in steam generator (SG) tubing, was replaced by higher chromium content material Alloy690 (Ni-30Cr-9Fe). This later shows a better resistance to IGSCC which may be linked to the growth of more protective oxide layer as chromium content is increased to 30 wt.%. The main goal of this study is to investigate: i) the influence of chromium content, ii) impact of iron addition on the corrosion and oxidation resistance of Ni-based alloys in primary water and superheated steam at 700°C. Furthermore, analytical approach in acidic solution is conducted at room temperature. This allowed to establish a relationship between alloying elements and physical properties of the oxide layers. For this purpose, Ni-xCr (14 ≤ x≤ 30 wt.%), Ni-xCr-8Fe (x=14,22 and 30 wt.%) model alloys and industrial material Alloy600 have been studied. To characterize the oxide scales, conventional technics were used: SEM, STEM, EDX, Potentiodynamic, EIS, Chronoamperometry, Mott-Schottky. Furthermore, steam oxidation kinetics was evaluated by means of weight gain measurements. To uncouple the effect of surface cold-work and the chemical composition of the base metal, mirror and electro polishing were carried out. In primary water, critical chromium content (20 wt.%), which corresponds to the minimum amount of chromium required to the transition from non-protective to protective and compact Cr-oxide layer, is determined. However, the analytical approach, using electrochemical technics, at room temperature elucidated the existence of optimum chromium content (26 wt.%) in terms of corrosion resistance. In superheat steam, oxidation kinetics and oxide scale characteristics showed the existence of optimum chromium content (24 wt.%) in terms of oxidation resistance. The corrosion and oxidation resistance is degraded as chromium content was increased more than optimal amount. Iron addition (8 wt.%) had a detrimental effect on the protectivess of the resulting oxide scales. Finally, this study showed that optimizing of chromium content is more appropriate method for enhancing corrosion and oxidation resistance, that increasing chromium content to high level is not necessary beneficial to those parameters. This work provides a useful knowledge to design new alternative materials. For this purpose, more investigations should be conducted to test other parameters such as: weldability, fabricability, thermal conductivity,etc
Pecheur, Dominique. "Evolution des précipités à base de zirconium lors de l'oxydation et de l'irradiation d'alliages de zirconium : impact sur la cinétique d'oxydation d'alliages de zirconium". Grenoble INPG, 1993. http://www.theses.fr/1993INPG0013.
Testo completoSalot, Raphaël. "Influence de la radiolyse sur la cinétique d'oxydation des alliages de zirconium en milieu R. E. P". Grenoble INPG, 1996. http://www.theses.fr/1996INPG0083.
Testo completoMoscu, Corcodel Alina. "Structural transformation under reaction conditions of supported PtSn nanoparticles characterized by in situ DRIFTS and kinetic modeling". Thesis, Lyon 1, 2015. http://www.theses.fr/2015LYO10177.
Testo completoThe selective oxidation of CO in the presence of a large excess of H2 (PROX) is considered as a crucial step in the purification of H 2 to be used in low-temperature fuel cells, which are clean sources of energy. The objective of this thesis was to better understand the reaction mechanisms taking place over promising catalysts based on Pt and Sn. Model Pt-Sn catalysts were prepared by a two-step method: (i) synthesis of metallic nanoparticules (NP) in a colloidal suspension followed by (ii) the deposition of these NPs onto a support. The first step of the method enabled to produce well-controlled Pt-Sn NPs in terms of size and composition. However, the NPs were partly destroyed during the deposition step followed by calcination, due to the reoxidation of Sn. The adsorption of CO followed by diffuse reflectance spectroscopy (DRIFTS) was used to characterize the nature of these solids following a reduction, which was able to regenerate an alloyed phase. The DRIFTS analysis enabled to discriminate between Pt in an alloyed phase and Pt on monometallic surfaces. The heat of CO adsorption measured by DRIFTS appeared to be much lower than that associated with the pure Pt phase. Surprinsingly, a segregation of Pt and Sn was observed under a CO/H2 mixture below 175°C. In situ analysis by DRIFTS of the PROX reaction indicated that the Pt-Sn alloy rapidly decomposed in the presence of O2, forming an intimate mixture of Pt and SnOx. No evidence of the presence of Pt -Sn alloyed phases could be obtained under PROX conditions, suggesting that the superior catalytic activity of the Pt –Sn materials were related to the Pt+SnOx mixture. A detailed PROX microkinetic model was developed over Pt+SnOx, based on those relevant to CO oxidation and PROX over pure Pt. This work epitomises the benefits in combining in situ spectroscopic study with kinetic modelling to better understand the structure of catalysts “at work” and reaction mechanisms
Zhang, Jie. "Synthèse de formaldéhyde par oxydation directe du méthane en microréacteur". Thesis, Vandoeuvre-les-Nancy, INPL, 2011. http://www.theses.fr/2011INPL060N/document.
Testo completoFormaldehyde is one of the world’s top organic intermediate chemicals. It is currently produced by a complex three-step process but a one-step process might require less energy. In this work, the direct gas phase partial oxidation of methane to formaldehyde has been studied through experiments and kinetic modeling. As formaldehyde is an intermediate in the sequential oxidation of methane, short residence times (<100 ms) have been considered in order to optimize its production. Thus, a quartz annular flow microreactor (annular space 0.5 mm wide), was chosen. The undertaken experiments consist of a systematic investigation of the effects of temperature (600-1000°C), residence time (20-80 ms), input composition XO2/XCH4 (0.5-15) and initial NO2 concentration (0-0.6%). Without NO2, the HCHO selectivity decreases with the increasing methane conversion. For a single pass operation, the best HCHO yield is 2.4% (950°C, 60 ms, XO2/XCH4 = 8). The addition of NO2 decreases the reaction initiation temperature by 300°C and it remarkably enhances the HCHO yield. The highest HCHO yield attains 9% (700°C, 30 ms, XO2/XCH4 =7) in the presence of NO2 (0.5%). For the reaction without NO2, the mechanism Gri-Mech 3.0 fits well the experimental results. For the reaction with NO2, by using the mechanism of Zalc et al. (2006) with some modifications, we obtained a good agreement between the experimental data and the model. The production and consumption flux analysis shows that the inter-conversion between NO2 and NO plays an important role in the reaction, because it continuously produces the reactive radicals OH• and it converts the radicals CH3• and CH3O2• to radicals CH3O•
Ayral, Catherine. "Elimination de polluants aromatiques par oxydation catalytique sur charbon actif". Thesis, Toulouse, INPT, 2009. http://www.theses.fr/2009INPT007G/document.
Testo completoThis work, on water treatment by catalytic Wet Air Oxidation (CWAO) using activated carbon (AC), aimed to study the interaction between oxidation-adsorption phenomena: how the oxidation of aromatic compounds on AC can modify its properties and specially its adsorption and oxidation characteristics (deactivation). Various commercials AC, and AC produced from activated sludge, have been characterized before and after oxidation by according methods such as textural characterization, elemental analysis (CHNSO), functional groups on carbon surfaces analysis, pH of the point of zero charge (pHpzc) analysis and thermogravimetric analysis (TGA); however, only their ash level was significantly different. In addition, the sludge based AC (SBAC) have a specific surface range of 90 to 265 m².g-1, which is lower than commercial AC, and with an ash level over 50%. Consequently they are less good adsorbents. However, the presence of metal, e.g. iron, has a positive affect on catalytic oxidation. The comparative study of catalytic oxidation with 4 commercial AC, show a severe deactivation (which increase with the pollutant concentration) on the first 3-4 utilizations before stabilization. The residual AC is clearly poor adsorbent. After stabilization, 2 commercials AC, only S23 and F22 CA, were studied on catalytic oxidation of phenol in term of apparent and intrinsic kinetics with including the diffusion effect in the model. The CWAO of 4 pure aromatic pollutants, and their various synthetic mixtures, showed mixing effects significantly: the most oxidation catalytic refractory pollutants were degraded rapidly when they mixed (e.g. 4-nitrophenol) but the kinetic was slow down for the pure pollutant whereas, the most oxidised pollutants, for pure solution, have an oxidation kinetic slower than when they mixed with others pollutants (e.g. Phenol, 4-chlorophenol). Therefore, the mixture tends to standardize from the individual behaviour. In conclude, the feasibility study of the oxidative regeneration process (AD-OX) was performed on industrial waste water. The regeneration AC as adsorbent is less limited than with mixtures of substituted phenols
Zekri, Mohamed el Mehdi. "Mise au point d'un réacteur photocatalytique pour la dépollution de l'eau". Thesis, Paris 11, 2012. http://www.theses.fr/2012PA112168/document.
Testo completoThe objective of this work is to develop a methodology dedicated to the design of a photocatalytic reactor for water purification. The principle is to go from photocatalysis as chemical process to photocatalysis as remediation method.Iit necessary for that to respond to two questions: - In such a system, what are the major physico-chemical phenomena? - Is there a way to predict the performance of our system?First of all, we tried to work on suspended photocatalysts to avoid a costly filtration step and technical difficulties. Thus, different types of titanium dioxide were deposited on substrates of different geometries.The first obtained medium was commercial titanium dioxide (P25 from Evonik and UV100 from Sachtleben) deposited on glass beads of 2 and 4 mm, inserted into an annular reactor illuminated by a single UV light source. The photoactivity of this media has been tested on phenol, the primary pollutant model chosen in this study. Hydroquinone and benzoquinone, two of its main degradation intermediates were also analyzed. The deposition efficiency has been estimated on different configurations. The results were satisfactory but did not reach a level comparable to that of photoactivity of TiO2 in suspend mode. Thus, we sought to improve the performance of our reaction system working on a support having a different geometry. Our choice fell on alumina foams perfectly matching the vacuum in the reactor. The same experimental protocol was applied to the foam. The results have shown photodegradation durability better than that obtained on glass beads and also the photoperformance exceeding that of titanium dioxide in suspend mode.To understand better the photoactivity of our media, we simulated by the Monte Carlo method the propagation of the light through the different photocatalysts (suspend mode or deposited). The results showed that the titanium dioxide suspension had the best absorption of light compared to TiO2 fixed on media. Nevertheless, absorption was located on a very small volume of the reactor and a better distribution of the light energy occurs in the alumina foams.The data obtained from these simulations, including the LVRPA "Local Volumetric Rate of Photon Absorption", allowed us to achieve the final step of our work, which is the construction of a predictive model of photocatalytic performance of the reaction system. Thus, we have introduced a term that reflects the probability that a photon absorbed by the photocatalyst gives a hydroxyl radical. The results obtained by our mathematical environment have shown a good correlation with experiments and helped us to draw some conclusions for the improving of our photocatalytic system
Pani, Fatos. "Hydrodynamique et transferts de matiere en reacteurs agites gaz-liquide et gaz-liquide-liquide : application oxydante du cuivre par lix 65n-hs". Paris, ENMP, 1987. http://www.theses.fr/1987ENMP0034.
Testo completoNowakowska, Milena. "Conversion thermique des goudrons provenant de la gazéification de la biomasse". Thesis, Université de Lorraine, 2014. http://www.theses.fr/2014LORR0092/document.
Testo completoTars are compounds limiting the optimal operation of thermochemical processes of biomass conversion. The reactions of these compounds were studied to better understand their formation, maturation and decay. The study of the decomposition of three model compounds from biomass was conducted with a jet stirred reactor. The studied compounds were anisole and guaiacol, representing the primary tars from lignin and the 5-methylfurfural, representing the primary tars from cellulose. The pyrolysis and the oxidation of these compounds were performed at atmospheric pressure, at a residence time of 2 s and at high dilution, and for a wide range of temperatures. The oxidation was carried out in stoichiometric conditions ([phi]= 1). Reaction products were quantified by gas chromatography and identified using mass spectrometry. Detailed kinetic mechanisms for the pyrolysis and oxidation (based on a combustion model for light aromatics) have been developed for each compound. Models predict well the conversion of reactants and the formation of the main products
Osowiecki, Raoul. "Evolution des additifs non polymériques des huiles moteur et influence sur leurs performances en service : aspects moléculaires et cinétiques". Thesis, Strasbourg, 2013. http://www.theses.fr/2013STRAF054.
Testo completoCurrent technologies used for diesel engines lead to an accelerated degradation of the non-polymeric additives from lubricants, such as antioxidants, antiwear, friction modifiers and detergency additives.Our work intends to identify the nature of the chemical modifications undergone by such additives during engine functioning. In this respect, an analytical protocol has been developed in order to investigate qualitatively and quantitatively these compound families in engine oils. Following this, the analytical methodology has then been used to study oils altered during engine bench tests and laboratory experiments. Thus, the evolution of the chemical composition, the nature of the degradation products and the alteration processes have been considered. Furthermore, kinetic models have been established for each family of additives.It appears from this study that the processes implied in the alteration of the additives during laboratory tests do not reproduce those existing while engine running. Further laboratory experiments are needed in order to develop tests mimicking more closely the conditions occurring during engine functioning
Olowe, A. Abiodun. "Corrosion aqueuse du fer en milieux sulfates : Mécanisme, cinétique et structures". Nancy 1, 1988. http://www.theses.fr/1988NAN10297.
Testo completoCadier, Muriel. "Nickelage chimique : analyse électrochimique en vue d'augmenter la vitesse de dépôt". Université Joseph Fourier (Grenoble), 1998. http://www.theses.fr/1998GRE10244.
Testo completoGarcia, Angela. "Kinetic modeling of oxygen absorption by unsaturated esters and linseed oil to be used as oxygen scavengers". Thesis, Paris, ENSAM, 2016. http://www.theses.fr/2016ENAM0001/document.
Testo completoOxygen scavengers (OS) are one of the most important technology of active packaging, because prevents oxidative degradation related with off-flavours, off-odours and microbial growth in food. Although active packaging has been proposed since 1970s, in developing countries with a large agricultural base, active packaging still remains unexplored both in terms of application and research, there is a lack of technical criteria on O2 scavenging films, labels, sheets, and trays. This PhD thesis is a contribution in the study of linseed oil as active ingredient for OS providing a kinetic characterization of its thermo-oxidation between 40°C and 110°C in atmospheres with different oxygen concentration. In the experimental approach, innovative application of TGA was proposed to study oxygen uptake capacity complemented by headspace and peroxide value measurements. The kinetic model, derived from a classic mechanistic scheme where initiation of thermo-oxidation results from decomposition of hydroperoxides, was capable to simulated linseed oil oxidation, and also oxygen absorptions of polypropylene films, of different thickness, containing 1% of linseed oil, with hypotheses of well dispersion of linseed oil in PP matrix, and oxygen diffusion governed by the PP matrix
Aurousseau, Marc. "Étude d'un procédé électrochimique de dépollution d'effluents gazeux contenant du dioxyde de soufre et des oxydes d'azote, par voie directe ou indirecte à l'aide du couple Redox Ce(III)/Ce(IV)". Vandoeuvre-les-Nancy, INPL, 1994. http://www.theses.fr/1994INPL138N.
Testo completoDumerval, Marie. "Effet des défauts d'implantation sur la corrosion des aciers inoxydables austénitiques en milieu primaire des réacteurs à eau pressurisée". Thesis, Grenoble, 2014. http://www.theses.fr/2014GRENI046/document.
Testo completoInternal parts of pressurized water reactor (PWR) vessels are often made of austenitic stainless steels (304L and 316L). These structural materials are exposed to an oxidizing medium under irradiation and mechanical stresses. Under these conditions, they can suffer damages by IASCC (Irradiation-Assisted Stress Corrosion Cracking). The first step in this cracking phenomenon is the initiation, which implies the breakdown of the passive layer. The nature and the structure of the oxide film formed on these steels are key factors in initiation of IASCC cracks. In this context, the objective of this work is first to better understand the oxidation mechanisms of stainless steels in primary medium and second to study the effects of irradiation induced defects on the oxide film formed on stainless steels in primary medium. Xenon ions and protons, were implanted in 316L-type austenitic stainless steel samples, respectively at an energy of 240 and 230 keV in order to simulate the irradiation defects. Implanted and non-implanted samples were exposed in a corrosion loop at 325°C to an aqueous medium containing 1000 ppm of boron, 2 ppm of lithium and 1,19.10-3 mol.L-1 of dissolved hydrogen. The samples were analyzed by TEM before and after exposure to primary medium in order to characterize both the defects generated by the implantation and the nature, structure, and morphology of the formed oxide. Comparing implanted and non-implanted samples has shown that the nature and the density of defects in the alloy subsurface played an important role on the composition (mainly on the content of Cr and Mo) and on the thickness of the inner layer. The study of the oxidation kinetics by coupling two ion beam analysis techniques (NRA and RBS) has revealed different behavior between the two types of samples: non-implanted and implanted. Tracer experiments (using D and 18O) were conducted to study the growth mechanism of the inner oxide layer and the associated transport mechanisms. The study of the oxygen and hydrogen transport through the inner layer and the underlying alloy, by SIMS and GD-OES, has resulted in writing a corrosion mechanism for austenitic stainless steels exposed to primary medium and linking this mechanism to hydrogen absorption in the alloy. Furthermore, the impact of implantation defects on these transport phenomena has been studied, highlighting the role of defects on oxide layer properties generating modification of the oxygen transport in the oxide scale. These results have helped to shed some light on the mechanism and kinetics involved in the formation of the oxide layer and on the hydrogen absorption in austenitic stainless steels exposed to primary medium and to point out the effect of implantation defects on the oxidation processes
Dausseins, Julie. "Étude du comportement à long terme d'accessoires en polyamide 66 utilisés dans les réseaux d'eau intérieurs". Thesis, Paris, ENSAM, 2015. http://www.theses.fr/2015ENAM0017/document.
Testo completoNowadays, chlorine dioxide is an alternative of chlorine for the disinfection of drinking water. Although its biocide ability is well known, scientific literature lacks of knowledge about its effects on organic materials in domestic water networks. The use of PA 66 for valves is quite recent: its long term behaviour is thus unknown. The aim of this study was to improve the knowledge of the interaction mechanisms between chlorine dioxide and a PA 66 matrix stabilized by blend of two antioxidants and reinforced by glass fibres, but also to propose a multi-scale method for the lifetime prediction of this composite material in service. First of all, a better description of the chemical reactions occurring within the material (oxidation, hydrolysis, polymer protection by antioxidants, chemical attack of polymer and antioxidants by disinfectant) has allowed elaborating a general degradation mechanistic scheme. Kinetic equations were derived from this mechanistic scheme for predicting the chemical changes, considering a heterogeneous distribution of antioxidants within the PA 66 matrix and taking into account most exposure conditions (water temperature, concentration in chemical reactants, time). Then, the aged material was tested in use conditions thanks to hydrostatic pressure experiments in order to identify its failure regime
Hakka, Mohammed Hichem. "Étude de l'oxydation en phase gazeuse de composants des gazoles et des biocarburants diesel". Thesis, Vandoeuvre-les-Nancy, INPL, 2010. http://www.theses.fr/2010INPL001N/document.
Testo completoBecause of the complexity of their compositions, the study of the oxidation of diesel and biodiesel fuels requires choosing model molecules (surrogates) representing the real mixtures. In this context, we have selected two molecules to represent the diesel fuel: n-decane, usually considered as model molecule of paraffin contained in diesel fuel, and n-hexadecane, molecule of reference for the estimation of the cetane number, and two molecules representing biodiesel fuel: methyl palmitate (C17H34O2, a saturated methyl ester) and methyl oleate (C19H36O2, an unsaturated methyl ester). The study of oxidation of these molecules has been conducted in a jet-stirred reactor, with an equivalence ratio of 1, temperatures between 550 and 1100 K, at atmospheric pressure and for a constant residence time of 1.5 sec. The formation of a large number of species has been observed which includes olefins, dienes, unsaturated methyl esters, cyclic ethers with different size of ring, ketones and aldehydes. Using two new versions of EXGAS software, detailed kinetic mechanisms for the oxidation of the studied molecules were generated and validated by comparaison with experiemental results. Finally, a comparison of the reactivity of n-decane, n-hexadecane, methyl palmitate and methyl oleate and amounts of formed products (including some pollutants) has been performed
Lavigne, André. "Oxydations cupro-catalysees des amines aliphatiques : etudes mecanistiques et applications synthetiques". Paris 6, 1987. http://www.theses.fr/1987PA066470.
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