Downhole acoustic data were acquired in very low-velocity, hydrate-bearing formations at five sites drilled on the Cascadia Margin during the Integrated Ocean Drilling Program (IODP) Expedition 311. P-wave velocity in marine sediments typically increases with depth as porosity decreases because of compaction. In general, Vp increases from ~1.6 at the seafloor to ~2.0 km/s ~300 m below seafloor at these sites. Gas hydrate-bearing intervals appear as high-velocity anomalies over this trend because solid hydrates stiffen the sediment. Logging-while-drilling (LWD) sonic technology, however, is challenged to recover accurate P-wave velocity in shallow sediments where velocities are low and approach the fluid velocity. Low formation Vp make the analysis of LWD sonic data difficult because of the strong effects of leaky-P wave modes, which typically have high amplitudes and are dispersive. We examine the frequency dispersion of borehole leaky-P modes and establish a minimum depth (approx 50-100 m) below the seafloor at each site where Vp can be accurately estimated using LWD data. Below this depth, Vp estimates from LWD sonic data compare well with wireline sonic logs and VSP interval velocities in nearby holes, but differ in detail due to local heterogeneity. We derive hydrate saturation using published models and the best estimate of Vp at these sites and compare results with independent resistivity-derived saturations.

One of the largest environmental threats believed to be facing us today is global warming due to the accumulation of green house gases (GHG). The concentrations of GHG in the atmosphere are a result of the net strength of different sinks and sources. Forests, in this context, are of particular interest because of their dual role as both sinks and sources. Most forests are net sinks for CO2 but others, such as drained forests, may be significant sources of both CO2 and N20. Consequently, it is essential to understand the fluxes of GHG between drained forests and the atmosphere in order to obtain accurate estimates of national GHG budgets. The findings reported in this thesis and the accompanying papers are based on dark chamber flux measurements of soil GHG fluxes and modelled annual net primary productions in five drained forest sites and two undrained sites situated on organic soil. Temporal variations in forest floor CO2, release could be explained, to a large extent, by differencies in temperature and groundwater level. The within-site spatial variation in soil GHG fluxes could only be explained to a very small extent by distance to tree stems. Much of the among-site variations in soil CO2 and CH4 release could be caused by differences in the mean annual groundwater table, while N20 emissions were strongly correlated to the carbon-to-nitrogen ratio of soil organic matter. Most poorly drained forested areas are probably net sinks for GHG as the CO2 uptake by trees more than compensates for the soil GHG emissions. However, the total drained forested area in Sweden was estimated to be a net source of GHG. The CO2 release from decomposition of soil organic matter stored before drainage was estimated to be substantial. Corresponding to 15% of the CO2 release from the consumption of fossil fuels. / <p>On the day of the public defence of the doctoral thesis the status of the articles I and II was: Conditionally accepted; article III was: Submitted and articles IV and V was: Manuscript. The title of article III was on the day of the public defence "Can the distribution of trees explain the spatial variation in N2O emissions from boreal forest soils?".</p>

This thesis explores the concept of displacement of sorbed methane and enhancement of methane recovery by injection of CO2 into coal, while sequestering CO2. The objective of this study was to investigate the diffusion behavior of San Juan Basin coal under single and competitive gas environments. The movement of gas in a coalbed reservoir starts in the coal matrix with diffusion towards the naturally occurring cleat network surrounding the matrix blocks. The gas production potential from coalbed reservoirs under different gas environments was, therefore, estimated by studying the diffusion behavior of the coal type. The results clearly showed that the rate of diffusion increases with decreasing reservoir pressure, the increase being exponential at low/very low pressure. As a final step, a simulation study was carried out using the experimental results to predict long-term gas production from coalbed reservoirs with and without CO2 injection. This was followed by a preliminary economic analysis in order to estimate the feasibility of enhanced recovery method by CO2 injection by calculating the net present value of a project with and without carbon credits. The results showed that it is possible to obtain significant improvement in methane recovery by CO2 injection. However, it becomes economically feasible only with carbon credits.

Made available in DSpace on 2016-06-02T20:34:23Z (GMT). No. of bitstreams: 1 3381.pdf: 10806200 bytes, checksum: 4024b6501ccd0766adc5fb20570e9760 (MD5) Previous issue date: 2010-11-26 / Universidade Federal de Sao Carlos / The Pd catalysts were prepared by wet impregnation method of the supports using an aqueous solution of palladium nitrate. (x)La2O3-Al2O3 carriers, with x = 0 to 20 wt %, were obtained by wet impregnation and sol gel methods. The supports and catalysts were characterized by N2 physisorption, X-ray diffraction, thermogravimetry, temperature-programmed reduction, Fourier transformed infrared spectroscopy of the adsorbed CO, X-ray photoelectron spectroscopy, transmission electron microscopy and dehydrogenation of cyclohexane reaction. The La2O3 presence on the carriers promotes a decrease in the Eaap and an increase in the TOFap and CH4 consumption values at 510 °C in the steam reforming of CH4 reaction. This increase in activity was related to Pdº*Pd&#61540;+-OLa interfacial species type formation. These interfacial species promote the formation of Pd° sites of higher electron density, most activ e to C-H bond cleavage, and are also likely to be oxidized by H2O and CO2 co-reagents, promoting the O * transfer to the metal surface, which act on the oxidation of chemisorbed carbon (C *). This fact makes that the determining steps process to be more balanced, promoting a greater of CH4 accessibility to the Pd surface. The nature of the supports has a high influence on the properties of Pd catalysts in autothermal reforming of CH4 reaction (ATR). The Pd/Al catalysts showed a high deactivation in the ATR, due to strong agglomeration of Pd crystallites during the time the catalyst was maintained at 800 °C. For La 2O3 containing catalysts, the Pdº*Pd&#61540;+-O-La interfacial species type formation promoted a higher activity and stability in ATR. However, was observed the formation of graphitic carbon type for Pd/12LaAl samples. The interfacial species promote both an increase in the CH4 activation rate, as in the removal of the C* species formed during CH4 activation. However, the CH4 activation and C* formation rate should be higher than diffusion or removal carbon rate. This effect coupled with the suitable particle size formed during the ATR tests results in a greater C* accumulation and growth in the filaments form. / Os catalisadores de Pd foram preparados por impregnação dos suportes utilizando-se uma solução aquosa de nitrato de paládio. Os suportes (x)La2O3-Al2O3, com x = 0 a 20 % em peso, foram obtidos pelos métodos de impregnação úmida e sol gel. Os suportes e catalisadores foram caracterizados por fisissorção de N2, difração de raios X, termogravimetria, redução à temperatura programada, espectroscopia na região do infravermelho do CO adsorvido, espectroscopia fotoeletrônica de raios X, microscopia eletrônica de transmissão e reação de desidrogenação do cicloexano. A presença de La2O3 nos suportes promove uma diminuição nos valores de Eaap e um aumento nos valores TOFap e consumo de CH4 a 510 °C na reação de reforma a vapor do CH4. A maior atividade se deve a formação de espécies interfaciais do tipo Pdº*Pd&#61540;+-O-La. Estas espécies favorecem a formação de sítios de Pd° de maior densidade eletrônica, mais ativos para a clivagem da ligação C-H, e também são susceptíveis de serem oxidadas pela H2O e CO2, promovendo a transferência de O* para a superfície do metal, a qual atuaria na oxidação do carbono quimissorvido (C*). Este fato faz com que as etapas determinantes do processo sejam mais equilibradas, promovendo uma maior acessibilidade do CH4 à superfície do Pd. A natureza do suporte tem uma alta influência nas propriedades dos catalisadores de Pd na reação de reforma autotérmica do CH4 (ATR). Os catalisadores de Pd/Al apresentaram uma alta desativação na ATR, devido ao acentuado crescimento dos cristalitos de Pd durante o tempo que o catalisador manteve-se a 800 °C. Para os catalisadores contendo La2O3, a formação de espécies interfaciais do tipo Pd0*Pd&#948;+O-La promoveu uma maior atividade e estabilidade na ATR. Todavia, verificou-se a formação de carbono do tipo grafítico para as amostras de Pd/12LaAl. A formação de espécies interfaciais promove um aumento tanto na velocidade de ativação do CH4, quanto na remoção das espécies de C* formado durante a ativação. No entanto, a taxa de ativação do CH4 e formação de C* devem ser superiores a taxa de difusão ou remoção deste carbono. Este fato somado ao tamanho de partícula adequado durante os ensaios de ATR resultam num maior acúmulo e crescimento de C* na forma de filamentos.

Dans cette thèse, des calculs ab initio et analytiques ont été effectués pour déterminer les surfaces d'énergie potentielle, de moment dipolaire et de polarisabilité des complexes de van der Waals faiblement liés CH4-N2 et C2H4-C2H4, pour une large gamme de distances intermoléculaires et de configurations, dans l’approximation des molécules en interaction rigides. Pour les calculs ab initio, la méthode CCSD(T), CCSD(T)-F12, ainsi que les méthodes moins couteuses MP2, MP2-F12, SAPT et DFT-SAPT ont été employées (pour toutes les méthodes,la base aug-cc-pVTZ a été utilisée). La correction BSSE a été prise en compte dans les calculs. Les calculs analytiques ont été réalisés dans le cadre de l'approximation classique aux grandes distances. Un modèle prenant en compte les effets d'échange dans la région des petits recouvrements des nuages électroniques des molécules en interaction a été suggéré pour décrire le moment dipolaire du complexe de van der Waals CH4-N2 sous une forme analytique, pour les grandes distances intermoléculaires incluant la région des puits de potentiel. Dans ce modèle, le moment dipolaire total est considéré comme résultant de la somme des contributions d'échange, d'induction et de dispersion. / In the present thesis both ab initio and analytical calculations were carried out for thepotential energy, dipole moment and polarizability surfaces of the weakly bound van der Waals complexes CH4-N2 and C2H4-C2H4 for a broad range of intermolecular separations and configurations in the approximation of the rigid interacting molecules. For ab initio calculations the CCSD(T), CCSD(T)-F12 and less computationally expensive methods such as MP2, MP2-F12, SAPT, DFT-SAPT were employed (for all methods the aug-cc-pVTZ basis set was used). The BSSE correction was taken into account during the calculations. The analytical calculations were performed in the framework of the classical long-range approximation. A model accounting the exchange effects in the range of small overlap of the electron shells of interacting molecules has been suggested to describe the dipole moment of the CH4-N2 van der Waals complexes in analytical form for large intermolecular separations including the range of potential wells. In this model the total dipole moment is considered to be the sum of exchange, induction and dispersion contributions.

Significant warming of Arctic and northern regions is ongoing and may greatly alter the carbon cycle of these regions. During the International Polar Year, an extensive study was carried out in the Eastern Canadian subarctic and Arctic in order to characterize CO2 and CH4 exchanges from these potentially sensitive ecosystems. The main objectives of this study were to identify the land cover and environmental factors leading to greatest CO2 and CH4 emissions in a highly heterogeneous subarctic landscape, to quantify interannual variability in the net ecosystem exchange of CO2 (NEE) in subarctic forest tundra and investigate the weather conditions that increase net uptake of CO2, and finally, to evaluate the general trends of mid-summer NEE along a latitudinal gradient spanning from 55° to the 72° north. At the landscape level, CO2 and CH4 exchanges showed large variability. Although CH4 emissions were greatest in wetlands, their areal coverage is small in the Kuujuarapik area and limited the influence of these CH4 sources. At the ecosystem level, large-scale atmospheric processes controlled growing season length and cumulative growing degree days which greatly influenced annual and seasonal NEE trends. The subarctic forest tundra near Kuujuarapik was a net source of CO2 in all 3 study years but the source strength was least with the greatest growing degree days while the length of the snow-free period appeared to be less important. Across a latitudinal gradient covering subarctic forest tundra to Arctic tundra, variations in summer NEE could be linked to surface organic carbon content with higher net CO2 uptake at sites with greater soil organic carbon. Warmer days tended to correlate with smaller daily net CO2 uptake (or greater net CO2 losses) but overall, warmer growing seasons reduced the net losses of CO2 on an annual basis. Carbon fluxes in Eastern Canadian subarctic and Arctic regions are highly variable in space and time but these observations help establish a baseline for future examinations of how these carbon exchanges may change with further warming.

[EN] In this work, a research on the durability of the hydrophilic behavior of films and nonwovens of polypropylene, PP (of different weights) using low-pressure discharge luminescence plasma technology with a mixture of gases CH4-O2 80:20, as well as on the improvement of technological properties (absorption) in such nonwovens for applications in the field of filtration has been carried out. Firstly, the effects of plasma on PP films with different treatment times have been studied in detail, optimizing previously the treatment power. The hydrophilic behavior variation (wettability) has been evaluated by studying the contact angles and surface energy with different measuring liquids. The variation of the chemical structure/composition (functionalization) of the surface has been studied for different times of treatment by attenuated total reflection Fourier transform infrared spectroscopy (FTIR-ATR) and the x-rays photoelectron spectroscopy (XPS). The evaluation of changes in the topography (morphology and surface roughness) has been done by scanning electron microscopy (SEM) and atomic force microscopy (AFM). As a complement, weight variation has been studied for obtaining information about deposition or etching of material on the film surface. Once the treatment time has been optimized, a study on the durability of the hydrophilic properties obtained has been carried out through the monitoring of changes in the contact angles, surface energy and the chemical composition/functionalization of film surface for different ageing times and in different conditions. Finally, the improvement of wettability on PP nonwoven substrates of different weights and its durability have been evaluated for different treatment times. At technological level, the improvement of the absorption and filtration properties of these substrates has been studied by measuring the absorption capacity and absorption time of the liquid as well as its propagation velocity. For the PP film, the increase of wettability depends on the power and treatment time with plasma CH4-O2 80:20, being 150 W and 60 seconds of treatment the optimal values. The main mechanism of this plasma is the surface functionalization by inclusion of active species (containing oxygen) by deposition of a thin layer of functionalized polymer (plasmapolymerisation) and slight modification of the topography (predominance of deposition against etching). In general, the hydrophobic recovery process (ageing) with CH4- O2 occurs to a lesser extent than in other gases (O2, N2, Ar, etc.) due to the presence of an organic component promotes the plasmapolymerisation and oxygen allows the formation of oxygen species. Improvement of treatment remains acceptable after three weeks of ageing at environmental conditions. Furthermore, ageing is more pronounced in more aggressive conditions (especially temperature), by promoting diffusion or movement of low molecular weight organic species as well as the reorganization of different polar groups towards the core of the material. In general, the mentioned plasma treatment causes a significant improvement in the wetting properties of different PP nonwoven substrates, regardless of the weight, and this is reflected through the improvement of various properties related to the absorption phenomena: absorption capacity and absorption velocity of the liquid and its wetting time. In this way, increases its absorption capacity and possibilities for using in filtration applications. Degradation marks or significant changes in surface morphology are not appreciated and the effects of the treatment are still at acceptable levels after three weeks of treatment. / [ES] En este trabajo,se ha llevado a cabo una investigación sobre la durabilidad del comportamiento hidrofílico de films y no tejidos de polipropileno,PP (de diferentes gramajes) mediante el empleo de tecnología de plasma de baja presión por descarga luminiscente con mezcla de gases CH4-O2 80:20,así como la mejora de propiedades tecnológicas (absorción) en dichos no tejidos para su aplicación en el campo de la filtración. En primer lugar,se han estudiado en detalle los efectos del plasma sobre los films de PP con diferentes tiempos de tratamiento optimizando inicialmente la potencia. La variación del comportamiento hidrofílico(humectabilidad) se ha evaluado mediante el estudio de los ángulos de contacto y energía superficial con diferentes líquidos de medida. La variación de la estructura/composición química (funcionalización) de la superficie se ha estudiado para diferentes tiempos de tratamiento mediante espectroscopía infrarroja por transformada de Fourier con reflectancia total atenuada(FTIR-ATR) y espectroscopía fotoelectrónica de rayos X(XPS). La evaluación de los cambios en la topografía (morfología y rugosidad) se ha realizado mediante microscopía electrónica de barrido (SEM) y microscopía de fuerza atómica (AFM). De forma complementaria,se ha estudiado la variación de peso para obtener información sobre la deposición o arranque de material en la superficie del film. Una vez optimizado el tiempo de tratamiento,se ha llevado a cabo un estudio sobre la durabilidad de las propiedades hidrofílicas obtenidas a través del seguimiento de los cambios en los ángulos de contacto, energía superficial y en la composición química/funcionalización de la superficie del film para diferentes tiempos de envejecimiento y en diferentes condiciones. Finalmente,se ha evaluado la mejora de la humectabilidad sobre substratos no tejidos de PP de diferentes gramajes a distintos tiempos de tratamiento así como su durabilidad. A nivel tecnológico,la mejora de las propiedades de absorción y filtración de dichos substratos se ha estudiado mediante la medida de la capacidad y el tiempo de absorción del líquido así como su velocidad de propagación. Para el film de PP, el incremento de humectabilidad es función del tiempo y potencia de tratamiento con plasma CH4-O2 80:20 siendo sus valores óptimos 150 W y 60 segundos de tratamiento. El mecanismo principal de actuación de dicho plasma es la funcionalización superficial por inserción de especies activas (que contienen oxígeno) por deposición de una fina capa de polímero funcionalizado (plasmapolimerización) y ligera modificación de la topografía (predominio de deposición frente a abrasión). De forma general, el proceso de recuperación hidrofóbica (envejecimiento) con CH4-O2 se produce en menor extensión que cuando se utilizan otros gases (O2,N2,Ar,etc.) debido a que la presencia de un componente orgánico favorece la plasmapolimerización y el oxígeno permite la formación de especies oxigenadas. La mejora del tratamiento se mantiene aceptable tras tres semanas de envejecimiento en condiciones ambientales. Asimismo,el envejecimiento es más acusado en condiciones más agresivas (especialmente de temperatura),por favorecer la difusión o movimiento de especies orgánicas de bajo peso molecular así como la reordenación de diferentes grupos polares hacia el interior. En general,el tratamiento con dicho plasma provoca una notable mejora en las propiedades humectantes de los diferentes substratos no tejidos de PP,independientemente del gramaje,y ésta queda reflejada a través de la mejora de varias propiedades ligadas a los fenómenos de absorción:capacidad y velocidad de absorción de líquido y tiempo de mojado. De esta forma,se incrementa su capacidad de absorción y las posibilidades de utilización en filtración. No se aprecian signos de degradación ni cambios significativos de morfología superficial y los efectos del tr / [CAT] En este treball, s'ha dut a terme una investigació sobre la durabilitat del comportament hidrofílic de films i no teixits de polipropilè, PP (de diferents gramatges) per mitjà de la utilització de tecnologia de plasma de baixa pressió per descàrrega luminiscent amb mescla de gasos CH4-O2 80:20 així com la millora de propietats tecnològiques (absorció) en aquests no teixits per a la seua aplicació en el camp de la filtració. En primer lloc, s'han estudiat en detall els efectes del plasma sobre els films de PP amb diferents temps de tractament optimitzant inicialment la potència. La variació del comportament hidrofílic (humectabilitat) s'ha avaluat per mitjà de l'estudi dels angles de contacte i energia superficial amb diferents líquids de mesura. La variació de l'estructura/composició química (funcionalització) de la superfície s'ha estudiat per a diferents temps de tractament per mitjà d'espectroscòpia infraroja per transformada de Fourier amb reflectància total atenuada (FTIR-ATR) i espectroscòpia fotoelectrónica de rajos X (XPS). L'avaluació dels canvis en la topografia (morfologia i rugositat) s'ha realitzat per mitjà de microscòpia electrònica d'agranat (SEM) i microscòpia de força atòmica (AFM). De forma complementària, s'ha estudiat la variació de pes per a obtindre informació sobre la deposició o arrancada de material en la superfície del film. Una vegada optimitzat el temps de tractament, s'ha dut a terme un estudi sobre la durabilitat de les propietats hidrofíliques obtingudes a través del seguiment dels canvis en els angles de contacte, energia superficial i en la composició química/funcionalització de la superfície del film per a diferents temps d'envelliment i en diferents condicions. Finalment, s'ha avaluat la millora de l'humectabilitat sobre substrats no teixits de PP de diferents gramatges a distints temps de tractament així com la seua durabilitat. A nivell tecnològic, la millora de les propietats d'absorció i filtració dels substrats s'ha estudiat per mitjà de la mesura de la capacitat i temps d'absorció del líquid així com la seua velocitat de propagació. Per al film de PP, l'increment de humectabilitat és funció del temps i potència de tractament amb plasma CH4-O2 80:20 sent els seus valors òptims 150 W i 60 segons de tractament. El mecanisme principal d'actuació d'aquest plasma és la funcionalització superficial per inserció d'espècies actives (que contenen oxigen) per deposició d'una fina capa de polímer funcionalitzat (plasmapolimerització) i lleugera modificació de la topografia (predomini de deposició enfront d'abrasió). De forma general, el procés de recuperació hidrofòbica (envelliment) amb CH4-O2 es produïx en menor extensió que quan s'utilitzen altres gasos (O2, N2, Ar, etc.) pel fet que la presència d'un component orgànic afavorix la plasmapolimerització i l'oxigen permet la formació d'espècies oxigenades. La millora del tractament es manté acceptable després de tres setmanes d'envelliment en condicions ambientals. Així mateix, l'envelliment és més acusat en condicions més agressives (especialment de temperatura), per afavorir la difusió o moviment d'espècies orgàniques de baix pes molecular així com la reordenació de diferents grups polars cap a l'interior. En general, el tractament amb aquest plasma provoca una notable millora en les propietats humectants dels diferents substrats no teixits de PP, independentment del gramatge, i ésta queda reflectida a través de la millora de diverses propietats lligades als fenòmens d'absorció: capacitat i velocitat d'absorció de líquid i temps de mullat. D'aquesta manera, s'incrementa la seua capacitat d'absorció i les possibilitats d'utilització en filtració. No s'aprecien signes de degradació ni canvis significatius de morfologia superficial i els efectes del tractament encara es mantenen en nivells acceptables després de tres setmanes del tractam / López Ferre, RM. (2015). ESTUDIO DE LA DURABILIDAD DEL PLASMA DE BAJA PRESIÓN CH4-O2 SOBRE FILMS Y NO TEJIDOS DE POLIPROPILENO. MEJORA DE LA ABSORCIÓN DE LOS NO TEJIDOS DE POLIPROPILENO PARA APLICACIONES EN FILTRACIÓN [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/58985 / TESIS

abstract: One strategic objective of the National Aeronautics and Space Administration (NASA) is to find life on distant worlds. Current and future missions either space telescopes or Earth-based observatories are frequently used to collect information through the detection of photons from exoplanet atmospheres. The primary challenge is to fully understand the nature of these exo-atmospheres. To this end, atmospheric modeling and sophisticated data analysis techniques are playing a key role in understanding the emission and transmission spectra of exoplanet atmospheres. Of critical importance to the interpretation of such data are the opacities (or absorption cross-sections) of key molecules and atoms. During my Doctor of Philosophy years, the central focus of my projects was assessing and leveraging these opacity data. I executed this task with three separate projects: 1) laboratory spectroscopic measurement of the infrared spectra of CH4 in H2 perturbing gas in order to extract pressure-broadening and pressure-shifts that are required to accurately model the chemical composition of exoplanet atmospheres; 2) computing the H2O opacity data using ab initio line list for pressure and temperature ranges of 10^-6–300 bar and 400–1500 K, and then utilizing these H2O data in radiative transfer models to generate transmission and emission exoplanetary spectra; and 3) assessing the impact of line positions in different H2O opacities on the interpretation of ground-based observational exoplanetary data through the cross-correlation technique. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2019

Autoignition and oxidation of two Methane (CH4) and Dimethyl Ether (CH3OCH3 or DME) mixtures in air were studied in shock tubes over a wide range of equivalence ratios at elevated temperatures and pressures. These experiments were conducted in the reflected shock region with pressures ranging from 0.8 to 35.7 atmospheres, temperatures ranging from 913 to 1650 K, and equivalence ratios of 2.0, 1.0, 0.5, and 0.3. Ignition delay times were obtained from shock-tube endwall pressure traces for fuel mixtures of CH4/CH3OCH3 in ratios of 80/20 percent volume and 60/40 percent volume, respectively. Close examination of the data revealed that energy release from the mixture is occurring in the time between the arrival of the incident shock wave and the ignition event. An adjustment scheme for temperature and pressure was devised to account for this energy release and its effect on the ignition of the mixture. Two separate ignition delay correlations were developed for these pressure- and temperature-adjusted data. These correlations estimate ignition delay from known temperature, pressure, and species mole fractions of methane, dimethyl ether, and air (0.21 O2 + 0.79 N2). The first correlation was developed for ignition delay occurring at temperatures greater than or equal to 1175 K and pressures ranging from 0.8 to 35.3 atm. The second correlation was developed for ignition delay occurring at temperatures less than or equal to 1175 K and pressures ranging from 18.5 to 40.0 atm. Overall good agreement was found to exist between the two correlations and the data of these experiments. Findings of these experiments also include that with pressures at or below ten atm, increased concentrations of dimethyl ether will consistently produce faster ignition times. At pressures greater than ten atmospheres it is possible for fuel rich mixtures with lower concentrations of dimethyl ether to give the fastest ignition times. This work represents the most thorough shock tube investigation for oxidation of methane with high concentration levels of dimethyl ether at gas turbine engine relevant temperatures and pressures. The findings of this study should serve as a validation for detailed chemical kinetics mechanisms.

L’étude de la dissociation de molécules poly-atomiques en surface est d’une importance à la fois fondamentale et industrielle. La compréhension du mécanisme et la dynamique réactionnelle sous-jacents représente un défi. Comme un système modèle, la dissociation de méthane sur la surface de nickel a fait l’objet de nombreuses études pour élucider les chemins de réaction et le transfert d’énergie parmi les différents degrés de liberté durant la réaction. La mode-spécifique ou liaison-spécifique réactivité pour la dissociation de CH4 sur Ni(111) et Ni(100) ont été mise en évidence récemment par des expériences de pointe du jet moléculaire. Jusqu’à présent, les études théoriques de la dynamique réactionnelle ont été effectuées avec un modèle simplifié dans lequel CH4 est décrit comme une molécule pseudo-diatomique. Le concept d’un groupe méthyle spectateur introduit dans un tel modèle impose des contraintes drastiques. Par exemple, l’indiscernabilité des quatre liaisons C-H de méthane est violée par le fait que la liaison C-H capable de se dissocier se singularise par rapport aux trois autres liaisons inertes. En réalité, n’importe quelle des quatre liaisons est susceptible de se dissocier. Par ailleurs, l’unique mode vibrationnel du modèle pseudo-diatomique ne ressemble à aucun des quatre modes vibrationnels principaux du méthane, qui décrivent tous des mouvements collectifs de plusieurs atomes. Lorsque tous les degrés de liberté sont pris en compte, la dimensionnalité de la surface de l’énergie potentielle pour CH4/Ni(111) est très élevée (15 degrés de liberté pour CH4 et certains degrés de liberté du substrat). Construire une surface de l’énergie potentielle fiable à une telle grande dimension est, en soi, un grand défi. A notre connaissance, ce défi n’a jamais été tenté auparavant pour quelconque réaction d’une molécule poly-atomique sur une surface métallique. En utilisant un champ de force réactif, nous avons développé, dans le présent travail, une surface de l’énergie potentielle qui prend en compte tous les 15 degrés de liberté de CH4 ainsi que ceux des 3 premières couches de NI(111). Des simulations de dynamique moléculaire ont été effectuées pour étudier la dynamique réaction de CH4 sur Ni(111) aussi bien dans son état fondamental vibrationnel que dans un état excité. Ces simulations ont permis de révéler des comportements dynamiques inattendus et très intéressants. / In the present work, we undertook a challenging task, i.e., construction a full-dimension potential energy surface (PES) for a benchmark poly-atomic molecular surface reaction, CH4/Ni(111), by using a reactive force field. Careful appraisal of the PES was made in order to establish the validity of the PES. The differences between the results for the transition state (dissociation barriers and structures) given by our PES and those by DFT calculations do not exceed 15%. The molecular dynamics simulation results obtained by using our PES are compared to experimental results for CH4 dissociation probability on Ni(111). For the vibrationally excited state, v3 (v=1, J=0), the agreement between our simulation results and the experimental ones is excellent. For the ground state, the sticking coefficient is somehow over-estimated because of the under-estimation of the dissociation barrier by about 150 meV with our reactive force field. Nevertheless, the overall agreement between simulation and experiment is pretty good. Within the help of the full-dimensional PES, we have extensively studied some important aspects of reaction dynamics, e.g., the effects of surface impact position, surface temperature, vibrationally excited state, rotationally excited states etc. For CH4 in ground state (v=0, J=0), the investigation of the effect of CH4 impact position shows that the top site is the most reactive one. The surface temperature strongly affects the reactivity of methane, especially in the region of the low incident energy near to the dissociation threshold, while in the high incident energy region, the effect is less important. For CH4 v3 (v=1, J=0), an important coupling between rotation and vibration is found. The rotation of CH4 can enhance its reactivity in the following way. In its ground state (v=0, J=0), CH4 does not rotate during its flight to the surface. In this case, only one of the two lowest C-H bonds pointing initially toward the surface can be cleaved while the two other bonds never break. In v3 (v=1, J=0) vibrational state, due to the rotation induced by vibration-rotation coupling, any of the four H atoms can be dissociated even if it forms a C-H bond which has an unfavorable initial orientation (i.e., pointing away from the substrate). The rotation of CH4 induced by vibration-rotation coupling near the substrate allows for bringing an unfavorable initial orientation of C-H bond to the right one required by a transition state (TS) during the adsorbate’s approaching to the substrate. As the enhanced reactivity of vibrationally excited molecules is concerned, the intuitively limpid and overwhelmingly accepted explanation is that the vibration-induced bond stretching helps bond breaking. Our simulation results show clearly that the vibration-induced CH4 rotation contributes an important part to the enhanced reactivity of a v3 (v=1, J=0) vibrationally excited CH4. A series of simulations to determine the sticking curves for CH4 in the vibrational ground state (ν=0) but excited to higher rotational levels (J=0-12) have also been performed. Due to its small level spacing, the lowest rotational excited states (J=1-3) of CH4 do not affect its reactivity on Ni(111) as observed experimentally. We found that rotation enhances significantly CH4 reactivity on Ni(111) with a deposited rotational energy amounting only to 12% of the dissociation barrier. Moreover, in a hypothetic simulation, we found also very striking evidences that rotation can even promote better dissociation of CH4 on Ni(111) than vibration. In a vibrationally excited CH4, its C-H bonds undergo alternate stretching and compressing and the latter hinders dissociation. In this case, the reactivity is inevitably modulated by vibration phase. However, the centrifugal force due to rotation tends always to stretch the C-H bonds for CH4 in rotationally excited states. / 多原子气相分子的分解，不仅在物理，化学及相关学科有着基本的重要性，而且可以促进工业进程，如工业制氢气。对其涉及的反应，即化学键的断裂与形成，在理解其反应机制和动力学上更是一项挑战。作为多原子气相-固相化学反应中最为典型的反应，甲烷分子在金属镍表面的分解，已经被广泛地研究从而理解其在动力学过程中的能量转化和反应路径。最近，选态分子束实验报道了有关甲烷在镍表面分解反应的重要特征，即模式选择性和化学键选择性。从理论角度来看，以前大多数理论研究都是基于一个简化模型，即将甲烷分子看成是一个赝双原子分子(CH4=RH,其中R=CH3)。在该简化模型中，将甲基团当做一个“spectator”会导致严重的限制性，如四个碳氢键的不可分辨性就被破坏。因为在简化模型中，只有一个可分解的碳氢键而其他三个碳氢键则被保护起来；而在实际的分解反应过程中，甲烷分子的任何一个碳氢化学键应该都有概率被分解掉。此外，在该赝双原子分子模型中，单键伸长振动模式不能类比于甲烷的四个基本振动模式，因为其每种基本振动模式都涉及多个原子的复合运动。如果不将甲烷处理成赝双原子分子，那么该体系（CH4/Ni(111)）的势能面的维度会很高，即甲烷的15 个自由度加上部分基地原子的自由度。欲建立一个如此高维度而且又可靠的势能面，本身就是一个值得挑战的研究任务。据我们所知，目前对多原子分子在金属表面反应的高维度势能面的报道几乎没有。在本论文中，我们运用键序反应力场（REBO），为体系CH4/Ni(111)，首次建立起一个全维度的势能面。该势能面的维度包含甲烷的15 个自由度和3 层基地原子的自由度。在经典分子动力学（和准经典分子动力学）模拟下，我们研究了甲烷处于基态和激发态时在金属表面的分解活性，并发现了一些非常有趣的结果。本论文包含以下六章：第一章：简单介绍了甲烷在过渡金属表面分解的最新进展。在选态分子束试验报道中，我们介绍了一些有关该反应的重要特征，如模式选择性，化学键选择性，表面温度效应，空间效应，旋转激发效应等。在理论工作方面，主要介绍了两个理论研究小组近期在简化模型下的一些量子动力学结果。第二章：对本文所运用的理论方法和近似做了基本的介绍。这些方法主要归纳于两类：i)电子结构计算；ii) 分子动力学模拟。我们重点介绍了这些方法和近似的特征。第三章：我们运用二阶矩近似力场(SMA)和键序反应力场(REBO)模拟了氢分子在金属钯表面的分解反应, 从而验证反应力场在模拟表面化学反应的适用性。该章讨论了在参数化反应力场时的一些影响因素，如有效数据库大小，不同排斥势以及长程作用项等，为对复杂体系的研究提供了有效的帮助。第四章：基于键序反应力场(REBO)，我们首次为CH4/Ni(111) 体系建立起一个全维度势能面(PES)。同时我们对该势能面(REBO(PES))做了全面评估，如比较势能面(REBO(PES))与DFT计算得到的过渡状态结构和与之对应的分解势垒，比较两者对于不同形式相互作用给出的势能变化等。此外，我们还直接模拟了甲烷在基态时的活性，其模拟结果与实验有着很好的符合度，从而进一步地说明了该势能面(REBO(PES))的可靠性。第五章：在全维度势能面下，我们深入地研究了甲烷处于不同状态时在镍表面分解的反应活性，即基态(v=0,J=0)，反对称振动态v3 (v=1,J=0)和旋转激发态(v=0,J=1-12)。对于基态的甲烷，我们定性并定量地分析了表面碰撞位置，表面温度对其分解概率的影响。对于反对称振动态的甲烷，我们观察到振动激发态的甲烷分子反应活性比基态甲烷的反应活性要大大地增强。究其根源在于，平动能量不易转换至旋转自由度，而振动能量则非常容易转入到旋转自由度。我们利用三个定量参数详细地阐述了这种振动耦合转动的重要性。此外，对于甲烷处于旋转激发态时，我们发现其激发状态非常有利于甲烷的分解，尽管其旋转能量只有分解势垒的12%。更为惊奇的是，对于甲烷分子而言，其旋转激发态比振动激发态更有利于其分解。其相应的物理解释是，对于振动激发的甲烷，它的碳氢键处于伸长与收缩的交替中，而后者却阻止其分解。对于旋转激发中的甲烷，其离心力一直促使碳氢键的伸长。第六章：总结和展望。我们总结了本文的主要结论以及给出一些将来需要进行的工作，如同位素效应等。