17 research outputs found

    An Experimental Study of the Flowfield on a Semispan Rectangular Wing with a Simulated Glaze Ice Accretion

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    Wind tunnel experiments were conducted in order to study the effect of a simulated glaze ice accretion on the flowfield of a semispan, reflection-plane, rectangular wing at Re = 1.5 million and M = 0.12. A laser Doppler velocimeter was used to map the flowfield on the upper surface of the model in both the clean and iced configurations at alpha = 0, 4, and 8 degrees angle of attack. At low angles of attack, the massive separation bubble aft of the leading edge ice horn was found to behave in a manner similar to laminar separation bubbles. At alpha = 0 and 4 degrees, the locations of transition and reattachment, as deduced from momentum thickness distributions, were found to be in good agreement with transition and reattachment locations in laminar separation bubbles. These values at y/b = 0.470, the centerline measurement location, matched well with data obtained on a similar but two dimensional model. The measured velocity profiles on the iced wing compared reasonably with the predicted profiles from Navier-Stokes computations. The iced-induced separation bubble was also found to have features similar to the recirculating region aft of rearward-facing steps. At alpha = 0 degrees and 4 degrees, reverse flow magnitudes and turbulence intensity levels were typical of those found in the recirculating region aft of rearward-facing steps. The calculated separation streamline aft of the ice horn at alpha = 4 degrees, y/b = 0.470 coincided with the locus of the maximum Reynolds normal stress. The maximum Reynolds normal stress peaked at two locations along the separation streamline. The location of the first peak-value coincided with the transition location, as deduced from the momentum thickness distributions. The location of the second peak was just upstream of reattachment, in good agreement with measurements of flows over similar obstacles. The intermittency factor in the vicinity of reattachment at alpha = 4 degrees, y/b = 0.470, revealed the time-dependent nature of the reattachment process. The size and extent of the separation bubble were found to be a function of angle of attack and the spanwise location. Three dimensional effects were found to be strongest at alpha = 8 degrees. The calculated separation and stagnation streamlines were found to vary little with spanwise location at alpha = 0 degrees. The calculated separation streamlines at alpha = 4 degrees revealed that the bubble was largest near the centerline measurement plane, whereas the tip-induced vortex flow and the model root-tunnel wall boundary-layer interaction reduced the size of the bubble. These effects were found to be most dramatic at alpha = 8 degrees

    Effect of In-Flight Ice Accretion on the Performance of a Multi-Element Airfoil

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    The effects of potential in-flight ice accretion on the aerodynamic performance of a multi-element high-lift airfoil have been investigated at moderate-to-high Reynolds numbers. The investigation was conducted in the Low Turbulence Pressure Tunnel (LTPT) at NASA Langley Research Center. Simulated ice shapes obtained from earlier testing in the Icing Research Tunnel (IRT) at NASA Lewis Research Center were used on all three elements of the multi-element configuration. Incremental performance effects due to the ice accretion are presented for both smooth and rough ice accretions. Reynolds number effects on the measured performance characteristics were also assessed. The present results confirm the importance of avoiding any ice accretions on the forward element of a lifting configuration

    CFD Vision 2030 Study: A Path to Revolutionary Computational Aerosciences

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    This report documents the results of a study to address the long range, strategic planning required by NASA's Revolutionary Computational Aerosciences (RCA) program in the area of computational fluid dynamics (CFD), including future software and hardware requirements for High Performance Computing (HPC). Specifically, the "Vision 2030" CFD study is to provide a knowledge-based forecast of the future computational capabilities required for turbulent, transitional, and reacting flow simulations across a broad Mach number regime, and to lay the foundation for the development of a future framework and/or environment where physics-based, accurate predictions of complex turbulent flows, including flow separation, can be accomplished routinely and efficiently in cooperation with other physics-based simulations to enable multi-physics analysis and design. Specific technical requirements from the aerospace industrial and scientific communities were obtained to determine critical capability gaps, anticipated technical challenges, and impediments to achieving the target CFD capability in 2030. A preliminary development plan and roadmap were created to help focus investments in technology development to help achieve the CFD vision in 2030

    Global age-sex-specific mortality, life expectancy, and population estimates in 204 countries and territories and 811 subnational locations, 1950–2021, and the impact of the COVID-19 pandemic: a comprehensive demographic analysis for the Global Burden of Disease Study 2021

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    Background: Estimates of demographic metrics are crucial to assess levels and trends of population health outcomes. The profound impact of the COVID-19 pandemic on populations worldwide has underscored the need for timely estimates to understand this unprecedented event within the context of long-term population health trends. The Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2021 provides new demographic estimates for 204 countries and territories and 811 additional subnational locations from 1950 to 2021, with a particular emphasis on changes in mortality and life expectancy that occurred during the 2020–21 COVID-19 pandemic period. Methods: 22 223 data sources from vital registration, sample registration, surveys, censuses, and other sources were used to estimate mortality, with a subset of these sources used exclusively to estimate excess mortality due to the COVID-19 pandemic. 2026 data sources were used for population estimation. Additional sources were used to estimate migration; the effects of the HIV epidemic; and demographic discontinuities due to conflicts, famines, natural disasters, and pandemics, which are used as inputs for estimating mortality and population. Spatiotemporal Gaussian process regression (ST-GPR) was used to generate under-5 mortality rates, which synthesised 30 763 location-years of vital registration and sample registration data, 1365 surveys and censuses, and 80 other sources. ST-GPR was also used to estimate adult mortality (between ages 15 and 59 years) based on information from 31 642 location-years of vital registration and sample registration data, 355 surveys and censuses, and 24 other sources. Estimates of child and adult mortality rates were then used to generate life tables with a relational model life table system. For countries with large HIV epidemics, life tables were adjusted using independent estimates of HIV-specific mortality generated via an epidemiological analysis of HIV prevalence surveys, antenatal clinic serosurveillance, and other data sources. Excess mortality due to the COVID-19 pandemic in 2020 and 2021 was determined by subtracting observed all-cause mortality (adjusted for late registration and mortality anomalies) from the mortality expected in the absence of the pandemic. Expected mortality was calculated based on historical trends using an ensemble of models. In location-years where all-cause mortality data were unavailable, we estimated excess mortality rates using a regression model with covariates pertaining to the pandemic. Population size was computed using a Bayesian hierarchical cohort component model. Life expectancy was calculated using age-specific mortality rates and standard demographic methods. Uncertainty intervals (UIs) were calculated for every metric using the 25th and 975th ordered values from a 1000-draw posterior distribution. Findings: Global all-cause mortality followed two distinct patterns over the study period: age-standardised mortality rates declined between 1950 and 2019 (a 62·8% [95% UI 60·5–65·1] decline), and increased during the COVID-19 pandemic period (2020–21; 5·1% [0·9–9·6] increase). In contrast with the overall reverse in mortality trends during the pandemic period, child mortality continued to decline, with 4·66 million (3·98–5·50) global deaths in children younger than 5 years in 2021 compared with 5·21 million (4·50–6·01) in 2019. An estimated 131 million (126–137) people died globally from all causes in 2020 and 2021 combined, of which 15·9 million (14·7–17·2) were due to the COVID-19 pandemic (measured by excess mortality, which includes deaths directly due to SARS-CoV-2 infection and those indirectly due to other social, economic, or behavioural changes associated with the pandemic). Excess mortality rates exceeded 150 deaths per 100 000 population during at least one year of the pandemic in 80 countries and territories, whereas 20 nations had a negative excess mortality rate in 2020 or 2021, indicating that all-cause mortality in these countries was lower during the pandemic than expected based on historical trends. Between 1950 and 2021, global life expectancy at birth increased by 22·7 years (20·8–24·8), from 49·0 years (46·7–51·3) to 71·7 years (70·9–72·5). Global life expectancy at birth declined by 1·6 years (1·0–2·2) between 2019 and 2021, reversing historical trends. An increase in life expectancy was only observed in 32 (15·7%) of 204 countries and territories between 2019 and 2021. The global population reached 7·89 billion (7·67–8·13) people in 2021, by which time 56 of 204 countries and territories had peaked and subsequently populations have declined. The largest proportion of population growth between 2020 and 2021 was in sub-Saharan Africa (39·5% [28·4–52·7]) and south Asia (26·3% [9·0–44·7]). From 2000 to 2021, the ratio of the population aged 65 years and older to the population aged younger than 15 years increased in 188 (92·2%) of 204 nations. Interpretation: Global adult mortality rates markedly increased during the COVID-19 pandemic in 2020 and 2021, reversing past decreasing trends, while child mortality rates continued to decline, albeit more slowly than in earlier years. Although COVID-19 had a substantial impact on many demographic indicators during the first 2 years of the pandemic, overall global health progress over the 72 years evaluated has been profound, with considerable improvements in mortality and life expectancy. Additionally, we observed a deceleration of global population growth since 2017, despite steady or increasing growth in lower-income countries, combined with a continued global shift of population age structures towards older ages. These demographic changes will likely present future challenges to health systems, economies, and societies. The comprehensive demographic estimates reported here will enable researchers, policy makers, health practitioners, and other key stakeholders to better understand and address the profound changes that have occurred in the global health landscape following the first 2 years of the COVID-19 pandemic, and longer-term trends beyond the pandemic

    Global burden and strength of evidence for 88 risk factors in 204 countries and 811 subnational locations, 1990–2021: a systematic analysis for the Global Burden of Disease Study 2021

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    Background: Understanding the health consequences associated with exposure to risk factors is necessary to inform public health policy and practice. To systematically quantify the contributions of risk factor exposures to specific health outcomes, the Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2021 aims to provide comprehensive estimates of exposure levels, relative health risks, and attributable burden of disease for 88 risk factors in 204 countries and territories and 811 subnational locations, from 1990 to 2021. Methods: The GBD 2021 risk factor analysis used data from 54 561 total distinct sources to produce epidemiological estimates for 88 risk factors and their associated health outcomes for a total of 631 risk–outcome pairs. Pairs were included on the basis of data-driven determination of a risk–outcome association. Age-sex-location-year-specific estimates were generated at global, regional, and national levels. Our approach followed the comparative risk assessment framework predicated on a causal web of hierarchically organised, potentially combinative, modifiable risks. Relative risks (RRs) of a given outcome occurring as a function of risk factor exposure were estimated separately for each risk–outcome pair, and summary exposure values (SEVs), representing risk-weighted exposure prevalence, and theoretical minimum risk exposure levels (TMRELs) were estimated for each risk factor. These estimates were used to calculate the population attributable fraction (PAF; ie, the proportional change in health risk that would occur if exposure to a risk factor were reduced to the TMREL). The product of PAFs and disease burden associated with a given outcome, measured in disability-adjusted life-years (DALYs), yielded measures of attributable burden (ie, the proportion of total disease burden attributable to a particular risk factor or combination of risk factors). Adjustments for mediation were applied to account for relationships involving risk factors that act indirectly on outcomes via intermediate risks. Attributable burden estimates were stratified by Socio-demographic Index (SDI) quintile and presented as counts, age-standardised rates, and rankings. To complement estimates of RR and attributable burden, newly developed burden of proof risk function (BPRF) methods were applied to yield supplementary, conservative interpretations of risk–outcome associations based on the consistency of underlying evidence, accounting for unexplained heterogeneity between input data from different studies. Estimates reported represent the mean value across 500 draws from the estimate's distribution, with 95% uncertainty intervals (UIs) calculated as the 2·5th and 97·5th percentile values across the draws. Findings: Among the specific risk factors analysed for this study, particulate matter air pollution was the leading contributor to the global disease burden in 2021, contributing 8·0% (95% UI 6·7–9·4) of total DALYs, followed by high systolic blood pressure (SBP; 7·8% [6·4–9·2]), smoking (5·7% [4·7–6·8]), low birthweight and short gestation (5·6% [4·8–6·3]), and high fasting plasma glucose (FPG; 5·4% [4·8–6·0]). For younger demographics (ie, those aged 0–4 years and 5–14 years), risks such as low birthweight and short gestation and unsafe water, sanitation, and handwashing (WaSH) were among the leading risk factors, while for older age groups, metabolic risks such as high SBP, high body-mass index (BMI), high FPG, and high LDL cholesterol had a greater impact. From 2000 to 2021, there was an observable shift in global health challenges, marked by a decline in the number of all-age DALYs broadly attributable to behavioural risks (decrease of 20·7% [13·9–27·7]) and environmental and occupational risks (decrease of 22·0% [15·5–28·8]), coupled with a 49·4% (42·3–56·9) increase in DALYs attributable to metabolic risks, all reflecting ageing populations and changing lifestyles on a global scale. Age-standardised global DALY rates attributable to high BMI and high FPG rose considerably (15·7% [9·9–21·7] for high BMI and 7·9% [3·3–12·9] for high FPG) over this period, with exposure to these risks increasing annually at rates of 1·8% (1·6–1·9) for high BMI and 1·3% (1·1–1·5) for high FPG. By contrast, the global risk-attributable burden and exposure to many other risk factors declined, notably for risks such as child growth failure and unsafe water source, with age-standardised attributable DALYs decreasing by 71·5% (64·4–78·8) for child growth failure and 66·3% (60·2–72·0) for unsafe water source. We separated risk factors into three groups according to trajectory over time: those with a decreasing attributable burden, due largely to declining risk exposure (eg, diet high in trans-fat and household air pollution) but also to proportionally smaller child and youth populations (eg, child and maternal malnutrition); those for which the burden increased moderately in spite of declining risk exposure, due largely to population ageing (eg, smoking); and those for which the burden increased considerably due to both increasing risk exposure and population ageing (eg, ambient particulate matter air pollution, high BMI, high FPG, and high SBP). Interpretation: Substantial progress has been made in reducing the global disease burden attributable to a range of risk factors, particularly those related to maternal and child health, WaSH, and household air pollution. Maintaining efforts to minimise the impact of these risk factors, especially in low SDI locations, is necessary to sustain progress. Successes in moderating the smoking-related burden by reducing risk exposure highlight the need to advance policies that reduce exposure to other leading risk factors such as ambient particulate matter air pollution and high SBP. Troubling increases in high FPG, high BMI, and other risk factors related to obesity and metabolic syndrome indicate an urgent need to identify and implement interventions

    Global age-sex-specific mortality, life expectancy, and population estimates in 204 countries and territories and 811 subnational locations, 1950–2021, and the impact of the COVID-19 pandemic: a comprehensive demographic analysis for the Global Burden of Disease Study 2021

    Get PDF
    BACKGROUND: Estimates of demographic metrics are crucial to assess levels and trends of population health outcomes. The profound impact of the COVID-19 pandemic on populations worldwide has underscored the need for timely estimates to understand this unprecedented event within the context of long-term population health trends. The Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2021 provides new demographic estimates for 204 countries and territories and 811 additional subnational locations from 1950 to 2021, with a particular emphasis on changes in mortality and life expectancy that occurred during the 2020–21 COVID-19 pandemic period. METHODS: 22 223 data sources from vital registration, sample registration, surveys, censuses, and other sources were used to estimate mortality, with a subset of these sources used exclusively to estimate excess mortality due to the COVID-19 pandemic. 2026 data sources were used for population estimation. Additional sources were used to estimate migration; the effects of the HIV epidemic; and demographic discontinuities due to conflicts, famines, natural disasters, and pandemics, which are used as inputs for estimating mortality and population. Spatiotemporal Gaussian process regression (ST-GPR) was used to generate under-5 mortality rates, which synthesised 30 763 location-years of vital registration and sample registration data, 1365 surveys and censuses, and 80 other sources. ST-GPR was also used to estimate adult mortality (between ages 15 and 59 years) based on information from 31 642 location-years of vital registration and sample registration data, 355 surveys and censuses, and 24 other sources. Estimates of child and adult mortality rates were then used to generate life tables with a relational model life table system. For countries with large HIV epidemics, life tables were adjusted using independent estimates of HIV-specific mortality generated via an epidemiological analysis of HIV prevalence surveys, antenatal clinic serosurveillance, and other data sources. Excess mortality due to the COVID-19 pandemic in 2020 and 2021 was determined by subtracting observed all-cause mortality (adjusted for late registration and mortality anomalies) from the mortality expected in the absence of the pandemic. Expected mortality was calculated based on historical trends using an ensemble of models. In location-years where all-cause mortality data were unavailable, we estimated excess mortality rates using a regression model with covariates pertaining to the pandemic. Population size was computed using a Bayesian hierarchical cohort component model. Life expectancy was calculated using age-specific mortality rates and standard demographic methods. Uncertainty intervals (UIs) were calculated for every metric using the 25th and 975th ordered values from a 1000-draw posterior distribution. FINDINGS: Global all-cause mortality followed two distinct patterns over the study period: age-standardised mortality rates declined between 1950 and 2019 (a 62·8% [95% UI 60·5–65·1] decline), and increased during the COVID-19 pandemic period (2020–21; 5·1% [0·9–9·6] increase). In contrast with the overall reverse in mortality trends during the pandemic period, child mortality continued to decline, with 4·66 million (3·98–5·50) global deaths in children younger than 5 years in 2021 compared with 5·21 million (4·50–6·01) in 2019. An estimated 131 million (126–137) people died globally from all causes in 2020 and 2021 combined, of which 15·9 million (14·7–17·2) were due to the COVID-19 pandemic (measured by excess mortality, which includes deaths directly due to SARS-CoV-2 infection and those indirectly due to other social, economic, or behavioural changes associated with the pandemic). Excess mortality rates exceeded 150 deaths per 100 000 population during at least one year of the pandemic in 80 countries and territories, whereas 20 nations had a negative excess mortality rate in 2020 or 2021, indicating that all-cause mortality in these countries was lower during the pandemic than expected based on historical trends. Between 1950 and 2021, global life expectancy at birth increased by 22·7 years (20·8–24·8), from 49·0 years (46·7–51·3) to 71·7 years (70·9–72·5). Global life expectancy at birth declined by 1·6 years (1·0–2·2) between 2019 and 2021, reversing historical trends. An increase in life expectancy was only observed in 32 (15·7%) of 204 countries and territories between 2019 and 2021. The global population reached 7·89 billion (7·67–8·13) people in 2021, by which time 56 of 204 countries and territories had peaked and subsequently populations have declined. The largest proportion of population growth between 2020 and 2021 was in sub-Saharan Africa (39·5% [28·4–52·7]) and south Asia (26·3% [9·0–44·7]). From 2000 to 2021, the ratio of the population aged 65 years and older to the population aged younger than 15 years increased in 188 (92·2%) of 204 nations. INTERPRETATION: Global adult mortality rates markedly increased during the COVID-19 pandemic in 2020 and 2021, reversing past decreasing trends, while child mortality rates continued to decline, albeit more slowly than in earlier years. Although COVID-19 had a substantial impact on many demographic indicators during the first 2 years of the pandemic, overall global health progress over the 72 years evaluated has been profound, with considerable improvements in mortality and life expectancy. Additionally, we observed a deceleration of global population growth since 2017, despite steady or increasing growth in lower-income countries, combined with a continued global shift of population age structures towards older ages. These demographic changes will likely present future challenges to health systems, economies, and societies. The comprehensive demographic estimates reported here will enable researchers, policy makers, health practitioners, and other key stakeholders to better understand and address the profound changes that have occurred in the global health landscape following the first 2 years of the COVID-19 pandemic, and longer-term trends beyond the pandemic. FUNDING: Bill & Melinda Gates Foundation

    An Experimental Study of the Flowfield on a Semispan Rectangular Wing With a Simulated Glaze Ice Accretion

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    252 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1993.The effect of a simulated glaze ice accretion on the flowfield of a semispan, reflection-plane, rectangular wing at Re = 1.5 million and M = 0.12 was investigated. A laser Doppler velocimeter was used to map the flowfield on the upper surface of the model in both the clean and iced configurations at α\alpha = 0, 4, and 8 degrees angle of attack.At low angles of attack, the massive separation bubble aft of the leading edge ice horn behaved in a manner similar to laminar separation bubbles. At α\alpha = 0\sp\circ and 4\sp\circ, the locations of transition and reattachment, as deduced from momentum thickness distributions, were in good agreement with transition and reattachment locations in laminar separation bubbles. These values at y/b = 0.470, the centerline measurement location, matched well with data obtained on a similar but 2-D model. The measured velocity profiles on the iced wing compared reasonably with the predicted profiles from Navier-Stokes computations.The iced-induced separation bubble also had features similar to the recirculating region aft of rearward-facing steps. At α\alpha = 0\sp\circ and 4\sp\circ, reverse flow magnitudes and turbulence intensity levels were typical of those found in the recirculating region aft of rearward-facing steps. The calculated separation streamline aft of the ice horn at α\alpha = 4\sp\circ, y/b = 0.470 coincided with the locus of the maximum Reynolds normal stress. The maximum Reynolds normal stress peaked at two locations along the separation streamline. The location of the first peak-value coincided with the transition location, as deduced from the momentum thickness distributions. The location of the second peak was just upstream of reattachment, in good agreement with measurements of flows over similar obstacles. The intermittency factor in the vicinity of reattachment at α\alpha = 4\sp\circ, y/b = 0.470, revealed the time-dependent nature of the reattachment process.The size and extent of the separation bubble were a function of angle of attack and spanwise location. Three dimensional effects were strongest at α\alpha = 8\sp\circ. The calculated separation and stagnation streamlines varied little with spanwise location at α\alpha = 0\sp\circ. The calculated separation streamlines at α\alpha = 4\sp\circ revealed that the bubble was largest near the centerline measurement plane, whereas the tip-induced vortex flow and the model root-tunnel wall boundary layer interaction reduced the size of the bubble. These effects were most dramatic at α\alpha = 8\sp\circ.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD

    Mécanismes de déshydrogénation du méthyl-cyclohexane catalysée par des agrégats sub-nanométriques de platine supportés sur alumine gamma : études couplées DFT, cinétique expérimentale et modélisation cinétique

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    Le reformage catalytique vise à transformer les naphtas en aromatiques à haut indice d'octane et à produire simultanément du dihydrogène. Le catalyseur utilisé est composé d’agrégats sub-nanométriques à base de platine hautement dispersées sur un support d’alumine-gamma dont le comportement en réaction pose de nombreuses questions. Nous étudions expérimentalement et théoriquement une réaction modèle qui sonde les sites métalliques, la déshydrogénation du methyl-cyclohexane en toluène. Une compréhension détaillée à l'échelle atomique des mécanismes impliqués et des paramètres cinétiques est nécessaire. Nous avons mise en œuvre des calculs DFT (PBE et PBE-dDsC) sur un modèle pertinent Pt13/alumine-gamma, afin de déterminer les intermédiaires, les états de transition et leurs enthalpies libres. Le mécanisme a été exploré via des étapes séquentielles de rupture des liaisons C-H. Une reconstruction des agrégats se produit le long du chemin réactionnel, mettant en évidence sa fluctionalité (confirmée par dynamique moléculaire). Les enthalpies libres d’activation de la rupture C-H, de migration d’hydrogène et de reconstruction de l’agrégat ont été systématiquement déterminées à T=625 K. L'enthalpie libre la plus élevée (ΔrG‡=95 kJ/mol) est trouvée pour la troisième rupture de liaison C-H sur le methyl-cyclohexène. L'intermédiaire le plus stable est le produit adsorbé {toluène+H2}. Cependant, d’autres étapes de rupture C-H ou de désorption du toluène sont compétitives. Les constantes de vitesse des étapes élémentaires obtenues par DFT sont introduites dans 8 modèles cinétiques différents de type Langmuir-Hinshelwood (LH). La nature de l'étape déterminante de la vitesse a été choisie en fonction des constantes de vitesse de chaque étape élémentaire individuelle, ou de la prise en compte de séquences d’étapes limitantes, grâce à une analyse de type « energetic span ». Nous avons finalement expérimentalement réalisé des tests catalytiques sur Pt/γ-alumine (0.3 wt% Pt) à différentes températures, temps de contact, pressions partielles d’hydrogène et de méthylcyclohexane, pour obtenir des données cinétiques expérimentales. L'enthalpie d'activation apparente de 196 kJ/mol calculée par l’un des meilleurs modèles LH (3ème rupture C-H limitante) est proche de l’expérience (195 kJ/mol). De plus, l’évolution des vitesses de réaction en fonction des pressions partielles d'hydrogène et de méthylcyclohexane est discutée au regard de l’expérience et des modèles. Même si les tendances sont recouvrées par les modèles, des écarts théorie-expérience sont mis au jour, ce qui ouvre des perspectives vers une modélisation microcinétique future.Catalytic reforming aims at transforming naphta into high octane aromatics and producing simultaneously dihydrogen. The catalyst used is composed of platinum-based sub-nanometric clusters highly dispersed on a gamma-alumina support which behavior under reaction conditions is the subject of numerous questions. We investigate experimentally and theoretically one model reaction probing the metal sites, the dehydrogenation of methyl-cyclohexane into toluene. A detailed atomic scale understanding of the mechanisms involved, and their related kinetic parameters, is required. We undertook DFT calculations with PBE and PBE-dDsC functionals on a relevant Pt13/γ-alumina model, in order to determine the intermediates, transition states and their free energies. The reaction mechanism was explored by assuming sequential C-H breaking steps. Reconstructions of the cluster and hydrogen migrations occur along the reaction pathway, highlighting its high fluctionality (also confirmed by molecular dynamics). Free energies of activation for C-H bond breaking, H migration and cluster’s reconstruction were systematically determined at T=625 K. The highest activation Gibbs free energy (ΔrG‡=95 kJ/mol) is found for the third C-H bond breaking on methyl-cyclohexene, while the most stable intermediate is the {toluene+H2} adsorbed product. However, other C-H bond breaking steps and eventually toluene desorption may compete. A comparison with the Pt (111) surface is also given. Rate constants of elementary steps estimated by DFT are introduced in 8 Langmuir-Hinshelwood (LH) kinetic models based on a single rate determining step (RDS) concept, or on a limiting steps sequence deduced from an energetic span analysis. We finally carried out experimental tests on Pt/γ-alumina catalysts (0.3 wt% Pt) at various temperatures, space times, hydrogen and methyl-cyclohexane partial pressures, to provide experimental kinetic data. The calculated apparent activation enthalpy is predicted to be 196 kJ/mol in close agreement with the experimental one (195 kJ/mol) for the best LH model (third C-H bond breaking as RDS). Moreover, the dependence of reaction rates on hydrogen and methyl-cyclohexane partial pressures are discussed with respect to experimental trends and models. Although the main trends are recovered by the kinetic model, some discrepancies are revealed. This work paves the way for a future microkinetic modeling

    Progress on Experimental and Computational Investigation of Juncture Flows

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    This paper describes a set of measurements taken at the Caltech Lucas Wind Tunnel, along with Computational Fluid Dynamic analyses, on a wing-body configuration. The configuration is designed to produce regions of separation in the juncture where the wing meets the body. Detailed on- and off-body measurements in the juncture flow are compared with RANS predictions. The results from the experimental measurements will become part of a database of high fidelity measurements, to be used for calibration of turbulence models and validation of emerging computational prediction techniques
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