Catalytic CO2 hydrogenation: study at the molecular scale using field emission techniques

An accurate characterization of the rhodium specimen was obtained via FIM experiments. Reaction behaviors between H2 and CO2 were observed in FEM mode at 700 K. At this temperature, CO desorption occurs, preventing CO+H2 reaction. Surface is mainly recovered by oxygen; reaction with hydrogen occurs. Finally, we can identify the reaction as the Reverse Water Gas Shift.

Evaluation of Information Entropy from Acoustic Emission Waveforms as a Fatigue Damage Metric for Al7075-T6

Information entropy measured from acoustic emission (AE) waveforms is shown to be an indicator of fatigue damage in a high-strength aluminum alloy. Several tension-tension fatigue experiments were performed with dogbone samples of aluminum alloy, Al7075-T6, a commonly used material in aerospace structures. Unlike previous studies in which fatigue damage is simply measured based on visible crack growth, this work investigated fatigue damage prior to crack initiation through the use of instantaneous elastic modulus degradation. Three methods of measuring the AE information entropy, regarded as a direct measure of microstructural disorder, are proposed and compared with traditional damage-related AE features. Results show that one of the three entropy measurement methods appears to better assess damage than the traditional AE features, while the other two entropies have unique trends that can differentiate between small and large cracks.

Periodic emission of droplets from an oscillating electrified meniscus of a low-viscosity, highly conductive liquid

The generation of identical droplets of controllable size in the micrometer range is a problem of much interest owing to the numerous technological applications of such droplets. This work reports an investigation of the regime of periodic emission of droplets from an electrified oscillating meniscus of a liquid of low viscosity and high electrical conductivity attached to the end of a capillary tube, which may be used to produce droplets more than ten times smaller than the diameter of the tube. To attain this periodic microdripping regime, termed axial spray mode II by Juraschek and Röllgen [R. Juraschek and F. W. Röllgen, Int. J. Mass Spectrom. 177, 1 (1998)], liquid is continuously supplied through the tube at a given constant flow rate, while a dc voltage is applied between the tube and a nearby counter electrode. The resulting electric field induces a stress at the surface of the liquid that stretches the meniscus until, in certain ranges of voltage and flow rate, it develops a ligament that eventually detaches, forming a single droplet, in a process that repeats itself periodically. While it is being stretched, the ligament develops a conical tip that emits ultrafine droplets, but the total mass emitted is practically contained in the main droplet. In the parametrical domain studied, we find that the process depends on two main dimensionless parameters, the flow rate nondimensionalized with the diameter of the tube and the capillary time, q, and the electric Bond number BE, which is a nondimensional measure of the square of the applied voltage. The meniscus oscillation frequency made nondimensional with the capillary time, f, is of order unity for very small flow rates and tends to decrease as the inverse of the square root of q for larger values of this parameter. The product of the meniscus mean volume times the oscillation frequency is nearly constant. The characteristic length and width of the liquid ligament immediately before its detachment approximately scale as powers of the flow rate and depend only weakly on the applied voltage. The diameter of the main droplets nondimensionalized with the diameter of the tube satisfies dd≈(6/π)1/3(q/f)1/3, from mass conservation, while the electric charge of these droplets is about 1/4 of the Rayleigh charge. At the minimum flow rate compatible with the periodic regimen, the dimensionless diameter of the droplets is smaller than one-tenth, which presents a way to use electrohydrodynamic atomization to generate droplets of highly conducting liquids in the micron-size range, in marked contrast with the cone-jet electrospray whose typical droplet size is in the nanometric regime for these liquids. In contrast with other microdripping regimes where the mass is emitted upon the periodic formation of a narrow capillary jet, the present regime gives one single droplet per oscillation, except for the almost massless fine aerosol emitted in the form of an electrospray.

Spectral self-action of THz emission from ionizing two-color laser pulses in gases

The spectrum of terahertz (THz) emission in gases via ionizing two-color femtosecond pulses is analyzed by means of a semi-analytic model and numerical simulations in 1D, 2D and 3D geometries taking into account propagation effects of both pump and THz fields. We show that produced THz signals interact with free electron trajectories and thus significantly influence further THz generation upon propagation, i.e., make the process inherently nonlocal. This self-action contributes to the observed strong spectral broadening of the generated THz field. We show that diffraction of the generated THz radiation is the limiting factor for the co-propagating low frequency amplitudes and thus for the self-action mechanism in 2D and 3D geometries.

Development of combined acidification and separation of slurry: effect on slurry fractions composition and gaseous emission

Doutoramento em Engenharia do Ambiente - Instituto Superior de Agronomia - UL

Microstructure, vibrational and visible emission properties of low frequency ultrasound (42 kHz) assisted ZnO nanostructures

Size and shape tuneable ZnO nanostructures were prepared by a low frequency ultrasound (42 kHz) route using various organic solvents as the reaction media. The crystalline nature, lattice parameters and microstructural parameters such as microstrain, stress and energy density of the prepared ZnO nanostructures were revealed through X-ray diffraction (XRD) analysis. The organic solvents influenced the size and morphology of the ZnO nanostructures, and interesting morphological changes involving a spherical to triangular shaped transition were observed. The visible emission properties and lattice vibrational characteristics of the nanostructures were drastically modified by the changes in size and shape. Raman spectral measurements revealed the presence of multiphonon processes in the ZnO nanostructures. The intensity of the visible emission band was found to vary with the size and morphology of the structures. The strongest visible emission band corresponded to the structure with the largest surface/volume ratio and could be attributed to surface oxygen vacancies. The control over the size and morphology of ZnO nanostructures has been presented as a means of determining the intensity of the visible emission band

Ruminal methane emission by dairy cattle in southeast Brazil.

ABSTRACT: Ruminal gases, particularly methane, generated during the fermentative process in rumen, represent a partial loss of feed energy and are also pointed to as an important factors in greenhouse effect. This study aimed at quantifying methane (CH 4) emission rates from lactating and dry cows and heifers, 24 month-old in average, on pasture under Southeast Brazil tropical conditions, using the tracer gas technique, sulphur hexafluoride (SF 6), four animals per category, distributed in four blocks. Measurements were performed in February and June, 2002, with Holstein and Brazilian Dairy Crossbred (Holstein ¾ x Gir (Zebu) ¼), maintained on fertilized Tanzania-grass (Panicum maximum Jacq. cv. Tanzania) and fertilized Brachiaria-grass (Brachiaria decumbens cv. Basilisk) pastures. Heifers of both breeds were maintained on unfertilized Brachiaria-grass to simulate conditions of extensive cattle farming systems. CH 4 and SF 6 levels were measured with gas chromatography. Differences in CH4 emissions were measured (p < 0.05) for genetical groups. Holstein produced more methane (299.3g day?1) than the Crossbred (264.2 g day?1). Lactating cows produced more methane (353.8 g day?1) than dry cows (268.8 g day?1) and heifers (222.6 g day?1). Holstein, with greater milk production potential, produced less CH4 (p < 0.05) per unit of dry matter intake (19.1 g kg?1) than the Crossbred (22.0 g kg?1). Methane emission by heifers grazing fertilized pasture (intensive system) was 222.6 g day?1, greater (p < 0.05) than that of heifers on unfertilized pasture (179.2 g day?1). Methane emission varied as function of animal category and management intensity of production system.

Can Fluorine-18-Fluorodeoxyglucose Positron Emission Tomography Be Used As a Useful Method to Evaluate the Treatment Response to Neoadjuvant Therapy Combined With Sorafenib and Anti-VEGF in Children Diagnosed With Metastatical Bone Sarcoma?

Background: The prognosis is still poor for patients with a metastatic bone tumor and new treatment approaches (anti-VEGF and tyrosine kinase inhibitors vs) are therefore needed. Objectives: The aim of our study was to evaluate how the primary and metastatic lesions of our patients with a bone tumor were affected by these treatments and to determine the importance of the 18F-FDG PET method. Patients and Methods: Twenty metastatic bone tumor cases were included. Sorafenib and anti-VEGF were added to the standard treatment in cases with widespread metastatic disease at diagnosis or after neoadjuvant chemotherapy showing less than 90% tumor necrosis in the surgical sample. Positron emission tomography (PET) imaging was performed at diagnosis, the preoperative period following neoadjuvant chemotherapy, during postoperative follow-up, and when treatment was discontinued. Results: The primary treatment region median SUVmax level decreased from 7.35 to 2.5 in the living patients (n = 16) while there was no significant decrease in the patients who succumbed to the disease (P < 0.001). Comparison of the pre- and post-treatment metastasis region median SUVmax levels in patients with metastatic involvement showed a decrease from 2.1 to 0 in the surviving patients but only from 4.8 to 3.2 in the deceased patients (P < 0.01). Survival results indicated that 28.6% of the patients receiving classical treatment only died while all the patients receiving additional sorafenib and anti-VEGF survived. Conclusions: 18F-PET may be a useful technique before and during the follow-up of neoadjuvant treatment in pediatric metastatic bone tumor patients. The addition of sorafenib and anti-VEGF to classical treatment has a favorable contribution to the response and therefore the survival duration.

A Cost Analysis Of Carbon Dioxide Emission Reduction Strategies For New Plants In Michigan's Electric Power Sector

This thesis attempts to find the least-cost strategy to reduce CO2 emission by replacing coal by other energy sources for electricity generation in the context of the proposed EPA’s regulation on CO2 emissions from existing coal-fired power plants. An ARIMA model is built to forecast coal consumption for electricity generation and its CO2 emissions in Michigan from 2016 to 2020. CO2 emission reduction costs are calculated under three emission reduction scenarios- reduction to 17%, 30% and 50% below the 2005 emission level. The impacts of Production Tax Credit (PTC) and the intermittency of renewable energy are also discussed. The results indicate that in most cases natural gas will be the best alternative to coal for electricity generation to realize CO2 reduction goals; if the PTC for wind power will continue after 2015, a natural gas and wind combination approach could be the best strategy based on the least-cost criterion.

Classical electrodynamics: retarded potentials and power emission by accelerated charges

L'obiettivo di questo lavoro è quello di analizzare la potenza emessa da una carica elettrica accelerata. Saranno studiati due casi speciali: accelerazione lineare e accelerazione circolare. Queste sono le configurazioni più frequenti e semplici da realizzare. Il primo passo consiste nel trovare un'espressione per il campo elettrico e il campo magnetico generati dalla carica. Questo sarà reso possibile dallo studio della distribuzione di carica di una sorgente puntiforme e dei potenziali che la descrivono. Nel passo successivo verrà calcolato il vettore di Poynting per una tale carica. Useremo questo risultato per trovare la potenza elettromagnetica irradiata totale integrando su tutte le direzioni di emissione. Nell'ultimo capitolo, infine, faremo uso di tutto ciò che è stato precedentemente trovato per studiare la potenza emessa da cariche negli acceleratori.

Positron Emission Tomography (PET) Tumor Segmentation and Quantification: Development of New Algorithms

Tumor functional volume (FV) and its mean activity concentration (mAC) are the quantities derived from positron emission tomography (PET). These quantities are used for estimating radiation dose for a therapy, evaluating the progression of a disease and also use it as a prognostic indicator for predicting outcome. PET images have low resolution, high noise and affected by partial volume effect (PVE). Manually segmenting each tumor is very cumbersome and very hard to reproduce. To solve the above problem I developed an algorithm, called iterative deconvolution thresholding segmentation (IDTS) algorithm; the algorithm segment the tumor, measures the FV, correct for the PVE and calculates mAC. The algorithm corrects for the PVE without the need to estimate camera’s point spread function (PSF); also does not require optimizing for a specific camera. My algorithm was tested in physical phantom studies, where hollow spheres (0.5-16 ml) were used to represent tumors with a homogeneous activity distribution. It was also tested on irregular shaped tumors with a heterogeneous activity profile which were acquired using physical and simulated phantom. The physical phantom studies were performed with different signal to background ratios (SBR) and with different acquisition times (1-5 min). The algorithm was applied on ten clinical data where the results were compared with manual segmentation and fixed percentage thresholding method called T50 and T60 in which 50% and 60% of the maximum intensity respectively is used as threshold. The average error in FV and mAC calculation was 30% and -35% for 0.5 ml tumor. The average error FV and mAC calculation were ~5% for 16 ml tumor. The overall FV error was ~10% for heterogeneous tumors in physical and simulated phantom data. The FV and mAC error for clinical image compared to manual segmentation was around -17% and 15% respectively. In summary my algorithm has potential to be applied on data acquired from different cameras as its not dependent on knowing the camera’s PSF. The algorithm can also improve dose estimation and treatment planning.

Effect of Pavement-Vehicle Interaction on Highway Fuel Consumption and Emission

Vehicle fuel consumption and emission are two important effectiveness measurements of sustainable transportation development. Pavement plays an essential role in goals of fuel economy improvement and greenhouse gas (GHG) emission reduction. The main objective of this dissertation study is to experimentally investigate the effect of pavement-vehicle interaction (PVI) on vehicle fuel consumption under highway driving conditions. The goal is to provide a better understanding on the role of pavement in the green transportation initiates. Four study phases are carried out. The first phase involves a preliminary field investigation to detect the fuel consumption differences between paired flexible-rigid pavement sections with repeat measurements. The second phase continues the field investigation by a more detailed and comprehensive experimental design and independently investigates the effect of pavement type on vehicle fuel consumption. The third study phase calibrates the HDM-IV fuel consumption model with data collected in the second field phase. The purpose is to understand how pavement deflection affects vehicle fuel consumption from a mechanistic approach. The last phase applies the calibrated HDM-IV model to Florida’s interstate network and estimates the total annual fuel consumption and CO2 emissions on different scenarios. The potential annual fuel savings and emission reductions are derived based on the estimation results. Statistical results from the two field studies both show fuel savings on rigid pavement compared to flexible pavement with the test conditions specified. The savings derived from the first phase are 2.50% for the passenger car at 112km/h, and 4.04% for 18-wheel tractor-trailer at 93km/h. The savings resulted from the second phase are 2.25% and 2.22% for passenger car at 93km/h and 112km/h, and 3.57% and 3.15% for the 6-wheel medium-duty truck at 89km/h and 105km/h. All savings are statistically significant at 95% Confidence Level (C.L.). From the calibrated HDM-IV model, one unit of pavement deflection (1mm) on flexible pavement can cause an excess fuel consumption by 0.234-0.311 L/100km for the passenger car and by 1.123-1.277 L/100km for the truck. The effect is more evident at lower highway speed than at higher highway speed. From the network level estimation, approximately 40 million gallons of fuel (combined gasoline and diesel) and 0.39 million tons of CO2 emission can be saved/reduced annually if all Florida’s interstate flexible pavement are converted to rigid pavement with the same roughness levels. Moreover, each 1-mile of flexible-rigid conversion can result in a reduction of 29 thousand gallons of fuel and 258 tons of CO2 emission yearly.

Search for VHE gamma-ray emission from Geminga pulsar and nebula with the MAGIC telescopes

The Geminga pulsar, one of the brighest gamma-ray sources, is a promising candidate for emission of very-high-energy (VHE > 100 GeV) pulsed gamma rays. Also, detection of a large nebula have been claimed by water Cherenkov instruments. We performed deep observations of Geminga with the MAGIC telescopes, yielding 63 hours of good-quality data, and searched for emission from the pulsar and pulsar wind nebula. We did not find any significant detection, and derived 95% confidence level upper limits. The resulting upper limits of 5.3 × 10^(−13) TeV cm^(−2)s^(−1) for the Geminga pulsar and 3.5 × 10^(−12) TeV cm^(−2)s^(−1) for the surrounding nebula at 50 GeV are the most constraining ones obtained so far at VHE. To complement the VHE observations, we also analyzed 5 years of Fermi-LAT data from Geminga, finding that the sub-exponential cut-off is preferred over the exponential cut-off that has been typically used in the literature. We also find that, above 10 GeV, the gamma-ray spectra from Geminga can be described with a power law with index softer than 5. The extrapolation of the power-law Fermi-LAT pulsed spectra to VHE goes well below the MAGIC upper limits, indicating that the detection of pulsed emission from Geminga with the current generation of Cherenkov telescopes is very difficult.

IMPROVED SAMPLE INTRODUCTION SYSTEMS FOR INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AND THEIR APPLICATION TO THE ANALYSIS OF SIMPLE AND COMPLEX MATRICES

The objective of this thesis is to explore new and improved methods for greater sample introduction efficiency and enhanced analytical performance with inductively coupled plasma optical emission spectrometry (ICP-OES). Three projects are discussed in which the capabilities and applications of ICP-OES are expanded: 1. In the first project, a conventional ultrasonic nebuliser was modified to replace the heater/condenser with an infrared heated pre-evaporation tube. In continuation from previous works with pre-evaporation, the current work investigated the effects of heating with infrared block and rope heaters on two different ICP-OES instruments. Comparisons were made between several methods and setups in which temperatures were varied. By monitoring changes to sensitivity, detection limit, precision, and robustness, and analyzing two certified reference materials, a method with improved sample introduction efficiency and comparable analytical performance to a previous method was established. 2. The second project involved improvements to a previous work in which a multimode sample introduction system (MSIS) was modified by inserting a pre-evaporation tube between the MSIS and torch. The new work focused on applying an infrared heated ceramic rope for pre-evaporation. This research was conducted in all three MSIS modes (nebulisation mode, hydride generation mode, and dual mode) and on two different ICP-OES instruments, and comparisons were made between conventional setups in terms of sensitivity, detection limit, precision, and robustness. By tracking both hydride-forming and non-hydride forming elements, the effects of heating in combination with hydride generation were probed. Finally, optimal methods were validated by analysis of two certified reference materials. 3. A final project was completed in collaboration with ZincNyx Energy Solutions. This project sought to develop a method for the overall analysis of a 12 M KOH zincate fuel, which is used in green energy backup systems. By employing various techniques including flow injection analysis and standard additions, a final procedure was formulated for the verification of K concentration, as well as the measurement of additives (Al, Fe, Mg, In, Si), corrosion products (such C from CO₃²¯), and Zn particles both in and filtered from solution. Furthermore, the effects of exposing the potassium zincate electrolyte fuel to air were assessed.

Powertrain Architectures and Technologies for New Emission and Fuel Consumption Standards

New powertrain design is highly influenced by CO2 and pollutant limits defined by legislations, the demand of fuel economy in for real conditions, high performances and acceptable cost. To reach the requirements coming from both end-users and legislations, several powertrain architectures and engine technologies are possible (e.g. SI or CI engines), with many new technologies, new fuels, and different degree of electrification. The benefits and costs given by the possible architectures and technology mix must be accurately evaluated by means of objective procedures and tools in order to choose among the best alternatives. This work presents a basic design methodology and a comparison at concept level of the main powertrain architectures and technologies that are currently being developed, considering technical benefits and their cost effectiveness. The analysis is carried out on the basis of studies from the technical literature, integrating missing data with evaluations performed by means of powertrain-vehicle simplified models, considering the most important powertrain architectures. Technology pathways for passenger cars up to 2025 and beyond have been defined. After that, with support of more detailed models and experimentations, the investigation has been focused on the more promising technologies to improve internal combustion engine, such as: water injection, low temperature combustions and heat recovery systems.