Determination of the activation energies of beef tallow and crude glycerin combustion using thermogravimetry

The present study deals with the determination of the activation energy for the thermal decomposition of two renewable fuels crude glycerin and beef tallow. The activation energies were investigated by using a thermogravimetric analyzer (TGA) in the temperature range of 25-600 degrees C in atmosphere of synthetic air. The TG curves of the thermal decomposition process of both samples were divided into several phases and the second, called PH2, was chosen for the kinetic study because it is associated with the combustion ignition. Differential Thermal Analysis (DTA) showed an endothermic event at the PH2 region for the crude glycerin corresponding to devolatilization, while for beef tallow, this step presented an exothermic event, called LTO (low-temperature oxidation), which is correlated with devolatilization followed by combustion. For the entire PH2, activation energy values for crude glycerin were between 90 kJ mol(-1) and 42 kJ mol(-1), while for the beef tallow they ranged from 50 kJ mol(-1) to 113 kJ mol (1). The activation energy values obtained at the pre-ignition stage - conversion between 0 and 0.45 - showed that the crude glycerin with higher values requires an additional energetic support at the start of combustion processes and the beef tallow ignites more easily, presenting lower values. According to the Wolfer's equation, a direct relation between the activation energy and the ignition delay is established and the results of this study provides useful data for the development and design of new combustion chambers and engines when non-traditional fuels are used as feedstock. (C) 2012 Elsevier Ltd. All rights reserved.

UV-Ozone Generation from Modified High Intensity Discharge Mercury Vapor Lamps for Treatment of Indium Tin Oxide Films

In a homemade UV-Ozone generator, different ignition tubes extracted from HID mercury vapor lamps were investigated, namely: 80, 125, 250 and 400 watts. The performance of the generator in function of the type of the ignition lamp was monitored by the measurements of the ozone concentration and the temperature increment. The results have shown that the 400 W set up presented the highest ozone production, which was used in the treatment of indium tin oxide (ITO) films. Polymer light emitting diodes were assembled using ITO films, treated for 10, 20 and 30 min, as an anode. The overall results indicate improvement of the threshold voltage (reduction) and electroluminescence of these devices.

Characterization and use of swine deep bedding ashes in cementitious composites

The deep bedding is a swine alternative production, especially in the finishing phase, whose byproduct can be recycled, reducing the environmental impact. The objectives of this study were to characterize the ash coming from the controlled burning of the swine deep bedding (SDBA) based on rice husk, and to evaluate their performance in composites as a partial substitute for Portland cement (PC). To measure the differences between SDBA and rice husk ash (RHA) as a reference, we have characterized: particle size distribution, real specific density, x-ray diffraction, electrical conductivity, scanning electron microscopy, chemical analysis and loss on ignition. Samples were prepared for two experimental series: control, and another one with the partial replacement of 30% of SDBA in relation to the mass of the Portland cement. According to the results obtained for physical and mechanical characterization, the composites with SDBA can be used as a constructive element in the rural construction.

Modellazione e simulazione di sistemi meccanici ad elevato numero di gradi di libertà mediante metodi non convenzionali e sistemi CAD

Recent developments in piston engine technology have increased performance in a very significant way. Diesel turbocharged/turbo compound engines, fuelled by jet fuels, have great performances. The focal point of this thesis is the transformation of the FIAT 1900 jtd diesel common rail engine for the installation on general aviation aircrafts like the CESSNA 172. All considerations about the diesel engine are supported by the studies that have taken place in the laboratories of the II Faculty of Engineering in Forlì. This work, mostly experimental, concerns the transformation of the automotive FIAT 1900 jtd – 4 cylinders – turbocharged – diesel common rail into an aircraft engine. The design philosophy of the aluminium alloy basement of the spark ignition engine have been transferred to the diesel version while the pistons and the head of the FIAT 1900 jtd are kept in the aircraft engine. Different solutions have been examined in this work. A first V 90° cylinders version that can develop up to 300 CV and whose weight is 30 kg, without auxiliaries and turbocharging group. The second version is a development of e original version of the diesel 1900 cc engine with an optimized crankshaft, that employ a special steel, 300M, and that is verified for the aircraft requirements. Another version with an augmented stroke and with a total displacement of 2500 cc has been examined; the result is a 30% engine heavier. The last version proposed is a 1600 cc diesel engine that work at 5000 rpm, with a reduced stroke and capable of more than 200 CV; it was inspired to the Yamaha R1 motorcycle engine. The diesel aircraft engine design keeps the bore of 82 mm, while the stroke is reduced to 64.6 mm, so the engine size is reduced along with weight. The basement weight, in GD AlSi 9 MgMn alloy, is 8,5 kg. Crankshaft, rods and accessories have been redesigned to comply to aircraft standards. The result is that the overall size is increased of only the 8% when referred to the Yamaha engine spark ignition version, while the basement weight increases of 53 %, even if the bore of the diesel version is 11% lager. The original FIAT 1900 jtd piston has been slightly modified with the combustion chamber reworked to the compression ratio of 15:1. The material adopted for the piston is the aluminium alloy A390.0-T5 commonly used in the automotive field. The piston weight is 0,5 kg for the diesel engine. The crankshaft is verified to torsional vibrations according to the Lloyd register of shipping requirements. The 300M special steel crankshaft total weight is of 14,5 kg. The result reached is a very small and light engine that may be certified for general aviation: the engine weight, without the supercharger, air inlet assembly, auxiliary generators and high pressure body, is 44,7 kg and the total engine weight, with enlightened HP pump body and the titanium alloy turbocharger is less than 100 kg, the total displacement is 1365 cm3 and the estimated output power is 220 CV. The direct conversion of automotive piston engine to aircrafts pays too huge weight penalties. In fact the main aircraft requirement is to optimize the power to weight ratio in order to obtain compact and fast engines for aeronautical use: this 1600 common rail diesel engine version demonstrates that these results can be reached.

Distribuzione e biodisponibilità dei metalli in traccia nei sedimenti della Pialassa Baiona

Il presente lavoro di tesi è stato realizzato al fine di valutare la distribuzione geografica ed i livelli ambientali di concentrazione per una serie di metalli (Cr, Cu, Ni, Zn, Mn, Co, V, Ba, Pb, Sr e Hg) presenti all’interno dei sedimenti della laguna costiera Pialassa Baiona, situata nei pressi del porto e dell’area industriale di Ravenna. L’area di studio considerata rappresenta un esempio di ambiente di transizione, dove i fattori fisici e chimici variano su scala spaziale e temporale e dove le attività antropiche, recenti e non, hanno provocato impatti significativi sullo stato di qualità dei sedimenti, delle acque e degli ecosistemi. Lo studio è stato progettato seguendo un disegno di campionamento ortogonale, che tiene conto del gradiente naturale terra-mare, tipico delle zone di transizione, e del gradiente antropico, legato alla vicinanza con l’area industriale. Sulla base di questo disegno sono state campionate 4 aree differenti e per ciascuna area sono stati scelti casualmente tre siti. La caratterizzazione dei sedimenti dal punto di vista chimico è stata effettuata determinando la frazione labile e quindi più biodisponibile dei metalli, oggetto del presente studio, per mezzo di una tecnica di estrazione parziale con HCl 1 M. Le concentrazioni biodisponibili ottenute sono state poi confrontate con il contenuto totale dei metalli, determinato mediante digestione totale al micronde. I sedimenti sono stati inoltre caratterizzati dal punto di vista granulometrico e del contenuto in sostanza organica (Loss on Ignition, LOI%). I risultati ottenuti dalle analisi chimiche sono stati confrontati con i valori tipi di fondo naturale del Mar Adriatico e con i valori guida di riferimento nazionale (SQA-MA) ed internazionale (ERL, ERM, TEL e PEL), al fine di valutare lo stato di qualità dei sedimenti della Baiona e di effettuare uno screening per individuare eventuali situazioni di rischio per gli organismi bentonici. I risultati ottenuti sono stati poi elaborati statisticamente con un analisi della varianza (ANOVA) con lo scopo di valutare la variabilità spaziale dei metalli nei campioni analizzati e la presenza di eventuali differenze significative.

Sviluppo di algoritmi di RCP per la stima della coppia indicata erogata da un motore a combustione interna.

Combustion control is one of the key factors to obtain better performances and lower pollutant emissions for diesel, spark ignition and HCCI engines. An algorithm that allows estimating, as an example, the mean indicated torque for each cylinder, could be easily used in control strategies, in order to carry out cylinders trade-off, control the cycle to cycle variation, or detect misfires. A tool that allows evaluating the 50% of Mass Fraction Burned (MFB50), or the net Cumulative Heat Release (CHRNET), or the ROHR peak value (Rate of Heat Release), could be used to optimize spark advance or to detect knock in gasoline engines and to optimize injection pattern in diesel engines. Modern management systems are based on the control of the mean indicated torque produced by the engine: they need a real or virtual sensor in order to compare the measured value with the target one. Many studies have been performed in order to obtain an accurate and reliable over time torque estimation. The aim of this PhD activity was to develop two different algorithms: the first one is based on the instantaneous engine speed fluctuations measurement. The speed signal is picked up directly from the sensor facing the toothed wheel mounted on the engine for other control purposes. The engine speed fluctuation amplitudes depend on the combustion and on the amount of torque delivered by each cylinder. The second algorithm processes in-cylinder pressure signals in the angular domain. In this case a crankshaft encoder is not necessary, because the angular reference can be obtained using a standard sensor wheel. The results obtained with these two methodologies are compared in order to evaluate which one is suitable for on board applications, depending on the accuracy required.

Der Austausch von Stickstoffmonoxid zwischen Boden und Atmosphäre unter besonderer Berücksichtigung des Bodenwassergehaltes

Stickstoffmonoxid (NO) ist als reaktives Spurengas eine wichtige Komponente atmosphärenchemischer Prozesse und hat somit einen bedeutenden Einfluss auf die Zusammensetzung der Atmosphäre. Eine Hauptquelle des Spurengases stellen bodenmikrobiologische Prozesse dar, deren regionaler und globaler Anteil weiterhin mit größeren Unsicherheiten geschätzt wird. Ursache für die schwere Abschätzbarkeit der NO-Freisetzung aus Böden ist die hohe räumliche Variabilität der steuernden Faktoren. Als einer der wichtigsten Faktoren, die die Freisetzung von NO aus Böden regeln, gilt der Bodenwassergehalt. Ziel der vorliegenden Arbeit ist es, den Zusammenhang zwischen NO-Freisetzung, Bodenwassergehalt, den Bodeneigenschaften und den Standortbedingungen zu untersuchen und diesen möglichst zu quantifizieren. Dazu sind Bodenproben unterschiedlicher Landnutzungen in einem kleineren Wassereinzugsgebiet im Rheingau im Labor, unter kontrollierten Bedingungen, untersucht. Der charakteristische Zusammenhang zwischen Bodenfeuchte und NO-Freisetzung, die sogenannte Bodenfeuchtekurve, kann demnach weitestgehend auf die gemessenen Bodenmerkmale der untersuchten Proben zurückgeführt werden. Anhand der Bodenmerkmale kann die Bodenfeuchtekurve zufriedenstellend vorhergesagt werden. Dabei zeigt vor allem der Humusgehalt der Böden einen dominierenden Einfluss. Er ist die Variable, die die Unterschiede der Böden beim Zusammenhang zwischen Bodenfeuchte und NO-Freisetzung am besten und hinreichend erklären kann. Zur Konstruktion der Bodenfeuchtekurve müssen die optimale Bodenfeuchte und die dabei herrschende Freisetzung, sowie die obere Bodenfeuchte, bei der keine NO-Freisetzung mehr stattfindet, bekannt sein. Diese charakteristischen Punkte lassen sich durch lineare Regressionsmodelle gut aus den Bodeneigenschaften ableiten. Auf räumlicher Ebene werden die Bodeneigenschaften durch die standörtlichen Bedingungen geprägt, die wiederum Ausdruck der landschaftlichen Ausstattung sind. In der Kulturlandschaft kann der Mensch aufgrund seiner Landnutzungsansprüche als der dominierende Faktor angesehen werden. Die Landnutzung orientiert sich an den landschaftlichen Bedingungen und bestimmt in hohem Maße wichtige Bodeneigenschaften, die zu den erklärenden Merkmalen bei der Beziehung zwischen Bodenwassergehalt und NO-Freisetzung gehören. Die in erster Linie wirtschaftlich orientierten Kartenwerke Bodenschätzung, Weinbergsbodenkartierung und forstliche Standortkartierung sind dementsprechend geeignete Grundlagen, um eine Regionalisierung der Landschaft in - bezüglich der NO-Freisetzung - weitgehend homogene Flächen durchführen zu können. Eine hierauf beruhende Regionalisierung ist dazu geeignet, die räumliche Variabilität der NO-Freisetzung in räumlich sinnvoller Auflösung besser abschätzen zu können.

Analisi preliminare di combustioni innovative su un motore diesel di piccola cilindrata

Analisi delle emissioni di inquinanti per combustioni innovative Dual-Fuel e Premixed Charge Compression Ignition (PCCI) operate su un motore Diesel, nel laboratorio di propulsione e macchine della Scuola d'Ingegneria e Architettura con sede a Forlì. Tale studio è stato realizzato in quanto la riduzione delle emissioni e dei consumi sono caratteristiche di primo impatto per la competitività sul mercato di un motore e poiché le emissioni di inquinanti sono regolate da standard europei che ne esigono la continua riduzione. L'obiettivo della ricerca è quello di definire un pattern di combustioni, variando il valore e la sincronizzazione dei parametri delle attuazioni, che consenta la riduzione di inquinanti senza compromettere le prestazioni. Capire come ottenere minori emissioni di inquinanti significa poter far rientrare anche i motori diesel nelle future normative EURO 6 (già definite ed in vigore da Settembre 2014), e di seguire studi paralleli sulla riduzione dei consumi sui quali sono già stati riscontrati risultati positivi.

Valutazione del contributo emissivo in condizioni non-stazionarie alle emissioni totali di una stufa a pellet domestica

The aim of this work is to evaluate the emissions of the main pollutants of a pellet stove, by trying to simulate the real use in domestic operations. All the operating phases of this system were considered: ignition, partial load, increase in power, and nominal load. In each phase, quantity and type of some pollutants in emissions were determined: the main pollutant gases (CO, NOx, SO2, H2S and volatile organic compounds (VOCs)), total dust (PM) and its content of polycyclic aromatic hydrocarbons (PAHs), regulated heavy metals (Ni, Cd, As and Pb), main soluble ions and Total Carbon (TC). Results show that emission factors of TSP, CO, and of the main determined pollutants (TC, Cd and PAHs) are higher during ignition phase. In particular, this phase prevalently contributes to PAHs emissions. During increase in power phase, gas and particulate emissions do not appreciably differ from nominal load ones; nevertheless, PAH emission factors are higher than steady state ones, but lower than ignition phase. Moreover, during not-steady state phases, PAH mixture is more toxic than during steady state phases. In conclusion, this study allowed to go deeper in pellet stove environmental impact, by pointing out how the different operating conditions can modify the emissions. These are different from certificated data, which are based exclusively on measurements in steady state conditions.

Generation and characterization of stable, highly concentrated titanium dioxide nanoparticle aerosols for rodent inhalation studies

The intensive use of nano-sized titanium dioxide (TiO2) particles in many different applications necessitates studies on their risk assessment as there are still open questions on their safe handling and utilization. For reliable risk assessment, the interaction of TiO2 nanoparticles (NP) with biological systems ideally needs to be investigated using physico-chemically uniform and well-characterized NP. In this article, we describe the reproducible production of TiO2 NP aerosols using spark ignition technology. Because currently no data are available on inhaled NP in the 10–50 nm diameter range, the emphasis was to generate NP as small as 20 nm for inhalation studies in rodents. For anticipated in vivo dosimetry analyses, TiO2 NP were radiolabeled with 48V by proton irradiation of the titanium electrodes of the spark generator. The dissolution rate of the 48V label was about 1% within the first day. The highly concentrated, polydisperse TiO2 NP aerosol (3–6 × 106 cm−3) proved to be constant over several hours in terms of its count median mobility diameter, its geometric standard deviation, and number concentration. Extensive characterization of NP chemical composition, physical structure, morphology, and specific surface area was performed. The originally generated amorphous TiO2 NP were converted into crystalline anatase TiO2 NP by thermal annealing at 950 °C. Both crystalline and amorphous 20-nm TiO2 NP were chain agglomerated/aggregated, consisting of primary particles in the range of 5 nm. Disintegration of the deposited TiO2 NP in lung tissue was not detectable within 24 h.

Spatial heterogeneity of soil nutrients and plant species in herb-dominated communities of contrasting land use

Recent interest in spatial pattern in terrestrial ecosystems has come from an awareness of theintimate relationship between spatial heterogeneity of soil resources and maintenance of plant species diversity. Soil and vegetation can vary spatially inresponse to several state factors of the system. In this study, we examined fine-scale spatial variability of soil nutrients and vascular plant species in contrasting herb-dominated communities (a pasture and an oldfield) to determine degree of spatial dependenceamong soil variables and plant community characteristics within these communities by sampling at 1-m intervals. Each site was divided into 25 1-m 2 plots. Mineral soil was sampled (2-cm diameter, 5-cm depth) from each of four 0.25-m2 quarters and combined into a single composite sample per plot. Soil organic matter was measured as loss-on-ignition. Extractable NH4 and NO3 were determined before and after laboratory incubation to determine potential net N mineralization and nitrification. Cations were analyzed using inductively coupled plasma emission spectrometry. Vegetation was assessed using estimated percent cover. Most soiland plant variables exhibited sharp contrasts betweenpasture and old-field sites, with the old field having significantly higher net N mineralization/nitrification, pH, Ca, Mg, Al, plant cover, and species diversity, richness, and evenness. Multiple regressions revealedthat all plant variables (species diversity, richness,evenness, and cover) were significantly related to soil characteristics (available nitrogen, organic matter,moisture, pH, Ca, and Mg) in the pasture; in the old field only cover was significantly related to soil characteristics (organic matter and moisture). Both sites contrasted sharply with respect to spatial pattern of soil variables, with the old field exhibiting a higher degree of spatial dependence. These results demonstrate that land-use practices can exert profound influence on spatial heterogeneity of both soil properties and vegetation in herb-dominated communities.

Technique to measure heats of reaction of Ti-B, Al-Ti-B, and Al-Ti-B4C powder blends

In this research, a modification to initiation aid ignition in bomb calorimetry that involves systemically blending levels of boron and potassium nitrate initiation aids with a bulk structural energetic elemental power blend is developed. A regression is used to estimate the nominal heat of reaction for the primary reaction. The technique is first applied to the synthesis of TiB2 as a validation study to see if close proximity to literature values can be achieved. The technique is then applied to two systems of interest, Al-Ti-B, and Al-Ti-B4C. In all three investigations, x-ray diffraction is used to characterize the product phases of the reactions to determine the extent and identity of the product phases and any by-products that may have formed as a result of adding the initiation aid. The experimental data indicates the technique approximates the heat of reaction value for the synthesis of TiB2 from Ti-B powder blends and the formation of TiB2 is supported by volume fraction analysis by x-ray diffraction. Application to the Al-Ti-B and Al-Ti-B4C blends show some correlation with variation of the initiation aid, with x-ray diffraction showing the formation of equilibrium products. However, these blends require further investigation to resolve more complex interactions and rule out extraneous variables.

Diesel spray mixing limited vaporization with non-ideal and multi-component fuel thermophysical property effects

Internal combustion engines are, and will continue to be, a primary mode of power generation for ground transportation. Challenges exist in meeting fuel consumption regulations and emission standards while upholding performance, as fuel prices rise, and resource depletion and environmental impacts are of increasing concern. Diesel engines are advantageous due to their inherent efficiency advantage over spark ignition engines; however, their NOx and soot emissions can be difficult to control and reduce due to an inherent tradeoff. Diesel combustion is spray and mixing controlled providing an intrinsic link between spray and emissions, motivating detailed, fundamental studies on spray, vaporization, mixing, and combustion characteristics under engine relevant conditions. An optical combustion vessel facility has been developed at Michigan Technological University for these studies, with detailed tests and analysis being conducted. In this combustion vessel facility a preburn procedure for thermodynamic state generation is used, and validated using chemical kinetics modeling both for the MTU vessel, and institutions comprising the Engine Combustion Network international collaborative research initiative. It is shown that minor species produced are representative of modern diesel engines running exhaust gas recirculation and do not impact the autoignition of n-heptane. Diesel spray testing of a high-pressure (2000 bar) multi-hole injector is undertaken including non-vaporizing, vaporizing, and combusting tests, with sprays characterized using Mie back scatter imaging diagnostics. Liquid phase spray parameter trends agree with literature. Fluctuations in liquid length about a quasi-steady value are quantified, along with plume to plume variations. Hypotheses are developed for their causes including fuel pressure fluctuations, nozzle cavitation, internal injector flow and geometry, chamber temperature gradients, and turbulence. These are explored using a mixing limited vaporization model with an equation of state approach for thermopyhysical properties. This model is also applied to single and multi-component surrogates. Results include the development of the combustion research facility and validated thermodynamic state generation procedure. The developed equation of state approach provides application for improving surrogate fuels, both single and multi-component, in terms of diesel spray liquid length, with knowledge of only critical fuel properties. Experimental studies are coupled with modeling incorporating improved thermodynamic non-ideal gas and fuel

Stochastic knock detection model for spark ignited engines

This report presents the development of a Stochastic Knock Detection (SKD) method for combustion knock detection in a spark-ignition engine using a model based design approach. Knock Signal Simulator (KSS) was developed as the plant model for the engine. The KSS as the plant model for the engine generates cycle-to-cycle accelerometer knock intensities following a stochastic approach with intensities that are generated using a Monte Carlo method from a lognormal distribution whose parameters have been predetermined from engine tests and dependent upon spark-timing, engine speed and load. The lognormal distribution has been shown to be a good approximation to the distribution of measured knock intensities over a range of engine conditions and spark-timings for multiple engines in previous studies. The SKD method is implemented in Knock Detection Module (KDM) which processes the knock intensities generated by KSS with a stochastic distribution estimation algorithm and outputs estimates of high and low knock intensity levels which characterize knock and reference level respectively. These estimates are then used to determine a knock factor which provides quantitative measure of knock level and can be used as a feedback signal to control engine knock. The knock factor is analyzed and compared with a traditional knock detection method to detect engine knock under various engine operating conditions. To verify the effectiveness of the SKD method, a knock controller was also developed and tested in a model-in-loop (MIL) system. The objective of the knock controller is to allow the engine to operate as close as possible to its border-line spark-timing without significant engine knock. The controller parameters were tuned to minimize the cycle-to-cycle variation in spark timing and the settling time of the controller in responding to step increase in spark advance resulting in the onset of engine knock. The simulation results showed that the combined system can be used adequately to model engine knock and evaluated knock control strategies for a wide range of engine operating conditions.

Development of a technique for achieving an optimum BSFC for LAF engine

The reserves of gasoline and diesel fuels are ever decreasing, which plays an important role in the technological development of automobiles. Numerous countries, especially the United States, wish to slowly decrease their fuel dependence on other countries by producing in house renewable fuels like biodiesels or ethanol. Therefore, the new automobile engines have to successfully run on a variety of fuels without significant changes to their designs. The current study focuses on assessing the potential of ethanol fuels to improve the performance of 'flex-fuel SI engines,' which literally means 'engines that are flexible in their fuel requirement.' Another important area within spark ignition (SI) engine research is the implementation of new technologies like Variable Valve Timing (VVT) or Variable Compression Ratio (VCR) to improve engine performance. These technologies add more complexity to the original system by adding extra degrees of freedom. Therefore, the potential of these technologies has to be evaluated before they are installed in any SI engine. The current study focuses on evaluating the advantages and drawbacks of these technologies, primarily from an engine brake efficiency perspective. The results show a significant improvement in engine efficiency with the use of VVT and VCR together. Spark ignition engines always operate at a lower compression ratio as compared to compression ignition (CI) engines primarily due to knock constraints. Therefore, even if the use of a higher compression ratio would result in a significant improvement in SI engine efficiency, the engine may still operate at a lower compression ratio due to knock limitations. Ethanol fuels extend the knock limit making the use of higher compression ratios possible. Hence, the current study focuses on using VVT, VCR, and ethanol-gasoline blends to improve overall engine performance. The results show that these technologies promise definite engine performance improvements provided both their positive and negative potentials have been evaluated prior to installation.