Alcohols and other oxygenates in automotive fuels

The aim of this research was to assess the effect of oxygenated hydrocarbons on the knocking characteristics of an engine when blended with low-leaded gasoline. Alcohols, ethers, esters and ketones were tested individually and in various combinations up to an oxygen content of 4% wt/wt in a blend with Series F-7 gasoline of 90, 92, 94 and 96 RON. Tests were carried out at wide open throttle, constant speed and standard timing setting. Engine speed was varied using a dynamometer and knock was detected by two piezoelectric transducers, one on the cylinder head monitoring all four cylinders and one monitoring the cylinder most prone to knock. The engine speeds associated with trace and light knock of a continuous nature were noted. Curves were produced for each oxygenate blend of base RON used against engine speed for the two knock conditions which were compared with those produced using pure Series F-7 fuels. From this a suggested RON of the blend was derived. RON increase was less when using a higher RON base fuel in the blend. Most individual oxygenates showed similar effects in similar concentrations when their oxygen content was comparable. Blends containing more than one oxygenate showed some variation with methanol/MTBE/3 methylbutan-2-one and methanol/MTBE/4 methyl pentan-2-one knocking less than expected and methanol/MTBE/TBA also showing good knock resistance. Further tests to optimise initial findings suggested a blend of methanol and MTBE to be superior although partial replacement of MTBE by 4 methyl pentan-2-one resulted in a fuel of comparable performance. Exhaust emissions were tested for a number of oxygenated blends in 2-star gasoline. 2-star and 4-star fuels were also tested for reference. All oxygenate blends reduced carbon monoxide emissions as expected and hydrocarbon emissions were also reduced. The largest reduction in carbon monoxide occurred using a 14.5 % (1 : 1 : 1) methanol/MTBE/4 methyl pentan-2-one blend. Hydrocarbon emissions were most markedly reduced by a blend containing 25.5 % 4 methyl pentan-2-one. Power output was tested for the blends and indicated a maximum increase of about 5 % at low engine speeds. The most advantageous blends were methanol/4 methyl pentan-2-one (6 : 5) 11% in 2-star and methanol/MTBE/4 methyl pentan-2-one (6 : 3 : 2) 11% in 2-star. In conclusion methanol/MTBE (6 : 5) and (5 : 5), and various combinations of methanol/MTBE/4 methyl pentan-2-one, notably (6 : 3 : 2) gave good results in all tests conducted. CFR testing of these blends showed them to increase both RON and MON substantially.

C-MEMS Based Micro Enzymatic Biofuel Cells

Miniaturized, self-sufficient bioelectronics powered by unconventional micropower may lead to a new generation of implantable, wireless, minimally invasive medical devices, such as pacemakers, defibrillators, drug-delivering pumps, sensor transmitters, and neurostimulators. Studies have shown that micro-enzymatic biofuel cells (EBFCs) are among the most intuitive candidates for in vivo micropower. In the fisrt part of this thesis, the prototype design of an EBFC chip, having 3D intedigitated microelectrode arrays was proposed to obtain an optimum design of 3D microelectrode arrays for carbon microelectromechanical systems (C-MEMS) based EBFCs. A detailed modeling solving partial differential equations (PDEs) by finite element techniques has been developed on the effect of 1) dimensions of microelectrodes, 2) spatial arrangement of 3D microelectrode arrays, 3) geometry of microelectrode on the EBFC performance based on COMSOL Multiphysics. In the second part of this thesis, in order to investigate the performance of an EBFC, behavior of an EBFC chip performance inside an artery has been studied. COMSOL Multiphysics software has also been applied to analyze mass transport for different orientations of an EBFC chip inside a blood artery. Two orientations: horizontal position (HP) and vertical position (VP) have been analyzed. The third part of this thesis has been focused on experimental work towards high performance EBFC. This work has integrated graphene/enzyme onto three-dimensional (3D) micropillar arrays in order to obtain efficient enzyme immobilization, enhanced enzyme loading and facilitate direct electron transfer. The developed 3D graphene/enzyme network based EBFC generated a maximum power density of 136.3 μWcm-2 at 0.59 V, which is almost 7 times of the maximum power density of the bare 3D carbon micropillar arrays based EBFC. To further improve the EBFC performance, reduced graphene oxide (rGO)/carbon nanotubes (CNTs) has been integrated onto 3D mciropillar arrays to further increase EBFC performance in the fourth part of this thesisThe developed rGO/CNTs based EBFC generated twice the maximum power density of rGO based EBFC. Through a comparison of experimental and theoretical results, the cell performance efficiency is noted to be 67%.

Evaluation of strontium-site-deficient Sr2Fe1.4Co0.1Mo0.5O6-δ-based perovskite oxides as intermediate temperature solid oxide fuel cell cathodes

In this paper strontium-site-deficient Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ-based perovskite oxides (S_xFCM) were prepared and evaluated as the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). All samples exhibited a cubic phase structure and the lattice shrinked with increasing the Sr-deficiency as shown in XRD patterns. XPS results determined that the transition elements (Co/Fe/Mo) in S_xFCM oxides were in a mixed valence state, demonstrating the small polaron hopping conductivity mechanism existed. Among the samples, S_1.950FCM presented the lowest coefficient of thermal expansion of 15.62 × 10^-6 K^-1, the highest conductivity value of 28 S cm^-1 at 500 °C, and the lowest interfacial polarization resistance of 0.093 Ω cm² at 800 °C, respectively. Furthermore, an anode-supported single cell with a S_1.950FCM cathode was prepared, demonstrating a maximum power density of 1.16 W cm^-2 at 800 °C by using wet H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that the introduction of Sr-deficiency can dramatically improve the electrochemical performance of Sr₂Fe_1.4Co_0.1Mo_0.5O_6-δ, showing great promise as a novel cathode candidate material for IT-SOFCs.

Fabrication and evaluation of NiO/Y2O3-stabilized-ZrO2 hollow fibers for anode-supported micro-tubular solid oxide fuel cells

In this work NiO/3mol% Y₂O₃-ZrO₂ (3YSZ) and NiO/8mol% Y₂O₃-ZrO₂ (8YSZ) hollow fibers were prepared by phase-inversion. The effect of different kinds of YSZ (3YSZ and 8YSZ) on the porosity, electrical conductivity, shrinkage and flexural strength of the hollow fibers were systematically evaluated. When compared with Ni-8YSZ the porosity and shrinkage of Ni-3YSZ hollow fibers increases while the electrical conductivity decreases, while at the same time also exhibiting enhanced flexural strength. Single cells with Ni-3YSZ and Ni-8YSZ hollow fibers as the supported anode were successfully fabricated showing maximum power densities of 0.53 and 0.67Wcm^-2 at 800°C, respectively. Furthermore, in order to improve the cell performance, a Ni-8YSZ anode functional layer was added between the electrolyte and Ni-YSZ hollow fiber. Here enhanced peak power densities of 0.79 and 0.73Wcm^-2 were achieved at 800°C for single cells with Ni-3YSZ and Ni-8YSZ hollow fibers, respectively.

High performance cobalt-free Cu1.4Mn1.6O4 spinel oxide as an intermediate temperature solid oxide fuel cell cathode

In this work Cu_1.4Mn_1.6O₄ (CMO) spinel oxide is prepared and evaluated as a novel cobalt-free cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). Single phase CMO powder with cubic structure is identified using XRD. XPS results confirm that mixed Cu⁺/Cu²⁺ and Mn³⁺/Mn⁴⁺ couples exist in the CMO sample, and a maximum conductivity of 78 S cm⁻¹ is achieved at 800 °C. Meanwhile, CMO oxide shows good thermal and chemical compatibility with a 10 mol% Sc₂O₃ stabilized ZrO₂ (ScSZ) electrolyte material. Impedance spectroscopy measurements reveals that CMO exhibits a low polarization resistance of 0.143 Ω cm² at 800 °C. Furthermore, a Ni-ScSZ/ScSZ/CMO single cell demonstrates a maximum power density of 1076 mW cm⁻² at 800 °C under H₂ (3% H₂O) as the fuel and ambient air as the oxidant. These results indicate that Cu_1.4Mn_1.6O₄ is a superior and promising cathode material for IT-SOFCs.

Fabrication and characterization of SSZ tape cast electrolyte-supported solid oxide fuel cells

A 10 mol%Sc₂O₃, 1 mol%CeO₂ stabilized-ZrO₂ (SSZ) powder was successfully prepared using the sol-gel method. Subsequent SSZ electrolyte pellets were prepared by tape casting technique and sintered at 1400 °C, 1450 °C, 1500 °C, 1550 °C and 1600 °C. These were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). SSZ showed a pure cubic phase after sintering, the grain size of SSZ increased with the increase of sintering temperature. The SSZ sintered at 1550 °C showed the highest ion conductivity. The maximum power densities of Ni-SSZ/SSZ/La_0.8Sr_0.2MnO_3-δ (LSM)-SSZ single cells sintered at 1550 °C were 0.18, 0.36, 0.51 and 0.72 W cm^-2 at 650, 700, 750 and 800 °C, respectively. The polarization resistance (R_p) of the single cell attained 0.201 Ω cm² at 800 °C.

Improved electrochemical performance of Sr2Fe1.5Mo0.4Nb0.1O6-δ -Sm0.2Ce0.8O2-δ composite cathodes by a one-pot method for intermediate temperature solid oxide fuel cells

In this paper, Sr₂Fe_1.5Mo_0.4Nb_0.1O_6-δ (SFMNb)-xSm_0.2Ce_0.8O_2-δ (SDC) (x = 0, 20, 30, 40, 50 wt%) composite cathode materials were synthesized by a one-pot combustion method to improve the electrochemical performance of SFMNb cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The fabrication of composite cathodes by adding SDC to SFMNb is conducive to providing extended electrochemical reaction zones for oxygen reduction reactions (ORR). X-ray diffraction (XRD) demonstrates that SFMNb is chemically compatible with SDC electrolytes at temperature up to 1100 °C. Scanning electron microscope (SEM) indicates that the SFMNb-SDC composite cathodes have a porous network nanostructure as well as the single phase SFMNb. The conductivity and thermal expansion coefficient of the composite cathodes decrease with the increased content of SDC, while the electrochemical impedance spectra (EIS) exhibits that SFMNb-40SDC composite cathode has optimal electrochemical performance with low polarization resistance (R_p) on the La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ electrolyte. The R_p of the SFMNb-40SDC composite cathode is about 0.047 Ω cm² at 800 °C in air. A single cell with SFMNb-40SDC cathode also displays favorable discharge performance, whose maximum power density is 1.22 W cm^-2 at 800 °C. All results indicate that SFMNb-40SDC composite material is a promising cathode candidate for IT-SOFCs.

Treatment of phenanthrene and benzene using microbial fuel cells operated continuously for possible in situ and ex situ applications

Bioelectrochemical systems could have potential for bioremediation of contaminants either in situ or ex situ. The treatment of a mixture of phenanthrene and benzene using two different tubular microbial fuel cells (MFCs) designed for either in situ and ex situ applications in aqueous systems was investigated over long operational periods (up to 155 days). For in situ deployments, simultaneous removal of the petroleum hydrocarbons (>90% in term of degradation efficiency) and bromate, used as catholyte, (up to 79%) with concomitant biogenic electricity generation (peak power density up to 6.75 mWm−2) were obtained at a hydraulic retention time (HRT) of 10 days. The tubular MFC could be operated successfully at copiotrophic (100 ppm phenanthrene, 2000 ppm benzene at HRT 30 days) and oligotrophic (phenanthrene and benzene, 50 ppb each, HRT 10 days) substrate conditions suggesting its effectiveness and robustness at extreme substrate concentrations in anoxic environments. In the MFC designed for ex situ deployments, optimum MFC performance was obtained at HRT of 30 h giving COD removal and maximum power output of approximately 77% and 6.75 mWm−2 respectively. The MFC exhibited the ability to resist organic shock loadings and could maintain stable MFC performance. Results of this study suggest the potential use of MFC technology for possible in situ/ex situ hydrocarbon-contaminated groundwater treatment or refinery effluents clean-up, even at extreme contaminant level conditions.

The phase diagram of the mercury-indium alloy system

The mercury-indium phase diagram has been investigated over the whole composition range from -78°C to the melting point of indium, using thermal analysis, X-ray and superconductivity techniques. This is believed to be the first application of superconductivity measurements to phase diagram investigations. A compound, HgIn, of very limited range of composition, melts congruently at -19.3°C; and gives rise to eutectics at 61.5 at. % indium and -31°C, and at 34.7% indium and -37.2°C. The β phase extends from 2.5 to 19.1 % indium and has a maximum melting point of -14.2°C at 14.2% indium. It forms a peritectic or eutectic at a temperature indistinguishable from the melting point of pure mercury with a solid solution in mercury containing some, but less than 0.3%, indium. A transition from face-centred tetragonal to face-centred cubic in the indium-rich solid solutions at about 93% indium gives rise to a peritectic at 108°C. The solubility of mercury in this face-centred cubic phase falls from about 22% at-31°C to 13% at -78°C. © 1963.

I progetti DET ammessi al finanziamento nell’ambito del Bando Industria 2015. Criticità emerse

Questa relazione tecnica viene redatta per la Giunta dei Direttori che si terrà il giorno 19/01/2010 su richiesta del Direttore, per riassumere lo stato di avanzamento dei progetti ammessi al finanziamento insieme alle criticità emerse in fase di avvio rendicontazione. La relazione si compone di una prima parte con riferimenti normativi e di riepilogo sui progetti totali presentati a livello nazionale, come CNR e come Dipartimento nelle tre Aree Tecnologiche di riferimento: Efficienza Energetica, Mobilità Sostenibile, Made in Italy. Una seconda parte riguarda la rendicontazione, la metodologia applicata e una descrizione delle criticità di due progetti PIACE - MILD. Verranno, inoltre, illustrate in riunione delle schede tecniche (v. all. 1 Ind.)riepilogative dei progetti presentati nelle aree Efficienza Energetica e Mobilità Sostenibile, realizzate in collaborazione della Sig.ra Silvia Presello.

Controle de uma microrrede ilhada baseada em geração eólica-diesel com alto nível de inserção de geração eólica

The insertion of distributed generation units in the electric power systems have contributed to the popularization of microgrid concepts. With the microgrids, several potential benefits can be achieved in regard to power quality and supply reliability. However, several technical challenges related to the control and operation of microgrids, which are associated with high insertion of generation systems based on static converters, must be overcame. Among the opportunities in the context of microgrids, there is the islanded operation of microgrids temporarily disconnected from the electric power systems and also the autonomous operation of geographically isolated microgrids. The frequency in large power systems is traditionally controlled by the generation units based on traditional synchronous generator. The insertion of distributed generation units based on static power converters may bring difficulties to the frequency control in microgrids, due to the reduction of the equivalent inertia of conventional synchronous generators present in islanded and isolated microgrids. In this context, it becomes necessary the proposition of new operational and control strategies for microgrids control, taking into account the presence of distributed generation units based on full-rated converter. This paper proposes an operational and control strategy for the islanded operation of a winddiesel microgrid with high insertion level of wind generation. The microgrid adopted in this study comprises of a wind energy conversion system with synchronous generator based on full rated converter, a diesel generator (DIG) and a dump load. Due to the high insertion level of wind generation, the wind unit operates in Vf mode and the diesel generator operates in PQ mode. The diesel generator and the dump load are used to regulate the DC-link voltage of the wind generation unit. The proposed control allows the islanded operation of the microgrid only with wind generation, wind-only mode (WO), and with wind-diesel generation, wind-diesel mode (WD). For the wind-only mode, with 100% of penetration level of wind generation, it is proposed a DC-link voltage control loop based on the use of a DC dump load. For the winddiesel mode, it is proposed a DC-link voltage control loop added to the diesel generator, which is connected to the AC side of the microgrid, in coordinated action with the dump load. The proposed operational and control strategy does not require the use of batteries and aims to maximize the energy production from wind generation, ensuring the uninterrupted operation of the microgrid. The results have showed that the operational and control strategy allowed the stable operation of the islanded microgrid and that the DC-link voltage control loop added to the diesel generator and the dump load proved to be effective during the typical variations of wind speed and load.

L'edilizia residenziale nell'era dell'economia circolare. Modelli e paradigmi per la rigenerazione delle periferie urbane

Il patrimonio residenziale italiano ammonta a 12,2 milioni di edifici, di cui il 57,5% ha più di 50 anni ed è stato costruito in assenza di normative specifiche, in termini di sicurezza sismica, resistenza al fuoco, efficienza energetica e accessibilità, e manifesta un’avanzata obsolescenza. Agire su questo patrimonio significa operare tramite le due macro categorie di intervento: demolizione/ricostruzione o riqualificazione energetica. Questa ricerca dottorale vuole indagare la demolizione/ricostruzione di comparti urbani periferici, costruiti tra 1945-1965, quale strategia di rigenerazione urbana, integrandola in un modello edilizio basato sui criteri dell’economia circolare. Vengono definite le caratteristiche costruttive e i principi di questo modello di progettazione ecosistemica, denominato Integrho, che coniuga i criteri di ecodesign nel ciclo di vita (Building in Layers, Design for Disassembly e il Design out Waste) con quelli di bioclimaticità e di adattabilità funzionale. Il lavoro è stato improntato secondo due livelli gerarchici, scala urbana e scala edilizia, tra loro correlate mediante quella intermedia dell’isolato, al fine di ottenere un obiettivo di natura metodologica: definire uno strumento di supporto decisionale, capace di indirizzare tra le categorie di intervento attraverso parametri oggettivi, valutati con analisi comparative speditive. Tale metodologia viene applicata al contesto di Bologna, e si fonda sulla creazione di un’approfondita base conoscitiva attraverso la catalogazione delle 8.209 pratiche edilizie di nuova costruzione presentate tra 1945 e il 1965. Tale strumento georeferenziato, contenente informazioni tipologiche, costruttive ecc., è impiegato per valutare in modo quantitativo e speditivo i consumi energetici, i materiali incorporati, gli impatti ambientali e i costi economici dei differenti scenari di intervento nel ciclo di vita. Infine, l’applicazione del modello edilizio Integrho e del paradigma Ri-Costruire per Ri-Generare ad uno degli isolati periferici selezionati, è impiegata come esemplificazione dell’intero processo, dalla fase conoscitiva a quella strumentale, al fine di verificarne l’attendibilità e l’applicabilità su larga scala.

Realizzazione di un Energy Harvester ibrido per applicazioni di monitoraggio strutturale

In questo studio è affrontato il progetto di un energy harvester destinato ad alimentare un nodo sensore impiegato per scopi di monitoraggio strutturale. La applicazione in questione è specifica per l'ambito ferroviario, dovendo il sistema essere collocato sul tirante di poligonazione della linea area di contatto. Sono state indagate modalità di conversione dell'energia dalle vibrazioni generate dal contatto fra catenaria e pantografo, studiandone la possibile integrazione con la conversione dell'energia solare tramite celle fotovoltaiche. Sono stati quindi progettati e realizzati due prototipi di energy harvester a vibrazioni, basati su tecnica di conversione rispettivamente elettromagnetica e piezoelettrica. La fase di progettazione è stata affinata tramite simulazioni MATLAB e COMSOL, utilizzando il metodo degli elementi finiti, ed è stato curato il progetto dei circuiti di regolazione della tensione generata dai dispositivi. Sulla base del consumo del nodo sensore misurato ne è stata simulata la alimentazione da parte di un energy harvester solare al variare del periodo dell'anno. I dispostivi realizzati sono stati valutati attraverso varie misurazioni e sono state indagate tra gli sviluppi futuri possibili approcci per il miglioramento della tecnologia realizzata.

Axis control optimization: autotuning techniques and frequency response analysis of industrial mechatronic systems

In the field of industrial automation, there is an increasing need to use optimal control systems that have low tracking errors and low power and energy consumption. The motors we are dealing with are mainly Permanent Magnet Synchronous Motors (PMSMs), controlled by 3 different types of controllers: a position controller, a speed controller, and a current controller. In this thesis, therefore, we are going to act on the gains of the first two controllers by going to find, through the TwinCAT 3 software, what might be the best set of parameters. To do this, starting with the default parameters recommended by TwinCAT, two main methods were used and then compared: the method of Ziegler and Nichols, which is a tabular method, and advanced tuning, an auto-tuning software method of TwinCAT. Therefore, in order to analyse which set of parameters was the best,several experiments were performed for each case, using the Motion Control Function Blocks. Moreover, some machines, such as large robotic arms, have vibration problems. To analyse them in detail, it was necessary to use the Bode Plot tool, which, through Bode plots, highlights in which frequencies there are resonance and anti-resonance peaks. This tool also makes it easier to figure out which and where to apply filters to improve control.

"Tecniche di Load Pull attivo a bassa frequenza per la caratterizzazione in banda base di transistori per applicazioni RF"

Una sempre crescente quantità di informazione digitale viene condivisa tra miliardi di dispositivi connessi in ogni angolo del pianeta. Per riuscire a sfruttare una banda più ampia ed aumentare la velocità di trasmissione dei dati, i prossimi standard di telecomunicazioni wireless dovranno adoperare frequenze operative sempre più alte, cercando di rispettare stringenti specifiche in termini di affidabilità ed efficienza energetica. In generale, le prestazioni di un transistor dipenderanno dalle terminazioni a cui esso è collegato. In un setup di caratterizzazione e test, è possibile, tramite un metodo noto come load pull attivo, sintetizzare un determinato valore di impedenza ad uno o più piani di riferimento all'interno di un circuito. Questa strategia si basa in generale sulla manipolazione del rapporto tra onde entranti ed uscenti da un piano di riferimento del dispositivo. Se da una parte tecniche di load pull attivo a banda larga a radiofrequenza hanno ricevuto un notevole interesse sia commerciale che accademico, dall'altra le strategie per la sintesi di impedenze presenti al terminale di alimentazione dell'amplificatore, sono state meno investigate. Questo elaborato si propone di introdurre un algoritmo per il load pull attivo a banda base per amplificatori per applicazioni RF. Dopo un'introduzione sui modelli comportamentali degli amplificatori, è stato considerato il problema degli effetti di memoria. È stata poi descritta la tecnica per l'emulazione di impedenze. Dapprima, è stato considerato il caso lineare. Poi, tramite il design di un amplificatore di potenza per applicazioni a radio frequenza usato come device under test (DUT), sono stati affrontati due esempi in presenza di non linearità, verificando la correttezza della tecnica proposta tramite l'uso di simulazioni.