Modulation Techniques for Multi-Phase Converters and Control Strategies for Multi-Phase Electric Drives

The ever-increasing spread of automation in industry puts the electrical engineer in a central role as a promoter of technological development in a sector such as the use of electricity, which is the basis of all the machinery and productive processes. Moreover the spread of drives for motor control and static converters with structures ever more complex, places the electrical engineer to face new challenges whose solution has as critical elements in the implementation of digital control techniques with the requirements of inexpensiveness and efficiency of the final product. The successfully application of solutions using non-conventional static converters awake an increasing interest in science and industry due to the promising opportunities. However, in the same time, new problems emerge whose solution is still under study and debate in the scientific community During the Ph.D. course several themes have been developed that, while obtaining the recent and growing interest of scientific community, have much space for the development of research activity and for industrial applications. The first area of research is related to the control of three phase induction motors with high dynamic performance and the sensorless control in the high speed range. The management of the operation of induction machine without position or speed sensors awakes interest in the industrial world due to the increased reliability and robustness of this solution combined with a lower cost of production and purchase of this technology compared to the others available in the market. During this dissertation control techniques will be proposed which are able to exploit the total dc link voltage and at the same time capable to exploit the maximum torque capability in whole speed range with good dynamic performance. The proposed solution preserves the simplicity of tuning of the regulators. Furthermore, in order to validate the effectiveness of presented solution, it is assessed in terms of performance and complexity and compared to two other algorithm presented in literature. The feasibility of the proposed algorithm is also tested on induction motor drive fed by a matrix converter. Another important research area is connected to the development of technology for vehicular applications. In this field the dynamic performances and the low power consumption is one of most important goals for an effective algorithm. Towards this direction, a control scheme for induction motor that integrates within a coherent solution some of the features that are commonly required to an electric vehicle drive is presented. The main features of the proposed control scheme are the capability to exploit the maximum torque in the whole speed range, a weak dependence on the motor parameters, a good robustness against the variations of the dc-link voltage and, whenever possible, the maximum efficiency. The second part of this dissertation is dedicated to the multi-phase systems. This technology, in fact, is characterized by a number of issues worthy of investigation that make it competitive with other technologies already on the market. Multiphase systems, allow to redistribute power at a higher number of phases, thus making possible the construction of electronic converters which otherwise would be very difficult to achieve due to the limits of present power electronics. Multiphase drives have an intrinsic reliability given by the possibility that a fault of a phase, caused by the possible failure of a component of the converter, can be solved without inefficiency of the machine or application of a pulsating torque. The control of the magnetic field spatial harmonics in the air-gap with order higher than one allows to reduce torque noise and to obtain high torque density motor and multi-motor applications. In one of the next chapters a control scheme able to increase the motor torque by adding a third harmonic component to the air-gap magnetic field will be presented. Above the base speed the control system reduces the motor flux in such a way to ensure the maximum torque capability. The presented analysis considers the drive constrains and shows how these limits modify the motor performance. The multi-motor applications are described by a well-defined number of multiphase machines, having series connected stator windings, with an opportune permutation of the phases these machines can be independently controlled with a single multi-phase inverter. In this dissertation this solution will be presented and an electric drive consisting of two five-phase PM tubular actuators fed by a single five-phase inverter will be presented. Finally the modulation strategies for a multi-phase inverter will be illustrated. The problem of the space vector modulation of multiphase inverters with an odd number of phases is solved in different way. An algorithmic approach and a look-up table solution will be proposed. The inverter output voltage capability will be investigated, showing that the proposed modulation strategy is able to fully exploit the dc input voltage either in sinusoidal or non-sinusoidal operating conditions. All this aspects are considered in the next chapters. In particular, Chapter 1 summarizes the mathematical model of induction motor. The Chapter 2 is a brief state of art on three-phase inverter. Chapter 3 proposes a stator flux vector control for a three- phase induction machine and compares this solution with two other algorithms presented in literature. Furthermore, in the same chapter, a complete electric drive based on matrix converter is presented. In Chapter 4 a control strategy suitable for electric vehicles is illustrated. Chapter 5 describes the mathematical model of multi-phase induction machines whereas chapter 6 analyzes the multi-phase inverter and its modulation strategies. Chapter 7 discusses the minimization of the power losses in IGBT multi-phase inverters with carrier-based pulse width modulation. In Chapter 8 an extended stator flux vector control for a seven-phase induction motor is presented. Chapter 9 concerns the high torque density applications and in Chapter 10 different fault tolerant control strategies are analyzed. Finally, the last chapter presents a positioning multi-motor drive consisting of two PM tubular five-phase actuators fed by a single five-phase inverter.

Geological and hydrogeological features affecting migration, multi-phase partitioning and degradation of chlorinated hydrocarbons through unconsolidated porous media.

Chlorinated solvents are the most ubiquitous organic contaminants found in groundwater since the last five decades. They generally reach groundwater as Dense Non-Aqueous Phase Liquid (DNAPL). This phase can migrate through aquifers, and also through aquitards, in ways that aqueous contaminants cannot. The complex phase partitioning to which chlorinated solvent DNAPLs can undergo (i.e. to the dissolved, vapor or sorbed phase), as well as their transformations (e.g. degradation), depend on the physico-chemical properties of the contaminants themselves and on features of the hydrogeological system. The main goal of the thesis is to provide new knowledge for the future investigations of sites contaminated by DNAPLs in alluvial settings, proposing innovative investigative approaches and emphasizing some of the key issues and main criticalities of this kind of contaminants in such a setting. To achieve this goal, the hydrogeologic setting below the city of Ferrara (Po plain, northern Italy), which is affected by scattered contamination by chlorinated solvents, has been investigated at different scales (regional and site specific), both from an intrinsic (i.e. groundwater flow systems) and specific (i.e. chlorinated solvent DNAPL behavior) point of view. Detailed investigations were carried out in particular in one selected test-site, known as “Caretti site”, where high-resolution vertical profiling of different kind of data were collected by means of multilevel monitoring systems and other innovative sampling and analytical techniques. This allowed to achieve a deep geological and hydrogeological knowledge of the system and to reconstruct in detail the architecture of contaminants in relationship to the features of the hosting porous medium. The results achieved in this thesis are useful not only at local scale, e.g. employable to interpret the origin of contamination in other sites of the Ferrara area, but also at global scale, in order to address future remediation and protection actions of similar hydrogeologic settings.

Nanocrystalline Silicon Based Films for Renewable Energy Applications

The present thesis is focused on the study of innovative Si-based materials for third generation photovoltaics. In particular, silicon oxi-nitride (SiOxNy) thin films and multilayer of Silicon Rich Carbide (SRC)/Si have been characterized in view of their application in photovoltaics. SiOxNy is a promising material for applications in thin-film solar cells as well as for wafer based silicon solar cells, like silicon heterojunction solar cells. However, many issues relevant to the material properties have not been studied yet, such as the role of the deposition condition and precursor gas concentrations on the optical and electronic properties of the films, the composition and structure of the nanocrystals. The results presented in the thesis aim to clarify the effects of annealing and oxygen incorporation within nc-SiOxNy films on its properties in view of the photovoltaic applications. Silicon nano-crystals (Si NCs) embedded in a dielectric matrix were proposed as absorbers in all-Si multi-junction solar cells due to the quantum confinement capability of Si NCs, that allows a better match to the solar spectrum thanks to the size induced tunability of the band gap. Despite the efficient solar radiation absorption capability of this structure, its charge collection and transport properties has still to be fully demonstrated. The results presented in the thesis aim to the understanding of the transport mechanisms at macroscopic and microscopic scale. Experimental results on SiOxNy thin films and SRC/Si multilayers have been obtained at macroscopical and microscopical level using different characterizations techniques, such as Atomic Force Microscopy, Reflection and Transmission measurements, High Resolution Transmission Electron Microscopy, Energy-Dispersive X-ray spectroscopy and Fourier Transform Infrared Spectroscopy. The deep knowledge and improved understanding of the basic physical properties of these quite complex, multi-phase and multi-component systems, made by nanocrystals and amorphous phases, will contribute to improve the efficiency of Si based solar cells.

Iva: crisi europea ed esperienza sammarinese

«I felt that the time had come to have a fresh look at the European VAT system. There were indeed a number of reasons which in my view justified taking this step»: da queste parole del Commissario Europeo Algirdas Šemeta trae ispirazione tale ricerca che ha l’obiettivo di ripercorrere, in primo luogo, le ragioni che hanno portato alla creazione di una imposta comunitaria plurifase sui consumi, ed in secondo luogo, i motivi per cui oggi è necessario un ripensamento sul tema. Le spinte ammodernatrici provengono anche dagli stessi organismi europei, che sono impegnati da anni in discussioni con gli Stati membri per arrivare alla definizione di una normativa che riesca a disegnare un sistema snello ed efficiente. Il primo importante passo in tale direzione è stato effettuato dalla stessa Commissione europea nel 2010 con l’elaborazione del Libro Verde sul futuro dell’IVA, in cui vengono evidenziati i profili critici del sistema e le possibili proposte di riforma. L’obiettivo di dare origine ad un EU VAT SYSTEM in grado di rendere la tassazione più semplice, efficace, neutrale ed anti frode. In questo lavoro si intendono sottolineare i principali elementi critici della normativa IVA comunitaria, ideando anche le modifiche che potrebbero migliorarli, al fine di creare un’ipotesi normativa capace di essere un modello ispiratore per la modifica del sistema di imposizione indiretta esistente nella Repubblica di San Marino che ad oggi si trova a doversi confrontare con una imposta monofase alle importazioni anch’essa, come l’IVA, oramai in crisi.

Structural changes and dynamic behaviour of vanadium oxide-based catalysts for gas-phase selective oxidations

Selective oxidation is one of the simplest functionalization methods and essentially all monomers used in manufacturing artificial fibers and plastics are obtained by catalytic oxidation processes. Formally, oxidation is considered as an increase in the oxidation number of the carbon atoms, then reactions such as dehydrogenation, ammoxidation, cyclization or chlorination are all oxidation reactions. In this field, most of processes for the synthesis of important chemicals used vanadium oxide-based catalysts. These catalytic systems are used either in the form of multicomponent mixed oxides and oxysalts, e.g., in the oxidation of n-butane (V/P/O) and of benzene (supported V/Mo/O) to maleic anhydride, or in the form of supported metal oxide, e.g., in the manufacture of phthalic anhydride by o-xylene oxidation, of sulphuric acid by oxidation of SO2, in the reduction of NOx with ammonia and in the ammoxidation of alkyl aromatics. In addition, supported vanadia catalysts have also been investigated for the oxidative dehydrogenation of alkanes to olefins , oxidation of pentane to maleic anhydride and the selective oxidation of methanol to formaldehyde or methyl formate [1]. During my PhD I focused my work on two gas phase selective oxidation reactions. The work was done at the Department of Industrial Chemistry and Materials (University of Bologna) in collaboration with Polynt SpA. Polynt is a leader company in the development, production and marketing of catalysts for gas-phase oxidation. In particular, I studied the catalytic system for n-butane oxidation to maleic anhydride (fluid bed technology) and for o-xylene oxidation to phthalic anhydride. Both reactions are catalyzed by systems based on vanadium, but catalysts are completely different. Part A is dedicated to the study of V/P/O catalyst for n-butane selective oxidation, while in the Part B the results of an investigation on TiO2-supported V2O5, catalyst for o-xylene oxidation are showed. In Part A, a general introduction about the importance of maleic anhydride, its uses, the industrial processes and the catalytic system are reported. The reaction is the only industrial direct oxidation of paraffins to a chemical intermediate. It is produced by n-butane oxidation either using fixed bed and fluid bed technology; in both cases the catalyst is the vanadyl pyrophosphate (VPP). Notwithstanding the good performances, the yield value didn’t exceed 60% and the system is continuously studied to improve activity and selectivity. The main open problem is the understanding of the real active phase working under reaction conditions. Several articles deal with the role of different crystalline and/or amorphous vanadium/phosphorous (VPO) compounds. In all cases, bulk VPP is assumed to constitute the core of the active phase, while two different hypotheses have been formulated concerning the catalytic surface. In one case the development of surface amorphous layers that play a direct role in the reaction is described, in the second case specific planes of crystalline VPP are assumed to contribute to the reaction pattern, and the redox process occurs reversibly between VPP and VOPO4. Both hypotheses are supported also by in-situ characterization techniques, but the experiments were performed with different catalysts and probably under slightly different working conditions. Due to complexity of the system, these differences could be the cause of the contradictions present in literature. Supposing that a key role could be played by P/V ratio, I prepared, characterized and tested two samples with different P/V ratio. Transformation occurring on catalytic surfaces under different conditions of temperature and gas-phase composition were studied by means of in-situ Raman spectroscopy, trying to investigate the changes that VPP undergoes during reaction. The goal is to understand which kind of compound constituting the catalyst surface is the most active and selective for butane oxidation reaction, and also which features the catalyst should possess to ensure the development of this surface (e.g. catalyst composition). On the basis of results from this study, it could be possible to project a new catalyst more active and selective with respect to the present ones. In fact, the second topic investigated is the possibility to reproduce the surface active layer of VPP onto a support. In general, supportation is a way to improve mechanical features of the catalysts and to overcome problems such as possible development of local hot spot temperatures, which could cause a decrease of selectivity at high conversion, and high costs of catalyst. In literature it is possible to find different works dealing with the development of supported catalysts, but in general intrinsic characteristics of VPP are worsened due to the chemical interaction between active phase and support. Moreover all these works deal with the supportation of VPP; on the contrary, my work is an attempt to build-up a V/P/O active layer on the surface of a zirconia support by thermal treatment of a precursor obtained by impregnation of a V5+ salt and of H3PO4. In-situ Raman analysis during the thermal treatment, as well as reactivity tests are used to investigate the parameters that may influence the generation of the active phase. Part B is devoted to the study of o-xylene oxidation of phthalic anhydride; industrially, the reaction is carried out in gas-phase using as catalysts a supported system formed by V2O5 on TiO2. The V/Ti/O system is quite complex; different vanadium species could be present on the titania surface, as a function of the vanadium content and of the titania surface area: (i) V species which is chemically bound to the support via oxo bridges (isolated V in octahedral or tetrahedral coordination, depending on the hydration degree), (ii) a polymeric species spread over titania, and (iii) bulk vanadium oxide, either amorphous or crystalline. The different species could have different catalytic properties therefore changing the relative amount of V species can be a way to optimize the catalytic performances of the system. For this reason, samples containing increasing amount of vanadium were prepared and tested in the oxidation of o-xylene, with the aim of find a correlations between V/Ti/O catalytic activity and the amount of the different vanadium species. The second part deals with the role of a gas-phase promoter. Catalytic surface can change under working conditions; the high temperatures and a different gas-phase composition could have an effect also on the formation of different V species. Furthermore, in the industrial practice, the vanadium oxide-based catalysts need the addition of gas-phase promoters in the feed stream, that although do not have a direct role in the reaction stoichiometry, when present leads to considerable improvement of catalytic performance. Starting point of my investigation is the possibility that steam, a component always present in oxidation reactions environment, could cause changes in the nature of catalytic surface under reaction conditions. For this reason, the dynamic phenomena occurring at the surface of a 7wt% V2O5 on TiO2 catalyst in the presence of steam is investigated by means of Raman spectroscopy. Moreover a correlation between the amount of the different vanadium species and catalytic performances have been searched. Finally, the role of dopants has been studied. The industrial V/Ti/O system contains several dopants; the nature and the relative amount of promoters may vary depending on catalyst supplier and on the technology employed for the process, either a single-bed or a multi-layer catalytic fixed-bed. Promoters have a quite remarkable effect on both activity and selectivity to phthalic anhydride. Their role is crucial, and the proper control of the relative amount of each component is fundamental for the process performance. Furthermore, it can not be excluded that the same promoter may play different role depending on reaction conditions (T, composition of gas phase..). The reaction network of phthalic anhydride formation is very complex and includes several parallel and consecutive reactions; for this reason a proper understanding of the role of each dopant cannot be separated from the analysis of the reaction scheme. One of the most important promoters at industrial level, which is always present in the catalytic formulations is Cs. It is known that Cs plays an important role on selectivity to phthalic anhydride, but the reasons of this phenomenon are not really clear. Therefore the effect of Cs on the reaction scheme has been investigated at two different temperature with the aim of evidencing in which step of the reaction network this promoter plays its role.

Heuristic algorithms for the Capacitated Location-Routing Problem and the Multi-Depot Vehicle Routing Problem

The Capacitated Location-Routing Problem (CLRP) is a NP-hard problem since it generalizes two well known NP-hard problems: the Capacitated Facility Location Problem (CFLP) and the Capacitated Vehicle Routing Problem (CVRP). The Multi-Depot Vehicle Routing Problem (MDVRP) is known to be a NP-hard since it is a generalization of the well known Vehicle Routing Problem (VRP), arising with one depot. This thesis addresses heuristics algorithms based on the well-know granular search idea introduced by Toth and Vigo (2003) to solve the CLRP and the MDVRP. Extensive computational experiments on benchmark instances for both problems have been performed to determine the effectiveness of the proposed algorithms. This work is organized as follows: Chapter 1 describes a detailed overview and a methodological review of the literature for the the Capacitated Location-Routing Problem (CLRP) and the Multi-Depot Vehicle Routing Problem (MDVRP). Chapter 2 describes a two-phase hybrid heuristic algorithm to solve the CLRP. Chapter 3 shows a computational comparison of heuristic algorithms for the CLRP. Chapter 4 presents a hybrid granular tabu search approach for solving the MDVRP.

Applications of High Speed Configurable Logic Devices in Modern Particle Physics Experiments

Several activities were conducted during my PhD activity. For the NEMO experiment a collaboration between the INFN/University groups of Catania and Bologna led to the development and production of a mixed signal acquisition board for the Nemo Km3 telescope. The research concerned the feasibility study for a different acquisition technique quite far from that adopted in the NEMO Phase 1 telescope. The DAQ board that we realized exploits the LIRA06 front-end chip for the analog acquisition of anodic an dynodic sources of a PMT (Photo-Multiplier Tube). The low-power analog acquisition allows to sample contemporaneously multiple channels of the PMT at different gain factors in order to increase the signal response linearity over a wider dynamic range. Also the auto triggering and self-event-classification features help to improve the acquisition performance and the knowledge on the neutrino event. A fully functional interface towards the first level data concentrator, the Floor Control Module, has been integrated as well on the board, and a specific firmware has been realized to comply with the present communication protocols. This stage of the project foresees the use of an FPGA, a high speed configurable device, to provide the board with a flexible digital logic control core. After the validation of the whole front-end architecture this feature would be probably integrated in a common mixed-signal ASIC (Application Specific Integrated Circuit). The volatile nature of the configuration memory of the FPGA implied the integration of a flash ISP (In System Programming) memory and a smart architecture for a safe remote reconfiguration of it. All the integrated features of the board have been tested. At the Catania laboratory the behavior of the LIRA chip has been investigated in the digital environment of the DAQ board and we succeeded in driving the acquisition with the FPGA. The PMT pulses generated with an arbitrary waveform generator were correctly triggered and acquired by the analog chip, and successively they were digitized by the on board ADC under the supervision of the FPGA. For the communication towards the data concentrator a test bench has been realized in Bologna where, thanks to a lending of the Roma University and INFN, a full readout chain equivalent to that present in the NEMO phase-1 was installed. These tests showed a good behavior of the digital electronic that was able to receive and to execute command imparted by the PC console and to answer back with a reply. The remotely configurable logic behaved well too and demonstrated, at least in principle, the validity of this technique. A new prototype board is now under development at the Catania laboratory as an evolution of the one described above. This board is going to be deployed within the NEMO Phase-2 tower in one of its floors dedicated to new front-end proposals. This board will integrate a new analog acquisition chip called SAS (Smart Auto-triggering Sampler) introducing thus a new analog front-end but inheriting most of the digital logic present in the current DAQ board discussed in this thesis. For what concern the activity on high-resolution vertex detectors, I worked within the SLIM5 collaboration for the characterization of a MAPS (Monolithic Active Pixel Sensor) device called APSEL-4D. The mentioned chip is a matrix of 4096 active pixel sensors with deep N-well implantations meant for charge collection and to shield the analog electronics from digital noise. The chip integrates the full-custom sensors matrix and the sparsifification/readout logic realized with standard-cells in STM CMOS technology 130 nm. For the chip characterization a test-beam has been set up on the 12 GeV PS (Proton Synchrotron) line facility at CERN of Geneva (CH). The collaboration prepared a silicon strip telescope and a DAQ system (hardware and software) for data acquisition and control of the telescope that allowed to store about 90 million events in 7 equivalent days of live-time of the beam. My activities concerned basically the realization of a firmware interface towards and from the MAPS chip in order to integrate it on the general DAQ system. Thereafter I worked on the DAQ software to implement on it a proper Slow Control interface of the APSEL4D. Several APSEL4D chips with different thinning have been tested during the test beam. Those with 100 and 300 um presented an overall efficiency of about 90% imparting a threshold of 450 electrons. The test-beam allowed to estimate also the resolution of the pixel sensor providing good results consistent with the pitch/sqrt(12) formula. The MAPS intrinsic resolution has been extracted from the width of the residual plot taking into account the multiple scattering effect.

Diagnostic techniques for EHD and MHD interaction

The impact of plasma technologies is growing both in the academic and in the industrial fields. Nowadays, a great interest is focused in plasma applications in aeronautics and astronautics domains. Plasma actuators based on the Magneto-Hydro-Dynamic (MHD) and Electro- Hydro-Dynamic (EHD) interactions are potentially able to suitably modify the fluid-dynamics characteristics around a flying body without utilizing moving parts. This could lead to the control of an aircraft with negligible response time, more reliability and improvements of the performance. In order to study the aforementioned interactions, a series of experiments and a wide number of diagnostic techniques have been utilized. The EHD interaction, realized by means of a Dielectric Barrier Discharge (DBD) actuator, and its impact on the boundary layer have been evaluated by means of two different experiments. In the first one a three phase multi-electrode flat panel actuator is used. Different external flow velocities (from 1 to 20m/s) and different values of the supplied voltage and frequency have been considered. Moreover a change of the phase sequence has been done to verify the influence of the electric field existing between successive phases. Measurements of the induced speed had shown the effect of the supply voltage and the frequency, and the phase order in the momentum transfer phenomenon. Gains in velocity, inside the boundary layer, of about 5m/s have been obtained. Spectroscopic measurements allowed to determine the rotational and the vibrational temperature of the plasma which lie in the range of 320 ÷ 440°K and of 3000 ÷ 3900°K respectively. A deviation from thermodynamic equilibrium had been found. The second EHD experiment is realized on a single electrode pair DBD actuator driven by nano-pulses superimposed to a DC or an AC bias. This new supply system separates the plasma formation mechanism from the acceleration action on the fluid, leading to an higher degree of the control of the process. Both the voltage and the frequency of the nano-pulses and the amplitude and the waveform of the bias have been varied during the experiment. Plasma jets and vortex behavior had been observed by means of fast Schlieren imaging. This allowed a deeper understanding of the EHD interaction process. A velocity increase in the boundary layer of about 2m/s had been measured. Thrust measurements have been performed by means of a scales and compared with experimental data reported in the literature. For similar voltage amplitudes thrust larger than those of the literature, had been observed. Surface charge measurements led to realize a modified DBD actuator able to obtain similar performances when compared with that of other experiments. However in this case a DC bias replacing the AC bias had been used. MHD interaction experiments had been carried out in a hypersonic wind tunnel in argon with a flow of Mach 6. Before the MHD experiments a thermal, fluid-dynamic and plasma characterization of the hypersonic argon plasma flow have been done. The electron temperature and the electron number density had been determined by means of emission spectroscopy and microwave absorption measurements. A deviation from thermodynamic equilibrium had been observed. The electron number density showed to be frozen at the stagnation region condition in the expansion through the nozzle. MHD experiments have been performed using two axial symmetric test bodies. Similar magnetic configurations were used. Permanent magnets inserted into the test body allowed to generate inside the plasma azimuthal currents around the conical shape of the body. These Faraday currents are responsible of the MHD body force which acts against the flow. The MHD interaction process has been observed by means of fast imaging, pressure and electrical measurements. Images showed bright rings due to the Faraday currents heating and exciting the plasma particles. Pressure measurements showed increases of the pressure in the regions where the MHD interaction is large. The pressure is 10 to 15% larger than when the MHD interaction process is silent. Finally by means of electrostatic probes mounted flush on the test body lateral surface Hall fields of about 500V/m had been measured. These results have been used for the validation of a numerical MHD code.

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Design and implementation of a novel multi-constellation FPGA-based dual frequency GNSS receiver for space applications

The PhD activity described in the document is part of the Microsatellite and Microsystem Laboratory of the II Faculty of Engineering, University of Bologna. The main objective is the design and development of a GNSS receiver for the orbit determination of microsatellites in low earth orbit. The development starts from the electronic design and goes up to the implementation of the navigation algorithms, covering all the aspects that are involved in this type of applications. The use of GPS receivers for orbit determination is a consolidated application used in many space missions, but the development of the new GNSS system within few years, such as the European Galileo, the Chinese COMPASS and the Russian modernized GLONASS, proposes new challenges and offers new opportunities to increase the orbit determination performances. The evaluation of improvements coming from the new systems together with the implementation of a receiver that is compatible with at least one of the new systems, are the main activities of the PhD. The activities can be divided in three section: receiver requirements definition and prototype implementation, design and analysis of the GNSS signal tracking algorithms, and design and analysis of the navigation algorithms. The receiver prototype is based on a Virtex FPGA by Xilinx, and includes a PowerPC processor. The architecture follows the software defined radio paradigm, so most of signal processing is performed in software while only what is strictly necessary is done in hardware. The tracking algorithms are implemented as a combination of Phase Locked Loop and Frequency Locked Loop for the carrier, and Delay Locked Loop with variable bandwidth for the code. The navigation algorithm is based on the extended Kalman filter and includes an accurate LEO orbit model.

Advanced Beamforming for Distributed and Multi-Beam Networks

Beamforming entails joint processing of multiple signals received or transmitted by an array of antennas. This thesis addresses the implementation of beamforming in two distinct systems, namely a distributed network of independent sensors, and a broad-band multi-beam satellite network. With the rising popularity of wireless sensors, scientists are taking advantage of the flexibility of these devices, which come with very low implementation costs. Simplicity, however, is intertwined with scarce power resources, which must be carefully rationed to ensure successful measurement campaigns throughout the whole duration of the application. In this scenario, distributed beamforming is a cooperative communication technique, which allows nodes in the network to emulate a virtual antenna array seeking power gains in the order of the size of the network itself, when required to deliver a common message signal to the receiver. To achieve a desired beamforming configuration, however, all nodes in the network must agree upon the same phase reference, which is challenging in a distributed set-up where all devices are independent. The first part of this thesis presents new algorithms for phase alignment, which prove to be more energy efficient than existing solutions. With the ever-growing demand for broad-band connectivity, satellite systems have the great potential to guarantee service where terrestrial systems can not penetrate. In order to satisfy the constantly increasing demand for throughput, satellites are equipped with multi-fed reflector antennas to resolve spatially separated signals. However, incrementing the number of feeds on the payload corresponds to burdening the link between the satellite and the gateway with an extensive amount of signaling, and to possibly calling for much more expensive multiple-gateway infrastructures. This thesis focuses on an on-board non-adaptive signal processing scheme denoted as Coarse Beamforming, whose objective is to reduce the communication load on the link between the ground station and space segment.

Computational modelling of human stem cell-derived cardiomyocytes - Texture descriptors for biological image processing

This thesis investigates two distinct research topics. The main topic (Part I) is the computational modelling of cardiomyocytes derived from human stem cells, both embryonic (hESC-CM) and induced-pluripotent (hiPSC-CM). The aim of this research line lies in developing models of the electrophysiology of hESC-CM and hiPSC-CM in order to integrate the available experimental data and getting in-silico models to be used for studying/making new hypotheses/planning experiments on aspects not fully understood yet, such as the maturation process, the functionality of the Ca2+ hangling or why the hESC-CM/hiPSC-CM action potentials (APs) show some differences with respect to APs from adult cardiomyocytes. Chapter I.1 introduces the main concepts about hESC-CMs/hiPSC-CMs, the cardiac AP, and computational modelling. Chapter I.2 presents the hESC-CM AP model, able to simulate the maturation process through two developmental stages, Early and Late, based on experimental and literature data. Chapter I.3 describes the hiPSC-CM AP model, able to simulate the ventricular-like and atrial-like phenotypes. This model was used to assess which currents are responsible for the differences between the ventricular-like AP and the adult ventricular AP. The secondary topic (Part II) consists in the study of texture descriptors for biological image processing. Chapter II.1 provides an overview on important texture descriptors such as Local Binary Pattern or Local Phase Quantization. Moreover the non-binary coding and the multi-threshold approach are here introduced. Chapter II.2 shows that the non-binary coding and the multi-threshold approach improve the classification performance of cellular/sub-cellular part images, taken from six datasets. Chapter II.3 describes the case study of the classification of indirect immunofluorescence images of HEp2 cells, used for the antinuclear antibody clinical test. Finally the general conclusions are reported.

High-Speed Laser Processing of Thin Single and Multi-Layer Films

Theoretical models are developed for the continuous-wave and pulsed laser incision and cut of thin single and multi-layer films. A one-dimensional steady-state model establishes the theoretical foundations of the problem by combining a power-balance integral with heat flow in the direction of laser motion. In this approach, classical modelling methods for laser processing are extended by introducing multi-layer optical absorption and thermal properties. The calculation domain is consequently divided in correspondence with the progressive removal of individual layers. A second, time-domain numerical model for the short-pulse laser ablation of metals accounts for changes in optical and thermal properties during a single laser pulse. With sufficient fluence, the target surface is heated towards its critical temperature and homogeneous boiling or "phase explosion" takes place. Improvements are seen over previous works with the more accurate calculation of optical absorption and shielding of the incident beam by the ablation products. A third, general time-domain numerical laser processing model combines ablation depth and energy absorption data from the short-pulse model with two-dimensional heat flow in an arbitrary multi-layer structure. Layer removal is the result of both progressive short-pulse ablation and classical vaporisation due to long-term heating of the sample. At low velocity, pulsed laser exposure of multi-layer films comprising aluminium-plastic and aluminium-paper are found to be characterised by short-pulse ablation of the metallic layer and vaporisation or degradation of the others due to thermal conduction from the former. At high velocity, all layers of the two films are ultimately removed by vaporisation or degradation as the average beam power is increased to achieve a complete cut. The transition velocity between the two characteristic removal types is shown to be a function of the pulse repetition rate. An experimental investigation validates the simulation results and provides new laser processing data for some typical packaging materials.

Earthquake forecasting and seismic hazard analysis: some insights on the testing phase and the modeling

This thesis is divided in three chapters. In the first chapter we analyse the results of the world forecasting experiment run by the Collaboratory for the Study of Earthquake Predictability (CSEP). We take the opportunity of this experiment to contribute to the definition of a more robust and reliable statistical procedure to evaluate earthquake forecasting models. We first present the models and the target earthquakes to be forecast. Then we explain the consistency and comparison tests that are used in CSEP experiments to evaluate the performance of the models. Introducing a methodology to create ensemble forecasting models, we show that models, when properly combined, are almost always better performing that any single model. In the second chapter we discuss in depth one of the basic features of PSHA: the declustering of the seismicity rates. We first introduce the Cornell-McGuire method for PSHA and we present the different motivations that stand behind the need of declustering seismic catalogs. Using a theorem of the modern probability (Le Cam's theorem) we show that the declustering is not necessary to obtain a Poissonian behaviour of the exceedances that is usually considered fundamental to transform exceedance rates in exceedance probabilities in the PSHA framework. We present a method to correct PSHA for declustering, building a more realistic PSHA. In the last chapter we explore the methods that are commonly used to take into account the epistemic uncertainty in PSHA. The most widely used method is the logic tree that stands at the basis of the most advanced seismic hazard maps. We illustrate the probabilistic structure of the logic tree, and then we show that this structure is not adequate to describe the epistemic uncertainty. We then propose a new probabilistic framework based on the ensemble modelling that properly accounts for epistemic uncertainties in PSHA.

Development Of New Toolkits For Orbit Determination Codes For Precise Radio Tracking Experiments

This thesis describes the developments of new models and toolkits for the orbit determination codes to support and improve the precise radio tracking experiments of the Cassini-Huygens mission, an interplanetary mission to study the Saturn system. The core of the orbit determination process is the comparison between observed observables and computed observables. Disturbances in either the observed or computed observables degrades the orbit determination process. Chapter 2 describes a detailed study of the numerical errors in the Doppler observables computed by NASA's ODP and MONTE, and ESA's AMFIN. A mathematical model of the numerical noise was developed and successfully validated analyzing against the Doppler observables computed by the ODP and MONTE, with typical relative errors smaller than 10%. The numerical noise proved to be, in general, an important source of noise in the orbit determination process and, in some conditions, it may becomes the dominant noise source. Three different approaches to reduce the numerical noise were proposed. Chapter 3 describes the development of the multiarc library, which allows to perform a multi-arc orbit determination with MONTE. The library was developed during the analysis of the Cassini radio science gravity experiments of the Saturn's satellite Rhea. Chapter 4 presents the estimation of the Rhea's gravity field obtained from a joint multi-arc analysis of Cassini R1 and R4 fly-bys, describing in details the spacecraft dynamical model used, the data selection and calibration procedure, and the analysis method followed. In particular, the approach of estimating the full unconstrained quadrupole gravity field was followed, obtaining a solution statistically not compatible with the condition of hydrostatic equilibrium. The solution proved to be stable and reliable. The normalized moment of inertia is in the range 0.37-0.4 indicating that Rhea's may be almost homogeneous, or at least characterized by a small degree of differentiation.