Characterization of fold-related fractures in the carbonate rocks of the Cingoli anticline, northern Apennines, Italy

Thrust fault-related folds in carbonate rocks are characterized by deformation accommodated by different structures, such as joints, faults, pressure solution seams, and deformation bands. Defining the development of fracture systems related to the folding process is significant both for theoretical and practical purposes. Fracture systems are useful constrains in order to understand the kinematical evolution of the fold. Furthermore, understanding the relationships between folding and fracturing provides a noteworthy contribution for reconstructing the geodynamic and the structural evolution of the studied area. Moreover, as fold-related fractures influence fluid flow through rocks, fracture systems are relevant for energy production (geothermal studies, methane and CO2 , storage and hydrocarbon exploration), environmental and social issues (pollutant distribution, aquifer characterization). The PhD project shows results of a study carried out in a multilayer carbonate anticline characterized by different mechanical properties. The aim of this study is to understand the factors which influence the fracture formation and to define their temporal sequence during the folding process. The studied are is located in the Cingoli anticline (Northern Apennines), which is characterized by a pelagic multilayer characterized by sequences with different mechanical stratigraphies. A multi-scale analysis has been made in several outcrops located in different structural positions. This project shows that the conceptual sketches proposed in literature and the strain distribution models outline well the geometrical orientation of most of the set of fractures observed in the Cingoli anticline. On the other hand, the present work suggests the relevance of the mechanical stratigraphy in particular controlling the type of fractures formed (e.g. pressure solution seams, joints or shear fractures) and their subsequent evolution. Through a multi-scale analysis, and on the basis of the temporal relationship between fracture sets and their orientation respect layering, I also suggest a conceptual model for fracture systems formation.

Photo- and redox-active supramolecular systems containing metal complexes

The aim of this Ph.D. project has been the photophysical and photochemical characterization of new photo- and redox-active supramolecular systems. In particular we studied two different classes of compounds: metal complexes and dendrimers. Two different families of bis-cyclometalated neutral Ir(III) complexes are presented and their photophysical properties are discussed. The first family of complexes contains two 2-phenylpyridyl (ppy) or 2-(4,6-difluorophenyl)pyridyl (F2ppy) cyclometalated ligands and an ancillary ligand constituted by a phenol-oxazoline (phox), which can be substituted in the third position with a fluorine group (Fphox). In the second part of this study, we present another family of bis-cyclometalated Ir(III) complexes in which the ancillary ligand could be a chiral or an achiral bis-oxazoline (box). We report on their structural, electrochemical, photophysical, and photochemical properties. Complexes containing phox and Fphox ancillary ligands show blue luminescence with very high quantum yield, while complexes with box ligands do not show particularly interesting photophysical properties. Surprisingly these complexes give an unexpected photoreaction when irradiated with UV light in presence of dioxygen. This photoreaction originates a stable, strong blue emitting and particularly interesting photoproduct. Three successive generations of a family of polyethyleneglycol (PEG)-coated Pd(II) tetrabenzoporphyrin (PdTBP)-based dendritic nanoprobes are presented, and their ability to sensitize singlet oxygen and inflict cellular photodamage are discussed. It was found that the size of the dendrimer has practically no effect on the singlet oxygen sensitization efficiency, that approximate the unity, in spite of the strong attenuation of the triplet quenching rate with an increase in the dendrimer generation. Nevertheless, when compared against a commonly used singlet oxygen sensitizer, as Photofrin, the phosphorescent probes were found to be non-phototoxic. The lack of phototoxicity is presumably due to the inability of PEGylated probes to associate with cell surfaces and/or penetrate cellular membranes. The results suggest that protected phosphorescent probes can be safely used for oxygen measurements in biological systems in vivo. A new family of two photoswitchable (G0(Azo) and G1(Azo)) dendrimers with an azobenzene core, two cyclam units as coordination sites for metal ions, and luminescent naphthalene units at the periphery have been characterized and their coordination abilities have been studied. Because of their proximity, the various functional groups of the dendrimer may interact, so that the properties of the dendrimers are different from those exhibited by the separated functional units. Both the naphthalene fluorescence and the azobenzene photoisomerization can be observed in the dendrimer, but it has been shown that (i) the fluorescent excited state of the naphthalene units is substantially quenched by excimer and exciplex formation and by energy transfer to the azobenzene units, and (ii) in the latter case the fluorescence quenching is accompanied by the photosensitized isomerization of the trans → cis, and, with higher efficiency, the cis → trans reaction. Complexation of these dendrimers, both trans and cis isomers, with Zn(II) ions shows that complexes of 1:1 and 2:1 metal per dendrimer stoichiometry are formed showing different photophysical and photochemical properties compared to the corresponding free ligands. Practically unitary efficiency of the sensitized isomerization of trans → cis and cis → trans reaction is observed, as well as a slight increase in the naphthalene monomer emission. These results are consistent with the coordination of the cyclam amine units with Zn(II), which prevents exciplex formation. No indication of a concomitant coordination of both cyclam to a single metal ion has been obtained both for trans and cis isomer.

Nonlinear Control Strategies for Cooperative Control of Multi-Robot Systems

This thesis deals with distributed control strategies for cooperative control of multi-robot systems. Specifically, distributed coordination strategies are presented for groups of mobile robots. The formation control problem is initially solved exploiting artificial potential fields. The purpose of the presented formation control algorithm is to drive a group of mobile robots to create a completely arbitrarily shaped formation. Robots are initially controlled to create a regular polygon formation. A bijective coordinate transformation is then exploited to extend the scope of this strategy, to obtain arbitrarily shaped formations. For this purpose, artificial potential fields are specifically designed, and robots are driven to follow their negative gradient. Artificial potential fields are then subsequently exploited to solve the coordinated path tracking problem, thus making the robots autonomously spread along predefined paths, and move along them in a coordinated way. Formation control problem is then solved exploiting a consensus based approach. Specifically, weighted graphs are used both to define the desired formation, and to implement collision avoidance. As expected for consensus based algorithms, this control strategy is experimentally shown to be robust to the presence of communication delays. The global connectivity maintenance issue is then considered. Specifically, an estimation procedure is introduced to allow each agent to compute its own estimate of the algebraic connectivity of the communication graph, in a distributed manner. This estimate is then exploited to develop a gradient based control strategy that ensures that the communication graph remains connected, as the system evolves. The proposed control strategy is developed initially for single-integrator kinematic agents, and is then extended to Lagrangian dynamical systems.

Pratiche del possibile: i Participatory Guarantee Systems e le scelte d'acquisto del consumatore brasiliano

Negli ultimi anni, parallelamente all’espansione del settore biologico, si è assistito a un crescente interesse per i modelli alternativi di garanzia dell’integrità e della genuinità dei prodotti biologici. Gruppi di piccoli agricoltori di tutto il mondo hanno iniziato a sviluppare approcci alternativi per affrontare i problemi connessi alla certificazione di terza parte. Queste pratiche sono note come Sistemi di Garanzia Partecipativa (PGS). Tali modelli: (i) si basano sugli standard di certificazione biologica dell’IFOAM, (ii) riguardano il complesso dei produttori di una comunità rurale, (iii) comportano l’inclusione di una grande varietà di attori e (iv) hanno lo scopo di ridurre al minimo burocrazia e costi semplificando le procedure di verifica e incorporando un elemento di educazione ambientale e sociale sia per i produttori sia per i consumatori. Gli obiettivi di questo lavoro di ricerca: • descrivere il funzionamento dei sistemi di garanzia partecipativa; • indicare i vantaggi della loro adozione nei Paesi in via di sviluppo e non; • illustrare il caso della Rede Ecovida de Agroecologia (Brasile); • offrire uno spunto di riflessione che riguarda il consumatore e la relativa fiducia nel modello PGS. L’impianto teorico fa riferimento alla Teoria delle Convenzioni. Sulla base del quadro teorico è stato costruito un questionario per i consumatori con lo scopo di testare l’appropriatezza delle ipotesi teoriche. I risultati finali riguardano la stima del livello di conoscenza attuale, la fiducia e la volontà d’acquisto dei prodotti PGS da parte dei consumatori nelle aree considerate. Sulla base di questa ricerca sarà possibile adattare ed esportare il modello empirico in altri paesi che presentano economie diverse per cercare di comprendere il potenziale campo di applicazione dei sistemi di garanzia partecipativa.

Hybrid portable systems for bio-nanosensors

The promising development in the routine nanofabrication and the increasing knowledge of the working principles of new classes of highly sensitive, label-free and possibly cost-effective bio-nanosensors for the detection of molecules in liquid environment, has rapidly increased the possibility to develop portable sensor devices that could have a great impact on many application fields, such as health-care, environment and food production, thanks to the intrinsic ability of these biosensors to detect, monitor and study events at the nanoscale. Moreover, there is a growing demand for low-cost, compact readout structures able to perform accurate preliminary tests on biosensors and/or to perform routine tests with respect to experimental conditions avoiding skilled personnel and bulky laboratory instruments. This thesis focuses on analysing, designing and testing novel implementation of bio-nanosensors in layered hybrid systems where microfluidic devices and microelectronic systems are fused in compact printed circuit board (PCB) technology. In particular the manuscript presents hybrid systems in two validating cases using nanopore and nanowire technology, demonstrating new features not covered by state of the art technologies and based on the use of two custom integrated circuits (ICs). As far as the nanopores interface system is concerned, an automatic setup has been developed for the concurrent formation of bilayer lipid membranes combined with a custom parallel readout electronic system creating a complete portable platform for nanopores or ion channels studies. On the other hand, referring to the nanowire readout hybrid interface, two systems enabling to perform parallel, real-time, complex impedance measurements based on lock-in technique, as well as impedance spectroscopy measurements have been developed. This feature enable to experimentally investigate the possibility to enrich informations on the bio-nanosensors concurrently acquiring impedance magnitude and phase thus investigating capacitive contributions of bioanalytical interactions on biosensor surface.

Water, sediment and soil physicochemical interactions in freshwater, brackish and saline systems

The physicochemical interactions between water, sediment and soil deeply influence the formation and development of the ecosystem. In this research, different freshwater, brackish and saline subaqueous environments of Northern Italy were chosen as study area to investigate the physicochemical processes which occur at the interface between water and sediments, as well as the effects of soil submergence on ecosystem development. In the freshwater system of the Reno river basin, the main purpose was to define the heavy metals hazard in water and sediments of natural and artificial water courses. Heavy metals partitioning and speciation allowed to assess the environmental risk linked to the critical action of dredging canal sediments, for the maintenance of the hydraulic safety of plain lands. In addition, some bioremediation techniques were experimented for protecting sediments from heavy metals contamination, and for giving an answer to the problem of sediments management. In the brackish system of S. Vitale park, the development of hydromorphic and subaqueous soils was investigated. The study of soil profiles highlighted the presence of a soil continuum among pedons subjected to different saturation degrees. This investigation allowed to the identification of both morphological and physicochemical indicators, which characterize the formation of subaqueous soils and describe the soil hydromorphism in transitional soil systems. In the saline system of Grado lagoon, an ecosystem approach was used to define the role of water oscillation in soil characterization and plants colonization. This study highlighted the close relationship and the mutual influence of soil submergence and aeration, tide oscillation and vegetation cover, on the soil development. In view of climate change, this study contribute to understand and suppose how soil and landscape could evolve. However, a complete evaluation of hydromorphic soil functionality will be achieved only involving physiological and biochemical expertise in these kind of studies.

Nanostructured Systems for Electrocatalysis of Reduction Reactions for Energy Conversion Applications

Oxygen Reduction Reaction (ORR) requires a platinum-based catalyst to reduce the activation barrier. One of the most promising materials as alternative catalysts are carbon-based, graphene and carbon nanotubes (CNT) derivatives. ORR on a carbon-based substrate involves the less efficient two electrons process and the optimal four electrons process. New synthetic strategies to produce tunable graphene-based materials utilizing graphene oxide (GO) as a base inspired the first part of this work. Hydrogen Evolution Reaction (HER) is a slow process requiring also platinum or palladium as catalyst. In the second part of this work, we develop and use a technique for Ni nanoparticles electrodeposition using NiCl2 as precursor in the presence of ascorbate ligands. Electrodeposition of nano-nickel onto flat glassy carbon (GC) and onto nitrogen-doped reduced graphene oxide (rGO-N) substrates are studied. State of the art catalysts for CO2RR requires rare metals rhenium or rhodium. In recent years significant research has been done on non-noble metals and molecular systems to use as electro and photo-catalysts (artificial photosynthesis). As Cu-Zn alloys show good CO2RR performance, here we applied the same nanoparticle electrosynthesis technique using as precursors CuCl2 and Cl2Zn and observed successful formation of the nanoparticles and a notable activity in presence of CO2. Using rhenium complexes as catalysts is another popular approach and di-nuclear complexes have a positive cooperative effect. More recently a growing family of pre-catalysts based on the earth-abundant metal manganese, has emerged as a promising, cheaper alternative. Here we study the cooperative effects of di-nuclear manganese complexes derivatives when used as homogeneous electrocatalysts, as well as a rhenium functionalized polymer used as heterogeneous electrocatalyst.

Optimization and development of low environmental impact propulsion systems

The aim of the Ph.D. research project was to explore Dual Fuel combustion and hybridization. Natural gas-diesel Dual Fuel combustion was experimentally investigated on a 4-Stroke, 2.8 L, turbocharged, light-duty Diesel engine, considering four operating points in the range between low to medium-high loads at 3000 rpm. Then, a numerical analysis was carried out using a customized version of the KIVA-3V code, in order to optimize the diesel injection strategy of the highest investigated load. A second KIVA-3V model was used to analyse the interchangeability between natural gas and biogas on an intermediate operating point. Since natural gas-diesel Dual Fuel combustion suffers from poor combustion efficiency at low loads, the effects of hydrogen enriched natural gas on Dual Fuel combustion were investigated using a validated Ansys Forte model, followed by an optimization of the diesel injection strategy and a sensitivity analysis to the swirl ratio, on the lowest investigated load. Since one of the main issues of Low Temperature Combustion engines is the low power density, 2-Stroke engines, thanks to the double frequency compared to 4-Stroke engines, may be more suitable to operate in Dual Fuel mode. Therefore, the application of gasoline-diesel Dual Fuel combustion to a modern 2-Stroke Diesel engine was analysed, starting from the investigation of gasoline injection and mixture formation. As far as hybridization is concerned, a MATLAB-Simulink model was built to compare a conventional (combustion) and a parallel-hybrid powertrain applied to a Formula SAE race car.

Models for reliability estimation of HVDC cable systems

The work carried out in this thesis aims at: - studying – in both simulative and experimental methods – the effect of electrical transients (i.e., Voltage Polarity Reversals VPRs, Temporary OverVoltages TOVs, and Superimposed Switching Impulses SSIs) on the aging phenomena in HVDC extruded cable insulations. Dielectric spectroscopy, conductivity measurements, Fourier Transform Infra-Red FTIR spectroscopy, and space charge measurements show variation in the insulating properties of the aged Cross-Linked Polyethylene XLPE specimens compared to non-aged ones. Scission in XLPE bonds and formation of aging chemical bonds is also noticed in aged insulations due to possible oxidation reactions. The aged materials show more ability to accumulate space charges compared to non-aged ones. An increase in both DC electrical conductivity and imaginary permittivity has been also noticed. - The development of life-based geometric design of HVDC cables in a detailed parametric analysis of all parameters that affect the design. Furthermore, the effect of both electrical and thermal transients on the design is also investigated. - The intrinsic thermal instability in HVDC cables and the effect of insulation characteristics on the thermal stability using a temperature and field iterative loop (using numerical methods – Finite Difference Method FDM). The dielectric loss coefficient is also calculated for DC cables and found to be less than that in AC cables. This emphasizes that the intrinsic thermal instability is critical in HVDC cables. - Fitting electrical conductivity models to the experimental measurements using both models found in the literature and modified models to find the best fit by considering the synergistic effect between field and temperature coefficients of electrical conductivity.

Synthesis and catalytic activity of new cu-based catalytic systems for the enhanced electrochemical CO2 reduction

This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.

Mars delivery service - development of the electro-mechanical systems of the Sample Fetch Rover for the Mars Sample Return Campaign

This thesis describes the development of the Sample Fetch Rover (SFR), studied for Mars Sample Return (MSR), an international campaign carried out in cooperation between the National Aeronautics and Space Administration (NASA) and the European Space Agency (ESA). The focus of this document is the design of the electro-mechanical systems of the rover. After placing this work into the general context of robotic planetary exploration and summarising the state of the art for what concerns Mars rovers, the architecture of the Mars Sample Return Campaign is presented. A complete overview of the current SFR architecture is provided, touching upon all the main subsystems of the spacecraft. For each area, it is discussed what are the design drivers, the chosen solutions and whether they use heritage technology (in particular from the ExoMars Rover) or new developments. This research focuses on two topics of particular interest, due to their relevance for the mission and the novelty of their design: locomotion and sample acquisition, which are discussed in depth. The early SFR locomotion concepts are summarised, covering the initial trade-offs and discarded designs for higher traverse performance. Once a consolidated architecture was reached, the locomotion subsystem was developed further, defining the details of the suspension, actuators, deployment mechanisms and wheels. This technology is presented here in detail, including some key analysis and test results that support the design and demonstrate how it responds to the mission requirements. Another major electro-mechanical system developed as part of this work is the one dedicated to sample tube acquisition. The concept of operations of this machinery was defined to be robust against the unknown conditions that characterise the mission. The design process led to a highly automated robotic system which is described here in its main components: vision system, robotic arm and tube storage.

Molecular and hybrid systems for solar-to-chemical energy conversion

My Ph.D. thesis was dedicated to the exploration of different paths to convert sunlight into the shape of chemical bonds, by the formation of solar fuels. During the past three years, I have focused my research on two of these, namely molecular hydrogen H2 and the reduced nicotinamide adenine dinucleotide enzyme cofactor NAD(P)H. The first could become the ideal energy carrier for a truly clean energy system; it currently represents the best chance to liberate humanity from its dependence on fossil fuels. To address this, I studied different systems which can achieve proton reduction upon light absorption. More specifically, part of my work was aimed to the development of a cost-effective and stable catalyst in combination with a well-known photochemical cycle. To this extent, I worked on transition metal oxides which, as demonstrated in this work, have been identified as promising H2 evolution catalysts, showing excellent activity, stability, and previously unreported versatility. Another branch of my work on hydrogen production dealt with the use of a new class of polymeric semiconductor materials to absorb light and convert it into H2. The second solar fuel mentioned above is a key component of the most powerful methods for chemical synthesis: enzyme catalysis. The high cost of the reduced forms prohibits large-scale utilization, so artificial photosynthetic approaches for regenerating it are being intensively studied. The first system I developed exploits the tremendous reducing properties of a scarcely known ruthenium complex which is able to reduce NAD+. Lastly, I sought to revert the classical role of the sacrificial electron donor to an active component of the system and, to boost the process, I build up an autonomous microfluidic system able to generate highly reproducible NAD(P)H amount, demonstrating the superior performance of microfluidic reactors over batch and representing another successful photochemical NAD(P)H regeneration system.