Design and Off-design modelling of advanced Power-to-Gas energy storage systems

Power-to-Gas storage systems have the potential to address grid-stability issues that arise when an increasing share of power is generated from sources that have a highly variable output. Although the proof-of-concept of these has been promising, the behaviour of the processes in off-design conditions is not easily predictable. The primary aim of this PhD project was to evaluate the performance of an original Power-to-Gas system, made up of innovative components. To achieve this, a numerical model has been developed to simulate the characteristics and the behaviour of the several components when the whole system is coupled with a renewable source. The developed model has been applied to a large variety of scenarios, evaluating the performance of the considered process and exploiting a limited amount of experimental data. The model has been then used to compare different Power-to-Gas concepts, in a real scenario of functioning. Several goals have been achieved. In the concept phase, the possibility to thermally integrate the high temperature components has been demonstrated. Then, the parameters that affect the energy performance of a Power-to-Gas system coupled with a renewable source have been identified, providing general recommendations on the design of hybrid systems; these parameters are: 1) the ratio between the storage system size and the renewable generator size; 2) the type of coupled renewable source; 3) the related production profile. Finally, from the results of the comparative analysis, it is highlighted that configurations with a highly oversized renewable source with respect to the storage system show the maximum achievable profit.

Modelling of ORC components and systems for low-medium temperature heat recovery applications with reduced environmental impact

Although its great potential as low to medium temperature waste heat recovery (WHR) solution, the ORC technology presents open challenges that still prevent its diffusion in the market, which are different depending on the application and the size at stake. Focusing on the micro range power size and low temperature heat sources, the ORC technology is still not mature due to the lack of appropriate machines and working fluids. Considering instead the medium to large size, the technology is already available but the investment is still risky. The intention of this thesis is to address some of the topical themes in the ORC field, paying special attention in the development of reliable models based on realistic data and accounting for the off-design performance of the ORC system and of each of its components. Concerning the “Micro-generation” application, this work: i) explores the modelling methodology, the performance and the optimal parameters of reciprocating piston expanders; ii) investigates the performance of such expander and of the whole micro-ORC system when using Hydrofluorocarbons as working fluid or their new low GWP alternatives and mixtures; iii) analyzes the innovative ORC reversible architecture (conceived for the energy storage), its optimal regulation strategy and its potential when inserted in typical small industrial frameworks. Regarding the “Industrial WHR” sector, this thesis examines the WHR opportunity of ORCs, with a focus on the natural gas compressor stations application. This work provides information about all the possible parameters that can influence the optimal sizing, the performance and thus the feasibility of installing an ORC system. New WHR configurations are explored: i) a first one, relying on the replacement of a compressor prime mover with an ORC; ii) a second one, which consists in the use of a supercritical CO2 cycle as heat recovery system.

Design methodologies of microwawe integrated circuits for satellite telecommunications

The running innovation processes of the microwave transistor technologies, used in the implementation of microwave circuits, have to be supported by the study and development of proper design methodologies which, depending on the applications, will fully exploit the technology potentialities. After the choice of the technology to be used in the particular application, the circuit designer has few degrees of freedom when carrying out his design; in the most cases, due to the technological constrains, all the foundries develop and provide customized processes optimized for a specific performance such as power, low-noise, linearity, broadband etc. For these reasons circuit design is always a “compromise”, an investigation for the best solution to reach a trade off between the desired performances. This approach becomes crucial in the design of microwave systems to be used in satellite applications; the tight space constraints impose to reach the best performances under proper electrical and thermal de-rated conditions, respect to the maximum ratings provided by the used technology, in order to ensure adequate levels of reliability. In particular this work is about one of the most critical components in the front-end of a satellite antenna, the High Power Amplifier (HPA). The HPA is the main power dissipation source and so the element which mostly engrave on space, weight and cost of telecommunication apparatus; it is clear from the above reasons that design strategies addressing optimization of power density, efficiency and reliability are of major concern. Many transactions and publications demonstrate different methods for the design of power amplifiers, highlighting the availability to obtain very good levels of output power, efficiency and gain. Starting from existing knowledge, the target of the research activities summarized in this dissertation was to develop a design methodology capable optimize power amplifier performances complying all the constraints imposed by the space applications, tacking into account the thermal behaviour in the same manner of the power and the efficiency. After a reminder of the existing theories about the power amplifier design, in the first section of this work, the effectiveness of the methodology based on the accurate control of the dynamic Load Line and her shaping will be described, explaining all steps in the design of two different kinds of high power amplifiers. Considering the trade-off between the main performances and reliability issues as the target of the design activity, we will demonstrate that the expected results could be obtained working on the characteristics of the Load Line at the intrinsic terminals of the selected active device. The methodology proposed in this first part is based on the assumption that designer has the availability of an accurate electrical model of the device; the variety of publications about this argument demonstrates that it is so difficult to carry out a CAD model capable to taking into account all the non-ideal phenomena which occur when the amplifier operates at such high frequency and power levels. For that, especially for the emerging technology of Gallium Nitride (GaN), in the second section a new approach for power amplifier design will be described, basing on the experimental characterization of the intrinsic Load Line by means of a low frequency high power measurements bench. Thanks to the possibility to develop my Ph.D. in an academic spin-off, MEC – Microwave Electronics for Communications, the results of this activity has been applied to important research programs requested by space agencies, with the aim support the technological transfer from universities to industrial world and to promote a science-based entrepreneurship. For these reasons the proposed design methodology will be explained basing on many experimental results.

Design and Characterization of New Luminescent Sensors and Labels

The aim of this Ph.D. project has been the design and characterization of new and more efficient luminescent tools, in particular sensors and labels, for analytical chemistry, medical diagnostics and imaging. Actually both the increasing temporal and spatial resolutions that are demanded by those branches, coupled to a sensitivity that is required to reach the single molecule resolution, can be provided by the wide range of techniques based on luminescence spectroscopy. As far as the development of new chemical sensors is concerned, as chemists we were interested in the preparation of new, efficient, sensing materials. In this context, we kept developing new molecular chemosensors, by exploiting the supramolecular approach, for different classes of analytes. In particular we studied a family of luminescent tetrapodal-hosts based on aminopyridinium units with pyrenyl groups for the detection of anions. These systems exhibited noticeable changes in the photophysical properties, depending on the nature of the anion; in particular, addition of chloride resulted in a conformational change, giving an initial increase in excimeric emission. A good selectivity for dicarboxylic acid was also found. In the search for higher sensitivities, we moved our attention also to systems able to perform amplification effects. In this context we described the metal ion binding properties of three photoactive poly-(arylene ethynylene) co-polymers with different complexing units and we highlighted, for one of them, a ten-fold amplification of the response in case of addition of Zn2+, Cu2+ and Hg2+ ions. In addition, we were able to demonstrate the formation of complexes with Yb3+ an Er3+ and an efficient sensitization of their typical metal centered NIR emission upon excitation of the polymer structure, this feature being of particular interest for their possible applications in optical imaging and in optical amplification for telecommunication purposes. An amplification effect was also observed during this research in silica nanoparticles derivatized with a suitable zinc probe. In this case we were able to prove, for the first time, that nanoparticles can work as “off-on” chemosensors with signal amplification. Fluorescent silica nanoparticles can be thus seen as innovative multicomponent systems in which the organization of photophysically active units gives rise to fruitful collective effects. These precious effects can be exploited for biological imaging, medical diagnostic and therapeutics, as evidenced also by some results reported in this thesis. In particular, the observed amplification effect has been obtained thanks to a suitable organization of molecular probe units onto the surface of the nanoparticles. In the effort of reaching a deeper inside in the mechanisms which lead to the final amplification effects, we also attempted to find a correlation between the synthetic route and the final organization of the active molecules in the silica network, and thus with those mutual interactions between one another which result in the emerging, collective behavior, responsible for the desired signal amplification. In this context, we firstly investigated the process of formation of silica nanoparticles doped with pyrene derivative and we showed that the dyes are not uniformly dispersed inside the silica matrix; thus, core-shell structures can be formed spontaneously in a one step synthesis. Moreover, as far as the design of new labels is concerned, we reported a new synthetic approach to obtain a class of robust, biocompatible silica core-shell nanoparticles able to show a long-term stability. Taking advantage of this new approach we also showed the synthesis and photophysical properties of core-shell NIR absorbing and emitting materials that proved to be very valuable for in-vivo imaging. In general, the dye doped silica nanoparticles prepared in the framework of this project can conjugate unique properties, such as a very high brightness, due to the possibility to include many fluorophores per nanoparticle, high stability, because of the shielding effect of the silica matrix, and, to date, no toxicity, with a simple and low-cost preparation. All these features make these nanostructures suitable to reach the low detection limits that are nowadays required for effective clinical and environmental applications, fulfilling in this way the initial expectations of this research project.

Decomposition Methods and Network Design Problems

Decomposition based approaches are recalled from primal and dual point of view. The possibility of building partially disaggregated reduced master problems is investigated. This extends the idea of aggregated-versus-disaggregated formulation to a gradual choice of alternative level of aggregation. Partial aggregation is applied to the linear multicommodity minimum cost flow problem. The possibility of having only partially aggregated bundles opens a wide range of alternatives with different trade-offs between the number of iterations and the required computation for solving it. This trade-off is explored for several sets of instances and the results are compared with the ones obtained by directly solving the natural node-arc formulation. An iterative solution process to the route assignment problem is proposed, based on the well-known Frank Wolfe algorithm. In order to provide a first feasible solution to the Frank Wolfe algorithm, a linear multicommodity min-cost flow problem is solved to optimality by using the decomposition techniques mentioned above. Solutions of this problem are useful for network orientation and design, especially in relation with public transportation systems as the Personal Rapid Transit. A single-commodity robust network design problem is addressed. In this, an undirected graph with edge costs is given together with a discrete set of balance matrices, representing different supply/demand scenarios. The goal is to determine the minimum cost installation of capacities on the edges such that the flow exchange is feasible for every scenario. A set of new instances that are computationally hard for the natural flow formulation are solved by means of a new heuristic algorithm. Finally, an efficient decomposition-based heuristic approach for a large scale stochastic unit commitment problem is presented. The addressed real-world stochastic problem employs at its core a deterministic unit commitment planning model developed by the California Independent System Operator (ISO).

Design and Prototyping High Endurance Multi-Rotor

The topic of this thesis fo cus on the preliminary design and the p erformance analysis of a multirotor platform. A multirotor is an electrically p owered Vertical Take Off (VTOL) machine with more than two rotors that lift and control the platform. Multirotor are agile, compact and robust, making them ideally suited for b oth indo or and outdo or application especially to carry-on several sensors like electro optical multisp ectral sensor or gas sensor. The main disadvantage is the limited endurance due to heavy Li-Po batteries and high disk loading through the use of different small prop ellers. At the same time, the design of the multirotor do es not follow any engineering principle but it follow the ideas of amateurs’ builder. An adaptation of the classic airplane design theory for the preliminary design is implemented to fill the gap and detailed study of the endurance is p erformed to define the right way to make this kind of VTOL platforms.

Design and synthesis of (pro)electrophilic compounds for investigating the multifactorial nature of neurodegenerative diseases: focus on inflammation-driven events

Neuroinflammation constitutes a major player in the etiopathology of neurodegenerative diseases (NDDs), by orchestrating several neurotoxic pathways which in concert lead to neurodegeneration. A positive feedback loop occurs between inflammation, microglia activation and misfolding processes that, alongside excitotoxicity and oxidative events, represent crucial features of this intricate scenario. The multi-layered nature of NDDs requires a deepen investigation on how these vicious cycles work. This could further help in the search for effective treatments. Electrophiles are critically involved in the modulation of a variety of neuroprotective responses. Thus, we envisioned their peculiar ability to switch on/off biological activities as a powerful tool for investigating the neurotoxic scenario driven by inflammation in NDDs. In particular, in this thesis project, we wanted to dissect at a molecular level the functional role of (pro)electrophilic moieties of previously synthesized thioesters of variously substituted trans-cinnamic acids, to identify crucial features which could interfere with amyloid aggregation as well as modulate Nrf2 and/or NF-κB activation. To this aim, we first synthesized new compounds to identify bioactive cores which could specifically modulate the intended target. Then, we systematically modified their structure to reach additional pathogenic pathways which could in tandem contribute to the inflammatory process. In particular, following the investigation of the mechanistic underpinnings involving the catechol feature in amyloid binding through the synthesis of new dihydroxyl derivatives, we incorporated the identified antiaggregating nucleus into constrained frames which could contrast neuroinflammation also through the modulation of CB2Rs. In parallel, Nrf2 and/or NF-κB antinflammatory structural requirements were combined with the neuroprotective cores of pioglitazone, an antidiabetic drug endowed with MAO-B inhibitory properties, and memantine, which notably contrasts excitotoxicity. By acting as Swiss army knives, the new set of molecules emerge as promising tools to deepen our insights into the complex scenario regulating NDDs.

Optimizing AI at the Edge: from network topology design to MCU deployment

The first topic analyzed in the thesis will be Neural Architecture Search (NAS). I will focus on two different tools that I developed, one to optimize the architecture of Temporal Convolutional Networks (TCNs), a convolutional model for time-series processing that has recently emerged, and one to optimize the data precision of tensors inside CNNs. The first NAS proposed explicitly targets the optimization of the most peculiar architectural parameters of TCNs, namely dilation, receptive field, and the number of features in each layer. Note that this is the first NAS that explicitly targets these networks. The second NAS proposed instead focuses on finding the most efficient data format for a target CNN, with the granularity of the layer filter. Note that applying these two NASes in sequence allows an "application designer" to minimize the structure of the neural network employed, minimizing the number of operations or the memory usage of the network. After that, the second topic described is the optimization of neural network deployment on edge devices. Importantly, exploiting edge platforms' scarce resources is critical for NN efficient execution on MCUs. To do so, I will introduce DORY (Deployment Oriented to memoRY) -- an automatic tool to deploy CNNs on low-cost MCUs. DORY, in different steps, can manage different levels of memory inside the MCU automatically, offload the computation workload (i.e., the different layers of a neural network) to dedicated hardware accelerators, and automatically generates ANSI C code that orchestrates off- and on-chip transfers with the computation phases. On top of this, I will introduce two optimized computation libraries that DORY can exploit to deploy TCNs and Transformers on edge efficiently. I conclude the thesis with two different applications on bio-signal analysis, i.e., heart rate tracking and sEMG-based gesture recognition.