The mechanics of impacts is not yet well understood due to the complexity of materials behaviour under extreme stress and strain conditions and is thus of challenge for fundamental research, as well as relevant in several areas of applied sciences and engineering. The involved complex contact and strain-rate dependent phenomena include geometrical and materials non-linearities, such as wave and fracture propagation, plasticity, buckling, and friction. The theoretical description of such non-linearities has reached a level of advance maturity only singularly, but when coupled -due to the severe mathematical complexity- remains limited. Moreover, related experimental tests are difficult and expensive, and usually not able to quantify and discriminate between the phenomena involved. In this scenario, computational simulation emerges as a fundamental and complementary tool for the investigation of such otherwise intractable problems. The aim of this PhD research was the development and use of computational models to investigate the behaviour of materials and structures undergoing simultaneously extreme contact stresses and strain-rates, and at different size and time scales. We focused on basic concepts not yet understood, studying both engineering and bio-inspired solutions. In particular, the developed models were applied to the analysis and optimization of macroscopic composite and of 2D-materials-based multilayer armours, to the buckling-governed behaviour of aerographite tetrapods and of the related networks, and to the crushing behaviour under compression of modified honeycomb structures. As validation of the used approaches, numerical-experimental-analytical comparisons are also proposed for each case.

The experimental work presented in this thesis is done to develop an innovative procedure to create a protective nanostructured coating inside the X-band radio frequency cavity, a key component in future particle accelerator. The scope of the multilayer coating is to prevent the breakdown due to high electric and magnetic field. In fact the electrical discharges damage, in irreversible way, the internal surface of the cavity and compromise the final operation of the device. The keen interest on the topic is due to decrease the length and the cost of the next generation linear accelerator. To do this it is essential to enhance the performance of X-band Linacs up to 100MV/m accelerating gradient and to maintain, high as possible, the electrical breakdown reliability. Several studies are made on different materials in order to develop these cavities [1] [2], but the use of physical vapor deposition technique (PVD), to obtain nanostructured coating directly on internal wall of these small sized cavities is not reported in literature. The size of the cavities is of order of few millimeters and the iris aperture ranges from 2 to 6mm: for this reason the direct PVD coating is not possible. Hence a mandrel, that is the negative shape of the cavity, is first coated using PVD technique and finally chemically dissolved after copper electroforming[3]. The novel nanostructured coating is a multilayer composed by two high purity and immiscible metals. One is Copper to guarantee electrical conductivity of the cavity and the second is Molybdenum because it is a refractory metal. Moreover the choice of immiscible materials is important, because these materials do not form alloy during the deposition phase. Keeping a well-defined interface is important to guarantee a barrier effect to the motion of the defects inside the cavity’s material[4][5]. The experimental part of the thesis is divided in three different parts: design and setup of the PVD deposition system, plasma discharge analysis and, finally, the characterization of the coatings. This work is a collaboration between Industrial Engineering Department (University of Trento) and the National Laboratory of Legnaro (National Institute of Nuclear Physics LNL-INFN), but this research involves several institutes in different countries: SLAC (USA), KEK (Japan) and UCLA (Los Angeles USA).

La fibra di canapa europea è l'unica fibra naturale con una certificazione di sostenibilità. La qualità della fibra è influenzata principalmente da genotipo, tecniche agronomiche, epoca di raccolta e metodo di macerazione. L'obiettivo principale della tesi è delineare le pratiche agronomiche e di post-raccolta per migliorare l'estrazione e la qualità della fibra, con particolare attenzione alla produzione di canapa multiuso ritardando la raccolta fino alla maturazione dei semi. Le prove di densità, fertilizzazione azotata e varietali sono state condotte in differenti ambienti Europei. La procedura di decorticazione standardizzata è stata confrontata con la linea longitudinale di estrazione della fibra per applicazioni di alto valore aggiunto. I test su bio-compositi di canapa sono stati effettuati con fibra pettinata per confrontarne le proprietà tra genotipi, epoca di raccolta e metodi di macerazione. I risultati di questa indagine suggeriscono che i) la densità di semina e la concimazione azotata ottimale sono tra 90-150 piante m-2 e 30-60 kg N ha-1; ii) le nuove varietà dallo stelo giallo presentano un'alta efficienza di decorticazione e una ridotta contaminazione da canapulo nella fibra, iii) la fibra di canapa, con proprietà comparabili a quelle del lino, si è dimostrata adatta per applicazioni in compositi di alto valore. / European hemp fibres are the only natural fibre with an established sustainability certification. Hemp fibre quality is affected by genotype, agronomic techniques, harvest time and retting method. The main objective of this thesis is to outline the agronomic and post-harvest practices for improved fibre extraction and fibre quality, with special attention to multipurpose hemp production delaying the harvest from the flowering stage until seed ripening is complete. Planting density and nitrogen fertilization trials and variety trials were conducted in contrasting environments in Europe. Stems were decorticated following a standardised procedure and longitudinal hemp line for textile and high-added values application was compared with lab-scaled decortication. Impregnated fibre bundle tests were carried out with hemp hackled fibre bundles to compare composites and back-calculated fibre properties between genotypes, harvest times and retting methods. Results of this investigation suggest that i) optimum plant density and nitrogen fertilization are between 90 and 150 plants m-2 and 30 and 60 Kg N ha-1 respectively; ii) new yellow stemmed varieties are characterized by high decortication efficiency and relative high cleanness of the extracted fibre and iii) long hemp fibre, having properties comparable to those of flax, proved to be suitable for high-tech composites applications.

La tesi ha lo scopo di individuare le coordinate fondamentali delle dinamiche di trasformazione che la città di Milano conobbe tra il VI ed il XII secolo dal punto di vista topografico, insediativo e monumentale. Attraverso l'analisi combinata di fonti scritte ed evidenze materiali vengono sistematicamente esaminati i quattro principali elementi caratterizzanti il fenomeno urbano in età medioevale: la topografia delle difese, la topografia cristiana, la topografia del potere e la topografia dell'insediamento. / The thesis aims to identify the fundamental coordinates of the transformation dynamics that the city of Milan underwent between the Sixth and the Twelfth Centuries from a topographical, settlement and monumental point of view. Through the combined analysis of written sources and material evidences, the four main elements characterizing the urban phenomenon in the Middle Ages are systematically examined: the topography of the defenses, the Christian topography, the topography of power and the topography of the settlement.

A new approach to obtain visible luminescence from sol-gel derived SiOC films is proposed. This novel method is based on a simple processing route to produce nanostructured multicomponent ceramics. According to this route, hybrid sol-gel derived precursors are converted to ceramic materials by a pyrolysis process in controlled atmosphere at 800-1000°C. Higher temperatures lead to formation of Si-rich SiOC, C-rich SiOC or stoichiometric SiOC according to the starting composition. The final composition, which is relevant to line emission, can be easily controlled through a number of processing parameters like the composition of the preceramic gel and the heat treatment conditions. Thus, this new processing method seems very well suited for the production of white emitting materials since the Si- and C-based emission can be tuned across the visible spectral range from UV-blue to red by controlling film composition. A further advantage of this method is that the thin films can be formed on Si or quartz wafers and this can serve as starting material to process more complex photonic devices such as waveguides or LEDs. In the amorphous state (800-100°C), all SiOC films showed UV-blue luminescence peaking at about 410 nm, which is attributed to defect states present in the matrix such as dangling bonds. The increase of the pyrolysis temperature (≥1100°C) led to the partition of SiOC and formation of SiC, C and Si phases. The intense green-yellow luminescence observed in stoichiometric SiOC films caused by the presence of SiC and very low amount of free C. On the other hand, Si rich SiOC film showed a very broad and extremely intense white luminescence peak centred at 620 nm covering almost all visible range (430 nm-900 nm) at 1200 °C. This behaviour is explained by the simultaneous presence of SiC, C and Si in the film. External quantum efficiency measurements yielded 11.5% and 5% efficiencies in Si rich SiOC and stoichiometric SiOC films, respectively, pyrolysed at 1200°C. On the other hand, C rich SiOC films did not show any noticeable improvement in PL, indicating that C excess in the SiOC system is detrimental for the luminescence behaviour. Solutions which used in thin film production have been characterized extensively by means of several characterization properties. Moreover, the related powders and bulks have been characterized for the sake of coherency and widen the study. In addition, a study on volumetric shrinkage of films and powders has been done. The results showed that the shrinkage in films happens almost 200°C earlier than powder and higher amount of siloxane release due to the low dimension, the shrinkage is higher than powders. The last part of the study dedicated to two different systems, SiBOCs and SiOCNs, in order to understand the effect of the boron addition on SiOC system and study the optical properties of the SiOCN. Tunable (color emission change) SiOC films is obtained with high quantum efficiency by adding very few amount of boron in SiOC. Moreover, the processing temperature is decreased and very broad emission is obtained. Finally, results showed that SiOCN PDC gives very high emission in UV range and they are promising materials for UV-LEDs.

The wettability and phase change phenomena of water are ubiquitous on biological and artificial surfaces. Properties like water repellency, self-cleaning, coalescence induced condensation jumping, anti-frosting, and dew harvesting arise on surfaces with particular structures and chemistry and are of particular interest for energy and water saving. This thesis collects different studies of wettability and phase change on natural and artificial surfaces: growth and self-ejection of condensation droplets on micro and nanostructured surfaces we fabricated, their applications, the Sliding on Frost of condensation droplets observed on the Cotinus Coggygria leaf, the dew harvesting property of the Old Man of the Andes Cactus enhanced by distance coalescence through microgrooves and finally, a theoretical study of viruses viability in sessile droplets. The first chapter introduces the theoretical framework of wettability and phase changes on surfaces. In the second chapter, we present the self-ejection of condensation droplets from hydrophobic nanostructured microstructures. We modelled analytically the droplets jumping and fabricated surfaces to verify the predictions. The fabricated geometry was inspired by the modelling and the available fabrication techniques. We tested the surfaces in condensation conditions. Using a high frame rate camera coupled with a long working distance microscopy objective, we investigated the growth and ejection transient. We then compared the experimental self-ejection velocity for various structures geometry with our analytical models. In Chapter 3, we investigated the applications of the fabricated surfaces reported in Chapter 2. In Chapter 4, we explore the condensation frosting on the leaf of Cotinus Coggygria, native of our woods and with interesting hydrophobic properties. Covered by wax nanotubules, it exhibits coalescence-induced condensation jumpings that may be a useful cleaning tool. Furthermore, the frost is delayed but not only for the jumping. Surprisingly, at temperatures some degrees below zero, we observed what we called ‘droplet Sliding on Frost bridges’, that further delays frosting. We described the feasibility of this sliding in terms of dynamic contact angles of the surface and contact angles of supercooled water on ice. By capturing high temporal and spatial resolution videos we investigated the sliding on frost and droplet recalescence (fast dendrite growth that partially solidify the liquid). The responsible for the failure of sliding for temperatures from about -8 ° C down appears to be the advancing angle of water on ice that increases with the subcooling rather than the recalescence that blocks the drop in place. These results add a piece to the fundamental research on the supercooled water-ice-vapour interfaces. As it often happens, biological surfaces offer a starting point for the study of fundamental mechanisms and the development of artificial surfaces with optimized properties. In the Chapter 5, the multifunctional roles of hairs and spines in Old Man of the Andes Cactus (Oreocereus trolli) are studied. We study the morphology of the appendages, the hairs wettability, mechanical properties of both, and the dew formation on spines. The longitudinal microgrooves on the spines cause a particular phenomenon of distant coalescence (DC), in which smaller droplets flow totally or partially into larger ones through the microgrooves, with consequent accumulation of water in a few large drops. An earlier study has shown artificial micro-grooved surfaces that exhibit DC are more efficient than flat ones at collecting and sliding dew, and thus these cactus spines could act as soil dew conveyors. The agreement between our analytical model and experimental data verifies that the flow is driven by the Laplace pressure difference between the drops. This allowed us to obtain a general criterion for predicting the total or partial emptying of the smaller drops as a function of the dynamic contact angles of a surface. Based on this criterion, an hydrophilic material with small contact angle hysteresis would allow a greater number of complete drops emptying. The COVID-19 pandemic has raised the problem of contagion from airborne and deposited droplets. In the last chapter, we report the state of the art of experiments on the viability of viruses in deposited droplets. Up to date, it has been experimentally highlighted that the relative viability of some viruses (RV) depends on the material chemistry, temperature, and interestingly, on relative humidity (RH) with a U-shaped trend. One of the current hypotheses is that the cumulative dose of salt concentration (CD) affects RV. We model the RV of viruses in sessile droplets by inserting a RV-CD relation in a model of droplet evaporation. By considering a saline water droplet (one salt) as the simplest approximation of real solutions, we analytically simulate the time evolution of salt concentration, vapor pressure, and droplet volume varying contact angles, droplet sizes, and RH in the range 0–100%. The results elucidate some previously not yet well-understood dynamics, demonstrating how three main regimes—directly implicated in nontrivial experimental trends of virus RV—can be recognized as the function of RH. The proposed approach could suggest a chart of a virus fate by predicting its survival time at a given temperature as a function of RH and contact angle. We found a good agreement with experimental data for various enveloped viruses and predicted in particular for the Phi6 virus, a surrogate of coronavirus, the characteristic U-shaped dependence of RV on RH. Given the generality of the model, once experimental data are available that link the vulnerability of a certain virus (such as SARS-CoV-2) to the concentrations of salts or other substances in terms of CD, it is envisioned that this approach could be employed for antivirus strategies and protocols for the prediction/reduction of human health risks associated with SARS-CoV-2 and other viruses.

To support the growing global demand for energy, new sustainable solutions are needed both economically and environmentally. Thermoelectric waste heat recovery and energy harvesting could contribute by increasing industrial process efficiency, as well as powering stand-alone devices, microgenerators, and small body appliances.The structural complexity of quaternary chalcogenide materials provides an opportunity for engineering defects and disorder, to modify and possibly improve specific properties. Cu2ZnSnS4 (CZTS, often kesterite), valued for the abundance and non-toxicity of the raw materials, seems particularly suited to explore these possibilities, as it presents several structural defects and polymorphic phase transformations. The aim of this doctoral work is to systematically investigate the effects of structural polymorphism, disorder, and defects on the thermoelectric properties of CZTS, with particular emphasis to their physical origin. A remarkable case is the order-disorder transition of tetragonal CZTS, which is found responsible for a sharp enhancement in the Seebeck coefficient due to a flattening and degeneracy of the electronic energy bands. This effect, involving a randomization of Cu and Zn cations in certain crystallographic planes, is verified in bulk and thin film samples, and applications are proposed to exploit the reversible dependence of electronic properties on disorder. Low-temperature mechanical alloying is instead discovered stabilizing a novel polymorph of CZTS, which disordered cubic structure is studied in detail, and proposed deriving from sphalerite-ZnS. The total cation disorder in this compound provides an uncommon occurrence in thermoelectricity: a concurrent optimization of Seebeck coefficient, electrical and thermal conductivity. These findings, besides providing new and general understanding of CZTS, can cast light on profitable mechanisms to enhance the thermoelectric performance of semiconducting chalcogenides, as well as delineate alternative and fruitful applications.

The present work regards the development of a methodology for the study of atmospheric particulate matter (PM) which is alternative to instrumental measurements. The methodology developed exploits the surfaces already present in the field as samplers of PM. In particular, conifer needles and building facades are employed to investigate different temporal ranges: conifer needles potentially retain particles circulating in the atmosphere from the recent past up to now, while building facades could retain particles from an older period up to know. The field of application of the approach developed are the situations in which a wide territory must be monitored, eventually including remote locations, or information on past pollution scenario must be reconstructed in the absence of monitoring stations. For instance, the evaluation of the improved efficiency of off-gas abatement systems of industrial plants is a typical case of application. These pollution sources affect large areas and might have been active before regulation on air quality required constant monitoring of their emissions. Typically in such a case the methodology could assist in evaluating how large was in the past and it is nowadays the area of impact of the plant. In general, such an approach could be valuable whenever relying on instrumental measurements is cost and time consuming in terms of installing a large network of monitoring stations to study the dispersion of pollutants from a single or few sources. To have a detailed description of the spatial distribution of pollutant particles, they are studied individually with subsequent higher magnification. Where no traces of a source are detected by scanning electron microscopy coupled with energy dispersive x-ray spectroscopy (SEM-EDXS), the samples are analyzed with the higher resolution of transmission electron microscopy coupled with energy dispersive x-ray spectroscopy (TEM-EDXS) and selected area electron diffraction (SAED) in order to make sure that no smaller particles, able to travel farther from their source, are present at a certain site. All data provided by electron microscopy analysis of particles collected by conifer needles are placed in the context of elemental concentrations measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES), which is a bulk analytical technique. The same is not possible for the data on single particles present on building facades given the inorganic matrix of the substrate, especially in the case of metal oxide paints, which does not allow the bulk measurement. Both the preparation of the samples for bulk analytical techniques and single particle analysis by electron microscopy were optimized. For method development and evaluation, the analytical protocol was applied to estimate spatial and temporal trends of accumulation of inorganic pollutants that can be related with changes in the emissions of atmospheric pollutants by an electric arc furnace (EAF) steelmaking plant located in a test site. The benefits of combining the single particle and bulk analytical techniques emerged especially for the discrimination of the emissions from different sources.

Silk fibroin is a widely studied material in the context of tissue engineering. Thanks to its versatility and impressive properties, the fields where silk fibroin is used have grown. In particular, silk fibroin has proved to be useful in all the cases when an interface with living tissues is needed (e.g. biophotonics, bioelectronics). As a consequence of this increasing interest, a wide range of protocols have been developed to prepare different materials starting from cocoons. The aim of this thesis is to investigate new strategies to fabricate silk fibroin-based materials, either improving previously developed protocols or proposing new methodologies both with the purpose to overcome certain limitations of current approaches and to propose new areas of application. We choose to work on three topics: the production of patterns using photolithography on a fibroin photoresist films (fibroin photocrosslinkable photoresist, FPP), the production of sponges made from a chemically modified version of the native protein (Methacrylated fibroin, Sil-MA), and the production of a solid bulk resin made starting from the regenerated protein. In the case of the FPP (and its counterpart made of sericine, SPP) the fabrication of films and pattern was restricted to the use of harsh chemicals. In addition, the resulting material had a roughness that limits its use in optical applications, making the determination of the refractive index (RI) not possible. The novelty of our work consisted in the modification of the original protocol to make it environmentally sustainable and to decrease the roughness in order to use ellipsometry to determine the RI dispersion. The broadly used silk-based sponges can be prepared by several protocols but they all suffer of the same limitations: the sponges are stabilized only by physical crosslinking (the change from the random to the crystalline secondary structure), and there are no clear models that correlate the sponge properties to their composition. We produced a new sponge, chemically crosslinked, whose stability was ensured by the creation, of chemical bonds between the protein chains during an UV curing. This task was accomplished using a simple protocol and a statistical method to model the composition-properties relations. The possibility to obtain a bulk, non-porous solid monolith from fibroin (solid-fibroin) has been received attention only in the last few years. This material is produced by a transition from solution to solid through solvent evaporation, a very slow process that takes weeks to be completed. The advantage of this transition is that it occurs at room temperature, allowing the addition of thermally degradable molecules (e.g. enzymes). We were able to optimize a procedure to produce the same material by compression of a silk sponge at high pressure and low temperature. The advantage of this method is the lower amount of time required to produce the material, minutes instead of days.

Il concetto di rete dell'informazione può diventare uno schema logico con cui descrivere l'evoluzione delle politiche sulle energie rinnovabili e sulla sostenibilità? La ricerca è stata svolta analizzando l'architettura delle due reti (internet e reti energetiche) e l'evoluzione del bene prodotto e distribuito nella rete energetica, l'energia, esplicitando l'accessibilità da parte della distribuzione mondiale delle risorse petrolifere tradizionali e delle risorse rinnovabili. La struttura metodologica del progetto di ricerca si basa due tipi di analisi teorica: 1) l'analisi della nascita delle società in rete attraverso le teorie di Manuel Castells (concetto di spazio di flussi) e di Saskia Sassen e l'evoluzione delle città (cap.2 e cap.5) 2) le analisi dei flussi dei materiali e delle energie avendo come riferimento metodologico l'approccio ecologico ideato dai ricercatori dell'istituto per il Clima, l'Ambiente e l'Energia di Wuppertal, Germania (cap.3 e cap.4) La contraddizione tra città innovative e città che sono ai livelli di enormi discariche o di baraccopoli è esposta nel cap.6 attraverso casi studio e progetto dei Programmi Europei. Nell'ultimo capitolo (cap.7) si riassumono le ipotesi di partenza e i risultati della ricerca e si espongono le questioni aperte. / Can internet logic scheme be used as a basis to describe public policies evolution on renewable energies production and sharing in urban areas all over the world? The research project analyses the two networks (internet and energetic grids) architectures in actual and future urban areas. This analysis is connected with present and future forecasts energy productions from traditional fuels and from renewable sources. Theoretical analysis is conducted following a double conceptual pathway: - societal networks (Manuel Castells theory) and urban areas evolution (Saskia Sassen and Mike Davis) in order to picture the evolution of cities and towns in modern economies and in developing countries (Chapters 2 and 5); - Material and Energy Flow Analysis (approach by Wuppertal Institute for Climate, Environment and Energy) applied to renewable energy (Chapters 3 and 4) In Chapter 6 case studies are exposed on the deep cleavage between two different worlds: innovative, rich towns on a side and the landfills cities, slums on the other side. In the last part hypothesis and thesis are put together and open questions are explained (Chapter 7).