Metamorfismo ercinico di bassa-pressione: evoluzione tettonico-metamorfica del complesso di mandatoriccio (massiccio della Sila - Calabria)

Low-pressure/high-temperature (LP/HT) metamorphic belts are characterised by rocks that experienced abnormal heat flow in shallow crustal levels (T > 600 °C; P < 4 kbar) resulting in anomalous geothermal gradients (60-150 °C/km). The abnormal amount of heat has been related to crustal underplating of mantle-derived basic magmas or to thermal perturbation linked to intrusion of large volumes of granitoids in the intermediate crust. In particular, in this latter context, magmatic or aqueous fluids are able to transport relevant amounts of heat by advection, thus favouring regional LP/HT metamorphism. However, the thermal perturbation consequent to heat released by cooling magmas is responsible also for contact metamorphic effects. A first problem is that time and space relationships between regional LP/HT metamorphism and contact metamorphism are usually unclear. A second problem is related to the high temperature conditions reached at different crustal levels. These, in some cases, can completely erase the previous metamorphic history. Notwithstanding this problem is very marked in lower crustal levels, petrologic and geochronologic studies usually concentrate in these attractive portions of the crust. However, only in the intermediate/upper-crustal levels of a LP/HT metamorphic belt the tectono-metamorphic events preceding the temperature peak, usually not preserved in the lower crustal portions, can be readily unravelled. The Hercynian Orogen of Western Europe is a well-documented example of a continental collision zone with widespread LP/HT metamorphism, intense crustal anatexis and granite magmatism. Owing to the exposure of a nearly continuous cross-section of the Hercynian continental crust, the Sila massif (northern Calabria) represents a favourable area to understand large-scale relationships between granitoids and LP/HT metamorphic rocks, and to discriminate regional LP/HT metamorphic events from contact metamorphic effects. Granulite-facies rocks of the lower crust and greenschist- to amphibolite-facies rocks of the intermediate-upper crust are separated by granitoids emplaced into the intermediate level during the late stages of the Hercynian orogeny. Up to now, advanced petrologic studies have been focused mostly in understanding P-T evolution of deeper crustal levels and magmatic bodies, whereas the metamorphic history of the shallower crustal levels is poorly constrained. The Hercynian upper crust exposed in Sila has been subdivided in two different metamorphic complexes by previous authors: the low- to very low-grade Bocchigliero complex and the greenschist- to amphibolite-facies Mandatoriccio complex. The latter contains favourable mineral assemblages in order to unravel the tectono-metamorphic evolution of the Hercynian upper crust. The Mandatoriccio complex consists mainly of metapelites, meta-arenites, acid metavolcanites and metabasites with rare intercalations of marbles and orthogneisses. Siliciclastic metasediments show a static porphyroblastic growth mainly of biotite, garnet, andalusite, staurolite and muscovite, whereas cordierite and fibrolite are less common. U-Pb ages and internal features of zircons suggest that the protoliths of the Mandatoriccio complex formed in a sedimentary basin filled by Cambrian to Silurian magmatic products as well as by siliciclastic sediments derived from older igneous and metamorphic rocks. In some localities, metamorphic rocks are injected by numerous aplite/pegmatite veins. Small granite bodies are also present and are always associated to spotted schists with large porphyroblasts. They occur along a NW-SE trending transcurrent cataclastic fault zone, which represents the tectonic contact between the Bocchigliero and the Mandatoriccio complexes. This cataclastic fault zone shows evidence of activity at least from middle-Miocene to Recent, indicating that brittle deformation post-dated the Hercynian orogeny. P-T pseudosections show that micaschists and paragneisses of the Mandatoriccio complex followed a clockwise P-T path characterised by four main prograde phases: thickening, peak-pressure condition, decompression and peak-temperature condition. During the thickening phase, garnet blastesis started up with spessartine-rich syntectonic core developed within micaschists and paragneisses. Coevally (340 ± 9.6 Ma), mafic sills and dykes injected the upper crustal volcaniclastic sedimentary sequence of the Mandatoriccio complex. After reaching the peak-pressure condition (≈4 kbar), the upper crust experienced a period of deformation quiescence marked by the static overgrowths of S2 by Almandine-rich-garnet rims and by porphyroblasts of biotite and staurolite. Probably, this metamorphic phase is related to isotherms relaxation after the thickening episode recorder by the Rb/Sr isotopic system (326 ± 6 Ma isochron age). The post-collisional period was mainly characterised by decompression with increasing temperature. This stage is documented by the andalusite+biotite coronas overgrown on staurolite porphyroblasts and represents a critical point of the metamorphic history, since metamorphic rocks begin to record a significant thermal perturbation. Peak-temperature conditions (≈620 °C) were reached at the end of this stage. They are well constrained by some reaction textures and mineral assemblages observed almost exclusively within paragneisses. The later appearance of fibrolitic sillimanite documents a small excursion of the P-T path across the And-Sil boundary due to the heating. Stephanian U-Pb ages of monazite crystals from the paragneiss, can be related to this heating phase. Similar monazite U-Pb ages from the micaschist combined with the lack of fibrolitic sillimanite suggest that, during the same thermal perturbation, micaschists recorded temperatures slightly lower than those reached by paragneisses. The metamorphic history ended with the crystallisation of cordierite mainly at the expense of andalusite. Consequently, the Ms+Bt+St+And+Sill+Crd mineral assemblage observed in the paragneisses is the result of a polyphasic evolution and is characterised by the metastable persistence of the staurolite in the stability fields of the cordierite. Geologic, geochronologic and petrographic data suggest that the thermal peak recorded by the intermediate/upper crust could be strictly connected with the emplacement of large amounts of granitoid magmas in the middle crust. Probably, the lithospheric extension in the relatively heated crust favoured ascent and emplacement of granitoids and further exhumation of metamorphic rocks. After a comparison among the tectono-metamorphic evolutions of the different Hercynian crustal levels exposed in Sila, it is concluded that the intermediate/upper crustal level offers the possibility to reconstruct a more detailed tectono-metamorphic history. The P-T paths proposed for the lower crustal levels probably underestimate the amount of the decompression. Apart from these considerations, the comparative analysis indicates that P-T paths at various crustal levels in the Sila cross section are well compatible with a unique geologic scenario, characterized by post-collisional extensional tectonics and magmas ascent.

Flow Field–Flow Fractionation for size analysis and characterization of nanoparticles for applications in Life Sciences

Nanotechnologies are rapidly expanding because of the opportunities that the new materials offer in many areas such as the manufacturing industry, food production, processing and preservation, and in the pharmaceutical and cosmetic industry. Size distribution of the nanoparticles determines their properties and is a fundamental parameter that needs to be monitored from the small-scale synthesis up to the bulk production and quality control of nanotech products on the market. A consequence of the increasing number of applications of nanomaterial is that the EU regulatory authorities are introducing the obligation for companies that make use of nanomaterials to acquire analytical platforms for the assessment of the size parameters of the nanomaterials. In this work, Asymmetrical Flow Field-Flow Fractionation (AF4) and Hollow Fiber F4 (HF5), hyphenated with Multiangle Light Scattering (MALS) are presented as tools for a deep functional characterization of nanoparticles. In particular, it is demonstrated the applicability of AF4-MALS for the characterization of liposomes in a wide series of mediums. Afterwards the technique is used to explore the functional features of a liposomal drug vector in terms of its biological and physical interaction with blood serum components: a comprehensive approach to understand the behavior of lipid vesicles in terms of drug release and fusion/interaction with other biological species is described, together with weaknesses and strength of the method. Afterwards the size characterization, size stability, and conjugation of azidothymidine drug molecules with a new generation of metastable drug vectors, the Metal Organic Frameworks, is discussed. Lastly, it is shown the applicability of HF5-ICP-MS for the rapid screening of samples of relevant nanorisk: rather than a deep and comprehensive characterization it this time shown a quick and smart methodology that within few steps provides qualitative information on the content of metallic nanoparticles in tattoo ink samples.

Peptide-based low molecular weight gelators for the preparation of self-assembled materials

Low molecular weight gelators (LMWGs) based on pseudo-peptides are here studied for the preparation of supramolecular materials. These compounds can self-assemble through non-covalent interactions such as hydrogen bonds and π-π stacking, forming fibres and gels. A wide variety of materials can be prepared starting from these building blocks, which can be tuned and functionalised depending on the application. In this work, derivatives of the three aromatic amino acids L-Phenylalanine, L-Tyrosine and L-DOPA (3,4-dihydroxiphenylalanine) were synthesised and tested as gelators for water or organic solvents. First, the optimal gelating conditions were studied for each compound, varying concentration, solvent and trigger. Then the materials were characterised in terms of mechanical properties and morphology. Water remediation from dye pollution was the first focus of this work. Organogels were studied as absorbent of dyes from contaminated water. Hydrogels functionalised with TiO2 nanoparticles and graphene platelets were proposed as efficient materials for the photo-degradation of dyes. An efficient method for the incorporation of graphene inside hydrogels using the gelator itself as dispersant was proposed. In these materials a high storage modulus coexists with good self-healing and biocompatibility. The incorporation of a mineral phase inside the gel matrix was then investigated, leading to the preparation of composite organic/inorganic materials. In a first study, the growth of calcium carbonate crystals was achieved inside the hydrogel, which preserved its structure after crystal formation. Then the self-assembled fibres made of LMWGs were used for the first time instead of the polymeric ones as reinforcement inside calcium phosphate cements (CPCs) for bone regeneration. Gel-to-crystal transitions occurring with time in a metastable gel were also examined. The formation of organic crystals in gels can be achieved in multicomponent systems, in which a second gelator constitutes the independent gel network. Finally, some compounds unable to gelate were tested as underwater adhesives.

Optimization of an innovative T6 heat treatment for the AlSi10Mg alloy processed by Laser-based Powder Bed Fusion: effect on microstructure, mechanical properties, and tribological behavior

Laser-based Powder Bed Fusion (L-PBF) technology is one of the most commonly used metal Additive Manufacturing (AM) techniques to produce highly customized and value-added parts. The AlSi10Mg alloy has received more attention in the L-PBF process due to its good printability, high strength/weight ratio, corrosion resistance, and relatively low cost. However, a deep understanding of the effect of heat treatments on this alloy's metastable microstructure is still required for developing tailored heat treatments for the L-PBF AlSi10Mg alloy to overcome the limits of the as-built condition. Several authors have already investigated the effects of conventional heat treatment on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy but often overlooked the peculiarities of the starting supersatured and ultrafine microstructure induced by rapid solidification. For this reason, the effects of innovative T6 heat treatment (T6R) on the microstructure and mechanical behavior of the L-PBF AlSi10Mg alloy were assessed. The short solution soaking time (10 min) and the relatively low temperature (510 °C) reduced the typical porosity growth at high temperatures and led to a homogeneous distribution of fine globular Si particles in the Al matrix. In addition, it increased the amount of Mg and Si in the solid solution available for precipitation hardening during the aging step. The mechanical (at room temperature and 200 °C) and tribological properties of the T6R alloy were evaluated and compared with other solutions, especially with an optimized direct-aged alloy (T5 alloy). Results showed that the innovative T6R alloy exhibits the best mechanical trade-off between strength and ductility, the highest fatigue strength among the analyzed conditions, and interesting tribological behavior. Furthermore, the high-temperature mechanical performances of the heat-treated L-PBF AlSi10Mg alloy make it suitable for structural components operating in mild service conditions at 200 °C.

Design and characterization of polymorphs and co-crystals of organic molecular semiconductors

In the last decades, organic semiconductors have attracted attention due to their possible employment in solution-processed optoelectronic and electronic devices. One of the advantages of solution processing is the possibility to process into flexible substrates at low cost. Organic molecular materials tend to form polymorphs, which can exhibit very different properties. In most cases, the control of the crystal structure is decisive to maximize the performance of the final device. Although organic electronics have progressed a lot, n-type organic semiconductors still lag behind p-type, presenting challenges such as air instability and poor solubility. NDI derivatives are promising candidates for applications in organic electronics due to their characteristics. Recently, the structure-properties relationship and the polymorphism of these molecules have gained attention. In the first part of this thesis, NDI-C6 thermal behavior was extensively explored which revealed two different behaviors depending on the annealing process. This study allowed to define the stability ranking of the NDI-C6 bulk forms and to determine the crystal structure of Form γ at 54°C. Additionally, the polymorphic and thermal behavior of thin films of NDI-C6 was also explored. It was possible to isolate pure Form α, Form β, Form γ and a new metastable Form ε. It was also possible to determine the stability ranking of the phases in thin films. OFETs were fabricated having different polymorphs as active layer, unfortunately the performance was not ideal. During the second part of this thesis, core-chlorinated NDIs with fluoroalkyl chains were studied. Initially, the focus was on the polymorphism of CF3-NDI that revealed a solvate form with a very interesting molecular arrangement suggesting the possibility to form charge transfer co-crystals. In the last part of the thesis, the synthesis and characterization of CT co-crystal with different NDI derivatives, and acceptor and as donor BTBT and ditBu-BTBT were explored.