Atmospheric corrosion of quaternary bronzes (Cu-Sn-Zn-Pb): laboratory tests (accelerated ageing in wet & dry conditions)and field studies (the Bottego monument in Parma, Italy).

The interactions between outdoor bronzes and the environment, which lead to bronze corrosion, require a better understanding in order to design effective conservation strategies in the Cultural Heritage field. In the present work, investigations on real patinas of the outdoor monument to Vittorio Bottego (Parma, Italy) and laboratory studies on accelerated corrosion testing of inhibited (by silane-based films, with and without ceria nanoparticles) and non-inhibited quaternary bronzes are reported and discussed. In particular, a wet&dry ageing method was used both for testing the efficiency of the inhibitor and for patinating bronze coupons before applying the inhibitor. A wide range of spectroscopic techniques has been used, for characterizing the core metal (SEM+EDS, XRF, AAS), the corroded surfaces (SEM+EDS, portable XRF, micro-Raman, ATR-IR, Py-GC-MS) and the ageing solutions (AAS). The main conclusions were: 1. The investigations on the Bottego monument confirmed the differentiation of the corrosion products as a function of the exposure geometry, already observed in previous works, further highlighting the need to take into account the different surface features when selecting conservation procedures such as the application of inhibitors (i.e. the relative Sn enrichment in unsheltered areas requires inhibitors which effectively interact not only with Cu but also with Sn). 2. The ageing (pre-patination) cycle on coupons was able to reproduce the relative Sn enrichment that actually happens in real patinated surfaces, making the bronze specimens representative of the real support for bronze inhibitors. 3. The non-toxic silane-based inhibitors display a good protective efficiency towards pre-patinated surfaces, differently from other widely used inhibitors such as benzotriazole (BTA) and its derivatives. 4. The 3-mercapto-propyl-trimethoxy-silane (PropS-SH) additivated with CeO2 nanoparticles generally offered a better corrosion protection than PropS-SH.

Properties of cosmic voids in dark energy simulations

The last decade has witnessed the establishment of a Standard Cosmological Model, which is based on two fundamental assumptions: the first one is the existence of a new non relativistic kind of particles, i. e. the Dark Matter (DM) that provides the potential wells in which structures create, while the second one is presence of the Dark Energy (DE), the simplest form of which is represented by the Cosmological Constant Λ, that sources the acceleration in the expansion of our Universe. These two features are summarized by the acronym ΛCDM, which is an abbreviation used to refer to the present Standard Cosmological Model. Although the Standard Cosmological Model shows a remarkably successful agreement with most of the available observations, it presents some longstanding unsolved problems. A possible way to solve these problems is represented by the introduction of a dynamical Dark Energy, in the form of the scalar field ϕ. In the coupled DE models, the scalar field ϕ features a direct interaction with matter in different regimes. Cosmic voids are large under-dense regions in the Universe devoided of matter. Being nearby empty of matter their dynamics is supposed to be dominated by DE, to the nature of which the properties of cosmic voids should be very sensitive. This thesis work is devoted to the statistical and geometrical analysis of cosmic voids in large N-body simulations of structure formation in the context of alternative competing cosmological models. In particular we used the ZOBOV code (see ref. Neyrinck 2008), a publicly available void finder algorithm, to identify voids in the Halos catalogues extraxted from CoDECS simulations (see ref. Baldi 2012 ). The CoDECS are the largest N-body simulations to date of interacting Dark Energy (DE) models. We identify suitable criteria to produce voids catalogues with the aim of comparing the properties of these objects in interacting DE scenarios to the standard ΛCDM model, at different redshifts. This thesis work is organized as follows: in chapter 1, the Standard Cosmological Model as well as the main properties of cosmic voids are intro- duced. In chapter 2, we will present the scalar field scenario. In chapter 3 the tools, the methods and the criteria by which a voids catalogue is created are described while in chapter 4 we discuss the statistical properties of cosmic voids included in our catalogues. In chapter 5 the geometrical properties of the catalogued cosmic voids are presented by means of their stacked profiles. In chapter 6 we summarized our results and we propose further developments of this work.

Electrical spectroscopy of rubrene bulk and thin film crystals

One of the most diffused electronic device is the field effect transistor (FET), contained in number of billions in each electronic device. Organic optoelectronics is an emerging field that exploits the unique properties of conjugated organic materials to develop new applications that require a combination of performance, low cost and processability. Organic single crystals are the material with best performances and purity among the variety of different form of organic semiconductors. This thesis is focused on electrical and optical characterization of Rubrene single crystal bulk and thin films. Rubrene bulk is well known but for the first time we studied thin films. The first Current-voltage characterization has been performed for the first time on three Rubrene thin films with three different thickness to extract the charge carriers mobility and to assess its crystalline structure. As results we see that mobility increase with thickness. Field effect transistor based on Rubrene thin films on $SiO_2$ have been characterize by current-voltage (I-V) analyses (at several temperatures) and reveals a hopping conduction. Hopping behavior probably is due to the lattice mismatch with the substrate or intrinsic defectivity of the thin films. To understand effects of contact resistance we tested thin films with the Transmission Line Method (TLM) method. The TLM method revealeds that contact resistance is negligible but evidenced a Schottky behavior in a limited but well determined range of T. To avoid this effect we carried out annealing treatment after the electrode evaporation iswe performed a compete I-V characterization as a function of in temperature to extract the electronic density of states (DOS) distribution through the Space Charge Limited Current (SCLC) method. The results show a DOS with an exponential trenddistribution, as expected. The measured mobility of thin films is about 0.1cm^2/Vs and it increases with the film thickness. Further studies are necessary to investigate the reason and improve performances. From photocurrent spectrum we calculated an Eg of about 2.2eV and both thin films and bulk have a good crystal order. Further measurement are necessary to solve some open problems