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.

Shear behavior of reinforced concrete slabs under concentrated load: an investigation through Sequentially Linear Analysis

ABSTRACT (italiano) Con crescente attenzione riguardo al problema della sicurezza di ponti e viadotti esistenti nei Paesi Bassi, lo scopo della presente tesi è quello di studiare, mediante la modellazione con Elementi Finiti ed il continuo confronto con risultati sperimentali, la risposta in esercizio di elementi che compongono infrastrutture del genere, ovvero lastre in calcestruzzo armato sollecitate da carichi concentrati. Tali elementi sono caratterizzati da un comportamento ed una crisi per taglio, la cui modellazione è, da un punto di vista computazionale, una sfida piuttosto ardua, a causa del loro comportamento fragile combinato a vari effetti tridimensionali. La tesi è incentrata sull'utilizzo della Sequentially Linear Analysis (SLA), un metodo di soluzione agli Elementi Finiti alternativo rispetto ai classici approcci incrementali e iterativi. Il vantaggio della SLA è quello di evitare i ben noti problemi di convergenza tipici delle analisi non lineari, specificando direttamente l'incremento di danno sull'elemento finito, attraverso la riduzione di rigidezze e resistenze nel particolare elemento finito, invece dell'incremento di carico o di spostamento. Il confronto tra i risultati di due prove di laboratorio su lastre in calcestruzzo armato e quelli della SLA ha dimostrato in entrambi i casi la robustezza del metodo, in termini di accuratezza dei diagrammi carico-spostamento, di distribuzione di tensioni e deformazioni e di rappresentazione del quadro fessurativo e dei meccanismi di crisi per taglio. Diverse variazioni dei più importanti parametri del modello sono state eseguite, evidenziando la forte incidenza sulle soluzioni dell'energia di frattura e del modello scelto per la riduzione del modulo elastico trasversale. Infine è stato effettuato un paragone tra la SLA ed il metodo non lineare di Newton-Raphson, il quale mostra la maggiore affidabilità della SLA nella valutazione di carichi e spostamenti ultimi insieme ad una significativa riduzione dei tempi computazionali. ABSTRACT (english) With increasing attention to the assessment of safety in existing dutch bridges and viaducts, the aim of the present thesis is to study, through the Finite Element modeling method and the continuous comparison with experimental results, the real response of elements that compose these infrastructures, i.e. reinforced concrete slabs subjected to concentrated loads. These elements are characterized by shear behavior and crisis, whose modeling is, from a computational point of view, a hard challenge, due to their brittle behavior combined with various 3D effects. The thesis is focused on the use of Sequentially Linear Analysis (SLA), an alternative solution technique to classical non linear Finite Element analyses that are based on incremental and iterative approaches. The advantage of SLA is to avoid the well-known convergence problems of non linear analyses by directly specifying a damage increment, in terms of a reduction of stiffness and strength in the particular finite element, instead of a load or displacement increment. The comparison between the results of two laboratory tests on reinforced concrete slabs and those obtained by SLA has shown in both the cases the robustness of the method, in terms of accuracy of load-displacements diagrams, of the distribution of stress and strain and of the representation of the cracking pattern and of the shear failure mechanisms. Different variations of the most important parameters have been performed, pointing out the strong incidence on the solutions of the fracture energy and of the chosen shear retention model. At last a confrontation between SLA and the non linear Newton-Raphson method has been executed, showing the better reliability of the SLA in the evaluation of the ultimate loads and displacements, together with a significant reduction of computational times.

Laboratory verification of predicted permanent deformation in asphalt materials following climate change.

In the past a change in temperature of 5°C most often occurred over intervals of thousands of years. According to estimates by the IPCC, in the XXI century is expected an increase in average temperatures in Europe between 1.8 and 4.0°C in the best case caused by emissions of carbon dioxide and other GHG from human activities. As well as on the environment and economic context, global warming will have effects even on road safety. Several studies have already shown how increasing temperature may cause a worsening of some types of road surface damages, especially rutting, a permanent deformation of the road structures consisting in the formation of a longitudinal depression in the wheelpath, mostly due to the rheological behavior of bitumen. This deformation evolves during the hot season because of the heating capacity of the asphalt layers, in fact, the road surface temperature is up to 24°C higher than air. In this thesis, through the use of Wheeltrack test, it was studied the behavior of some types of asphalt concrete mixtures subjected to fatigue testing at different temperatures. The objectives of this study are: to determine the strain variation of different bituminous mixture subjected to fatigue testing at different temperature conditions; to investigate the effect of aggregates, bitumen and mixtures’ characteristics on rutting. Samples were made in the laboratory mostly using an already prepared mixtures, the others preparing the asphalt concrete from the grading curve and bitumen content. The same procedure was performed for each specimen: preparation, compaction using the roller compactor, cooling and heating before the test. The tests were carried out at 40 - 50 - 60°C in order to obtain the evolution of deformation with temperature variation, except some mixtures for which the tests were carried out only at 50°C. In the elaboration of the results were considered testing parameters, component properties and the characteristics of the mixture. Among the testing parameters, temperature was varied for each sample. The mixtures responded to this variation with a different behavior (linear logarithmic and exponential) not directly correlated with the asphalt characteristics; the others parameters as load, passage frequency and test condition were kept constant. According to the results obtained, the main contribution to deformation is due to the type of binder used, it was found that the modified bitumen have a better response than the same mixtures containing traditional bitumen; to the porosity which affects negatively the behavior of the samples and to the homogeneity ceteris paribus. The granulometric composition did not seem to have interfered with the results. Overall has emerged at working temperature, a decisive importance of bitumen composition, than the other characteristics of the mixture, that tends to disappear with heating in favor of increased dependence of rutting resistance from the granulometric composition of the sample considered. In particular it is essential, rather than the mechanical characteristics of the binder, its chemical properties given by the polymeric modification. To confirm some considered results, the maximum bulk density and the air voids content were determined. Tests have been conducted in the laboratories of the Civil Engineering Department at NTNU in Trondheim according to European Standards.

Development of an instrumented customizable total knee prosthesis for experimental tests.

Total knee arthroplasty (TKA) has revolutionized the life of millions of patients and it is the most efficient treatment in cases of osteoarthritis. The increase in life expectancy has lowered the average age of the patient, which requires a more enduring and performing prosthesis. To improve the design of implants and satisfying the patient's needs, a deep understanding of the knee Biomechanics is needed. To overcome the uncertainties of numerical models, recently instrumented knee prostheses are spreading. The aim of the thesis was to design and manifacture a new prototype of instrumented implant, able to measure kinetics and kinematics (in terms of medial and lateral forces and patellofemoral forces) of different interchangeable designs of prosthesis during experiments tests within a research laboratory, on robotic knee simulator. Unlike previous prototypes it was not aimed for industrial applications, but purely focusing on research. After a careful study of the literature, and a preliminary analytic study, the device was created modifying the structure of a commercial prosthesis and transforming it in a load cell. For monitoring the kinematics of the femoral component a three-layers, piezoelettric position sensor was manifactured using a Velostat foil. This sensor has responded well to pilot test. Once completed, such device can be used to validate existing numerical models of the knee and of TKA and create new ones, more accurate.It can lead to refinement of surgical techniques, to enhancement of prosthetic designs and, once validated, and if properly modified, it can be used also intraoperatively.