Outdoor bronze conservation: assessment of protective treatments by accelerated aging and of treatment removal procedures by laser cleaning

Outdoor bronzes exposed to the environment form naturally a layer called patina, which may be able to protect the metallic substrate. However, since the last century, with the appearance of acid rains, a strong change in the nature and properties of the copper based patinas occurred [1]. Studies and general observations have established that bronze corrosion patinas created by acid rain are not only disfiguring in terms of loss of detail and homogeneity, but are also unstable [2]. The unstable patina is partially leached away by rainwater. This leaching is represented by green streaking on bronze monuments [3]. Because of the instability of the patina, conservation techniques are usually required. On a bronze object exposed to the outdoor environment, there are different actions of the rainfall and other atmospheric agents as a function of the monument shape. In fact, we recognize sheltered and unsheltered areas as regards exposure to rainwater [4]. As a consequence of these different actions, two main patina types are formed on monuments exposed to the outdoor environment. These patinas have different electrochemical, morphological and compositional characteristics [1]. In the case of sheltered areas, the patina contains mainly copper products, stratified above a layer strongly enriched in insoluble Sn oxides, located at the interface with the uncorroded metal. Moreover, different colors of the patina result from the exposure geometry. The surface color may be pale green for unsheltered areas, and green and mat black for sheltered areas [4]. Thus, in real outdoor bronze monuments, the corrosion behavior is strongly influenced by the exposure geometry. This must be taken into account when designing conservation procedures, since the patina is in most cases the support on which corrosion inhibitors are applied. Presently, for protecting outdoor bronzes against atmospheric corrosion, inhibitors and protective treatments are used. BTA and its derivatives, which are the most common inhibitors used for copper and its alloy, were found to be toxic for the environment and human health [5, 6]. Moreover, it has been demonstrated that BTA is efficient when applied on bare copper but not as efficient when applied on bare bronze [7]. Thus it was necessary to find alternative compounds. Silane-based inhibitors (already successfully tested on copper and other metallic substrates [8]), were taken into consideration as a non-toxic, environmentally friendly alternative to BTA derivatives for bronze protection. The purpose of this thesis was based on the assessment of the efficiency of a selected compound, to protect the bronze against corrosion, which is the 3-mercapto-propyl-trimethoxy-silane (PropS-SH). It was selected thanks to the collaboration with the Corrosion Studies Centre “Aldo Daccò” at the Università di Ferrara. Since previous studies [9, 10, 11] demonstrated that the addition of nanoparticles to silane-based inhibitors leads to an increase of the protective efficiency, we also wanted to evaluate the influence of the addition of CeO2, La2O3, TiO2 nanoparticles on the protective efficiency of 3-mercapto-propyl-trimethoxy-silane, applied on pre-patinated bronze surfaces. This study is the first section of the thesis. Since restorers have to work on patinated bronzes and not on bare metal (except for contemporary art), it is important to be able to recreate the patina, under laboratory conditions, either in sheltered or unsheltered conditions to test the coating and to obtain reliable results. Therefore, at the University of Bologna, different devices have been designed to simulate the real outdoor conditions and to create a patina which is representative of real application conditions of inhibitor or protective treatments. In particular, accelerated ageing devices by wet & dry (simulating the action of stagnant rain in sheltered areas [12]) and by dropping (simulating the leaching action of the rain in unsheltered areas [1]) tests were used. In the present work, we used the dropping test as a method to produce pre-patinated bronze surfaces for the application of a candidate inhibitor as well as for evaluating its protective efficiency on aged bronze (unsheltered areas). In this thesis, gilded bronzes were also studied. When they are exposed to the outside environment, a corrosion phenomenon appears which is due to the electrochemical couple gold/copper where copper is the anode. In the presence of an electrolyte, this phenomenon results in the formation of corrosion products than will cause a blistering of the gold (or a break-up and loss of the film in some cases). Moreover, because of the diffusion of the copper salts to the surface, aggregates and a greenish film will be formed on the surface of the sample [13]. By coating gilded samples with PropS-SH and PropS-SH containing nano-particles and carrying out accelerated ageing by the dropping test, a discussion is possible on the effectiveness of this coating, either with nano-particles or not, against the corrosion process. This part is the section 2 of this thesis. Finally, a discussion about laser treatment aiming at the assessment of reversibility/re-applicability of the PropS-SH coating can be found in section 3 of this thesis. Because the protective layer loses its efficiency with time, it is necessary to find a way of removing the silane layer, before applying a new one on the “bare” patina. One request is to minimize the damages that a laser treatment would create on the patina. Therefore, different laser fluences (energy/surface) were applied on the sample surface during the treatment process in order to find the best range of fluence. In particular, we made a characterization of surfaces before and after removal of PropS-SH (applied on a naturally patinated surface, and subsequently aged by natural exposure) with laser methods. The laser removal treatment was done by the CNR Institute of Applied Physics “Nello Carrara” of Sesto Fiorentino in Florence. In all the three sections of the thesis, a range of non-destructive spectroscopic methods (Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), μ-Raman spectroscopy, X-Ray diffractometry (XRD)) were used for characterizing the corroded surfaces. AAS (Atomic Absorption Spectroscopy) was used to analyze the ageing solutions from the dropping test in sections 1 and 2.

Waste management in Forlì-Cesena province: Life Cycle Assessment (LCA) of Forlì incinerator

This work assesses the environmental impact of a municipal solid waste incinerator with energy recovery in Forlì-Cesena province (Emilia-Romagna region, Italy). The methodology used is Life Cycle Assessment (LCA). As the plant already applies the best technologies available in waste treatment, this study focuses on the fate of the residues (bottom and fly ash) produced during combustion. Nine scenarios are made, based on different ash treatment disposing/recycling techniques. The functional unit is the amount of waste incinerated in 2011. Boundaries are set from waste arrival in the plant to the disposal/recovery of the residues produced, with energy recovery. Only the operative period is considered. Software used is GaBi 4 and the LCIA method used is CML2001. The impact categories analyzed are: abiotic depletion, acidification, eutrophication, freshwater aquatic ecotoxicity, global warming, human toxicity, ozone layer depletion, photochemical oxidant formation, terrestrial ecotoxicity and primary energy demand. Most of the data are taken from Herambiente. When primary data are not available, data from Ecoinvent and GaBi databases or literature data are used. The whole incineration process is sustainable, due to the relevant avoided impact given by co-generator. As far as regards bottom ash treatment, the most influential process is the impact savings from iron recovery. Bottom ash recycling in road construction or as building material are both valid alternatives, even if the first option faces legislative limits in Italy. Regarding fly ash inertization, the adding of cement and Ferrox treatment results the most feasible alternatives. However, this inertized fly ash can maintain its hazardous nature. The only method to ensure the stability of an inertized fly ash is to couple two different stabilization treatments. Ash stabilization technologies shall improve with the same rate of the flexibility of the national legislation about incineration residues recycling.

A novel marker for heart failure: Cross sectional area assessment in a large vein by conductance catheter.

The present study investigates the feasibility of a new application able to check the heart failure status in a patient through the estimation of the venous distension. In this way it would be possible to follow up patients, avoiding invasive or expensive exams such as cardiac catheterization and echocardiography. Moreover, the devices would also be able to diagnose the decline of the disease, in order to allow a new adaptation to therapy, and vice versa to check the improvement in the patient’s conditions after the CRT device implant. This thesis is essentially divided into three parts: an analytical model was used to obtain an estimation of the error committed for the calculation of the CSA and to understand how the accuracy and sensitivity depend on the different configurations of the electrodes and the catheter position inside the vein; secondly, an in-vitro experiment was carried out in order to verify the practical feasibility for these kinds of measurements, in a very simplified model; in the end, several animal experiments were done to test the in-vivo practicability of the proposed method. The obtained results showed the feasibility of this approach. In fact, the error committed in the estimation of CSA, during the animal experiments, can be considered acceptable (CSAerror_max ≈ -14%). Moreover, it has been demonstrated that the conductance catheter allows assessing, not only the vein CSA, but also the breathing of the animal.

Updating of Finite Element Models using static and dynamic optical strains with application to damage assessment

In the recent years, vibration-based structural damage identification has been subject of significant research in structural engineering. The basic idea of vibration-based methods is that damage induces mechanical properties changes that cause anomalies in the dynamic response of the structure, which measures allow to localize damage and its extension. Vibration measured data, such as frequencies and mode shapes, can be used in the Finite Element Model Updating in order to adjust structural parameters sensible at damage (e.g. Young’s Modulus). The novel aspect of this thesis is the introduction into the objective function of accurate measures of strains mode shapes, evaluated through FBG sensors. After a review of the relevant literature, the case of study, i.e. an irregular prestressed concrete beam destined for roofing of industrial structures, will be presented. The mathematical model was built through FE models, studying static and dynamic behaviour of the element. Another analytical model was developed, based on the ‘Ritz method’, in order to investigate the possible interaction between the RC beam and the steel supporting table used for testing. Experimental data, recorded through the contemporary use of different measurement techniques (optical fibers, accelerometers, LVDTs) were compared whit theoretical data, allowing to detect the best model, for which have been outlined the settings for the updating procedure.

Ray-tracing assessment of the robustness of Physical Layer Security key generation protocol

Nowadays, information security is a very important topic. In particular, wireless networks are experiencing an ongoing widespread diffusion, also thanks the increasing number of Internet Of Things devices, which generate and transmit a lot of data: protecting wireless communications is of fundamental importance, possibly through an easy but secure method. Physical Layer Security is an umbrella of techniques that leverages the characteristic of the wireless channel to generate security for the transmission. In particular, the Physical Layer based-Key generation aims at allowing two users to generate a random symmetric keys in an autonomous way, hence without the aid of a trusted third entity. Physical Layer based-Key generation relies on observations of the wireless channel, from which harvesting entropy: however, an attacker might possesses a channel simulator, for example a Ray Tracing simulator, to replicate the channel between the legitimate users, in order to guess the secret key and break the security of the communication. This thesis work is focused on the possibility to carry out a so called Ray Tracing attack: the method utilized for the assessment consist of a set of channel measurements, in different channel conditions, that are then compared with the simulated channel from the ray tracing, to compute the mutual information between the measurements and simulations. Furthermore, it is also presented the possibility of using the Ray Tracing as a tool to evaluate the impact of channel parameters (e.g. the bandwidth or the directivity of the antenna) on the Physical Layer based-Key generation. The measurements have been carried out at the Barkhausen Institut gGmbH in Dresden (GE), in the framework of the existing cooperation agreement between BI and the Dept. of Electrical, Electronics and Information Engineering "G. Marconi" (DEI) at the University of Bologna.

WEC-Sim Application for the Assessment of Wave Energy Generation in the Tyrrhenian Sea and the North Sea Through the 2-Body Point Absorber (2BPA) and the Oscillating Surge Wave Energy Converter (OSWEC)

In recent years, developed countries have turned their attention to clean and renewable energy, such as wind energy and wave energy that can be converted to electrical power. Companies and academic groups worldwide are investigating several wave energy ideas today. Accordingly, this thesis studies the numerical simulation of the dynamic response of the wave energy converters (WECs) subjected to the ocean waves. This study considers a two-body point absorber (2BPA) and an oscillating surge wave energy converter (OSWEC). The first aim is to mesh the bodies of the earlier mentioned WECs to calculate their hydrostatic properties using axiMesh.m and Mesh.m functions provided by NEMOH. The second aim is to calculate the first-order hydrodynamic coefficients of the WECs using the NEMOH BEM solver and to study the ability of this method to eliminate irregular frequencies. The third is to generate a *.h5 file for 2BPA and OSWEC devices, in which all the hydrodynamic data are included. The BEMIO, a pre-and post-processing tool developed by WEC-Sim, is used in this study to create *.h5 files. The primary and final goal is to run the wave energy converter Simulator (WEC-Sim) to simulate the dynamic responses of WECs studied in this thesis and estimate their power performance at different sites located in the Mediterranean Sea and the North Sea. The hydrodynamic data obtained by the NEMOH BEM solver for the 2BPA and OSWEC devices studied in this thesis is imported to WEC-Sim using BEMIO. Lastly, the power matrices and annual energy production (AEP) of WECs are estimated for different sites located in the Sea of Sicily, Sea of Sardinia, Adriatic Sea, Tyrrhenian Sea, and the North Sea. To this end, the NEMOH and WEC-Sim are still the most practical tools to estimate the power generation of WECs numerically.

Life cycle assessment (lca) of six separation methods of polyethylene and aluminum in tetra pak

In food and beverage industry, packaging plays a crucial role in protecting food and beverages and maintaining their organoleptic properties. Their disposal, unfortunately, is still difficult, mainly because there is a lack of economically viable systems for separating composite and multilayer materials. It is therefore necessary not only to increase research in this area, but also to set up pilot plants and implement these technologies on an industrial scale. LCA (Life Cycle Assessment) can fulfil these purposes. It allows an assessment of the potential environmental impacts associated with a product, service or process. The objective of this thesis work is to analyze the environmental performance of six separation methods, designed for separating the polymeric from the aluminum fraction in multilayered packaging. The first four methods utilize the chemical dissolution technique using Biodiesel, Cyclohexane, 2-Methyltetrahydrofuran (2-MeTHF) and Cyclopentyl-methyl-ether (CPME) as solvents. The last two applied the mechanical delamination technique with surfactant-activated water, using Ammonium laurate and Triethanolamine laurate as surfactants, respectively. For all six methods, the LCA methodology was applied and the corresponding models were built with the GaBi software version 10.6.2.9, specifically for LCA analyses. Unfortunately, due to a lack of data, it was not possible to obtain the results of the dissolution methods with the solvents 2-MeTHF and CPME; for the other methods, however, the individual environmental performances were calculated. Results revealed that the methods with the best environmental performance are method 2, for dissolution methods, and method 5, for delamination methods. This result is confirmed both by the analysis of normalized and weighted results and by the analysis of 'original' results. An hotspots analysis was also conducted.