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.

Gilded bronze conservation: assessment of protective treatments by accelerated ageing and of treatment removal procedures by laser cleaning

In the current study, we analyze the effectiveness of an organosilane compound, 3-mercapto-propyl-tri-methoxy-silane (abbreviated PropS-SH), in the corrosion protection of fire-gilded bronzes. Firstly, the coating was applied on as-gilded bronze. Subsequently, it was also applied on pre-patinated bronze, because the substrate on which protective coatings are applied in real conservation interventions are corroded artifacts (cleaning procedures never remove all the corrosion products). Aiming to obtain results that simulate the situation of real artifacts, a dropping test that simulates outdoor exposure in runoff conditions (unsheltered areas of monuments) was employed in order to prepatinate the gilded bronze samples, which are the substrate for applying the protective coating. The preparation of the samples by applying the protective coating was performed in collaboration with the Corrosion Studies Centre “Aldo Daccò” from Ferrara University. After the artificial exposure cycles the samples underwent investigations through a variety of spectroscopic methods including SEM, Raman, FIB, AAS and color measurements. In order to evaluate the possible removal of the organosilane coating, protected samples were subjected to laser cleaning tests and characterized by SEM/EDS so as to assess the changes in composition and morphology of the treated surfaces. The laser cleaning treatment was performed at the Institute of Applied Physics “Nello Carrara” (CNR Sesto Fiorentino (FI)). The morphology and chemical composition of the samples was observed before and after the operation in order to obtain information about the fluence and type of laser which are best suited to the removal of this type of coating.

Characterization of moisture susceptibility of asphaltic bitumen

La ricerca riguarda lo studio delle modifiche indotte dalla diffusione di acqua e umidità nelle pavimentazioni stradali con riferimento ai materiali bituminosi. Lo scopo è stato quello di analizzare le implicazioni che si sviluppano a livello chimico e reologico in vari bitumi. In questo progetto oltre alla fase sperimentale, è stato utilizzato un software per la simulazione agli elementi finiti. Per quanto concerne la fase di laboratorio, è stato sviluppato un nuovo protocollo di condizionamento. Tre diversi bitumi sono stati soggetti alla diffusione di acqua in forma liquida o vapore, a determinate condizioni ambientali e per svariati intervalli temporali. Grazie a l’utilizzo di due camere climatiche il condizionamento è stato realizzato in modo uniforme a precisi valori temperatura e umidità mantenuti stabili. I materiali analizzati: un bitume soft, uno hard, ed infine uno modificato con l’aggiunta di polimeri. Il dispositivo FTIR-ATR è stato utilizzato per la caratterizzazione chimica, mentre il comportamento reologico è stato analizzato tramite test eseguiti con il DSR. Le avanzate tecnologie presenti nel laboratorio della TU Delft hanno consentito di ottenere notevoli risultati. L’analisi è stata condotta con l’obiettivo di evidenziare i diversi cambiamenti indotti dalla diffusione di acqua liquida o vapore e per analizzare l’influenza della temperatura, del tipo del bitume e dell’incremento del tempo di condizionamento. Una analisi analoga è stata condotta parallelamente, con lo scopo di investigare la correlazione tra il processo di invecchiamento e la diffusione di umidità. Infine, la simulazione agli elementi finiti è stata sviluppata tramite il software CAPA-3D per analizzare il comportamento del bitume in periodi più estesi di diffusione di umidità. Inoltre, il comportamento dei bitumi è stato studiato anche in presenza di particelle di riempitivo. Particelle granitiche e calcaree sono state aggiunte ai bitumi in differenti percentuali.

Rheological Characterization of Bitumen and Asphalt including the effect of Added-recycled Material

This thesis evaluates the rheological behaviour of asphalt mixtures and the corresponding extracted binders from the mixtures containing different amounts of Reclaimed Asphalt (RA). Generally, the use of RA is limited to certain amounts. The study materials are Stone Mastic Asphalts including a control sample with 0% RA, and other samples with RA rates of 30%, 60% and 100%. Another set of studied mixtures are Asphalt Concretes (AC) types with again a control mix having 0% RA rate and the other mixtures designs containing 30%, 60% and 90% of reclaimed asphalt which also contain additives. In addition to the bitumen samples extracted from asphalt mixes, there are bitumen samples directly extracted from the original RA. To characterize the viscoelastic behaviour of the binders, Dynamic Shear Rheometer (DSR) tests were conducted on bitumen specimens. The resulting influence of the RA content in the bituminous binders are illustrated through master curves, black diagrams and Cole-Cole plots with regressing these experimental data by the application of the analogical 2S2P1D and the analytical CA model. The advantage of the CA model is in its limited number of parameters and thus is a simple model to use. The 2S2P1D model is an analogical rheological model for the prediction of the linear viscoelastic properties of both asphalt binders and mixtures. In order to study the influence of RA on mixtures, the Indirect Tensile Test (ITT) has been conducted. The master curves of different mixture samples are evaluated by regressing the test data points to a sigmoidal function and subsequently by comparing the master curves, the influence of RA materials is studied. The thesis also focusses on the applicability and also differences of CA model and 2S2P1D model for bitumen samples and the sigmoid function for the mixtures and presents the influence of the RA rate on the investigated model parameters.

Accelerated ageing methodologies for the evaluation of particulate matter role in the corrosion of outdoor-exposed bronzes

Deterioration phenomena occurring on outdoor cultural heritage have been the subject of several studies, but relatively few works investigated the specific role of Particulate Matter (PM) in the corrosion of metals. This topic is really complex and, besides field exposures, accelerated ageing tests are also necessary to isolate and understand deterioration mechanisms due to PM. For this reason, the development of a methodology that allows to reproduce and analyze the effect of PM on alloys through accelerated ageing in climatic chamber has been started. On quaternary bronze specimens, single salts and a mix of them were deposited via two deposition methods: dry (directly depositing the salt on the surface) and wet (dropping a salt solution and drying it), simulating the initial chemical activation of the salts by RH% variations or by raindrops, respectively. Then, to better mimic the composition of real PM, a mixture containing a soluble salts, a mineral, a black carbon and an organic fraction was formulated and spread on the samples. The samples were placed in a climatic chamber and exposed to cyclic variations of T and RH for three weeks. The ageing cycles were set according to predictions on salt deliquescence/recrystallization through E-AIM model and to the evaluation of regional climatic data. The surface evolution was followed by SEM-EDX, Raman, AT-IR and UV-Vis Spectrophotometry. At the end of the test, mass losses were determined and corroded metals removed by pickling were analyzed by AAS. On the basis of the obtained results, the tested procedures seem to be promising in accelerating and mimicking realistic corrosion phenomena, as under the selected conditions, corrosion products typically found at different exposure time (from days to years) on outdoor bronzes were able to progressively form and evolve. Moreover, the two deposition modes simulating different condition of chemical activation of PM deposits allow to obtain complementary information.

Effects of Accelerated Hygroscopic Ageing on Interlaminar Shear Strength and Glass Transition Temperature of CFRP

This study, which is undertaken in cooperation with Riba-COMPOSITES, investigates the effects of hygroscopic ageing on the Interlaminar Shear Strength and Glass Transition Temperature of short-beams made of carbon fibre reinforced polymer (CFRP) composites provided by two different vendors. The materials have the same weave pattern but differ in the epoxy resin formulation. The tests are done in accordance with ASTM. Accelerated ageing techniques are carried out by immersion of the specimens in deionized water at 70°C for different periods of time, developing different degrees of ageing. The results of the tests confirm that hygroscopic ageing causes a loss of properties and a depression of the glass transition temperature in both the materials. However, since one of the two materials shows more constant property degradation, its behaviour in service conditions should be more easily predictable.

Results of the ageing campaign of the photomultiplier Hamamatsu R760

Il guadagno di un PMT è il fattore di amplificazione tra la corrente generata dal fotocatodo e quella finale dell’anodo. Quando un PMT è soggetto a una sorgente luminosa per lunghi periodi di tempo (processo noto come "invecchiamento"), il suo guadagno tende a diminuire. In questa tesi sono riportati i risultati della campagna di invecchiamento di un fotomoltiplicatore Hamamatsu R760. In particolare, è stato studiato come variasse il guadagno in funzione della carica integrata dal PMT tramite due principali tipi di misure: quella del guadagno assoluto, che consiste in singole misure di guadagno nella condizione di emissione di un singolo fotoelettrone alla volta, e quelle di guadagno relativo, le quali hanno permesso di studiare la dipendenza tra guadagno e voltaggio applicato al PMT. Il PMT in esame è stato fatto invecchiare fino a una carica integrata totale pari a 342 C. Una volta raggiunti i 282 C, è stato spento per 20 giorni, in modo da studiare l’eventuale capacità di recuperare guadagno durante i periodi di inattività. É stata osservata una rapida decrescita del guadagno nei primi 40 C integrati, com- inciando da 7.79 · 10^6 fino a un valore pari a 1.68 · 10^6, seguita da oscillazioni minori attorno a una decrescita lineare media. Dopo il periodo di inattività non è stato rilevato alcun recupero significativo di guadagno. Il guadagno del PMT dipende dal voltaggio applicato tramite una legge a potenza, i cui parametri sono stati misurati. In particolare, gli esponenti di tale relazione sono stati soggetti a una decrescita rapida iniziale (nei primi 40 C di carica integrata), seguita da una stabilizzazione. Inoltre, sono stati ricavati i valori di tensione da applicare al PMT per mantenere il guadagno a un valore costante di 1.5 · 10^5 in funzione della carica integrata. Questo valore è stato scelto come punto di lavoro per il rivelatore PLUME installato nell’esperimento LHCb, che utilizzerà questo tipo di PMT per la sua campagna di misure.

Bitumen aggregate adhesion and bitumen rheology of hard modified binders

The waterproofing of hydraulic structure is done traiditionally like laying road on dam surface but with specific modified binders. An italian firm recently patented a new method that is re-adaptation of typical surface treatment of roads. The purpose of this study is to find out best aggregate-bitumen mixture that can perform well under service conditions of a large hydraulic structure such as dams. So, 4 different hard modified bitumen were tested with 2 aggregate types i.e. limestone and basalt. The experimental program contained the testing of bitumen aggregate adhesion, using the rolling bottle test and rheology of hard modified binders using multiple stress creep and recovery test and dynamic viscosity test. The results and discussion are presented in detail in this work.