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.

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.