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.

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.

Evaluation of green algae deployment for organic pollutant removal in urban wastewater through ERE-CALUX potency assessment

The interest of the scientific community towards organic pollutants in freshwater streams is fairly recent. During the past 50 years, thousands of chemicals have been synthesized and released into the general environment. Nowadays their occurrence and effects on several organism, invertebrates, fish, birds, reptiles and also humans are well documented. Because of their action, some of these chemicals have been defined as Endocrine Disrupters Compounds (EDCs) and the public health implications of these EDCs have been the subject of scientific debate. Most interestingly, among those that were noticed to have some influence and effects on the endocrine system were the estrone, the 17β-estradiol, the 17α-estradiol, the estriol, the 17α-ethinylestradiol, the testosterone and the progesterone. This project focused its attention on the 17β-estradiol. Estradiol, or more precisely, 17β-estradiol (also commonly referred to as E2) is a human sex hormone. It belongs to the class of steroid hormones. In spite of the effort to remove these substances from the effluents, the actual wastewater treatment plants are not able to degrade or inactivate these organic compounds that are continually poured in the ecosystem. Through this work a new system for the wastewater treatment was tested, to assess the decrease of the estradiol in the water. It involved the action of Chlorella vulgaris, a fresh water green microalga belonging to the family of the Chlorellaceae. This microorganism was selected for its adaptability and for its photosynthetic efficiency. To detect the decrease of the target compound in the water a CALUX bioassay analysis was chosen. Three different experiments were carried on to pursue the aim of the project. By analysing their results several aspects emerged. It was assessed the presence of EDCs inside the water used to prepare the culture media. C. vulgaris, under controlled conditions, could be efficient for this purpose, although further researches are essential to deepen the knowledge of this complex phenomenon. Ultimately by assessing the toxicity of the effluent against C. vulgaris, it was clear that at determined concentrations, it could affect the normal growth rate of this microorganism.

Implementation of enhanced biological phosphorus removal (ebpr) wastewater treatment processes enriched with different microbial communities

The EBPR (Enhanced Biological Phosphorus Removal) is a type of secondary treatment in WWTPs (WasteWater Treatment Plants), quite largely used in full-scale plants worldwide. The phosphorus occurring in aquatic systems in high amounts can cause eutrophication and consequently the death of fauna and flora. A specific biomass is used in order to remove the phosphorus, the so-called PAOs (Polyphosphate Accumulating Organisms) that accumulate the phosphorus in form of polyphosphate in their cells. Some of these organisms, the so-called DPAO (Denitrifying Polyphosphate Accumulating Organisms) use as electron acceptor the nitrate or nitrite, contributing in this way also to the removal of these compounds from the wastewater, but there could be side reactions leading to the formation of nitrous oxides. The aim of this project was to simulate in laboratory scale a EBPR, acclimatizing and enriching the specialized biomass. Two bioreactors were operated as Sequencing Batch Reactors, one enriched in Accumulibacter, the other in Tetrasphaera (both PAOs): Tetrasphaera microorganisms are able to uptake aminoacids as carbon source, Accumulibacter uptake organic carbon (volatile fatty acids, VFA). In order to measure the removal of COD, phosphorus and nitrogen-derivate compounds, different analysis were performed: spectrophotometric measure of phosphorus, nitrate, nitrite and ammonia concentrations, TOC (Total Organic Carbon, measuring the carbon consumption), VFA via HPLC (High Performance Liquid Chromatography), total and volatile suspended solids following standard methods APHA, qualitative microorganism population via FISH (Fluorescence In Situ Hybridization). Batch test were also performed to monitor the NOx production. Both specialized populations accumulated as a result of SBR operations; however, Accumulibacter were found to uptake phosphates at higher extents. Both populations were able to remove efficiently nitrates and organic compounds occurring in the feeding. The experimental work was carried out at FCT of Universidade Nova de Lisboa (FCT-UNL) from February to July 2014.