1. The impact of urban rain on the changes of bare and artificially patinated bronze during 9-year exposureTadeja Kosec, Mirjam Bajt Leban, Polonca Ropret, Matjaž Finšgar, 2024, pregledni znanstveni članek Povzetek: Atmospheric pollutants in the air form acid rain which interacts with bronze surfaces exposed in urban outdoor environment. In this study, different types of patinas on bronze were investigated during and after 9 years of exposure to urban environment in moderately polluted continental city. Natural bronze patina and artificial brown sulphide, green chloride, and green–blue nitrate patinas were investigated. Visual assessment was carried out at defined periods. After 9 years of exposure, an electrochemical study was performed to investigate the electrochemical activity of the patinas in artificial urban rain. Additionally, the patinas were characterised using a variety of techniques, including metallographic examination, scanning electron microscopy/energy dispersive X-ray spectroscopy, Raman spectroscopy, X-ray diffraction analysis, X-ray-photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry to analyse the surface morphology, chemical composition, and stratigraphic features of the patinas. Evolution of the patinas was shown to be a result of both, the composition of the acid rain and the hydrophobicity of the patinated surfaces.
Ključne besede: bronze, bronze, corrosion, patina characterization
Objavljeno v DiRROS: 29.04.2024; Ogledov: 42; Prenosov: 14
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2. B-IMPACT project : eco-friendly and non-hazardous coatings for the protection of outdoor bronzesGiulia Masi, Maëlenn Aufray, A. Balbo, E. Bernardi, Maria Chiara Bignozzi, Cristina Chiavari, J. Esvan, Nina Gartner, V. Grassi, Claudie Josse, Tadeja Kosec, Carla Martini, Cecilia Monticelli, Luka Škrlep, W. Sperotto, Erika Švara Fabjan, E. Tedesco, F. Zanotto, Luc Robbiola, 2020, objavljeni znanstveni prispevek na konferenci Povzetek: Application of protective coatings is the most widely used conservation treatment for outdoor bronzes. Eco-friendly and non-hazardous coatings are currently needed for conservation of outdoor bronze monuments. To fulfil this need, the M-ERA.NET European research project B-IMPACT (Bronze-IMproved non-hazardous PAtina CoaTings) aimed at assessing the protectiveness of innovative coatings for historical and modern bronze monuments exposed outdoors.
In this project, two bronze substrates (historical Cu-Sn-Zn-Pb and modern Cu-Si-Mn alloys) were artificially patinated, by acid rain solution using dropping test and by "liver of sulphur" procedure (K2S aqueous solution) to obtain black patina, respectively. Subsequently, the application of several newly developed protective coatings was carried out and their performance was investigated by preliminary electrochemical tests. In the following steps of the work, the assessment of the best-performing coatings was carried out and their performance was compared to Incralac, one of the most widely used protective coatings in conservation practice. A multi-analytical approach was adopted, considering artificial ageing (carried out in representative conditions, including exposure to rain runoff, stagnant rain and UV radiation) and metal release, as well as visual aspect (so as to include aesthetical impact among the coating selection parameters) and morphological and structural evolution of the coated surfaces due to simulated outdoor exposure. Lastly, also the health impact of selected coatings was assessed by occupational hazard tests. The removability and re-applicability of the best-performing coatings were also assessed. The best alternatives to the conventional Incralac exhibited were: (i) fluoroacrylate blended with methacryloxy-propyl-trimethoxy-silane (FA-MS) applied on patinated Cu-Sn-Zn-Pb bronze and (ii) 3-mercapto-propyl-trimethoxysilane (PropS-SH) applied on patinated Cu-Si-Mn bronze.
Ključne besede: bronze, patina, protective coatings, eco-friendly, corrosion, aging
Objavljeno v DiRROS: 01.03.2024; Ogledov: 131; Prenosov: 69
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3. Development of multi-component fluoropolymer based coating on simulated outdoor patina on quaternary bronzeTadeja Kosec, Luka Škrlep, Erika Švara Fabjan, Andrijana Sever Škapin, Giulia Masi, Elena Bernardi, Cristina Chiavari, Claudie Josse, Jerome Esvan, Luc Robbiola, 2019, izvirni znanstveni članek Povzetek: Bronze reacts with oxygen, humidity, and pollutants in the atmosphere so that a patina forms. Natural exposure to an outdoor atmosphere can be simulated and accelerated in order to achieve a patina that mimics outdoor ancient patina. In order to avoid the uncontrolled dissolving of either the natural or artificially formed patina, protection of the patina is needed.
In this study, a multi-component fluoropolymer based coating for the protection of bronze patina was developed. In order to provide various functionalities of the coating (such as the hydrophobicity of the coating surface, obtaining interactions within the coating itself as well as a bronze substrate and inhibiting the corrosion processes), a fluoroacrylate coating with appropriate adhesion promoter was suggested, with and without a silane modified benzotriazole inhibitor. The protective efficiency and durability of the applied coatings were investigated electrochemically using potentiodynamic tests and electrochemical impedance spectroscopy in a simulated acid rain solution. All of the developed coatings showed a significant decrease in the corrosion current density. The self-assembled single layer coating (FA-MS) also showed 100% inhibition efficiency. After ageing the coating remained transparent and did not change by UV exposure and/or thermal cycling. The patina and coating investigations using FIB-SEM and EDX showed that the latter coating (FA-MS) successfully covered the surface of the patinated bronze. The mechanism of the bonding was proposed and supported with the spectroscopic observation of a thin and even coating.
Ključne besede: bronze, patina, fluoropolymer coating, atmospheric corrosion
Objavljeno v DiRROS: 25.10.2023; Ogledov: 345; Prenosov: 186
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4. Corrosion protection of brown and green patinated bronzeTadeja Kosec, Živa Novak, Erika Švara Fabjan, Luka Škrlep, Andrijana Sever Škapin, Polonca Ropret, 2021, izvirni znanstveni članek Povzetek: Bronze surfaces, whether bare or patinated, tend to change when exposed to an outdoor atmosphere. Art made of bronze which is exposed to the outdoors is usually artificially patinated. This patina changes when exposed to rain, especially in polluted rain, where sulphuric, nitric or carbonic acids are present.
In order to gain optimal protection of different patinas and consequently reduce the patina changes over the time different protection systems were developed, tested and tailored. Three types of patina (brown, green sulphate, and green persulphate) were prepared, protected and subsequently studied. The protections were based on two coatings (i) fluoropolymer based coating (FA-MS) and (ii) newly developed fluoropolymer based coating with addition of mercaptopropyl groups, named as alternative fluoropolymer coating (FA-MS-SH). Both the pure patinas applied on bronze surfaces as well as the bare bronze were electrochemically tested, first unprotected and then following the application of two different types of protection. After the protection was applied to the pa- tinas, the change in colour was defined. Different techniques were utilised in order to define the morphology and structure of the patinas, as well as the change in colour following application of the coating. It was shown that a fluoropolymer coating (FA-MS) provided the most efficient protection to bare bronze and the sulphate patina, while a newly proposed alternative fluoropolymer coating (FA-MS-SH) offered good protection to bare and brown patinated bronze. A mechanism for the protection of bare and patinated bronze was suggested.
Ključne besede: bronze, patina, protection
Objavljeno v DiRROS: 17.07.2023; Ogledov: 288; Prenosov: 171
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5. Exploring the protection mechanism of a combined fluoropolymer coating on sulphide patinated bronzeTadeja Kosec, Živa Novak, Erika Švara Fabjan, Luka Škrlep, Matjaž Finšgar, 2022, izvirni znanstveni članek Povzetek: When bronze or artificially patinated bronze is exposed to an outdoor environment that contains aggressive ions such as sulphates, nitrates, and carbonates, the surface of the bronze changes its appearance due to the formation of corrosion products on the surface. Research is being conducted on versatile protective measures that can be used to protect the surface from these changes. A recently synthesised fluoropolymer-based coating with mercaptopropyl groups, i.e. a 3-component fluoropolymer coating FA-MS-SH (silane-modified poly methylmethacrylate (MS) with added mercaptopropyltrimethoxy silane (SH) and a fluoroacrylate (FA)) was explored in detail in this work where its protective mechanism on sulphide patinated bronze was investigated. Electrochemical tests were conducted on the sulphide patinated bronze with and without the 3-component coating FA-MS-SH. Furthermore, FA, MS and SH alone and various combinations and concentrations of FA-MS were studied in order to determine the protective effect and properties of each component. Colour change and contact angle measurements were also defined. FIB-SEM measurements and GCIB-XPS depth profiles were carried out to study surface bonding with the sulphide patina in detail.
A mechanism for the protection of sulphide patinated bronze was presented through the use of a multianalytical tool approach. It was shown that FA physisorbed on the patinated surface, while MS and blends of the components chemisorbed on the layer of sulphide patinated bronze, also resulting in the surface being efficiently protected from corrosion processes.
Ključne besede: bronze, protection, brown patina, fluoropolymer coating
Objavljeno v DiRROS: 31.05.2023; Ogledov: 329; Prenosov: 192
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