1. Diketopyrrolopyrrole pigment core@multi-layer ▫$SiO_2$▫ shell with improved photochemical stabilityErika Švara Fabjan, Zineb Saghi, Paul A. Midgley, Mojca Otoničar, Goran Dražić, Miran Gaberšček, Andrijana Sever Škapin, 2018, original scientific article Abstract: A model organic pigment (diketopyrrolopyrrole) is encapsulated by a silica coating in order to improve its photochemical stability. Unlike in previous works where single-layer silica coatings were used for similar purposes, we here propose creation of a multi-layer silica shell synthesized via in-situ sol-gel method, which should significantly improve the homogeneity and thus the protection ability of the coating. This is done by repeating the basic two-step process (pigment surface modification and silica encapsulation) several times, creating the final protective shell in a layer-by-layer fashion. The compositional and structural properties of the prepared coatings is studied using Fourier-transform infrared spectroscopy, differential thermal and thermogravimetric analysis, nitrogen adsorption measurements and transmission electron microscopy. Photochemical stability of non-encapsulated and encapsulated pigment particles is evaluated via the so-called fast-irradiation method. Various correlations between the essential coating properties, such as thickness, porosity, SiO2 content, and the corresponding photochemical stability of the samples are established and discussed in detail. As a whole, our results confirm the basic hypothesis, that multiple-layered silica shells show improved pigment protection ability in comparison to the single-layer coatings.
Keywords: organic pigments, silica coating, encapsulation, morphology, photocemical stability
Published in DiRROS: 27.03.2024; Views: 143; Downloads: 57
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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, published scientific conference contribution Abstract: 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.
Keywords: bronze, patina, protective coatings, eco-friendly, corrosion, aging
Published in DiRROS: 01.03.2024; Views: 148; Downloads: 74
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3. SBA-15 mesoporous particles with adsorbed cresol red dye and functionalized with 3-aminopropyl groups : materials properties and dye release studiesErika Švara Fabjan, Romana Cerc Korošec, Klara Šifrer, Andrijana Sever Škapin, Ramon Martinez Manez, 2024, original scientific article Abstract: Research in the field of sensing has focused on tailoring the responsiveness of materials through the variation in materials properties achieved via functionalization of the mesoporous matrix. pH indicator dyes capable of protonation/deprotonation reactions are known to display different forms, resulting in changes in colour. This research focused on the preparation of mesoporous substrates SBA-15 with integrated pH indicator dye o-cresolsulphonephtalein (cresol red) grafted with (3-aminopropy) trimethoxysilane (gaining functionalized-SBA-15 material) in order to gain a colour change response following release of the dye. UV-Vis reflectance and absorbance spectra were used to evaluate forms of cresol red. The textural properties, including specific surface area, pore size distribution and pore volume were evaluated using nitrogen sorption, and XRD analysis was conducted to evaluate crystallinity of the material and pore ordering. The presence of 3-aminopropyl groups was determined by thermal decomposition using TGA–DSC/MS. The functionalized SBA-15 materials loaded with cresol red mostly retained ordering of the pores and showed a slight reduction in surface area. Functionalization changed the surface properties of the material. In the non-functionalized SBA-15, cresol red was present in both double (H2L) and single (HL−) protonated forms, whereas in the functionalized SBA-15 the deprotonated L2−form prevailed. Through desorption experiments cresol red was successfully desorbed from selected sample to different media. The change of colour caused by alterations in the form of the dye once released from the mesoporous silica material into the medium was confirmed. The form of cresol red released was determined by the pH of the medium.
Keywords: mezoporozni materiali, SBA-15, funkcionalizacija, uravnavanje odzivnosti, zaznavanje
Published in DiRROS: 13.02.2024; Views: 192; Downloads: 126
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4. 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, original scientific article Abstract: 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.
Keywords: bronze, patina, fluoropolymer coating, atmospheric corrosion
Published in DiRROS: 25.10.2023; Views: 383; Downloads: 212
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5. Colorimetric cutoff indication of relative humidity based on selectively functionalized mesoporous silicaErika Švara Fabjan, Peter Nadrah, Anja Ajdovec, Matija Tomšič, Goran Dražić, Matjaž Mazaj, Nataša Zabukovec Logar, Andrijana Sever Škapin, 2020, original scientific article Abstract: We present a novel % cutoff concept of colorimetric indication of relative humidity based on dye dissolution in condensed water in capillaries of selectively functionalized mesoporours host SiO2 material. Consistently high levels of indoor air humidity induces mold and algae growth which represent a potential risks for human health and have deteriorating effect on walls as well. Simple localized humidity detection of high humidity with naked eye especially at places with low air circulation, where growth of mold usually starts first, is therefore highly desirable. The reporting dye was integrated in the non-functionalized mesoporous silica matrix with different pore diameters and selective-functionalized mesoporous silica material. After exposure to the environment of different air humidities the dye dissolved in water causing color change of adsorbent. With the use of adsorbents with different mesopore diameters high ability to tune the value of relative humidity when complete capillary condensation occurred was achieved. Materials with pore diameters of 3.0%nm, 3.5%nm and 7.0%nm exhibit gradual color change when reaching relative humidity up to 55, 79 and 88 RH% respectively. After selective methylation of the material with 7.0%nm pore diameter, non-gradual cutoff color change was achieved. Sample exhibited color change at narrow range of relative humidity (cutoff color change). Due to selective functionalized outer surface the dye dissolution occur only in condensed water in pores and therefore provide colorimetric indication only in this range. Selectively modified silica material has a great potential for a straightforward detection of high humid environment.
Keywords: turn-on colorimetric probe, selective functionalization, mesoporous silica, relative humidity, capillary condensation
Published in DiRROS: 05.09.2023; Views: 326; Downloads: 240
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6. Corrosion protection of brown and green patinated bronzeTadeja Kosec, Živa Novak, Erika Švara Fabjan, Luka Škrlep, Andrijana Sever Škapin, Polonca Ropret, 2021, original scientific article Abstract: 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.
Keywords: bronze, patina, protection
Published in DiRROS: 17.07.2023; Views: 323; Downloads: 185
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7. Exploring the protection mechanism of a combined fluoropolymer coating on sulphide patinated bronzeTadeja Kosec, Živa Novak, Erika Švara Fabjan, Luka Škrlep, Matjaž Finšgar, 2022, original scientific article Abstract: 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.
Keywords: bronze, protection, brown patina, fluoropolymer coating
Published in DiRROS: 31.05.2023; Views: 366; Downloads: 207
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8. Properties of the fluoroacrylate and methacryloxypropyl-trimethoxysilane applied to a layer of Cu2O on bronze as either single or multi-component coatingsLuka Škrlep, Tadeja Kosec, Matjaž Finšgar, Andrijana Sever Škapin, Erika Švara Fabjan, 2023, original scientific article Abstract: Various coatings have been developed and explored to protect bronze surfaces against the uncontrolled formation of different corrosion products when exposed to outdoor environments.
In this research, the surfaces of artificially-formed oxidized bronze patinas (OB), consisting of Cu2O, were covered with either a single-component (fluoroacrylate, FA or methacryloxypropyl-trimethoxysilane, MS) or multi-component (a mixture of FA and MS, FA-MS) fluoropolymer coating and investigated. Variations in the concentration of each component in the coating were studied. Electrochemical tests were performed to determine the corrosion protection efficiency, followed by detailed surface analyses of the OBs, both uncoated and covered with single and multi-component coatings. A variety of investigative methods were used, including focused ion beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and time-of-flight secondary ion mass spectrometry (ToF-SIMS).
The coating made from a combination of FA and MS resulted in a very high protection efficiency. Despite the increased hydrophilicity of the single MS component, however, it was shown to efficiently protect the oxidized bronze surface. The FA-MS systems showed high hydrophobicity, but no improvement was measured in the efficiency of the corrosion protection when it was compared to the coating that contained 10% MS. According to XPS and ToF-SIMS imaging, the FA component of the FA-MS coating was not present only on the uppermost surface of the coating but throughout the whole coating, which could affect its corrosion protection efficiency.
Keywords: bronze, Cu2O layer on bronze, fluoropolymer coating, protection efficiency, surface spectroscopy
Published in DiRROS: 30.05.2023; Views: 364; Downloads: 191
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