Development and application of an electrochemical probe for localized corrosion measurements on cultural heritage artifacts
Source abstract
Abstract
Abstract Non-invasive characterization of electrochemical properties is crucial for the preservation of cultural artifacts as it allows detailed analysis while avoiding mechanical damage. This study presents a portable electrochemical probe developed for localized corrosion measurements on metal surfaces, ensuring non-invasive interaction through a suspended drop of electrolyte solution. The probe was validated on reference samples and applied to bronze statues from San Casciano dei Bagni, Italy. The results show agreement with data from conventional three-electrode cells and confirm the effectiveness of the probe in detecting active corrosion sites. Furthermore, the application of the probe before and after a conservation treatment showed differences in the response of the different corrosion products. This work underlines the potential of the probe for in situ electrochemical assessments and provides conservators with a practical tool to evaluate and guide conservation measures.
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Research context
OpenAlex topics: Corrosion Behavior and Inhibition · Concrete Corrosion and Durability · Hydrogen embrittlement and corrosion behaviors in metals
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (34)
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1. Ikić, D. & Otmačić Ćurković, H. Protection of patinated bronze with long-chain phosphonic acid/organic coating combined system. Materials 16, 1660 (2023).10.3390/ma16041660 ↗
2. Artesani, A., Di Turo, F., Zucchelli, M. & Traviglia, A. Recent advances in protective coatings for cultural heritage–an overview. Coatings 16, 217 (2020).10.3390/coatings10030217 ↗
3. Towarek, A., Mistewicz, A., Pilecka-Pietrusińska, E., Zdunek, J. & Mizera, J. Corrosion degradation of archaeological lead: a review and case study. J. Archaeol. Sci. Rep. 45, 103611 (2022).
4. Mikić, D., Otmačić Ćurković, H., Kosec, T. & Peko, N. An electrochemical and spectroscopic study of surfaces on bronze sculptures exposed to urban environment. Materials 14, 2063 (2021).10.3390/ma14082063 ↗
5. Robbiola, L. et al. New insight into the nature and properties of pale green surfaces of outdoor bronze monuments. Appl. Phys. A Mater. Sci. Process 92, 161–169 (2008).10.1007/s00339-008-4468-4 ↗
6. Apchain, E. et al. Efficiency and durability of protective treatments on cultural heritage copper corrosion layers. Corros. Sci. 183, 109319 (2021).10.1016/j.corsci.2021.109319 ↗
7. Chiavari, C. et al. Influence of natural patinas of outdoor quaternary bronzes on conservation treatments. In METAL 2013: Proc. Interim Meeting of the ICOM-CC Metal Working Group 159–168 (ICOM-CC Metal Working Group, 2013).
8. Masi, G. et al. Characterization of typical patinas simulating bronze corrosion in outdoor conditions. Mater. Chem. Phys. 200, 308–321 (2017).10.1016/j.matchemphys.2017.07.091 ↗
9. Bernard, M. C. & Joiret, S. Understanding corrosion of ancient metals for the conservation of cultural heritage. Electrochim. Acta 54, 5199–5205 (2009).10.1016/j.electacta.2009.01.036 ↗
10. Di Turo, F. Limits and perspectives of archaeometric analysis of archaeological metals: a focus on the electrochemistry for studying ancient bronze coins. J. Cultural Herit. 43, 271–281 (2020).10.1016/j.culher.2019.10.006 ↗
11. Doménech-Carbó, A. et al. Monitoring stabilizing procedures of archaeological iron using electrochemical impedance spectroscopy. J. Solid State Electrochem. 18, 399–409 (2014).10.1007/s10008-013-2232-y ↗
12. Ramírez Barat, B. & Cano, E. In situ electrochemical impedance spectroscopy measurements and their interpretation for the diagnostic of metallic cultural heritage: a review. ChemElectroChem 5, 2698–2716 (2018).10.1002/celc.201800844 ↗
13. Angelini, E., Grassini, S., Parvis, M. & Zucchi, F. An in situ investigation of the corrosion behaviour of a weathering steel work of art. Surf. Interface Anal. 44, 942–946 (2012).10.1002/sia.3842 ↗
14. Cano, E., Crespo, A., Lafuente, D. & Ramirez Barat, B. A novel gel polymer electrolyte cell for in-situ application of corrosion electrochemical techniques. Electrochem. Commun. 41, 16–19 (2014).10.1016/j.elecom.2014.01.016 ↗
15. Ramírez Barat, B., Cano, E. & Letardi, P. Advances in the design of a gel-cell electrochemical sensor for corrosion measurements on metallic cultural heritage. Sens. Actuators B 261, 572–580 (2018).10.1016/j.snb.2018.01.180 ↗
16. Jia, M., Hu, P. & Hu, G. An easy-to-assemble probe for in situ corrosion testing of archaeological metal. Electrochem. Commun. 147, 107427 (2023).10.1016/j.elecom.2023.107427 ↗
17. Šoič, I., Šoljič, I., Eškinja, M., Mujezinovič, A. & Martinez, S. The novel paste electrolyte measuring cell for EIS testing of the commonly used surface protection on bronze. Prog. Org. Coatings 177, 107442 (2023).10.1016/j.porgcoat.2023.107442 ↗
18. Panindre, A. M., Chang, K. H., Weirich, T. & Frankel, G. Syringe cell for electrochemical testing. Corrosion 74, 847–850 (2018).10.5006/2847 ↗
19. Mariotti, E. & Tabolli, J. The Rediscovered Sanctuary. New Excavations and Research at Bagno Grande in San Casciano dei Bagni (in Italian) (Sillabe, 2021).
20. Tabolli, J. The Etruscan and Roman thermo-mineral sanctuary of Bagno Grande at San Casciano dei Bagni (Siena): aims and perspectives ‘behind-the-scenes’ of the ongoing multidisciplinary research project. Folder 556, 1–23 (2023).
21. Osanna, M. & Tabolli, J. Encountering the Thermo-Mineral Spring of Bagno Grande in the Design of the Exhibition at the Archaeological National Museum of Naples (La Rivista di Engramma, 2024).
22. Spotorno, R. et al. Corrosion behavior of two Cu-based shape memory alloys in NaCl solution: an electrochemical study. Mater. Corros. 75, 1155–1172 (2024).10.1002/maco.202314227 ↗
23. Stern, M. & Geary, A. L. Electrochemical polarization: I. A theoretical analysis of the shape of polarization curves. J. Electrochem. Soc. 104, 56–63 (1957).10.1149/1.2428496 ↗
24. Alves, R. F. et al. Effect of small vanadium addition on the microstructure, transformation temperatures, and corrosion behavior of a Cu72Al17Mn11 shape memory alloy. J. Mater. Res. Technol. 24, 6009–6021 (2023).10.1016/j.jmrt.2023.04.213 ↗
25. Brug, G. J., van den Eeden, A. L. G., Sluyters-Rehbach, M. & Sluyters, J. H. The analysis of electrode impedances complicated by the presence of a constant phase element. J. Electroanal. Chem. Interfacial Electrochem. 176, 275–295 (1984).10.1016/S0022-0728(84)80324-1 ↗
26. Chiavari, C., Colledan, A., Frignani, A. & Brunoro, G. Corrosion evaluation of traditional and new bronzes for artistic castings. Mater. Chem. Phys. 95, 252–259 (2006).10.1016/j.matchemphys.2005.06.034 ↗
27. Canepa, P., Ghiara, G., Spotorno, R., Canepa, M. & Cavalleri, O. Structural vs. electrochemical investigation of niobium oxide layers anodically grown in a Ca and P containing electrolyte. J. Alloys Compd. 851, 156937 (2021).10.1016/j.jallcom.2020.156937 ↗
28. Khademi, M. & Barz, D. P. J. Structure of the electrical double layer revisited: electrode capacitance in aqueous solutions. Langmuir 36, 4250 (2020).10.1021/acs.langmuir.0c00024 ↗
29. Feliu, S. Jr. Electrochemical impedance spectroscopy for the measurement of the corrosion rate of magnesium alloys: brief review and challenges. Metals 10, 775 (2020).10.3390/met10060775 ↗
30. Bakhtiari-Zamani, H., Saebnoori, E., Bakhsheshi-Rad, H. R. & Berto, F. Corrosion and wear behavior of TiO2/TiN duplex coatings on titanium by plasma electrolytic oxidation and gas nitriding. Materials 15, 8300 (2022).10.3390/ma15238300 ↗
31. Liang, Z., Jiang, K. & Zhang, T. Corrosion behaviour of lead bronze from the Western Zhou Dynasty in an archaeological-soil medium. Corros. Sci. 191, 109721 (2021).10.1016/j.corsci.2021.109721 ↗
32. Souissi, N., Sidot, E., Bousselmi, L., Triki, E. & Robbiola, L. Corrosion behaviour of Cu–10Sn bronze in aerated NaCl aqueous media – electrochemical investigation. Corros. Sci. 49, 3333–3347 (2007).10.1016/j.corsci.2007.01.013 ↗
33. Fan, Z. et al. Comparison and study of the corrosion differences of bronze alloys in oxygen-free and oxygen-containing conditions. Corros. Sci. 241, 112553 (2024).10.1016/j.corsci.2024.112553 ↗
34. Cao, H., Liang, Z., Wang, Y. & Jin, H. Study of initial corrosion and protection behavior of bronze from the Western Zhou Dynasty assisted by BTA. Corros. Sci. 239, 112419 (2024).10.1016/j.corsci.2024.112419 ↗