Comparative Laser Spectroscopy Diagnostics for Ancient Metallic Artefacts Exposed to Environmental Pollution
Abstract
:1. Introduction
2. Artworks and Diagnostic Methods
2.1. Historical Objects
2.1. Experimental Procedures
- JEOL JSM-6380LA. The EDS, preliminary and qualitative only measurements were performed at 20 kV.
- HITACHI S-3500N. The investigations included observations in SE and BSE modes and point analyses of the chemical composition by EDS. The EDS measurements were performed at 15 kV and 30 kV.
3. Experimental Results and Discussion
3.1. Corroded Copper Sheets
3.2. The Two Putti Figures
3.3. Archaeological Objects
3.3.1. Bracelet and Fibula from Jasna Góra Monastery, Częstochowa
3.3.2. Bows from Wilanów Palace Museum in Warsaw
4. Conclusions
Acknowledgments
References
- Chitty, W.J.; Dillmann, P.; L’Hostis, V.; Lombard, C. Long-term corrosion resistance of metallic reinforcements in concrete, a study of corrosion mechanisms based on archaeological artefacts. Corr. Sci 2005, 47, 1555–1581. [Google Scholar]
- Selwyn, L. Metals and Corrosion—A Handbook for the Conservation Professional; Canadian Conservation Institute: Ottawa, Canada, 2004. [Google Scholar]
- Korenberg, C.; Baldwin, A. Laser cleaning tests on archaeological copper alloys using an ND:YAG Laser. Laser Chemistry 2006, 2006. ID 75831.. [Google Scholar]
- Pini, R.; Siano, S.; Salimbeni, R.; Pasquinucci, M.; Miccio, M. Tests of laser cleaning on archeological metal artefacts. J. Cult. Herit 2000, 1, S129–S137. [Google Scholar]
- Drayman-Weisser, T. DIALOGUE/89—The Conservation of Bronze Sculptures in the Outdoor Environment: A Dialogue among Conservators, Curators, Environmental Scientists, and Corrosion Engineers; NACE: Houston, TX, USA, 1992.
- Gallese, F.; Laguzzi, G.; Luvidi, L.; Ferrari, V.; Takacs, S.; Venturi, G.; Cesa, P. Comparative investigation into the corrosion of different bronze alloys suitable for outdoor sculptures. Corr. Sci 2008, 50, 954–961. [Google Scholar]
- Ynsa, M.D.; Chamon, J.; Gutierrez, P.C.; Gomez-Morilla, I.; Enguita, O.; Pardo, A.I.; Arroyo, M.; Barrio, J.; Ferretti, M.; Climent-Font, A. Study of ancient Islamic gilded pieces combining PIXE-RBS on external microprobe with sem images. Appl. Phys. A-Mater 2008, 92, 235–241. [Google Scholar]
- Matteini, M.; Lalli, C.; Tosini, I.; Giusti, A.; Siano, S. Laser and chemical cleaning tests for the conservation of the Porta del Paradiso by Lorenzo Ghiberti. J. Cult. Herit 2003, 4, 147s–151s. [Google Scholar]
- EUREKA E!316 Project. Technologies for Conservation of Copper Alloy Monuments. Available online: http://www.eurekanetwork.org/project/-/id/316 (accessed on 25 January 2010).
- Abraham, M.H.; Grime, G.W.; Northover, J.P.; Smith, C.W. PIXE and RBS as a tool for the analysis of historic copper halfpennies. Nucl. Instrum. Meth. B 1999, 150, 651–655. [Google Scholar]
- Rodríguez-Acuña, F.; Genescá, J.; Uruchurtu, J. Electrochemical evaluation of patinas formed on nineteenth century bronze bells. J. App. Electrochem. 2009, (in press).. [Google Scholar]
- Luciano, G.; Leardi, R.; Letardi, P. Principal component analysis of colour measurements of patinas and coating systems for outdoor bronze monuments. J. Cult. Herit 2009, 10, 331–337. [Google Scholar]
- PL0259 Project MATLAS. website. Available online: http://www.matlas.eu (accessed on 25 January 2010).
- Clark, R.J.H. The scientific investigation of artwork and archaeological artefacts: Raman microscopy as a structural, analytical and forensic tool. Appl. Phys. A-Mater 2007, 89, 833–840. [Google Scholar]
- Bernard, M.C.; Joiret, S. Understanding corrosion of ancient metals for the conservation of cultural heritage. Electrochim. Acta 2009, 54, 5199–5205. [Google Scholar]
- Fantoni, R.; Caneve, L.; Colao, F.; Fornarini, L.; Lazic, V.; Spizzichino, V. Methodologies for laboratory Laser Induced Breakdown Spectroscopy semi-quantitative and quantitative analysis—A review. Spectrochim. Acta. B 2008, 63, 1097–1108. [Google Scholar]
- De Giacomo, A.; Dell’Aglio, M.; De Pascale, O.; Gaudiuso, R.; Santagata, A.; Teghil, R. Laser Induced Breakdown Spectroscopy methodology for the analysis of copper-based-alloys used in ancient artworks. Spectrochim. Acta. B 2008, 63, 585–590. [Google Scholar]
- Miziolek, A.W.; Palleschi, V.; Schechter, I. Laser Induced Breakdown Spectroscopy; Cambridge University Press: New York, NY, USA, 2006; pp. 136–152. [Google Scholar]
- Lv, J.; Lai, F.C.; Lin, L.M.; Lin, Y.Z.; Huang, Z.G.; Chen, R. Thermal stability of Ag films in air prepared by thermal evaporation. Appl. Surf. Sci 2007, 253, 7036–7040. [Google Scholar]
- Graedel, T.E.; Nassau, K.; Franey, J.P. Copper patinas formed in the atmosphere—I. Introduction. Corr. Sci 1987, 27, 639–657. [Google Scholar]
- FitzGerald, K.P.; Nairn, J.; Skennerton, G.; Atrens, A. Atmospheric corrosion of copper and the colour, structure and composition of natural patinas on copper. Corr. Sci 2006, 48, 2480–2509. [Google Scholar]
- Garbacz, H.; Fortuna, E.; Marczak, J.; Strzelec, M.; Rycyk, A; Koss, A.; Zatorska, A.; Kurzydłowski, K.J. Laser cleaning of copper sheets. App. Phys. A-Mater. 2010, (in press).. [Google Scholar]
- Frost, R.L.; Martens, W.N.; Rintoul, L.; Mahmutagic, E.; Kloprogge, J.T. Raman spectroscopic study of azurite and malachite at 298 and 77 K. J. Raman Spectrosc 2002, 33, 252–259. [Google Scholar]
- Hayez, V.; Guillaume, J.; Hubin, A.; Terryn, H. Micro-Raman spectroscopy for the study of corrosion products on copper alloys: setting up of a reference database and studying works of art. J. Raman Spectrosc 2004, 35, 732–738. [Google Scholar]
- Fabrizi, M.; Ganiaris, H.; Tarling, S.; Scott, D.A. The Occurrence of Sampleite, a Complex Copper Phosphate, as a Corrosion Product on Copper Alloy Objects from Memphis, Egypt. Stud. Conserv 1989, 34, 45–51. [Google Scholar]
- Garbacz, H.; Koss, A.; Marczak, J.; Mróz, J.; Onyszczuk, T.; Rycyk, A.; Sarzyński, A.; Skrzeczanowski, W.; Strzelec, M.; Zatorska, A. Optimized laser cleaning of metal artworks—evaluation of determinants. Proceedings of the 6th International Conference on Laser Assisted Net Shape Engineering, Erlangen, Germany, September 2010. (accepted)..
wt.% | C | O | Al | Si | P | S | Cl | Ca | Fe | Cu |
---|---|---|---|---|---|---|---|---|---|---|
lowest | 0 | 25.75 | 0.35 | 0.52 | 0.62 | 6.37 | 0.60 | 0 | 0 | 49.68 |
highest | 3.40 | 37.34 | 0.48 | 1.00 | 0.85 | 7.27 | 1.06 | 0.20 | 1.02 | 61.25 |
Point | Cu | O | S | C | Cl | Fe | Ca | Zn |
---|---|---|---|---|---|---|---|---|
2 | 40–55 | 25–35 | 10 | 1–5 | ||||
3 | 35–45 | 25–40 | several | * | 1–3 | 1–4 | 1–1.5 | 6–11 |
Object | Composition (wt%) |
---|---|
| Bracelet made from leaded tin bronze: Cu 82.0; Sn 16.0; Pb 1.5; Fe 0.5 |
| Fibula made from leaded tin bronze: Cu 77.4; Sn 21.5; Pb 1.1 |
| Bow made from leaded tin bronze: Cu 85.0; Sn 11.5; Pb 3.0; Fe 0.5 |
| Bow made from red bronze containing copper, tin, zinc and lead: Cu 67.0; Sn 17.5; Zn 12.5; Pb 3.0 |
© 2010 by the authors; licensee MDPI, Basel, Switzerland. This article is an Open Access article distributed under the terms and conditions of the Creative Commons Attribution license ( http://creativecommons.org/licenses/by/3.0/).
Share and Cite
Ciupiński, Ł.; Fortuna-Zaleśna, E.; Garbacz, H.; Koss, A.; Kurzydłowski, K.J.; Marczak, J.; Mróz, J.; Onyszczuk, T.; Rycyk, A.; Sarzyński, A.; et al. Comparative Laser Spectroscopy Diagnostics for Ancient Metallic Artefacts Exposed to Environmental Pollution. Sensors 2010, 10, 4926-4949. https://doi.org/10.3390/s100504926
Ciupiński Ł, Fortuna-Zaleśna E, Garbacz H, Koss A, Kurzydłowski KJ, Marczak J, Mróz J, Onyszczuk T, Rycyk A, Sarzyński A, et al. Comparative Laser Spectroscopy Diagnostics for Ancient Metallic Artefacts Exposed to Environmental Pollution. Sensors. 2010; 10(5):4926-4949. https://doi.org/10.3390/s100504926
Chicago/Turabian StyleCiupiński, Łukasz, Elżbieta Fortuna-Zaleśna, Halina Garbacz, Andrzej Koss, Krzysztof J. Kurzydłowski, Jan Marczak, Janusz Mróz, Tomasz Onyszczuk, Antoni Rycyk, Antoni Sarzyński, and et al. 2010. "Comparative Laser Spectroscopy Diagnostics for Ancient Metallic Artefacts Exposed to Environmental Pollution" Sensors 10, no. 5: 4926-4949. https://doi.org/10.3390/s100504926