Skip to main content
SpringerLink
Log in

Laser-induced breakdown spectroscopy study of silversmith pieces: the case of a Spanish canopy of the nineteenth century

  • Published:
Applied Physics A Aims and scope Submit manuscript

Abstract

Canopies of needlework velvet or silversmith pieces placed on twelve or more battens are widely employed in Spanish catholic ceremonies to cover the image of the virgin. In this paper, we focus our interest on those pieces made of silver. These silver crafts suffered a revolution in the nineteenth century with the development of an electrolyte system that can be applied over carved metal pieces, in order to obtain a silver layer by electrodeposition similar in appearance to the original sterling silver and cheaper. The aim of this research was the application of laser-induced breakdown spectroscopy (LIBS) to the study of a canopy of the nineteenth century in order to assess the techniques used for its manufacturing and the identification of replacement and restoration of original pieces. The LIBS depth profiles show the presence of a micron silver layer over an alloy of copper and zinc in most of the surfaces. Corrosion products, alloy missing, and the restoration with copper layers were detected. These results are consistent with those obtained by scanning electron microscopy with energy-dispersive of X-ray with the advantage that LIBS is a methodology that allows analysing metal pieces without sampling or preparation. In summary, LIBS is a technique that allows the study of silversmith pieces with electrochemical preparation according to the Ruolz technique, and it is also possible to detect subsequent restoration or corrosion zones.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. F. Colao, R. Fantoni, P. Ortiz, M.A. Vazquez, J.M. Martin, R. Ortiz, N. Idris, Quarry identification of historical building materials by means of laser induced breakdown spectroscopy, X-ray fluorescence and chemometric analysis. Spectrochim. Acta B 65(8), 688 (2010)

    Article  ADS  Google Scholar 

  2. P. Ortiz, M.A. Vazquez, R. Ortiz, J.M. Martin, T. Ctvrtnickova, M.P. Mateo, G. Nicolas, Investigation of environmental pollution effects on stone monuments in the case of Santa Maria la Blanca, Seville (Spain). Appl. Phys. A Mater. Sci. Process. 100(3), 965 (2010)

    Article  ADS  Google Scholar 

  3. T. Ctvrtnickova, L. Cabalin, J. Laserna, V. Kanicky, G. Nicolas, Laser ablation of powdered samples and analysis by means of laser-induced breakdown spectroscopy. Appl. Surf. Sci. 255(10), 5329 (2009)

    Article  ADS  Google Scholar 

  4. M.P. Mateo, T. Ctvrtnickova, G. Nicolas, Characterization of pigments used in painting by means of laser-induced plasma and attenuated total reflectance FTIR spectroscopy. Appl. Surf. Sci. 255(10), 5172 (2009)

    Article  ADS  Google Scholar 

  5. P. Ortiz, R. Ortiz, J.M. Martín, M.A. Vázquez, T. Ctvrtnickova, M.P. Mateo, G. Nicolás, A. Gómez, Characterization Of Crust And Deposits Found In Churches of Seville, in Proceedings of the 8th International Symposium on the Conservation of Monuments in the Mediterranean Basin, vol. II, pp. 116–130 (2010)

  6. C. Fotakis, D. Anglos, V. Zafiropulos, S. Georgiou, V. Tornari, Lasers in the Preservation of Cultural Heritage: Principles and Applications (Taylor & Francis, New York, 2007)

    Google Scholar 

  7. V. Lazic, R. Fantoni, F. Colao, A. Santagata, A. Morona, V. Spizzichino, Quantitative laser-induced breakdown spectroscopy analysis of ancient marbles and corrections on the variability of plasma parameters and of ablation rate “Q”. J. Anal. At. Spectrom. 19, 429 (2004)

    Article  Google Scholar 

  8. Y. Yoon, T. Kim, M. Yang, K. Lee, G. Lee, Quantitative analysis of pottery glaze by laser induced breakdown spectroscopy. Microchem. J. 68, 251 (2001)

    Article  Google Scholar 

  9. D. Anglos, Laser-induced breakdown spectroscopy in art and archaeology. Appl. Spectrosc. 55, 186A (2001)

    Article  ADS  Google Scholar 

  10. F.J. Fortes, J. Cuñat, L.M. Cabalin, J.J. Laserna, In situ analytical assessment and chemical imaging of historical buildings using a man-portable laser system. Appl. Spectrosc. 61, 558 (2007)

    Article  ADS  Google Scholar 

  11. M. Castillejo, M. Martín, D. Silva, T. Stratoudaki, D. Anglos, L. Burgio, R.J.H. Clark, Laser-induced breakdown spectroscopy and Raman microscopy for analysis of pigments in polychromes. J. Cult. Herit. 1, S297 (2000)

    Article  Google Scholar 

  12. F.J. Fortes Román, L.M. Cabalín Robles, J.J. Laserna Vázquez, Aplicaciones de las técnicas láser en análisis y conservación del patrimonio, in PH, ed. IAPH, vol. 74, pp 74–93 (2010)

  13. A. Nevin, G. Spoto, D. Anglos, Laser spectroscopies for elemental and molecular analysis in art and archaeology. Appl. Phys. A 106(2), 339–361 (2012)

    Article  ADS  Google Scholar 

  14. V. Spizzichino, R. Fantoni, Laser induced breakdown spectroscopy in archeometry: a review of its application and future perspectives. Spectrochim. Acta B 99, 201–209 (2014)

    Article  ADS  Google Scholar 

  15. K. Melessanaki, M. Mateo, S.C. Ferrence, P.P. Betancourt, D. Anglos, The application of LIBS for the análisis of archeological ceramic and metal artifacts. Appl. Surf. Sci. 197, 156 (2002)

    Article  ADS  Google Scholar 

  16. L.E. Garcia-Ayuso, J. Amador-Hernandez, J.M. Fernandez-Romero, M.D. Luque de Castro, Characterization of jewellery products by laser-induced breakdown spectroscopy. Anal. Chim. Acta 457(2), 247 (2002)

    Article  Google Scholar 

  17. A. Arafat, M. Na’es, V. Kantarelou, N. Haddad, A. Giakoumaki, V. Argyropoulos, D. Anglos, A.G. Karydas, Combined in situ micro-XRF, LIBS and SEM-EDS analysis of base metal and corrosion products for Islamic copper alloyed artefacts from Umm Qais museum, Jordan. J. Cult. Herit. 14(3), 261 (2013)

    Article  Google Scholar 

  18. M. Ouja, M. Castillejo, W. Maracineanu, M. Simileanu, R. Radvan, V. Zafiropulos, D. Ferro, LIBS analysis of metal artefacts from Sucevita Monastery, Romania. Lasers in the Conservation of Artworks, p. 133 (2008)

  19. Y. Lou, Q. Zhou, R. Li, Detection of Silver Jewelry with Orthogonal Double-pulse LIBS, Mechatronics and Intelligent Materials Iii, Pts 1–3 706–708, 752 (2013)

  20. J.J. Laserna, L.M. Cabalın, F.J. Fortes, LIBS as an advanced tool in the chronocultural study of archaeometallurgical objects. International conference on conservation strategies for saving indoor metallic collections with a special section on legal issues in the conservation of cultural heritage, Cairo, Egypt (February, 2007)

  21. S. Guirado, F.J. Fortes, V. Lazic b, J.J. Laserna, Chemical analysis of archeological materials in submarine environments using laser-induced breakdown spectroscopy. On-site trials in the Mediterranean Sea. Spectrochim. Acta B 74–75, 137–143 (2012)

    Article  Google Scholar 

  22. A. De Giacomo, M. Dell’Aglio, F. Colao, R. Fantoni, V. Lazic, Double-pulse LIBS in bulk water and sumerged bronze samples. Appl. Surf. Sci. 247(1–4), 157 (2005)

    Article  ADS  Google Scholar 

  23. M. Simileanu, R. Radvan, N. Puscas, Underwater LIBS investigations setup for metals identification. Univ. Politeh. Buchar. Sci. Bull. Ser. A Appl. Math. Phys. 72(4), 209 (2010)

    Google Scholar 

  24. J. Asmus, J. Elford, D. Magde, V. Parfenov, Underwater inverse LIBS (iLIBS) for marine archaeology, in Proceedings of SPIE 8790, Optics for Arts, Architecture, and Archaeology IV, vol. 8790 (2013)

  25. M.P. Mateo, T. Ctvrtnickova, E. Fernandez, J.A. Ramos, A. Yanez, G. Nicolas, Laser cleaning of varnishes and contaminants on brass. Appl. Surf. Sci. 255(10), 5579 (2009)

    Article  ADS  Google Scholar 

  26. V.V. Golovlev, M.J. Gresalfi, J.C. Miller, D. Anglos, K. Melesanaki, V. Zafiropulos, G. Romer, P. Messier, Laser characterization and cleaning of 19th century daguerreotypes II. JCH 4, 134s–139s (2003)

    Article  Google Scholar 

  27. P.V. Maravelaki, V. Zafiropulos, V. Kilikoglou, M. Kalaitzaki, C. Fotakis, Laser-induced breakdown spectroscopy as a diagnostic technique for the laser cleaning of marble. Spectrochim. Acta B 52, 41 (1996)

    Article  ADS  Google Scholar 

  28. M. Abdelhamid, S. Grassini, E. Angelini, G.M. Ingo, M.A. Harith, Depth profiling of coated metallic artifacts adopting laser-induced breakdown spectrometry. Spectrochim. Acta B 65, 695–701 (2010)

    Article  ADS  Google Scholar 

  29. K.A. Tereszchuk, J.M. Vadillo, J.J. Laserna, Depth profile analysis of layered samples using glow discharge assisted laser-induced breakdown spectrometry (GD-LIBS). Spectrochim. Acta B 64, 378–383 (2009)

    Article  ADS  Google Scholar 

  30. L.P. del Campo, F. Marmolejo, A. Gomez, A. Bocalandro, M. Bethencourt, Tradición e innovación en las artes industriales: el palio de plata de 1871 de F. Isaura, in PH, ed. IAPH, vol. 69, pp. 20–33 (2009

  31. D. Scott, D. Stevens, Electrotypes in science and art. Stud. Conserv. 58(3), 189–198 (2013)

    Article  Google Scholar 

  32. A. Lins, Gilding techniques of the renaissance and after, in Gilded metals: history, technology and conservation, ed. by T. Drayman-Weisser (Archetype Publications Ltd, London, 2000), pp. 241–265

    Google Scholar 

  33. S. La-Niece, in Silvering in Metal Plating and Patination, ed. S. La-Niece, P. Craddock (Butterworth-Heinemann Publishers, 1993), pp. 201–210

  34. E. Turner, in Silver Plating in the 18th Century in Metal Plating and Patination, ed. S. La-Niece, P. Craddock (Butterworth-Heinemann Publishers, 1993), pp. 211–222

  35. M. Bethencourt, A. Gómez, Aplicación de técnicas analíticas SEM/EDX y metalográficas para la datación y restauración de una pieza de orfebrería religiosa del Siglo XIX, in Libro de Proceedings del XI Congreso Nacional de Materiales, pp. 221–224 (2010)

  36. CNR-ICR, Materiali lapidei: Campionamento. Normal 3/80, 1–6 (1980)

Download references

Acknowledgments

This study has been partially supported by the agreements IAPH&UPO and the Excellence Project of Junta de Andalucia HUM-6775 (RIVUPH).

Author information

Authors and Affiliations

  1. Instituto Andaluz de Patrimonio Histórico (IAPH), Isla de la Cartuja, Camino de los Descubrimientos S/N, 41092, Seville, Spain

    M. A. Gómez-Morón

  2. Department of Physical, Chemical and Natural Systems, Universidad Pablo de Olavide, Carretera de Utrera Km 1, ES-41013, Sevilla, España

    P. Ortiz, R. Ortiz & J. M. Martín

  3. Laser Applications Laboratory, University of A Coruña, C/Mendizábal s/n, 15403, Ferrol, Spain

    M. P. Mateo & G. Nicolás

Authors
  1. M. A. Gómez-Morón
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. P. Ortiz
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. R. Ortiz
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. J. M. Martín
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. M. P. Mateo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. G. Nicolás
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to P. Ortiz.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gómez-Morón, M.A., Ortiz, P., Ortiz, R. et al. Laser-induced breakdown spectroscopy study of silversmith pieces: the case of a Spanish canopy of the nineteenth century. Appl. Phys. A 122, 548 (2016). https://doi.org/10.1007/s00339-016-0051-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00339-016-0051-6

Keywords

Search

Navigation