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Efficiency of applying ammonium oxalate for protection of monumental limestone by poultice, immersion and brushing methods

Abstract

Samples of cretaceous limestone have been treated with three application methods (poultice, immersion and brushing) using different concentrations of ammonium oxalate solution (AmOx) and varying treatment time in order to test the efficiency of surface and in-depth formation of a protective layer of calcium oxalate (CaOx). Synchrotron-based microanalytical techniques (SR-μXRD with 12.5 μm×7.5 μm (H×V) probe size, SR-μFTIR with 10 μm×10 μm and 8 μm×20 μm probe sizes) and laboratory μFTIR, XRD and SEM have been employed for analysis of the treated samples. Synchrotron-based techniques showed variations in the CaOx distribution along the surface on a micrometer scale. All treatments resulted in the development of a CaOx layer with a maximum thickness of approximately 40 μm. Application by the brushing method with 10 1-min applications with 5-min breaks during one hour showed a development of the calcium oxalate layer equivalent to the poultice treatment taking 10 h. This treatment could be preferred for large marble or limestone surfaces where poultice usage is economically not feasible.

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References

  1. 1.

    E. Hansen, E. Doehne, J. Fidler, J. Larson, B. Martin, M. Matteini, C. Rodríguez-Navarro, E.S. Pardo, C. Price, A. De Tagle, J.M. Teutonico, N. Weiss, Rev. Conserv. 4, 13 (2003)

    Google Scholar 

  2. 2.

    V. Fassina, Proceedings, Le Pellicole Ad Ossalati Origine e Significato nella Conservazione delle Opere D’Arte (Centro ‘Gino Bozza’, Milano, 1989), p. 381

    Google Scholar 

  3. 3.

    M. Realini, L. Toniolo, International Symposium II: The Oxalate Films in the Conservation of Works of Art (Editeam, Castello D’Argile, 1996), p. 539

    Google Scholar 

  4. 4.

    K. Kouzeli, N. Beloyannis, C. Tolias, Y. Dogani, in Le Pellicole Ad Ossalati Origine e Significato nella Conservazione delle Opere D’Arte, ed. by V. Fassina (Centro ‘Gino Bozza’, Milano, 1989), pp. 327–336

    Google Scholar 

  5. 5.

    D. Camuffo, Sci. Total Environ. 128, 205 (1993)

    Article  Google Scholar 

  6. 6.

    M. Matteini, Conserv. Sci. Cult. Herit. 8, 13 (2008)

    Google Scholar 

  7. 7.

    D. Pinna, B. Salvadori, S. Porcinai, Constr. Build. Mater. 25, 2723 (2011)

    Article  Google Scholar 

  8. 8.

    M. Matteini, A. Moles, in Le Pitture Murali: Techniche, Problemi, Conservazione, ed. by A. Moles (Centro Di, Florence, 1990), pp. 297–302

    Google Scholar 

  9. 9.

    M. Matteini, A. Moles, S. Giovannoni, in Proceedings of the 3rd International Symposium: The Conservation of Monuments in the Mediterranean Basin: Stone and Monuments: Methodologies for the Analyses of Weathering and Conservation, ed. by V. Fassina, H. Ott, F. Zezza (Soprintendenza ai Beni Artistici e Storici di Venizia, Venice, 1994), pp. 155–162

    Google Scholar 

  10. 10.

    M. Matteini, A. Moles, G. Lanterna, M.R. Nepoti, in International Symposium II: The Oxalate Films in the Conservation of Works of Art, ed. by M. Realini, L. Toniolo (Editeam, Castellio D’Argile, 1996), pp. 425–440

    Google Scholar 

  11. 11.

    M. Ambrosi, P. Baglioni, P.R. David, L. Dei, R. Giorgi, C. Lalli, A. Mairani, M. Matteini, M. Rizzi, G. Schonhaut, G. Lanterna, in Proceedings, Science and Technology for the Safeguard of Cultural Heritage in the Mediterranean Basin, ed. by A. Guarino (Elsevier, Paris, 2000), pp. 855–858

    Google Scholar 

  12. 12.

    A. Mairani, M. Matteini, M. Rizzi, OPD, Restauro 12, 146 (2000)

    Google Scholar 

  13. 13.

    B. Doherty, M. Pamplona, M. Matteini, A. Sgamellotti, B. Brunetti, J. Cult. Herit. 8(2), 186 (2007)

    Article  Google Scholar 

  14. 14.

    http://whc.unesco.org/en/list/97

  15. 15.

    X’Pert HighScore Plus (PANalytical B.V., Almelo, 2004)

  16. 16.

    ICDD—International Centre for Diffraction Data, in Powder Diffraction File PDF-2 (ICDD, Newtown Square, PA, 2004)

  17. 17.

    http://www.cytospec.com; CytoSpec ver. 1.2, CytoSpec, Inc., USA (2005)

  18. 18.

    W. De Nolf, K. Janssens, Surf. Interface Anal. 42(5), 411 (2010) Spec. Issue: Surf. Sci. Appl. Forens. Anal.

    Article  Google Scholar 

  19. 19.

    A.M. Cody, R.D. Cody, J. Cryst. Growth 151, 369 (1995)

    ADS  Article  Google Scholar 

  20. 20.

    C. Ricci, C. Miliani, B.G. Brunetti, A. Sgamellotti, Talanta 69, 1221 (2006)

    Article  Google Scholar 

  21. 21.

    B. Doherty, M. Pamplona, R. Selvaggi, C. Milliani, M. Matteini, A. Sgamellotti, B. Brunetti, Appl. Surf. Sci. 253(10), 4477 (2007)

    ADS  Article  Google Scholar 

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Acknowledgements

We would like to thank Dr. Paul Dumas from the SMIS beamline at the ‘SOLEIL’ synchrotron in Saint-Aubin (France) for his help in the statistical analysis of the IR maps. Also, we would like to thank Dr. Cristian Mocuta from the DIFFABS beamline at the ‘SOLEIL’ synchrotron for his great help during the XRD depth measurements. We also appreciate the help of Dr. Philippe Lerch from the IR beamline at the ‘Swiss Light Source synchrotron, Paul Scherrer Institute’ in Villigen (Switzerland) during the surface IR measurements.

This research was supported by the Interuniversity Attraction Poles Programme—Belgian Science Policy (IUAP VI/16). The text also presents results of GOA ‘XANES meets ELNES’ (Research Fund, University of Antwerp, Belgium) and from FWO (Brussels, Belgium) project nos. G.0704.08 and G.01769.09.

The research leading to these results has received financial support by the Access to Research Infrastructures activity in the 7th Framework Programme of the EU (CHARISMA Grant Agreement No. 228330).

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Correspondence to D. Mudronja.

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Mudronja, D., Vanmeert, F., Hellemans, K. et al. Efficiency of applying ammonium oxalate for protection of monumental limestone by poultice, immersion and brushing methods. Appl. Phys. A 111, 109–119 (2013). https://doi.org/10.1007/s00339-012-7365-9

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Keywords

  • Oxalate
  • Calcium Oxalate
  • Ammonium Oxalate
  • Stone Surface
  • AmOx