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Non-destructive characterization of oriental porcelain glazes and blue underglaze pigments using μ-EDXRF, μ-Raman and VP-SEM

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Abstract

The study of ancient materials with recognized cultural and economic value is a challenge to scientists and conservators, since it is usually necessary an approach through non-destructive techniques. Difficulties in establishing a correct analytical strategy are often significantly increased by the lack of knowledge on manufacture technologies and raw materials employed combined with the diversity of decay processes that may have acted during the lifetime of the cultural artefacts. A non-destructive characterization was performed on the glaze and underglaze pigments from a group of Chinese porcelain shards dated from the late Ming Dynasty (1368–1644) excavated at the Monastery of Santa Clara-a-Velha in Coimbra (Portugal). Chemical analysis was performed using micro-energy dispersive X-ray fluorescence spectrometry (μ-EDXRF). Mineralogical characterization was achieved by Raman microscopy (μ-Raman) and observation of small-surface crystallization dark spots with a metallic lustre in areas with high pigment concentration was done by variable pressure scanning electron microscopy (VP-SEM). Cobalt aluminate was identified as the blue underglaze pigment and a comparison of blue and dark blue pigments was performed by the ratio of Co, Mn, and Fe oxides, indicating a compositional difference between the two blue tonalities. Manganese oxide compounds were also identified as colouring agents in dark blue areas and surface migration of manganese compounds was verified.

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References

  1. J.M.R.S. Alves, J.R. Calvão, J.S. Ramos, A.J. Massano, N. Thomas, R. Trewinnart, W. Zhang, Porcelain route: Ming and Qind Dynasties (Fundação Oriente, Lisboa, 1998), p. 331

    Google Scholar 

  2. D. de Waal, J. Raman. Spectrosc. 35, 646 (2004)

    Article  ADS  Google Scholar 

  3. R. Wen, C.S. Wang, Z.W. Mao, Y.Y. Huang, A.M. Pollard, Archaeometry 49, 101 (2007)

    Article  Google Scholar 

  4. M.O. Figueiredo, T.P. Silva, J.P. Veiga, J. Electron Spectrosc. Rel. Phenom. 185, 97 (2012)

    Article  Google Scholar 

  5. M.I. Dias, M.I. Prudêncio, M.A. Pinto De Matos, A.L. Rodrigues, J. Archaeol. Sci. 40, 3046 (2013)

    Article  Google Scholar 

  6. M.O. Figueiredo, J.P. Veiga, T.P. Silva, J.P. Mirão, S. Pascarelli, Nucl. Instr. Meth. B 238, 134 (2005)

    Article  ADS  Google Scholar 

  7. J.P. Veiga, M.O. Figueiredo, X-Ray. Spectrom. 37, 458 (2008)

    Article  Google Scholar 

  8. J.P. Veiga, M.O. Figueiredo, Appl. Phys. A 92, 229 (2008)

    Article  ADS  Google Scholar 

  9. M.O. Figueiredo, P. Veiga, T.P. Silva, Appl. Phys. A 92, 151 (2008)

    Article  ADS  Google Scholar 

  10. K. Janssens, G. Vittiglio, I. Deraedt, A. Aerts, B. Vekemans, L. Vincze, F. Wei, I. Deryck, O. Schalm, F. Adams, A. Rindby, A. Knöchel, A. Simionovici, A. Snigirev, X-Ray. Spectrom. 29, 73 (2000)

    Article  Google Scholar 

  11. A. Lima, T. Medici, A.P. Matos, M. Verità, J. Archaeol. Sci. 39, 1238 (2012)

    Article  Google Scholar 

  12. L.I. Gambini, A. Côrte-Real, Mosteiro de Santa Clara-a-velha: História. (2012) http://santaclaraavelha.drcc.pt/site/index.php, Accessed 20 June 2013

  13. A. Guilherme, J. Coroado, M.L. Carvalho, Anal. Bioanal. Chem. 395, 2029 (2009)

    Article  Google Scholar 

  14. C.P. Santos, Oriental. Art. 49, 3 (2003)

    ADS  Google Scholar 

  15. A. Côrte-Real, P. César Santos, T. Mourão, F. Pato de Macedo, Património-Estudos 2, 23 (2002)

  16. B. Báez Garzón, J. Larrazabal Galarza, P. Dórdio, Mosteiro de Santa Clara-aVelha, Coimbra. Relatório do estudo do subgrupo da cerâmica vermelha de pasta fina decorada a engobe branco, (Internal Report, Coimbra, 2005)

  17. B. Vekemens, K. Janssens, L. Vincze, F. Adams, P. Van Espen, X-Ray. Spectrom. 23, 278 (1994)

    Article  Google Scholar 

  18. R.H. Brill, Chemical analyses of early glasses. The Corning Museum of Glass, vol 2. Corning, New York (1999) pp. 544

  19. Chemical Analysis Committee of the S.G.T., Glass Technol. 14, 5 (1973)

  20. C. Yaocheng, Oriental. Art. 60, 1 (1994)

    Google Scholar 

  21. K.N. Yu, J.M. Miao, Appl. Radiat. Lsot. 48, 959 (1997)

    Article  Google Scholar 

  22. K.N. Yu, J.M. Miao, X-Ray. Spectrom. 28, 19 (1999)

    Article  Google Scholar 

  23. H.S. Cheng, B. Zhang, D. Zhu, F.J. Yang, X.M. Sun, M.S. Guo, Nucl. Instr. Meth. Phys. Res., Sect. B 240, 527 (2005)

    Google Scholar 

  24. N. Wood, Chinese Glazes: their origins, chemistry, and recreation (University of Pennsylvania Press, Philadelphia, 2011), pp. 217–269

    Google Scholar 

  25. P. Colomban, Appl. Phys. A 79, 167 (2004)

    Article  ADS  Google Scholar 

  26. B. Gratuze, I. Soulier, J.N. Barrandon, D. Foy, Revue dÁrcheométrie 16, 97 (1992)

    Google Scholar 

  27. P.L. Leung, H. Luo, X-Ray Spectrom. 29, 34 (2000)

    Article  Google Scholar 

  28. J. Wu, P.L. Leung, J.Z. Li, M.J. Stokes, M.T.W. Li, X-Ray. Spectrom. 29, 239 (2000)

    Article  Google Scholar 

  29. A. Manceau, A.I. Gorshkov, V.A. Drits, Am. Mineral. 77, 1133 (1992)

    Google Scholar 

  30. D. Feng, B.R. Su, Sci. China. Ser. E. Techn. Sc. 51, 249 (2008)

    Google Scholar 

  31. D. de Waal, J. Raman. Spectrosc. 38, 956 (2007)

    Article  ADS  Google Scholar 

  32. L.D. Kock, D. de Waal, J. Raman. Spectrosc. 38, 1480 (2007)

    Article  ADS  Google Scholar 

  33. M. Llusar, A. Forés, J.A. Badenes, J. Calbo, M.A. Tena, G. Monrós, J. Eur. Ceram. Soc. 21, 1121 (2001)

    Article  Google Scholar 

  34. K.N. Yu, J.M. Miao, Archeometry 40, 1475 (1998)

    Article  Google Scholar 

  35. G. Padeletti, P. Fermo, Appl. Phys. A 79, 241 (2004)

    Article  ADS  Google Scholar 

  36. G. Padeletti, G.M. Ingo, A. Bouquillon, S. Pages-Camagna, M. Aucuturier, S. Roehrs, P. Fermo, Appl. Phys. A 83, 475 (2006)

    Article  ADS  Google Scholar 

  37. S. Berthier, G. Padeletti, P. Fermo, A. Bouquillon, M. Aucuturier, E. Charron, V. Reillon, Appl. Phys. A 83, 573 (2006)

    Article  ADS  Google Scholar 

  38. E. Karasu, S. Turan, J. Eur. Ceram. Soc. 22, 1447 (2002)

    Article  Google Scholar 

  39. C. González, J.I. Gutiérrez, J.R. González-Velasco, A. Cid, A. Arranz, J.F. Arranz, J. Thermal. Anal. 47, 93 (1996)

    Article  Google Scholar 

  40. M.C. Caggiania, P. Colomban, J. Raman. Spectrosc. 42, 790 (2011)

    Article  ADS  Google Scholar 

  41. E. Widjaja, G.H. Lim, Q. Lim, A.B. Mashadi, M. Garland, J. Raman. Spectrosc. 42, 377 (2011)

    Article  ADS  Google Scholar 

  42. C.M. Julien, M. Massot, C. Poinsignon, Spectrochimica. Acta. Part A 60, 689 (2004)

    Article  ADS  Google Scholar 

  43. N. Mironova-Ulmane, A. Kuzmin, M. Grube, J. Alloy, J. Alloy. Comp. 480, 97 (2009)

    Article  Google Scholar 

Download references

Acknowledgments

The authors wish to acknowledge Dr. Artur Côrte-Real, coordinator of the project of recuperation and valorisation of the Santa Clara-a-Velha Monastery and surrounding grounds, IPPAR; Dra. Ligia Gambini present coordinator of Mosteiro Santa Clara-a-Velha project; Dr. Maria Antónia Pinto de Matos from The National Museum of Ancient Art (MNAA-Museu Nacional de Arte Antiga). J.P. Veiga acknowledges the Portuguese Fundação para a Ciência e Tecnologia (FCT) financial support through PEst-C/CTM/LA0025/2013–14 (Strategic Project-LA 25-2013–2014).

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Authors and Affiliations

  1. REQUIMTE-CQFB, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal

    M. L. Coutinho

  2. Departamento de Conservação e Restauro, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal

    M. L. Coutinho

  3. Research Unit VICARTE, Vidro e Cerâmica para as Artes, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal

    V. S. F. Muralha

  4. Laboratório HÉRCULES, Universidade de Évora, Largo Marquês de Marialva, 8, 7000-554, Évora, Portugal

    J. Mirão

  5. CENIMAT/I3N, Departamento de Ciência dos Materiais, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal

    J. P. Veiga

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  1. M. L. Coutinho
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  2. V. S. F. Muralha
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  4. J. P. Veiga
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Correspondence to J. P. Veiga.

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Coutinho, M.L., Muralha, V.S.F., Mirão, J. et al. Non-destructive characterization of oriental porcelain glazes and blue underglaze pigments using μ-EDXRF, μ-Raman and VP-SEM. Appl. Phys. A 114, 695–703 (2014). https://doi.org/10.1007/s00339-013-8147-8

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  • DOI: https://doi.org/10.1007/s00339-013-8147-8

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