Research article

Micro-Raman spectroscopy for the characterization of artistic patinas produced on copper-based alloys†

  1. Valeria Bongiorno1,
  2. Serena Campodonico1,2,*,
  3. Roberta Caffara1,
  4. Paolo Piccardo1,2,
  5. Maria Maddalena Carnasciali1,2

Article first published online: 13 SEP 2012

DOI: 10.1002/jrs.4167

Issue

Journal of Raman Spectroscopy

Journal of Raman Spectroscopy

Special Issue: Raman spectroscopy in art and archaeology

Volume 43, Issue 11, pages 1617–1622, November 2012

Additional Information

How to Cite

Bongiorno, V., Campodonico, S., Caffara, R., Piccardo, P. and Carnasciali, M. M. (2012), Micro-Raman spectroscopy for the characterization of artistic patinas produced on copper-based alloys. J. Raman Spectrosc., 43: 1617–1622. doi: 10.1002/jrs.4167

Author Information

  1. 1

    Dipartimento di Chimica e Chimica Industriale (DCCI), Università degli Studi di Genova, Genoa, Italy

  2. 2

    INSTM Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, Florence, Italy

* Serena Campodonico, Dipartimento di Chimica e Chimica Industriale (DCCI), Università degli Studi di Genova, Via Dodecaneso 31, 16146 Genoa, Italy.
E-mail: serenacampodonico@gmail.com

  • †

    This article is part of the Journal of Raman Spectroscopy special issue entitled “Raman spectroscopy in art and archaeology” edited by Juan Manuel Madariaga and Danilo Bersani.

Publication History

  1. Issue published online: 21 NOV 2012
  2. Article first published online: 13 SEP 2012
  3. Manuscript Accepted: 18 JUL 2012
  4. Manuscript Revised: 19 JUN 2012
  5. Manuscript Received: 22 DEC 2011

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Keywords:

  • artistic patina;
  • statuary bronzes;
  • reactivity;
  • Micro-Raman spectroscopy;
  • SEM-EDXS

In order to contribute to the improvement of restoration and conservation sciences of metallic artefacts belonging to Cultural Heritage, a wide research has been started on the study of artificial (artistic) and natural (corrosion or alteration) patinas of copper-based alloys.

Micro-Raman spectroscopy (μRS) coupled with scanning electron microscopy (SEM) equipped with energy Dispersive X-Ray Spectroscopy (EDXS) were applied for the characterization of a number of patinas made on metallic substrate reproducing the typical copper-based alloys used for statuary. A non alloyed copper sheet has been also used to simulate the architectural cover typically used after a specific cold spray coating.

To reach these goals, a number of patinas were experimentally produced in our laboratory using the torch technique and reactive solutions based on water as a solvent containing, respectively, copper nitrate, iron nitrate and potassium sulfide (‘liver of sulfur’). The only exception is a sample reproducing the architectural cover of a recent building nearly completely covered with copper sheets coated with copper salts.

All the produced patinas were aged in a salt spray chamber and then studied with μRS, SEM and EDXS in order to understand their evolution between the two known terms and therefore the reactions involved in all patinas. μRS allowed us to detect as main constituents of the ‘artistic’ patinas, before and after ageing: copper oxides (Cuprite and Tenorite), copper nitrates (Rouaite and Gerhardtite), copper chlorides (Botallackite, Atacamite and Paratacamite), a copper sulfate (Posnjakite), iron oxides (Magnetite and Hematite) and an iron hydroxide (Limonite). Copyright © 2012 John Wiley & Sons, Ltd.

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