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Characterisation of metal carboxylates by Raman and infrared spectroscopy in works of art

Otero, Vanessa ; Sanches, Diogo ; Montagner, Cristina ; Vilarigues, Márcia ; Carlyle, Leslie ; Lopes, João A. ; Melo, Maria J.

Journal of Raman spectroscopy, 2014-11, Vol.45 (11-12), p.1197-1206 [Periódico revisado por pares]

Bognor Regis: Blackwell Publishing Ltd

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  • Título:
    Characterisation of metal carboxylates by Raman and infrared spectroscopy in works of art
  • Autor: Otero, Vanessa ; Sanches, Diogo ; Montagner, Cristina ; Vilarigues, Márcia ; Carlyle, Leslie ; Lopes, João A. ; Melo, Maria J.
  • Assuntos: Carboxylates ; Cations ; conservation ; Copper ; Infrared radiation ; metal carboxylates ; oil paintings ; Principal component analysis ; Raman microscopy: μ-Raman ; Spectra ; μ-Fourier transform infrared spectroscopy: μ-FTIR
  • É parte de: Journal of Raman spectroscopy, 2014-11, Vol.45 (11-12), p.1197-1206
  • Notas: istex:ED1DEE7DC8FD441E5827799916268AB1FC465473
    Supporting info itemSupporting info item
    REQUIMTE - No. PEst-C/EQB/LA0006/2013
    ArticleID:JRS4520
    This article is part of the special issue of the Journal of Raman Spectroscopy entitled "Raman in Art and Archaeology 2013" edited by Polonca Ropret and Juan Manuel Madariaga.
    ark:/67375/WNG-6QQ8KVCK-0
    Fundação para a Ciência e a Tecnologia (FCT) - No. PTDC/EAT-EAT/113612/2009
    FCT-MCTES - No. SFRH/BD/74574/2010; No. SFRH/BD/66488/2009; No. SFRH/BD/65690/2009
    This article is part of the special issue of the Journal of Raman Spectroscopy entitled “Raman in Art and Archaeology 2013” edited by Polonca Ropret and Juan Manuel Madariaga.
    ObjectType-Article-1
    SourceType-Scholarly Journals-1
    ObjectType-Feature-2
    content type line 23
  • Descrição: This work introduces the complementary use of μ‐Raman and μ‐Fourier transform infrared (IR) spectroscopy for the detection of specific carbon chains and cations for the identification of metal carboxylates within oil paint microsamples. Metal carboxylates (metal soaps) form naturally when free fatty acids react with metal cations and may also be found as additives or degradation products. Twenty‐two metal carboxylates were synthesised, and their spectra assembled in a reference database. Metal salts of cations commonly present in oil paintings were used, including lead, zinc, calcium, cadmium, copper and manganese. The fatty acids selected were the saturated acids palmitic (C16 : 0) and stearic (C18 : 0) and the polyunsaturated oleic acid (C18 : 1). Azelaic acid (C9 diacid), a product resulting from autoxidation of polyunsaturated acids, was also included. Metal carboxylates were characterised by Raman and IR spectroscopy, and their structures were confirmed by X‐ray diffraction. Raman and IR spectroscopy proved to be complementary techniques for a full identification of the metal carboxylates in complex aged paint. Raman enables the differentiation of the carbon chain length in the C–C stretching region (1120–1040 cm−1), and IR distinguishes the metal cation in the COO− stretching absorption region (1650–1380 cm−1). Principal component analysis was applied to the spectra in order to facilitate a fast and accurate method to discriminate between the different metal carboxylates and to aide in their identification. Finally, spectra from case studies were successfully projected in the principal component analysis models built, enabling a higher confidence level for the identification of copper palmitate and copper azelate in two 19th‐century Portuguese oil paintings. Copyright © 2014 John Wiley & Sons, Ltd. Raman and infrared spectroscopy proved to be complementary techniques for a full identification of metal carboxylates in a complex aged paint; while Raman allows a clear identification of the chain length, infrared enables the identification of the metal cation. Using a reference database, principal component analysis models were developed, enabling a fast and reliable method to characterise metal soaps within complex aged oil paint systems. Applying this methodology, copper palmitate and copper azelate were detected in two 19th‐century oil paintings.
  • Editor: Bognor Regis: Blackwell Publishing Ltd
  • Idioma: Inglês
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  • Realização: ABCD-USP USP   Logos de Redes Sociais: Freepik

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