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Digital archive of theses discussed at the University of Pisa


Thesis etd-01142015-090313

Thesis type
Tesi di dottorato di ricerca
Thesis title
Development of innovative analytical tools based on chromatography and mass spectrometry for the characterization and ageing studies of modern materials in artworks
Academic discipline
Course of study
tutor Prof. Modugno, Francesca
  • Cromatografia
  • oli moderni
  • resine alchidiche
  • Spettrometria di massa
  • vernici sintetiche
Graduation session start date
Release date
The introduction of industrial materials in modern and contemporary art has led to new issues in the conservation of artworks, with respect to the well known problematics related to classical art. At present, conservation scientists are facing new challenges for the understanding of the behavior of these materials: new analytical procedures and methodologies need to be developed.
In this Ph.D. project, two classes of modern artistic materials were selected and studied, namely lipid-based paint materials (drying oils and alkyd resins) and low molecular weight synthetic resins (Laropal A81 and Regalrez 1094). The first chapter “Modern materials in art” presents an overview of the modern materials used in art, and the state-of-the-art on the last advancements in the analytical approaches used for the characterization and the ageing studies of modern lipid materials and low molecular weight synthetic resins.
In the second chapter “Core shell stationary phases for a novel separation of triglycerides by high performance liquid chromatography with electrospray-quadrupole-time of flight mass spectrometer” the results obtained for the characterization of the triglyceride profiles in fresh and aged oils are presented. A new high performance liquid chromatography-mass spectrometric method using a core shell column, with an high resolution tandem mass spectrometer as detection system, was developed and validated for the triglyceride profiling of lipid materials. These new method was applied for the characterization of tri- and diglycerides in fresh oils (linseed, safflower, walnut, tung, poppy seed, castor, almond, sunflower, soybean and olive oils) and to identify the oxidized triglycerides after one year of natural ageing. The use of tandem mass spectrometry allowed the identification of more than 40 different species. The developed analytical approach was applied for the characterization of a set of oil paint tubes from the Edvard Munch’s atelier (1939-1944) and one micro-sample from a Munch’s painting.
The third chapter “Alkyd resins and paints: characterization using integrated mass spectrometry” reports on the results obtained for the characterization and the ageing studies of alkyd resins using the above mentioned multi-analytical approach based on mass spectrometry. The procedure entailed also the analyses with gas chromatography/mass spectrometry and flow injection-ESI-Q-TOF for the characterization of alkyd paints and industrial alkyd resins. The combined approach allowed the identification of free triglycerides when present and of the synthesis reaction products, such as pentaerythritol and phthalic acid esters, and triglycerides estolides. A set of alkyd paints layers was artificially aged using acetic acid vapors in order to evaluate the influence of VOCs during the curing of the paint layer. The results were integrated with the results obtained with spectroscopic techniques (e.g. FTIR) in order to describe the main degradation processes of both the organic and inorganic components.
The fourth chapter “Mass spectrometric techniques for the characterization of low molecular weight synthetic resins” describes the characterization and ageing study of Regalrez 1094 and Laropal A81. The molecular structure of these two low molecular weight resins, recently introduced as paint varnishes, was characterized using an approach based on three mass spectrometric techniques during three years of natural ageing.
In Chapter five, “Py-GC/MS and GC/MS for the characterization of modern and contemporary artworks”, the analytical results obtained for the characterization of paint samples from different artworks are reported. I participated in diagnostic campaigns on Cinema Airone (Rome, 1953-1954) by Giuseppe Capogrossi, Tuttomondo (Pisa, 1989) and Necker Hospital's murals (Paris, 1987) by Keith Haring, Die Grosse Fracht (Pistoia, 2007) by Anselm Kiefer, the Munch sketches (Oslo, 1909-1916), Salto di Qualità (Milan, 2008) by Patrizia Zara and the Caverna dell’Antimateria (Pistoia, 1958-1959) by Giuseppe Gallizio. The analysis were carried out in connection with conservation or restoration interventions.