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Supervisors:
Prof. Celia Duce, Prof. Ilaria Bonaduce

Title:
Physical-chemical characterization of the curing process of modern oil paints

Abstract:
Despite the introduction of synthetic binders, oil paint has been confirmed as one of the most appreciated media by the modern artists. Nowadays, the lack of knowledge on the nature of the changes in paint formulations is revealing critical when dealing with the new conservation challenges posed by modern and contemporary painted art. In the last few years, the evidence of new degradation phenomena has led scientists to study the causes.
Recent studies hypothesized that some degradation phenomena taking place in modern oil paintings are related to the chemical nature of the polymeric network, and in particular, to a lack of polymerization and a high degree of oxidation. Unfortunately, the molecular characterization of the formed polymeric network of oil paints still represents a complex task. A useful approach to improve our understanding of the chemical structure of an oil polymeric film is to characterise the processes that lead to its formation: the curing.
The curing of an oil paint is an autoxidative process that entitles two main competitive phenomena: cross-linking and oxidation. The competition between cross-linking and oxidation depends on both internal and external factors such as the oil type, pigment(s), additive(s), artistic practice and environmental conditions. In this context, although, the curing mechanism of traditional siccative oils, as linseed oil, has been widely studied, alkali refined linseed oil and semi-siccative oils as safflower oil, employed in industrial formulations, have been only partially investigated.
The project is divided into three main parts. The first devotes to developing a systematic approach based on differential scanning calorimetry, thermogravimetry, gas chromatography-mass spectrometry, analytical pyrolysis coupled with GC-MS, HPLC-MS and SPME-GC-MS in order to investigate the curing and maturing processes of oil paints. The second part aims to reveal the effect of two important pigments, lead white and ultramarine blue in the curing process of linseed oil and safflower oil, with a focus on the effect of ultramarine blue in the autoxidation of safflower oil by study the curing process of methyl linoleate as a model system of semi-siccative oil. The third part concerns the application of the implemented multy-analytical approach on the study of customized industrial oil paints supplied by Williamsburg Oil Paints in order to study the effect of different driers on the curing process of alkali refined linseed oil.

Publications:
• S. Pizzimenti*, F. Saitta*, M. Signorelli, M. R. Tinè, I. Bonaduce, C. Duce, D. Fessas. Oil crystallization properties as an index for monitoring early stage curing of oil-based paints: DSC analysis on linseed oil systems. Journal of Thermal Analysis and Calorimetry. 2022. https://doi.org/10.1007/s10973-022-11227-5
• S. Pizzimenti, L. Bernazzani, M. R. Tinè, C. Duce and I. Bonaduce. Unravelling the effect of carbon black in the autoxidation mechanism of polyunsaturated oils. Journal of Thermal Analysis and Calorimetry. 2022. https://doi.org/10.1007/s10973-021-11165-8
• F. Modugno, J.La Nasa, S. Pizzimenti, I. Bonaduce, M.P. Colombini. Analisi dei leganti organici nelle Superfici 207, 538 e 553 di Giuseppe Capogrossi mediante tecniche basate su pirolisi analitica, gas cromatografia e spettrometria di massa. Le opere di Giuseppe Capogrossi. Indagini, studi e restauri. Tab Edizioni. ISBN 978-88-9295-127-3. 2021. https://www.tabedizioni.it/shop/product/le-opere-di-giuseppe-capogrossi-461
• L. Vannoni*, S. Pizzimenti*, G. Caroti, J. La Nasa, C. Duce, I. Bonaduce. Disclosing the chemistry of oil curing by mass spectrometry using methyl linoleate as a model binder. Microchemical Journal, Springer. 2021. https://doi.org/10.1016/j.microc.2021.107012
• Pizzimenti S., Bernazzani L., Tinè M.R., Treil V., Duce C., and Bonaduce I. Oxidation and Cross-Linking in the Curing of Air-Drying Artists’ Oil Paints. ACS Polymer Material Science. 2021. https://doi.org/10.1021/acsapm.0c01441
• Saitta F., Signorelli M.; Bramanti E., Pizzimenti S., Pelosi C., Duce C., Bonaduce I., Tiné M.R., Fessas D. DSC on ovalbumin-hematite “tempera” paints: the role of water and pigment on protein stability. Thermochimica Acta. 2020. https://doi.org/10.1016/j.tca.2020.178780
• La Nasa J., Moretti P., Maniccia E., Pizzimenti S., Colombini M.P., Miliani C., Modugno F., Carnazza P., De Luca D. Discovering Giuseppe Capogrossi: Study of the Painting Materials in Three Works of Art Stored at Galleria Nazionale (Rome). Heritage. 2020. https:// doi.org/10.3390/heritage3030052
• Spepi*, A.; Pizzimenti*, S.; Duce, C.; Vozzi, G.; De Maria, C.; Tine, M. R. Chemico-physical characterization and evaluation of coating properties of two commercial organosilicons: Hydrophase® and Disboxan 450®. Journal of Calorimetry and Thermal Analysis. (2019): https://link.springer.com/article/10.1007/s10973-019-08830-4
* These authors contributed equally to this work

Oral communications at congress
:
S.Pizzimenti, G.Caroti, C., L. Bernazzani, M. R.Tinè, M.Hintz, I. Bonaduce, “The curing process of historical and contemporary oil paints” Chemistry for the Future 2021, Department of Chemistry and Industrial Chemistry, University of Pisa, Online, June 30 – July 2 2021
S.Pizzimenti, C.Duce, C., L. Bernazzani, M. R.Tinè, M.Hintz, I. Bonaduce, “Oil paints: the competition between cross-linking and oxidative degradation phenomena”, School of Physical Chemistry 2021. Supramolecular Interactions in Biological Systems, Società Chimica Italiana, Divisione di Chimica Fisica, Online, June 15-24 2021
S.Pizzimenti, C. Duce, L. Bernazzani, M. R.Tinè, M.Hintz, I. Bonaduce. “Effect of primary and auxiliary driers on the curing process of oil paints”. Consorzio Interuniversitario reattività chimica e catalisi (CIRCC), XVII PhD-Chem Day, online April 29 2021.
S. Pizzimenti, C. Duce, L. Bernazzani, M. R.Tinè, I. Bonaduce. “A new approach to elucidate the role of metal-based driers on the oxygen uptake kinetic of industrial oil paints”. XLII National Conference on Calorimetry, Thermal Analysis and Applied Thermodynamics, January 27 - 28 2021 Online, Udine
S.Pizzimenti, C. Duce, M.R. Tinè, I. Bonaduce. “A physico-chemical investigation on the curing of lead white oil paints”. Workshop Chemistry of Lead in Oil Paintings. Amsterdam, February 20-21 2020
S.Pizzimenti, A. Spepi, C. Duce, G. Vozzi, C. De Maria, M. P. Colombini, M.R. Tinè. “La selezione dei materiali impiegati per l’impermeabilizzazione di Tuttomondo. Uno studio su Hydrophase® e Disboxan 450®”. Scuola di calorimetria e analisi termica. applicazioni alla diagnostica e conservazione dei beni culturali. Centro Conservazione e Restauro – La Venaria Reale. Venaria Reale (Turin), February – 11-13 2020
S.Pizzimenti, C. Duce, M.R. Tine’, K.J. van den Berg, I. Bonaduce. “Modern oil paint: as recent as fragile!” 1st Short Summer School on Calorimetry and Thermal Analysis. Rome, August 27 2019.
S. Pizzimenti, C. Duce, M. R. Tine’, I. Bonaduce, F. Saitta, M. Signorelli, D. Fessas. “The DSC monitoring of oil melting to follow the oil curing”. 5th Central and Eastern European Conference on Thermal Analysis and Calorimetry and 14th Mediterranean Conference on Calorimetry and Thermal Analysis. Rome, August 27-30 2019. Winner of a grant for the participation
S.Pizzimenti, C. Duce, M.R. Tinè, M.P. Colombini, I. Bonaduce. “A thermoanalytical study on the oils present into modern paint tubes”. AICAT 2018. XL National Congress on Calorimetry Thermal Analysis and Applied Thermodynamics. Pisa, December 17–19 2018.
S.Pizzimenti, C.Duce, M.R. Tinè, M.P. Colombini, K.J. van den Berg, I. Bonaduce.“The effects of pigments and additives on the curing of oil paints. A calorimetric and thermoanalytical approach integrated with mass spectrometric techniques”. XVII Congresso Nazionale Chimica dell'Ambiente e dei Beni Culturali (SCI). Genova, June 24-27 2018. Winner of a grant for the participation

Other contribution in oral communications at congress:
• Tiné M.R., Duce C., Bernazzani L., Pizzimenti S., Pulidori E., Lezzerini M., Mazzoleni P., Barone G., “Thermal behavior and microstructural characterization of natural clayey materials, sands, volcanic ashes and geopolymer composites”, 5th Central and Eastern European Conference on Thermal Analysis and Calorimetry and 14th Mediterranean Conference on Calorimetry and Thermal Analysis. Rome, August 27-30 2019.
• E. Maniccia, F.Modugno, J. La Nasa, S. Pizzimenti, P. Carnazza, I. Bonaduce, M. P. Colombini, D. De Luca, Costanza Miliani, Patrizia Moretti. “Investigation of painting technique in three paintings by Giuseppe Capogrossi at the Galleria Nazionale di Arte Moderna e Contemporanea (Rome)”. Convegno Tematico AIAr 2019. Dalla Conoscenza alla Valorizzazione: il Ruolo dell’archeometria nei Musei. Reggio Calabria. Museo Archeologico Nazionale (Reggio Calabria, Italy). March 27–29, 2019.

Poster communications at congress:
• S.Pizzimenti, C. Duce, M.R. Tinè, L.Bernazzani, I. Bonaduce. “A new approach to elucidate the role of metal-based driers on the oxygen uptake kinetic of industrial oil paints”. XLII National Conference on Calorimetry, Thermal Analysis and Applied Thermodynamics. Udine/online January 27-28 2021.
• S.Pizzimenti, C.Duce, I.Bonaduce, M.R. Tinè. “Calorimetric and thermoanalytical techniques in the cultural heritage field”. Le scienze e I beni culturali: innovazione e multidisciplinarietà. Workshop, University of Milan, February 26, 2019.
• S.Pizzimenti, C. Duce, M.R. Tinè, I. Bonaduce. “A study on the curing process of oil paint models”. Chemistry for the Future 2018. University of Pisa, July 4th -6th, 2018.

Other contribution in poster communications at congress:
• S.Pizzimenti, M.R.Tinè, C. Duce, I. Bonaduce. “A thermoanalytical study of the curing process of linseed oil influenced by lead white and ultramarine blue pigments”. ESTAC12, Brasov (Romania), August 27-30, 2018. Winner of The Best Poster Prize

 

DCCI|UNIPI
Dipartimento di Chimica e Chimica Industriale
Department of Chemistry and Industrial Chemistry
Via G. Moruzzi, 13 - Pisa, Italy
DSCM
Corso di Dottorato in Scienze Chimiche e dei Materiali
Doctoral School in Chemistry and Material Science
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