Abstract
Carbon black-based particles are widely employed as pigment and they are known to slow down the drying time of oil paints. In this work, the effect of amorphous carbon black on the mechanism and speed of autoxidation of a polyunsaturated oil was investigated. Moreover, the effect of the addition of aluminium stearate and zinc stearate was studied. These are two common additives used in the artists’ paint industry to facilitate pigment dispersion. The curing of the oil paints with and without the addition of the two stearates at 80 °C under airflow was followed by isothermal Thermogravimetry. The oxygen uptake profiles were fitted by a semi-empiric equation to comparatively study the kinetics of the oil oxidation and estimate oxidative degradation. Moreover, model paintings were left to cure at ambient conditions and Differential Scanning Calorimetry was then used to monitor their curing progress over time and to evaluate the stability of peroxides formed in the paint layers. Gas Chromatography–Mass Spectrometry was performed at 7 and 12 months of natural ageing of the model paintings, to investigate the non-covalently cross-linked fractions. Analytical Pyrolysis coupled with Gas Chromatography–Mass Spectrometry was used to characterise the whole organic fraction of the model paintings, including the cross-linked network. Amorphous carbon has an antioxidant effect and inhibits the radical chain propagation. The presence of aluminium and zinc stearates in the black paint affects the autoxidation process, by leading, in the first months, to a faster consumption of unsaturated moieties, and, accordingly, to accelerate and increase peroxides formation. After a few months though, the whole curing slows down, and active peroxides and radicals are still present even after 12 months.
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References
Mayer R. Artist's handbook of Materials and techniques: revised and updated. Viking Books. 1991.
Honzíček J. Curing of air-drying paints: a critical review. Ind Eng Chem Res. 2019;58(28):12485–505.
Bonaduce I, Duce C, Lluveras-Tenorio A, Lee J, Ormsby B, Burnstock A, et al. Conservation issues of modern oil paintings: a molecular model on paint curing. Acc Chem Res. 2019;52(12):3397–406. https://doi.org/10.1021/acs.accounts.9b00296.
Lluveras-Tenorio A, Spepi A, Pieraccioni M, Legnaioli S, Lorenzetti G, Palleschi V, et al. A multi-analytical characterization of artists’ carbon-based black pigments. J Therm Anal Calorim. 2019;138(5):3287–99. https://doi.org/10.1007/s10973-019-08910-5.
van Loon A, Boon JJ. Characterization of the deterioration of bone black in the 17th century Oranjezaal paintings using electron-microscopic and micro-spectroscopic imaging techniques. Spectrochim Acta Part B. 2004;59(10–11):1601–9.
Spahr ME, Rothon R. Carbon black as a polymer filler. In: Palsule S, editor. Polymers and polymeric composites: A reference series. Berlin, Heidelberg: Springer Berlin Heidelberg; 2016. pp. 1–31.
Winter J. The characterization of pigments based on carbon. Stud Conserv. 1983;28(2):49–66. https://doi.org/10.1179/sic.1983.28.2.49.
Vila A, Ferrer N, García JF. Chemical composition of contemporary black printing inks based on infrared spectroscopy: basic information for the characterization and discrimination of artistic prints. Anal Chim Acta. 2007;591(1):97–105.
Donnet J-B. Carbon black: Science and technology. 2nd ed. CRC Press; 1993.
Ataeefard M. Production of black toner through emulsion aggregation of magnetite, carbon black, and styrene-acrylic co-polymer: investigation on the effect of variation in components. J Compos Mater. 2015;49(13):1553–61. https://doi.org/10.1177/0021998314536069.
Ghasemi-Kahrizsangi A, Neshati J, Shariatpanahi H, Akbarinezhad E. Improving the UV degradation resistance of epoxy coatings using modified carbon black nanoparticles. Prog Org Coat. 2015;85:199–207. https://doi.org/10.1016/j.porgcoat.2015.04.011.
Liu M, Horrocks A. Effect of carbon black on UV stability of LLDPE films under artificial weathering conditions. Polym Degrad Stab. 2002;75(3):485–99. https://doi.org/10.1016/S0141-3910(01)00252-X.
Wang X, Zhao J, Chen M, Ma L, Zhao X, Dang Z-M, et al. Improved self-healing of polyethylene/carbon black nanocomposites by their shape memory effect. J Phys Chem B. 2013;117(5):1467–74. https://doi.org/10.1021/jp3098796.
Leong C-K, Chung D. Carbon black dispersions as thermal pastes that surpass solder in providing high thermal contact conductance. Carbon. 2003;41(13):2459–69. https://doi.org/10.1016/S0008-6223(03)00247-1.
Sumita M, Sakata K, Asai S, Miyasaka K, Nakagawa H. Dispersion of fillers and the electrical conductivity of polymer blends filled with carbon black. Polym Bull. 1991;25(2):265–71. https://doi.org/10.1007/BF00310802.
Hayashi K, Iwasaki K, Morii H, Xia B, Okuyama K. Carbon-coated non-magnetic iron oxide particles for the substrate of multi-layered magnetic recording media. J Nanoparticle Res. 2001;3(2):149–56. https://doi.org/10.1023/A:1017501412585.
Hosseini SM, Razzaghi-Kashani M. Catalytic and networking effects of carbon black on the kinetics and conversion of sulfur vulcanization in styrene butadiene rubber. Soft Matter. 2018;14(45):9194–208. https://doi.org/10.1080/10641220009351406.
Leblanc JL. Rubber–filler interactions and rheological properties in filled compounds. Prog Polym Sci. 2002;27(4):627–87.
Karasek L, Sumita M. Characterization of dispersion state of filler and polymer-filler interactions in rubber-carbon black composites. J Mater Sci. 1996;31(2):281–9. https://doi.org/10.1007/BF01139141.
Li Z, Zhang J, Chen S. Effects of carbon blacks with various structures on vulcanization and reinforcement of filled ethylene-propylene-diene rubber. EXPRESS Polym Lett. 2008;2(10):695–704. https://doi.org/10.3144/expresspolymlett.2008.83.
Tumosa CS (2001) A brief history of aluminum stearate as a component of paint.
Izzo FC (2011) 20th century artists’ oil paints: a chemical-physical survey.
van den Berg KJ, Burnstock A, Schilling M (2019) Notes on metal soap extenders in modern oil paints: history, use, degradation, and analysis. Metal soaps in art. Springer. pp 329–42.
Tempest H, Burnstock A, Saltmarsh P, editors. Sensitivity of oil paint surfaces to aqueous and other solvents. New Insights into the Cleaning of Paintings: Proceedings from the Cleaning 2010 International Conference, Universidad Politecnica de Valencia and Museum Conservation Institute; 2013: Smithsonian Institution. pp. 107–114
Hermans JJ, Keune K, Van Loon A, Iedema PD (2019) Toward a complete molecular model for the formation of metal soaps in oil paints. Metal soaps in art, Springer, pp. 47–67.
Noble P, Boon JJ, Parkin HM (2007) Metal soap degradation of oil paintings: aggregates, increased transparency and efflorescence. AIC paintings specialty group postprints, Providence, Rhode Island, pp 1–15.
Osmond G, Boon JJ, Puskar L, Drennan J. Metal stearate distributions in modern artists’ oil paints: surface and cross-sectional investigation of reference paint films using conventional and synchrotron infrared microspectroscopy. Appl Spectrosc. 2012;66(10):1136–44.
Baij L, Hermans JJ, Keune K, Iedema P. Time-dependent ATR-FTIR spectroscopic studies on fatty acid diffusion and the formation of metal soaps in oil paint model systems. Angew Chem Int Edit. 2018;57(25):7351–4.
Odlyha M. Investigation of the binding media of paintings by thermoanalytical and spectroscopic techniques. Thermochim Acta. 1995;269:705–27.
Tuman SJ, Chamberlain D, Scholsky KM, Soucek MD. Differential scanning calorimetry study of linseed oil cured with metal catalysts. Prog Org Coat. 1996;28(4):251–8.
Burmester A. Investigation of paint media by differential scanning calorimetry (DSC). Stud Conserv. 1992;37(2):73–81.
Prati S, Chiavari G, Cam D. DSC application in the conservation field. J Therm Anal Calorim. 2001;66(1):315–27.
Rudnik E, Szczucinska A, Gwardiak H, Szulc A, Winiarska A. Comparative studies of oxidative stability of linseed oil. Thermochim Acta. 2001;370(1–2):135–40.
Ploeger R, Scalarone D, Chiantore O. Thermal analytical study of the oxidative stability of artists’ alkyd paints. Polym Degrad Stab. 2009;94(11):2036–41.
Izzo FC, Zendri E, Biscontin G, Balliana E. TG–DSC analysis applied to contemporary oil paints. J Therm Anal Calorim. 2011;104(2):541–6. https://doi.org/10.1007/s10973-011-1468-y.
Lazzari M, Chiantore O. Drying and oxidative degradation of linseed oil. Polym Degrad Stab. 1999;65(2):303–13. https://doi.org/10.1016/S0141-3910(99)00020-8.
Mallégol J, Gonon L, Commereuc S, Verney V. Thermal (DSC) and chemical (iodometric titration) methods for peroxides measurements in order to monitor drying extent of alkyd resins. Prog Org Coat. 2001;41(1):171–6. https://doi.org/10.1016/S0300-9440(01)00144-8.
Pizzimenti S, Bernazzani L, Tinè MR, Treil V, Duce C, Bonaduce I. Oxidation and cross-linking in the curing of air-drying artists’ oil paints. ACS Appl Polym Mater. 2021. https://doi.org/10.1021/acsapm.0c01441.
Tamburini D, Sardi D, Spepi A, Duce C, Tinè MR, Colombini MP, et al. An investigation into the curing of urushi and tung oil films by thermoanalytical and mass spectrometric techniques. Polym Degrad Stab. 2016;134:251–64. https://doi.org/10.1016/j.polymdegradstab.2016.10.015.
Duce C, Bernazzani L, Bramanti E, Spepi A, Colombini M, Tiné M. Alkyd artists’ paints: Do pigments affect the stability of the resin? A TG and DSC study on fast-drying oil colours. Polym Degrad Stab. 2014;105:48–58. https://doi.org/10.1016/j.polymdegradstab.2014.03.035.
Bonaduce I, Carlyle L, Colombini MP, Duce C, Ferrari C, Ribechini E, et al. New insights into the ageing of linseed oil paint binder: a qualitative and quantitative analytical study. PLoS ONE. 2012;7(11): e49333. https://doi.org/10.1371/journal.pone.0049333.
Colombini MP, Modugno F, Fuoco R, Tognazzi A. A GC-MS study on the deterioration of lipidic paint binders. Microchem J. 2002;73(1–2):175–85. https://doi.org/10.1016/S0026-265X(02)00062-0.
Hess P, O’Hare G. Oxidation of linseed oil. Ind Eng Chem Res. 1950;42(7):1424–31.
Labuza TP, Dugan L Jr. Kinetics of lipid oxidation in foods. Crit Rev Food Sci Nutr. 1971;2(3):355–405.
Schaich KM. Lipid oxidation: theoretical aspects. Bailey's industrial oil and fat products. Wiley Online Library. 2005
Honzicek J. Curing of air-drying paints: a critical review. Ind Eng Chem Res. 2019;58(28):12485–505. https://doi.org/10.1021/acs.iecr.9b02567.
Van Loon A, Boon J, editors. The whitening of oil paints films containing bone black. In: Conference proceedings 14th triennial meeting of the Icom Committee for conservation in The hague (I. Verger ed.), James & James, London; 2005. pp. 511–518.
Cataldo F. A model compound study about carbon black and diene rubber interaction: the reactivity of C60 fullerene with squalene. Fullerene Sci Technol. 2000;8(3):153–64.
Kovacs E, Wolkober Z, editors. The effect of the chemical and physical properties of carbon black on the thermal and photooxidation of polyethylene. Journal of Polymer Science: Polymer Symposia; John Wiley & Sons.1976. pp. 171–180.
Bigger SW, Delatycki O. The effects of pigments on the photostability of polyethylene. J Mater Sci. 1989;24(6):1946–52. https://doi.org/10.1007/BF02385404.
Ploeger R, Scalarone D, Chiantore O. The characterization of commercial artists’ alkyd paints. J Cult Herit. 2008;9(4):412–9.
Mwila J, Miraftab M, Horrocks A. Effect of carbon black on the oxidation of polyolefins—an overview. Polym Degrad Stab. 1994;44(3):351–6. https://doi.org/10.1016/0141-3910(94)90094-9.
Acknowledgements
The authors would like to thank Carmen dell’Urso for GC-MS analysis of paint samples. The work was performed within the context of the JPI CMOP project: “Cleaning of Modern Oil Paints” (Heritage Plus Joint Call project 2015−2018).
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SP: Investigation; Data curation; Methodology; Writing—original draft; LB: Conceptualization; Data curation; Methodology; Supervision; Writing—review & editing; MRT: Data curation; Methodology; Supervision; Writing—review & editing; CD: Conceptualization; Data curation; Methodology; Supervision; Writing—review & editing. IB: Conceptualization; Data curation; Methodology; Supervision; Writing—review & editing.
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Pizzimenti, S., Bernazzani, L., Tinè, M.R. et al. Unravelling the effect of carbon black in the autoxidation mechanism of polyunsaturated oils. J Therm Anal Calorim 147, 5451–5462 (2022). https://doi.org/10.1007/s10973-021-11165-8
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DOI: https://doi.org/10.1007/s10973-021-11165-8