journal article·2025-07-28Open access

Research into physicochemical changes in the retouching paints used at the National Museum in Krakow

Marek Bucki, Joanna Zwinczak, Krzysztof Kruczała

npj Heritage Science· Volume 13· Issue 1

Abstract

Abstract This paper presents a comparative analysis of the durability of six commercial and modified retouching paints containing ultramarine blue or cadmium yellow pigments. The paints were subjected to high temperatures, light, and naturally aged for 4 years. The analysis focuses on evaluating chemical and physical changes leading to alterations in colour and wettability. The controlled museum environment does not entirely eliminate the detrimental impact of these factors, therefore the restoration procedure must be undertaken. The conservation of 18th-century paintings (Czartoryski Princes collection, National Museum in Kraków) has contributed to the study of changes in retouching media and the selection of the best ones. An analysis of commercial paints with similar compositions revealed notable differences in colour stability and mechanical properties. In the case of watercolors containing Arabic gum, the primary degradation process was the organic component evaporation. Conversely, for cycloketones and aldehydes resin-based paints, oxidation was the predominant process.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Cultural Heritage Materials Analysis · Conservation Techniques and Studies · Building materials and conservation

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (52)

Show source-provided references
1. de la Rie, E. R., Lomax, S. Q., Palmer, M., Glinsman, L. D. & Maines, C. A. An investigation of the photochemical stability of urea-aldehyde resin retouching paints: removability tests and colour spectroscopy. Stud. Conserv. 45, 51–59 (2000).10.1179/sic.2000.45.Supplement-1.51 ↗
2. Szmit-Naud, E. Research on materials for easel painting retouches: part 1. Pict. Restor. 23, 5–10 (2003).
3. Szmit-Naud, E. Research on materials for easel painting retouches: part 2. Pict. Restor. 24, 5–9 (2003).
4. Mecklenburg Marion, F. Determining the Acceptable Ranges of Relative Humidity and Temperature in Museums and Galleries: Part 2, Structural Response to Temperature 1–56 (Smithsonian Museum Conservation Institute, 2007).
5. Tringa, E., Kavroudakis, D. & Tolika, K. Microclimate-monitoring: examining the indoor environment of Greek museums and historical buildings in the face of climate change. Heritage 7, 1400–1418 (2024).10.3390/heritage7030067 ↗
6. Laaksovirta, E. Studying restoration painting. Tahiti 11, 63–81 (2021).10.23995/tht.112171 ↗
7. Bratasz, Ł, Akoglu, K. G. & Kékicheff, P. Fracture saturation in paintings makes them less vulnerable to environmental variations in museums. Herit. Sci. 8, 11 (2020).10.1186/s40494-020-0352-0 ↗
8. de la Rie, E. R., Michelin, A., Ngako, M., Del Federico, E. & Del Grosso, C. Photo-catalytic degradation of binding media of ultramarine blue containing paint layers: a new perspective on the phenomenon of “ultramarine disease” in paintings. Polym. Degrad. Stab. 144, 43–52 (2017).10.1016/j.polymdegradstab.2017.08.002 ↗
9. Ibrahim, M., Issa, Y. M., Abdel-Maksoud, G. & Magdy, M. A comprehensive analytical approach for monitoring the physico-chemical changes of the paintings after exposure to environmental risks. Spectrosc. Lett. 54, 1–12 (2021).10.1080/00387010.2020.1843183 ↗
10. Izzo, F. C., van den Berg, K. J., van Keulen, H., Ferriani, B. & Zendri, E. Modern oil paints—formulations, organic additives and degradation: some case studies. In Issues in Contemporary Oil Paint (ed. K.J. van den Berg. et al) 75–104 (Springer International Publishing, 2014).10.1007/978-3-319-10100-2_5 ↗
11. Honzíček, J. Curing of air-drying paints: a critical review. Ind. Eng. Chem. Res. 58, 12485–12505 (2019).10.1021/acs.iecr.9b02567 ↗
12. Yuningsih, I., Rahayu, I. S., Lumongga, D. & Darmawan, W. Wettability and adherence of acrylic paints on long and short rotation teaks. Wood Mater. Sci. Eng. 15, 1–8 (2020).10.1080/17480272.2019.1575903 ↗
13. Schuler, B. et al. Structure and properties of multiphase particles and their impact on the performance of architectural coatings. Prog. Org. Coat. 40, 139–140 (2000).10.1016/S0300-9440(00)00136-3 ↗
14. Henke, M., Krystofiak, T., Adela Salca, E. & Lis, B. Gloss level, type of paper and colour of HDF boards finished with the energy-saving acrylic paint system. Appl. Sci. 14, 394 (2023).10.3390/app14010394 ↗
15. Bailão, A. Application of a methodology for retouching. CeROArt. 6,1–10 (2010).10.4000/ceroart.1603 ↗
16. Engel, N. L. & Zumbühl, S. An evaluation of selected retouching media for acrylic emulsion paint. J. Am. Inst. Conserv. 54, 224–237 (2015).10.1179/0197136015Z.00000000060 ↗
17. Abagale, S. A., Twumasi, S. K. & Awudza, J. A. M. Chemical studies on the composition of natural paint pigment materials from the Kassena-Nankana District of the Upper East region of Ghana. Chem. Mater. Res. 3, 13–23 (2013).
18. Yadav, S. et al. A brief review on natural dyes, pigments: recent advances and future perspectives. Results Chem. 5, 100733 (2023).10.1016/j.rechem.2022.100733 ↗
19. Izzo, F. C., Balliana, E., Pinton, F. & Zendri, E. A preliminary study of the composition of commercial oil, acrylic and vinyl paints and their behaviour after accelerated ageing conditions. Conserv. Sci. Cult. Herit. 14, 353–369 (2014).
20. Aceto, M., Agostino, A., Fenoglio, G. & Picollo, M. Non-invasive differentiation between natural and synthetic ultramarine blue pigments by means of 250–900 nm FORS analysis. Anal. Methods 5, 4184 (2013).10.1039/c3ay40583d ↗
21. Plesters, J. Ultramarine blue, natural and artificial. Stud. Conserv. 11, 62–75 (1966).
22. Farsang, S., Caracas, R., Adachi, B. M. T., Schnyder, C. & Zajacz, Z. S2- and S3- radicals and the S42- polysulfide ion in lazurite, haüyne, and synthetic ultramarine blue revealed by resonance Raman spectroscopy. Am. Mineral. 108, 2234–2243 (2023).10.2138/am-2022-8655 ↗
23. Gobeltz, N., Demortier, A., Lelieur, J. P. & Duhayon, C. Correlation between EPR, Raman and colorimetric characteristics of the blue ultramarine pigments. J. Chem. Soc. Faraday Trans. 94, 677–681 (1998).10.1039/a707619c ↗
24. Van Der Snickt, G. et al. Characterization of a degraded cadmium yellow (CdS) pigment in an oil painting by means of synchrotron radiation based X-ray techniques. Anal. Chem. 81, 2600–2610 (2009).10.1021/ac802518z ↗
25. Wu, J. et al. Research and development of cadmium sulphoselenide red pigment. J. Wuhan. Univ. Technol. Mater. Sci. Ed. 30, 1247–1254 (2015).10.1007/s11595-015-1303-6 ↗
26. Pandey, P., Bhimrao, B. & Kiran, U. V. Degradation of paints and its microbial effect on health and environment. J. Crit. Rev. 7, 4879–4884 (2020).
27. Aze, S. V., Baronnet, A. & Grauby, O. Red lead darkening in wall paintings: natural ageing of experimental wall paintings versus artificial ageing tests. Eur. J. Mineral. 19, 883–890 (2007).10.1127/0935-1221/2007/0019-1771 ↗
28. Nardelli, F. et al. The stability of paintings and the molecular structure of the oil paint polymeric network. Sci. Rep. 11, 14202 (2021).10.1038/s41598-021-93268-8 ↗
29. Macro, N., Ioele, M. & Lazzari, M. A simple multi-analytical approach for the detection of oxidative and biological degradation of polymers in contemporary artworks. Microchem. J. 157, 104919 (2020).10.1016/j.microc.2020.104919 ↗
30. Erhardt, D., Tumosa, C. S. & Mecklenburg, M. F. Natural and accelerated thermal aging of oil paint films. Stud. Conserv. 45, 65–69 (2000).10.1179/sic.2000.45.Supplement-1.65 ↗
31. Kohout, J. et al. Effect of aluminosilicates’ particle size distribution on the microstructural and mechanical properties of metakaolinite-based geopolymers. Materials 16, 5008 (2023).10.3390/ma16145008 ↗
32. Refaat, F., Marey Mahmoud, H., El-Sabbagh, B. & Brania, A. Evaluating thermal and UV stability of some protective coatings for historical murals in Egypt. Adv. Res. Conserv. Sci. 1, 37–47 (2020).10.21608/arcs.2020.28415.1003 ↗
33. Farmakalidis, H. V. et al. Accelerated thermal ageing of acrylic copolymers, cyclohexanone-based and urea-aldehyde resins used in paintings conservation. Mediterr. Archaeol. Archaeom. 16, 213–228 (2016).
34. Cimino, D., Lamuraglia, R., Saccani, I., Berzioli, M. & Izzo, F. C. Assessing the (In)stability of urban art paints: from real case studies to laboratory investigations of degradation processes and preservation possibilities. Heritage 5, 581–609 (2022).10.3390/heritage5020033 ↗
35. Pieralli, I. et al. A formulation for a new environmentally friendly varnish for paintings. Coatings 13, 1566 (2023).10.3390/coatings13091566 ↗
36. D’Angelo, J. FT-IR determination of aliphatic and aromatic CH contents of fossil leaf compressions. Part 2: applications. Anuario Latinoamericano de Educación Química 18, 34–38 (2004).
37. Collado-Montero, F. J., Calero-Castillo, A. I., Melgosa, M. & Medina, V. J. Colorimetric evaluation of pictorial coatings in conservation of plasterworks from the Islamic tradition. Stud. Conserv. 64, 1–11 (2019).10.1080/00393630.2018.1460924 ↗
38. Ly, B. C. K., Dyer, E. B., Feig, J. L., Chien, A. L. & Del Bino, S. Research techniques made simple: cutaneous colorimetry: a reliable technique for objective skin color measurement. J. Invest. Dermatol. 140, 3–12 (2020).10.1016/j.jid.2019.11.003 ↗
39. Mokrzycki, W. & Tatol, M. Color difference delta E-A survey colour difference ΔE-A survey. Mach. Graph. Vision. 20, 383–411 (2011).
40. Spałek, T., Pietrzyk, P. & Sojka, Z. Application of the genetic algorithm joint with the Powell method to nonlinear least-squares fitting of powder EPR spectra. J. Chem. Inf. Model. 45, 18–29 (2005).10.1021/ci049863s ↗
41. George, K. M. et al. FT-IR quantification of the carbonyl functional group in aqueous-phase secondary organic aerosol from phenols. Atmos. Environ. 100, 230–237 (2015).10.1016/j.atmosenv.2014.11.011 ↗
42. Espinosa-Andrews, H., Sandoval-Castilla, O., Vázquez-Torres, H., Vernon-Carter, E. J. & Lobato-Calleros, C. Determination of the gum Arabic–chitosan interactions by Fourier Transform Infrared Spectroscopy and characterization of the microstructure and rheological features of their coacervates. Carbohydr. Polym. 79, 541–546 (2010).10.1016/j.carbpol.2009.08.040 ↗
43. Aguiar, H., Serra, J., González, P. & León, B. Structural study of sol-gel silicate glasses by IR and Raman spectroscopies. J. Non Cryst. Solids 355, 475–480 (2009).10.1016/j.jnoncrysol.2009.01.010 ↗
44. Chukanov, N. V., Sapozhnikov, A. N., Shendrik, R. Y., Vigasina, M. F. & Steudel, R. Spectroscopic and crystal-chemical features of sodalite-group minerals from gem lazurite deposits. Minerals 10, 1042 (2020).10.3390/min10111042 ↗
45. Steelman, K. L., Boyd, C. E. & Bates, L. N. Implications for rock art dating from the Lower Pecos Canyonlands, TX: a review. Quat. Geochronol. 63, 101167 (2021).10.1016/j.quageo.2021.101167 ↗
46. Bruni, S., Cariati, F., Casadio, F. & Toniolo, L. Spectrochemical characterization by micro-FTIR spectroscopy of blue pigments in different polychrome works of art. Vib. Spectrosc. 20, 15–25 (1999).10.1016/S0924-2031(98)00096-4 ↗
47. Rowe, M. W. Dating of rock paintings in the Americas: a word of caution. Palethnologie 5, 573–584 (2013).
48. Moretto, L. M., Orsega, E. F. & Mazzocchin, G. A. Spectroscopic methods for the analysis of celadonite and glauconite in Roman green wall paintings. J. Cult. Herit. 12, 384–391 (2011).10.1016/j.culher.2011.04.003 ↗
49. Reinen, D. & Lindner, G. G. The nature of the chalcogen colour centres in ultramarine-type solids. Chem. Soc. Rev. 28, 74–85 (1999).10.1039/a704920j ↗
50. Więckowski, A. Ultramarine study by EPR. Phys. Status Solidi B 42, 125–130 (1970).10.1002/pssb.19700420112 ↗
51. Wiȩckowski, A. B., Wojtowicz, W. & Śliwa-Nieściór, J. Temperature dependence of the EPR linewidth of ultramarine blue. Magn. Reson. Chem. 37, 150–153 (1999).10.1002/(SICI)1097-458X(199912)37:13<S150::AID-MRC577>3.0.CO;2-V ↗
52. Orsega, E. F., Agnoli, F. & Mazzocchin, G. A. An EPR study on ancient and newly synthesized Egyptian blue. Talanta 68, 831–835 (2006).10.1016/j.talanta.2005.06.001 ↗