Stability and Degradation Issues of Manganese Violet Pigment in Polymeric Paints: Morphological and Chemical Changes Under SO2 and Humidity Exposure
Source abstract
Abstract
This study focuses on investigating the stability of modern and contemporary paints based on manganese violet pigment PV16 (NH4MnP2O7) when exposed to atmospheric pollutants, specifically sulfur dioxide (SO2) in the presence of high relative humidity. In particular, this study aims to investigate the role of PV16 in increasing the degradation processes of various modern binders. Therefore, the objectives of this research can be divided into (i) evaluating the chemical modifications involving PV16, (ii) investigating the degradation processes that occur in different organic matrices (i.e., drying oil, alkyd resin, and acrylic and styrene–acrylic emulsions), and (iii) comparing the chemical stability of model and commercial paints. The paints were analyzed by 3D Optical Microscopy, Attenuated total Reflection–Fourier-Transform Infrared spectroscopy (ATR-FTIR) and μ-Raman Spectroscopy, Scanning Electron Microscope coupled with Energy Dispersive X-Ray spectroscopy (SEM-EDX), X-Ray Powder Diffraction (XRPD), Fiber Optic Reflectance Spectroscopy (FORS), Pyrolysis–Gas Chromatography–Mass Spectrometry (Py-GC/MS), and Thermally assisted Hydrolysis and Methylation (THM) of Py-GC/MS (THM-Py-GC/MS). The results show that when exposed to high relative humidity and SO2, PV16 presents a colorimetric change from violet to grey; several compounds crystallize on the surface; and, depending on the binder, various degradation reactions occur. This study highlights the susceptibility of manganese violet pigment PV16 under certain environmental conditions, which may be considered to define adequate conservation strategies for works of art containing this specific pigment. Additionally, the results obtained within this investigation point out the need to expand the chemical knowledge of this material for engineering, sensing, and industrial applications.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Pigment Synthesis and Properties · Cultural Heritage Materials Analysis · Color Science and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Environmental Sciences, Informatics, and Statistics, Ca’ Foscari University of Venice, 30173 Venice, Italy
Academy of Fine Arts Vienna, Institute for Natural Sciences and Technology in the Art, A-1010 Vienna, Austria
Academy of Fine Arts Vienna, Institute for Conservation-Restoration, Modern and Contemporary Art, A-1010 Vienna, Austria
Department of Molecular Sciences and Nanosystems, Ca’ Foscari University of Venice, 30173 Venice, Italy
Institute for Conservation and Restoration, University of Applied Arts Vienna, A-1090 Vienna, Austria
References (86)
Show source-provided references
1. Grzywacz, C.M. (2006). Monitoring for Gaseous Pollutants in Museum Environments, Getty Publications.
2. Leonardo da Vinci’s “Last Supper”: A case study to evaluate the influence of visitors on the Museum preservation systems10.1007/s11356-021-13741-9 ↗
3. Corrosive Effects of Mixtures of Pollutants10.1080/00022470.1985.10465940 ↗
4. Atmospheric corrosion of historical industrial structures
5. European Environment Agency (2013). Air Pollution Fact Sheet 2013.
6. Pozo-Antonio, J.S., Rivas, T., Dionísio, A., Barral, D., and Cardell, C. (2020). Effect of a SO2 Rich Atmosphere on Tempera Paint Mock-Ups. Part 1: Accelerated Aging of Smalt and Lapis Lazuli-Based Paints. Minerals, 10.10.3390/min10050427 ↗
7. Effects of relative humidity on heterogeneous reaction of SO2 with CaCO3 particles and formation of CaSO4·2H2O crystal as secondary aerosol10.1016/j.atmosenv.2021.118776 ↗
8. Measurements for indoor air quality assessment at the Capodimonte Museum in Naples (Italy)
9. Faulkner, E.B., and Hollenberg, J.C. (2021). Coloring the Cosmetic World: Using Pigments in Decorative Cosmetic Formulations, Wiley. [2nd ed.].10.1002/9781119558163 ↗
10. Rajadurai, R.S., Lee, J.-H., Choi, E., and Kang, J.-W. (2020). MnNH4P2O7-Based Coating for High Temperature Assessment on the Surfaces of Cement Composites. Coatings, 10.10.3390/coatings10040396 ↗
11. Finlay, V. (2014). The Brilliant History of Color in Art, J. Paul Getty Museum. [1st ed.].
12. Kirby, J., Stonor, K., Roy, A., Burnstock, A., Grout, R., and White, R. (2003). Seurat’s Painting Practice: Theory, Development and Technology. National Gallery Technical Bulletin, The National Gallery. Available online: https://www.nationalgallery.org.uk/research/research-resources/technical-bulletin/seurats-painting-practice-theory-development-and-technology.
13. Exploring the private universe of Henri Matisse in The Red Studio10.1186/s40494-022-00797-0 ↗
14. Analysis of paintings from the nineteenth century Brazilian painter Rodolfo Amoedo using EDXRF portable system10.1002/xrs.1167 ↗
15. Joaquin Sorolla’s pigment characterisation of the paintings “Vision of Spain” by means of EDXRF portable system10.1002/xrs.1339 ↗
16. Molecular and structural characterization of some violet phosphate pigments for their non-invasive identification in modern paintings10.1016/j.saa.2016.09.017 ↗
17. A Technical Study of the Materials and Methods Used by David B. Milne in his Oil Paintings
18. Disclosing Jackson Pollock’s palette in Alchemy (1947) by non-invasive spectroscopies10.1186/s40494-016-0089-y ↗
19. Insight into Sam Francis’ painting techniques through the analytical study of twenty-eight artworks made between 1946 and 199210.1007/s00339-016-0485-x ↗
20. Sabatini, F. (2018). Ageing and Fading of Organic Pigments in Art: A Multi-Analytical Study Based on Mass Spectrometric Techniques. [Ph.D. Thesis, University of Pisa].
21. La Nasa, J., Doherty, B., Rosi, F., Braccini, C., Broers, F.T.H., Degano, I., Matinero, J.M., Miliani, C., Modugno, F., and Sabatini, F. (2021). An integrated analytical study of crayons from the original art materials collection of the MUNCH museum in Oslo. Sci. Rep., 11.10.1038/s41598-021-86031-6 ↗
22. SO2− and NOx− initiated atmospheric degradation of polymeric films: Morphological and chemical changes, influence of relative humidity and inorganic pigments10.1016/j.microc.2021.106087 ↗
23. Pagnin, L., Wiesinger, R., Koyun, A.N., and Schreiner, M. (2021). The effect of pollutant gases on surfactant migration in acrylic emulsion films: A comparative study and preliminary evaluation of surface cleaning. Polymers, 13.10.3390/polym13121941 ↗
24. Pagnin, L., Calvini, R., Sterflinger, K., and Izzo, F.C. (2022). Data Fusion Approach to Simultaneously Evaluate the Degradation Process Caused by Ozone and Humidity on Modern Paint Materials. Polymers, 14.10.3390/polym14091787 ↗
25. Pagnin, L., Zendri, E., and Izzo, F.C. (2022). How Can Ozone and Relative Humidity Affect Artists’ Alkyd Paints? A FT-IR and Py-GC/MS Systematic Study. Polymers, 14.10.3390/polym14091831 ↗
26. Aegerter, M.A., and Mennig, M. (2004). Sol-Gel Technologies for Glass Producers and Users, Springer.10.1007/978-0-387-88953-5 ↗
27. Indoor air quality at the Correr Museum, Venice, Italy10.1016/S0048-9697(99)00262-4 ↗
28. Air quality monitoring in a museum for preventive conservation: Results of a three-year study in the Plantin-Moretus Museum in Antwerp, Belgium10.1016/j.microc.2013.05.006 ↗
29. 20th century artists’ oil paints: The case of the Olii by Lucio Fontana10.1016/j.culher.2013.11.003 ↗
30. Pintus, V., Baragona, A.J., Cappa, F., Haiml, C., Hierl, C., Sterflinger, K., and Schreiner, M. (2022). Multi-Analytical Investigations of Andy Warhol’s “Orange Car Crash”: Polymeric Materials in Modern Paints. Polymers, 14.10.3390/polym14030633 ↗
31. Nguyen, D.K., Bach, Q.-V., Lee, J.-H., and Kim, I.-T. (2018). Synthesis and Irreversible Thermochromic Sensor Applications of Manganese Violet. Materials, 11.10.3390/ma11091693 ↗
32. Structure and vibrational spectra of a new trihydrate diphosphate, MnNH4NaP2O7·3H2O10.1002/jrs.1078 ↗
33. Synthesis, Rietveld refinements, Infrared and Raman spectroscopy studies of the sodium diphosphate NaCryFe1−yP2O7 (0 ≤ y ≤ 1)10.1016/j.molstruc.2015.09.014 ↗
34. Raman spectrum of ammonium di-hydrogen phosphate10.1007/BF03170812 ↗
35. Spectra of phosphorus compounds-The infra-red spectra of orthophosphates10.1016/0371-1951(64)80094-1 ↗
36. Derrick, M.R., Landry, J.M., and Stulik, D.C. (1999). Infrared Spectroscopy in Conservation Science, The Getty Conservation Institute.
37. Thermal Treatment of Kaolin: Effect on the Pozzolanic Activity10.1016/j.mspro.2012.06.046 ↗
38. Raman Spectroscopic Study of Kaolinite in Aqueous Suspension10.1346/CCMN.1985.0330602 ↗
39. Relating highly distorted Jahn–Teller MnO6 to colouration in manganese violet pigments10.1039/c2jm33731b ↗
40. Nicholas Walsh, V.C. (2008). Pigment Compendium: A Dictionary and Optical Microscopy of Historical Pigments, Taylor & Francis Ltd.
41. Wicks, Z.W. (2007). Alkyd Resins. Encyclopedia of Polymer Science and Technology, John Wiley & Sons Ltd.10.1002/0471440264.pst016.pub2 ↗
42. A review of synthetic binding media in twentieth-century paints10.1080/01410096.2000.9995156 ↗
43. Polymer blend systems for water-borne paints10.1016/S0300-9440(98)00021-6 ↗
44. Androver Gracia, I. (2001). Applicazioni Della Spettrofotometria IR allo Studio dei Beni Culturali, Il Prato.
45. Silverstein, R.M., Kiemle, D.J., Webster, F.X., Bryce, D.L., and Zanardi, F. (2016). Identificazione Spettrometrica di Composti Organici, CEA. [3rd ed.].
46. Library of FT-Raman spectra of pigments, minerals, pigment media and varnishes, and supplement to existing library of Raman spectra of pigments with visible excitation10.1016/S1386-1425(00)00495-9 ↗
47. Vibrational Spectroscopies and Chemometry for Nondestructive Identification and Differentiation of Painting Binders10.1155/2017/3475659 ↗
48. Izzo, F.C. (2010). 20th Century Artists’ Oil Paints: A Chemical-Physical Survey. [Ph.D. Thesis, Università Ca’ Foscari Venezia]. Available online: http://dspace.unive.it/handle/10579/1100.
49. Colombini, M.P., and Modugno, F. (2009). Organic Mass Spectrometry in Art and Archaeology, Wiley.10.1002/9780470741917 ↗
50. Tammekivi, E., Vahur, S., Vilbaste, M., and Leito, I. (2021). Quantitative GC-MS Analysis of Artificially Aged Paints with Variable Pigment and Linseed Oil Ratios. Molecules, 26.10.3390/molecules26082218 ↗
51. Pigment and Binder Concentrations in Modern Paint Samples Determined by IR and Raman Spectroscopy10.1002/anie.201713413 ↗
52. Learner, T.J.S. (2004). Analysis of Modern Paints, The Getty Conservation Institute.
53. The Effects of Surface Cleaning on Acrylic Emulsion Paintings: A Preliminary Investigation
54. A preliminary FTIR-based exploration of the surfactant phase-separation process in contemporary mural paintings
55. Structural and Ionic Conductivity Studies on Nanochitosan Incorporated Polymer Electrolytes for Rechargeable Magnesium Batteries10.7598/cst2012.198 ↗
56. de A.; Malek, K. Infrared and Raman spectroscopy of automotive paints for forensic identification of natural weathering10.1039/C7AY02684F ↗
57. Bauer, P., and Buettner, A. (2018). Characterization of Odorous and Potentially Harmful Substances in Artists’ Acrylic Paint. Front. Public Health, 6.10.3389/fpubh.2018.00350 ↗
58. Analytical characterization of artist’s paint systems based on emulsion polymers and synthetic organic pigments10.1016/j.jaap.2018.09.001 ↗
59. Synthesis and evaluation of new anti-microbial additive based on pyrazole and triazole derivative incorporated physically into polyurethane varnish10.21608/ejchem.2014.1030 ↗
60. Chemical Reaction of Sulfur Dioxide at High Humidity and Temperature: Implications for Accelerated Testing10.1149/1.2127480 ↗
61. Infrared spectra of sodium phosphate glasses10.1016/S0022-3093(98)00711-X ↗
62. Vibrational spectroscopy of the sulphate mineral sturmanite from Kuruman manganese deposits, South Africa10.1016/j.saa.2014.04.115 ↗
63. Raman study of cation effect on sulfate vibration modes in solid state and in aqueous solutions10.1002/jrs.4374 ↗
64. IR and polarized Raman spectra of (NH4)2M(SO4)2 · 6H2O(M =Zn, Mn)10.1016/0022-4596(88)90375-1 ↗
65. Jeong, D.I., Kim, S., Koo, J.S., Lee, S.Y., Kim, M., Kim, K.Y., Azad, M.O.K., Karmakar, M., Chu, S., and Chae, B.-J. (2023). Manganese Sulfate Nanocomposites Fabricated by Hot-Melt Extrusion for Chemodynamic Therapy of Colorectal Cancer. Pharmaceutics, 15.10.3390/pharmaceutics15071831 ↗
66. Synthesis of MnPO4·H2O by refluxing process at atmospheric pressure10.1016/j.solidstatesciences.2010.02.014 ↗
67. A Raman and infrared spectroscopic study of the sulphate mineral aluminite Al2(SO4)(OH)4·7H2O10.1016/j.saa.2015.04.011 ↗
68. Raman spectra of some crystalline nitrates and sulphates10.1007/BF03049125 ↗
69. Socrates, G. (2001). Infrared and Raman Characteristic Group Frequencies: Tables and Charts, J. Wiley and Sons. [3rd ed.].
70. Raman Spectroscopic Investigation of Speciation in MnSO4(aq)10.1007/s10953-014-0145-8 ↗
71. Emission of octahedrally coordinated Mn3+ in garnets10.1016/S1386-1425(98)00106-1 ↗
72. Optical Spectra of Transition-Metal Ions in Corundum10.1063/1.1732364 ↗
73. Optical transitions in Mn3+ -doped garnets10.1103/PhysRevB.57.2203 ↗
74. Langbeinite-type (NH4)2Mn2(SO4)310.1107/S1600536805011736 ↗
75. The drying of linseed oil investigated by Fourier transform infrared spectroscopy: Historical recipes and influence of lead compounds10.1016/j.porgcoat.2015.12.010 ↗
76. FTIR study of ageing of fast drying oil colour (FDOC) alkyd paint replicas10.1016/j.saa.2014.03.123 ↗
77. A Critical Review on the Analysis of Metal Soaps in Oil Paintings10.1002/open.202100166 ↗
78. Chemical reaction kinetics of sulfur dioxide and oxygen with unsaturated drying oils
79. Oxidation and Cross-Linking in the Curing of Air-Drying Artists’ Oil Paints10.1021/acsapm.0c01441 ↗
80. Drying and oxidative degradation of linseed oil10.1016/S0141-3910(99)00020-8 ↗
81. Effects of acetic acid vapour on the ageing of alkyd paint layers: Multi-analytical approach for the evaluation of the degradation processes10.1016/j.polymdegradstab.2014.04.010 ↗
82. Evaluation of accelerated weathering tests for three paint systems: A comparative study of their aging behaviour10.1016/S0141-3910(01)00005-2 ↗
83. Accelerated UV ageing studies of acrylic, alkyd, and polyvinyl acetate paints: Influence of inorganic pigments10.1016/j.microc.2015.07.009 ↗
84. Effect of sulfonating agent in the properties of styrene copolymers for PEMFC membranes10.1016/j.ijhydene.2022.07.022 ↗
85. Degradation reactions during sulphonation of poly(styrene-co-acrylic acid) used as membranes10.1016/j.polymdegradstab.2014.06.002 ↗
86. Study of the stability of a series of synthetic colorants applied with styrene-acrylic copolymer, widely used in contemporary paintings, concerning the effects of accelerated ageing10.1016/j.culher.2010.02.003 ↗