Ultramarine Blue in Edvard Munch’s Collection: A Multi-Analytical Study of Early 20th Century Commercial Oil Paints
Abstract
:1. Introduction
1.1. Industrial Manufacturing of Modern Paints
1.2. An Overview on Ultramarine Blue Pigment
2. Experimental Section
2.1. Sampling
2.2. Hirox 3D Microscope Acquisition
2.3. ATR-FTIR Spectroscopy
2.4. μ-Raman Spectroscopy
2.5. SEM-EDS
2.6. GC-MS
3. Results
3.1. Paint Surface Observations in Two Paintings
3.2. Micro-Invasive Analyses
3.3. SEM-EDS
3.4. GC-MS
4. Discussion
4.1. Characterization of Pigments, Binding Media, and Additives Present in Industrial Paint Tubes
4.2. Considerations on the Darkening Observed in Paintings in Relation to the Composition of Paint Tubes from Munch’s Collection
5. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Tube ID | Color on Label | Binder on Original Label | Brand | Production Coutry | Analyses Performed |
---|---|---|---|---|---|
MM.I.01638 | Blau outremer extra | oil | Ambor | France | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.1632 | Blau outremer extra | oil | Ambor | France | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.02126 | Outremer N 2 clair | oil | Lefranc | France | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.01959 | Bleu d’outremer | oil | Blockx Fils | Belgium | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.02219 | Ultramarin dunkel | oil | Mussini Ölfarben Schmincke | Germany | ATR-FTIR, µ-RAMAN, GC-MS, SEM-EDS |
MM.I.02330 | Ultramarin, extra | oil | Vilhem Pacht | Denmark | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.02384 | Light ultramarin | oil | Winsor & Newton | England | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.02387 | Brilliant ultramarin | oil | Winsor & Newton | England | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.02354 | Brilliant ultramarin | oil | Winsor & Newton | England | ATR-FTIR, µ-RAMAN, GC-MS |
MM.I.02424 | Deep ultramarine | oil | Winsor & Newton | England | ATR-FTIR, µ-RAMAN, GC-MS |
ID Tube | Analytical Results | Pigments and Other Inorganic Compounds |
---|---|---|
MM.I.01638—Ambor | ATR-FTIR: 980 cm−1, 3699 cm−1, 3619 cm−1, 1098 cm−1, 629 cm−1, 1404 cm−1, 1086 cm−1, 871 cm−1 Raman: 1088 cm−1, 547 cm−1, 280 cm−1, 252 cm−1 | Ultramarine blue, Calcium carbonate, kaolinite |
MM.I.01632—Ambor | ATR-FTIR: 980 cm−1, 1404 cm−1, 1086 cm−1, 871 cm−1 Raman: 547 cm−1, 252 cm−1, 401 cm−1, 217 cm−1 | Ultramarine blue, sulphates, calcium carbonate, Fe oxides? |
MM.I.01959—Blockx Fils | ATR-FTIR: 980 cm−1, 1404 cm−1, 1086 cm−1, 871 cm−1 Raman: 547 cm−1, 252 cm−1 | Ultramarine blue, Calcium carbonate |
MM.I.02126—Lefranc | ATR-FTIR: 980 cm−1, 1480 cm−1, 1421 cm−1, 884 cm−1, 854 cm−1, 800 cm−1 Raman: 547 cm−1, 252 cm−1 | Ultramarine blue, Mg carbonate |
MM.I.02330—Vilhem Pacht | ATR-FTIR: 980 cm−1, 1620 cm−1, 1370 cm−1, 1315 cm−1, 370 cm−1 Raman: 547 cm−1, 252 cm−1 | Ultramarine blue, Zn white, Zn oxalates |
MM.I.02219—Mussini | ATR-FTIR: 980 cm−1 Raman: 547 cm−1, 252 cm−1 SEM-EDS: Pb, Si, Al, Na, C, O | Ultramarine blue, Lead white |
MM.I.02424—Winsor & Newton | ATR-FTIR: 2080 cm−1, 1611 cm−1, 1480 cm−1, 1421 cm−1, 884 cm−1, 854 cm−1, 800 cm−1 Raman: 2150 cm−1, 2120 cm−1 | Prussian blue, Carbon, Mg carbonate |
MM.I.02384—Winsor & Newton | ATR-FTIR: 980 cm−1, 1480 cm−1, 1421 cm−1, 884 cm−1, 854 cm−1, 800 cm−1 Raman: 547 cm−1, 252 cm−1 | Ultramarine blue, Mg carbonate |
MM.I.02354—Winsor & Newton | ATR-FTIR: 980 cm−1, 1480 cm−1, 1421 cm−1, 884 cm−1, 854 cm−1, 800 cm−1 Raman: 547 cm−1, 252 cm−1 | Ultramarine blue, Mg carbonate |
MM.I.02387—Winsor & Newton | ATR-FTIR: 980 cm−1, 1480 cm−1, 1421 cm−1, 884 cm−1, 854 cm−1, 800 cm−1 Raman: 547 cm−1, 252 cm−1 | Ultramarine blue, Mg carbonate |
ID Tube | Analytical Results | Binding Admixtures and Other Organic Compounds |
---|---|---|
MM.I.01638—Ambor | ATR-FTIR: 2925 cm−1, 2855–2850 cm−1, 1740 cm−1, 1710 cm−1, 1625 cm−1, 1460 cm−1, 1410–15 cm−1, 1242 cm−1, 1165–60 cm−1 Raman: 3100–3000 cm−1, 3000–2800 cm−1, 2885–2880 cm−1, 2855–2850 cm−1, 1720 cm−1, 1690 cm−1, 1660 cm−1, 1610–1600 cm−1, 1440–30 cm−1, 1380 cm−1, ~1300 cm−1, 1296 cm−1, 1136 cm−1, 1065–60 cm−1, 1549 cm−1, 1529 cm−1, 1457 cm−1, 1409 cm−1, 1397 cm−1 GC-MS: tetradehydroabietic, 7-methoxy- | Safflower/sunflower oil, Pinaceae resin, free fatty acids, Zn oleate |
MM.I.01632—Ambor | ATR-FTIR: oil as above Raman: oil as above, 1458 cm−1, 1439 cm−1 GC-MS: tetradehydroabietic, 7-methoxy-, margaric, pentadecanoiic acid | Sunflower oil + castor oil + fish liver oil? Pinaceae resin, Animal fats, levulinic acid, metal soaps |
MM.I.01959—Blockx Fils | ATR-FTIR: oil as above Raman: oil as above GC-MS: Aleuritic acid | Safflower oil?, Shellac resin, Free fatty acids |
MM.I.02126—Lefranc | ATR-FTIR: oil as above Raman: oil as above GC-MS: Lignoceric, behenic, levulinic acids | Peanut oil + Sunflower oil?, Levulinic acid |
MM.I.02330—Vilhem Pacht | ATR-FTIR: oil as above Raman: oil as above GC-MS: levulinic, margaric, aleuritic acids | Sunflower/peanut oil?, Shellac resin, levulinic acid, margaric acid |
MM.I.02219—Mussini | ATR-FTIR: oil as above Raman: oil as above, 1460 cm−1, 1441 cm−1, 1416 cm−1, 1297 cm−1, 1129 cm−1, 1101 cm−1, 1063 cm−1 SEM-EDS: Pb, Si, Al, Na, C, O GC-MS: tetradehydroabietic, 7-methoxy-, margaric, pentadecanoic, behenic, lignoceric, cerotic, melissic acids | Sunflower oil + Peanut oil, Animal fats, Pinaceae resin, Levulinic acid, Lead soaps, (Lead palmitate) |
MM.I.02424—Winsor & Newton | ATR-FTIR: oil as above Raman: oil as above GC-MS: tetradehydroabietic, 7-methoxy-, behenic, lignoceric, erucic, cerotic, melissic acids | Oil + Peanut oil, Animal fats, Pinaceae resin, beeswax |
MM.I.02384—Winsor & Newton | ATR-FTIR: oil as above, ~1500 cm−1 Raman: oil as above, 1430 cm−1, ~1290 cm−1, ~1130 cm−1, ~1060 cm−1 GC-MS: Aleuritic, margaric, pentadecanoic acids | Sunflower oil?, Shellac resin, Animal fats, metal soaps |
MM.I.02354—Winsor & Newton | ATR-FTIR: oil as above Raman: oil as above GC-MS: margaric, pentadecanoic. Aleuritic, levulinic acids | Sunflower oil, Animal fats, Shellac resin, Levulinic acid, metal soaps |
MM.I.02387—Winsor & Newton | ATR-FTIR: oil as above, ~1500 cm−1 Raman: oil as above, 1430 cm−1, ~1290 cm−1, ~1130 cm−1, ~1060 cm−1 GC-MS: behenic, lignoceric, margaric, pentadecanoic, levulinic acids | Oil + Peanut oil, Animal fats, Levulinic acid, metal soaps |
Detected Compound | AMBOR | BLOCKX FILS | LEFRANC | VILH. PACHT | MUSSINI | WINSOR & NEWTON | |||||
---|---|---|---|---|---|---|---|---|---|---|---|
MM.I.01638 | MM.I.01632 | MM.I.01959 | MM.I.02126 | MM.I.02330 | MM.I.02219 | MM.I.02424 | MM.02384 | MM.I.02354 | MM.I.02387 | ||
Compounds detected | Pimelic acid, methyl ester | v | v | v | v | v | v | v | v | ||
Levulinic acid, methyl ester | v | v | v | v | v | ||||||
Octanoic acid, 8-hydroxy-, methyl ester | v | v | v | v | |||||||
Decanoic acid, 9-oxo-ME | v | v | v | v | |||||||
Caprylic acid, methyl ester | v | v | |||||||||
8-Methoxytetradecanoic acid | v | v | v | v | v | v | |||||
Undecanedioic acid, 4-oxo-, dimethyl ester | v | v | v | v | |||||||
Butanoic acid, methyl ester | v | v | v | v | v | v | v | v | v | ||
Pentadecanoic acid, methyl ester | v | v | v | v | v | v | v | ||||
Palmitoleic acid, methyl ester | v | v | v | v | v | v | v | v | |||
Aleuritic acid, methyl ester, trimethyl eter | v | v | v | v | v | v | |||||
3-Oxo-1,8-octanedicarboxylic acid, dimethyl ester | v | v | v | v | v | v | v | v | |||
Margaric acid, methyl ester | v | v | v | v | v | v | v | ||||
Octadecanoic acid, 9,10-epoxy-, methyl ester | v | v | v | v | v | v | v | ||||
Octadecanoic acid, 10-oxo-, methyl ester | v | v | v | v | v | v | v | v | |||
Octadecanoic acid, 9,10-dihydroxy-, methyl ester | v | v | v | v | v | v | v | v | v | v | |
Tetradehydroabietic, 7-methoxy-, methyl ester | v | v | v | v | |||||||
Eicosane, methyl ester | |||||||||||
Ethyl stearate, 9,12-diepoxy | v | ||||||||||
Erucic acid,methyl ester | v | ||||||||||
Behenic acid, methyl ester | v | v | v | v | v | v | v | ||||
Methyl Ricinoleate | v | ||||||||||
Heptacosane, methyl ester | |||||||||||
Lignoceric acid, methyl ester | v | v | v | v | v | ||||||
Hexacosanoic, methyl ester | v | ||||||||||
Docosane, methyl ester | |||||||||||
Cerotic acid, methyl ester | v | v | |||||||||
Hentriacontane, methyl ester | |||||||||||
Melissic acid, methyl ester | v |
Detected Compound | AMBOR | BLOCKX FILS | LEFRANC | VILH. PACHT | MUSSINI | WINSOR & NEWTON | |||||
---|---|---|---|---|---|---|---|---|---|---|---|
MM.I.01638 | MM.I.01632 | MM.I.01959 | MM.I.02126 | MM.I.02330 | MM.I.02219 | MM.I.02424 | MM.02384 | MM.I.02354 | MM.I.02387 | ||
Fatty acids (W%) | Suberic acid, methyl ester | 11.22 | 17.80 | 13.44 | 5.77 | 5.88 | 15.31 | 6.01 | 10.54 | 5.14 | 7.94 |
Azelaic acid, methyl ester | 29.57 | 39.76 | 31.61 | 24.67 | 17.85 | 32.47 | 14.76 | 34.11 | 22.16 | 20.10 | |
Sebacic acid, methyl ester | 4.24 | 7.08 | 4.60 | 1.56 | 1.62 | 4.00 | 2.61 | 5.34 | 1.79 | 2.60 | |
Myristic acid, methyl ester | 1.11 | 1.37 | 1.47 | 1.62 | 1.59 | 1.85 | 1.13 | 1.66 | 1.42 | 1.49 | |
Palmitic acid, methyl ester | 15.52 | 13.53 | 19.97 | 26.13 | 27.40 | 25.78 | 18.61 | 16.84 | 22.76 | 34.87 | |
Oleic acid, methyl ester | 13.43 | 7.48 | 3.53 | 18.29 | 21.78 | 1.05 | 27.81 | 3.82 | 21.09 | 7.21 | |
Stearic acid,methyl ester | 6.16 | 6.09 | 8.44 | 11.52 | 12.82 | 11.73 | 17.91 | 14.78 | 11.38 | 19.09 | |
Linoleic acid, methyl ester | 1.43 | 0.82 | - | 0.93 | 0.03 | 0.13 | 1.98 | 0.09 | 0.30 | 0.97 | |
Linolenic acid, methyl ester | 1.02 | 0.90 | - | - | - | 0.33 | 0.18 | - | 0.24 | 0.12 | |
Glycerol | 16.29 | 5.16 | 16.93 | 9.51 | 11.02 | 7.35 | 9.00 | 12.82 | 13.71 | 5.60 | |
Molar ratios among fatty acids | A/P | 1.91 | 2.94 | 1.58 | 0.94 | 0.65 | 1.26 | 0.79 | 2.03 | 0.97 | 0.58 |
P/S | 2.52 | 2.22 | 2.37 | 2.27 | 2.14 | 2.20 | 1.04 | 1.14 | 2.00 | 1.83 | |
%D | 45.03 | 64.65 | 49.65 | 32.00 | 25.36 | 51.78 | 23.39 | 49.99 | 29.09 | 30.64 | |
O/S | 2.18 | 1.23 | 0.42 | 1.59 | 1.70 | 0.09 | 1.55 | 0.26 | 1.85 | 0.38 | |
A/Sub | 2.64 | 2.23 | 2.35 | 4.28 | 3.03 | 2.12 | 2.46 | 3.24 | 4.31 | 2.53 |
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Boracchi, B.G.; Ferrer, E.-J.S.; Gnemmi, M.; Falchi, L.; Izzo, F.C.; Sandu, I.C.A. Ultramarine Blue in Edvard Munch’s Collection: A Multi-Analytical Study of Early 20th Century Commercial Oil Paints. Heritage 2024, 7, 4027-4044. https://doi.org/10.3390/heritage7080190
Boracchi BG, Ferrer E-JS, Gnemmi M, Falchi L, Izzo FC, Sandu ICA. Ultramarine Blue in Edvard Munch’s Collection: A Multi-Analytical Study of Early 20th Century Commercial Oil Paints. Heritage. 2024; 7(8):4027-4044. https://doi.org/10.3390/heritage7080190
Chicago/Turabian StyleBoracchi, Beatrice G., Eun-Jin Strand Ferrer, Margherita Gnemmi, Laura Falchi, Francesca Caterina Izzo, and Irina Crina Anca Sandu. 2024. "Ultramarine Blue in Edvard Munch’s Collection: A Multi-Analytical Study of Early 20th Century Commercial Oil Paints" Heritage 7, no. 8: 4027-4044. https://doi.org/10.3390/heritage7080190