Blue pigments

Blue pigments are natural or synthetic materials, traditionally made from minerals. Being water-insoluble by definition, blue pigments used to make the blue colors in inks and paints. Some major blue pigments are indigo, Prussian blue, and copper phthalocyanine.[1] Historically, lapis lazuli was important.

History

The earliest use of blue pigments in Europe uncovered by archeologists were from the Final Palaeolithic (c. 14 000–11 700 BP) open-air site of Mühlheim-Dietesheim (Germany).[2]

The discovery of Egyptian blue (CaCuSi4O10) was promoted by the Egyptian pharaohs who sponsored the creation of new pigments to be used in art.[3] Other civilizations combined organic and mineral materials to create blue pigments ranging from azure-blue like the Maya blue[4] to the Han blue (BaCuSi4O10), which was developed by the Chinese Han dynasty and manipulated to produce a light or dark blue color.[5]

Cobalt blue (CoAl2O4) was first described in 1777. Very stable, it has been traditionally used as a coloring agent in ceramics.[4][6][7][8] Ultramarine (Na7Al6Si6O24S3) was made by grinding the forbiddingly expensive lapis lazuli into a powder until a cheaper synthetic form was invented in 1826 by the French industrialist Jean Baptiste Guimet and in 1828 by the German chemist Christian Gmelin.[9] Prussian blue (Fe4[Fe(CN)6]3) was first described by the German polymath Johann Leonhard Frisch and the president of the Prussian Academy of Sciences, Gottfried Wilhelm Leibniz, in 1708.[10][11] Azurite (Cu3(CO3)2(OH)2) is a soft, deep-blue copper mineral produced by weathering copper ore deposits; it was used since ancient times and was first recorded by the first century Roman writer Pliny the Elder.[12] Phthalocyanine Blue BN was first prepared in 1927 and has wide range of applications.

Major contemporary blue pigments

Indigo

Although sometimes considered a dye, indigo is a pigment (insoluble in water). Unlike many traditional mineral-based blues, indigo is an organic compound. It was once obtained by laborious extraction from various plants. Subsequent to the discovery of synthetic dyes, such as mauvine, a chemical route was discovered to this material. In 2022, about 20,000 tonnes were produced, making indigo the dominant blue pigment in terms of volume. It is mainly used for the production of blue jeans.[13] It is also used as a food colorant, and is listed in the United States as FD&C Blue No. 2.

Copper phthalocyanine

Copper phthalocyanine ("phthalo blue") is a synthetic blue pigment frequently used in paints, inks, and dyes. It is highly valued for its superior properties such as light fastness, tinting strength, covering power and resistance to the effects of alkalis and acids. It has the appearance of a blue powder, insoluble in most solvents including water.[14]

Prussian blue

Prussian blue (PB) is a dark blue pigment containing iron and cyanide produced by the oxidation of ferrous ferrocyanide salts. In crude but reproducible form, it was invented in Berlin between 1704 and 1710. It had an immediate impact on the pigment market, because its intense deep blue color approached the quality of ultramarine at a much lower price and superior longevity. Subsequent work led to a rational route to well defined PB. In 1995, an estimated 13 000–15 000 tons were produced, mainly for printing inks

PB was also widely adopted by major European artists, notably Thomas Gainsborough and Canaletto, who used it to paint the Venetian sky.[15] It was also used by Japanese artists, including Hokusai, for the deeper blues of waves.

Ultramarine

Ultramarine was historically a prestigious and expensive blue pigment. It was produced from lapis lazuli, a mineral whose major source was the mines of Sar-e-Sang in what is now northeastern Afghanistan.[16] It is now produced industrially by heating aluminosilicates with sulfur. It is widely used in coloring plastics. paints, laundry applications, cosmetics, and toys. The 1990 estimated production was 20 000 tons.[1]

It was the most expensive blue used by Renaissance artists (because it was imported from Afghanistan). It was often reserved for special purposes, such as painting the robes of the Virgin Mary.[17] Johannes Vermeer used ultramarine only for the most important surfaces where he wanted to attract attention. Pietro Perugino, in his depiction of the Madonna and Child on the Certosa de Pavio Altarpiece, painted only the top level of the Virgin's robes in ultramarine, with azurite beneath.[18]

Ultramarine became more widely used after its synthesis in the 19th century, which lowered its price substantially.[19] Synthetic ultramarine was widely appreciated by the French impressionists, and Vincent van Gogh used both French ultramarine and cobalt blue for his painting The Starry Night (1889).[20]

Cobalt blue

Cobalt blue is a synthetic blue pigment was invented in 1803 as a rival to ultramarine. It was made by the process of sintering, that is by compacting and forming a solid mass of material by heat or pressure without melting it to the point of liquefaction. It combined cobalt(II) oxide with aluminum(III) oxide (alumina) at 1200 °C. It was also used as colorant, particularly in blue glass and as the blue pigment used for centuries in Chinese blue and white porcelain, beginning in the late eighth or early ninth century.[21]

Cobalt glass, or smalt, is a variation of cobalt blue. It is made of ground blue potassium glass containing cobalt blue. It was widely used in painting in the 16th and the 17th centuries. Smalt was popular because of its low cost; it was widely used by Dutch and Flemish painters, including Hans Holbein the Younger.[22]

YInMn Blue

YInMn Blue is an inorganic pigment was discovered only in 2009.[4][23] It has been used in water, oil, and acrylic paints from paint vendors.

Obsolete, disused, and minor blue pigments

Egyptian blue

Egyptian blue was the first synthetic blue pigment. It was made from a mixture of silica, lime, copper salts, and an alkali. It was widely used in The Fourth Dynasty of ancient Egypt (c. 2613 to 2494 BC).[24] Egyptian blue is responsible for the blue colour seen very commonly in Egyptian faience. It is no longer used.

  • Egyptian blue
  • Temple of Hathor ceiling relief, Dendera (c. 22-21 BC)
  • Faience senet board belonging to Amenhotep III (c. 1390-1353 BC)
  • Faience pyxis from northern Syria (c. 750-700 BC)

Azurite

Azurite pigment is derived from the soft, deep-blue copper mineral of the same name, which forms from the weathering of copper ore deposits. It was mentioned in Pliny the Elder's Natural History under the Greek name kuanos (κυανός: "deep blue," root of English cyan) and the Latin name caeruleum. The modern English name of the mineral reflects this association, since both azurite and azure are derived via Arabic from the Persian lazhward (لاژورد), an area known for its deposits of another deep-blue stone, lapis. Azurite was often used in the Renaissance and later as a less expensive substitute for ultramarine. Lower layers would be painted in azurite, with the most visible portions painted in ultramarine. The drawback of the pigment is that it degrades and darkens over time.[25]

Han blue

Han blue (also called Chinese blue) is a synthetic barium copper silicate pigment used in ancient and imperial China from the Western Zhou period (1045–771 BC) until the end of the Han dynasty (circa 220 AD). Han blue and the chemically related Han purple were used to decorate hu vessels during the Han dynasty, and were also used for mural paintings in tombs of the same period.[26]

  • Fresco mural, Temple of the Murals at Bonampak (c. 790)
  • Pages 34–36 of the Madrid Codex (c. 1200–1500)
  • Ceiling mural at the Convento de la Asunción Tecamachalco, Puebla (1562)
    Juan Gerson

Maya blue

Maya blue is a synthetic turquoise-blue pigment made by infusing indigo pigments (particularly those derived from the anil shrub) into palygorskite, a clay that binds and stabilises the indigo such that it becomes resistant to weathering.[27] Developed in Mesoamerica in the first millennium AD, it saw wide use in the region, most prominently in the art of the Maya civilisation. It is known on media from pottery to murals to codices, and also played an important role in ritual sacrifices of both objects and people: silt at the bottom of the Sacred Cenote at Chichén Itzá is heavily stained with Maya blue, washed off the hundreds of sacrificial offerings cast into the cenote during the city's occupation.[28] Maya blue continued to be used into the Spanish colonial period; though falling out of widespread use in the Maya region during the 16th century, some areas apparently continued to produce it for export, as Cuban colonial paintings of the 18th and 19th century have been found to make use of Maya blue probably imported from Campeche.[29]

Cerulean blue

Cerulean blue was created in 1789 by the Swiss chemist Albrecht Höpfner.[30] Subsequently, there was a limited German production under the name of Cölinblau. The primary chemical constituent of the pigment is cobalt(II) stannate (Co
2SnO
4).[31]

See also

Notes and citations

  1. ^ a b Buxbaum, Gunter; Printzen, Helmut; Mansmann, Manfred; Räde, Dieter; Trenczek, Gerhard; Wilhelm, Volker; Schwarz, Stefanie; Wienand, Henning; Adel, Jörg; Adrian, Gerhard; Brandt, Karl; Cork, William B.; Winkeler, Heinrich; Mayer, Wielfried; Schneider, Klaus (2009). "Pigments, Inorganic, 3. Colored Pigments". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.n20_n02. ISBN 978-3527306732.
  2. ^ Wisher, Izzy; Birch, Thomas; Andreasen, Rasmus; Canosa, Elyse; Norrehed, Sara; Reguer, Solenn; Lemasson, Quentin; Oras, Ester; Johanson, Kristiina; Kinnaird, Tim; Birndorfer, Thomas; Pedersen, Jesper Borre; Scott, James; Pearce, Christof; Riede, Felix (2025). "The earliest evidence of blue pigment use in Europe". Antiquity. 99 (408): 1464–1479. doi:10.15184/aqy.2025.10184. ISSN 0003-598X.
  3. ^ Jaksch, H.; et al. (November 1983). "Egyptian blue — Cuprorivaite a window to ancient Egyptian technology". Naturwissenschaften. 70 (11): 525–535. Bibcode:1983NW.....70..525J. doi:10.1007/BF00376668. ISSN 1432-1904. S2CID 2457936.
  4. ^ a b c Smith, Andrew E.; Mizoguchi, Hiroshi; Delaney, Kris; Spaldin, Nicola A.; Sleight, Arthur W.; Subramanian, M. A. (2009). "Mn3+ in Trigonal Bipyramidal Coordination: A New Blue Chromophore". J. Am. Chem. Soc. 131: 17084–17086. doi:10.1021/ja9080666. PMID 19899792.
  5. ^ Berke, Heinz (18 April 2007). "The Invention of Blue and Purple Pigments in Ancient Times". ChemInform. 38 (19). doi:10.1002/chin.200719227.
  6. ^ Parmelee, Cullen Warner & Harman, Cameron Gerald (1973). Ceramic Glazes. Cahners Books. p. 491. ISBN 978-0-8436-0609-6.
  7. ^ Needham, Joseph; et al. (2004). Science and Civilisation in China. Cambridge University Press. p. 659. ISBN 978-0-521-83833-7.
  8. ^ Maerz, A. & Paul, M. Rea (1930). A dictionary of color. New York: McGraw-Hill Book Co. OCLC 1150631.
  9. ^ Gmelin, C. G. (1828). "Ueber die künstliche Darstellung einer dem Ultramarin ähnlichen Farbe" [On the artificial preparation of a pigment similar to ultramarine]. Naturwissenschaftliche Abhandlungen. Herausgeben von Einer Gesellschaft in Würtemberg (Scientific Essays. Published by a Society in Würtemberg) (in German). 2 (10): 191–224. Bibcode:1828AnP....90..363.. doi:10.1002/andp.18280901022.
  10. ^ Woodward, John (1724). "IV. Præparatio cærulei prussiaci ex germaniâ missa ad Johannem Woodward, M. D. Prof. Med. Gresh. R. S. S." Philosophical Transactions of the Royal Society of London. 33 (381): 15–17. doi:10.1098/rstl.1724.0005.
  11. ^ Frisch, Johann Leonard; et al. (1976) [1896]. Der Briefwechsel mit Gottfried Wilhelm Leibniz [Correspondence with Gottfried Wilhelm Leibniz] (in German). Hildesheim: G. Olms. ISBN 978-3-487-06071-2. OCLC 3303263.
  12. ^ Zigan, F. & Schuster, H. D. (1972). "Verfeinerung der Struktur von Azurit, Cu3(OH)2(CO3)2, durch Neutronenbeugung" [Refinement of the structure of azurite Cu3(OH)2(CO3)2 by neutron diffraction]. Zeitschrift für Kristallographie (in German). 135 (5–6): 416–436. Bibcode:1972ZK....135..416Z. doi:10.1524/zkri.1972.135.5-6.416. ISSN 0044-2968. S2CID 95738208.
  13. ^ Paul, Roshan; Blackburn, Richard S.; Bechtold, Thomas (2021). "Indigo and Indigo Colorants". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a14_149.pub3. ISBN 3527306730.
  14. ^ Löbbert, Gerd (2000). "Phthalocyanines". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a20_213. ISBN 978-3-527-30673-2..
  15. ^ Bomford and Roy, A Closer Look – Colour, the National Gallery, London (2009), p. 37
  16. ^ Bomford and Roy, A Closer Look at Colour (2009), pp. 28–37
  17. ^ Varichon, (2005) p. 164
  18. ^ Pastoureau, Michel, Bleu – Histoire d'une couleur (2000), p. 100
  19. ^ Maerz and Paul (1930). A Dictionary of Color New York: McGraw Hill p. 206
  20. ^ Yonghui Zhao, Roy S. Berns, Lawrence A. Taplin, James Coddington, "An Investigation of Multispectral Imaging for the Mapping of Pigments in Paintings", in Proc. SPIE 6810, Computer Image Analysis in the Study of Art, 681007 (29 February 2008)
  21. ^ "Chinese pottery: The Yuan dynasty (1206–1368)". Archived 2017-12-29 at the Wayback Machine Encyclopædia Britannica Online. Accessed 7 June 2018.
  22. ^ Smalt Pigments through the Ages
  23. ^ Cascone, Sarah (20 June 2016). "The Chemist Who Discovered the World's Newest Blue Explains Its Miraculous Properties". Artnet News. Archived from the original on 4 April 2020.
  24. ^ McCouat, Philip (2018). "Egyptian blue: The colour of technology". artinsociety.com. Journal of Art in Society. Archived from the original on 2019-03-28. Retrieved 2019-05-29.
  25. ^ Gettens, R.J. and Fitzhugh, E.W., Azurite and Blue Verditer, in Artists’ Pigments. A Handbook of Their History and Characteristics, Vol. 2: A. Roy (Ed.) Oxford University Press 1993, p. 23–24
  26. ^ FitzHugh, E. W. and Zycherman, L. A. 1992. A Purple Barium Copper Silicate Pigment from Early China. Studies in Conservation 28/1, 15–23.
  27. ^ Sánchez del Río, M.; Doménech, A.; Doménech-Carbó, M. T.; Vázquez de Agredos Pascual, M. L.; Suárez, M.; García-Romero, E. (2011). "18". In Galàn, E.; Singer, A. (eds.). Developments in Clay Science 3: Developments in Palygorskite-Sepiolite Research. Elsevier. pp. 453–481. ISBN 978-0-444-53607-5.
  28. ^ Arnold, D. E.; Branden, J. R.; Williams, P. R.; Feinman, G. M.; Brown, J. P. (2008). "The first direct evidence for the production of Maya Blue: rediscovery of a technology". Antiquity. 82 (315): 151–164. doi:10.1017/s0003598x00096514.
  29. ^ Tagle, A. A.; Paschinger, H.; Richard, H.; Infante, G. (1990). "Maya blue: its presence in Cuban colonial wall paintings". Studies in Conservation. 35 (3): 156–159. doi:10.1179/sic.1990.35.3.156.
  30. ^ Höpfner, Albrecht (1789). "Einige kleine Chymische Versuche vom Herausgeber". Magazin für die Naturkunde Helvetiens. 4: 41–47.
  31. ^ "Cerulean blue - Overview". webexhibits.org. Pigments through the Ages. Retrieved 20 November 2017.

Bibliography

  • Pastoureau, Michel (2000). Bleu : Histoire d'une couleur (in French). Paris: Editions du Seuil. ISBN 978-2-02-086991-1.
  • Varichon, Anne (2005). Couleurs : pigments et teintures dans les mains des peuples (in French). Paris: Editions du Seuil. ISBN 978-2-02-084697-4.
  • Bomford, David; Roy, Ashok (2009). A Closer Look - Colour. London: National Gallery. ISBN 978-1857094428.
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