Ultramarine

Ultramarine is a deep blue color pigment which was originally

Ultramarine
made by grinding lapis lazuli into a powder.[2] The name comes
from the Latin ultramarinus, literally "beyond the sea", because
the pigment was imported into Europe from mines in Afghanistan Color coordinates
by Italian traders during the 14th and 15th centuries.[3] Hex triplet #120A8F
sRGBB (r, g, b) (18, 10, 143)
Ultramarine was the finest and most expensive blue used by
Renaissance painters. It was often used for the robes of the Virgin CMYKH (c, m, y, k) (87, 93, 0, 44)
Mary, and symbolized holiness and humility. It remained an HSV (h, s, v) (244°, 93%, 56%)
extremely expensive pigment until a synthetic ultramarine was
Source [1]
invented in 1826.
ISCC–NBS Vivid blue
descriptor

Contents B: Normalized to [0–255] (byte)

H: Normalized to [0–100] (hundred)
Chemistry
Production
Structure and classification of ultramarines
Applications
History
In the Middle Ages and the Renaissance
In the 17th and 18th century
19th century – the invention of synthetic ultramarine
General terminology
See also
Notes
Synthetic ultramarine pigment
Further reading
External links

Chemistry
The pigment consists primarily of a zeolite-based mineral containing small amounts of polysulfides. It occurs
in nature as a proximate component of lapis lazuli containing a blue cubic mineral called lazurite. In the Colour
Index International, the pigment of ultramarine is identified as P. Blue 29 77007.[4] The major component of
lazurite is a complex sulfur-containing sodium-silicate (Na8–10 Al6 Si6 O24 S2–4 ), which makes ultramarine the
most complex of all mineral pigments.[5] Some chloride is often present in the crystal lattice as well. The blue
color of the pigment is due to the S−3 radical anion, which contains an unpaired electron.[6]

Production
The raw materials used in the manufacture of synthetic ultramarine are the following:
 white kaolin,
anhydrous sodium sulfate (Na2SO4),
anhydrous sodium carbonate (Na2CO3),
powdered sulfur,
powdered charcoal or relatively ash-free coal, or colophony in lumps.[7]

The preparation is typically made in steps:

The first part of the process takes place at 700 to 750 °C in a closed furnace, so that sulfur,
carbon and organic substances give reducing conditions. This yields a yellow-green product
sometimes used as a pigment.
In the second step, air or sulfur dioxide at 350 to 450 °C is used to oxidise sulfide in the
intermediate product to S2 and Sn chromophore molecules, resulting in the blue (or purple, pink
or red) pigment.[8]
The mixture is heated in a kiln, sometimes in brick-sized amounts.
The resultant solids are then ground and washed, as is the case in any other insoluble
pigment's manufacturing process; the chemical reaction produces large amounts of sulfur
dioxide. (Flue-gas desulfurization is thus essential to its manufacture where SO2 pollution is
regulated.)

"Ultramarine poor in silica" is obtained by fusing a mixture of soft clay, sodium sulfate, charcoal, sodium
carbonate and sulfur. The product is at first white, but soon turns green "green ultramarine" when it is mixed
with sulfur and heated. The sulfur burns, and a fine blue pigment is obtained. "Ultramarine rich in silica" is
generally obtained by heating a mixture of pure clay, very fine white sand, sulfur and charcoal in a muffle
furnace. A blue product is obtained at once, but a red tinge often results. The different ultramarines—green,
blue, red and violet—are finely ground and washed with water.[7]

Synthetic ultramarine is a more vivid blue than natural ultramarine, since the particles in synthetic ultramarine
are smaller and more uniform than the particles in natural ultramarine and therefore diffuse light more
evenly.[9] Its color is unaffected by light nor by contact with oil or lime as used in painting. Hydrochloric acid
immediately bleaches it with liberation of hydrogen sulfide. Even a small addition of zinc oxide to the reddish
varieties especially causes a considerable diminution in the intensity of the color.[7]
 Lapis lazuli specimen Natural ultramarine Synthetic ultramarine blue
(rough), Afghanistan

Synthetic ultramarine
violet

Structure and classification of ultramarines

Ultramarine is the aluminosilicate zeolite with a sodalite structure. Sodalite consists of interconnected
aluminosilicate cages. Some of these cages contain polysulfide (Sn−
x ) groups that are the chromophore (color
+
centre). The negative charge on these ions is balanced by Na ions that also occupy these cages.[6]

The chromophore is proposed to be S−4 or S4 .[6]

Applications
Synthetic ultramarine, being very cheap, is largely used for wall painting, the printing of paper hangings and
calico, etc., and also as a corrective for the yellowish tinge often present in things meant to be white, such as
linen, paper, etc. Bluing or "Laundry blue" is a suspension of synthetic ultramarine (or the chemically different
prussian blue) that is used for this purpose when washing white clothes. It is also often found in make-up such
as mascaras or eye shadows. Large quantities are used in the manufacture of paper, and especially for
producing a kind of pale blue writing paper which was popular in Britain.[7] During World War I, the RAF
painted the outer roundels with a color made from Ultramarine Blue. This became BS 108(381C) Aircraft
Blue. It was replaced in the 1960s by a new color made on Phthalocyanine Blue, BS110(381C) Roundel Blue.

History
The name derives from Middle Latin ultramarinus, literally "beyond the sea" because it was imported from
Asia by sea.[3] In the past, it has also been known as azzurrum ultramarine, azzurrum transmarinum, azzuro
oltramarino, azur d'Acre, pierre d'azur, Lazurstein. Current terminology for ultramarine includes natural
ultramarine (English), outremer lapis (French), Ultramarin echt (German), oltremare genuino (Italian), and
ultramarino verdadero (Spanish). The first recorded use of ultramarine as a color name in English was in
1598.[10]

The first noted use of lapis lazuli as a pigment can be seen in the 6th and 7th-century AD cave paintings in
Afghanistani Zoroastrian and Buddhist temples, near the most famous source of the mineral. Lapis lazuli has
also been identified in Chinese paintings from the 10th and 11th centuries, in Indian mural paintings from the
11th, 12th, and 17th centuries, and on Anglo-Saxon and Norman illuminated manuscripts from c.1100.

In the Middle Ages and the Renaissance

 The Wilton Diptych (1395– The blue robes of the Pietro Perugino
1399) is an example of the Virgin Mary by economized on this
use of ultramarine in 14th Masaccio (1426) were painting of the Virgin
century England painted with Mary (about 1500) by
ultramarine. using azurite for the
underpainting of the
robe, then adding a
layer of ultramarine on
top.

Titian made dramatic use of ultramarine in the

sky and draperies of Bacchus and Ariadne
(1520–23).

During the Renaissance, ultramarine was the finest and most expensive blue that could be used by painters.
The 15th century artist Cennino Cennini wrote in his painters' handbook: "Ultramarine blue is a glorious,
lovely and absolutely perfect pigment beyond all the pigments. It would not be possible to say anything about
or do anything to it which would not make it more so."[11] Natural ultramarine is the most difficult pigment to
grind by hand, and for all except the highest quality of mineral, sheer grinding and washing produces only a
pale grayish blue powder.[12][13] At the beginning of the 13th century, an improved method came into use,
described by Cennino Cennini in the 15th century. This process consisted of mixing the ground material with
melted wax, resins, and oils, wrapping the resulting mass in a cloth, and then kneading it in a dilute lye
solution. The blue particles collect at the bottom of the pot, while the impurities and colorless crystals remain.
This process was performed at least three times, with each successive extraction generating a lower quality
material. The final extraction, consisting largely of colorless material as well as a few blue particles, brings
forth ultramarine ash which is prized as a glaze for its pale blue transparency.[14]

The pigment was most extensively used during the 14th through 15th centuries, as its brilliance complemented
the vermilion and gold of illuminated manuscripts and Italian panel paintings. It was valued chiefly on account
of its brilliancy of tone and its inertness in opposition to sunlight, oil, and slaked lime. It is, however, extremely
susceptible to even minute and dilute mineral acids and acid vapors. Dilute HCl, HNO3 , and H2 SO4 rapidly
destroy the blue color, producing hydrogen sulfide (H2 S) in the process. Acetic acid attacks the pigment at a
much slower rate than mineral acids. Ultramarine was only used for frescoes when it was applied "secco"
because fresco's absorption rate made its use cost prohibitive. The pigment was mixed with a binding medium
like egg to form a tempera and applied over dry plaster (such as Giotto di Bondone's frescos in the Cappella
degli Scrovegni or Arena Chapel in Padua).

European artists used the pigment sparingly, reserving their highest quality blues for the robes of Mary and the
Christ child. As a result of the high price, artists sometimes economized by using a cheaper blue, azurite, for
under painting. Most likely imported to Europe through Venice, the pigment was seldom seen in German art or
art from countries north of Italy. Due to a shortage of azurite in the late 16th and 17th century, the price for the
already-expensive ultramarine increased dramatically.[13]

In the 17th and 18th century

 Sassoferrato's depiction of the Girl with a Pearl Earring, by
Blessed Virgin Mary, c. 1654. Johannes Vermeer (c. 1665)
Her blue cloak is painted in
ultramarine.[15]

Lady Standing at a Virginal, by

Johannes Vermeer (c. 1675)

The turban of the Girl with a Pearl Earring by Vermeer is painted with a mixture of ultramarine and lead
white, with a thin glaze of pure ultramarine over it.[16]

In Vermeer's Lady standing at a virginal, the ultramarine pigment in the seat cushion in the foreground has
deteriorated and turned paler with time. Johannes Vermeer made extensive use of ultramarine in his paintings.
In Lady standing at a virginal, the young woman's dress is painted with a mixture of ultramarine and green
earth, and ultramarine was also used to add shadows in the flesh tones.[17]
Scientific analysis by the National Gallery in London of Lady standing at a virginal showed that the
ultramarine in the blue seat cushion in the foreground had degraded and become paler with time; it would have
been a deeper blue when originally painted.[18]

19th century – the invention of synthetic ultramarine

The beginning of the development of artificial ultramarine blue was known from Goethe. In about 1787, he
observed the blue deposits on the walls of lime kilns near Palermo in Italy. He was aware of the use of these
glassy deposits as a substitute for lapis lazuli in decorative applications. He did not, however, mention if it was
suitable to grind for a pigment.[19][20]

In 1814, Tassaert observed the spontaneous formation of a blue compound, very similar to ultramarine, if not
identical with it, in a lime kiln at St. Gobain,[21] which caused the Societé pour l'Encouragement d'Industrie to
offer, in 1824, a prize for the artificial production of the precious color. Processes were devised by Jean
Baptiste Guimet (1826) and by Christian Gmelin (1828), then professor of chemistry in Tübingen; while
Guimet kept his process a secret, Gmelin published his, and thus became the originator of the "artificial
ultramarine" industry.[22][7]

General terminology
Ultramarine is a blue made from natural lapis lazuli, or its synthetic equivalent which is sometimes called
"French Ultramarine".[23] Variants of the pigment "ultramarine red", "ultramarine green", "ultramarine violet"
are known, and are based on similar chemistry and crystal structure.[24]

More generally "ultramarine blue" can refer to a vivid blue. The term "ultramarine green" indicates a dark
green, barium chromate is sometimes referred to as "ultramarine yellow".[23] Ultramarine pigment has also
been termed "Gmelin's blue", "Guimet's blue", "New blue", "Oriental blue" and "Permanent blue".[25]

See also
International Klein Blue – Deep blue pigment first mixed by the French artist Yves Klein, a
patented pigment by artist Yves Klein that relied heavily on ultramarine blue,
List of inorganic pigments

Notes
1. https://www.colorhexa.com/120a8f
2. Webster's New World Dictionary of American English, Third College Edition 1988.
3. "ultramarine" (http://www.etymonline.com/index.php?search=ultramarine). Online Etymology
Dictionary. Retrieved 2011-06-30.
4. "The Color of Art Pigment Database: Pigment Blue - PB" (http://www.artiscreation.com/blue.htm
l#pb29). Art is Creation. Retrieved 2018-10-11.
5. Plesters, Joyce (1966). "Ultramarine Blue, Natural and Artificial". Studies in Conservation. 11
(2): 62–91. doi:10.2307/1505446 (https://doi.org/10.2307%2F1505446). JSTOR 1505446 (http
s://www.jstor.org/stable/1505446).
6. G. Buxbaum et al. "Pigments, Inorganic, 3. Colored Pigments" in Ullmann's Encyclopedia of
Industrial Chemistry, 2012, Wiley-VCH, Weinheim. doi:10.1002/14356007.n20_n02 (https://doi.
org/10.1002%2F14356007.n20_n02)
 7. One or more of the preceding sentences incorporates text from a publication now in the
public domain: Chisholm, Hugh, ed. (1911). "Ultramarine". Encyclopædia Britannica (11th ed.).
Cambridge University Press.
8. "Manufacture of ultramarine" (http://www.freepatentsonline.com/2441952.pdf) (PDF).
www.freepatentsonline.com.
9. "Ultramarine-Blue-Pigment - Analysis, Applications, Process, Patent, Consultants, Company
Profiles, Suppliers, Market, Report" (http://www.primaryinfo.com/projects/ultramarine-blue-pigm
ent.htm). www.primaryinfo.com. Retrieved 2018-10-11.
10. Maerz and Paul A Dictionary of Color New York:1930--McGraw Hill Page 206
11. Lara Broecke, Cennino Cennini's Il Libro dell'Arte, a New English Translation and Commentary
with Italian Transcription, Archetype 2015, p. 89.
12. "palette_grinding_and_materials" (http://www.essentialvermeer.com/palette/palette_grinding_a
nd_materials.html#.VINmSjGG-9E). www.essentialvermeer.com. Retrieved 2014. Check date
values in: |accessdate= (help)
13. "The blue color" (http://artelisaart.blogspot.se/2012/03/famous-blue-history-of-color-in-middle.ht
ml). artelisaart.blogspot.se. 2012-03-28. Retrieved 2014. Check date values in:
|accessdate= (help)
14. Lara Broecke, Cennino Cennini's Il Libro dell'Arte: a New English Translation and Commentary
with Italian Transcription, Archetype 2015, pp. 89-90.
15. "assoferrato-the-virgin-in-prayer" (http://www.nationalgallery.org.uk/paintings/sassoferrato-the-v
irgin-in-prayer). www.nationalgallery.org.uk. Retrieved 2014. Check date values in:
|accessdate= (help)
16. [1] (http://www.girl-with-a-pearl-earring.info/palette.htm) Description of the painting at www.girl-
with-a-pear-earring.info/pallette.htm.
17. [2] (http://www.nationalgallery.org.uk/paintings/research/meaning-of-making/vermeer-and-techn
ique/vermeers-palette) National Gallery of London discussion of Vermeer's palette
18. [3] (http://www.nationalgallery.org.uk/paintings/research/meaning-of-making/vermeer-and-techn
ique/altered-appearance-of-ultramarine) National Gallery essay on the altered appearance of
ultramarine in the paintings of Vermeer
19. Goethe, Wolfgang (1914). Italiensche Reise (https://archive.org/stream/goethesitalienis00goetu
oft#page/264/mode/2up) [Italian Journey] (in German). Leipzig, Germany: Insel Verlag. p. 265.
From p. 265: "Doch wissen sie, außer diesen beiden, … andern kirchlichen Verzierungen mit
Glück angewendet." (Yet they [viz, the stone cutters of Palermo] know, besides these two [types
of stone], still more about a material, a product of the fire of their lime kilns. In these is found,
after roasting [the lime], a type of glassy flux, which passes from the brightest blue color to the
darkest, even to the blackest. These lumps, like other rocks, are cut into thin slabs, appraised
according to the level of their color and purity, and, with luck, used instead of lapis lazuli in the
inlaying of altars, tombs, and other church decorations.)
20. Elsner, L. (1841). "Chemische Untersuchung über die blaue Färbung des Ultramarins" (https://b
abel.hathitrust.org/cgi/pt?id=njp.32101076785466;view=1up;seq=399) [Chemical investigation
of the blue color of ultramarine]. Journal für Praktische Chemie (in German). 24: 385–397.
doi:10.1002/prac.18410240157 (https://doi.org/10.1002%2Fprac.18410240157). From pp. 385–
386: "Allein es scheint weniger bekannt zu sein, … von Altären u.s.w. gebraucht würde." (Yet it
seems to be less well known that von Göthe in the year 1787 during his stay in Palermo (see
his Italian Journey) cited a similar observation, as he recounted that in the Sicilian lime ovens,
a product of fire, a sort of glassy flux, is found, [which is] of a light blue to dark blue color, [and]
which was used as lapis lazuli by local artisans during the inlaying of altars, etc.)
21. Tessaërt gave a sample of the pigment to the French chemist Louis Nicolas Vauquelin for
analysis: Vauquelin (1814). "Note sur une couleur bleue artificielle analogue à l'outremer" (http
s://babel.hathitrust.org/cgi/pt?id=nyp.33433062722727;view=1up;seq=98) [Note on an artificial
blue color similar to ultramarine]. Annales de Chimie et de Physique (in French). 89: 88–91.
22. See:
Gmelin, C.G. (1828). "Ueber die künstliche Darstellung einer dem Ultramarin ähnlichen
Farbe" (https://books.google.com/books?id=ZjArAAAAcAAJ&pg=PA191) [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: 191–224.
Gmelin, C.G. (1828). "Ueber die künstliche Darstellung einer dem Ultramarin ähnlichen
Farbe" (https://babel.hathitrust.org/cgi/pt?id=umn.31951d00316722w;view=1up;seq=377)
[On the artificial preparation of a pigment similar to ultramarine]. Annalen der Physik und
Chemie. 2nd series (in German). 14: 363–371.
Watts, Henry (1869). "Ultramarine" (https://books.google.com/books?id=WVNOaYdeSXgC
&pg=PA937). A Dictionary of Chemistry and the Allied Branches of Other Sciences. vol. 5.
London, England: Longmans, Green, and Co. p. 937.
23. Paterson, Ian (2003), A dictionary of colour, pp. 35, 169, 228, 396
24. Eastaugh, Nicholas; Walsh, Valentine; Chaplin, Tracey; Siddall, Ruth (2008), Pigment
Compendium – A Dictionary and Optical Microscopy of Historical Pigments, pp. 585–587,
ISBN 978-0-7506-8980-9
25. Kelly, Kenneth Low; Judd, Deane Brewster (1976), Color: Universal Language and Dictionary
of Names, U.S. Department of Commerce, National Bureau of Standards, p. 150

Further reading
Bomford, David (2000). A Closer Look – Colour (https://archive.org/details/colour0000bomf).
National Gallery Company Limited. ISBN 978-1-85709-442-8.
Broecke, Lara (2015). Cennino Cennini's Il Libro dell'Arte: a New English Translation and
Commentary with Italian Transcription. Archetype. ISBN 978-1-909492-28-8.
Mangla, Ravi (8 June 2015), "True blue: a brief history of ultramarine (http://www.theparisrevie
w.org/blog/2015/06/08/true-blue/)", Paris Review—Daily.
Plesters, J. (1993), "Ultramarine Blue, Natural and Artificial", in Artists’ Pigments. A Handbook
of Their History and Characteristics, Vol. 2: A. Roy (Ed.) Oxford University Press, p. 37-66

External links
Discussion of ultramarine (http://aic.stanford.edu/jaic/articles/jaic30-02-001.html) in an article
on blue pigments in early Sienese paintings from The Journal of the American Institute for
Conservation
National Gallery essay (http://www.nationalgallery.org.uk/paintings/research/meaning-of-makin
g/vermeer-and-technique/altered-appearance-of-ultramarine) on the altered appearance of
ultramarine in the paintings of Vermeer
Ultramarine natural (http://colourlex.com/project/ultramarine-natural/), ColourLex
Ultramarine artificial (http://colourlex.com/project/ultramarine-artificial/), ColourLex
Shades and tints and color harmonies of ultramarine (https://www.htmlcsscolor.com/hex/120A8
F), HTMLCSScolor.com
More shades and tints and color harmonies of ultramarine (https://www.htmlcsscolor.com/hex/3
117A7), HTMLCSScolor.com
An alternative ultramarine color (#5A7CC2) from (https://www.pantone.com/color-finder/17-403
7-TPX) Pantone, pantone.com

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