Ultramarine

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Biography

Ultramarine is a blue pigment consisting primarily of a zeolite -based mineral containing small amounts of polysulfide s. It occurs in nature as a proximate component of lapis lazuli . The pigment color code is P. Blue 29 77007. Ultramarine is the most complex of the mineral pigments, a complex sulfur-containing sodio-silicate (Na_8-10Al₆Si₆O₂₄S_2-4) containing a blue cubic mineral called lazurite (the major component in lapis lazuli). Some chloride is often present in the crystal lattice as well. The blue color of the pigment is due to the S3-|S₃^{& minus;} radical (chemistry)|radical anion , which contains an unpaired electron .G. Buxbaum et al. "Pigments, Inorganic, 3. Colored Pigments" in Ullmann's Encyclopedia of Industrial Chemistry, 2012, Wiley-VCH, Weinheim.

Etymology and history

The name derives from Middle Latin ultramarinus , literally "beyond the sea" because it was imported from Asia by sea. 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 include 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.Maerz and Paul A Dictionary of Color New York:1930--McGraw Hill Page 206

The first noted use of lapis lazuli as a pigment can be seen in the 6th- and 7th-century AD cave paintings in Afghanistan i 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.

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. At the beginning of the 13th century an improved method came into use, described by the 15th century artist Cennino Cennini . This process consisted of mixing the ground material with melted wax , resin s, and oil s, 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 in the mass. 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 (painting technique)|glaze for its pale blue transparency.

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 calcium oxide|lime . It is, however, extremely susceptible to even minute and dilute mineral acid s and acid vapors. Dilute HCl, HNO₃, and H₂SO₄ rapidly destroy the blue color, producing hydrogen sulfide (H₂S) in the process. Acetic acid attacks the pigment at a much slower rate than mineral acids. Ultramarine was only used for fresco es 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 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 (mother of Jesus)|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 demand for the already-expensive ultramarine increased dramatically. In 1814 Tassaert observed the spontaneous formation of a blue compound, very similar to ultramarine, if not identical with it, in a calcium oxide|lime kiln at St. Gobain, 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; but while Guimet kept his process a secret Gmelin published his, and thus became the originator of the "artificial ultramarine" industry.

Ultramarine blue is now commonly used by many types of contemporary artists, with Yves Klein being prominent. Since 1958 Klein has produced striking monochromatic sculptures from his own patented pigment International Klein Blue which relies heavily on ultramarine blue.

Production

The raw materials used in the manufacture are: (1) iron -free kaolin , or some other kind of pure clay , which should contain its silica and alumina as nearly as possible in the proportion of SiO₂:Al₂O₃ demanded by the formula assigned to ideal kaolin (a deficit of silica, however, it appears can be made up for by addition of the calculated weight of finely divided silica); (2) anhydrous Na₂SO₄; (3) anhydrous Na₂CO₃; (4) powdered sulfur ; and (5) powdered charcoal or relatively ash-free coal , or colophony in lumps.

The mixture is heated in a kiln, sometimes in brick-sized amounts. The resultant solids are then ground and washed as per any other insoluble pigment manufacturing process. The chemical reaction produces large amounts of sulfur dioxide meaning that Flue-gas desulfurization|Flue gas desulfurization is an essential part of its manufacture to comply with pollution regulations. Large chimneys were used to disperse sulfur dioxide produced in the process, resulting in ultramarine tinting the surrounding ground surfaces and roof vents with a blue color. (Google Maps offers views of two such synthetic ultramarine manufacturing sites, one near (now defunct) ,another in .)and another in Ambattur,Chennai,Tamil Nadu India .)

"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& mdash;green, blue, red and violet& mdash;are finely ground and washed with water.

Synthetic alternatives

Synthetic ultramarine is a more vivid blue than natural ultramarine, since the particles in synthetic ultramarine are smaller and more uniform than natural ultramarine and therefore diffusion|diffuse light more evenly.

Artificial, like natural, ultramarine has a magnificent blue color, which is not affected 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 -white (oxide of zinc) to the reddish varieties especially causes a considerable diminution in the intensity of the color, while dilution with artificial precipitated sulfate of lime ("annalin") or sulfate of baryta ("blanc fix") acts pretty much as one would expect. Synthetic ultramarine being very cheap, it is largely used for wall painting, the printing of paperhangings 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 (fabric)|Bluing or "Laundry blue" is a solution of synthetic ultramarine (sometimes, prussian blue ) that is used for this purpose when washing white clothes. 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 is popular in United Kingdom|Britain . During World War I the RAF painted the outer roundels with a color which was made on 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.

Structure

Ultramarine is based on the sodalite structure which is a 3 dimensional aluminosilicate cage containing 3 sulfur atoms bonded together to form an ion. These ions are charge balanced by cations of sodium in the natural material. The sodium ions can be ion exchanged with lithium and potassium as described above. The modification of the ions has a dramatic effect on the structure of the cages. Lithium being smaller than sodium causes the cage to contract whilst potassium being large causes the cage to expand. The modification of the cage structure and the interaction of the different cations with the central sulfur species modifies the coloration of the final pigment.

By treating blue ultramarine with silver nitrate solution, "silver-ultramarine" is obtained as a yellow powder. This compound gives a blue potassium - and lithium -ultramarine when treated with the corresponding chloride , and an ethyl group|ethyl -ultramarine when treated with ethyl iodide . Selenium - and tellurium -ultramarine, in which these elements replace the sulfur, have also been prepared.

Electric ultramarine

Ultramarine in human culture

Music

Ultramarine (band)|Ultramarine are a United Kingdom|UK -based Ambient music|ambient / ambient house band, formed in the early 1990s by Paul Hammond and Ian Cooper.

Panelology

The International Ultramarine Corps , formerly the Ultramarine Corps , is a fictional team of superheroes published by DC Comics .

Tabletop games

In the Games Workshop game Warhammer 40,000|Warhammer 40k The premier chapter of space marines are called Ultramarines. Their armor is painted ultramarine blue.

Copyright Citations

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