The first noted use of lapis lazuli as a pigment can be seen in the 6th- and 7th-century AD cave paintings in Afghanistan temples, near the most famous source of the mineral. Lapis lazuli has also been identified in Chinese paintings from the 10th and 11th centuries and in Indian mural paintings from the 11th, 12th, and 17th centuries. 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, 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 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 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. From the beginning of the 16th century this pigment began to be imported into Europe from "over the sea," as azurrum ultramarinum. As lapis lazuli only yields from 2 to 3% of the pigment, it is not surprising to learn that the pigment used to be weighed up with gold. 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 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. Because of this susceptibility, ultramarine is never used for frescoes.
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, Italy, 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 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 colour. Processes were devised by Jean Baptiste Guimet (1826) and by Christian Gmelin (1828), then professor of chemistry in Tubingen; but while Guimet kept his process a secret Gmelin published his, and thus became the originator of the "artificial ultramarine" industry.
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:Al2O2 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 sulphate of soda; (3) anhydrous carbonate of soda; (4) sulphur (in the state of powder); and (5) powdered charcoal or relatively ash-free coal, or colophony in lumps. "Ultramarine poor in silica" is obtained by fusing a mixture of soft clay, sodium sulphate, charcoal, soda and sulphur. The product is at first white, but soon turns green ("green ultramarine") when it is mixed with sulphur and heated. The sulphur fires, 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, sulphur 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. Synthetic ultramarine is not as vivid a blue as natural ultramarine, since the particles in synthetic ultramarine are smaller and more uniform than natural ultramarine and therefore diffuse light more evenly. Synthetic ultramarine is also not as permanent as natural ultramarine.
Artificial, like natural, ultramarine has a magnificent blue colour, 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. It is remarkable that even a small addition of zinc-white (oxide of zinc) to the reddish varieties especially causes a considerable diminution in the intensity of the colour, while dilution with artificial precipitated sulphate of lime ("annalin") or sulphate of baryta ("blanc fix") acts pretty much as one would expect. 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. Large quantities are used in the manufacture of paper, and especially for producing that kind of pale blue writing paper which is so popular in Great Britain.
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-ultramarine when treated with ethyl iodide. Selenium- and tellurium-ultramarine, in which these elements replace the sulphur, have also been prepared.
from a 1911 encyclopedia, with modern information edited in