Ультрамарин: История, состав и использование пигмента

Deep blue purple color pigment which was originally made with ground lapis lazuli
the pigment and the color

Ultramarine is a deep blue color pigment which was originally made by grinding lapis lazuli into a powder. Its lengthy grinding and washing process makes the natural pigment quite valuable—roughly ten times more expensive than the stone it comes from and as expensive as gold. The name ultramarine comes from the Latin ultramarinus. The word means 'beyond the sea', as the pigment was imported by Italian traders during the 14th and 15th centuries from mines in Afghanistan. Much of the expansion of ultramarine can be attributed to Venice which historically was the port of entry for lapis lazuli in Europe. Ultramarine was the finest and most expensive blue used by Renaissance painters. It was often used for the robes of the Virgin Mary and symbolized holiness and humility. It remained an extremely expensive pigment until a synthetic ultramarine was invented in 1826. Ultramarine is a permanent pigment when under ideal preservation conditions. Otherwise, it is susceptible to discoloration and fading.

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. The major component of lazurite is a complex sulfur containing sodium silicate (Na8–10Al6Si6O24S2–4), which makes ultramarine the most complex of all mineral pigments. Some chloride is often present in the crystal lattice as well. The blue color of the pigment is due to the S3 radical anion, which contains an unpaired electron.

The best samples of ultramarine are a uniform deep blue while other specimens are of paler color. Particle size distribution has been found to vary among samples of ultramarine from various workshops. Numerous grinding techniques used by painters have resulted in different pigment/medium ratios and particle size distributions. The grinding and purification process results in pigment with particles of various geometries. Different grades of pigment may have been used for different areas in a painting, a characteristic that is sometimes used in art authentication.

International Klein Blue (IKB) a deep blue hue first mixed by the French artist Yves Klein.

Electric ultramarine is the tone of ultramarine that is halfway between blue and violet on the RGB (HSV) color wheel, the expression of the HSV color space of the RGB color model.

Ultramarine is the aluminosilicate zeolite with a sodalite structure. Sodalite consists of interconnected aluminosilicate cages. Some of these cages contain polysulfide (Sxn−) groups that are the chromophore (color centre). The negative charge on these ions is balanced by ions that also occupy these cages. The first noted use of lapis lazuli as a pigment can be seen in 6th and 7th century paintings in Zoroastrian and Buddhist cave temples in Afghanistan, near the most famous source of the mineral. Lapis lazuli has 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. Archaeological evidence and early literature reveal that lapis lazuli was used as a semi precious stone and decorative building stone from early Egyptian times. The mineral is described by the classical authors Theophrastus and Pliny. There is no evidence that lapis lazuli was used ground as a painting pigment by ancient Greeks and Romans. Like ancient Egyptians, they had access to a satisfactory blue colorant in the synthetic copper silicate pigment, Egyptian blue. During the Renaissance, ultramarine was the finest and most expensive blue that could be used by painters. Color infrared photogenic studies of ultramarine in 13th and 14th century Sienese panel paintings have revealed that historically, ultramarine has been diluted with white lead pigment in an effort to use the color more sparingly given its high price. 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." Natural ultramarine is a 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. 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 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 frescoes when it was applied secco because frescoes' 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 in Giotto di Bondone's frescos in the Cappella degli Scrovegni or the Arena Chapel in Padua. European artists used the pigment sparingly, reserving their highest quality blues for the robes of Mary and the Christ child, possibly in an effort to show piety, spending as a means of expressing devotion. 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.

Johannes Vermeer made extensive use of ultramarine in his paintings. The turban of the Girl with a Pearl Earring is painted with a mixture of ultramarine and lead white, with a thin glaze of pure ultramarine over it. In Lady Standing at a Virginal, the young woman's dress is painted with a mixture of ultramarine and green earth, and ultramarine was used to add shadows in the flesh tones. 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.

The beginning of the development of artificial ultramarine blue is known from Goethe. In about 1787, he observed the blue deposits on the walls of lime kilns near Palermo in Sicily. He was aware of the use of these glassy deposits as a substitute for lapis lazuli in decorative applications. He did not mention if it was suitable to grind for a pigment. 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. In 1824, this caused the [[Société d'encouragement pour l'industrie nationale to offer 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 became the originator of the "artificial ultramarine" industry. More generally "ultramarine blue" can refer to a vivid blue. The term ultramarine can also refer to other pigments. Variants of the pigment such as "ultramarine red," "ultramarine green," and "ultramarine violet" all resemble ultramarine with respect to their chemistry and crystal structure. The term "ultramarine green" indicates a dark green while barium chromate is sometimes referred to as "ultramarine yellow".