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Synthetic ultramarine pigment Ultramarinepigment.jpg
Synthetic ultramarine pigment

Ultramarine is a deep blue color pigment which was originally made by grinding lapis lazuli into a powder.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 by Italian traders during the 14th and 15th centuries. [3]

Blue A primary colour between purple and green

Blue is one of the three primary colours of pigments in painting and traditional colour theory, as well as in the RGB colour model. It lies between violet and green on the spectrum of visible light. The eye perceives blue when observing light with a dominant wavelength between approximately 450 and 495 nanometres. Most blues contain a slight mixture of other colours; azure contains some green, while ultramarine contains some violet. The clear daytime sky and the deep sea appear blue because of an optical effect known as Rayleigh scattering. An optical effect called Tyndall scattering explains blue eyes. Distant objects appear more blue because of another optical effect called aerial perspective.

Color Characteristic of human visual perception

Color, or colour, is the characteristic of human visual perception described through color categories, with names such as red, orange, yellow, green, blue, or purple. This perception of color derives from the stimulation of cone cells in the human eye by electromagnetic radiation in the visible spectrum. Color categories and physical specifications of color are associated with objects through the wavelength of the light that is reflected from them. This reflection is governed by the object's physical properties such as light absorption, emission spectra, etc.

Pigment material that changes the color of reflected or transmitted light

A pigment is a material that changes the color of reflected or transmitted light as the result of wavelength-selective absorption. This physical process differs from fluorescence, phosphorescence, and other forms of luminescence, in which a material emits light. Most materials selectively absorb certain wavelengths of light. Materials that humans have chosen and developed for use as pigments usually have special properties that make them useful for coloring other materials. A pigment must have a high tinting strength relative to the materials it colors. It must be stable in solid form at ambient temperatures.


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.

Renaissance European cultural period, 14th to 17th century

The Renaissance is a period in European history, covering the span between the 14th and 17th centuries and marking the transition from the Middle Ages to modernity. The traditional view focuses more on the early modern aspects of the Renaissance and argues that it was a break from the past, but many historians today focus more on its medieval aspects and argue that it was an extension of the middle ages.


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 (Na8–10Al6Si6O24S2–4), 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
radical anion, which contains an unpaired electron. [6]

Zeolite Microporous, aluminosilicate minerals commonly used as commercial adsorbents and catalysts

Zeolites are microporous, aluminosilicate minerals commonly used as commercial adsorbents and catalysts. The term zeolite was originally coined in 1756 by Swedish mineralogist Axel Fredrik Cronstedt, who observed that rapidly heating the material, believed to have been stilbite, produced large amounts of steam from water that had been adsorbed by the material. Based on this, he called the material zeolite, from the Greek ζέω (zéō), meaning "to boil" and λίθος (líthos), meaning "stone". The classic reference for the field has been Breck's book Zeolite Molecular Sieves: Structure, Chemistry, And Use.


Polysulfides are a class of chemical compounds containing chains of sulfur atoms. There are two main classes of polysulfides: anions and organic polysulfides. Anions have the general formula S2−
. These anions are the conjugate bases of the hydrogen polysulfides H2Sn. Organic polysulfides generally have the formulae RSnR, where R = alkyl or aryl.

Lapis lazuli A contact metamorphic rock containing lazurite, pyrite and calcite

Lapis lazuli, or lapis for short, is a deep blue metamorphic rock used as a semi-precious stone that has been prized since antiquity for its intense color.


The raw materials used in the manufacture of synthetic ultramarine are the following:

Iron Chemical element with atomic number 26

Iron is a chemical element with symbol Fe and atomic number 26. It is a metal, that belongs to the first transition series and group 8 of the periodic table. It is by mass the most common element on Earth, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust.

Clay A finely-grained natural rock or soil material that combines one or more clay minerals

Clay is a finely-grained natural rock or soil material that combines one or more clay minerals with possible traces of quartz (SiO2), metal oxides (Al2O3, MgO etc.) and organic matter. Geologic clay deposits are mostly composed of phyllosilicate minerals containing variable amounts of water trapped in the mineral structure. Clays are plastic due to particle size and geometry as well as water content, and become hard, brittle and non–plastic upon drying or firing. Depending on the soil's content in which it is found, clay can appear in various colours from white to dull grey or brown to deep orange-red.

The preparation is typically made in steps:

Chromophore the part of a molecule responsible for its color

A chromophore is the part of a molecule responsible for its color. The color that is seen by our eyes is the one not absorbed within a certain wavelength spectrum of visible light. The chromophore is a region in the molecule where the energy difference between two separate molecular orbitals falls within the range of the visible spectrum. Visible light that hits the chromophore can thus be absorbed by exciting an electron from its ground state into an excited state. In biological molecules that serve to capture or detect light energy, the chromophore is the moiety that causes a conformational change of the molecule when hit by light.

Sulfur dioxide chemical compound

Sulfur dioxide is the chemical compound with the formula SO
. It is a toxic gas responsible for the smell of burnt matches. It is released naturally by volcanic activity and is produced as a by-product of the burning of fossil fuels contaminated with sulfur compounds and copper extraction.

Flue-gas desulfurization

Flue-gas desulfurization (FGD) is a set of technologies used to remove sulfur dioxide from exhaust flue gases of fossil-fuel power plants, and from the emissions of other sulfur oxide emitting processes.

"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]

Sand A granular material composed of finely divided rock and mineral particles, from 0.063 to 2 mm diameter

Sand is a granular material composed of finely divided rock and mineral particles. It is defined by size, being finer than gravel and coarser than silt. Sand can also refer to a textural class of soil or soil type; i.e., a soil containing more than 85 percent sand-sized particles by mass.

Muffle furnace

A muffle furnace or muffle oven is a furnace in which the subject material is isolated from the fuel and all of the products of combustion, including gases and flying ash. After the development of high-temperature heating elements and widespread electrification in developed countries, new muffle furnaces quickly moved to electric designs.

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]

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
) 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
or S4. [6]


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. 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.


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

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 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 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

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]

While it made a magnificent blue, it did have its defects; 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


  1. https://www.colorhexa.com/120a8f
  2. Webster's New World Dictionary of American English, Third College Edition 1988.
  3. 1 2 "ultramarine". Online Etymology Dictionary. Retrieved 2011-06-30.
  4. "The Color of Art Pigment Database: Pigment Blue - PB". 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. JSTOR   1505446.
  6. 1 2 3 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
  7. 1 2 3 4 5 Wikisource-logo.svg 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" (PDF). www.freepatentsonline.com.
  9. "Ultramarine-Blue-Pigment - Analysis, Applications, Process, Patent, Consultants, Company Profiles, Suppliers, Market, Report". 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". www.essentialvermeer.com. Retrieved 2014.Check date values in: |accessdate= (help)
  13. 1 2 "The blue color". 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". www.nationalgallery.org.uk. Retrieved 2014.Check date values in: |accessdate= (help)
  16. Description of the painting at www.girl-with-a-pear-earring.info/pallette.htm.
  17. National Gallery of London discussion of Vermeer's palette
  18. National Gallery essay on the altered appearance of ultramarine in the paintings of Vermeer
  19. Goethe, Wolfgang (1914). Italiensche Reise [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" [Chemical investigation of the blue color of ultramarine]. Journal für Praktische Chemie (in German). 24: 385–397. doi:10.1002/prac.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" [Note on an artificial blue color similar to ultramarine]. Annales de Chimie et de Physique (in French). 89: 88–91.
  22. See:
  23. 1 2 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 (440), U.S. Department of Commerce, National Bureau of Standards, p. 150

Further reading

Related Research Articles

Violet (color) color

Violet is the color at the end of the visible spectrum of light between blue and the invisible ultraviolet. Violet color has a dominant wavelength of approximately 380-450 nanometers. Light with a shorter wavelength than violet but longer than X-rays and gamma rays is called ultraviolet. In the color wheel historically used by painters, it is located between blue and purple. On the screens of computer monitors and television sets, a color which looks similar to violet is made, with the RGB color model, by mixing red and blue light, with the blue twice as bright as the red. This is not true violet, for it does not match the color of a single wavelength shorter than that of blue light.

Lazurite A feldspathoid and a member of the sodalite group

Lazurite is a tectosilicate mineral with sulfate, sulfur and chloride with formula: (Na,Ca)8[(S,Cl,SO4,OH)2|(Al6Si6O24)]. It is a feldspathoid and a member of the sodalite group. Lazurite crystallizes in the isometric system although well formed crystals are rare. It is usually massive and forms the bulk of the gemstone lapis lazuli.

Vermilion color

Vermilion is both a brilliant red or scarlet pigment, originally made from the powdered mineral cinnabar, and the name of the resulting color. It was widely used in the art and decoration of Ancient Rome, in the illuminated manuscripts of the Middle Ages, in the paintings of the Renaissance, as sindoor in India, and in the art and lacquerware of China.

Sodalite tectosilicate mineral

Sodalite is a rich royal blue tectosilicate mineral widely used as an ornamental gemstone. Although massive sodalite samples are opaque, crystals are usually transparent to translucent. Sodalite is a member of the sodalite group with hauyne, nosean, lazurite and tugtupite.

Azurite carbonate mineral

Azurite is a soft, deep blue copper mineral produced by weathering of copper ore deposits. In the early 19th century, it was also known as chessylite after the type locality at Chessy-les-Mines near Lyon, France. The mineral, a carbonate with the chemical formula Cu3(CO3)2(OH)2, has been known since ancient times, and 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 blue of azurite is exceptionally deep and clear, and for that reason the mineral has tended to be associated since antiquity with the deep blue color of low-humidity desert and winter skies. 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 lazuli ("stone of azure").

Umber brown or reddish-brown earth pigment

Umber is a natural brown or reddish-brown earth pigment that contains iron oxide and manganese oxide. Umber is darker than the other similar earth pigments, ochre and sienna.

Azure (color) colour

Azure is a bright cyan-blue color that is often described as the color of the sky on a clear day.

Venetian red is a light and warm (somewhat unsaturated) pigment that is a darker shade of scarlet, derived from nearly pure ferric oxide (Fe2O3) of the hematite type. Modern versions are frequently made with synthetic red iron oxide.

Cennino Cennini Italian painter

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Fresco-secco fresco painting technique

Fresco-secco is a wall painting technique where pigments mixed with an organic binder and/or lime are applied onto a dry plaster. The paints used can e.g. be casein paint, tempera, oil paint, silicate mineral paint. If the pigments are mixed with lime water or lime milk and applied to a dry plaster the technique is called lime secco painting. The secco technique contrasts with the fresco technique, where the painting is executed on a layer of wet plaster.

Sinopia dark reddish-brown natural earth pigment

Sinopia is a dark reddish-brown natural earth pigment, whose reddish colour comes from hematite, a dehydrated form of iron oxide. It was widely used in Classical Antiquity and the Middle Ages for painting, and during the Renaissance it was often used on the rough initial layer of plaster for the underdrawing for a fresco. The word came to be used both for the pigment and for the preparatory drawing itself, which may be revealed when a fresco is stripped from its wall for transfer.

Egyptian blue, also known as calcium copper silicate (CaCuSi4O10 or CaOCuO(SiO2)4 (calcium copper tetrasilicate)) or cuprorivaite, is a pigment used in ancient Egypt for thousands of years. It is considered to be the first synthetic pigment. It was known to the Romans by the name caeruleum – see also the English word cerulean. After the Roman era, Egyptian blue fell from use and the manner of its creation was forgotten.


Turnsole or folium was a dyestuff prepared from the annual plant Chrozophora tinctoria.

Hiroshi Ōnishi painter and University Professor

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Conservation and restoration of frescos

The conservation and restoration of frescoes is the process of caring for and maintaining frescos, and includes documentation, examination, research, and treatment to insure their long-term viability, when desired.

Marian blue

Marian blue is a tone of the color celeste named for its use with the Virgin Mary.