Deep green isolated fluorite crystal resembling a truncated octahedron, set upon a micaceous matrix, from Erongo Mountain, Erongo Region, Namibia (overall size: 50 mm × 27 mm, crystal size: 19 mm wide, 30 g)
Fluorite (also called fluorspar) is the mineral form of calcium fluoride, CaF2. It belongs to the halide minerals. It crystallizes in isometriccubic habit, although octahedral and more complex isometric forms are not uncommon.
Pure fluorite is colourless and transparent, both in visible and ultraviolet light, but impurities usually make it a colorful mineral and the stone has ornamental and lapidary uses. Industrially, fluorite is used as a flux for smelting, and in the production of certain glasses and enamels. The purest grades of fluorite are a source of fluoride for hydrofluoric acid manufacture, which is the intermediate source of most fluorine-containing fine chemicals. Optically clear transparent fluorite has anomalous partial dispersion, that is, its refractive index varies with the wavelength of light in a manner that differs from that of commonly used glases, so fluorite is useful in making apochromatic lenses, making it valuable, particularly in photographic optics. Fluorite optics are also usable in the far-ultraviolet and mid-infrared ranges, where conventional glasses are too opaque for use. Fluorite also has low dispersion, and a high refractive index for its density, which can make it useful for some specialized purposes in optics.
History and etymology
The word fluorite is derived from the Latin verb fluere, meaning to flow. The mineral is used as a flux in iron smelting to decrease the viscosity of slag. The term flux comes from the Latin adjective fluxus, meaning flowing, loose, slack. The mineral fluorite was originally termed fluorspar and was first discussed in print in a 1530 work Bermannvs sive de re metallica dialogus [Bermannus; or dialogue about the nature of metals], by Georgius Agricola, as a mineral noted for its usefulness as a flux.[7][8] Agricola, a German scientist with expertise in philology, mining, and metallurgy, named fluorspar as a Neo-Latinization of the GermanFlussspat from Fluss (stream, river) and Spat (meaning a nonmetallic mineral akin to gypsum, spærstān, spear stone, referring to its crystalline projections).[9][10]
In 1852, fluorite gave its name to the phenomenon of fluorescence, which is prominent in fluorites from certain locations, due to certain impurities in the crystal. Fluorite also gave the name to its constitutive element fluorine.[3] Currently, the word "fluorspar" is most commonly used for fluorite as an industrial and chemical commodity, while "fluorite" is used mineralogically and in most other senses.
In archeology, gemmology, classical studies, and Egyptology, the Latin terms murrina and myrrhina refer to fluorite.[11] In book 37 of his Naturalis Historia, Pliny the Elder describes it as a precious stone with purple and white mottling, whose objects carved from it, the Romans prize.
Fluorite forms as a late-crystallizing mineral in felsicigneous rocks typically through hydrothermal activity.[14] It is particularly common in granitic pegmatites. It may occur as a vein deposit formed through hydrothermal activity particularly in limestones. In such vein deposits it can be associated with galena, sphalerite, barite, quartz, and calcite. Fluorite can also be found as a constituent of sedimentary rocks either as grains or as the cementing material in sandstone.[14]
It is a common mineral mainly distributed in South Africa, China, Mexico, Mongolia, the United Kingdom, the United States, Canada, Tanzania, Rwanda and Argentina.
The world reserves of fluorite are estimated at 230 million tonnes (Mt) with the largest deposits being in South Africa (about 41 Mt), Mexico (32 Mt) and China (24 Mt). China is leading the world production with about 3 Mt annually (in 2010), followed by Mexico (1.0 Mt), Mongolia (0.45 Mt), Russia (0.22 Mt), South Africa (0.13 Mt), Spain (0.12 Mt) and Namibia (0.11 Mt).[15][needs update]
One of the largest deposits of fluorspar in North America is located on the Burin Peninsula, Newfoundland, Canada. The first official recognition of fluorspar in the area was recorded by geologist J.B. Jukes in 1843. He noted an occurrence of "galena" or lead ore and fluoride of lime on the west side of St. Lawrence harbour. It is recorded that interest in the commercial mining of fluorspar began in 1928 with the first ore being extracted in 1933. Eventually, at Iron Springs Mine, the shafts reached depths of 970 feet (300m). In the St. Lawrence area, the veins are persistent for great lengths and several of them have wide lenses. The area with veins of known workable size comprises about 60 square miles (160km2).[16][17][18]
In 2018, Canada Fluorspar Inc. commenced mine production again[19] in St. Lawrence; in spring 2019, the company was planned to develop a new shipping port on the west side of Burin Peninsula as a more affordable means of moving their product to markets,[20] and they successfully sent the first shipload of ore from the new port on July 31, 2021. This marks the first time in 30 years that ore has been shipped directly out of St. Lawrence.[21]
Cubic crystals up to 20cm across have been found at Dalnegorsk, Russia.[22] The largest documented single crystal of fluorite was a cube 2.12 meters in size and weighing approximately 16 tonnes.[23]
Fluorite on barite from the Berbes mine, Ribadesella, Asturias (Spain). Fluorite crystal, 2.2 cm.
In Asturias (Spain) there are several fluorite deposits known internationally for the quality of the specimens they have yielded. In the area of Berbes, Ribadesella, fluorite appears as cubic crystals, sometimes with dodecahedron modifications, which can reach a size of up to 10 cm of edge, with internal colour zoning, almost always violet in colour. It is associated with quartz and leafy aggregates of baryte. In the Emilio mine, in Loroñe, Colunga, the fluorite crystals, cubes with small modifications of other figures, are colourless and transparent. They can reach 10 cm of edge. In the Moscona mine, in Villabona, the fluorite crystals, cubic without modifications of other shapes, are yellow, up to 3 cm of edge. They are associated with large crystals of calcite and barite.[24]
One of the most famous of the older-known localities of fluorite is Castleton in Derbyshire, England, where, under the name of "Derbyshire Blue John", purple-blue fluorite was extracted from several mines or caves. During the 19th century, this attractive fluorite was mined for its ornamental value. The mineral Blue John is now scarce, and only a few hundred kilograms are mined each year for ornamental and lapidary use. Mining still takes place in Blue John Cavern and Treak Cliff Cavern.[25]
Recently discovered deposits in China have produced fluorite with coloring and banding similar to the classic Blue John stone.[26]
Many samples of fluorite exhibit fluorescence under ultraviolet light, a property that takes its name from fluorite.[27] Many minerals, as well as other substances, fluoresce. Fluorescence involves the elevation of electron energy levels by quanta of ultraviolet light, followed by the progressive falling back of the electrons into their previous energy state, releasing quanta of visible light in the process. In fluorite, the visible light emitted is most commonly blue, but red, purple, yellow, green, and white also occur. The fluorescence of fluorite may be due to mineral impurities, such as yttrium and ytterbium, or organic matter, such as volatile hydrocarbons in the crystal lattice. In particular, the blue fluorescence seen in fluorites from certain parts of Great Britain responsible for the naming of the phenomenon of fluorescence itself, has been attributed to the presence of inclusions of divalent europium in the crystal.[29] Natural samples containing rare earth impurities such as erbium have also been observed to display upconversion fluorescence, in which infrared light stimulates emission of visible light, a phenomenon usually only reported in synthetic materials.[30]
One fluorescent variety of fluorite is chlorophane, which is reddish or purple in color and fluoresces brightly in emerald green when heated (thermoluminescence), or when illuminated with ultraviolet light.
The color of visible light emitted when a sample of fluorite is fluorescing depends on where the original specimen was collected; different impurities having been included in the crystal lattice in different places. Neither does all fluorite fluoresce equally brightly, even from the same locality. Therefore, ultraviolet light is not a reliable tool for the identification of specimens, nor for quantifying the mineral in mixtures. For example, among British fluorites, those from Northumberland, County Durham, and eastern Cumbria are the most consistently fluorescent, whereas fluorite from Yorkshire, Derbyshire, and Cornwall, if they fluoresce at all, are generally only feebly fluorescent.
Fluorite is allochromatic, meaning that it can be tinted with elemental impurities. Fluorite comes in a wide range of colors and has consequently been dubbed "the most colorful mineral in the world". Every color of the rainbow in various shades is represented by fluorite samples, along with white, black, and clear crystals. The most common colors are purple, blue, green, yellow, or colorless. Less common are pink, red, white, brown, and black. Color zoning or banding is commonly present. The color of the fluorite is determined by factors including impurities, exposure to radiation, and the absence of voids of the color centers.
Pastel green fluorite crystal on galena
A golden yellow with hints of purple fluorite
Freestanding purple fluorite cluster between two quartzes
Light to dark burgundy color fluorite
Transparent teal color fluorite with purple highlights
Grass-green fluorite octahedrons clustered on a quartz-rich matrix
Uses
Source of fluorine and fluoride
Fluorite is a major source of hydrogen fluoride, a commodity chemical used to produce a wide range of materials. Hydrogen fluoride is liberated from the mineral by the action of concentrated sulfuric acid:
The resulting HF is converted into fluorine, fluorocarbons, and diverse fluoride materials. As of the late 1990s, five billion kilograms were mined annually.[32]
There are three principal types of industrial use for natural fluorite, commonly referred to as "fluorspar" in these industries, corresponding to different grades of purity. Metallurgical grade fluorite (60–85% CaF2), the lowest of the three grades, has traditionally been used as a flux to lower the melting point of raw materials in steel production to aid the removal of impurities, and later in the production of aluminium. Ceramic grade fluorite (85–95% CaF2) is used in the manufacture of opalescentglass, enamels, and cooking utensils. The highest grade, "acid grade fluorite" (97% or more CaF2), accounts for about 95% of fluorite consumption in the US where it is used to make hydrogen fluoride and hydrofluoric acid by reacting the fluorite with sulfuric acid.[33]
Internationally, acid-grade fluorite is also used in the production of AlF3 and cryolite (Na3AlF6), which are the main fluorine compounds used in aluminium smelting. Alumina is dissolved in a bath that consists primarily of molten Na3AlF6, AlF3, and fluorite (CaF2) to allow electrolytic recovery of aluminium. Fluorine losses are replaced entirely by the addition of AlF3, the majority of which react with excess sodium from the alumina to form Na3AlF6.[33]
Niche uses
Crawford Cup (Roman, 50-100 CE) in the collection of the British Museum. Made of fluorite.
Lapidary uses
Natural fluorite mineral has ornamental and lapidary uses. Fluorite may be drilled into beads and used in jewelry, although due to its relative softness it is not widely used as a semiprecious stone. It is also used for ornamental carvings, with expert carvings taking advantage of the stone's zonation.
In the laboratory, calcium fluoride is commonly used as a window material for both infrared and ultraviolet wavelengths, since it is transparent in these regions (about 0.15µm to 9µm) and exhibits an extremely low change in refractive index with wavelength. Furthermore, the material is attacked by few reagents. At wavelengths as short as 157nm, a common wavelength used for semiconductor stepper manufacture for integrated circuitlithography, the refractive index of calcium fluoride shows some non-linearity at high power densities, which has inhibited its use for this purpose. In the early years of the 21st century, the stepper market for calcium fluoride collapsed, and many large manufacturing facilities have been closed. Canon and other manufacturers have used synthetically grown crystals of calcium fluoride components in lenses to aid apochromatic design, and to reduce light dispersion. This use has largely been superseded by newer glasses and computer-aided design. As an infrared optical material, calcium fluoride is widely available and was sometimes known by the Eastman Kodak trademarked name "Irtran-3", although this designation is obsolete.
Fluorite should not be confused with fluoro-crown (or fluorine crown) glass, a type of low-dispersion glass that has special optical properties approaching fluorite. True fluorite is not a glass but a crystalline material. Lenses or optical groups made using this low dispersion glass as one or more elements exhibit less chromatic aberration than those utilizing conventional, less expensive crown glass and flint glass elements to make an achromatic lens. Optical groups employ a combination of different types of glass; each type of glass refracts light in a different way. By using combinations of different types of glass, lens manufacturers are able to cancel out or significantly reduce unwanted characteristics; chromatic aberration being the most important. The best of such lens designs are often called apochromatic (see above). Fluoro-crown glass (such as Schott FK51) usually in combination with an appropriate "flint" glass (such as Schott KzFSN 2) can give very high performance in telescope objective lenses, as well as microscope objectives, and camera telephoto lenses. Fluorite elements are similarly paired with complementary "flint" elements (such as Schott LaK 10).[35] The refractive qualities of fluorite and of certain flint elements provide a lower and more uniform dispersion across the spectrum of visible light, thereby keeping colors focused more closely together. Lenses made with fluorite are superior to fluoro-crown based lenses, at least for doublet telescope objectives; but are more difficult to produce and more costly.[36]
The use of fluorite for prisms and lenses was studied and promoted by Victor Schumann near the end of the 19th century.[37] Naturally occurring fluorite crystals without optical defects were only large enough to produce microscope objectives.
With the advent of synthetically grown fluorite crystals in the 1950s - 60s, it could be used instead of glass in some high-performance optical telescope and camera lens elements. In telescopes, fluorite elements allow high-resolution images of astronomical objects at high magnifications. Canon Inc. produces synthetic fluorite crystals that are used in their better telephoto lenses. The use of fluorite for telescope lenses has declined since the 1990s, as newer designs using fluoro-crown glass, including triplets, have offered comparable performance at lower prices. Fluorite and various combinations of fluoride compounds can be made into synthetic crystals which have applications in lasers and special optics for UV and infrared.[38]
Exposure tools for the semiconductor industry make use of fluorite optical elements for ultraviolet light at wavelengths of about 157 nanometers. Fluorite has a uniquely high transparency at this wavelength. Fluorite objective lenses are manufactured by the larger microscope firms (Nikon, Olympus, Carl Zeiss and Leica). Their transparence to ultraviolet light enables them to be used for fluorescence microscopy.[39] The fluorite also serves to correct optical aberrations in these lenses. Nikon has previously manufactured at least one fluorite and synthetic quartz element camera lens (105mm f/4.5 UV) for the production of ultraviolet images.[40]Konica produced a fluorite lens for their SLR cameras – the Hexanon 300mm f/6.3.
Source of fluorine gas in nature
In 2012, the first source of naturally occurring fluorine gas was found in fluorite mines in Bavaria, Germany. It was previously thought that fluorine gas did not occur naturally because it is so reactive, and would rapidly react with other chemicals.[41] Fluorite is normally colorless, but some varied forms found nearby look black, and are known as 'fetid fluorite' or antozonite. The minerals, containing small amounts of uranium and its daughter products, release radiation sufficiently energetic to induce oxidation of fluoride anions within the structure, to fluorine that becomes trapped inside the mineral. The color of fetid fluorite is predominantly due to the calcium atoms remaining. Solid-state fluorine-19 NMR carried out on the gas contained in the antozonite, revealed a peak at 425ppm, which is consistent with F2.[42]
In optics, chromatic aberration (CA), also called chromatic distortion and spherochromatism, is a failure of a lens to focus all colors to the same point. It is caused by dispersion: the refractive index of the lens elements varies with the wavelength of light. The refractive index of most transparent materials decreases with increasing wavelength. Since the focal length of a lens depends on the refractive index, this variation in refractive index affects focusing. Chromatic aberration manifests itself as "fringes" of color along boundaries that separate dark and bright parts of the image.
Strontianite (SrCO3) is an important raw material for the extraction of strontium. It is a rare carbonate mineral and one of only a few strontium minerals. It is a member of the aragonite group.
An achromatic lens or achromat is a lens that is designed to limit the effects of chromatic and spherical aberration. Achromatic lenses are corrected to bring two wavelengths into focus on the same plane. Wavelengths in between these two then have better focus error than could be obtained with a simple lens.
Optics is the branch of physics which involves the behavior and properties of light, including its interactions with matter and the construction of instruments that use or detect it. Optics usually describes the behavior of visible, ultraviolet, and infrared light. Because light is an electromagnetic wave, other forms of electromagnetic radiation such as X-rays, microwaves, and radio waves exhibit similar properties.
Fused quartz, fused silica or quartz glass is a glass consisting of almost pure silica (silicon dioxide, SiO2) in amorphous (non-crystalline) form. This differs from all other commercial glasses in which other ingredients are added which change the glasses' optical and physical properties, such as lowering the melt temperature. Fused quartz, therefore, has high working and melting temperatures, making it less desirable for most common applications.
Calcium fluoride is the inorganic compound of the elements calcium and fluorine with the formula CaF2. It is a white solid that is practically insoluble in water. It occurs as the mineral fluorite (also called fluorspar), which is often deeply coloured owing to impurities.
An apochromat, or apochromatic lens (apo), is a photographic or other lens that has better correction of chromatic and spherical aberration than the much more common achromat lenses.
Scheelite is a calcium tungstate mineral with the chemical formula CaWO4. It is an important ore of tungsten (wolfram). Scheelite is originally named after Swedish chemist Carl Wilhelm Scheele (1742–1786). Well-formed crystals are sought by collectors and are occasionally fashioned into gemstones when suitably free of flaws. Scheelite has been synthesized using the Czochralski process; the material produced may be used to imitate diamond, as a scintillator, or as a solid-state lasing medium. It was also used in radium paint in the same fashion as was zinc sulphide, and Thomas Edison invented a fluoroscope with a calcium tungstate-coated screen, making the images six times brighter than those with barium platinocyanide; the latter chemical allowed Röntgen to discover X-rays in early November 1895. Note, the semi-precious stone marketed as 'blue scheelite' is actually a rock type consisting mostly of calcite and dolomite, with occasional traces of yellow-orange scheelite.
Magnesium fluoride is an ionically bonded inorganic compound with the formula MgF2. The compound is a white crystalline salt and is transparent over a wide range of wavelengths, with commercial uses in optics that are also used in space telescopes. It occurs naturally as the rare mineral sellaite.
Barytocalcite is an anhydrous barium calcium carbonate mineral with the chemical formula BaCa(CO3)2. It is trimorphous with alstonite and paralstonite, that is to say the three minerals have the same formula but different structures. Baryte and quartz pseudomorphs after barytocalcite have been observed.
ZBLAN is the most stable, and consequently the most used, fluoride glass, a subcategory of the heavy metal fluoride glass (HMFG) group. Typically its composition is 53% ZrF4, 20% BaF2, 4% LaF3, 3% AlF3 and 20% NaF. ZBLAN is not a single material but rather has a spectrum of compositions, many of which are still untried. The biggest library in the world of ZBLAN glass compositions is currently owned by Le Verre Fluore, the oldest company working on HMFG technology. Other current ZBLAN fiber manufacturers are Thorlabs and KDD Fiberlabs. Hafnium fluoride is chemically similar to zirconium fluoride, and is sometimes used in place of it.
Strontium fluoride, SrF2, also called strontium difluoride and strontium(II) fluoride, is a fluoride of strontium. It is a brittle white crystalline solid. In nature, it appears as the very rare mineral strontiofluorite.
Fluorapatite, often with the alternate spelling of fluoroapatite, is a phosphate mineral with the formula Ca5(PO4)3F (calcium fluorophosphate). Fluorapatite is a hard crystalline solid. Although samples can have various color (green, brown, blue, yellow, violet, or colorless), the pure mineral is colorless, as expected for a material lacking transition metals. Along with hydroxylapatite, it can be a component of tooth enamel, but for industrial use both minerals are mined in the form of phosphate rock, whose usual mineral composition is primarily fluorapatite but often with significant amounts of the other.
Low-dispersion glass is a type of glass with a reduction in chromatic aberration. Crown glass is an example of a relatively inexpensive low-dispersion glass.
Canon FL 300mm lens refers to two telephoto prime lenses made by Canon. The lenses have an FL type mount which fits the Canon FL line of cameras.
Fluorine is relatively rare in the universe compared to other elements of nearby atomic weight. On Earth, fluorine is essentially found only in mineral compounds because of its reactivity. The main commercial source, fluorite, is a common mineral.
Fluorine is a relatively new element in human applications. In ancient times, only minor uses of fluorine-containing minerals existed. The industrial use of fluorite, fluorine's source mineral, was first described by early scientist Georgius Agricola in the 16th century, in the context of smelting. The name "fluorite" derives from Agricola's invented Latin terminology. In the late 18th century, hydrofluoric acid was discovered. By the early 19th century, it was recognized that fluorine was a bound element within compounds, similar to chlorine. Fluorite was determined to be calcium fluoride.
Talmessite is a hydrated calcium magnesium arsenate, often with significant amounts of cobalt or nickel. It was named in 1960 for the type locality, the Talmessi mine, Anarak district, Iran. It forms a series with β-Roselite, where cobalt replaces some of the magnesium, and with gaitite, where zinc replaces the magnesium. All these minerals are members of the fairfieldite group. Talmessite is dimorphic with wendwilsonite.
Hendricksite is a member of the trioctahedral micas group. The mineral was named by Clifford Frondel and Jun Ito in honor of Sterling Brown Hendricks, who studied micas. It was approved in 1966 by the IMA.
Optical glass refers to a quality of glass suitable for the manufacture of optical systems such as optical lenses, prisms or mirrors. Unlike window glass or crystal, whose formula is adapted to the desired aesthetic effect, optical glass contains additives designed to modify certain optical or mechanical properties of the glass: refractive index, dispersion, transmittance, thermal expansion and other parameters. Lenses produced for optical applications use a wide variety of materials, from silica and conventional borosilicates to elements such as germanium and fluorite, some of which are essential for glass transparency in areas other than the visible spectrum.
↑ Anthony, John W.; Bideaux, Richard A.; Bladh, Kenneth W.; Nichols, Monte C., eds. (1990). "Fluorite". Handbook of Mineralogy(PDF). Vol.III (Halides, Hydroxides, Oxides). Chantilly, VA, US: Mineralogical Society of America. ISBN0962209724. Archived(PDF) from the original on 2006-09-06. Retrieved December 5, 2011.
↑ Strong, D. F.; Fryer, B. J.; Kerrich, R. (1984). "Genesis of the St. Lawrence fluorspar deposits as indicated by fluid inclusion, rare earth element, and isotopic data". Economic Geology. 79 (5): 1142. Bibcode:1984EcGeo..79.1142S. doi:10.2113/gsecongeo.79.5.1142.
↑ Korbel, P. and Novak, M. (2002) The Complete Encyclopedia of Minerals, Book Sales, ISBN0785815201.
↑ Rickwood, P. C. (1981). "The largest crystals"(PDF). American Mineralogist. 66: 885–907. Archived(PDF) from the original on 2009-06-20.
↑ Calvo Sevillano, Guiomar; Calvo Rebollar, Miguel (2006). "Fluorite from Spain. Every color under the Sun". Fluorite. The Collector's Choice. Connecticut, USA: Lithographie LLC. Connecticut, USA. pp.38–42.
↑ Hill, Graham; Holman, John (2000). Chemistry in context. Nelson Thornes. ISBN0174482760.
↑ Stokes, G. G. (1853). "On the Change of Refrangibility of Light. No. II". Philosophical Transactions of the Royal Society of London. 143: 385–396, at p. 387. doi:10.1098/rstl.1853.0016. JSTOR108570. S2CID186207789.
↑ Aigueperse, Jean; Paul Mollard; Didier Devilliers; Marius Chemla; Robert Faron; Renée Romano; Jean Pierre Cuer (2005). "Fluorine Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a11_307. ISBN3527306730.
1 2 Miller, M. Michael. Fluorspar, USGS 2009 Minerals Yearbook
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