Calcium fluoride
Overview
 
Calcium fluoride is the inorganic compound
Inorganic compound
Inorganic compounds have traditionally been considered to be of inanimate, non-biological origin. In contrast, organic compounds have an explicit biological origin. However, over the past century, the classification of inorganic vs organic compounds has become less important to scientists,...

 with the formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....

 CaF2. This ion
Ion
An ion is an atom or molecule in which the total number of electrons is not equal to the total number of protons, giving it a net positive or negative electrical charge. The name was given by physicist Michael Faraday for the substances that allow a current to pass between electrodes in a...

ic compound
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...

 of calcium
Calcium
Calcium is the chemical element with the symbol Ca and atomic number 20. It has an atomic mass of 40.078 amu. Calcium is a soft gray alkaline earth metal, and is the fifth-most-abundant element by mass in the Earth's crust...

 and fluorine
Fluorine
Fluorine is the chemical element with atomic number 9, represented by the symbol F. It is the lightest element of the halogen column of the periodic table and has a single stable isotope, fluorine-19. At standard pressure and temperature, fluorine is a pale yellow gas composed of diatomic...

 occurs naturally as the mineral fluorite
Fluorite
Fluorite is a halide mineral composed of calcium fluoride, CaF2. It is an isometric mineral with a cubic habit, though octahedral and more complex isometric forms are not uncommon...

 (also called fluorspar). It is the source of most of the world's fluorine. This insoluble solid adopts a cubic structure wherein calcium is coordinated to eight fluoride anions and each F ion is surrounded by four Ca2+ ions. Although perfectly packed crystalline samples are colorless, the mineral is often deeply colored due to the presence of F-center
F-Center
An F-Center or Farbe center is a type of crystallographic defect in which an anionic vacancy in a crystal is filled by one or more electrons, depending on the charge of the missing ion in the crystal. Electrons in such a vacancy tend to absorb light in the visible spectrum such that a material...

s.
The mineral fluorspar is abundant, widespread, and mainly of interest as a precursor to HF.
Encyclopedia
Calcium fluoride is the inorganic compound
Inorganic compound
Inorganic compounds have traditionally been considered to be of inanimate, non-biological origin. In contrast, organic compounds have an explicit biological origin. However, over the past century, the classification of inorganic vs organic compounds has become less important to scientists,...

 with the formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....

 CaF2. This ion
Ion
An ion is an atom or molecule in which the total number of electrons is not equal to the total number of protons, giving it a net positive or negative electrical charge. The name was given by physicist Michael Faraday for the substances that allow a current to pass between electrodes in a...

ic compound
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...

 of calcium
Calcium
Calcium is the chemical element with the symbol Ca and atomic number 20. It has an atomic mass of 40.078 amu. Calcium is a soft gray alkaline earth metal, and is the fifth-most-abundant element by mass in the Earth's crust...

 and fluorine
Fluorine
Fluorine is the chemical element with atomic number 9, represented by the symbol F. It is the lightest element of the halogen column of the periodic table and has a single stable isotope, fluorine-19. At standard pressure and temperature, fluorine is a pale yellow gas composed of diatomic...

 occurs naturally as the mineral fluorite
Fluorite
Fluorite is a halide mineral composed of calcium fluoride, CaF2. It is an isometric mineral with a cubic habit, though octahedral and more complex isometric forms are not uncommon...

 (also called fluorspar). It is the source of most of the world's fluorine. This insoluble solid adopts a cubic structure wherein calcium is coordinated to eight fluoride anions and each F ion is surrounded by four Ca2+ ions. Although perfectly packed crystalline samples are colorless, the mineral is often deeply colored due to the presence of F-center
F-Center
An F-Center or Farbe center is a type of crystallographic defect in which an anionic vacancy in a crystal is filled by one or more electrons, depending on the charge of the missing ion in the crystal. Electrons in such a vacancy tend to absorb light in the visible spectrum such that a material...

s.

Chemical structure

Preparation

The mineral fluorspar is abundant, widespread, and mainly of interest as a precursor to HF. Thus, little motivation exists for the preparation of CaF2. High purity CaF2 is produced by treating calcium carbonate
Calcium carbonate
Calcium carbonate is a chemical compound with the formula CaCO3. It is a common substance found in rocks in all parts of the world, and is the main component of shells of marine organisms, snails, coal balls, pearls, and eggshells. Calcium carbonate is the active ingredient in agricultural lime,...

 with hydrofluoric acid
Hydrofluoric acid
Hydrofluoric acid is a solution of hydrogen fluoride in water. It is a valued source of fluorine and is the precursor to numerous pharmaceuticals such as fluoxetine and diverse materials such as PTFE ....

:
CaCO3 + 2 HF → CaF2 + CO2 + H2O

Source of HF

Naturally occurring CaF2 is the principal source of hydrogen fluoride
Hydrogen fluoride
Hydrogen fluoride is a chemical compound with the formula HF. This colorless gas is the principal industrial source of fluorine, often in the aqueous form as hydrofluoric acid, and thus is the precursor to many important compounds including pharmaceuticals and polymers . HF is widely used in the...

, 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
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...

:
CaF2(s
Solid
Solid is one of the three classical states of matter . It is characterized by structural rigidity and resistance to changes of shape or volume. Unlike a liquid, a solid object does not flow to take on the shape of its container, nor does it expand to fill the entire volume available to it like a...

) + H2SO4CaSO4
Calcium sulfate
Calcium sulfate is a common laboratory and industrial chemical. In the form of γ-anhydrite , it is used as a desiccant. It is also used as a coagulant in products like tofu. In the natural state, unrefined calcium sulfate is a translucent, crystalline white rock...

(solid) + 2 HF(g
Gas
Gas is one of the three classical states of matter . Near absolute zero, a substance exists as a solid. As heat is added to this substance it melts into a liquid at its melting point , boils into a gas at its boiling point, and if heated high enough would enter a plasma state in which the electrons...

)

The resulting HF is converted into fluorine, fluorocarbon
Fluorocarbon
Fluorocarbons, sometimes referred to as perfluorocarbons or PFCs, are organofluorine compounds that contain only carbon and fluorine bonded together in strong carbon–fluorine bonds. Fluoroalkanes that contain only single bonds are more chemically and thermally stable than alkanes...

s, and diverse fluoride materials. As of the late 1990s, five billion kilograms were mined annually.

Applications

In the laboratory, calcium fluoride is commonly used as a window material for both infrared
Infrared
Infrared light is electromagnetic radiation with a wavelength longer than that of visible light, measured from the nominal edge of visible red light at 0.74 micrometres , and extending conventionally to 300 µm...

 and ultraviolet
Ultraviolet
Ultraviolet light is electromagnetic radiation with a wavelength shorter than that of visible light, but longer than X-rays, in the range 10 nm to 400 nm, and energies from 3 eV to 124 eV...

 wavelengths, since it is transparent in these regions (about 0.15 µm to 9 µm) and exhibits extremely low refractive index
Refractive index
In optics the refractive index or index of refraction of a substance or medium is a measure of the speed of light in that medium. It is expressed as a ratio of the speed of light in vacuum relative to that in the considered medium....

. Furthermore the material is attacked by few reagents. At wavelengths as short as 157 nm, a common wavelength used for semiconductor
Semiconductor
A semiconductor is a material with electrical conductivity due to electron flow intermediate in magnitude between that of a conductor and an insulator. This means a conductivity roughly in the range of 103 to 10−8 siemens per centimeter...

 stepper manufacture for integrated circuit
Integrated circuit
An integrated circuit or monolithic integrated circuit is an electronic circuit manufactured by the patterned diffusion of trace elements into the surface of a thin substrate of semiconductor material...

 lithography
Photolithography
Photolithography is a process used in microfabrication to selectively remove parts of a thin film or the bulk of a substrate. It uses light to transfer a geometric pattern from a photomask to a light-sensitive chemical "photoresist", or simply "resist," on the substrate...

, 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
Canon Inc.
is a Japanese multinational corporation that specialises in the manufacture of imaging and optical products, including cameras, camcorders, photocopiers, steppers and computer printers. Its headquarters are located in Ōta, Tokyo, Japan.-Origins:...

 and other manufacturers have used synthetically grown crystals of calcium fluoride components in lenses to aid apochromatic design, and to reduce light dispersion
Dispersion (optics)
In optics, dispersion is the phenomenon in which the phase velocity of a wave depends on its frequency, or alternatively when the group velocity depends on the frequency.Media having such a property are termed dispersive media...

. 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
Eastman Kodak
Eastman Kodak Company is a multinational imaging and photographic equipment, materials and services company headquarted in Rochester, New York, United States. It was founded by George Eastman in 1892....

 trademarked name "Irtran-3," although this designation is obsolete.

Uranium
Uranium
Uranium is a silvery-white metallic chemical element in the actinide series of the periodic table, with atomic number 92. It is assigned the chemical symbol U. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons...

-doped
Doping (semiconductor)
In semiconductor production, doping intentionally introduces impurities into an extremely pure semiconductor for the purpose of modulating its electrical properties. The impurities are dependent upon the type of semiconductor. Lightly and moderately doped semiconductors are referred to as extrinsic...

 calcium fluoride was the second type of solid state laser invented, in the 1960s. Peter Sorokin and Mirek Stevenson at IBM
IBM
International Business Machines Corporation or IBM is an American multinational technology and consulting corporation headquartered in Armonk, New York, United States. IBM manufactures and sells computer hardware and software, and it offers infrastructure, hosting and consulting services in areas...

's laboratories in Yorktown Heights (US) achieved lasing at 2.5 µm shortly after Maiman's ruby laser
Ruby laser
A ruby laser is a solid-state laser that uses a synthetic ruby crystal as its gain medium. The first working laser was a ruby laser made by Theodore H. "Ted" Maiman at Hughes Research Laboratories on May 16, 1960....

.

It is also used as a flux for melting and liquid processing of iron, steel and their composites. Its action is based on its similar melting point to iron, on its ability to dissolve oxides and on its ability to wet oxides and metals.

Safety

Fluorides are toxic to humans, however CaF2 is considered relatively harmless due to its extreme insolubility. The situation is analogous to BaSO4
Barium sulfate
Barium sulfate is the inorganic compound with the chemical formula BaSO4. It is a white crystalline solid that is odorless and insoluble in water. It occurs as the mineral barite, which is the main commercial source of barium and materials prepared from it...

, where the toxicity normally associated with Ba2+ is offset by the very low solubility of its sulfate derivative.

External links

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