Barium Borate
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Barium borate is an inorganic compound, a
borate A borate is any of several boron oxyanions, negative ions consisting of boron and oxygen, such as orthoborate , metaborate , or tetraborate ; or any salt with such anions, such as sodium metaborate, and disodium tetraborate . The name also re ...
of barium with a chemical formula BaB2O4 or Ba(BO2)2. It is available as a hydrate or dehydrated form, as white powder or colorless crystals. The crystals exist in the high-temperature α phase and low-temperature β phase, abbreviated as BBO; both phases are
birefringent Birefringence is the optical property of a material having a refractive index that depends on the polarization and propagation direction of light. These optically anisotropic materials are said to be birefringent (or birefractive). The birefring ...
, and BBO is a common
nonlinear optical Nonlinear optics (NLO) is the branch of optics that describes the behaviour of light in ''nonlinear media'', that is, media in which the polarization density P responds non-linearly to the electric field E of the light. The non-linearity is typic ...
material. Barium borate was discovered and developed by Chen Chuangtian and others of the Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences The Chinese Academy of Sciences (CAS); ), known by Academia Sinica in English until the 1980s, is the national academy of the People's Republic of China for natural sciences. It has historical origins in the Academia Sinica during the Republi ...
.


Properties

Barium borate exists in three major crystalline forms: alpha, beta, and gamma. The low-temperature beta phase converts into the alpha phase upon heating to 925 °C. β-Barium borate (BBO) differs from the α form by the positions of the barium ions within the crystal. Both phases are birefringent, however the α phase possesses centric symmetry and thus does not have the same nonlinear properties as the β phase. Alpha barium borate, α-BaB2O4 is an optical material with a very wide optical transmission window from about 190 nm to 3500 nm. It has good mechanical properties and is a suitable material for high-power
ultraviolet Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation ...
polarization
optics Optics is the branch of physics that studies the behaviour and properties of light, including its interactions with matter and the construction of instruments that use or detect it. Optics usually describes the behaviour of visible, ultrav ...
. It can replace calcite,
titanium dioxide Titanium dioxide, also known as titanium(IV) oxide or titania , is the inorganic compound with the chemical formula . When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or CI 77891. It is a white solid that is insolub ...
or
lithium niobate Lithium niobate () is a non-naturally-occurring salt consisting of niobium, lithium, and oxygen. Its single crystals are an important material for optical waveguides, mobile phones, piezoelectric sensors, optical modulators and various other linea ...
in
Glan–Taylor prism A Glan–Taylor prism is a type of prism which is used as a polarizer or polarizing beam splitter. It is one of the most common types of modern polarizing prism. It was first described by Archard and Taylor in 1948. The prism is made of two r ...
s,
Glan–Thompson prism A Glan–Thompson prism is a type of polarizing prism similar to the Nicol and Glan–Foucault prisms. Design A Glan–Thompson prism consists of two right-angled calcite prisms that are cemented together by their long faces. The optical ax ...
s, walk-off beam splitters and other optical components. It has low
hygroscopic Hygroscopy is the phenomenon of attracting and holding water molecules via either absorption or adsorption from the surrounding environment, which is usually at normal or room temperature. If water molecules become suspended among the substan ...
ity, and its
Mohs hardness The Mohs scale of mineral hardness () is a qualitative ordinal scale, from 1 to 10, characterizing scratch resistance of various minerals through the ability of harder material to scratch softer material. The scale was introduced in 1812 by t ...
is 4.5. Its damage threshold is 1 GW/cm2 at 1064 nm and 500 MW/cm2 at 355 nm. Beta barium borate, β-BaB2O4, is a nonlinear optical material transparent in the range ~190–3300 nm. It can be used for
spontaneous parametric down-conversion Spontaneous parametric down-conversion (also known as SPDC, parametric fluorescence or parametric scattering) is a nonlinear instant optical process that converts one photon of higher energy (namely, a pump photon), into a pair of photons (namely, ...
. Its
Mohs hardness The Mohs scale of mineral hardness () is a qualitative ordinal scale, from 1 to 10, characterizing scratch resistance of various minerals through the ability of harder material to scratch softer material. The scale was introduced in 1812 by t ...
is also 4.5. Gamma barium borate, γ-BaB2O4, discovered recently, was produced by heating beta barium borate 900 °C under 3 GPa of pressure. It was found to have a monoclinic crystal structure. Barium borate has strong negative uniaxial birefringence and can be phase-matched for type I (''ooe'')
second-harmonic generation Second-harmonic generation (SHG, also called frequency doubling) is a nonlinear optical process in which two photons with the same frequency interact with a nonlinear material, are "combined", and generate a new photon with twice the energy o ...
from 409.6 to 3500 nm. The temperature sensitivity of the indices of refraction is low, leading to an unusually large (55 °C) temperature phase-matching bandwidth.


Synthesis

Barium borate can be prepared by reaction of an aqueous solution of
boric acid Boric acid, more specifically orthoboric acid, is a compound of boron, oxygen, and hydrogen with formula . It may also be called hydrogen borate or boracic acid. It is usually encountered as colorless crystals or a white powder, that dissolve ...
with
barium hydroxide Barium hydroxide is a chemical compound with the chemical formula Ba(OH)2. The monohydrate (''x'' = 1), known as baryta or baryta-water, is one of the principal compounds of barium. This white granular monohydrate is the usual commercial form. ...
. The prepared γ-barium borate contains
water of crystallization In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization i ...
that can not be completely removed by drying at 120 °C. Dehydrated γ-barium borate can be prepared by heating to 300–400 °C.
Calcination Calcination refers to thermal treatment of a solid chemical compound (e.g. mixed carbonate ores) whereby the compound is raised to high temperature without melting under restricted supply of ambient oxygen (i.e. gaseous O2 fraction of air), gener ...
at about 600–800 °C causes complete conversion to the β form. BBO prepared by this method does not contain trace amounts of BaB2O2Ross, Sidney D. "Barium borate preparation" issued January 30, 1990 BBO crystals for nonlinear optics can be grown from fluxed melt of barium borate,
sodium oxide Sodium oxide is a chemical compound with the formula Na2 O. It is used in ceramics and glasses. It is a white solid but the compound is rarely encountered. Instead "sodium oxide" is used to describe components of various materials such as glass ...
and sodium chloride.
Thin film A thin film is a layer of material ranging from fractions of a nanometer ( monolayer) to several micrometers in thickness. The controlled synthesis of materials as thin films (a process referred to as deposition) is a fundamental step in many ...
s of barium borate can be prepared by
MOCVD Metalorganic vapour-phase epitaxy (MOVPE), also known as organometallic vapour-phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a chemical vapour deposition method used to produce single- or polycrystalline thin films. ...
from barium(II) hydro-tri(1-pyrazolyl)borate. Different phases can be obtained depending on deposition temperatures. Thin films of beta-barium borate can be prepared by sol-gel synthesis. Barium borate monohydrate is prepared from the solution of
barium sulfide Barium sulfide is the inorganic compound with the formula Ba S. BaS is the barium compound produced on the largest scale. It is an important precursor to other barium compounds including BaCO3 and the pigment lithopone, ZnS/BaSO4. Like other ...
and sodium tetraborate. It is a white powder. It is used as an additive to e.g. paints as
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
, mold inhibitor, and
corrosion inhibitor In chemistry, a corrosion inhibitor or anti-corrosive is a chemical compound that, when added to a liquid or gas, decreases the corrosion rate of a material, typically a metal or an alloy, that comes into contact with the fluid. The effectiveness ...
. It is also used as a white
pigment A pigment is a colored material that is completely or nearly insoluble in water. In contrast, dyes are typically soluble, at least at some stage in their use. Generally dyes are often organic compounds whereas pigments are often inorganic compou ...
. Barium borate dihydrate is prepared from the solution of
sodium metaborate Sodium metaborate is a chemical compound of sodium, boron, and oxygen with formula . However, the metaborate ion is trimeric in the anhydrous solid, therefore a more correct formula is or . The formula can be written also as · to highlight the ...
and
barium chloride Barium chloride is an inorganic compound with the formula Ba Cl2. It is one of the most common water-soluble salts of barium. Like most other water-soluble barium salts, it is white, highly toxic, and imparts a yellow-green coloration to a flame. ...
at 90–95 °C. After cooling to room temperature, white powder is precipitated. Barium borate dihydrate loses water at above 140 °C. It is used as a
flame retardant The term flame retardants subsumes a diverse group of chemicals that are added to manufactured materials, such as plastics and textiles, and surface finishes and coatings. Flame retardants are activated by the presence of an ignition source and ...
for paints, textiles, and paper.


Applications

BBO is a popular nonlinear optical crystal. Quantum linked photons are producible with beta barium borate. Barium borate is a
bactericide A bactericide or bacteriocide, sometimes abbreviated Bcidal, is a substance which kills bacteria. Bactericides are disinfectants, antiseptics, or antibiotics. However, material surfaces can also have bactericidal properties based solely on thei ...
and fungicide. It is added to paints, coatings, adhesives, plastics, and paper products. Barium borate is resistant to
ultraviolet Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation ...
radiation. It can act as
UV stabilizer In polymer chemistry photo-oxidation (sometimes: oxidative photodegradation) is the degradation of a polymer surface due to the combined action of light and oxygen. It is the most significant factor in the weathering of plastics. Photo-oxidatio ...
for polyvinyl chloride. The solubility of barium borate is a disadvantage when used as a pigment.
Silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , most commonly found in nature as quartz and in various living organisms. In many parts of the world, silica is the major constituent of sand. Silica is ...
-coated powders are available. The alkaline properties and the anodic passivation properties of the borate ion enhance the anticorrosion performance. Commonly available barium metaborate pigment comes in three grades; Grade I is a barium metaborate itself, grade II is compounded with 27%
zinc oxide Zinc oxide is an inorganic compound with the formula . It is a white powder that is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cement ...
, and grade III is compounded with 18% of
zinc oxide Zinc oxide is an inorganic compound with the formula . It is a white powder that is insoluble in water. ZnO is used as an additive in numerous materials and products including cosmetics, food supplements, rubbers, plastics, ceramics, glass, cement ...
and 29%
calcium sulfate Calcium sulfate (or calcium sulphate) is the inorganic compound with the formula CaSO4 and related hydrates. In the form of γ-anhydrite (the anhydrous form), it is used as a desiccant. One particular hydrate is better known as plaster of Paris ...
. Barium borate shows synergistic performance with
zinc borate Zinc borate is an inorganic compound, a borate of zinc. It is a white crystalline or amorphous powder insoluble in water. Its toxicity is low. Its melting point is 980 °C. Variants Several variants of zinc borate exist, differing by the zinc/bo ...
. Barium borate is used as a flux in some
barium titanate Barium titanate (BTO) is an inorganic compound with chemical formula BaTiO3. Barium titanate appears white as a powder and is transparent when prepared as large crystals. It is a ferroelectric, pyroelectric, and piezoelectric ceramic material ...
and lead zirconate
EIA Class 2 dielectric A ceramic capacitor is a fixed-value capacitor where the ceramic material acts as the dielectric. It is constructed of two or more alternating layers of ceramic and a metal layer acting as the electrodes. The composition of the ceramic material de ...
ceramic A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain ...
formulations for ceramic capacitors, in amount of about 2%. The barium-boron ratio is critical for flux performance; BaB2O2 content adversely affects the performance of the flux. Barium borate- fly ash
glass Glass is a non-crystalline, often transparent, amorphous solid that has widespread practical, technological, and decorative use in, for example, window panes, tableware, and optics. Glass is most often formed by rapid cooling ( quenching ...
can be used as
radiation shielding Radiation protection, also known as radiological protection, is defined by the International Atomic Energy Agency (IAEA) as "The protection of people from harmful effects of exposure to ionizing radiation, and the means for achieving this". Exposur ...
. Such glasses are superior in performance to
concrete Concrete is a composite material composed of fine and coarse aggregate bonded together with a fluid cement (cement paste) that hardens (cures) over time. Concrete is the second-most-used substance in the world after water, and is the most wid ...
and to other barium borate glasses.


References

{{Borates Barium compounds Borates Nonlinear optical materials Flame retardants Corrosion inhibitors Disinfectants Fungicides Inorganic pigments