Boron

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Boron
Contents

1 Introduction
2 History and etymology
3 Characteristics
o
3.1 Allotropes
o
3.2 Chemistry of the element

3.2.1 Chemical compounds

3.2.1.1 Organo boron chemistry

3.2.1.2 Compounds of B(I) and B(II)


o
3.3 Isotopes

3.3.1 Commercial isotope enrichment

3.3.2 Enriched boron (boron-10)

3.3.3 Depleted boron (boron-11)

3.3.4 NMR spectroscopy


o
3.4 Occurrence
4 Production
o
4.1 Market trend
5 Applications
o
5.1 Glass and ceramics
o
5.2 Detergent formulations and bleaching agents
o
5.3 Insecticides
o
5.4 Semi conductors
o
5.5 Magnets
o
5.6 High-hardness and abrasive compounds

5.6.1 Boron carbide

5.6.2 Other super hard boron compounds


o
5.7 Shielding in nuclear reactors
o
5.8 Other nonmedical uses
o
5.9 Research areas
6 Biological role
o
6.1 Analytical quantification
7 Boron pharmaceuticals and bio logicals
o
7.1 Health issues

Copyright Tarek Kakhia. All rights reserved. http://tarek.kakhia.org

Black - brown.
1 Introduction :
Boron is the chemical element with atomic number 5 and the
chemical symbol B. Boron is a metalloid. Because boron is not
produced by stellarnucleo synthesis, it is a low- abundance element in
both the solar system and the Earth's crust. However, boron is
concentrated on Earth by the water-solubility of its more common
naturally occurring compounds, the borate minerals. These are mined
industrially as evaporate ores , such as borax and kernite .
Chemically uncombined boron is not found naturally on Earth.
Industrially, very pure isolated boron is produced with difficulty, as
boron tends to form refractory materials containing small amounts of
carbon or other elements. Several allotropes of boron exist:
amorphous boron is a brown powder and crystalline boron is black,
extremely hard (about 9.5 on Mohs' scale), and a poor conductor at
room temperature. Elemental boron is used as a dopant in the
semiconductor industry.
The major industrial-scale uses of boron compounds are in
sodium per borate bleaches, and the borax component of fiberglass
insulation. Boron polymers and ceramics play specialized roles as
high-strength lightweight structural and refractory materials. Boron
compounds are used in silica-based glasses and ceramics to give them
resistance to thermal shock. Boron-containing reagents are used for
the synthesis of organic compounds, as intermediate in the synthesis
of fine chemicals. A few boron-containing organic pharmaceuticals
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are used, or are in study. Natural boron is composed of two stable


isotopes, one of which (boron-10) has a number of uses as a neutroncapturing agent.
In biology, borates have low toxicity in mammals (similar to
table salt), but are more toxic to arthropods and are used as
insecticides. Boric acid is mildly anti microbial , and a natural boron containing organic antibiotic is known. Boron is essential to life.
Small amounts of boron compounds play a strengthening role in the
cell walls of all plants, making boron necessary in soils. Experiments
indicate a role for boron as an ultra trace element in animals , but the
nature of its role in animal physiology is unknown.
Name , Symbol , Number
Element category
Group , period , block
Standard atomic weight
Electron configuration
Electrons per shell
Phase
Liquid density at m.p.
Melting point
Boiling point
Heat of fusion
Heat of vaporization
Molar heat capacity
Oxidation states
Electro negativity
Ionization energies
(more)
Atomic radius
Covalent radius

Boron , B , 5
metalloid
13, 2, p
11
[He] 2s2 2p1
2, 3
solid
2.08 gcm3
2076 C
3927 C
50.2 kJmol1
480 kJmol1
11.087 Jmol1K1
3, 2, 1 (mildly acidic oxide)
2.04 ( Pauling scale)
1st : 800.6 kJmol1
2nd : 2427.1 kJmol1
3rd : 3659.7 kJmol1
90 pm
84 3 pm
3

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Van der Waals radius


Magnetic ordering
Electrical resistivity
Thermal conductivity
Thermal expansion

192 pm
diamagnetic
(20 C) ~106 m
27.4 Wm1K1
(25 C) ( form) 57 [3]
mm1K1
(20 C) 16,200 ms1
~9.5

Speed of sound (thin rod)


Mohs hardness
Most stable isotopes
Main article: Isotopes of boron

iso NA
half-life
DM DE (MeV)
10
10
B 19.9 % *
B is stable with 5 neutrons
11
11
B 80.1 % *
B is stable with 6 neutrons
*Boron -10 content may be as low as 19.1% and as
high as 20.3 % in natural samples. Boron-11 is
the remainder in such cases.

DP

2 - History and etymology


The name boron originates from the Arabic word buraq or
the Persian word burah ; which are names for the mineral borax .

Sassolite
Boron compounds were known thousands of years ago. Borax
was known from the deserts of western Tibet, where it received the
name of tincal, derived from the Sanskrit. Borax glazes were used in
China from AD300, and some tincal even reached the West, where
the Persian alchemist Jbir ibn Hayyn seems to mention it in 700.
4

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Marco Polo brought some glazes back to Italy in the 13th century.
Agricola, around 1600, reports the use of borax as a flux in
metallurgy. In 1777, boric acid was recognized in the hot springs
(soffioni) near Florence, Italy, and became known as sal sedativum,
with mainly medical uses. The rare mineral is called sassolite, which
is found at Sasso, Italy. Sasso was the main source of European borax
from 1827 to 1872, at which date American sources replaced it.
Boron compounds were relatively rarely used chemicals until the late
1800s when Francis Marion Smith's Pacific Coast Borax Company
first popularized these compounds and made them in volume and
hence cheap
Boron was not recognized as an element until it was isolated by
Sir Humphry Davy and by Joseph Louis Gay - Lussac and Louis
Jacques Thnard In 1808 Davy observed that electric current sent
through a solution of borates produced a brown precipitate on one of
the electrodes. In his subsequent experiments he used potassium to
reduce boric acid instead of electrolysis. He produced enough boron
to confirm a new element and named the element boracium. GayLussac and The nard use iron to reduce boric acid at high
temperatures. They showed by oxidizing boron with air that boric acid
is a oxidation product of boron . Jns Jakob Berzelius identified boron
as an element in 1824 . Pure boron was arguably first produced by the
American chemist Ezekiel Weintraub in 1909 .
3 Characteristics :
3 1 - Allotropes :
Boron is similar to carbon in its capability to form stable
covalently bonded molecular networks. Even nominally disordered
(amorphous) boron contains regular boron icosahedra which are,
however, bonded randomly to each other without long-range order.
Crystalline boron is a very hard, black material with a high melting
point of above 2000 C. It exists in four major polymorphs: , ,
and T. Whereas , and T phases are based on B12 icosahedra, the phase can be described as a rock salt - type arrangement of the
icosahedra and B2 atomic pairs.[20] It can be produced by compressing
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other boron phases to 1220 GPa and heating to 1500 1800 C; it


remains stable after releasing the temperature and pressure. The T
phase is produced at similar pressures, but higher temperatures of
1800 2200 C. As to the and phases, they might both coexist at
ambient conditions with the phase being more stable. Compressing
boron above 160 GPa produces a boron phase with an as yet unknown
structure, and this phase is a super conductor at temperatures 6 12 K.

Boron phase
Symmetry

Rhombohedral Rhombohedral Orthorhombic Tetragonal

Atoms/unit
12
cell

~105

28

Density
(g/cm3)

2.46

2.35

2.52

Vickers
hardness
(GPa)

42

45

5058

Bulk
modulus
(GPa)

185

224

227

Bandgap
(eV)

1.6

2.1

2.36

3 2 - Chemistry of the element :


Elemental boron is rare and poorly studied because the material
is extremely difficult to prepare. Most studies on "boron" involve
samples that contain small amounts of carbon. Chemically, boron
behaves more closely to silicon than to aluminium. Crystalline boron
is chemically inert and resistant to attack by boiling hydrofluoric or
hydrochloric acid. When finely divided, it is attacked slowly by hot
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concentrated hydrogen peroxide, hot concentrated nitric acid, hot


sulfuric acid or hot mixture of sulfuric and chromic acids.[16][32]
The rate of oxidation of boron depends upon the crystallinity,
particle size, purity and temperature. Boron does not react with air at
room temperature, but at higher temperatures it burns to form boron
trioxide :
4 B + 3 O 2 2 B 2 O3
Boron undergoes halogenations to give tri halides , for
example:
2 B + 3 Br2 2 BBr3
These tri halides in practice are usually made from the oxides.
3 2 - 1 - Chemical compounds :
In its most familiar compounds, boron has the formal oxidation
state III. These include oxides, sulfides, nitrides, and halides.
The tri halides adopt a planar trigonal structure. These
compounds are Lewis acids in that they readily form adducts with
electron - pair donors, which are called Lewis bases. For example,
fluoride (F-) and boron tri fluoride (BF3) combined to give the tetra
fluoro borate anion, BF4-. Boron tri fluoride is used in the
petrochemical industry as a catalyst. The halides react with water to
form boric acid.
Boron is found in nature on Earth entirely as various oxides of
B(III), often associated with other elements. The more than one
hundred borates all feature boron in oxidation state +3. These mineral
resemble silicates in some respect, although boron is often found not
only in a tetrahedral coordination with oxygen, but also in a trigonal
planar configuration. Unlike silicates, the boron minerals never
feature boron with coordination number greater than four. A typical
motif is exemplified by the tetra borate anions of the common mineral
borax, shown at left. The formal negative charge of the tetrahedral
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borate centers is balanced by metal cations in the minerals, such as the


sodium (Na+) in borax.
The boron nitrides are notable for the variety of structures
that they adopt. They adopt structures analogous to various allotropes
of carbon, including graphite, diamond, and nano tubes. In the
diamond - like structure called cubic boron nitride ( trade name
Borazon ) , boron atoms exist in the tetrahedral structure of carbons
atoms in diamond, but one in every four B - N bonds can be viewed
as a coordinate covalent bond, wherein two electrons are donated by
the nitrogen atom which acts as the Lewis base to a bond to the Lewis
acidic boron (III) centre . Cubic boron nitride, among other
applications , is used as an abrasive, as it has a hardness comparable
with diamond (the two substances are able to produce scratches on
each other). In the BN compound analogue of graphite, hexagonal
boron nitride (h-BN), the positively-charged boron and negativelycharged nitrogen atoms in each plane lie adjacent to the oppositely
charged atom in the next plane. Consequently graphite and h-BN have
very different properties: both are lubricants, as these planes slip past
each other. However, h-BN is a relatively poor electrical and thermal
conductor in the planar direction.
3 2 - 1 - 1 - Organo boron chemistry :
A large number of organo boron compounds are known and
many are useful in organic synthesis. Organo boron (III) compounds
are usually tetrahedral or trigonal planar, for example, tetra phenyl
borate (B(C6H5)4-) vs tri phenyl borane (B(C6H5)3). Many are
produced from hydro boration , which employs diborane (B2H6).
3 2 - 1 - 2 - Compounds of B (I) and B (II)
Although these are not found on Earth naturally, boron forms a
variety of stable compounds with formal oxidation state less than
three. As for many covalent compounds, formal oxidation states are
often of little meaning in boron hydrides and metal borides. The
halides also form derivatives of B(I) and B(II). BF, iso electronic
with N2, is not isolable in condensed form, but B2F4 and B4Cl4 are
well characterized .
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Binary metal - boron compounds, the metal borides, feature


boron in oxidation state less than III. Illustrative is magnesium di
boride (MgB2). Each boron has a formal 1 charge and magnesium is
assigned a formal charge of 2+. In this material, the boron centers are
trigonal planar, with an extra double bond for each boron, with the
boron atoms forming sheets akin to the carbon in graphite. However,
unlike the case with hexagonal boron nitride which by comparison
lacks electrons in the plane of the covalent atoms, the delocalized
electrons in the plane of magnesium di boride allow it to conduct
electricity similar to iso electronic graphite. In addition, in 2001 this
material was found to be a high-temperature super conductor.
Certain other metal borides find specialized applications as
hard materials for cutting tools.
From the structural perspective, the most distinctive chemical
compounds of boron are the hydrides. Included in this series are the
cluster compounds do deca borate (B12H122-), deca borane (B10H14),
and the carboranes such as C2B10H12. Characteristically such
compounds feature boron with coordination numbers greater than
four.
3 3 - Isotopes

Ball-and-stick model of superconductor magnesium di boride.


Boron atoms lie in hexagonal aromatic graphite-like layers, with a
charge of 1 per boron. Magnesium (II) ions lie between layers
Boron has two naturally occurring and stable isotopes , 11B
( 80.1 % ) and 10B ( 19.9 % ) . The mass difference results in a wide
range of 11B values, which are defined as a fractional difference
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between the 11B and 10B and traditionally expressed in parts per
thousand, in natural waters ranging from 16 to +59. There are 13
known isotopes of boron, the shortest-lived isotope is 7B which
decays through proton emission and alpha decay. It has a half-life of
3.51022 s. Isotopic fractionation of boron is controlled by the
exchange reactions of the boron species B(OH)3 and [B(OH)4].
Boron isotopes are also fractionated during mineral crystallization,
during H2O phase changes in hydrothermal systems, and during
hydrothermal alteration of rock. The latter effect results in
preferential removal of the 10B(OH)4 ion onto clays. It results in
solutions enriched in 11B(OH)3 and therefore may be responsible for
the large 11B enrichment in seawater relative to both oceanic crust
and continental crust; this difference may act as an isotopic signature.
The exotic 17B exhibits a nuclear halo, i.e. its radius is appreciably
larger than that predicted by the liquid drop model.
The 10B isotope is good at capturing thermal neutrons . Natural
boron is about 20% 10B and 80 % 11B. The nuclear industry enriches
natural boron to nearly pure 10B. The less-valuable by-product,
depleted boron, is nearly pure 11B.
3 3 - 1 - Commercial isotope enrichment
Because of its high neutron cross-section, boron-10 is often used
to control fission in nuclear reactors as a neutron-capturing substance.
Several industrial-scale enrichment processes have been developed,
however only the fractionated vacuum distillation of the di methyl
ether adduct of boron tri fluoride (DME-BF3) and column chromate
graphy of borates are being used.
3 3 - 2 - Enriched boron ( boron -10 )
Enriched boron or 10B is used in both radiation shielding and in
boron neutron capture therapy. In the latter, a compound containing
10
B is attached to a muscle near a tumor. The patient is then treated
with a relatively low dose of thermal neutrons. This causes energetic
and short range alpha radiation from the boron to bombard the tumor.

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Neutron cross section of boron ( top curve is for 10B and bottom
curve for 11B )
In nuclear reactors , 10B is used for reactivity control and in
emergency shutdown systems. It can serve either function in the form
of borosilicate control rods or as boric acid. In pressurized water
reactors, boric acid is added to the reactor coolant when the plant is
shut down for refueling. It is then slowly filtered out over many
months as fissile material is used up and the fuel becomes less
reactive.
In future manned interplanetary spacecraft, 10B has a theoretical
role as structural material (as boron fibers or BN nano tube material)
which would also serve a special role in the radiation shield. One of
the difficulties in dealing with cosmic rays, which are mostly high
energy protons, is that some secondary radiation from interaction of
cosmic rays and spacecraft materials is high energy spallation
neutrons. Such neutrons can be moderated by materials high in light
elements such as poly ethylene, but the moderated neutrons continue
to be a radiation hazard unless actively absorbed in the shielding.
Among light elements that absorb thermal neutrons, 6Li and 10B
appear as potential spacecraft structural materials which serve both
for mechanical reinforcement and radiation protection .
3 3 - 3 - Depleted boron ( boron -11 )
Cosmic radiation will produce secondary neutrons if it hits
spacecraft structures. Those neutrons will be captured in 10B, if it is
11

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present in the spacecraft's semi conductors, producing a gamma ray,


an alpha particle, and a lithium ion. These resultant decay products
may then irradiate nearby semiconductor 'chip' structures, causing
data loss (bit flipping, or single event upset ) . In radiation hardened
semiconductor designs, one countermeasure is to use depleted boron
which is greatly enriched in 11B and contains almost no 10B. 11B is
largely immune to radiation damage. Depleted boron is a by-product
of the nuclear industry.
11

B is also a candidate as a fuel for aneutronic fusion. When


struck by a proton with energy of about 500 keV, it produces three
alpha particles and 8.7 MeV of energy. Most other fusion reactions
involving hydrogen and helium produce penetrating neutron radiation,
which weakens reactor structures and induces long term radioactivity
thereby endangering operating personnel. Whereas, the alpha particles
from 11B fusion can be turned directly into electric power, and all
radiation stops as soon as the reactor is turned off.
3 3 - 4 - NMR spectroscopy :
Both 10B and 11B possess nuclear spin. The nuclear spin of 10B is
3 and that of 11B is 3/2. These isotopes are, therefore, of use in nuclear
magnetic resonance spectroscopy; and spectrometers specially
adapted to detecting the boron-11 nuclei are available commercially.
The 10B and 11B nuclei also cause splitting in the resonances of
attached nuclei.
3 4 - Occurrence

Borax crystals

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Boron is a relatively rare element in the Earth's crust,


representing only 0.001 %. The worldwide commercial borate
deposits are estimated at 10 million tones . Turkey and the United
States are the world's largest producers of boron . Turkey has almost
72 % of the worlds boron reserves . Boron does not appear on Earth
in elemental form but is found combined in borax , boric acid ,
colemanite , kernite , ulexite and borates. Boric acid is sometimes
found in volcanic spring waters .
Ulexite is one of over a hundred borate minerals; it is a fibrous
crystal where individual fibers can guide light like optical fibers.
Economically important sources of boron are rasorite (kernite)
and tincal (borax ore). They are both found in the Mojave Desert of
California, but the largest borax deposits are in Central and Western
Turkey including the provinces of Eskiehir , Ktahya and Balkesir.
4 - Production
The production of boron compounds does not involve
formation of elemental boron, but exploits the convenient availability
of borates.
The earliest routes to elemental boron involved reduction of
boric oxide with metals such as magnesium or aluminium. However
the product is almost always contaminated with metal borides. Pure
boron can be prepared by reducing volatile boron halides with
hydrogen at high temperatures. Ultrapure boron, for the use in
semiconductor industry, is produced by the decomposition of
diborane at high temperatures and then further purified with the zone
melting or Czochralski processes .
4 1 - Market trend
Estimated global consumption of boron rose to a record
1.8 million tones of B2O3 in 2005, following a period of strong
growth in demand from Asia, Europe and North America. Boron
mining and refining capacities are considered to be adequate to meet
expected levels of growth through the next decade.
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The form in which boron is consumed has changed in recent


years. The use of ores like colemanite has declined following
concerns over arsenic content. Consumers have moved towards the
use of refined borates and boric acid that have a lower pollutant
content. The average cost of crystalline boron is $ 5 / g.
Increasing demand for boric acid has led a number of
producers to invest in additional capacity. Eti Mine Company of
Turkey opened a new boric acid plant with the production capacity of
100,000 tones per year at Emet in 2003. Rio Tinto Group increased
the capacity of its boron plant from 260,000 tones per year in 2003 to
310,000 tones per year by May 2005, with plans to grow this to
366,000 tones per year in 2006. Chinese boron producers have been
unable to meet rapidly growing demand for high quality borates. This
has led to imports of sodium tetra borate (borax) growing by a
hundredfold between 2000 and 2005 and boric acid imports
increasing by 28 % per year over the same period.
The rise in global demand has been driven by high growth
rates in fiber glass and borosilicate production. A rapid increase in
the manufacture of reinforcement-grade fiberglass in Asia with a
consequent increase in demand for borates has offset the
development of boron-free reinforcement-grade fiberglass in Europe
and the USA. The recent rises in energy prices may lead to greater
use of insulation-grade fiberglass, with consequent growth in the
boron consumption. Roskill Consulting Group forecasts that world
demand for boron will grow by 3.4 % per year to reach 21 million
tonnes by 2010. The highest growth in demand is expected to be in
Asia where demand could rise by an average 5.7 % per year.
5 - Applications
Nearly all boron ore extracted from the Earth is destined for
refinement into boric acid and sodium tetra borate penta hydrate . In
the United States, 70 % of the boron is used for the production of
glass and ceramics.

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5 - 1 - Glass and ceramics :

Borosilicate glassware. Displayed are two beakers and a test tube.


Borosilicate glass , which is typically 1215 % B2O3, 80 % SiO2
, and 2 % Al2O3 , has a low coefficient of thermal expansion giving it
a good resistance to thermal shock. Duran and Pyrex are two major
brand names for this glass, used both in laboratory glass ware and in
consumer cook ware and bake ware , chiefly for this resistance.
Boron filaments are high - strength, light weight materials that
are used chiefly for advanced aerospace structures as a component of
composite materials, as well as limited production consumer and
sporting goods such as golf clubs and fishing rods . The fibers can be
produced by chemical vapor deposition of boron on a tungsten
filament .
Boron fibers and sub-millimeter sized crystalline boron springs
are produced by laser-assisted chemical vapor deposition. Translation
of the focused laser beam allows to produce even complex helical
structures. Such structures show good mechanical properties ( elastic
modulus 450 GPa, fracture strain 3.7 % , fracture stress 17 GPa) and
can be applied as reinforcement of ceramics or in micromechanical
systems.
5 - 2 - Detergent formulations and bleaching agents :
Borax is used in various household laundry and cleaning
products, including the well - known "20 Mule Team Borax" laundry
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booster and "Boraxo" powdered hand soap. It is also present in some


tooth bleaching formulas.
Sodium per borate serves as a source of active oxygen in many
detergents, laundry detergents, cleaning products, and laundry
bleaches. However, despite its name, "Bora teem" laundry bleach no
longer contains any boron compounds, using sodium percarbonate
instead as a bleaching agent.
5 - 3 - Insecticides
Boric acid is used as an insecticide , notably against ants, fleas,
and cockroaches.
5 - 1 - Semi conductors
Boron is a useful dopant for such semiconductors as silicon,
germanium, and silicon carbide. Having one fewer valence electron
than the host atom, it donates a hole resulting in p-type conductivity.
Traditional method of introducing boron into semiconductors is via
its atomic diffusion at high temperatures. This process uses either
solid (B2O3), liquid (BBr3), or gaseous boron sources (B2H6 or BF3).
However, after 1970s, it was mostly replaced by ion implantation,
which relies mostly on BF3 as a boron source.[71] Boron trichloride
gas is also an important chemical in semiconductor industry, however
not for doping but rather for plasma etching of metals and their
oxides. Tri ethyl borane is also injected into vapor deposition reactors
as a boron source. Examples are the plasma deposition of boroncontaining hard carbon films, silicon nitride - boron nitride films, and
for doping of diamond film with boron.
5 - 5 Magnets :
Boron is a component of neodymium magnets (Nd2Fe14B),
which are the strongest type of permanent magnet. They are found in
a variety of domestic and professional electromechanical and
electronic devices, such as magnetic resonance imaging (MRI),
various motors and actuators, computer HDDs, CD and DVD players,
mobile phones, timer switches, speakers, and so on.
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5 - 6 - High - hardness and abrasive compounds

Boron carbide is used for inner plates of ballistic vests


Several boron compounds are known for their extreme hardness
and toughness.
Boron carbide and cubic boron nitride powders are widely used
as abrasives. Metal borides are used for coating tools through
chemical vapor deposition or physical vapor deposition. Implantation
of boron ions into metals and alloys, through ion implantation or ion
beam deposition, results in a spectacular increase in surface
resistance and micro hardness. Laser alloying has also been
successfully used for the same purpose. These borides are an
alternative to diamond coated tools, and their ( treated ) surfaces have
similar properties to those of the bulk boride.
5 6 - 1 - Boron carbide
Boron carbide is a ceramic material which is obtained by
decomposing B2O3 with carbon in the electric furnace :
2 B2O3 + 7 C B4C + 6 CO
Boron carbide's structure is only approximately B4C,
and it shows a clear depletion of carbon from this suggested
stoichiometric ratio. This is due to its very complex structure. The
substance can be seen with empirical formula B12C3 (i.e., with B12
dodecahedra being a motif), but with less carbon as the suggested C3
units are replaced with B-C chains, and there are smaller (B6)
octahedra present as well.
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The repeating polymer plus semi - crystalline structure of boron


carbide gives it great structural strength per weight. It is used in tank
armor, bullet proof vests, and numerous other structural applications.
Boron carbide's ability to absorb neutrons without forming longlived radio nuclides (especially when doped with extra boron-10)
makes the material attractive as an absorbent for neutron radiation
arising in nuclear power plants. Nuclear applications of boron carbide
include shielding, control rods and shut-down pellets. Within control
Mechanical properties of BCN solids and ReB2
Material

Diamond

cubicBC2N

cubicBC5

cubicB4C ReB2
BN

Vickers hardness
115
(GPa)

76

71

62

38

Fracture
toughness
m1/2)

4.5

9.5

6.8

3.5

(MPa 5.3

22

rods, boron carbide is often powdered, to increase its surface area.[75]


5 6 - 2 - Other super hard boron compounds
Hetero diamond (also called BCN);

Boron nitride. This material is isoelectronic to carbon.


Similar to carbon, it has both hexagonal (soft graphite-like h-BN) and
cubic (hard, diamond-like c-BN) forms. h-BN is used as a high
temperature component and lubricant. c-BN, also known under
commercial name borazon, is a superior abrasive. Its hardness is only
slightly smaller, but chemical stability is superior to that of diamond.

Rhenium di 5 6 - 1 - boride can be produced at ambient


pressures, but is rather expensive because of rhenium. The hardness
of ReB2 exhibits considerable anisotropy because of its hexagonal

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layered structure. Its value is comparable to that of tungsten carbide,


silicon carbide, titanium di boride or zirconium diboride.

AlMgB14 + TiB2 composites possess high hardness and


wear resistance and are used in either bulk form or as coatings for
components exposed to high temperatures and wear loads.
5 7 - Shielding in nuclear reactors :
Boron shielding is used as a control for nuclear reactors, taking
advantage of its high cross-section for neutron capture.
5 8 - Other non medical uses

Boron - containing emergency flare

Launch of Apollo 15 Saturn V rocket , using tri ethyl borane ignitor


Because of its distinctive green flame, amorphous boron is
used in pyrotechnic flares . Starch and casein - based adhesives
contain sodium tetra borate deca hydrate ( Na2B4O710 H2O)

Some anti - corrosion systems contain borax .

Sodium borates are used as a flux for soldering silver and


gold and with ammonium chloride for welding ferrous metals.[82]
They are also fire retarding additives to plastics and rubber articles.[83]

19

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Boric acid ( also known as ortho boric acid ) H3BO3 is


used in the production of textile fiberglass and flat panel displays and
in many PVAc and PVOH based adhesives.

Tri ethyl borane is a substance which ignites the JP-7 fuel


of the Pratt & Whitney J58 turbojet/ramjet engines powering the
Lockheed SR-71 Blackbird. It was also used to ignite the F-1 Engines
on the Saturn V Rocket utilized by NASA's Apollo and Skylab
programs from 1967 until 1973. Tri ethyl borane is suitable for this
because of its pyrophoric properties, especially the fact that it burns
with a very high temperature. Tri ethyl borane is an industrial initiator
in radical reactions, where it is effective even at low temperatures.

5 9 - Research areas
Magnesium di boride is an important super conducting material
with the transition temperature of 39 K . Mg B2 wires are produced
with the powder-in-tube process and applied in superconducting
magnets.
Amorphous boron is used as a melting point depressant in
nickel - chromium braze alloys .
Hexagonal boron nitride forms atomically thin layers, which
have been used to enhance the electron mobility in graphene devices .
It also forms nano tubular structures ( BNNTs ) , which have with
high strength, high chemical stability, and high thermal conductivity,
among its list of desirable properties .
6 - Biological role :
There is a boron-containing natural antibiotic , boro mycin ,
isolated from streptomyces . Boron is an essential plant nutrient,
required primarily for maintaining the integrity of cell walls.
Conversely, high soil concentrations of > 1.0 ppm can cause marginal
and tip necrosis in leaves as well as poor overall growth performance.
Levels as low as 0.8 ppm can cause these same symptoms to appear in
plants particularly sensitive to boron in the soil. Nearly all plants,
even those somewhat tolerant of boron in the soil, will show at least
some symptoms of boron toxicity when boron content in the soil is
21

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greater than 1.8 ppm. When this content exceeds 2.0 ppm, few plants
will perform well and some may not survive. When boron levels in
plant tissue exceed 200 ppm symptoms of boron toxicity are likely to
appear.
As an ultra trace element , boron is necessary for the optimal
health of rats, although it is necessary in such small amounts that ultra
purified foods and dust filtration of air is necessary to induce boron
deficiency, which manifest as poor coat or hair quality. Presumably,
boron is necessary to other mammals. No deficiency syndrome in
humans has been described. Small amounts of boron occur widely in
the diet, and the amounts needed in the diet would, by analogy with
rodent studies, be very small. The exact physiological role of boron in
the animal kingdom is poorly understood.
Boron occurs in all foods produced from plants. Since 1989 its
nutritional value has been argued. It is thought that boron plays
several biochemical roles in animals, including humans . The U.S.
Department of agriculture conducted an experiment in which
postmenopausal women took 3 mg of boron a day. The results
showed that supplemental boron reduced excretion of calcium by
44%, and activated estrogen and vitamin D , suggesting a possible
role in the suppression of osteoporosis. However, whether these
effects were conventionally nutritional, or medicinal, could not be
determined. The US National Institutes of Health quotes this source:
Total daily boron intake in normal human diets ranges from
2.1 4.3 mg boron / day.
6 1 - Analytical quantification :
For determination of boron content in food or materials the
colorimetric curcumin method is used. Boron has to be transferred to
boric acid or borates and on reaction with curcumin in acidic solution,
a red colored boron - chelate complex, rosocyanine, is formed .

21

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7 - Boron pharmaceuticals and biologicals


Boric acid has antiseptic, antifungal, and antiviral properties
and for this reasons is applied as a water clarifier in swimming pool
water treatment. Mild solutions of boric acid have been used as eye
antiseptics.
A number of potential boronated pharmaceuticals using boron
-10 , have been prepared for use in boron neutron capture therapy
( BNCT ) .
Some boron compounds show promise in treating arthritis,
though none have as yet been generally approved for the purpose.
Boron is used as an intermediate in pharmaceutical synthesis,
but it appeared as an active element in its first-approved organic
pharmaceutical in bortezomib , a new class of drug called proteasome
inhibitors, which are active in myeloma and one form of lymphoma.
The boron atom in bortezomib binds the catalytic site of the 26S
proteasome with high affinity and specificity.
7 - 1 - Health issues
Elemental boron, boron oxide , boric acid , borates, and many
organo boron compounds are non - toxic to humans and animals
( approximately similar to table salt ) . The LD50 ( dose at which there
is 50 % mortality ) for animals is about 6 g per kg of body weight.
Substances with LD50 above 2 g are considered non-toxic. The
minimum lethal dose for humans has not been established, but an
intake of 4 g / day was reported without incidents, and medical
dosages of 20 g of boric acid for neutron capture therapy caused no
problems. Fish have survived for 30 min in a saturated boric acid
solution and can survive longer in strong borax solutions . Boric acid
is more toxic to insects than to mammals, and is routinely used as an
insecticide.
The boranes and similar gaseous compounds are quite
poisonous. As usual, it is not an element that is intrinsically
poisonous, but toxicity depends on structure .
22

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The boranes ( boron hydrogen compounds ) are toxic as well as


highly flammable and require special care when handling. Sodium
boro hydride presents a fire hazard due to its reducing nature, and the
liberation of hydrogen on contact with acid. Boron halides are
corrosive.
Congenital endothelial dystrophy type 2, a rare form of corneal
dystrophy, is linked to mutations in SLC4A11 gene that encodes a
transporter reportedly regulating the intracellular concentration of
boron.

23

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Allotropes of boron

Boron (likely mixed allotropes)

Amorphous boron

Contents

1 Introduction
2 Summary of properties
3 - rhombo hedral boron
4 - rhombo hedral boron
5 - boron
6 Tetragonal boron phases
7 High - pressure super conducting phase
8 Amorphous boron
1 Introduction :

Elemental boron can exist in several allotropes, the most


common of which are crystalline boron and brown amorphous boron.
Crystalline boron has four major polymorphs: , , and T. Whereas
the phase is most stable and others are metastable, the
transformation rate is negligible at room temperature, and thus all
those phases can exist at ambient conditions.
Crystalline boron is a very hard (Vickers hardness comparable
to that of cubic boron nitride), black, diamagnetic material with a
melting point of 2080 C. Pure elemental boron is difficult to extract.
24

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The earliest methods involved reduction of boric oxide with metals


such as magnesium or aluminum. However the product is almost
always contaminated with metal borides. Pure boron can be prepared
by reducing volatile boron halides with hydrogen at high temperatures
. Very pure boron, for the use in semiconductor industry, is produced
by the decomposition of diborane at high temperatures and then
further purified with the zone melting or Czochralski processes. Even
more difficult is to prepare pure single crystals of pure boron phases,
because of polymorphism, reactivity of boron with impurities, etc.;
typical crystal size is ~0.1 mm.
2 - Summary of properties :
Boron phase

T
Rhombohedral Rhombohedral Orthorhombic Tetragonal
Symmetry
Atoms/unit cell
12
~105
28
192
3
Density (g/cm )
2.46
2.35
2.52
2.36
Vickers hardness (GPa) 42
45
5058
Bulk modulus (GPa) 224
184
227
Bandgap (eV)
2
1.6
2.1

A fragment of phase diagram of boron reproduced from

Structure of -boron

Structure of -boron

25

Structure of -boron

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3 - - rhombohedral boron :
-rhombohedral boron has a unit cell of twelve boron atoms.
The structure consists of B12 icosahedra in which each boron atom has
five nearest neighbors within the icosahedrons . If the bonding were
the conventional covalent type then each boron would have donated 5
electrons. However, boron has only 3 valence electrons, and it is
thought that the bonding in the B12 icosahedra is achieved by the socalled 3-center electron-deficient bonds where the electron charge is
accumulated at the center of a triangle formed by 3 adjacent atoms.[12]
The isolated B12 icosahedra are not stable; thus boron is not a
molecular solid, but the icosahedra in it are connected by strong
covalent bonds.
4 - - rhombohedral boron
- rhombohedral boron has a sub cell containing 105108
atoms or a unit cell of 320 atoms. Many atoms form B 12
icosahedra, but there are also a large number of non-icosahedral
atoms as well. For long time, it was unclear whether the or phase
is most stable at ambient conditions; however, gradually a consensus
was reached that phase as the thermodynamically stable allotrope.
5 - boron :

-boron: Comparison of X-ray diffraction data of Wentorf[7] (bottom)


with the modern data
The - phase can be described as a Na Cl - type arrangement of
two types of clusters, B12 icosahedra and B2 pairs . It can be produced
26

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by compressing other boron phases to 1220 GPa, heating to 1500


1800 0C and is quenchable to ambient conditions . There is evidence
of significant charge transfer from B2 pairs to the B12 icosahedra in
this structure ; in particular, lattice dynamics suggests the presence of
significant long - range electrostatic interactions.
This phase was reported by Wentorf in 1965, however neither
structure nor chemical composition were established. The structure
was solved using ab initio crystal structure prediction calculations and
confirmed using single crystal X - ray diffraction.
6 - Tetragonal boron phases :
Two tetragonal phases have been reported, T-50 (or -tetragonal
boron) and T-192 (or -tetragonal boron) with 50 and 192 atoms in
the unit cell, respectively. Whereas T-50 has been assigned to a
compound (nitride (B50N2) or carbide (B50C2)), T-192 is a genuine
pure boron phase. It was produced in 1960 by hydrogen reduction of
BBr3 on hot tungsten, rhenium or tantalum filaments at temperatures
1270 1550 C (i.e. chemical vapor deposition). Further studies have
reproduced the synthesis and confirmed the absence of impurities in
this phase.
7 High - pressure super conducting phase :
Compressing boron above 160 GPa produces a boron phase with
an as yet unknown structure. Contrary to other phases, which are semi
conductors, this phase is a metal and becomes a super conductor with
a critical temperature increasing from 4 K at 160 GPa to 11 K at 250
GPa . This structural transformation occurs at pressures at which
theory predicts the icosahedra to dissociate.
8 - Amorphous boron :
Amorphous boron contains B12 regular icosahedra that are
randomly bonded to each other without long range order. Pure
amorphous boron can be produced by thermal decomposition of
diborane at temperatures below 1000 C. Annealing at 1000 C
converts amorphous boron to -rhombohedral boron. Amorphous
27

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boron nano wires (30 60 nm thick) or fibers can be produced by


magnetron sputtering and laser-assisted chemical vapor deposition,
respectively; and they also convert to -rhombohedral boron nano
wires upon annealing at 1000 C.

28

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Boron Ore
Important Boron Ore are :
I . Borane
II . Borax
III . Kernite

I - Borane

BH3 di merises to di borane ,


B2H6.

Ball-and-stick model of borane,


BH3, which is highly reactive.

Contents :

1 Introduction
2 Generic formula of boranes
3 Naming conventions
4 Cluster types
5 Bonding in boranes
6 Chemistry of boranes
o
6.1 Properties and reactivity trends
o
6.2 Synthesis and general reactivity
7 History
1 Introduction :

In chemistry, a borane is a chemical compound of boron and


hydrogen. The boranes comprise a large group of compounds with the
generic formulae of BxHy. These compounds do not occur in nature.
Many of the boranes readily oxidize on contact with air, some
29

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violently. The parent member BH3 is called borane, but it is known


only in the gaseous state, and dimerises to form di borane, B2H6. The
larger boranes all consist of boron clusters that are poly hedral, some
of which exist as isomers. For example, isomers of B20H26 are based
on the fusion of two 10-atom clusters.
The most important boranes are diborane B2H6, penta borane
B5H9, and deca borane B10H14.
The development of the chemistry of boron hydrides led to new
experimental techniques and theoretical concepts. Boron hydrides
have been studied as potential fuels, for rockets and for automotive
uses . Over the past several decades, the scope of boron hydride
chemistry has grown to include cages containing atoms other than
boron, such as carbon in the carboranes and metals in the metalla
boranes , wherein one or more boron atoms are substituted by metal
atoms.
2 - Generic formula of boranes :
The four series of single-cluster boranes have the following
general formulae, where "n" is the number of boron atoms:
Type
formula notes
closo BnHn2 No neutral BnHn+2 boranes are known
nido
BnHn+4
arachno BnHn+6
hypho BnHn+8 only adducts established
There also exists a series of substituted neutral hypercloso boranes that have the theoretical formulae BnHn. Examples include
B12(OCH2Ph)12 , which is a stable derivative of hypercloso-B12H12 .
3 - Naming conventions :
The naming of neutral boranes is illustrated by the following
examples, where the Greek prefix shows the number of boron atoms
and the number of hydrogen atoms is in brackets :
31

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B5H9 penta borane (9)


B6H12 hexa borane (12)

The naming of anions is illustrated by the following, where the


hydrogen count is specified first followed by the boron count, and
finally the overall charge in brackets:

B5H8 octa hydro penta borate (1)

Optionally closo nido etc. (see above) can be added :

B5H9 , nidopenta borane (9)


B4H10 , arachnotetra borane (10)
B6H62, hexa hydroclosohexa borate (2)

Under stand ably many of the compounds have abbreviated


common names.
4 - Cluster types :
It was realized in the early 1970s that the geometry of boron
clusters are related and that they approximate to deltahedra or to
deltahedra with one or more vertices missing. The deltahedra that are
found in borane chemistry are (using the names favoured by most
chemists)
deltahedron
vertices
Trigonal bipyramid
5
Octahedron
6
Pentagonal bipyramid
7
Dodecahedron
8
Tri capped trigonal prism 9
Bi capped square antiprism 10
Octa deca hedron
11
Icosahedron
12
One feature of these deltahedra is that boron atoms at the
vertices may have different numbers of boron atoms as near neighbors
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For example, in the pentagonal bipyramid, 2 borons have 3 neighbors,


3 have 4 neighbors , whereas in the octahedral cluster all vertices are
the same, each boron having 4 neighbors. These differences between
the boron atoms in different positions are important in determining
structure, as they have different chemical shifts in the 11B NMR
spectra.

Penta borane- [9], B5 H9 Tetra borane ,B4 H10

Diborane, B2 H6

Decaborane-[14], B10H14

B12H122-

B6H10 is a typical example. Its geometry is, in essence, a 7boron framework (pentagonal bipyramid), missing a vertex that had
the highest number of near neighbors , e.g. , a vertex with 5 neighbors
The extra hydrogen atoms bridge around the open face. A notable
exception to this general scheme is that of B 8H12, which would be
expected to have a nido- geometry ( based on B9H92 missing 1
vertex), but is similar in geometry to B8H14, which is based on
B10H102.
The names for the series of boranes are derived from this
general scheme for the cluster geometries:32

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Hyper closo - (from the Greek for "over cage") a closed


complete cluster, e.g., B8Cl8 is a slightly distorted dodecahedron
closo- (from the Greek for "cage") a closed complete
cluster, e.g., icosa hedral B12H122
nido - ( from the Latin for "nest" ) B occupies n vertices of
an n+1 deltahedron , e.g., B5H9 an octahedron missing 1 vertex
arachno- (from the Greek for "spiders web") B occupies n
vertices of an n+2 deltahedron e.g. B4H10 an octahedron missing 2
vertices
hypho- (from the Greek for "net") B occupies n vertices of
an n+3 deltahedron possibly B8H16 has this structure, an
octahedron missing 3 vertices
conjuncto- 2 or more of the above are fused together, eg.,
the edge or two vertex fused B19H221, face or three vertex fused
B21H181, and four vertex fused B20H16

5 - Bonding in boranes :
Boranes are electron - deficient and pose a problem for
conventional descriptions of covalent bonding that involves shared
electron pairs. BH3 is a trigonal planar molecule ( D3h molecular
symmetry ) . Diborane has a hydrogen - bridged structure, see the
diborane article. The description of the bonding in the larger boranes
formulated by William Lipscomb involved:

3-center 2-electron B-H-B hydrogen bridges


3-center 2-electron B-B-B bonds
2-center 2-electron bonds (in B-B, B-H and BH2)

The styx number was introduced to aid in electron counting


where s = count of 3-center B-H-B bonds; t = count of 3-center B-B-B
bonds; y = count of 2-center B-B bonds and x = count of BH2 groups.
Lipscomb's methodology has largely been superseded by a molecular
orbital approach, although it still affords insights. The results of this
have been summarized in a simple but powerful rule, PSEPT, often
known as Wade's rules, that can be used to predict the cluster type,
closo-, nido-, etc. The power of this rule is its ease of use and general
applicability to many different cluster types other than boranes. There
33

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are continuing efforts by theoretical chemists to improve the treatment


of the bonding in boranes an example is Stone's tensor surface
harmonic treatment of cluster bonding. A recent development is fourcenter two - electron bond .
6 - Chemistry of boranes :
6 - 1 - Properties and reactivity trends :
Boranes are all colourless and diamagnetic. They are reactive
compounds and some are pyrophoric. The majority are highly
poisonous and require special handling precautions.
closo
There is no known neutral closo borane. Salts of the closo
anions, BnHn2 are stable in neutral aqueous solution, and their
stabilities increase with size. The salt K2B12H12 is stable up to 700o.
nido
Penta borane (9) and deca borane (14) are the most stable
nidoboranes, in contrast to nido B8H12 that decomposes above 35o.
arachno
Generally these are more reactive than nidoboranes and again
larger compounds tend to be more stable.
6 - 2 - Synthesis and general reactivity
Borane BH3
This is an important intermediate in the pyrolosis of diborane to
produce higher boranes.
Diborane B2H6 and higher boranes

34

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Diborane is made industrially by the reduction of BF3, and is the


starting point for preparing the higher boranes. It has been studied
extensively.
General reactivity :
Typical reactions of boranes are :
* electrophilic substitution
* nucleophilic substitution by Lewis bases
* deprotonation by strong bases
* cluster building reactions with boro hydrides
* reaction of a nido- borane with an alkyne to give a carborane
cluster
Boranes can act as ligands in coordination compounds.
Hapticities of 1 to 6 have been found, with electron donation
involving bridging H atoms or donation from B - B bonds. For
example, nido-B6H10 can replace ethene in Zeise's salt to produce
Fe (2-B6H10) (CO)4.
Boranes can react to form hetero boranes , e.g., carboranes or
metalloboranes (clusters that contain boron and metal atoms).
7 History :
The development of the chemistry of boranes posed two
challenges to chemists. First, new laboratory techniques had to be
developed to handle these very reactive compounds; second, the
structures of the compounds challenged the accepted theories of
chemical bonding.
The German chemist Alfred Stock first characterized the series
of boron-hydrogen compounds. His group developed the glass
vacuum line and techniques for handling the compounds. However,
exposure to mercury (used in mercury diffusion pumps and float
valves) caused Stock to develop mercury poisoning, which he
documented in the first scientific papers on the subject. The chemical
bonding of the borane clusters was investigated by Lipscomb and his
35

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co-workers. Lipscomb was awarded the Nobel prize in Chemistry in


1976 for this work. PSEPT, (Wades rules) can be used to predict the
structures of boranes .
Interest in boranes increased during World War II due to the
potential of uranium borohydride for enrichment of the uranium
isotopes. In the US, a team led by Schlesinger developed the basic
chemistry of the boron hydrides and the related aluminium hydrides.
Although uranium borohydride was not utilized for isotopic
separations, Schessingers work laid the foundation for a host of
boron hydride reagents for organic synthesis, most of which were
developed by his student Herbert C. Brown. Borane - based reagents
are now widely used in organic synthesis. For example, sodium
borohydride is the standard reagent for converting aldehydes and
ketones to alcohols. Brown was awarded the Nobel prize in Chemistry
in 1979 for this work.[2] In the 1950s and early '60s, the US and USSR
investigated boron hydrides as high-energy fuels ( ethyl boranes , for
example) for high speed aircraft , such as the XB-70 Valkyrie. The
development of advanced surface-to-air missiles made the fast aircraft
redundant, and the fuel programs were terminated, although tri ethyl
borane (TEB) was later used to ignite the engines of the SR-71
Blackbird.

36

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II - Borax

IUPAC name :
Sodium tetra borate deca hydrate
Na2B4O7 10 H2O or
Molecular Formula
Na2[B4O5(OH)4] 8H2O
Molar Mass
381 ( deca hydrate)
Appearance
white solid
Density
1.73 g / cm (solid)
Melting point
743 C (anhydrous)
Boiling point
1575 C

Old steam tractor and Borax wagons, Death Valley


Contents

1 Introduction
2 Uses
o
2.1 House hold products
o
2.2 Buffer
37

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2.3 Co - complex ing


o
2.4 Flux
o
2.5 Small - scale mining
o
2.6 Putty
o
2.7 Food additive
o
2.8 Other uses
3 Natural sources
4 Toxicity
5 Chemistry
o

1 Introduction :
Borax, also known as sodium borate, sodium tetra borate, or
disodium tetra borate , is an important boron compound, a mineral,
and a salt of boric acid. It is usually a white powder consisting of soft
colorless crystals that dissolve easily in water.
Borax has a wide variety of uses. It is a component of many
detergents, cosmetics, and enamel glazes. It is also used to make
buffer solutions in biochemistry, as a fire retardant, as an anti-fungal
compound for fiber glass, as an insecticide, as a flux in metallurgy, a
texturing agent in cooking, and as a precursor for other boron
compounds.
The term borax is used for a number of closely related minerals
or chemical compounds that differ in their crystal water content, but
usually refers to the deca hydrate. Commercially sold borax is usually
partially dehydrated.
The word borax is Persian and originates in the Middle-Persian
brak.
Borax first came into common use in the late 19th century when
Francis Marion Smith's Pacific Coast Borax Company began to
market and popularize a large variety of applications under the
famous 20 Mule Team Borax trademark, named for the method by
which borax was originally hauled out of the California and Nevada
deserts in large enough quantities to make it cheap and commonly
available.
38

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2 - Uses :
2 1 - House hold products :
Borax is used in various household laundry and cleaning
products, including the "20 Mule Team Borax" laundry booster and
"Boraxo" powdered hand soap. However, despite its name,
"Borateem" laundry bleach no longer contains borax or other boron
compounds.
Borax is also present in some tooth bleaching formulas.
2 2 - Buffer
Sodium borate is used in biochemical and chemical laboratories
to make buffers, e.g. for gel electrophoresis of DNA, such as TBE or
the newer SB buffer or BBS (borate buffered saline) in coating
procedures. Borate buffers (usually at pH 8) are also used as
preferential equilibration solution in DMP-based crosslinking
reactions.
2 3 Co - complexing
Borax as a source of borate has been used to take advantage of
the co - complexing ability of borate with other agents in water to
form complex ions with various substances. Borate and a suitable
polymer bed are used to chromatograph non - glycosylated
hemoglobin differentially from glycosylated hemoglobin (chiefly
HbA1c), which is an indicator of long term hyperglycemia in diabetes
mellitus. Borate and a proprietary synthetic amino acid, Deselex
(from Henkel) have been used to complex water "hardness" cations to
make a non - precipitating water "softener". Borate alone does not
have a high affinity for "hardness" cations, although it has been used
for that purpose.
2 4 Flux :
A mixture of borax and ammonium chloride is used as a flux
when welding iron and steel. It lowers the melting point of the
unwanted iron oxide (scale), allowing it to run off. Borax is also used
39

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mixed with water as a flux when soldering jewelry metals such as


gold or silver. It allows the molten solder to flow evenly over the joint
in question. Borax is also a good flux for 'pre - tinning' tungsten with
zinc - making the tungsten soft - solder able .
2 5 - Small - scale mining :
Borax is replacing mercury as the preferred method for
extracting gold in small - scale mining facilities. The method is called
the borax method and is used in the Philippines .
2 6 Putty :
A rubbery polymer some times called flubber , gluep or glurch
can be made by cross linking polyvinyl alcohol with a borax . Making
flubber from polyvinyl acetate based glues, such as Elmer's Glue, and
borax is a common elementary education experiment.
2 7 Food additive :
Borax, given the E number E285, is used as a food additive in
some countries but is banned in the United States. As a consequence,
certain foods, such as caviar, produced for sale in the U.S. contain
higher levels of salt to assist preservation . Its use as a cooking
ingredient is to add a firm rubbery texture to the food, or as a
preservative. In oriental cooking it is mostly used for its texturing
properties. In Asia, Borax ( Chinese : pinyin : png sh ) was found to
have been added to some Chinese foods like the hand - pulled noodles
lamian and some rice noodles like Shahe fen , Kway Teow, and Chee
Cheong Fun recipes . In Indonesia it is a common, but forbidden,
additive to such foods as noodles, bakso ( meat balls ) , and steamed
rice. The country's Directorate of Consumer Protection warns of the
risk of liver cancer with high consumption over a period of 510
years.
2 8 Other uses :

Ingredient in enamel glazes


Component of glass , pottery , and ceramics
41

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Borax can be used as an additive in ceramic slips and


glazes to improve fit on wet , green ware , and bisque.
Fire retardant
Anti - fungal compound for fiber glass and cellulose
insulation
Moth proofing 10 % solution for wool
Anti - fungal foot soak
Physical insecticide to kill ants , cockroaches and fleas
Precursor for sodium per borate mono hydrate that is used
in detergents, as well as for boric acid and other borates
Tackifier ingredient in casein , starch and dextrin based
adhesives
Precursor for Boric acid, a tackifier ingredient in polyvinyl
acetate, polyvinyl alcohol based adhesives
Treatment for thrush in horses' hooves
Used to make indelible ink for dip pens by dissolving
shellac into heated borax
Curing agent for snake skins
Curing agent for salmon eggs, for use in sport fishing for
salmon
Swimming pool buffering agent to control the pH
Neutron absorber, used in nuclear reactors and spent fuel
pools to control reactivity and to shut down a nuclear chain
reaction
As a micronutrient fertilizer to correct boron-deficient
soils .
To clean the brain cavity of a skull for mounting
To color fires with a green tint
Was traditionally used to coat dry - cured meats such as
hams to protect them from becoming fly - blown during further
storage.
Is found in some commercial vitamin supplements
For stopping car radiator and engine block leaks
As an important component in Slime

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3 - Natural sources :
Borax occurs naturally in evaporite deposits produced by the
repeated evaporation of seasonal lakes. The most commercially
important deposits are found in Turkey; Boron, California; and
Searles Lake, California. Also, it has been found at many other
locations in the Southwestern United States, the Atacama desert in
Chile, and in Tibet and Romania. Borax can also be produced
synthetically from other boron compounds. Naturally occurring
Borax, (known by the trade name Rasorite - 46 in USA and many
other countries) is refined by a process of re-crystallization .
4 Toxicity :
Borax , sodium tetra borate deca hydrate , is not acutely toxic.
Its LD50 (median lethal dose) score is tested at 2.66 g / kg in rats: a
significant dose of the chemical is needed to cause severe symptoms
or death. The lethal dose is not necessarily the same for humans.
Sufficient exposure to borax dust can cause respiratory and skin
irritation. Ingestion may cause gastrointestinal distress including
nausea, persistent vomiting, abdominal pain, and diarrhea. Effects on
the vascular system and brain include headaches and lethargy, but are
less frequent. "In severe poisonings, a beefy red skin rash affecting
palms, soles, buttocks and scrotum has been described. With severe
poisoning, erythematous and exfoliative rash, unconsciousness,
respiratory depression, and renal failure " .
A reassessment of boric acid/borax by the United States
Environmental Protection Agency Office of Pesticide Programs found
potential developmental toxicity (especially effects on the testes).[21]
Boric acid solutions used as an eye wash or on abraded skin are
known to be particularly toxic to infants, especially after repeated use,
because of the slow elimination rate . At a recent European
Diagnostics Manufacturing Association (EDMA) meeting, several
new additions to the Substance of Very High Concern (SVHC)
candidate list in relation to the Registration, Evaluation, Authorization
and restriction of Chemicals Regulations 2007 (REACH) were
discussed. The registration and review completed as part of REACH
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has changed the classification of Sodium Tetraborate CAS 1303-96-4


to toxic for reproduction.
5 - Chemistry :
The term borax is often used for a number of closely related
minerals or chemical compounds that differ in their crystal water
content :

Anhydrous borax (Na2B4O7)


Borax penta hydrate (Na2B4O75H2O)
Borax deca hydrate (Na2B4O710H2O)

Borax is generally described as Na2B4O710H2O. How ever, it is


better formulated as Na2[B4O5(OH)4]8H2O, since borax contains the
[B4O5(OH)4]2 ion. In this structure, there are two four-coordinate
boron atoms ( two BO4 tetra hedra ) and two three-coordinate boron
atoms ( two BO3 triangles ) .
Borax is also easily converted to boric acid and other borates,
which have many applications. Its reaction with hydrochloric acid to
form boric acid is :
Na2B4O710H2O + 2HCl 4 B(OH)3 [or H3BO3] + 2NaCl + 5H2O
The "deca hydrate" is sufficiently stable to find use as a
primary standard for acid base titrimetry .
When borax is added to a flame , it produces a yellow green
color. This property has been tried in amateur fire works , but
borax in this use is not popular because its waters of hydration
inhibit combustion of compositions and make it an inferior source
of the boron that is responsible for most of the green color, and that
is overwhelmed by the yellow contributed to the flame by sodium.
How ever, commercially available borax can be mixed with
flammables such as methanol to give the characteristic green flame
of boron when ignited, which then slowly gives way to the
characteristic yellow - orange flame of the sodium.
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III - Kernite
Category
Chemical formula
Molar mass
Color
Crystal habit
Crystal system
Mohs scale hardness
Luster
Streak
Specific gravity
Optical properties
Refractive index

Birefringence
Other characteristics

Inoborates
Na2B4O6(OH)2 3(H2O)
290
Colorless , white
Crystalline - Coarse - Occurs as well formed coarse sized crystals
Monoclinic,
2.5 - 3
Vitreous - Pearly
white
1.9 - 1.92, Average = 1.91
Biaxial (-), 2V=80
n = 1.454,
n = 1.472,
n = 1.488
=0.0340
Non - radioactive, non-fluorescent ,
non - magnetic

Kernite, also known as rasorite is a hydrated sodium borate


hydroxide mineral with formula Na2B4O6(OH)23H2O. It is a colorless
to white mineral crystallizing in the monoclinic crystal system
typically occurring as prismatic to acicular crystals or granular
masses. It is relatively soft with Mohs hardness of 2.5 to 3 and light
with a specific gravity of 1.91. It exhibits perfect cleavage and a
brittle fracture. Kernite is used to produce borax which can be used in
a variety of soaps.
The mineral was discovered in 1926 in Kern County, California
and later named for the county. Kern County was the only known
source of kernite for many years, but kernite is now also mined in
Argentina, Spain, and Turkey. It occurs in sedimentary evaporite
deposits in arid regions. The largest documented single crystal of
kernite measured 2.44 x 0.9 x 0.9 m3 and weighed ~3.8 tons.
44

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Borazon or Cubic Boron Nitride ( CBN )


1 Introduction :
Borazon is a brand name of a cubic form of boron nitride
(CBN). It is one of the hardest known materials, along with various
forms of diamond and boron nitride. Borazon is a crystal created by
heating equal quantities of boron and nitrogen at temperatures greater
than 1800 C at 7 GPa (1 million lbf / in). Borazon is the only
substance other than those listed above that can scratch a diamond. A
diamond will also scratch Borazon.
Borazon was first produced in 1957 by Robert H. Wentorf, Jr., a
physical chemist working for the General Electric Company.[2] In
1969, General Electric adopted the name Borazon as its trade mark
for the material.
2 - Uses and production ;
Prior to the production of Borazon, diamond was the preferred
abrasive used for grinding very hard super alloys but it could not be
used effectively on steels because carbon tends to dissolve in iron at
high temperatures. Aluminium oxide was the conventional abrasive
used on hardened steel tools.
Borazon replaced aluminium oxide for grinding hardened steels
due to its far superior abrasive properties, comparable to that of
diamond . Borazon is used in industrial applications to shape tools, as
it can withstand temperatures greater than 2000 C , much higher than
that of a pure diamond at 871 C . Other uses include jewellery
designing , glass cutting and laceration of diamonds .
CBN - coated grinding wheels, referred to as Borazon wheels,
are routinely used in the machining of hard ferrous metals, cast irons,
and nickel - base and cobalt - base super alloys . They can grind more
material , to a higher degree of accuracy , than any other abrasive.
The limiting factor in the life of such tools is typically determined not
by wear on the cutting surface but by its break - down and separation
from the metal core resulting from failure of the bonding layer .
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Boric acid

Contents

1 Introduction
2 Occurrence
3 Preparation
4 Properties
5 Crystal structure
6 Toxicology
7 Uses
o
7.1 Medicinal
o
7.2 Laboratory
o
7.3 Insecticidal
o
7.4 Preservation
o
7.5 Lubrication
o
7.6 Nuclear power
o
7.7 Industrial
o
7.8 Pyrotechnics
1 Introduction :

Boric acid, also called hydrogen borate or boracic acid or


ortho boric acid or acidum boricum, is a weak acid of boron often
used as an antiseptic, insecticide, flame retardant, as a neutron
absorber, and as a precursor of other chemical compounds. It exists in
the form of colorless crystals or a white powder and dissolves in
water. It has the chemical formula H3BO3, sometimes written B(OH)3.
When occurring as a mineral, it is called sassolite.
IUPAC Name : Boric acid ,Tri hydroxide boron
Other Names : Ortho boric acid , Boracic acid ,
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Sassolite , Optibor , Borofax


Molecular formula H3 BO3
Molar mass
62 g mol1
Appearance
White crystalline solid
Density
1.435 g / cm3
Melting point
170.9 C
Boiling point
300 C
2.52 g / 100 mL (0 C)
4.72 g / 100 mL (20 C)
Solubility in water
5.7 g / 100 mL (25C)
19.10 g / 100 mL (80 C)
27.53 g / 100 mL (100 C)
Soluble in lower alcohols
Solubility in other
moderately soluble in pyridine
solvents
very slightly soluble in acetone
Acidity (pKa)
9.24
Molecular shape
Trigonal planar
Dipole moment
Zero
Hazards
Harmful (Xn)
EU classification
Flash point
LD50

Non - flammable.
2660 mg / kg, oral ( rat )
Phase behaviour
Thermodynamic data
Solid , liquid , gas
Spectral data
UV , IR , NMR , MS
2 - Occurrence :
The free acid is found native in certain volcanic districts such as
Tuscany, the Lipari Islands and Nevada, issuing mixed with steam
from fissures in the ground; it is also found as a constituent of many
minerals ( borax , boracites , boronatrocaicite and colemanite ) . The
47

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presence of boric acid and its salts has been noted in seawater. It also
exists in plants and especially in almost all fruits.
Boric acid was first prepared by Wilhelm Homberg (1652
1715) from borax, by the action of mineral acids, and was given the
name sal sedativum Hombergi ("sedative salt of Homberg"). However
Borates, including boric acid, have been used since the time of the
Greeks for cleaning, preserving food, and other activities .
3 - Preparation :
Boric acid may be prepared by reacting borax (sodium tetra
borate deca hydrate) with a mineral acid, such as hydrochloric acid :
Na2B4O7 10H2O + 2 HCl
4 B(OH)3 [or H3BO3] + 2 NaCl + 5 H2O
4 - Properties
Boric acid is soluble in boiling water. When heated above 170
C, it dehydrates, forming meta boric acid (HBO2):
H3BO3 HBO2 + H2O
Meta boric acid is a white, cubic crystalline solid and is only
slightly soluble in water. Meta boric acid melts at about 236 C, and
when heated above about 300 C further dehydrates, forming tetra
boric acid or pyro boric acid (H2B4O7) :
4 HBO2 H2B4O7 + H2O
The term boric acid may sometimes refer to any of these
compounds. Further heating leads to boron trioxide.
H2B4O7 2 B2O3 + H2O
Boric acid does not dissociate in aqueous solution as a Brn sted
acid , but is a Lewis acid which interacts with water molecules to
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form the tetra hydroxy borate ion, as confirmed by Raman


spectroscopy :
B (OH) 4 + H+

B (OH)3 + H2O

( Ka = 5.8x1010 mol / l ; pKa = 9.24 )


Poly borate anions are formed at pH 7 10 if the boron
concentration is higher than about 0.025 mol/L. The best known of
these is the tetra borate ion, found in the mineral borax:
4 B (OH) 4 + 2 H+

B4O 2 7 + 9 H2O

Boric acid makes an important contribution to the absorption


of low frequency sound in seawater .
5 - Crystal structure
Crystalline boric acid consists of layers of B(OH)3 molecules
held together by hydrogen bonds. The distance between two adjacent
layers is 318 pm.
6 - Toxicology
Based on mammalian median lethal dose ( LD50 ) rating of
2,660 mg / kg body mass, boric acid is poisonous if taken internally or
inhaled in large quantities. The Thirteenth Edition of the Merck Index
indicates that the LD50 of boric acid is 5.14 g/kg for oral dosages
given to rats, and that 5 to 20 g/kg has produced death in adult
humans. The LD50 of salt is reported to be 3.75 g / kg in rats
according to the Merck Index.
Long term exposure to boric acid may be of more concern,
causing kidney damage and eventually kidney failure (see links
below). Although it does not appear to be carcinogenic, studies in
dogs have reported testicular atrophy after exposure to 32 mg / kg bw
/ day for 90 days. This level is far lower than the LD50 .
According to boric acid IUCLID Dataset published by the
European Commission, boric acid in high doses shows significant
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developmental toxicity and teratogenicity in rabbit, rat, and mouse


fetuses as well as cardiovascular defects, skeletal variations, mild
kidney lesions , As a consequence, in August 2008, in the 30th ATP
to EU directive 67 / 548 / EEC, the EC decided to amend its
classification as reprotoxic category 2 and to apply the risk phrases
R60 ( may impair fertility ) and R61 ( may cause harm to the unborn
child ) .
7 - Uses :
7 1 Medicinal :
Boric acid solutions used as an eye wash or on abraded skin
are known to be especially toxic to infants, especially after repeated
use because of its slow elimination rate.
Boric acid can be used as an antiseptic for minor burns or cuts
and is sometimes used in dressings or salves. Boric acid is applied in
a very dilute solution as an eye wash in a 1.5 % solution ( 1 tbsp per
quart or 15 cm3 per L ) of sterilized water. Boric acid eye wash,
typically administered using an eye cup, relieves the eyes after they
become irritated from long periods of swimming in the chlorinated
water of a swimming pool .
As an anti - bacterial compound, boric acid can also be used
as an acne treatment. Boric acid can be used to treat yeast and fungal
infections such as candidiasis ( vaginal yeast infections ) by inserting
a vaginal suppository containing 600 mg of boric acid daily for 14
days or for yeast infection of the male pubic region (jock-itch or
strong genital odor) by applying the powder to the skin all over the
pubic region for several days to a week. It is also used as prevention
of athlete's foot, by inserting powder in the socks or stockings, and in
solution can be used to treat some kinds of otitis externa (ear
infection) in both humans and animals. The preservative in urine
sample bottles (red cap) in the UK is boric acid.

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7 2 Laboratory :
Tris borate - EDTA (TBE buffer) is widely used for the
electro phoresis of nucleic acids and has a higher buffer capacity than
a Tris acetate - EDTA TAE buffer . It can be used for DNA and
RNA poly acryl amide and agarose gel electro phoresis. Is used as a
reagent and precursor of other substances, e.g. tetra acetyl di borate.
7 3 Insecticidal
Boric acid was first registered in the US as an insecticide in
1948 for control of cockroaches , termites , fire ants , fleas ,
silverfish, and many other insects. The product is generally
considered to be safe to use in household kitchens to control
cockroaches and ants . It acts as a stomach poison affecting the
insects' metabolism, and the dry powder is abrasive to the insects'
exoskeleton .
Boric acid is also made into a paste or gel form as a
powerful and effective insecticide much safer to humans than many
other insecticides. The paste or gel has attractants in it to attract
insects. The boric acid slowly causes dehydration ,
7 4 Preservation
In combination with its use as an insecticide, boric acid also
prevents and destroys existing wet and dry rot in timbers. It can be
used in combination with an ethylene glycol carrier to treat external
wood against fungal and insect attack. It is possible to buy borate impregnated rods for insertion into wood via drill holes where
dampness and moisture is known to collect and sit. It is available in a
gel form and inject able paste form for treating rot affected wood
without the need to replace the timber. Concentrates of borate-based
treatments can be used to prevent slime, mycelium and algae growth,
even in marine environments.
Boric acid is added to salt in the curing of cattle hides,
calfskins and sheep skins . This helps to control bacteria development
and helps to control insects.
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7 5 Lubrication
Colloidal suspensions of nano particles of boric acid
dissolved in petroleum or vegetable oil can form a remarkable
lubricant on ceramic or metal surfaces with a coefficient of sliding
friction that decreases with increasing pressure to a value ranging
from 0.10 to 0.02. Self - lubricating H3BO3 films result from a
spontaneous chemical reaction between water molecules and B2O3
coatings in a humid environment. In bulk-scale, an inverse
relationship exists between friction coefficient and Hertzian contact
pressure induced by applied load.
Boric acid is used to lubricate carrom and novuss boards,
allowing for faster play.
7 6 Nuclear power :
Boric acid is used in nuclear power plants as a neutron poison
to slow down the rate at which fission is occurring. Fission chain
reactions are generally driven by the amount of neutrons present (as
products from previous fissions). Natural boron is 20 % boron-10 and
about 80% boron-11. Boron-10 has a high cross-section for
absorption of low energy (thermal) neutrons. By adding more boric
acid to the reactor coolant which circulates through the reactor, the
probability that a neutron can survive to cause fission is reduced.
Therefore, changes in boric acid concentration effectively regulate the
rate of fission taking place in the reactor. This method is only used in
pressurized water reactors (PWRs). Boron is also dissolved into the
spent fuel pools containing used uranium rods. The concentration is
high enough to keep neutron multiplication at a minimum.
7 7 Industrial :
The primary industrial use of boric acid is in the manufacture of
mono filament fiber glass usually referred to as textile fiber glass .
Textile fiber glass is used to reinforce plastics in applications that
range from boats, to industrial piping to computer circuit boards.

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In the jewelry industry, boric acid is often used in combination


with denatured alcohol to reduce surface oxidation and fire scale from
forming on metals during annealing and soldering operations.
Boric acid is used in the production of the glass in LCD flat
panel displays.
In electro plating , boric acid is used as part of some
proprietary formulas . One such known formula calls for about a 1 to
10 ratio of H3BO3 to NiSO4, a very small portion of sodium lauryl
sulfate and a small portion of H2SO4.
It is also used in the manufacturing of ramming mass, a fine
silica - containing powder used for producing induction furnace
linings and ceramics.
Boric acid is one of the most commonly used substances that
can neutralize active hydro fluoric acid (HF). It works by forcing the
free F- anions into complex salts. This process defeats the extreme
toxicity of hydro fluoric acid , particularly its ability to sequester
ionic calcium from blood serum which can lead to cardiac arrest
( amongst other things ) ; such an event can occur from just minor
skin contact with HF.
Boric acid is added to borax for use as welding flux by black
smiths and farriers .
Boric acid, in combination with silicone oil, is used to
manufacture Silly Putty.
7 8 Pyrotechnics
It is used in pyrotechnics to prevent the amide - forming
reaction between aluminium and nitrates. A small amount of boric
acid is added to the composition to neutralize alkaline amides that can
react with the aluminium .
Boric acid can be used as a colorant to make fire green. For
example , when dissolved in methanol it is popularly used among fire
jugglers and fire spinners to create a deep green flame.
53

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Boron Arsenide
1 Introduction :
Boron arsenide is a chemical compound of boron and arsenic.
It is a cubic (sphalerite) semiconductor with a lattice constant of
0.4777 nm and an indirect band gap of roughly 1.5 eV. It can be
alloyed with gallium arsenide.
Boron arsenide also occurs as an icosahedral boride , B12As2. It
belongs to R-3m space group with a rhombohedral structure based on
clusters of boron atoms and two - atom As - As chains. It's a wide
band gap semiconductor ( 3.47 eV ) with the extraordinary ability to
self-heal radiation damage . This form can be grown on substrates
such as silicon carbide.
Molecular Formula
Molar Mass
Density
Melting point
Solubility in water
Band gap
Hazards
EU classification

B As or B12 As 2
86 g / mol
5.22 g / cm3, solid
2027 C
Insoluble
1.50 eV ( B As ) ;
3.47 eV ( B12 As2 )
N/A

2 - Applications :
Solar cells can be fabricated from boron arsenide. It's also an
attractive choice for devices exposed to radiation which can severely
degrade the electrical properties of conventional semiconductors,
causing devices to cease functioning. Among the particularly
intriguing possible applications for B12 As2 are beta cells, devices
capable of producing electrical energy by coupling a radioactive beta
emitter to a semiconductor junction, another space electronics.
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Boron Carbide

Contents :

1 Introduction
2 Crystal structure
3 Properties
4 Preparation
5 Uses
1 Introduction :

Boron carbide (chemical formula approximately B4C) is an


extremely hard boroncarbon ceramic material used in tank armor,
bulletproof vests, and numerous industrial applications. With a Mohs
hardness of above 9, it is one of the hardest materials known, behind
cubic boron nitride and diamond.
Boron carbide was discovered in the 19th century as a byproduct of reactions involving metal borides, however, its chemical
formula was unknown. It was not until the 1930s that the chemical
composition was estimated as B4C.[1] There remained, however,
controversy as to whether or not the material had this exact 4:1
stoichiometry , as in practice the material is always slightly carbondeficient with regard to this formula, and X-ray crystallography
shows that its structure is highly complex, with a mixture of C-B-C
chains and B12 icosahedra. These features argued against a very
simple exact B4C empirical formula . Because of the B12 structural
unit, the chemical formula of "ideal" boron carbide is often written
not as B4 C, but as B12 C3 , and the carbon deficiency of boron carbide
described in terms of a combination of the B12 C3 and B12 C2 units.
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The ability of boron carbide to absorb neutrons with out forming


long lived radionuclides makes it attractive as an absorbent for
neutron radiation arising in nuclear power plants. Nuclear applications
of boron carbide include shielding, control rod and shut down pellets.
Within control rods, boron carbide is often powdered, to increase its
surface area .
IUPAC Name : Boron Carbide
Other Names :Tetrabor
Molecular
B4 C
Formula
Molar Mass
55 g / mol
dark gray or black
Appearance
powder, odorless
Density
2.52 g /cm3, solid.
Melting point
2763 C
Boiling point
3500 C
Solubility in
insoluble
water
Acidity (pKa)
6 7 ( 20 C )
Crystal structure Rhombohedral

2 - Crystal structure :
Boron carbide has a complex crystal structure typical of
icosahedron - based borides. There, B12 icosahedra form a
rhombohedral lattice unit (space group: R3m (No. 166), lattice
constants: a = 0.56 nm and c = 1.212 nm) surrounding a C - B - C
chain that resides at the center of the unit cell, and both carbon atoms
bridge the neighboring three icosahedra. This structure is layered: the
B12 icosahedra and bridging carbons form a network plane that
spreads parallel to the c-plane and stacks along the c-axis. The lattice
has two basic structure units the B12 icosahedron and the B6
octahedron. Because of the small size of the B6 octahedra , they
56

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cannot interconnect. Instead, they bond to the B12 icosahedra in the


neighboring layer, and this decreases bonding strength in the c- plane.
Because of the B12 structural unit, the chemical formula of
"ideal" boron carbide is often written not as B4C, but as B12C3, and
the carbon deficiency of boron carbide described in terms of a
combination of the B12C3 and B12C2 units.
3 Properties :
Boron carbide is known as a robust material having high
hardness, high cross section for absorption of neutrons (i.e. good
shielding properties against neutrons), stability to ionizing radiation
and most chemicals . Its Vickers hardness (38 GPa) and fracture
toughness (3.5 MPam1/2) approach the corresponding values for
diamond (115 GPa and 5.3 MPam1/2).
4 - Preparation :
Boron carbide was first synthesized by Henri Moissan in 1899,
by reduction of boron trioxide either with carbon or magnesium in
presence of carbon in an electric arc furnace . In the case of carbon,
the reaction occurs at temperatures above the melting point of B4 C
and is accompanied by liberation of large amount of carbon monoxide
2 B2 O3 + 7 C B4 C + 6 CO
If magnesium is used, the reaction can be carried out in a
graphite furnace, and the magnesium byproducts are removed by
treatment with acid .
5 Uses :

Padlocks
Personal and vehicle anti - ballistic armor plating.
Grit blasting nozzles.
High - pressure water jet cutter nozzles.
Scratch and wear resistant coatings.
Cutting tools and dies.
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Abrasives.
Neutron absorber in nuclear reactors.
Metal matrix composites.
High energy fuel for solid fuel Ramjets.

58

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Boron Mono Fluoride


Contents

1 Introduction
2 Structure
3 Preparation
4 Reactions
5 Ligand
1 Introduction :

boron mono fluoride or fluoro borylene is a chemical


compound with formula BF, one atom of boron and one of fluorine. It
was discovered as an unstable gas and only in 2009 found to be a
stable ligand combining with transition metals, in the same way as
carbon monoxide. It is a sub halide , containing fewer than the normal
number of fluorine atoms, compared with boron tri fluoride. BF is iso
electronic with carbon monoxide and di nitrogen .
Other Names : Boron fluoride , Boron (I) fluoride ,
Fluoro boronene , Fluoro borylene
Molecular formula
BF
Molar mass
30 g mol1
Std enthalpy of formation fHo298 115.90 kJ mol-1
Standard molar entropy So298
200.48 J K-1 mol-1
2 Structure :
The experimental B - F bond length is 1.263 angstrom . One
reported computed bond order for the molecule is 1.4.
3 - Preparation
Boron mono fluoride can be prepared by passing boron tri
fluoride gas at 2000 C over a boron rod. It can be condensed at liquid
nitrogen temperatures ( -196 ) .
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4 - Reactions
BF can react with itself to form polymers of boron containing
fluorine with between 10 and 14 boron atoms. BF reacts with BF3 to
form B2F4. BF and B2 F4 further combine to form B3F5. B3F5 is
unstable above -50 and forms B8F12. This substance is a yellow oil.
BF reacts with acetylenes to make the 1,4-diboracyclohexadiene
ring system. BF can condense with 2-butyne forming 1,4- di fluoro 2,3,5,6 - tetra methyl -1,4- di bora cyclo hexadiene. Also it reacts with
acetylene to make 1,4- di fluoro -1,4- di bora cyclo hexadiene.
5 Ligand :
The first case of BF being a ligand on a transition element was
demonstrated in 2009 with the compound (C5H5)2 Ru2 (CO)4 (-BF).
The BF was bound to both ruthenium atoms as a bridge . Vidovic and
Aldridge reacted Na Ru (CO)2(C5H5) with (Et2O):BF3 . Note that the
BF was formed in place rather than added on.
Earlier in 1968 K. Kmpfer , H. Nth , W. Petz , and G. Schmid
claimed that Fe (BF) (CO)4 was formed in the reaction of B2F4 with
Fe(CO)5 , however this has not been reproduced .

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Boron Nitrate

- Introduction :
Boron nitrate is a boron compound with the formula B (NO3)3.
Like graphene , boron nitrate is a two - dimensional material.

IUPAC name : boron (3+) tri nitrate


Molecular formula
B N3 O 9
Molar mass
197 g mol1

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Boron Nitride
Contents

1 Introduction
2 Structure
3 Properties
o
3.1 Physical
o
3.2 Thermal stability
o
3.3 Chemical stability
o
3.4 Thermal conductivity
4 Synthesis
o
4.1 Preparation and reactivity of hexagonal BN
o
4.2 Intercalation of hexagonal BN
o
4.3 Preparation of cubic BN
o
4.4 Preparation of wurtzite BN
o
4.5 Production statistics
5 Applications
o
5.1 Hexagonal BN
o
5.2 Cubic boron nitride
o
5.3 Amorphous boron nitride
6 Other BN forms
o
6.1 Boron nitride fibers
o
6.2 Boron nitride nano mesh
o
6.3 Boron nitride nano tubes
o
6.4 Composites containing BN
7 Health issues
1 Introduction :

Boron nitride is a chemical compound with chemical formula


BN, consisting of equal numbers of boron and nitrogen atoms. BN is
isoelectronic to a similarly structured carbon lattice and thus exists in
various crystalline forms. The hexagonal form corresponding to
graphite is the most stable and softest among BN polymorphs, and is
there fore used as a lubricant and an additive to cosmetic products.
The cubic (sphalerite structure) variety analogous to diamond is called
c-BN. Its hardness is inferior only to diamond, but its thermal and
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chemical stability is superior. The rare wurtzite BN modification is


similar to lonsdaleite and may even be harder than the cubic form.
Boron nitride is not found in nature and is there fore produced
synthetically from boric acid or boron trioxide. The initial product is
amorphous BN powder, which is converted to crystalline h -BN by
heating in nitrogen flow at temperatures above 1500 C . c- BN is
made by annealing h-BN powder at higher temperatures, under
pressures above 5 GPa. Contrary to diamond, larger c-BN pellets can
be produced by fusing (sintering) relatively cheap c-BN powders. As
a result, c-BN is widely used in mechanical applications.
Because of excellent thermal and chemical stability, boron
nitride ceramics are traditionally used as parts of high-temperature
equipment. Boron nitride has a great potential in nanotechnology.
Nano tubes of BN can be produced that have a structure similar to that
of carbon nano tubes, i.e. graphene (or BN) sheets rolled on
themselves, however the properties are very different: whereas carbon
nanotubes can be metallic or semiconducting depending on the rolling
direction and radius, a BN nano tube is an electrical insulator with a
wide band gap of ~5.5 eV (same as in diamond), which is almost
independent of tube chirality and morphology. Similar to other BN
forms, BN nano tubes are more thermally and chemically stable than
carbon nano tubes which favors them for some applications.
IUPAC Name : Boron Nitride
Molecular Formula
Molar Mass
Appearance
Density
Melting point
Electron mobility
Refractive index (nD)
Crystal structure
Thermochemistry

BN
25 g mol1
Colorless crystals
2.1 (hBN) g cm3 ;
3.45 (cBN) g cm3
2973 C ( sublimes (cBN))
200 cm2/(Vs) (cBN)
1.8 (hBN); 2.1 (cBN)
hexagonal , sphalerite , wurtzite
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Std enthalpy of formation fHo298 -250.91 kJ mol1


Standard molar entropy So298
14.77 J K1 mol1
Hazards
2 Structure :
Boron nitride has been produced in an amorphous (a-BN) and
crystalline forms. The most stable crystalline form is the hexagonal
one, also called h-BN, -BN, or g-BN (graphitic BN). It has a layered
structure similar to graphite. Within each layer, boron and nitrogen
atoms are bound by strong covalent bonds, whereas the layers are
held together by weak van der Waals forces. The interlayer "registry"
of these sheets differs, however, from the pattern seen for graphite,
because the atoms are eclipsed, with boron atoms lying over and
above nitrogen atoms. This registry reflects the polarity of the B-N
bonds. Still, h-BN and graphite are very close neighbors and even the
BC6N hybrids have been synthesized where carbon substitutes for
some B and N atoms.
As diamond is less stable than graphite, cubic BN is less stable
than h-BN, but the conversion rate between those forms is negligible
at room temperature. The cubic form has the sphalerite crystal
structure, same as diamond structure, and is also called -BN or cBN. The wurtzite BN form (w-BN) has similar structure as lonsdaleite
rare hexagonal polymorph of carbon. In both c-BN and w-BN boron
and nitrogen atoms are grouped into tetrahedra , but the angles
between neighboring tetrahedra are different.

-BN, hexagonal

-BN, sphalerite structure BN, wurtzite structure

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3 Properties :
3 1 Physical :
Properties of amorphous and crystalline BN, graphite and diamond.
Some properties of h-BN and graphite differ within the basal planes
() and perpendicular to them ()
Material

Density (g/cm3)

a-BN
2.28

Mohs hardness

h-BN

c-BN w-BN graphite diamond

~2.1

3.45

3.49

~2.1

3.515

12

~10

~10

12

10

45

34

400

400

Knoop hardness
(GPa)

10

Bulk modulus
(GPa)

100

36.5

Thermal
conductivity
(W/cm K)

0.03

6; 0.3
7.4

Thermal expansion
(106/C)

34

440

220;
620
0.020.8

2.7;
38

1.2

2.7

1.5;
25

0.8

5.5

Bandgap (eV)

5.05

5.2

6.4

4.5
5.5

Refractive index

1.7

1.8

2.1

2.05

Magnetic
susceptibility
(emu/g)

100

0.48;
-17.3

2.4
0.2..2.7; 20..-28

1.6

The partly ionic structure of BN layers in h-BN reduces


covalency and electrical conductivity, whereas the interlayer
interaction increases resulting in higher hardness of h-BN relative to
graphite. The reduced electron-delocalization in hexagonal-BN is also
indicated by its absence of color and a large band gap. Very different
bonding strong covalent within the basal planes (planes where
boron and nitrogen atoms are covalently bonded) and weak between
them causes high anisotropy of most properties of h-BN.
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For example, the hardness, electrical and thermal conductivity


are much higher within the planes than perpendicular to them. On the
contrary, the properties of c-BN and w-BN are more homogeneous.
Those materials are extremely hard, with the hardness of c-BN
being slightly smaller and w-BN even higher than that of diamond.[10]
Because of much better stability to heat and metals, c-BN surpasses
diamond in mechanical applications . The thermal conductivity of BN
is among the highest of all electric insulators (see table).
Boron nitride can be doped p-type with Be and n-type with
boron, sulfur, silicon or if co-doped with carbon and nitrogen.[7] Both
hexagonal and cubic BN are wide-gap semiconductors with a band
gap energy corresponding to the UV region. If voltage is applied to hBN or c-BN, then it emits UV light in the range 215250 nm and
therefore can potentially be used as light emitting diodes (LEDs) or
lasers.
Little is known on melting behavior of boron nitride. It
sublimates at 2973 C at normal pressure releasing nitrogen gas and
boron, but melts at elevated pressure.
3 2 - Thermal stability :
Hexagonal and cubic (and probably w-BN) BN show
remarkable chemical and thermal stabilities. For example, h-BN is
stable to decomposition in temperatures up to 1000 C in air, 1400 C
in vacuum, and 2800 C in an inert atmosphere. The reactivity of hBN and c-BN is relatively similar, and the data for c-BN are
summarized in the table below.
Reactivity of c-BN with solids
Solid

Ambient

Action

Threshold T (C)

Mo

102 Pa vacuum

reaction

1360

Ni

102 Pa vacuum

wetting

1360

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Fe, Ni, Co

argon

react

Al

102 Pa vacuum

wetting and
1050
reaction

Si

103 Pa vacuum

wetting

1500

Cu, Ag, Au, 3


10 Pa vacuum
Ga, In, Ge, Sn

no wetting

1100

no wetting

2200

Al2O3 + B2O3

102 Pa vacuum

14001500

no reaction 1360

Thermal stability of c-BN can be summarized as follows :


In air or oxygen: B2O3 protective layer prevents further
oxidation to ~1300 C; no conversion to hexagonal form at
1400 C.
In nitrogen: some conversion to h-BN at 1525 C after 12 h.
5
In vacuum (10
Pa): conversion to h-BN at 15501600 C.

3 3 - Chemical stability :
Boron nitride is insoluble in usual acids, but is soluble in
alkaline molten salts and nitrides, such as Li OH , K OH, Na OH ,
Na2CO3, NaNO3, Li3N, Mg3N2, Sr3N2, Ba3N2 or Li3BN2, which are
therefore used to etch BN.
3 4 - Thermal conductivity :
The theoretical thermal conductivity of hexagonal Boron nitride
nano ribbons (BNNRs) can approach 17002000 W/(mK), which has
the same order of magnitude as the experimental measured value for
graphene , and can be comparable to the theoretical calculations for
graphene nano ribbons . Moreover, the thermal transport in the
BNNRs is anisotropic. The thermal conductivity of zigzag - edged
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BNNRs is about 20 % larger than that of armchair - edged nano


ribbons at room temperature .
4 Synthesis :
Boron nitride has not been found in nature and therefore is
produced synthetically. The most common raw materials for BN
synthesis, boric acid and boron trioxide are produced on industrial
scales by treating minerals borax and colemanite with sulfuric acid or
hydrochloric acid:
Na2B4O710H2O (borax) + H2SO4
4 H3BO3 (boric acid) + Na2SO4 + 5 H2O
Boron trioxide is obtained by heating boric acid .
4 1 - Preparation and reactivity of hexagonal BN :
Hexagonal boron nitride is obtained by the reacting boron
trioxide (B2O3) or boric acid (B(OH)3) with ammonia (NH3) or urea
(CO(NH2)2) in nitrogen atmosphere :
B2O3 + 2 NH3 2 BN + 3 H2O (T = 900 C)
B(OH)3 + NH3 BN + 3 H2O (T = 900 C)
B2O3 + CO(NH2)2 2 BN + CO2 + 2 H2O (T > 1000 C)
B2O3 + 3 CaB6 + 10 N2 20 BN + 3 CaO (T > 1500 C)
The resulting disordered (amorphous) boron nitride contains 92
95 % BN and 5 8 % B2O3. The remaining B2O3 can be evaporated in
a second step at temperatures > 1500 C in order to achieve BN
concentration > 98 %. Such annealing also crystallizes BN, the size of
the crystallites increasing with the annealing temperature .
h-BN parts can be fabricated inexpensively by hot-pressing with
subsequent machining. The parts are made from boron nitride
powders adding boron oxide for better compressibility. Thin films of
boron nitride can be obtained by chemical vapor deposition from
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boron tri chloride and nitrogen precursors . Combustion of boron


powder in nitrogen plasma at 5500 C yields ultrafine boron nitride
used for lubricants and toners.
Boron nitride reacts with iodine fluoride in tri chloro fluoro
methane at 30 C to produce an extremely sensitive contact
explosive, NI3, in low yield .
4 2 - Intercalation of hexagonal BN :

Structure of hexagonal boron nitride intercalated with potassium


(B4N4K)
Similar to graphite, various molecules, such as NH3 or alkali
metals , can be intercalated into hexagonal boron nitride, that is
inserted between its layers. Both experiment and theory suggest the
intercalation is much more difficult for BN than for graphite .
4 3 - Preparation of cubic BN :
Synthesis of c-BN uses same methods as that of diamond: Cubic
boron nitride is produced by treating hexagonal boron nitride at high
pressure and temperature, much as synthetic diamond is produced
from graphite. Direct conversion of hexagonal boron nitride to the
cubic form has been observed at pressures between 5 and 18 GPa and
temperatures between 1730 and 3230 C, that is similar parameters as
for direct graphite-diamond conversion . The addition of a small
amount of boron oxide can lower the required pressure to 47 GPa
and temperature to 1500 C. As in diamond synthesis, to further
reduce the conversion pressures and temperatures, a catalyst is added,
such as lithium, potassium, or magnesium, their nitrides, their
fluoronitrides, water with ammonium compounds, or hydrazine.[30][31]
Other industrial synthesis methods, again borrowed from diamond
growth, use crystal growth in a temperature gradient, or explosive
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shock wave. The shock wave method is used to produce material


called hetero diamond, a super hard compound of boron, carbon, and
nitrogen.
Low-pressure deposition of thin films of cubic boron nitride is
possible. As in diamond growth, the major problem is to suppress the
growth of hexagonal phases ( h-BN or graphite, respectively ) .
Whereas in diamond growth this is achieved by adding hydrogen gas,
boron tri fluoride is used for c-BN. Ion beam deposition, plasmaenhanced chemical vapor deposition, pulsed laser deposition, reactive
sputtering, and other physical vapor deposition methods are used as
well.
4 4 - Preparation of wurtzite BN
Wurtzite BN can be obtained via static high - pressure or
dynamic shock methods . The limits of its stability are not well
defined. Both c-BN and w-BN are formed by compressing h-BN, but
formation of w-BN occurs at much lower temperatures close to
1700 C.
4 5 - Production statistics :
Where as the production and consumption figures for the raw
materials used for BN synthesis, namely boric acid and boron
trioxide, are well known , the corresponding numbers for the boron
nitride are not listed in statistical reports. An estimate for the 1999
world production is 300 to 350 metric tons. The major producers and
consumers of BN are located in the United States, Japan, China and
Germany. In 2000, prices varied from about $ 75 / kg to $ 120 / kg for
standard industrial - quality h-BN and were about up to $ 200 $ 400
/ kg for high purity BN grades .
5 - Applications :
5 1 - Hexagonal BN :
Hexagonal BN is the most widely used polymorph. It is a good
lubricant at both low and high temperatures (up to 900 C, even in an
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oxidizing atmosphere). h-BN lubricant is particularly useful when the


electrical conductivity or chemical reactivity of graphite (alternative
lubricant) would be problematic. Another advantage of h-BN over
graphite is that its lubricity does not require water or gas molecules
trapped between the layers. Therefore, h-BN lubricants can be used
even in vacuum, e.g. in space applications. The lubricating properties
of fine-grained h-BN are used in cosmetics, paints, dental cements,
and pencil leads.

Ceramic BN crucible
Hexagonal BN was first used in cosmetics around 1940 in
Japan. However, because of its high price, h-BN was soon abandoned
for this application. Its use was revitalized in the late 1990s with the
optimization h-BN production processes, and currently h-BN is used
by nearly all leading producers of cosmetic products for foundations,
make-up, eye shadows, blushers, kohl pencils, lipsticks and other
skincare products.[11]
Because of its excellent thermal and chemical stability, boron
nitride ceramics are traditionally used as parts of high-temperature
equipment. h-BN can be included in ceramics, alloys, resins, plastics,
rubbers, and other materials, giving them self-lubricating properties.
Such materials are suitable for construction of e.g. bearings and in
steelmaking.[11] Plastics filled with BN have less thermal expansion as
well as higher thermal conductivity and electrical resistivity. Due to
its excellent dielectric and thermal properties, BN is used in
electronics e.g. as a substrate for semiconductors, microwavetransparent windows, and as a structural material for seals.
Hexagonal BN is used in xerographic process and laser printers
as a charge leakage barrier layer of the photo drum . In the automotive
industry, h-BN mixed with a binder (boron oxide) is used for sealing
oxygen sensors, which provide feedback for adjusting fuel flow. The
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binder utilizes the unique temperature stability and insulating


properties of h-BN.
Parts can be made of h-BN by hot pressing. Union Carbide
Corporation produces three grades of BN. HBN, with boron oxide
binder, usable to 550b 850 C in oxidizing atmosphere and up to
1600 C in vacuum, but due to the boron oxide content is sensitive to
water. HBR uses calcium borate binder and is usable at 1600 C.
HBC grade uses no binder and can be used to 3000 C .
5 2 - Cubic boron nitride :
Cubic boron nitride (CBN or c-BN) is widely used as an
abrasive . Its usefulness arises from its insolubility in iron, nickel, and
related alloys at high temperatures, whereas diamond is soluble in
these metals to give carbides. Polycrystalline c-BN (PCBN) abrasives
are therefore used for machining steel, whereas diamond abrasives are
preferred for aluminum alloys, ceramics, and stone. When in contact
with oxygen at high temperatures, BN forms a passivation layer of
boron oxide. Boron nitride binds well with metals, due to formation of
interlayers of metal borides or nitrides. Materials with cubic boron
nitride crystals are often used in the tool bits of cutting tools. For
grinding applications, softer binders, e.g. resin, porous ceramics, and
soft metals, are used. Ceramic binders can be used as well.
Commercial products are known under names "Borazon" (by
Diamond Innovations), and "Elbor" or "Cubonite" (by Russian
vendors). Similar to diamond, the combination in c-BN of highest
thermal conductivity and electrical resistivity is ideal for heat
spreaders. Contrary to diamond, large c-BN pellets can be produced
in a simple process (called sintering) of annealing c-BN powders in
nitrogen flow at temperatures slightly below the BN decomposition
temperature. This ability of c-BN and h-BN powders to fuse allows
cheap production of large BN parts . As cubic boron nitride consists
of light atoms and is very robust chemically and mechanically, it is
one of the popular materials for X-ray membranes: low mass results
in small X-ray absorption, and good mechanical properties allow
usage of thin membranes , thus further reducing the absorption.
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5 - 3 - Amorphous boron nitride :


Layers of amorphous boron nitride (a-BN) are used in some
semiconductor devices, e.g. MISFETs. They can be prepared by
chemical decomposition of tri chloro borazine with caesium, or by
thermal chemical vapor deposition methods. Thermal CVD can be
also used for deposition of h-BN layers, or at high temperatures, c-BN
6 - Other BN forms :
6 1 - Boron nitride fibers :
Hexagonal BN can be prepared in the form of fibers, structurally
similar to carbon fibers, by thermal decomposition of extruded
borazine (B3N3H6) fibers with addition of boron oxide in a nitrogen
atmosphere at 1800 C. An alternative method is thermal
decomposition of cellulose fibers impregnated with boric acid or
ammonium tetra borate in an atmosphere of ammonia and nitrogen
above 1000 C. Boron nitride fibers are used as reinforcement in
composite materials, with the matrix materials ranging from organic
resins to ceramics to metals (see Metal matrix composites).
6 2 - Boron nitride nano mesh :

Perspective view of nano mesh


(structure ends at the back of the figure)
Boron nitride nano mesh is an inorganic nano structured two dimensional material. It consists of a single BN layer, which forms by
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self-assembly a highly regular mesh after high-temperature exposure


of a clean rhodium or ruthenium surface to borazine under ultra-high
vacuum. The nanomesh looks like an assembly of hexagonal pores.
The distance between 2 pore centers is 3.2 nm and the pore diameter
is ~2 nm.
The boron nitride nanomesh is not only stable to decomposition
under vacuum , air and some liquids , but also up to temperatures of
800 C. In addition, it shows the extraordinary ability to trap
molecules and metallic clusters which have similar sizes to the
nanomesh pores, forming a well- ordered array. These characteristics
promise interesting applications of the nano mesh in areas like nano
catalysis , surface functionalisation , spintronics, quantum computing
and data storage media like hard drives.
6 2 - Boron nitride nano tubes :
Boron nitride nano tubes were theoretically predicted in 1994
and experimentally discovered in 1995. They can be imagined as a
rolled up sheet of boron nitride. Structurally, it is a close analog of the
carbon nanotube, namely a long cylinder with diameter of several to
hundred nanometers and length of many micrometers, except carbon
atoms are alternately substituted by nitrogen and boron atoms.
However, the properties of BN nano tubes are very different: whereas
carbon nano tubes can be metallic or semiconducting depending on
the rolling direction and radius, a BN nano tube is an electrical
insulator with a band gap of ~5.5 eV, basically independent of tube
chirality and morphology. In addition, a layered BN structure is much
more thermally and chemically stable than a graphitic carbon
structure.
All well - established techniques of carbon nano tube growth,
such as arc - discharge , laser ablation and chemical vapor deposition ,
are used to synthesize BN nano tubes. BN nano tubes can also be
produced by ball milling of amorphous boron, mixed with a catalyst:
iron powder, under NH3 atmosphere. Subsequent annealing at
~1100 C in nitrogen flow transforms most of the product into BN.
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Electrical and field emission properties of the thus prepared


nano tubes can be tuned by doping with gold atoms via sputtering of
gold on the nano tubes. Doping rare - earth atoms of europium turns a
BN nano tube into a phosphor material emitting visible light under
electron excitation .
Like BN fibers, boron nitride nano tubes show promise for
aerospace applications where integration of boron and in particular
the light isotope of boron (10B) into structural materials improves their
radiation-shielding properties; the improvement is due to strong
neutron absorption by 10B. Such 10BN materials are of particular
theoretical value as composite structural materials in future manned
interplanetary spacecraft, where absorption - shielding from cosmic
ray spallation neutrons is expected to be a particular asset in light
construction materials.
6 4 - Composites containing BN :
Addition of boron nitride to silicon nitride ceramics improves
the thermal shock resistance of the resulting material. For the same
purpose, BN is added also to silicon nitride - alumina and titanium
nitride-alumina ceramics. Other materials being reinforced with BN
are, e.g., alumina and zirconia , borosilicate glasses, glass ceramics,
enamels, and composite ceramics with titanium boride-boron nitride
and titanium boride- aluminium nitride-boron nitride and silicon
carbide-boron nitride composition .
7 - Health issues :
Boron nitride ( along with Si3N4, Nb N , and BNC ) is reported
to show weak fibrogenic activity and cause pneumoconiosis. The
maximum concentration recommended for nitrides of nonmetals is
10 mg / m3 for BN and 4 for Al N or Zr N .

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Boron Oxide
Boron oxide may refer to :

I Boron Monoxide (B2O)


II Boron Sub Oxide (B6O)
III Boron Tri Oxide (B2O3) - the most common form

I . Boron Monoxide
Boron monoxide (B2O) is a chemical compound of boron and
oxygen. Two experimental studies have proposed existence of
diamond - like and graphite - like B2O, as for boron nitride and
carbon solids. How ever , a later , systematic , experimental study of
boron oxide phase diagram suggests that B2O is unstable . The
instability of the graphite - like B2O phase was also predicted
theoretically.
IUPAC name : Boron (I) oxide
Other names : Di- boron monoxide
Molecular Formula
B2 O
Molar mass
38 g / mol

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II . Boron Sub Oxide


Boron Sub Oxide (chemical formula B6O) is a solid compound
of boron and oxygen. Its structure is built of eight icosahedra at the
apexes of the rhombohedral unit cell (space group R3-m). Each
icosahedron is composed of twelve boron atoms. Two oxygen atoms
are located in the interstices along the [111] rhombohedral direction.
Due to its short inter atomic bond lengths and strongly covalent
character, B6O displays a range of outstanding physical and chemical
properties such as great hardness (close to that of diamond, rhenium
diboride and boron nitride), low mass density, high thermal
conductivity, high chemical inertness, and excellent wear resistance.[3]
B6O can be synthesized by reducing B2O3 with boron or by
oxidation of boron with zinc oxide or other oxidants. These boron sub
oxide materials formed at or near ambient pressure are generally
oxygen deficient (B6Ox , x < 0.9) and have poor crystallinity and very
small grain size (less than 5 m). High pressure applied during the
synthesis of B6O can significantly increase the crystallinity, oxygen
stoichiometry, and crystal size of the products. Mixtures of boron and
B2O3 powders were usually used as starting materials in the reported
methods for B6O synthesis.
Oxygen - deficient boron sub oxide ( B6Ox, x <0.9 ) might form
icosahedral particles, which are neither single crystals nor quasi
crystals , but twinned groups of twenty tetrahedral crystals.
IUPAC name : Boron Sub Oxide
Other names : Hexa boron monoxide
Molecular Formula
B6 O
Molar mass
81 g / mol
Reddish icosahedral
Appearance
twinned crystals
Density
2.56 g / cm3
Melting point
2000 C
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Boron trioxide
Contents

1 Introduction
2 Preparation
3 Hardness
4 Applications
1 Introduction :

Boron trioxide (or diboron trioxide) is one of the oxides of


boron. It is a white, glassy solid with the formula B2O3. It is almost
always found as the vitreous ( amorphic ) form ; however, it can be
crystallized after extensive annealing. It is one of the most difficult
compounds known to crystallize.
Glassy boron oxide (g-B2O3) is thought to be composed of
boroxol rings which are six- membere d rings composed of alternating
3-coordinate boron and 2 - coordinate oxygen. This view is
controversial, however, because no model has ever been made of
glassy boron oxide of the correct density containing a large number of
six- membered rings. The rings are thought to make a few BO3
triangles, but mostly link (polymerize) into ribbons and sheets. The
crystalline form (- B2O3) see structure in the infobox ) is exclusively
composed of BO3 triangles. This trigonal , quartz - like network
undergoes a coesite - like transformation to monoclinic - B2O3 at
several giga pascals and is 9.5 GPa .
Other names : boron oxide , diboron trioxide , boron
sesqui oxide , boric oxide , boria , Boric acid anhydride
Molecular Formula
B2 O3
Molar Mass
69.6 g / mol
Appearance
white, glassy solid
2.46 g /cm3, liquid ;
Density
2.55 g /cm3, trigonal ;
3.11 3.146 g /cm3, onoclinic
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Melting Point
Boiling Point
Solubility in water
Solubility
Acidity (pKa)
LD50
Thermodynamic
data
Spectral data

450 C (trigonal)
510 C (tetrahedral)
1860 C, sublimates at 1500 C
22 g / L
partially soluble in methanol
~4
3150 mg/kg (oral, rat)
Phase behaviour
Solid, liquid, gas
UV, IR, NMR, MS

2 - Preparation :
Boron trioxide is produced by treating borax with sulfuric acid
in a fusion furnace. At temperatures above 750 C, the molten boron
oxide layer separates out from sodium sulfate. It is then decanted,
cooled and obtained in 96 97 % purity.
Another method is heating boric acid above ~300 C. Boric acid
will initially decompose into water steam and meta boric acid (HBO2)
at around 170 C, and further heating above 300 C will produce
more steam and boron trioxide. The reactions are :
H3BO3 HBO2 + H2O
2 HBO2 B2O3 + H2O
Boric acid goes to anhydrous microcrystalline B2O3 in a heated
fluidized bed. Carefully controlled heating rate avoids gumming as
water evolves. Molten boron oxide attacks silicates. Internally
graphitized tubes via acetylene thermal decomposition are passivated .
Crystallization of molten - B2 O3 at ambient pressure is
strongly kinetically disfavored (compare liquid and crystal densities).
Threshold conditions for crystallization of the amorphous solid are 10
k bar and ~ 200 C .
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3 - Hardness :
The bulk modulus of - B2 O3 is rather high ( K = 180 GPa ) .
The Vickers hardness of g- B2 O3 is 1.5 GPa and of -B2O3 is 16 GPa.

4 - Applications
Fluxing agent for glass and enamels
Starting material for synthesizing other boron
compounds such as boron carbide
An additive used in glass fibers (optical fibres)
It is used in the production of borosilicate glass
The inert capping layer in the LEC process for the
production of gallium arsenide single crystal
As an acid catalyst in organic synthesis

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Boron Phosphide
Contents

1 Introduction
2 History
3 Appearance
4 Chemical properties
5 Physical properties [4]
1 Introduction :

Boron phosphide (BP) is a chemical compound of boron and


phosphorus. It is a semiconductor .
Molecular Formula
Molar Mass
Appearance
Density
Melting point
Band gap
Electron mobility
Thermal conductivity
Refractive index (nD)
Crystal structure
Coordination geometry

BP
42 g / mol
maroon powder
2.90 g / cm3
1100 C ( decomposes )
2 eV ( indirect )
5400 cm2/(V*s) (300 K)
4 W/(cm*K) (300 K)
3.05 (0.63 m)
Zinc Blende
Tetrahedral

2 History :
Crystals of boron phosphide have been synthesized by Henri
Moissan as early as in 1891 .
3 - Appearance
Pure BP is almost transparent, n-type crystals are orange-red
whereas p-type ones are dark red [4].
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4 - Chemical properties :
BP is not attacked by acids or boiling aqueous alkali water
solutions. It is only attacked by molten alkalis .
5 - Physical properties :
coefficient of thermal expansion ~3x106 /K
heat capacity CP ~ 0.8 J/(g*K) (300 K)
Debye temperature = 1000 K
relatively high micro hardness of 32 GPa (100 g load).
2
electron and hole mobilities of few hundred cm / (V*s)
(up to 500)

82

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Boron sulfide
1 Introduction :
Boron sulfide is the chemical compound with the formula B2S3.
This polymeric material that has been of interest as a component of
high-tech glasses and as a reagent for preparing organo sulfur
compounds. Like the sulfides of silicon and phosphorus, B 2S3 reacts
with water, including atmospheric moisture to release H2S. Thus,
samples must be handled under anhydrous conditions.
Like the boron oxides, B2S3 readily forms glasses when blended
with other sulfides such as P4S10. Such glasses absorb lower
frequencies of Infra-red energy relative to conventional borosilicate
glasses.
B2S3 converts ketones into the corresponding thiones. For
example, the conversion of benzophenone to its thione proceeds as
follows:
B2S3 + 3 (C6H5)2C= O B2O3 + 3 (C6H5)2C= S
In practice, B2S3 would be used in excess.
IUPAC Name : Boron sulfide
Other Names : Boron tri sulfide
Molecular Formula B2S3
Molar Mass
118 g / mol
Appearance
colorless crystals
Density
1.55 g / cm3, solid
Melting point
563 C
Boiling point
decomposes at high T
Solubility in water
decomposes
Crystal structure
monoclinic

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2 Synthesis :
Besides other methods the boron sulfide can be obtained by
the reaction of iron or manganese boride with hydrogen sulfide at
temperatures of 300C.
2 Fe B + 4 H2S B2S3 + Fe S + 4 H2
The first synthesis was done by Jns Jakob Berzelius in 1824
by direct reaction of amorphous boron with sulfur vapor.
2 B + 3 S B 2S 3
Another synthesis was favoured by Friedrich Whler and Henri
Etienne Sainte-Claire Deville first published in 1858, starting from
boron and hydrogen sulfide.
2 B + 3 H2S B2S3 + 3 H2

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Boron Tri Bromide


Contents

1 Introduction
2 Chemical properties
3 Synthesis
4 History
5 Applications
1 Introduction :

Boron tri bromide, BBr3, is a colorless, fuming liquid


compound containing boron and bromine. It is usually made by
heating boron trioxide with carbon in the presence of bromine: this
generates free boron which reacts vigorously with the bromine. It is
very volatile and fumes in air because it reacts vigorously with water
to form boric acid and hydrogen bromide.
IUPAC name : Boron tri bromide
Other names : Tri bromo borane
Molecular Formula
B Br3
Molar Mass
250.5 g / mol
Appearance
colorless to amber liquid
Density
2.643 g / cm3
Melting point
46.3 C
Boiling point
91.3 C
Solubility in water
reacts violently
Refractive index (nD)
1.00207
Specific heat capacity, C 0.2706 J/K
GHS pictograms
GHS signal word
Flash point

DANGER
-18 C
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2 - Chemical properties :
Boron tri bromide is commercially available and is a strong
Lewis acid. It is an excellent demethylating or dealkylating agent for
ethers, often in the production of pharmaceuticals. Additionally, it
also finds applications in olefin polymerization and in Friedel - Crafts
chemistry as a Lewis acid catalyst. The electronics industry uses
boron tri bromide as a boron source in pre - deposition processes for
doping in the manufacture of semi conductors.
3 - Synthesis :
The reaction of boron carbide with bromine at temperatures
above 300 C leads to the formation of boron tri bromide. The product
can be purified by vacuum distillation.
4 History :
The first synthesis was done by M. Poggiale in 1846 by reacting
boron trioxide with carbon and bromine at high temperatures :
B2O3 + 3 C + 3 Br2 2 BBr3 + 3 CO
An improvement of this method was developed by F. Whler
and Deville in 1857. By starting from amorphous boron the
reaction temperatures are lower and no carbon monoxide is
produced :
2 B + 3 Br2 2 BBr3
5 - Applications :
Pharmaceutical Manufacturing
Image Processing
Semiconductor Doping
Semiconductor Plasma Etching
Photovoltaic Manufacturing
Reagent for Various Chemical Processes.

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Boron Tri Chloride

Contents

1 Introduction
2 Production and properties
3 Uses
4 Safety
1 Introduction :

Boron tri chloride is a chemical compound with the formula


BCl3. This colorless gas is a valuable reagent in organic synthesis. It
is also dangerously reactive.
2 - Production and properties :
Boron reacts with halogens to give the corresponding trihalides.
Boron tri chloride is, however, produced industrially by direct
chlorination of boron oxide and carbon at 500 C.
B2O3 + 3 C + 3 Cl2 2 BCl3 + 3 CO
The synthesis is analogous to the Kroll process for the
conversion of titanium dioxide to titanium tetrachloride. In the
laboratory BF3 reacted with AlCl3 gives BCl3 via halogen exchange.
BCl3 is a trigonal planar molecule like the other boron tri halides ,
and has a bond length of 175pm. It has a zero dipole moment because
it is symmetric and therefore the dipole moments associated with the
bonds cancel each other out. Boron tri chloride does not form dimers,
although there is some evidence that may indicate dimerisation at
very low temperatures (20K). NMR studies of mixtures of boron
trihalides shows the presence of mixed halides which may indicate a
four centre intermediate e.g. a dimer. The absence of dimerisation
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contrasts with the other tri halides of group 13 which contain 4 or 6


coordinate metal centers , for example see AlCl3 and GaCl3. A degree
of -bonding has been proposed to explain the short B Cl distance
although there is some debate as to its extent.
BCl3 is a Lewis acid readily forming adducts with tertiary
amines, phosphines, ethers, thioethers, and halide ions. For example,
BCl3S(CH3)2 (CAS# 5523-19-3) is often employed as a conveniently
handled source of BCl3 because this solid (m.p. 88-90 C) releases
BCl3:
(CH3)2SBCl3 (CH3)2S + BCl3
When boron tri chloride is passed at low pressure through
devices delivering an electric discharge, diboron tetrachloride,[5]
Cl2B-BCl2, and tetra boron tetrachloride, formula B4Cl4, are formed.
Colourless diboron tetrachloride (m.p. -93 C) has a planar molecule
in the solid, (similar to dinitrogen tetroxide, but in the gas phase the
structure is staggered . It decomposes at room temperatures to give a
series of mono chlorides having the general formula (BCl)n, in which
n may be 8, 9, 10, or 11; the compounds with formulas B8Cl8 and
B9Cl9 are known to contain closed cages of boron atoms.
The mixed aryl and alkyl boron chlorides are also of interest.
Phenyl boron dichloride is commercially available. Such species can
be prepared by the reaction of BCl3 with organotin reagents :
2 BCl3 + R4Sn 2 RBCl2 + R2SnCl2
3 - Uses :
Boron tri chloride is a starting material for the production of
elemental boron. It is also used in the refining of aluminium,
magnesium, zinc, and copper alloys to remove nitrides, carbides, and
oxides from molten metal. It has been used as a soldering flux for
alloys of aluminium, iron, zinc, tungsten, and monel. Aluminum
castings can be improved by treating the melt with boron tri chloride
vapors. In the manufacture of electrical resistors, a uniform and
lasting adhesive carbon film can be put over a ceramic base using
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BCl3. It has been used in the field of high energy fuels and rocket
propellants as a source of boron to raise BTU value. BCl3 is also used
in plasma etching in semiconductor manufacturing. This gas etches
metal oxides by formation of a volatile B O Cl x compounds.
B Cl3 is used as a reagent in the synthesis of organic
compounds. Like the corresponding bromide, it cleaves C-O bonds in
ethers.

4 - Safety
BCl3 is an aggressive reagent that releases hydrogen chloride
upon exposure to moisture or alcohols. The dimethyl sulfide adduct
is safer to use, when possible.

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Boron Tri Fluoride

Contents

1 Introduction
2 Structure and bonding
3 Synthesis and handling
4 Reactions
o
4.1 Comparative Lewis acidity
o
4.2 Hydrolysis
5 Uses
6 Discovery
1 Introduction :

Boron tri fluoride is the chemical compound with the formula


BF3. This pungent colourless toxic gas forms white fumes in moist
air. It is a useful Lewis acid and a versatile building block for other
boron compounds.
Molecular Formula
Molar mass
Appearance
Density
Melting point
Boiling point
Solubility in water
Solubility

B F3
68 g / mol (anhydrous)
104 g / mol (dihydrate)
colorless gas (anhydrous)
colorless liquid (dihydrate)
0.00276 g /cm3 ( anhydrous gas)
1.64 g/cm3 (dihydrate)
126.8 C
100.3 C
very soluble
soluble in benzene, toluene,
hexane, chloroform and
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methylene chloride
Hazards
GHS pictograms
GHS signal word
EU classification
Flash point

Template:GHS04
DANGER
Very toxic (T+)
Corrosive (C)
non-flammable

2 - Structure and bonding :


The geometry of a molecule of BF3 is trigonal planar. The D3h
symmetry conforms with the prediction of VSEPR theory. The
molecule has no dipole moment by virtue of its high symmetry. The
molecule is iso electronic with the carbonate anion, CO32.
BF3 is commonly referred to as "electron deficient," a
description that is reinforced by its exothermic reactivity toward
Lewis bases.
In the boron tri halides, BX3, the length of the B-F bonds (1.30
) is shorter than would be expected for single bonds, [3] and this
shortness may indicate stronger B-X -bonding in the fluoride. A
facile explanation invokes the symmetry-allowed overlap of a p
orbital on the boron atom with the in-phase combination of the three
similarly oriented p orbitals on fluorine atoms.
3 - Synthesis and handling :
BF3 is manufactured by the reaction of boron oxides with
hydrogen fluoride:
B2O3 + 6 HF 2 BF3 + 3 H2O
Typically the HF is produced in situ from sulfuric acid and
fluorite (CaF2). Approximately 2300 - 4500 tones of boron tri
fluoride are produced every year.
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On a laboratory scale, BF3 is produced by the thermal


decomposition of diazonium salts :
Ph N2 B F4 Ph F + BF3 + N2
Anhydrous boron tri fluoride has a normal boiling temperature
of 100.3 C and a critical temperature of 12.3 C, so that it can be
stored as a refrigerated liquid only between those temperatures.
Storage or transport vessels should be designed to withstand internal
pressure, since a refrigeration system failure could cause pressures to
rise to the critical pressure of 49.85 bar (4.985 MPa).
Boron tri fluoride is corrosive. Suitable metals for equipment
handling boron trifluoride include stainless steel, monel, and
hastelloy. In presence of moisture it corrodes steel, including
stainless steel. It reacts with polyamides. Poly tetra fluoro ethylene,
poly chloro tri fluoro ethylene, poly vinylidene fluoride, and poly
propylene show satisfactory resistance. The grease used in the
equipment should be fluoro carbon based, as boron tri fluoride reacts
with the hydrocarbon-based ones.
4 - Reactions :
Unlike the aluminium tri halides, the boron tri halides are all
monomeric . They undergo rapid halide exchange reactions:
B F3 + B Cl3 B F2 Cl + B Cl2 F
Because of the facility of this exchange process, the mixed
halides cannot be obtained in pure form.
Boron tri fluoride is a versatile Lewis acid that forms adducts
with such Lewis bases as fluoride and ethers :
Cs F + B F3 Cs B F4
O (C2H5)2 + B F3 B F3 O (C2H5)2
Tetra fluoro borate salts are commonly employed as noncoordinating anions. The adduct with diethyl ether, boron tri fluoride
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diethyl etherate or just boron tri fluoride etherate (BF3O(Et)2) is a


conveniently handled liquid and consequently is a widely encountered
as a laboratory source of BF3. It is stable as a solution in ether, but not
stoichio metrically. Another common adduct is the adduct with
dimethyl sulfide (BF3S(Me)2), which can be handled as a neat liquid.
4 1 - Comparative Lewis acidity :
All three lighter boron tri halides, BX3 (X = F, Cl, Br) form
stable adducts with common Lewis bases. Their relative Lewis
acidities can be evaluated in terms of the relative exo thermicities of
the adduct - forming reaction. Such measurements have revealed the
following sequence for the Lewis acidity:
BF3 < BCl3 < BBr3 ( strongest Lewis acid )
This trend is commonly attributed to the degree of - bonding in
the planar boron tri halide that would be lost upon pyramidalization of
the BX3 molecule. which follows this trend:
BF3 > BCl3 > BBr3 ( most easily pyramidalized )
The criteria for evaluating the relative strength of -bonding are
not clear, however. One suggestion is that the F atom is small
compared to the larger Cl and Br atoms, and the lone pair electron in
pz of F is readily and easily donated and overlapped to empty p z
orbital of boron. As a result, the pi donation of F is greater than that of
Cl or Br.
In an alternative explanation, the low Lewis acidity for BF 3 is
attributed to the relative weakness of the bond in the adducts F3B-L.

4 2 Hydrolysis :
Boron tri fluoride reacts with water to give boric acid and fluoro
boric acid. The reaction commences with the formation of the aquo
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adduct, H2O-BF3, which then loses HF that gives fluoboric acid with
boron tri fluoride.
4 BF3 + 3 H2O 3 HBF4 + "B(OH)3"
The heavier tri halides do not undergo analogous reactions,
possibly the lower stability of the tetrahedral ions BX4- (X = Cl, Br).
Because of the high acidity of fluoro boric acid, the fluoro borate ion
can be used to isolate particularly electrophilic cations, such as
diazonium ions, that are otherwise difficult to isolate as solids.
5 Uses :
Boron tri fluoride is most importantly used as a reagent in
organic chemistry, typically as a Lewis acid. Examples :
initiates polymerisation reactions of unsaturated
compounds such as poly ethers

as a catalyst in some isomerization, alkylation,


esterification, condensation, Mukaiyama aldol addition, and other
reactions

Other uses:
applied as dopant in ion implantation

p-type dopant for epitaxially grown silicon

used in sensitive neutron detectors in ionization chambers


and devices to monitor radiation levels in the Earth's atmosphere

in fumigation

as a flux for soldering magnesium

to prepare diborane

6 Discovery :
Boron tri fluoride was discovered in 1808 by Joseph Louis GayLussac and Louis Jacques Thnard, who were trying to isolate "fluoric
acid" (i.e. hydro fluoric acid) by combining calcium fluoride with
vitrified boric acid; the resulting vapours failed to etch glass, so they
named it fluoboric gas.
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Boron Tri Iodide


- Introduction :
Boron tri iodide is a chemical compound of boron and iodine
with chemical formula BI3. It has a trigonal planar molecular
geometry. It is a crystalline solid. Its dielectric constant is 5.38 and its
heat of vaporization is 40.5 kJ / mol.
For information on the three lighter boron tri halides ( BF3 ,
BCl3 and B Br3 ) , see Boron _tri fluoride.
Molecular formula
Molar mass
Appearance
Density
Melting point
Boiling point
Solubility in water
Flash point

B I3
391.5 g / mol
crystalline solid
3.35 g / cm3 (50 C)
49.9 C
210 C,
insoluble
-18 C

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Boronic Acid

The general structure of a boronic acid, where R is a substituent.


Contents

1 Introduction
2 Boronic acids
o
2.1 Synthesis
3 Boronate esters
4 Boronic acids in organic chemistry
o
4.1 Suzuki coupling reaction
o
4.2 Chan-Lam coupling
o
4.3 Liebeskind - Srogl coupling
o
4.4 Conjugate addition
o
4.5 Oxidation
o
4.6 Homologization
o
4.7 Electrophilic allyl shifts
o
4.8 Hydrolysis
o
4.9 C- H coupling reactions
5 Boronic acids in supramolecular chemistry
o
5.1 Saccharide recognition
6 Boronic acids and esters
7 Borate salts
1 Introduction :

A boronic acid is an alkyl or aryl substituted boric acid


containing a carbon boron bond belonging to the larger class of
organo boranes . Boronic acids act as Lewis acids. Their unique
feature is that they are capable of forming reversible covalent
complexes with sugars, amino acids, hydroxamic acids , etc.
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(molecules with vicinal, (1,2) or occasionally (1,3) substituted Lewis


base donors (alcohol, amine, carboxylate)). The pKa of a boronic acid
is ~9, but they can form tetrahedral boronate complexes with pKa ~7.
They are occasionally used in the area of molecular recognition to
bind to saccharides for fluorescent detection or selective transport of
saccharides across membranes.
Boronic acids are used extensively in organic chemistry as
chemical building blocks and intermediates predominantly in the
Suzuki coupling. A key concept in its chemistry is trans metallation of
its organic residue to a transition metal.
The compound bortezomib with a boronic acid group is a drug
used in chemotherapy. The boron atom in this molecule is a key
substructure because through it certain proteasomes are blocked that
would otherwise degrade proteins.
2 - Boronic acids :
Many air-stable boronic acids are commercially available. They
are characterized by high melting points. Since boronic acids easily
lose water to form the cyclic trimeric anhydride, commercial material
oftentimes contains substantial quantities of this anhydride. This does
not affect reactivity.
Boronic acid

Molar
mass

Melting
point C

Phenyl boronic acid

Phenyl

122

216219

2-Thienyl boronic acid

Thiophene

128

138140

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Methyl boronic acid

60

9194

cis- Propenyl boronic


propene
acid

86

6570

Trans

boronic acid

86

123127

Propenyl

Methyl

propene

2 - 1 Synthesis :
Boronic acids can be obtained via several methods. The most
common way is reaction of organo metallic compounds based on
lithium or magnesium ( Grignards ) with borate esters. For example
phenyl boronic acid is produced from phenyl magnesium bromide and
tri methyl borate followed by hydrolysis .
Ph Mg Br + B (OMe)3 PhB (OMe)2 + Me O Mg Br
Ph B (OMe)2 + H2O Ph B (OH)2 + Me OH
Another method is reaction of an arylsilane (RSiR3) with boron
tri bromide (BBr3) in a trans metallation to RBBr2 followed by acidic
hydrolysis.
A third method is by palladium catalyzed reaction of aryl
halides and tri flates with di boronyl esters in a coupling reaction. An
alternative to esters in this method is the use of di boronic acid or
tetra hydroxy di boron ([B(OH2)]2).
3 - Boronate esters
Boronate esters are esters formed between a boronic acid
and an alcohol.

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Compound

General formula

Boronic acid

RB(OH)2

General structure

Boronate ester RB(OR)2


Comparison between boronic acids and boronate esters
The compounds can be obtained from borate esters by condensation
with alcohols and diols. Phenyl boronic acid can be self condensed to
the cyclic trimer called tri phenyl anhydride or tri phenyl boroxin .
Structural
Molar Boiling
Boronic ester
Diol
formula
mass point (C)
Allylboronic acid
pinacol
pinacol ester

168

50 53
(5 mmHg)

Phenyl boronic
tri
acid tri methylene methylene
glycol ester
glycol

162

106
(2 mmHg)

Di iso propoxy
methyl borane

144

105 -107

iso
propanol

Compounds with 5- membered cyclic structures containing the C - O


B O - C linkage are called dioxa borolanes and those with 6 membered rings dioxa borinanes.
4 - Boronic acids in organic chemistry :
4 - 1 - Suzuki coupling reaction :
Boronic acids are used in organic chemistry in the Suzuki
reaction. In this reaction the boron atom exchanges its aryl group with
an alkoxy group from palladium.
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4 - 2 - Chan - Lam coupling :


In the Chan-Lam coupling the alkyl, alkenyl or aryl boronic
acid reacts with a N-H or O-H containing compound with Cu(II) such
as copper(II) acetate and oxygen and a base such as pyridine forming
a new carbonnitrogen bond or carbonoxygen bond for example in
this reaction of 2-pyridone with trans-1-hexenylboronic acid:

The reaction mechanism sequence is deprotonation of the


amine, coordination of the amine to the copper(II), trans metallation
(transferring the alkyl boron group to copper and the copper acetate
group to boron) , oxidation of Cu (II) to Cu (III) by oxygen and
finally reductive elimination of Cu (III) to Cu (I) with formation of
the product. Direct reductive elimination of Cu (II) to Cu (0) also
takes place but is very slow. In catalytic systems oxygen also
regenerates the Cu (II) catalyst.
4 - 3 - Liebeskind - Srogl coupling
In the Liebeskind - Srogl coupling a thiol ester is coupled with a
boronic acid to produce a ketone.
4 - 4 - Conjugate addition
The boronic acid organic residue is a nucleophile in conjugate
addition also in conjunction with a metal. In one study the pinacol
ester of allyl boronic acid is reacted with dibenzylidene acetone in a
such a conjugate addition :
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The catalyst system in this reaction is tris( dibenzylidene acetone )


di palladium (0) / tri cyclo hexyl phosphine .
Another conjugate addition is that of gramine with phenylboronic
acid catalyzed by cyclo octadiene rhodium chloride dimer [13]:

4 - 5 - Oxidation
Boronic esters are oxidized to the corresponding alcohols with
base and hydrogen peroxide ( for an example see: carbenoid )
4 - 6 - Homologization
In boronic ester homologization an alkyl group shifts from
boron in a boronate to carbon :

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Boronic ester homologization mechanism

Homologization application
In this reaction dichloro methyl lithium converts the boronic
ester into a boronate. A lewis acid then induces a rearrangement of the
alkyl group with displacement of the chlorine group. Finally an
organo metallic reagent such as a Grignard reagent displaces the
second chlorine atom effectively leading to insertion of an RCH2
group into the C- B bond . Another reaction featuring a boronate alkyl
migration is the Petasis reaction.
4 7 - Electrophilic allyl shifts
Allyl boronic esters engage in electrophilic allyl shifts very
much like silicon pendant in the Sakurai reaction. In one study a
diallylation reagent combines both :

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4 8 - Hydrolysis
Hydrolysis of boronic esters back to the boronic acid and the
alcohol can be accomplished in certain systems with thionyl chloride
and pyridine. Aryl Boronic acids or esters may be hydrolyzed to the
corresponding phenols by reaction with hydroxylamine at room
temperature.
48-

C - H coupling reactions

The diboron compound bis (pinacolato) diboron reacts with


aromatic hetero cycles or simple arenes to an arylboronate ester with
iridium catalyst [IrCl(COD)]2 (a modification of Crabtree's catalyst)
and base 4,4-di-tert-butyl-2,2-bipyridine in a C-H coupling reaction
for example with benzene:

In one modification the arene reacts 1 on 1 ( instead of a large


excess ) with cheaper pinacolborane

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Unlike in ordinary electrophilic aromatic substitution (EAS)


where electronic effects dominate, the regioselectivity in this reaction
type is solely determined by the steric bulk of the iridium complex.
This is exploited in a meta - bromination of m - xylene which by
standard AES would give the ortho product :

5 - Boronic acids in supra molecular chemistry :


5 - 1 - Saccharide recognition

An example of a diboronic acid based fluorescent sensor


bound to a sugar acid, reported by James and coworkers in J. Am.
Chem. Soc., 2004, 126(49), 16179-16186.

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The covalent pair-wise interaction between boronic acids and


1,2- or 1,3-diols in aqueous systems is rapid and reversible. As such
the equilibrium established between boronic acids and the hydroxyl
groups present on saccharides has been successfully employed to
develop a range of sensors for saccharides . One of the key
advantages with this dynamic covalent strategy lies in the ability of
boronic acids to overcome the challenge of binding neutral species in
aqueous media. If arranged correctly, the introduction of a tertiary
amine within these supra molecular systems will permit binding to
occur at physiological pH and allow signaling mechanisms such as
photo induced electron transfer mediated fluorescence emission to
report the binding event.
Potential applications for this research include systems to
monitor diabetic blood glucose levels. As the sensors employ an
optical response, monitoring could be achieved using minimally
invasive methods, one such example is the investigation of a contact
lens doped with boronic acid based sensors to monitor glucose levels
within ocular fluid.
6 - Borinic acids and esters
Borinic acids and borinate esters have the general structure
R2BOR.
compound

general formula

borinic acid

R2BOH

borinate ester

R2BOR

general structure

7 - Borate salts :
Borate salts are ate complexes and have the general structure
R4B M+ for example potassium tetra phenyl borate ( IUPAC name:
potassium tetra phenyl boranuide ) .
-

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Boro Phospho Silicate Glass


Boro phospho silicate glass, commonly known as BPSG, is a
type of silicate glass that includes additives of both boron and
phosphorus. Silicate glasses such as PSG and Boro phospho silicate
glass are commonly used in semi conductor device fabrication for
inter metal layers , i.e., insulating layers deposited between
succeedingly higher metal or conducting layers.
BPSG has been implicated in increasing a device's susceptibility
to soft errors since the Boron-10 isotope is good at capturing thermal
neutrons from cosmic radiation. It then undergoes fission producing a
gamma ray, an alpha particle, and a lithium ion. These products may
then dump charge into nearby structures, causing data loss (bit
flipping, or single event upset).
In critical designs, depleted boron consisting almost entirely of
Boron-11 is used to avoid this effect as a radiation hardening
measure. Boron-11 is a by-product of the nuclear industry.

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Boro Silicate Glass

Boro silicate glassware ( two beakers and a test tube ) .


Contents

1 Introduction
2 History
3 Manufacturing process
4 Physical characteristics
5 Usage
6 Boro silicate nano particles
7 In lamp working
1 Introduction :

Borosilicate glass is a type of glass with the main glass-forming


constituents silica and boron oxide. Boro silicate glasses are known
for having very low coefficients of thermal expansion (~3 106 / C
at 20C), making them resistant to thermal shock, more so than any
other common glass. Such glass is less subject to thermal stress and is
commonly used for the construction of reagent bottles.
2 History :
Boro silicate glass was first developed by German glassmaker
Otto Schott in the late 19th century and sold under the brand name
"Duran" in 1893. After Corning Glass Works introduced Pyrex in
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1915, the name became a synonym for borosilicate glass in the


English - speaking world.
The European manufacturer of Pyrex, Arc International, uses
borosilicate glass in its Pyrex glass kitchen products ; how ever , the
U.S. manufacturer of Pyrex kitchenware uses tempered soda - lime
glass. Thus Pyrex can refer to either soda - lime glass or borosilicate
glass when discussing kitchen glassware, while Pyrex, Bomex, Duran
and Kimax all refer to borosilicate glass when discussing laboratory
glass ware.
Most borosilicate glass is colorless. Colored borosilicate, for the
studio glass trade, was first widely brought onto the market in 1986
when Paul Trautman founded North star Glass works . In 2000,
former North star Glass works employee Henry Grimmett started
Glass Alchemy and developed the first cadmium Crayon Colors and
aventurine Sparkle colors in the borosilicate palette.
In addition to the quartz, sodium carbonate, and calcium
carbonate traditionally used in glassmaking, boron is used in the
manufacture of borosilicate glass. Typically, the resulting glass
composition is about 70 % silica, 10 % boron oxide, 8 % sodium
oxide, 8 % potassium oxide, and 1 % calcium oxide (lime). Though
somewhat more difficult to make than traditional glass (Corning
conducted a major revamp of their operations to make it), it is
economical to produce; its superior durability, chemical and heat
resistance finds excellent use in chemical laboratory equipment,
cookware, lighting and, in certain cases, windows.
3 - Manufacturing process :
Boro silicate glass is created by adding boron to the traditional
glass maker's frit of silicate sand, soda, and ground lime. Since boro
silicate glass melts at a higher temperature than ordinary silicate glass,
some new techniques were required for industrial production.
Borrowing from the welding trade, burners combining oxygen with
natural gas were required.

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4 - Physical characteristics :
Borosilicate glass has a very low thermal expansion coefficient
( 3.3 x 10-6/K ) , about one-third that of ordinary glass. This reduces
material stresses caused by temperature gradients which makes
borosilicate the most suitable kind of glass for certain applications
(see below).
The softening point ( temperature at which viscosity is
approximately 107.6 poise ) of type 7740 Pyrex is 820 C .
Boro silicate glass is less dense than ordinary glass.
While more resistant to thermal shock than other types of glass,
borosilicate glass can still crack or shatter when subject to rapid or
uneven temperature variations. When broken, borosilicate glass tends
to crack into large pieces rather than shattering (it will snap rather
than splinter).
Optically, boro silicate glasses are crown glasses with low
dispersion (Abbe numbers around 65) and relatively low refractive
indices (1.511.54 across the visible range).
5 - Usage :
Virtually all modern laboratory glassware is borosilicate glass. It
is so widely used in this application due to its chemical and thermal
resistance and good optical clarity, but the glass can be reacted with
sodium hydride to produce sodium boro hydride , a common
laboratory reducing agent. Fused quartz is also found in some
laboratory equipment when its higher melting point and transmission
of UV are required (e.g. for tube furnace liners and UV cavettos ) ,
but the cost and difficulty of working with quartz make it excessive
for the majority of laboratory equipment.
During the mid-twentieth century, borosilicate glass tubing was
used to pipe coolants (often distilled water) through high power
vacuum tube based electronic equipment, such as commercial
broadcast transmitters.
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Glass cook ware is another common usage. Boro silicate glass is


used for measuring cups, featuring screen printed markings providing
graduated measurements, which are widely used in American
kitchens.
Aquarium heaters are some times made of borosilicate glass.
Due to its high heat resistance, it can tolerate the significant
temperature difference between the water and the nichrome heating
element.
Many high - quality flashlights use borosilicate glass for the
lens. This allows for a higher percentage of light transmittance
through the lens compared to plastics and lower-quality glass.
Several types of High-Intensity Discharge (HID) lamps, such as
mercury vapor and metal halide lamps, use borosilicate glass as the
outer envelope material.
Specialty marijuana and tobacco pipes are made from
borosilicate glass. The high heat resistance makes the pipes more
durable.
Most pre manufactured glass guitar slides are also made of
borosilicate glass.
New lamp working techniques led to artistic applications such
as contemporary glass marbles. The modern studio glass movement
has responded to color. "The availability of colors began to increase
when companies such as Glass Alchemy introduced the Crayon
Colors, which brought a whole new vivacity to the glass industry." [6]
Borosilicate is commonly used in the glass blowing form of lamp
working and the artists create a range of products ranging from
jewelry, kitchen ware , to sculpture as well as for artistic glass tobacco
pipes.
Boro silicate glass is some times used for high-quality beverage
glassware. Borosilicate glass lends kitchen- and glass ware increased
durability along with microwave and dish washer compatibility.
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Most astronomical reflecting telescope glass mirror components


are made of borosilicate glass because of its low coefficient of
expansion with heat. This makes very precise optical surfaces
possible that change very little with temperature, and matched glass
mirror components that "track" across temperature changes and retain
the optical system's characteristics.
The optical glass most often used for making instrument lenses
is Schott BK-7 (or the equivalent from other makers), a very finely
made borosilicate crown glass . It is also designated as 517642 glass
after its 1.517 refractive index and 64.2 Abbe number. Other less
costly borosilicate glasses, such as Schott B270 or the equivalent, are
used to make "crown glass" eyeglass lenses. Ordinary lower-cost
borosilicate glass, like that used to make kitchenware and even
reflecting telescope mirrors, cannot be used for high-quality lenses
because of the striations and inclusions common to lower grades of
this type of glass. The maximum working temperature is 515
fahrenheit. While it transitions to a liquid starting at 550 degrees
Fahrenheit (just before it turns red hot ) , it is not workable until it
reaches over 1000 fahrenheit . That means that in order to industrially
produce this glass, oxygen/fuel torches must be used. Glassblowers
borrowed technology and techniques from welders.
Boro silicate is also a material of choice for evacuated tube solar
thermal technology, because of its high strength and heat resistance.
Borosilicate glasses also find application in the semiconductor
industry in the development of micro electro mechanical systems
(MEMS), as part of stacks of etched silica wafers bonded to the
etched boro silicate glass.
The thermal insulation tiles on the Space Shuttle were coated
with a borosilicate glass.
Lighting manufacturers use borosilicate glass in their refractors.
Additionally, borosilicate tubing is used as the feedstock for the
production of parenteral drug packaging, such as vials and pre-filled
syringes, and is also used for the production of ampoules and dental
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cartridges. The chemical resistance of borosilicate glass minimizes the


migration of sodium ions from the glass matrix thus making it well
suited for inject able drug applications. This type of glass is typically
referred to as USP / EP JP Type I.
Borosilicate glasses are used for immobilization and disposal of
radioactive wastes. In most countries high-level radioactive waste has
been incorporated into alkali borosilicate or phosphate vitreous waste
forms for many years and vitrification is an established technology.[8]
Vitrification is a particularly attractive immobilization route because
of the high chemical durability of the vitrified glass product. This
characteristic has been used by industry for centuries . The chemical
resistance of glass can allow it to remain in a corrosive environment
for many thousands and even millions of years.
6 Boro silicate nano particles
It was initially thought that borosilicate glass could not be
formed into nano particles, since an unstable boron oxide precursor
prevented successful forming of these shapes. However, in 2008 a
team of researchers from the Swiss Federal Institute of Technology at
Lausanne were successful in forming borosilicate nano particles of
100 to 500 nanometers in diameter. The researchers formed a gel of
tetra ethyl ortho silicate and tri methoxy boroxine. When this gel is
exposed to water under proper conditions, a dynamic reaction ensues
which results in the nano particles.
7 - In lamp working :
Boro silicate, or "boro" as it is often referred to, is used
extensively in the glass blowing process lamp working, which
involves using a burner torch to melt and form glass, using a variety
of metal and graphite tools. Borosilicate is referred to as "hard glass"
and has a higher melting point than "soft glass" which is used in
glassblowing formed in large furnaces and large rods. Raw glass used
in lampworking comes in glass rods for solid work and glass tubes for
hollow work tubes and vessels / containers. Lamp working is used to
make complex and custom scientific apparatus; most major
universities have a lamp working shop to manufacture and repair their
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glass ware. For this kind of "scientific glass blowing", the


specifications must be exact and the glass blower must be highly
skilled and precise. Lamp working is also done as art and common
items made include goblets, pipes, paper weights and pendants.

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Pyrex

A Pyrex flask.
Contents

1 Introduction
2 History of the Pyrex Brand
3 Design
4 Composition
5 Use in laboratory ware
6 Problems With Pyrex
7 Usage in telescopes
1 Introduction :

Pyrex is a brand name for glass ware , introduced by Corning


Incorporated in 1915.
Originally, Pyrex was made from borosilicate glass. In the
1940s the composition was changed for some products to tempered
soda - lime glass , which is the most common form of glass used in
glass bake ware in the US and has higher mechanical strength so is
less vulnerable to breakage when dropped ( the leading cause of
breakage in glass bake ware ) . In 1998, Corning divested its
consumer products division which subsequently adopted the name
World Kitchen.
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In 1908, Eugene Sullivan, Director of Research at Corning


Glass Works, developed Nonex , a boro silicate low- expansion glass,
to reduce breakage in shock-resistant lantern globes and battery jars.
(Borosilicate glass was originally developed at the Jena Glass works
by Otto Schott, which Sullivan had learned about as a doctoral student
in Leipzig, Germany.) Jesse Littleton of Corning discovered the
cooking potential of boro silicate glass by giving his wife a casserole
dish made from a cut-down Nonex battery jar. Corning removed the
lead from Nonex , and developed Pyrex as a consumer product. Pyrex
glass bake ware products are to be found in an estimated 80 % of
American homes and approaching 400 million units have been sold
since the divestiture in 1998 alone.
Pyrex kitchen glassware manufactured for sale in the United
States is made at the World Kitchen facility in Charleroi,
Pennsylvania. Pyrex products for the European Union are made at a
factory in France.
2 - History of the Pyrex Brand :

Pyrex measuring cup, manufactured and sold in the U.S. (circa 1980)
features graduations in both metric and U.S. Customary systems.
Borosilicate glass was first made by the German chemist and
glass technologist Otto Schott, founder of Schott AG in 1893, 22
years before Corning produced the Pyrex brand. Schott AG sold the
product under the name "Duran." In the English-speaking world,
however, in the midst of World War I, Corning's Pyrex brand of
borosilicate glass offered a non-German alternative. Ever since, the
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name Pyrex has been widely used as a genericized trademark for


borosilicate glass in the English-speaking world.
Corning sold off its Consumer Products division in 1998 as
World Kitchen but retained the Pyrex brand name, licensing it to
World Kitchen and other companies that produce Pyrex-branded
cookware (e.g. Newell Rubbermaid's Newell Cookware Europe). The
brand in Europe, the Middle East and Africa is currently owned by
Arc International who acquired the European business in early 2006
from Newell Rubbermaid, who had acquired it from Corning in the
1990s.
A Corning executive gave the following account of the
etymology of the Pyrex brand name:
The word PYREX is probably a purely arbitrary word which
was devised in 1915 as a trade-mark for products manufactured and
sold by Corning Glass Works. While some people have thought that it
was made up from the Greek pyr and the Latin rex we have always
taken the position that no graduate of Harvard would be guilty of such
a classical hybrid. Actually, we had a number of prior trade-marks
ending in the letters ex. One of the first commercial products to be
sold under the new mark was a pie plate and in the interests of
euphonism the letter r was inserted between pie and ex and the whole
thing condensed to PYREX.
Pyrex kitchen products in Europe made and sold by a subsidiary
of Arc International tableware company are made from borosilicate
glass.
3 Design :
In 1958 an internal design department was started by John B.
Ward. He redesigned the Pyrex ovenware and Flame ware. Over the
years designers such as Penny Sparke, Betty Baugh, Smart Design,
TEAMS Design, and others have contributed to the design of the line.
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4 Composition :
Older Pyrex (pre 1900s), European Pyrex, and Pyrex laboratory
glass ware, is made of borosilicate glass. According to the National
Institute of Standards and Technology, borosilicate Pyrex is
composed of (as percentage of weight) : 14 % boron, 51 % oxygen,
. 3 % sodium, 1 % aluminium, 38 % silicon, and less than 1 %
potassium.
According to glass supplier Pulles and Hannique, borosilicate
Pyrex is made of Corning 7740 glass, and is equivalent in formulation
to Schott Glass 8830 glass sold under the "Duran" brand name. The
composition of both Corning 7740 and Schott 8830 is given as 80.6%
SiO2, 12.6 % B2O3 , 4.2 % Na2O , 2.2 % Al2O3 , 0.04 % Fe2O3, 0.1 %
CaO, 0.05 % MgO , and 0.1 % Cl.
How ever, the Pyrex glass cookware made in Charleroi,
Pennsylvania is made of tempered soda-lime glass.[13]

5 - Use in laboratory ware :


Because Pyrex borosilicate glass has a high thermal resistance, it
is often used in the manufacture of laboratory ware. In Europe,
Scilabware Limited manufactures more than 800 items under the
Pyrex brand name including beakers, bottles, flasks, dishes and test
tubes.
6 - Problems With Pyrex :
Pyrex, when used as windows in plasma etchers in the
semiconductor industry, tends to explode if hydrogen flame-polished
to eliminate surface roughness in restoring the window properties, for
this reason, quartz glass is preferred.
7 - Usage in telescopes :
Because of its low expansion characteristics, Pyrex is often the
material of choice for reflective optics in astronomy applications. The
California Institute of Technology's 200-inch (5.1 m) telescope mirror
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at Palomar Observatory was cast by Corning during 1934 1936 out


of boro silicate glass.
In 1932, George Ellery Hale approached Corning with the
challenge of fabricating the required optic for his Palomar project. A
previous effort to fabricate the optic from fused quartz had failed.
Corning's first attempt was a failure, the cast blank having voids.
Using lessons learned, Corning was successful in the casting of the
second blank. After a year of cooling, during which it was almost lost
to a flood, in 1935 the blank was completed. The first blank now
resides in Corning's Museum of Glass.

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Sodium Per Borate

Contents

1 Introduction
2 Preparation and chemistry
3 Structure
4 Uses
1 Introduction :

Sodium per borate (PBS) is a white, odorless, water-soluble


chemical compound with the chemical composition NaBO3. It
crystallizes as the mono hydrate, NaBO3H2O, tri hydrate,
NaBO33H2O and tetra hydrate, NaBO34H2O. The mono hydrate and
tetra hydrate are the commercially important forms. The elementary
structural unit of sodium per borates is a dimer anion B2O4(OH)42, in
which two boron atoms are joined by two peroxo bridges in a chairshaped 6 - membered ring, and the simplistic NaBO3nH2O-type
formulas are just a convenient way to express the average chemical
composition.
Other names : PBS-1 (mono) , PBS - 4 (tetra)
UN number
1479
Molecular Formula
Na BO3 nH2O
100 g / mol ( mono hydrate ) ;
Molar mass
154 g / mol ( tetra hydrate )
Appearance
white powders
Flash point
Non - flammable

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2 - Preparation and chemistry :


Sodium per borate is manufactured by reaction of disodium tetra
borate penta hydrate , hydrogen peroxide, and sodium hydroxide. The
mono hydrate form dissolves better than the tetra hydrate and has
higher heat stability; it is prepared by heating the tetra hydrate.
Sodium per borate undergoes hydrolysis in contact with water,
producing hydrogen peroxide and borate.
3 Structure :
Unlike sodium per carbonate and per phosphate, the sodium per
borate is not simply an adduct with hydrogen peroxide, and it does not
contain individual and does not contain a BO3 ions. Rather, there is a
cyclic dimer anion B2O4(OH)42, in which two boron atoms are joined
by two peroxo bridges in a chair-shaped 6-membered ring . This
makes the substance more stable, and safer for handling and storage.
The formula of the sodium salt is thus Na2H4B2O8 .
4 Uses :
It serves as a source of active oxygen in many detergents,
laundry detergents, cleaning products, and laundry bleaches . It is
also present in some tooth bleaching formulas. It is used as a
bleaching agent for internal bleaching of a non vital root treated tooth.
The sodium per borate is placed inside the tooth and left in place for
an extended period of time to allow it to diffuse into the tooth and
bleach stains from the inside out. It has antiseptic properties and can
act as a disinfectant. It is also used as a "disappearing" preservative in
some brands of eye drops.
Sodium per borate is a less aggressive bleach than sodium
hypochlorite, causing less degradation to dyes and textiles. Borates
also have some non-oxidative bleaching properties.
Sodium per borate releases oxygen rapidly at temperatures over
60C. To make it active at lower temperatures (40 60 C), it has to
be mixed with a suitable activator, typically tetra acetyl ethylene
diamine (TAED).
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