Aluminium magnesium boride
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Aluminum magnesium boride or Al3Mg3B56 colliqually known as BAM is a
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
of
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
,
magnesium Magnesium is a chemical element with the symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 of the periodic ta ...
and
boron Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the ''boron group'' it has th ...
. Whereas its nominal formula is AlMgB14, the chemical composition is closer to Al0.75Mg0.75B14. It is a
ceramic A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain ...
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
that is highly resistive to wear and has an extremely low coefficient of sliding friction, reaching a record value of 0.04 in unlubricated and 0.02 in lubricated AlMgB14−TiB2 composites. First reported in 1970, BAM has an orthorhombic structure with four
icosahedral In geometry, an icosahedron ( or ) is a polyhedron with 20 faces. The name comes and . The plural can be either "icosahedra" () or "icosahedrons". There are infinitely many non- similar shapes of icosahedra, some of them being more symmetrica ...
B12 units per unit cell. This ultrahard material has a
coefficient of thermal expansion Thermal expansion is the tendency of matter to change its shape A shape or figure is a graphics, graphical representation of an object or its external boundary, outline, or external Surface (mathematics), surface, as opposed to other pro ...
comparable to that of other widely used materials such as steel and concrete.


Synthesis

BAM powders are commercially produced by heating a nearly
stoichiometric Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions. Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equal ...
mixture of elemental boron (low grade because it contains magnesium) and aluminium for a few hours at a temperature in the range 900 °C to 1500 °C. Spurious phases are then dissolved in hot
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...
. To ease the reaction and make the product more homogeneous, the starting mixture can be processed in a high-energy
ball mill A ball mill is a type of grinder used to grind or blend materials for use in mineral dressing processes, paints, pyrotechnics, ceramics, and selective laser sintering. It works on the principle of impact and attrition: size reduction is done ...
. All pretreatments are carried out in a dry, inert atmosphere to avoid oxidation of the metal powders. BAM films can be coated on silicon or metals by
pulsed laser deposition Pulsed laser deposition (PLD) is a physical vapor deposition (PVD) technique where a high-power pulsed laser beam is focused inside a vacuum chamber to strike a target of the material that is to be deposited. This material is vaporized from the t ...
, using AlMgB14 powder as a target, whereas bulk samples are obtained by
sintering Clinker nodules produced by sintering Sintering or frittage is the process of compacting and forming a solid mass of material by pressure or heat without melting it to the point of liquefaction. Sintering happens as part of a manufacturing ...
the powder. BAM usually contains small amounts of impurity elements (e.g., oxygen and iron) that enter the material during preparation. It is thought that the presence of iron (most often introduced as wear debris from mill vials and media) serves as a
sintering Clinker nodules produced by sintering Sintering or frittage is the process of compacting and forming a solid mass of material by pressure or heat without melting it to the point of liquefaction. Sintering happens as part of a manufacturing ...
aid. BAM can be alloyed with
silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic tab ...
,
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
,
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
,
titanium diboride Titanium diboride (TiB2) is an extremely hard ceramic which has excellent heat conductivity, oxidation stability and wear resistance. TiB2 is also a reasonable electrical conductor,J. Schmidt et al. "Preparation of titanium diboride TiB2 by spark p ...
(TiB2), aluminium nitride (AlN),
titanium carbide Titanium carbide, Ti C, is an extremely hard ( Mohs 9–9.5) refractory ceramic material, similar to tungsten carbide. It has the appearance of black powder with the sodium chloride (face-centered cubic) crystal structure. It occurs in nature ...
(TiC) or
boron nitride Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal ...
(BN).


Properties

BAM has the lowest known unlubricated coefficient of friction (0.04) possibly due to self-lubrication.


Structure

Most
superhard material A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are virtually incompressible solids with high electron density and high bond covalency. As a result of their u ...
s have simple, high-symmetry crystal structures, e.g.,
diamond cubic The diamond cubic crystal structure is a repeating pattern of 8 atoms that certain materials may adopt as they solidify. While the first known example was diamond, other elements in group 14 also adopt this structure, including α-tin, the sem ...
or
zinc blende Sphalerite (sometimes spelled sphaelerite) is a sulfide mineral with the chemical formula . It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in sedimentary exhalative, Mississippi-Va ...
. However, BAM has a complex, low-symmetry crystal structure with 64 atoms per unit cell. The
unit cell In geometry, biology, mineralogy and solid state physics, a unit cell is a repeating unit formed by the vectors spanning the points of a lattice. Despite its suggestive name, the unit cell (unlike a unit vector, for example) does not necessaril ...
is
orthorhombic In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic lattices result from stretching a cubic lattice along two of its orthogonal pairs by two different factors, resulting in a rectangular prism with a r ...
and its most salient feature is four boron-containing
icosahedra In geometry, an icosahedron ( or ) is a polyhedron with 20 faces. The name comes and . The plural can be either "icosahedra" () or "icosahedrons". There are infinitely many non- similar shapes of icosahedra, some of them being more symmetrica ...
. Each icosahedron contains 12 boron atoms. Eight more boron atoms connect the icosahedra to the other elements in the unit cell. The occupancy of metal sites in the lattice is lower than one, and thus, while the material is usually identified with the formula AlMgB14, its chemical composition is closer to Al0.75Mg0.75B14. Such non-
stoichiometry Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions. Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equal ...
is common for borides (see
crystal structure of boron-rich metal borides Metals, and specifically rare-earth elements, form numerous chemical complexes with boron. Their crystal structure and chemical bonding depend strongly on the metal element M and on its atomic ratio to boron. When B/M ratio exceeds 12, boron atom ...
and
boron carbide Boron carbide (chemical formula approximately B4C) is an extremely hard boron–carbon ceramic, a covalent material used in tank armor, bulletproof vests, engine sabotage powders, as well as numerous industrial applications. With a Vickers hard ...
). The unit cell parameters of BAM are ''a'' = 1.0313 nm, ''b'' = 0.8115 nm, ''c'' = 0.5848 nm, ''Z'' = 4 (four structure units per unit cell),
space group In mathematics, physics and chemistry, a space group is the symmetry group of an object in space, usually in three dimensions. The elements of a space group (its symmetry operations) are the rigid transformations of an object that leave it unchan ...
''Imma'',
Pearson symbol The Pearson symbol, or Pearson notation, is used in crystallography as a means of describing a crystal structure, and was originated by W. B. Pearson. The symbol is made up of two letters followed by a number. For example: * Diamond structure ...
oI68, density 2.59 g/cm3. The melting point is roughly estimated as 2000 °C.


Optoelectronic

BAM has a bandgap of about ~1.5 eV. Significant absorption is observed at sub-bandgap energies and attributed to metal atoms. Electrical resistivity depends on the sample purity and is about 104 Ohm·cm. The
Seebeck coefficient The Seebeck coefficient (also known as thermopower, thermoelectric power, and thermoelectric sensitivity) of a material is a measure of the magnitude of an induced thermoelectric voltage in response to a temperature difference across that material ...
is relatively high, between −5.4 and −8.0 mV/K. This property originates from electron transfer from metal atoms to the boron icosahedra and is favorable for thermoelectric applications.


Hardness & Fracture toughness

The
microhardness Indentation hardness tests are used in mechanical engineering to determine the hardness of a material to deformation. Several such tests exist, wherein the examined material is indented until an impression is formed; these tests can be performed on ...
of BAM powders is 32–35 GPa. It can be increased to 45 GPa by alloying with Boron rich Titanium Boride, Fracture toughness can be increased with TiB2 or by depositing a quasi-amorphous BAM film. Addition of AlN or TiC to BAM reduces its hardness. By definition, a hardness value exceeding 40 GPa makes BAM a
superhard material A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are virtually incompressible solids with high electron density and high bond covalency. As a result of their u ...
. In the BAM−TiB2 composite, the maximum hardness and toughness are achieved at ~60 vol.% of TiB2. The wear rate is improved by increasing the TiB2 content to 70–80% at the expense of ~10% hardness loss. The TiB2 additive is a wear-resistant material itself with a hardness of 28–35 GPa.


Thermal expansion

The
thermal expansion Thermal expansion is the tendency of matter to change its shape, area, volume, and density in response to a change in temperature, usually not including phase transitions. Temperature is a monotonic function of the average molecular kinetic ...
coefficient (TEC, also known as Coefficient Of Thermal Expansion, COTE) for AlMgB14 was measured as 9 K−1 by dilatometry and by high temperature
X-ray diffraction X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...
using synchrotron radiation. This value is fairly close to the COTE of widely used materials such as steel, titanium and concrete. Based on the hardness values reported for AlMgB14 and the materials themselves being used as wear resistant coatings, the COTE of AlMgB14 could be used in determining coating application methods and the performance of the parts once in service.


Friction

A composite of BAM and TiB2 (70 volume percent of TiB2) has one of the lowest values of
friction coefficient Friction is the force resisting the relative motion of solid surfaces, fluid layers, and material elements sliding against each other. There are several types of friction: *Dry friction is a force that opposes the relative lateral motion of t ...
s, which amounts to 0.04–0.05 in dry scratching by a diamond tip (cf. 0.04 for Teflon) and decreases to 0.02 in water-glycol-based lubricants.


Applications

BAM is commercially available and is being studied for potential applications. For example, pistons, seals and blades on pumps could be coated with BAM or BAM + TiB2 to reduce friction between parts and to increase wear resistance. The reduction in friction would reduce energy use. BAM could also be coated onto cutting tools. The reduced friction would lessen the force necessary to cut an object, extend tool life, and possibly allow increased cutting speeds. Coatings only 2–3 micrometers thick have been found to improve efficiency and reduce wear in cutting tools.Tough nanocoatins boost industrial energy efficiency
. Ames Laboratory. Press release. Department of Energy. 18 Nov. 2008.


See also

*
Non-stick surface A non-stick surface is engineered to reduce the ability of other materials to stick to it. Non-stick cookware is a common application, where the non-stick coating allows food to brown without sticking to the pan. Non-stick is often used to refer ...


References


External links


Material slicker than Teflon
New Scientist Article on BAM.

Press Release with photos. {{magnesium compounds Ceramic materials Superhard materials Dry lubricants Borides Aluminium compounds Magnesium compounds