Rhenium diboride

Last updated
Rhenium diboride
Magnesium-diboride-3D-balls.png
Names
IUPAC name
Rhenium diboride
Identifiers
3D model (JSmol)
EC Number
  • 234-959-3
PubChem CID
  • InChI=1S/2B.Re
    Key: OLXPHXSOQYDZNT-UHFFFAOYSA-N
  • B#[Re]#B
Properties
ReB2
Molar mass 207.83 g/mol
Appearanceblack powder
Density 12.7 g/cm3
Melting point 2,400 °C (4,350 °F; 2,670 K) [1]
none
Structure
Hexagonal, Space group P63/mmc.
Hazards
GHS labelling:
GHS-pictogram-exclam.svg [2]
Warning [2]
H315, H319, H335 [2]
P261, P280, P304+P340, P305+P351+P338, P405, P501 [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Rhenium diboride (ReB2) is a synthetic high-hardness material that was first synthesized in 1962. [3] [4] The compound is formed from a mixture of rhenium, noted for its resistance to high pressure, and boron, which forms short, strong covalent bonds with rhenium. It has regained popularity in recent times in hopes of finding a material that possesses hardness comparable to that of diamond. [5]

Contents

Unlike other high-hardness synthetic materials, such as the c-BN, rhenium diboride can be synthesized at ambient pressure, [4] potentially simplifying a mass production. However, the high cost of rhenium and commercial availability of alternatives such as polycrystalline c-BN, make a prospect of large-scale applications less likely. [4]

Synthesis

Rhenium diboride, ReB2 Rhenium Diboride.jpg
Rhenium diboride, ReB2

ReB2 can be synthesized by at least three different methods at standard atmospheric pressure: solid-state metathesis, melting in an electric arc, and direct heating of the elements. [5]

In the metathesis reaction, rhenium trichloride and magnesium diboride are mixed and heated in an inert atmosphere and the magnesium chloride byproduct is washed away. Excess boron is needed to prevent the formation of other phases such as Re7B3 and Re3B.

In the arc-melting method, rhenium and boron powders are mixed and a large electric current is passed through the mixture, also in an inert atmosphere.

In the direct reaction method, the rhenium-boron mixture is sealed in a vacuum and held at a high temperature over a longer period (1,000 °C for five days).

At least the last two methods are capable of producing pure ReB2 without any other phases, as confirmed by X-ray crystallography.

Hardness

Rhenium diboride is occasionally, and controversially, [4] [6] cited as a "superhard material" due to its high hardness level. However, tested in the asymptotic-hardness region, as recommended for hard and superhard materials, [4] rhenium diboride demonstrates a Vickers hardness of only 30.1 ± 1.3 GPa at 4.9 N, well below the generally-accepted threshold of 40 GPa or more needed to classify it as "superhard". [4] Another research has estimated the Hv of full-dense ReB2 at about 22 GPa under an applied load of 2.94 N, [6] comparable to that of tungsten carbide, silicon carbide, titanium diboride or zirconium diboride. [6]

Values greater than 40 GPa have been observed only in tests with very low loads, which is not a suitable testing method for this type of solids. [4] In one test, the lowest tested load of 0.49 N yielded the average hardness of 48 ± 5.6 GPa and a maximum hardness of 55.5 GPa, which is comparable to the hardness of cubic boron nitride (c-BN) under an equivalent load. [5] Such phenomenon of inverse relationship between the applied load and hardness is known as the indentation size effect. [5]

In recent times, there has been a significant amount of research into improving the hardness and other properties of the ReB2. In one study, the hardness for the ReB2(R-3m) polymorph was estimated at 41.7 GPa, while for the ReB2(P63/mmc) it was placed at c.a. 40.6 GPa. [7] In another study, a fully dense B4C-27wt.% ReB2 ceramic composite nanopowder was fabricated by spark plasma sintering. It has exhibited a microhardness of 50 ± 3 GPa under a 49 N load in the asymptotic-hardness region and had a 3.2 g/cm3 density, comparable with the hardness and density of the c-BN. [8]

The hardness of ReB2 exhibits considerable anisotropy because of its hexagonal layered structure, being greatest along the c axis. Two factors contribute to the high hardness of ReB2: a high density of valence electrons, and an abundance of short covalent bonds. [5] [9] Rhenium has one of the highest valence electron densities of any transition metal (476 electrons/nm3, compare to 572 electrons/nm3 for osmium and 705 electrons/nm3 for diamond [10] ). The addition of boron requires only a 5% expansion of the rhenium lattice because the small boron atoms fill the existing spaces between the rhenium atoms. Furthermore, the electronegativities of rhenium and boron are close enough (1.9 and 2.04 on the Pauling scale) that they form covalent bonds in which the electrons are shared almost equally.

See also

Related Research Articles

<span class="mw-page-title-main">Boron nitride</span> Refractory compound of boron and nitrogen with formula BN

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 form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite but slightly softer than the cubic form.

<span class="mw-page-title-main">Boron</span> Chemical element, symbol B and atomic number 5

Boron is a chemical element; it has 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 three valence electrons for forming covalent bonds, resulting in many compounds such as boric acid, the mineral sodium borate, and the ultra-hard crystals of boron carbide and boron nitride.

<span class="mw-page-title-main">Boron carbide</span> Extremely hard ceramic compound

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 hardness of >30 GPa, it is one of the hardest known materials, behind cubic boron nitride and diamond.

<span class="mw-page-title-main">Titanium diboride</span> Chemical compound

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, so it can be used as a cathode material in aluminium smelting and can be shaped by electrical discharge machining.

<span class="mw-page-title-main">Superhard material</span> Material with Vickers hardness exceeding 40 gigapascals

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 unique properties, these materials are of great interest in many industrial areas including, but not limited to, abrasives, polishing and cutting tools, disc brakes, and wear-resistant and protective coatings.

A boride is a compound between boron and a less electronegative element, for example silicon boride (SiB3 and SiB6). The borides are a very large group of compounds that are generally high melting and are covalent more than ionic in nature. Some borides exhibit very useful physical properties. The term boride is also loosely applied to compounds such as B12As2 (N.B. Arsenic has an electronegativity higher than boron) that is often referred to as icosahedral boride.

<span class="mw-page-title-main">Aggregated diamond nanorod</span> Nanocrystalline form of diamond

Aggregated diamond nanorods, or ADNRs, are a nanocrystalline form of diamond, also known as nanodiamond or hyperdiamond.

<span class="mw-page-title-main">Boron compounds</span>

Boron compounds are compounds containing the element boron. In the most familiar compounds, boron has the formal oxidation state +3. These include oxides, sulfides, nitrides, and halides.

Osmium compounds are compounds containing the element osmium (Os). Osmium forms compounds with oxidation states ranging from −2 to +8. The most common oxidation states are +2, +3, +4, and +8. The +8 oxidation state is notable for being the highest attained by any chemical element aside from iridium's +9 and is encountered only in xenon, ruthenium, hassium, iridium, and plutonium. The oxidation states −1 and −2 represented by the two reactive compounds Na
2
[Os
4
(CO)
13
]
and Na
2
[Os(CO)
4
]
are used in the synthesis of osmium cluster compounds.

Heterodiamond is a superhard material containing boron, carbon, and nitrogen (BCN). It is formed at high temperatures and high pressures, e.g., by application of an explosive shock wave to a mixture of diamond and cubic boron nitride (c-BN). The heterodiamond is a polycrystalline material coagulated with nano-crystallites and the fine powder is tinged with deep bluish black. The heterodiamond has both the high hardness of diamond and the excellent heat resistance of cubic BN. These characteristic properties are due to the diamond structure combined with the sp3 σ-bonds among carbon and the heteroatoms.

<span class="mw-page-title-main">Boron suboxide</span> Chemical compound

Boron suboxide (chemical formula B6O) is a solid compound with a structure built of eight icosahedra at the apexes of the rhombohedral unit cell. 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 interatomic bond lengths and strongly covalent character, B6O displays a range of outstanding physical and chemical properties such as great hardness (close to that of rhenium diboride and boron nitride), low mass density, high thermal conductivity, high chemical inertness, and excellent wear resistance.

<span class="mw-page-title-main">Zirconium diboride</span> Chemical compound

Zirconium diboride (ZrB2) is a highly covalent refractory ceramic material with a hexagonal crystal structure. ZrB2 is an ultra-high temperature ceramic (UHTC) with a melting point of 3246 °C. This along with its relatively low density of ~6.09 g/cm3 (measured density may be higher due to hafnium impurities) and good high temperature strength makes it a candidate for high temperature aerospace applications such as hypersonic flight or rocket propulsion systems. It is an unusual ceramic, having relatively high thermal and electrical conductivities, properties it shares with isostructural titanium diboride and hafnium diboride.

Aluminium magnesium boride or Al3Mg3B56, colloquially known as BAM, is a chemical compound of aluminium, magnesium and boron. Whereas its nominal formula is AlMgB14, the chemical composition is closer to Al0.75Mg0.75B14. It is a ceramic alloy 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 B12 units per unit cell. This ultrahard material has a coefficient of thermal expansion comparable to that of other widely used materials such as steel and concrete.

<span class="mw-page-title-main">Osmium borides</span>

Osmium borides are compounds of osmium and boron. Their most remarkable property is potentially high hardness. It is thought that a combination of high electron density of osmium with the strength of boron-osmium covalent bonds will make osmium borides superhard materials, however this has not been demonstrated yet. For example, OsB2 is hard (hardness comparable to that of sapphire), but not superhard.

<span class="mw-page-title-main">Ruthenium boride</span> High hardness element compounds of ruthenium and boron

Ruthenium borides are compounds of ruthenium and boron. Their most remarkable property is potentially high hardness. Vickers hardness HV = 50 GPa was reported for thin films composed of RuB2 and Ru2B3 phases. This value is significantly higher than those of bulk RuB2 or Ru2B3, but it has to be confirmed independently, as measurements on superhard materials are intrinsically difficult. For example, note that the initial report on extreme hardness of related material rhenium diboride was probably too optimistic.

<span class="mw-page-title-main">Tungsten borides</span>

Tungsten borides are compounds of tungsten and boron. Their most remarkable property is high hardness. The Vickers hardness of WB or WB2 crystals is ~20 GPa and that of WB4 is ~30 GPa for loads exceeding 3 N.

<span class="mw-page-title-main">Allotropes of boron</span> Materials made only out of boron

Boron can be prepared in several crystalline and amorphous forms. Well known crystalline forms are α-rhombohedral (α-R), β-rhombohedral (β-R), and β-tetragonal (β-T). In special circumstances, boron can also be synthesized in the form of its α-tetragonal (α-T) and γ-orthorhombic (γ) allotropes. Two amorphous forms, one a finely divided powder and the other a glassy solid, are also known. Although at least 14 more allotropes have been reported, these other forms are based on tenuous evidence or have not been experimentally confirmed, or are thought to represent mixed allotropes, or boron frameworks stabilized by impurities. Whereas the β-rhombohedral phase is the most stable and the others are metastable, the transformation rate is negligible at room temperature, and thus all five phases can exist at ambient conditions. Amorphous powder boron and polycrystalline β-rhombohedral boron are the most common forms. The latter allotrope is a very hard grey material, about ten percent lighter than aluminium and with a melting point (2080 °C) several hundred degrees higher than that of steel.

Diboride may refer to:

Ultra-high-temperature ceramics (UHTCs) are a type of refractory ceramics that can withstand extremely high temperatures without degrading, often above 2,000 °C. They also often have high thermal conductivities and are highly resistant to thermal shock, meaning they can withstand sudden and extreme changes in temperature without cracking or breaking. Chemically, they are usually borides, carbides, nitrides, and oxides of early transition metals.

<span class="mw-page-title-main">Niobium diboride</span> Chemical compound

Niobium diboride (NbB2) is a highly covalent refractory ceramic material with a hexagonal crystal structure.

References

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