Hafnium carbide

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Hafnium carbide
NaCl polyhedra.png
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.031.910 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-114-1
PubChem CID
  • InChI=1S/C.Hf/q-1;+1 Yes check.svgY
    Key: NVDNLVYQHRUYJA-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C.Hf/q-1;+1/rCHf/c1-2
    Key: NVDNLVYQHRUYJA-GLWNXBRTAK
  • [Hf+]#[C-]
Properties
HfC
Molar mass 190.50 g/mol
Appearanceblack odorless powder
Density 12.2 g/cm3 [1]
Melting point 3,958 °C (7,156 °F; 4,231 K) [2]
insoluble
Structure
Cubic crystal system, cF8
Fm3m, No. 225
Hazards
GHS labelling:
GHS-pictogram-flamme.svg
Warning
H228
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
2
1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Hafnium carbide (Hf C) is a chemical compound of hafnium and carbon. Previously the material was estimated to have a melting point of about 3,900 °C. [2] More recent tests have been able to conclusively prove that the substance has an even higher melting point of 3,958 °C exceeding those of tantalum carbide and tantalum hafnium carbide which were both previously estimated to be higher. [3] However, it has a low oxidation resistance, with the oxidation starting at temperatures as low as 430 °C. [4] Experimental testing in 2018 confirmed the higher melting point yielding a result of 3,982 (±30°C) with a small possibility that the melting point may even exceed 4,000°C. [5]

Atomistic simulations conducted in 2015 predicted that a similar compound, hafnium carbonitride (HfCN), could have a melting point exceeding even that of hafnium carbide. [6] Experimental evidence gathered in 2020 confirmed that it did indeed have a higher melting point exceeding 4,000 °C, [7] with more recent ab initio molecular dynamics calculations predicting the HfC0.75N0.22 phase to have a melting point as high as 4,110 ± 62 °C, highest known for any material. [8]

Hafnium carbide is usually carbon deficient and therefore its composition is often expressed as HfCx (x = 0.5 to 1.0). It has a cubic (rock-salt) crystal structure at any value of x. [9]

Hafnium carbide powder is obtained by the reduction of hafnium(IV) oxide with carbon at 1,800 to 2,000 °C. A long processing time is required to remove all oxygen. Alternatively, high-purity HfC coatings can be obtained by chemical vapor deposition from a gas mixture of methane, hydrogen, and vaporized hafnium(IV) chloride.

Because of the technical complexity and high cost of the synthesis, HfC has a very limited use, despite its favorable properties such as high hardness (greater than 9 Mohs [10] ) and melting point. [2]

The magnetic properties of HfCx change from paramagnetic for x ≤ 0.8 to diamagnetic at larger x. An inverse behavior (dia-paramagnetic transition with increasing x) is observed for TaCx, despite its having the same crystal structure as HfCx. [11]

See also

Related Research Articles

<span class="mw-page-title-main">Hafnium</span> Chemical element, symbol Hf and atomic number 72

Hafnium is a chemical element; it has symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869, though it was not identified until 1922, by Dirk Coster and George de Hevesy. making it one of the last two stable elements to be discovered. Hafnium is named after Hafnia, the Latin name for Copenhagen, where it was discovered.

<span class="mw-page-title-main">Niobium</span> Chemical element, symbol Nb and atomic number 41

Niobium is a chemical element; it has symbol Nb and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has similar ductility to iron. Niobium oxidizes in Earth's atmosphere very slowly, hence its application in jewelry as a hypoallergenic alternative to nickel. Niobium is often found in the minerals pyrochlore and columbite, hence the former name "columbium". Its name comes from Greek mythology: Niobe, daughter of Tantalus, the namesake of tantalum. The name reflects the great similarity between the two elements in their physical and chemical properties, which makes them difficult to distinguish.

<span class="mw-page-title-main">Tantalum</span> Chemical element, symbol Ta and atomic number 73

Tantalum is a chemical element; it has symbol Ta and atomic number 73. Previously known as tantalium, it is named after Tantalus, a figure in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that is highly corrosion-resistant. It is part of the refractory metals group, which are widely used as components of strong high-melting-point alloys. It is a group 5 element, along with vanadium and niobium, and it always occurs in geologic sources together with the chemically similar niobium, mainly in the mineral groups tantalite, columbite and coltan.

<span class="mw-page-title-main">Melting point</span> Temperature at which a solid turns liquid

The melting point of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends on pressure and is usually specified at a standard pressure such as 1 atmosphere or 100 kPa.

Refractory metals are a class of metals that are extraordinarily resistant to heat and wear. The expression is mostly used in the context of materials science, metallurgy and engineering. The definition of which elements belong to this group differs. The most common definition includes five elements: two of the fifth period and three of the sixth period. They all share some properties, including a melting point above 2000 °C and high hardness at room temperature. They are chemically inert and have a relatively high density. Their high melting points make powder metallurgy the method of choice for fabricating components from these metals. Some of their applications include tools to work metals at high temperatures, wire filaments, casting molds, and chemical reaction vessels in corrosive environments. Partly due to the high melting point, refractory metals are stable against creep deformation to very high temperatures.

<span class="mw-page-title-main">Thorium dioxide</span> Chemical compound

Thorium dioxide (ThO2), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in colour. Also known as thoria, it is mainly a by-product of lanthanide and uranium production. Thorianite is the name of the mineralogical form of thorium dioxide. It is moderately rare and crystallizes in an isometric system. The melting point of thorium oxide is 3300 °C – the highest of all known oxides. Only a few elements (including tungsten and carbon) and a few compounds (including tantalum carbide) have higher melting points. All thorium compounds, including the dioxide, are radioactive because there are no stable isotopes of thorium.

<span class="mw-page-title-main">Refractory</span> Materials resistant to decomposition under high temperatures

In materials science, a refractory is a material that is resistant to decomposition by heat or chemical attack that retains its strength and rigidity at high temperatures. They are inorganic, non-metallic compounds that may be porous or non-porous, and their crystallinity varies widely: they may be crystalline, polycrystalline, amorphous, or composite. They are typically composed of oxides, carbides or nitrides of the following elements: silicon, aluminium, magnesium, calcium, boron, chromium and zirconium. Many refractories are ceramics, but some such as graphite are not, and some ceramics such as clay pottery are not considered refractory. Refractories are distinguished from the refractory metals, which are elemental metals and their alloys that have high melting temperatures.

<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">Tantalum carbide</span> Chemical compound

Tantalum carbides (TaC) form a family of binary chemical compounds of tantalum and carbon with the empirical formula TaCx, where x usually varies between 0.4 and 1. They are extremely hard, brittle, refractory ceramic materials with metallic electrical conductivity. They appear as brown-gray powders, which are usually processed by sintering.

<span class="mw-page-title-main">Titanium nitride</span> Ceramic material

Titanium nitride is an extremely hard ceramic material, often used as a physical vapor deposition (PVD) coating on titanium alloys, steel, carbide, and aluminium components to improve the substrate's surface properties.

<span class="mw-page-title-main">Hafnium tetrachloride</span> Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

<span class="mw-page-title-main">Hot cathode</span> Type of electrode

In vacuum tubes and gas-filled tubes, a hot cathode or thermionic cathode is a cathode electrode which is heated to make it emit electrons due to thermionic emission. This is in contrast to a cold cathode, which does not have a heating element. The heating element is usually an electrical filament heated by a separate electric current passing through it. Hot cathodes typically achieve much higher power density than cold cathodes, emitting significantly more electrons from the same surface area. Cold cathodes rely on field electron emission or secondary electron emission from positive ion bombardment, and do not require heating. There are two types of hot cathode. In a directly heated cathode, the filament is the cathode and emits the electrons. In an indirectly heated cathode, the filament or heater heats a separate metal cathode electrode which emits the electrons.

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

Zirconium carbide (ZrC) is an extremely hard refractory ceramic material, commercially used in tool bits for cutting tools. It is usually processed by sintering.

<span class="mw-page-title-main">Hafnium(IV) oxide</span> Chemical compound

Hafnium(IV) oxide is the inorganic compound with the formula HfO
2
. Also known as hafnium dioxide or hafnia, this colourless solid is one of the most common and stable compounds of hafnium. It is an electrical insulator with a band gap of 5.3~5.7 eV. Hafnium dioxide is an intermediate in some processes that give hafnium metal.

Tantalum hafnium carbide is a refractory chemical compound with a general formula TaxHfyCx+y, which can be considered as a solid solution of tantalum carbide and hafnium carbide. It was originally thought to have the highest melting of any known substance but new research has proven that hafnium carbonitride has a higher melting point.

<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.

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.

Hafnium carbonitride (HfCN) is an ultra-high temperature ceramic (UHTC) mixed anion compound composed of hafnium (Hf), carbon (C) and nitrogen (N).

Hafnium compounds are compounds containing the element hafnium (Hf). Due to the lanthanide contraction, the ionic radius of hafnium(IV) (0.78 ångström) is almost the same as that of zirconium(IV) (0.79 angstroms). Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties. Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides. At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon. Some compounds of hafnium in lower oxidation states are known.

References

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  4. Shimada, Shiro (October 1992). "Oxidation Kinetics of Hafnium Carbide in the Temperature Range of 480° to 600°C". Journal of the American Ceramic Society . 75 (10): 2671–2678. doi:10.1111/j.1151-2916.1992.tb05487.x.
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