Tungsten carbide

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Contents

Tungsten carbide
Tungsten carbide inserts.jpg
Names
IUPAC name
Tungsten carbide
Other names
Tungsten(IV) carbide
Tungsten tetracarbide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.031.918 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-123-0
PubChem CID
RTECS number
  • YO7250000
UNII
UN number 3178
  • InChI=1S/C.W/q-1;+1 X mark.svgN
    Key: UONOETXJSWQNOL-UHFFFAOYSA-N X mark.svgN
  • (W+≡C−):[C-]#[W+]
Properties
WC
Molar mass 195.85 g·mol−1
AppearanceGrey-black lustrous solid
Density 15.6 g/cm3 [1]
Melting point 2,785–2,830 °C (5,045–5,126 °F; 3,058–3,103 K) [2] [3]
Boiling point 6,000 °C (10,830 °F; 6,270 K)
at 760 mmHg [3]
Insoluble
Solubility Soluble in HNO
3 , HF [2]
1·10−5 cm3/mol [2]
Thermal conductivity 110 W/(m·K) [4]
Structure
Hexagonal, hP2 [5]
P6m2, No. 187 [5]
6m2 [5]
a = 2.906 Å, c = 2.837 Å [5]
α = 90°, β = 90°, γ = 120°
Trigonal prismatic (center at C) [6]
Thermochemistry
39.8 J/(mol·K) [4]
Std molar
entropy (S⦵298)
32.1 J/mol·K
Related compounds
Other anions
Tungsten boride
Tungsten nitride
Other cations
Molybdenum carbide
Titanium carbide
Silicon carbide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tungsten carbide (chemical formula: WC) is a chemical compound (specifically, a carbide) containing equal parts of tungsten and carbon atoms. In its most basic form, tungsten carbide is a fine gray powder, but it can be pressed and formed into shapes through sintering [7] for use in industrial machinery, cutting tools, chisels, abrasives, armor-piercing bullets and jewelry.

Tungsten carbide is approximately three times as stiff as steel, with a Young's modulus of approximately 530–700 GPa, [4] [8] [9] [10] and is twice as dense as steel. It is comparable with corundum (α- Al
2O
3 ) in hardness, approaching that of a diamond, [7] and can be polished and finished only with abrasives of superior hardness such as cubic boron nitride and diamond powder, wheels and compounds. Tungsten carbide tools can be operated at cutting speeds much higher than high-speed steel (a special steel blend for cutting tools). [7]

Tungsten carbide powder was first synthesized by H. Moissan in 1893, and the industrial production of the cemented form started 20 to 25 years later (between 1913 and 1918). [8]

Naming

Colloquially among workers in various industries (such as machining), tungsten carbide is often simply called carbide.

Synthesis

Powder

Tungsten carbide powder is prepared by reaction of tungsten metal (or powder) and carbon at 1,400–2,000 °C. [11] Other methods include a lower temperature fluid bed process that reacts either tungsten metal (or powder) or blue WO
3 with CO/CO2 gas mixture and H
2 gas between 900 and 1,200 °C. [12]

WC can also be produced by heating WO3 with graphite, either directly at 900 °C or in hydrogen at 670 °C, followed by carburization in argon at 1,000 °C. [13] Chemical vapor deposition methods that have been investigated include: [11]

WCl
6 + H
2 + CH
4 → WC + 6 HCl
WF
6 + 2 H
2 + CH
3OH → WC + 6 HF + H
2O

Cemented form

Solid tungsten carbide is prepared using techniques from powder metallurgy developed in the 1920s. [7] Powdered tungsten carbide is mixed with another powdered metal, usually cobalt (alternatives include nickel, iron and paraffin wax [8] ) which acts as a binder. [7] The mixture is pressed, then sintered by heating it to temperatures of 1,400 °C (2,550 °F) to 1,600 °C (2,910 °F); the binder melts, wets, and partially dissolves the tungsten grains, binding them together. [7] The cobalt-tungsten composites specifically are known by a number of trade names, including Widia and Carboloy. [7]

Chemical properties

There are two well-characterized compounds of tungsten and carbon: tungsten carbide, WC, and tungsten semicarbide, W
2C. Both compounds may be present in coatings and the proportions can depend on the coating method. [14]

Another meta-stable compound of tungsten and carbon can be created by heating the WC phase to high temperatures using plasma, then quenching in inert gas (plasma spheroidization). [15] This process causes macrocrystalline WC particles to spheroidize and results in the non-stoichiometric high temperature phase WC
1-x existing in a meta-stable form at room temperature. The fine microstructure of this phase provides high hardness (2800–3500 HV) combined with good toughness when compared with other tungsten carbide compounds. The meta-stable nature of this compound results in reduced high temperature stability.[ citation needed ]

At high temperatures WC decomposes to tungsten and carbon and this can occur during high-temperature thermal spray, e.g., in high velocity oxygen fuel (HVOF) and high energy plasma (HEP) methods. [16]

Oxidation of WC starts at 500–600 °C (773–873 K). [11] It is resistant to acids and is only attacked by hydrofluoric acid/nitric acid (HF/HNO
3) mixtures above room temperature. [11] It reacts with fluorine gas at room temperature and chlorine above 400 °C (673 K) and is unreactive to dry H
2 up to its melting point. [11] Finely powdered WC oxidizes readily in hydrogen peroxide aqueous solutions. [17] At high temperatures and pressures it reacts with aqueous sodium carbonate forming sodium tungstate, a procedure used for recovery of scrap cemented carbide due to its selectivity.[ citation needed ]

Physical properties

Tungsten carbide has a high melting point at 2,870 °C (3,140 K), a boiling point of 6,000 °C (6,270 K) when under a pressure equivalent to 1 standard atmosphere (101.325 kilopascals), [3] a thermal conductivity of 110 W/m·K, [4] and a coefficient of thermal expansion of 5.5 μm/m·K. [8]

Tungsten carbide is extremely hard, ranking about 9 to 9.5 on the Mohs scale, and with a Vickers number of around 2600. [9] It has a Young's modulus of approximately 530–700 GPa, [4] [8] [9] [10] a bulk modulus of 379-381 GPa, [18] and a shear modulus of 274 GPa. [19] It has an ultimate tensile strength of 344 MPa, [10] an ultimate compression strength of about 2.7 GPa and a Poisson's ratio of 0.31. [19]

The speed of a longitudinal wave (the speed of sound) through a thin rod of tungsten carbide is 6220 m/s. [20]

Tungsten carbide's low electrical resistivity of about 0.2 μΩ·m is comparable with that of some metals (e.g. vanadium 0.2 μΩ·m). [11] [21]

WC is readily wetted by both molten nickel and cobalt. [22] Investigation of the phase diagram of the W-C-Co system shows that WC and Co form a pseudo binary eutectic. The phase diagram also shows that there are so-called η-carbides with composition (W,Co)
6C that can be formed and the brittleness of these phases makes control of the carbon content in WC-Co cemented carbides important. [22] In the presence of a molten phase such as cobalt, abnormal grain growth is known to occur in the sintering of tungsten carbide, with this having significant effects on the performance of the product material.[ citation needed ]

Structure

a-Tungsten carbide in the unit cell A-WC-polyhedral.png
α-Tungsten carbide in the unit cell
a-WC structure, carbon atoms are gray. Alpha tungsten carbide crystal structure.png
α-WC structure, carbon atoms are gray.

There are two forms of WC, a hexagonal form, α-WC (hP2, space group P6m2, No. 187), [5] [6] and a cubic high-temperature form, β-WC, which has the rock salt structure. [23] The hexagonal form can be visualized as made up of a simple hexagonal lattice of metal atoms of layers lying directly over one another (i.e. not close packed), with carbon atoms filling half the interstices giving both tungsten and carbon a regular trigonal prismatic, 6 coordination. [6] From the unit cell dimensions [24] the following bond lengths can be determined: the distance between the tungsten atoms in a hexagonally packed layer is 291 pm, the shortest distance between tungsten atoms in adjoining layers is 284 pm, and the tungsten carbon bond length is 220 pm. The tungsten-carbon bond length is therefore comparable to the single bond in W(CH
3)
6 (218 pm) in which there is strongly distorted trigonal prismatic coordination of tungsten. [25]

Molecular WC has been investigated and this gas phase species has a bond length of 171 pm for 184
W12
C. [26]

Applications

Cutting tools for machining

Cemented carbide drill and end mills Tungsten carbide.jpg
Cemented carbide drill and end mills

Sintered tungsten carbide–cobalt cutting tools are very abrasion resistant and can also withstand higher temperatures than standard high-speed steel (HSS) tools. Carbide cutting surfaces are often used for machining tough materials such as carbon steel or stainless steel, and in applications where steel tools would wear quickly, such as high-quantity and high-precision production. Because carbide tools maintain a sharp cutting edge better than steel tools, they generally produce a better finish on parts, and their temperature resistance allows faster machining. The material is usually called cemented carbide, solid carbide, hardmetal or tungsten-carbide cobalt. It is a metal matrix composite, where tungsten carbide particles are the aggregate, and metallic cobalt serves as the matrix. [27] [28] It has been found wear and oxidation properties of cemented carbide can be improved by replacing cobalt with iron aluminide. [29] [30] [31] Tungsten carbide cutting tools can be further enhanced with coatings such as titanium aluminium nitride or titanium chromium nitride to increase their thermal stability, and prolong tool life.[ citation needed ]

Ammunition

Tungsten carbide, in its monolithic sintered form, or much more often in cemented tungsten carbide cobalt composite (see above), is often used in armor-piercing ammunition, especially where depleted uranium is not available or is politically unacceptable. W
2C projectiles were first used by German Luftwaffe tank-hunter squadrons in World War II. However, owing to the limited German reserves of tungsten, W
2C material was reserved for making machine tools and small numbers of projectiles. It is an effective penetrator due to its combination of great hardness and very high density. [32] [33]

Tungsten carbide ammunition is now generally of the sabot type. SLAP, or saboted light armour penetrator, where a plastic sabot discards at the barrel muzzle, is one of the primary types of saboted small arms ammunition. Non-discarding jackets, regardless of the jacket material, are not perceived as sabots but as bullets. Both of the designs are, however, common in designated light armor-piercing small arms ammunition. Discarding sabots such as are used with M1A1 Abrams main gun are more commonplace in precision high-velocity gun ammunition. [34] [35]

Mining and foundation drilling

A tricone roller cone assembly from a raiseboring reamer, showing the protruding tungsten carbide buttons inset into the rollers Drill bit 2-italy.JPG
A tricone roller cone assembly from a raiseboring reamer, showing the protruding tungsten carbide buttons inset into the rollers

Tungsten carbide is used extensively in mining in top hammer rock drill bits, downhole hammers, roller-cutters, long wall plough chisels, long wall shearer picks, raiseboring reamers, and tunnel boring machines. In these applications it is also used for wear and corrosion resistant components in inlet control for well screens, sub-assemblies, seal rings and bushings common in oil and gas drilling. [36] It is generally utilised as a button insert, mounted in a surrounding matrix of steel that forms the substance of the bit. As the tungsten carbide button is worn away the softer steel matrix containing it is also worn away, exposing yet more button insert.[ citation needed ]

Nuclear

A re-creation of the experiment involved in the 1945 demon core incident. The sphere of plutonium is surrounded by tungsten carbide blocks acting as neutron reflectors. Partially-reflected-plutonium-sphere.jpeg
A re-creation of the experiment involved in the 1945 demon core incident. The sphere of plutonium is surrounded by tungsten carbide blocks acting as neutron reflectors.

Tungsten carbide is also an effective neutron reflector and as such was used during early investigations into nuclear chain reactions, particularly for weapons. A criticality accident occurred at Los Alamos National Laboratory on 21 August 1945 when Harry Daghlian accidentally dropped a tungsten carbide brick onto a plutonium sphere, known as the demon core, causing the subcritical mass to go supercritical with the reflected neutrons. He fell into a coma and died 25 days after the accident. [37] [38] [39]

Sports usage

A Nokian bicycle tire with tungsten carbide spikes. The spikes are surrounded by aluminum. Nokian Gazza Extreme 294 29er.jpg
A Nokian bicycle tire with tungsten carbide spikes. The spikes are surrounded by aluminum.

Trekking poles, used by many hikers for balance and to reduce pressure on leg joints, generally use carbide tips in order to gain traction when placed on hard surfaces (like rock); carbide tips last much longer than other types of tip. [40]

While ski pole tips are generally not made of carbide, since they do not need to be especially hard even to break through layers of ice, rollerski tips usually are. Roller skiing emulates cross country skiing and is used by many skiers to train during warm weather months.[ citation needed ]

Sharpened carbide tipped spikes (known as studs) can be inserted into the drive tracks of snowmobiles. These studs enhance traction on icy surfaces. Longer v-shaped segments fit into grooved rods called wear rods under each snowmobile ski. The relatively sharp carbide edges enhance steering on harder icy surfaces. The carbide tips and segments reduce wear encountered when the snowmobile must cross roads and other abrasive surfaces. [41]

Car, motorcycle and bicycle tires with tungsten carbide studs provide better traction on ice. They are generally preferred to steel studs because of their superior resistance to wear. [42]

Tungsten carbide may be used in farriery, the shoeing of horses, to improve traction on slippery surfaces such as roads or ice. Carbide-tipped hoof nails may be used to attach the shoes; [43] in the United States, borium – chips of tungsten carbide in a matrix of softer metal such as bronze or mild steel – may be welded to small areas of the underside of the shoe before fitting. [44] : 73 

Surgical instruments and medical

Tungsten carbide is also used for making surgical instruments meant for open surgery (scissors, forceps, hemostats, blade-handles, etc.) and laparoscopic surgery (graspers, scissors/cutter, needle holder, cautery, etc.). They are much costlier than their stainless-steel counterparts and require delicate handling, but give better performance. [45]

Jewelry

Tungsten carbide ring Tungsten Carbide.jpg
Tungsten carbide ring

Tungsten carbide, typically in the form of a cemented carbide (carbide particles brazed together by metal), has become a popular material in the bridal jewelry industry due to its extreme hardness and high resistance to scratching. [46] [47] Even with high-impact resistance, this extreme hardness also means that it can occasionally be shattered under certain circumstances. [48] Some consider this useful, since an impact would shatter a tungsten ring, quickly removing it, where precious metals would bend flat and require cutting. Tungsten carbide is roughly 10 times harder than 18k gold. In addition to its design and high polish, part of its attraction to consumers is its technical nature. [46] Special tools, such as locking pliers, may be required if such a ring must be removed quickly (e.g. due to medical emergency following a hand injury accompanied by swelling). [49]

Other

Spherical tungsten carbide under scanning electron microscope, magnification x950, Material Laboratory Spherical Tungster Carbide under Scanning Electron Microscope.png
Spherical tungsten carbide under scanning electron microscope, magnification x950, Material Laboratory

Tungsten carbide is widely used to make the rotating ball in the tips of ballpoint pens that disperse ink during writing. [50]

English guitarist Martin Simpson uses a custom-made tungsten carbide guitar slide. [51] [ better source needed ] The hardness, weight, and density of the slide give it superior sustain and volume compared to standard glass, steel, ceramic, or brass slides.[ citation needed ]

Tungsten carbide has been investigated for its potential use as a catalyst and it has been found to resemble platinum in its catalysis of the production of water from hydrogen and oxygen at room temperature, the reduction of tungsten trioxide by hydrogen in the presence of water, and the isomerisation of 2,2-dimethylpropane to 2-methylbutane. [52] It has been proposed as a replacement for the iridium catalyst in hydrazine-powered satellite thrusters. [53]

A tungsten carbide coating has been utilized on brake discs in high performance automotive applications to improve performance, increase service intervals and reduce brake dust. [54]

Toxicity

The primary health risks associated with tungsten carbide relate to inhalation of dust, leading to silicosis-like pulmonary fibrosis. [55] Cobalt-cemented tungsten carbide is also anticipated to be a human carcinogen by the American National Toxicology Program. [56]

Related Research Articles

<span class="mw-page-title-main">Tungsten</span> Chemical element with atomic number 74 (W)

Tungsten is a chemical element; it has symbol W and atomic number 74. It is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a distinct element in 1781 and first isolated as a metal in 1783. Its important ores include scheelite and wolframite, the latter lending the element its alternative name.

In materials science, a metal matrix composite (MMC) is a composite material with fibers or particles dispersed in a metallic matrix, such as copper, aluminum, or steel. The secondary phase is typically a ceramic or another metal. They are typically classified according to the type of reinforcement: short discontinuous fibers (whiskers), continuous fibers, or particulates. There is some overlap between MMCs and cermets, with the latter typically consisting of less than 20% metal by volume. When at least three materials are present, it is called a hybrid composite. MMCs can have much higher strength-to-weight ratios, stiffness, and ductility than traditional materials, so they are often used in demanding applications. MMCs typically have lower thermal and electrical conductivity and poor resistance to radiation, limiting their use in the very harshest environments.

<span class="mw-page-title-main">Powder metallurgy</span> Process of sintering metal powders

Powder metallurgy (PM) is a term covering a wide range of ways in which materials or components are made from metal powders. PM processes are sometimes used to reduce or eliminate the need for subtractive processes in manufacturing, lowering material losses and reducing the cost of the final product. This occurs especially often with small metal parts, like gears for small machines. Some porous products, allowing liquid or gas to permeate them, are produced in this way. They are also used when melting a material is impractical, due to it having a high melting point, or an alloy of two mutually insoluble materials, such as a mixture of copper and graphite.

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">Carbon steel</span> Steel in which the main interstitial alloying constituent is carbon

Carbon steel is a steel with carbon content from about 0.05 up to 2.1 percent by weight. The definition of carbon steel from the American Iron and Steel Institute (AISI) states:

<span class="mw-page-title-main">Tool steel</span> Any of various steels that are particularly well-suited to be made into tools and tooling

Tool steel is any of various carbon steels and alloy steels that are particularly well-suited to be made into tools and tooling, including cutting tools, dies, hand tools, knives, and others. Their suitability comes from their distinctive hardness, resistance to abrasion and deformation, and their ability to hold a cutting edge at elevated temperatures. As a result, tool steels are suited for use in the shaping of other materials, as for example in cutting, machining, stamping, or forging.

<span class="mw-page-title-main">High-speed steel</span> Subset of tool steels

High-speed steel is a subset of tool steels, commonly used as cutting tool material.

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

Titanium carbide, TiC, is an extremely hard refractory ceramic material, similar to tungsten carbide. It has the appearance of black powder with the sodium chloride crystal structure.

Cryogenic hardening is a cryogenic treatment process where the material is cooled to approximately −185 °C (−301 °F), usually using liquid nitrogen. It can have a profound effect on the mechanical properties of certain steels, provided their composition and prior heat treatment are such that they retain some austenite at room temperature. It is designed to increase the amount of martensite in the steel's crystal structure, increasing its strength and hardness, sometimes at the cost of toughness. Presently this treatment is being used on tool steels, high-carbon, high-chromium steels and in some cases to cemented carbide to obtain excellent wear resistance. Recent research shows that there is precipitation of fine carbides in the matrix during this treatment which imparts very high wear resistance to the steels.

<span class="mw-page-title-main">Spark plasma sintering</span>

Spark plasma sintering (SPS), also known as field assisted sintering technique (FAST) or pulsed electric current sintering (PECS), or plasma pressure compaction (P2C) is a sintering technique.

<span class="mw-page-title-main">Chromium(II) carbide</span> Chemical compound

Chromium(II) carbide is a ceramic compound that exists in several chemical compositions: Cr3C2, Cr7C3, and Cr23C6. At standard conditions it exists as a gray solid. It is extremely hard and corrosion resistant. It is also a refractory compound, which means that it retains its strength at high temperatures as well. These properties make it useful as an additive to metal alloys. When chromium carbide crystals are integrated into the surface of a metal it improves the wear resistance and corrosion resistance of the metal, and maintains these properties at elevated temperatures. The hardest and most commonly used composition for this purpose is Cr3C2.

<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">Alloy steel</span> Steel alloyed with a variety of elements

Alloy steel is steel that is alloyed with a variety of elements in amounts between 1.0% and 50% by weight, typically to improve its mechanical properties.

Boriding, also called boronizing, is the process by which boron is added to a metal or alloy. It is a type of surface hardening. In this process boron atoms are diffused into the surface of a metal component. The resulting surface contains metal borides, such as iron borides, nickel borides, and cobalt borides, As pure materials, these borides have extremely high hardness and wear resistance. Their favorable properties are manifested even when they are a small fraction of the bulk solid. Boronized metal parts are extremely wear resistant and will often last two to five times longer than components treated with conventional heat treatments such as hardening, carburizing, nitriding, nitrocarburizing or induction hardening. Most borided steel surfaces will have iron boride layer hardnesses ranging from 1200-1600 HV. Nickel-based superalloys such as Inconel and Hastalloys will typically have nickel boride layer hardnesses of 1700-2300 HV.

<span class="mw-page-title-main">Diamond tool</span> Cutting tool with diamond grains

A diamond tool is a cutting tool with diamond grains fixed on the functional parts of the tool via a bonding material or another method. As diamond is a superhard material, diamond tools have many advantages as compared with tools made with common abrasives such as corundum and silicon carbide.

<span class="mw-page-title-main">Cold saw</span> Type of circular saw

A cold saw is a circular saw designed to cut metal which uses a toothed blade to transfer the heat generated by cutting to the chips created by the saw blade, allowing both the blade and material being cut to remain cool. This is in contrast to an abrasive saw, which abrades the metal and generates a great deal of heat absorbed by the material being cut and saw blade.

<span class="mw-page-title-main">Cemented carbide</span> Type of composite material

Cemented carbides are a class of hard materials used extensively for cutting tools, as well as in other industrial applications. It consists of fine particles of carbide cemented into a composite by a binder metal. Cemented carbides commonly use tungsten carbide (WC), titanium carbide (TiC), or tantalum carbide (TaC) as the aggregate. Mentions of "carbide" or "tungsten carbide" in industrial contexts usually refer to these cemented composites.

Cutting tool materials are materials that are used to make cutting tools which are used in machining but not other cutting tools like knives or punches.

Iron aluminides are intermetallic compounds of iron and aluminium - they typically contain ~18% Al or more.

References

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    3    , Co
    3    O
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