Tungsten carbide

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Tungsten carbide

Tungsten carbide milling bits Identifiers CAS number 12070-12-1 Properties Molecular formula WC Molar mass 195.86 gmol-1 Appearance grey-black lustrous solid Density 15.8 gcm-3, solid Melting point 2870 C, 5198 F (3143 K) Boiling point 6000C, 10832 F (6273 K) Solubility in water Insoluble. Structure Hexagonal, hP2, Crystal structure space group = P6m2, No. 187[1] Hazards EU classification not listed Related compounds Tungsten boride Other anions Tungsten nitride Molybdenum carbide Other cations Titanium carbide Silicon carbide (verify) (what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references

Tungsten carbide (WC) is an inorganic chemical compound containing equal parts of tungsten and carbon atoms. Colloquially, tungsten carbide is often simply called carbide. In its most basic form, it is a fine gray powder, but it can be pressed and formed into shapes for use in industrial machinery, tools, abrasives, as well as jewelry. Tungsten carbide is approximately three times stiffer than steel, with a Young's modulus of approximately 550 GPa,[2] and is much denser than steel or titanium. It is comparable with corundum (-Al2O3) or sapphire in hardness and can only be polished and finished with abrasives of superior hardness such as cubic boron nitride and diamond amongst others, in the form of powder, wheels, and compounds.

Contents
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1 Chemical properties 2 Physical properties 3 Structure 4 Applications o 4.1 Machine tools o 4.2 Military o 4.3 Sports o 4.4 Domestic 5 Toxicity 6 References 7 External links

[edit] Chemical properties

There are two well characterized compounds of tungsten and carbon, WC and tungsten semicarbide, W2C. Both compounds may be present in coatings and the proportions can depend on the coating method.[3] WC can be prepared by reaction of tungsten metal and carbon at 14002000 C.[4] Other methods include a patented fluid bed process that reacts either tungsten metal or blue WO3 with CO/CO2 mixture and H2 between 900 and 1200 C.[5] Chemical vapor deposition methods that have been investigated include:[4] WC can also be produced by heating WO3 with graphite in hydrogen at 670 C following by carburization in Ar at 1000 C or directly heating WO3 with graphite at 900C. [6]

tungsten hexachloride with hydrogen, as a reducing agent, and methane, as the source of carbon at 670 C (1,238 F) WCl6 + H2 + CH4 WC + 6 HCl

reacting tungsten hexafluoride with hydrogen, as reducing agent, and methanol, as source of carbon at 350 C (662 F) WF6 + 2 H2 + CH3OH WC + 6 HF + H2O

At high temperatures WC decomposes to tungsten and carbon and this can occur during high-temperature thermal spray, e.g. high velocity oxygen fuel (HVOF) and high energy plasma (HEP) methods.[7] Oxidation of WC starts at 500600 C.[4] It is resistant to acids and is only attacked by hydrofluoric acid/nitric acid (HF/HNO3) mixtures above room temperature.[4] It reacts with fluorine gas at room temperature and chlorine above 400 C (752 F) and is unreactive to dry H2 up to its melting point.[4]

WC 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.[8] It has been proposed as a replacement for the iridium catalyst in hydrazine powered satellite thrusters.[9]

[edit] Physical properties

Tungsten carbide is high melting, 2,870 C (5,200 F), extremely hard (8.59.0 Mohs scale, Vickers hardness number = 2242) with low electrical resistivity (~2107 Ohmm), comparable with that of some metals (e.g. vanadium 2107 Ohmm).[4][10] WC is readily wetted by both molten nickel and cobalt.[11] 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 -carbides with composition (W,Co)6C that can be formed and the fact that these phases are brittle is the reason why control of the carbon content in WC-Co hard metals is important.[11]

[edit] Structure

-WC structure, carbon atoms are gray.[1] There are two forms of WC, a hexagonal form, -WC (hP2, space group P6m2, No. 187),[1][12] and a cubic high-temperature form, -WC, which has the rock salt structure.[13] The hexagonal form can be visualized as made up of hexagonally close packed layers of metal atoms with layers lying directly over one another, with carbon atoms filling half the interstices giving both tungsten and carbon a regular trigonal prismatic, 6 coordination.[12] From the unit cell dimensions[14] 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(CH3)6 (218 pm) in which there is strongly distorted trigonal prismatic coordination of tungsten.[15] Molecular WC has been investigated and this gas phase species has a bond length of 171 pm for 184W12C.[16]

[edit] Applications
[edit] Machine tools

This section does not cite any references or sources. Please help improve this section by adding citations to reliable sources. Unsourced material may be challenged and removed. (November 2010) See also: Cemented carbide Carbide cutting surfaces are often used for machining through materials such as carbon steel or stainless steel, as well as in situations where other tools would wear away, such as highquantity production runs. Carbide generally produces a better finish on the part, and allows faster machining. Carbide tools can also withstand higher temperatures than standard high speed steel tools. The material is usually called cemented carbide, hardmetal or tungstencarbide cobalt: it is a metal matrix composite where tungsten carbide particles are the aggregate and metallic cobalt serves as the matrix.

[edit] Military
This section does not cite any references or sources. Please help improve this section by adding citations to reliable sources. Unsourced material may be challenged and removed. (November 2010) Tungsten carbide is often used in armor-piercing ammunition, especially where depleted uranium is not available or is politically unacceptable. The first use of W2C projectiles occurred in German Luftwaffe tank-hunter squadrons, which used 37 mm autocannon equipped Junkers Ju 87G dive bomber aircraft to destroy Soviet T-34 tanks in World War II. Owing to the limited German reserves of tungsten, W2C material was reserved for making machine tools and small numbers of projectiles for elite combat pilots, like Hans-Ulrich Rudel. It is an effective penetrator due to its combination of great hardness and very high density. Tungsten carbide ammunition can be of the sabot type (a large arrow surrounded by a discarding push cylinder) or a subcaliber ammunition, where copper or other relatively soft material is used to encase the hard penetrating core, the two parts being separated only on impact. The latter is more common in small-caliber arms, while sabots are usually reserved for artillery use. 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 K. Daghlian, Jr. accidentally dropped a tungsten carbide brick onto a plutonium sphere, causing the subcritical mass to go supercritical with the reflected neutrons.

[edit] Sports
This section does not cite any references or sources. Please help improve this section by adding citations to reliable sources. Unsourced material may be challenged and removed. (November 2010)

A Nokian tire with tungsten carbide spikes. The spikes are surrounded in aluminum. Hard carbides, especially tungsten carbide, are used by athletes, generally on poles which strike hard surfaces. 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. 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. 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. Some tire manufacturers, such as Nokian and Schwalbe, offer bicycle tires with tungsten carbide studs for better traction on ice. These are generally preferred to steel studs because of their superior resistance to wear. 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,[17] or alternatively borium, tungsten carbide in a matrix of softer metal, may be welded to small areas of the underside of the shoe before fitting.[18]

[edit] Domestic
Tungsten carbide is sometimes used to make the rotating ball in the tips of ballpoint pens that disperse ink during writing.[19]

A tungsten carbide ring Tungsten carbide can now be found in the inventory of some jewelers, most notably as a primary material in men's wedding rings. When used in this application the bands appear with a lustrous dark hue often buffed to a mirror finish. The color is more similar to that of hematite than to that of platinum. The finish is highly resistant to scratches and scuffs, holding its mirror-like shine for years. Although it is possible to inlay precious metals, woods, and other materials, these are less scratch-resistant than tungsten carbide. A common misconception concerning tungsten carbide rings is that they cannot be removed in the case of emergency medical treatment, requiring the finger to be removed instead. This is not true. Emergency care providers have specialized tools that allow them to easily break tungsten rings into large pieces. As a result, it is easier and less dangerous to remove tungsten carbide rings than gold, silver, or titanium without injuring the hand or finger.[20] An easier way to remove tungsten carbide rings is to use a tool such as a vise, which can be used to shatter the ring.[21] Many manufacturers of this emerging jewelry material state that the use of a cobalt binder may cause unwanted reactions between the cobalt and the natural oils on human skin. Skin oils cause the cobalt to leach from the material. This is said to cause possible irritation of the skin and permanent staining of the jewelry itself. Many manufacturers now advertise that their jewelry is "cobalt free". This is achieved by replacing the cobalt with nickel as a binder.[22]

[edit] Toxicity
The primary health risks associated with carbide relate to inhalation of dust, leading to fibrosis.[23] CobaltTungsten Carbide is also reasonably anticipated to be a human carcinogen by the National Toxicology Program.[24]

[edit] References
1. ^ a b c Krawitz, Aaron D.; Reichel, Daniel G.; Hitterman, Richard (1989). "Thermal Expansion of Tungsten Carbide at Low Temperature". Journal of the American Ceramic Society 72 (3): 515. doi:10.1111/j.1151-2916.1989.tb06169.x. 2. ^ Elastic Properties and Young Modulus for some Materials 3. ^ Jacobs, L.; M. M. Hyland; M. De Bonte (1998). "Comparative study of WC-cermet coatings sprayed via the HVOF and the HVAF Process". Journal of Thermal Spray Technology 7 (2): 213218. doi:10.1361/105996398770350954. 4. ^ a b c d e f Pierson, Hugh O. (1992). Handbook of Chemical Vapor Deposition (CVD): Principles, Technology, and Applications. William Andrew Inc.. ISBN 0815513003. 5. ^ Lackner, A.,Filzwieser A. "Gas carburizing of tungsten carbide (WC) powder" U.S. Patent 6,447,742 (2002) 6. ^ Zhong, Y.; et al. (2011). Journal of Materials Science 46: 6323. doi:10.1007/s10853-010-4937-y. 7. ^ Nerz, J.; B. Kushner; A. Rotolico (1992). "Microstructural evaluation of tungsten carbide-cobalt coatings". Journal of Thermal Spray Technology 1 (2): 147152. doi:10.1007/BF02659015.

8. ^ Levy, R. B.; M. Boudart (1973). "Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis". Science 181 (4099): 547549. doi:10.1126/science.181.4099.547. PMID 17777803. 9. ^ Rodrigues, J.A.J.; G.M. Cruz; G. Bugli; M. Boudart; G. Djga-Mariadassou; (1997). "Nitride and carbide of molybdenum and tungsten as substitutes of iridium for the catalysts used for space communication". Catalysis Letters 45: 12. doi:10.1023/A:1019059410876. 10. ^ Kittel, Charles (1995). Introduction to Solid State Physics (7 ed.). Wiley-India. ISBN 108126510455. 11. ^ a b Ettmayer, Peter; Walter Lengauer (1994). Carbides: transition metal solid state chemistry encyclopedia of inorganic chemistry. John Wiley & Sons. ISBN 0471936200. 12. ^ a b Wells, A. F. (1984). Structural Inorganic Chemistry (5 ed.). Oxford Science Publications. ISBN 0198553706. 13. ^ Sara, R. V. (1965). "Phase Equilibria in the System TungstenCarbon". Journal of the American Ceramic Society 48 (5): 251257. doi:10.1111/j.11512916.1965.tb14731.x. 14. ^ Rudy, E.; F. Benesovsky (1962). "Untersuchungen im System Tantal-WolframKohlenstoff". Monatshefte fr chemie 93 (3): 11761195. doi:10.1007/BF01189609. 15. ^ Kleinhenz, Sven; Valrie Pfennig; Konrad Seppelt (1998). "Preparation and Structures of [W(CH3)6], [Re(CH3)6], [Nb(CH3)6]-, and [Ta(CH3)6]-". ChemistryA European Journal 4 (9): 168791. doi:10.1002/(SICI)15213765(19980904)4:9<1687::AID-CHEM1687>3.0.CO;2-R. 16. ^ Sickafoose, S.M.; A.W. Smith; M. D. Morse (2002). "Optical spectroscopy of tungsten carbide (WC)". J. Chem. Phys. 116 (993): 993. doi:10.1063/1.1427068. 17. ^ "Road nail". Mustad Hoof Nails. Retrieved July 2011. 18. ^ Breningstall, F. Thomas. "Winter shoes". Windt im Wald Farm. Retrieved July 2011. 19. ^ "How does a ballpoint pen work?". Engineering. HowStuffWorks. 1998-2007. Retrieved 2007-11-16. 20. ^ "Are tungsten rings almost impossible to remove in an emergency?". Tungsten Direct. Retrieved 2011-05-26. 21. ^ "How To Remove A Tungsten Rings". Fable Designs. Retrieved 2009-05-12. 22. ^ "Tungsten Carbide Manufacturing". Forever Metals. Retrieved 2008-08-30. 23. ^ Sprince, NL.; Chamberlin, RI.; Hales, CA.; Weber, AL.; Kazemi, H. (Oct 1984). "Respiratory disease in tungsten carbide production workers". Chest 86 (4): 54957. doi:10.1378/chest.86.4.549. PMID 6434250. 24. ^ "12th Report on Carcinogens". National Toxicology Program. Retrieved 2011-0624.

[edit] External links

International Chemical Safety Card 1320 NIOSH Pocket Guide to Chemical Hazards

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Tungsten compounds Carbides Superhard materials

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