|Steels and other iron–carbon alloy phases|
|Other iron-based materials|
Cementite, also known as iron carbide, is an intermetallic compound of iron and carbon, more precisely an intermediate transition metal carbide with the formula Fe3C. By weight, it is 6.67% carbon and 93.3% iron. It has an orthorhombic crystal structure. It is a hard, brittle material, normally classified as a ceramic in its pure form, though it is more important in ferrous metallurgy. While iron carbide is present in most steels and cast irons, it is produced as a raw material in the Iron Carbide process, which belongs to the family of alternative ironmaking technologies
In the iron–carbon system (i.e. plain-carbon steels and cast irons) it is a common constituent because ferrite can contain at most 0.02wt% of uncombined carbon. Therefore, in carbon steels and cast irons that are slowly cooled a portion of the element is in the form of cementite. It forms directly from the melt in the case of white cast iron. In carbon steel, it either forms from austenite during cooling or from martensite during tempering. An intimate mixture with ferrite, the other product of austenite, forms a lamellar structure called pearlite.
While cementite is thermodynamically unstable, eventually being converted to ferrite and graphite at higher temperatures, it does not decompose on heating at temperatures below the eutectoid temperature of the metastable Iron-Carbon phase diagram, which is of the order of 1000 K.
A natural iron carbide (containing minor amounts of nickel and cobalt) occurs in iron meteorites and is called cohenite after the German mineralogist Emil Cohen, who first described it. As carbon is one of the possible minor light alloy components of metallic planetary cores, the high-pressure/high-temperature properties of cementite (Fe3C) as a simple proxy for cohenite are studied experimentally. The figure shows the compressional behaviour at room temperature.
Other iron carbides
There are other forms of metastable iron carbides that have been identified in tempered steel and in the industrial Fischer-Tropsch process. These include Epsilon (ε) carbide, hexagonal close-packed Fe2-3C, precipitates in plain-carbon steels of carbon content > 0.2%, tempered at 100-200 °C. Non-stoichiometric ε-carbide dissolves above ~200 °C, where Hägg carbides and cementite begin to form. Hägg carbide, monoclinic Fe5C2, precipitates in hardened tool steels tempered at 200-300 °C. Characterization of different iron carbides is not at all a trivial task, and often X-ray diffraction is complemented by Mössbauer spectroscopy.
- Smith & Hashemi 2006, p. 363.
- Durand-Charre 2003.
- Smith & Hashemi 2006, pp. 366–372.
- S.W.J. Smith; W. White; S.G. Barker (1911). "The Magnetic Transition Temperature of Cementite". Proc. Phys. Soc. London. 24 (1): 62–69. doi:10.1088/1478-7814/24/1/310.
- Vagn F. Buchwald, Handbook of Iron Meteorites, University of California Press 1975.
- G. Hägg, Z. Krist., Vol. 89, p 92-94, 1934.
- Smith, William F. (1981). Structure and properties of engineering alloys. New York: McGraw-Hill. pp. 61–62. ISBN 0-07-0585601.
- Smith, William F.; Hashemi, Javad (2006). Foundations of Materials Science and Engineering (4th ed.). McGraw-Hill. ISBN 0-07-295358-6.
- Durand-Charre, Madeleine (2004). Microstructure of Steels and Cast Irons. Springer. ISBN 978-3-642-05897-4.
- Crystal structure of cementite at NRL
- Crystal Structure of Cementite, Cambridge University
- Alternative Ironmaking Technologies
- L.J.E. Cohen Nature of Carbides of Iron, Bullettin 631 US Bureau of Mines
- Pycalphad: Thermodynamic calculation of cementite http://pycalphad.readthedocs.org/en/latest/examples/CementiteAnalysis.html based on
- Hallstedt, Bengt; Djurovic, Dejan; von Appen, Jörg; Dronskowski, Richard; Dick, Alexey; Körmann, Fritz; Hickel, Tilmann; Neugebauer, Jörg (March 2010). "Thermodynamic properties of cementite (Fe3C)". Calphad. 34 (1): 129–133. doi:10.1016/j.calphad.2010.01.004.
- Ester Esna du Plessis The Crystal Structures of Iron Carbides, Ph.D. Thesis, University of Johannesburg, 2006 https://books.google.it/books/about/The_Crystal_Structures_of_the_Iron_Carbi.html?id=AN6QtgAACAAJ&redir_esc=y
- Le Caer, G.; Dubois, J. M.; Pijolat, M.; Perrichon, V.; Bussiere, P. (November 1982). "Characterization by Moessbauer spectroscopy of iron carbides formed by Fischer-Tropsch synthesis". The Journal of Physical Chemistry. 86 (24): 4799–4808. doi:10.1021/j100221a030.
- Bauer-Grosse, E.; Frantz, C.; Le Caer, G.; Heiman, N. (June 1981). "Formation of Fe7C3 and Fe5C2 type metastable carbides during the crystallization of an amorphous Fe75C25 alloy". Journal of Non-Crystalline Solids. 44 (2-3): 277–286. doi:10.1016/0022-3093(81)90030-2.