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Aluminium carbide, chemical formula Al4C3, is a carbide of aluminium. It has the appearance of pale yellow to brown crystals. It is stable up to 1400 °C. It decomposes in water with the production of methane.

Structure

Aluminium carbide has an unusual crystal structure that consists of alternating layers of Al2C and Al2C2. Each aluminium atom is coordinated to 4 carbon atoms to give a tetrahedral arrangement. Carbon atoms exist in 2 different binding environments; one is a deformed octahedron of 6 Al atoms at a distance of 217 pm. The other is a distorted trigonal bipyramidal structure of 4 Al atoms at 190–194 pm and a fifth Al atom at 221 pm.[3][4] Other carbides (IUPAC nomenclature: methides) also exhibit complex structures.
Reactions

Aluminium carbide hydrolyses with evolution of methane. The reaction proceeds at room temperature but is rapidly accelerated by heating.[5]

Al4C3 + 12 H2O → 4 Al(OH)3 + 3 CH4

Similar reactions occur with other protic reagents:[1]

Al4C3 + 12 HCl → 4 AlCl3 + 3 CH4

Reactive hot isostatic pressing (hipping) at ≈40 MPa of the appropriate mixtures of Ti, Al4C3 graphite, for 15 hours at 1300 °C yields predominantly single-phase samples of Ti2AlC0.5N0.5, 30 hours at 1300 °C yields predominantly single-phase samples of Ti2AlC (Titanium aluminium carbide).[6]

Preparation

Aluminium carbide is prepared by direct reaction of aluminium and carbon in an electric arc furnace.[3]

4 Al + 3 C → Al4C3

An alternative reaction begins with alumina, but it is less favorable because of generation of carbon monoxide.

2 Al2O3 + 9 C → Al4C3 + 6 CO

Silicon carbide also reacts with aluminium to yield Al4C3. This conversion limits the mechanical applications of SiC, because Al4C3 is more brittle than SiC.[7]

4 Al + 3 SiC → Al4C3 + 3 Si

In aluminium-matrix composites reinforced with silicon carbide, the chemical reactions between silicon carbide and molten aluminium generate a layer of aluminium carbide on the silicon carbide particles, which decreases the strength of the material, although it increases the wettability of the SiC particles.[8] This tendency can be decreased by coating the silicon carbide particles with a suitable oxide or nitride, preoxidation of the particles to form a silica coating, or using a layer of sacrificial metal.[9]

An aluminium-aluminium carbide composite material can be made by mechanical alloying, by mixing aluminium powder with graphite particles.

Occurrence

Small amounts of aluminium carbide are a common impurity of technical calcium carbide. In electrolytic manufacturing of aluminium, aluminium carbide forms as a corrosion product of the graphite electrodes.[10]

In metal matrix composites based on aluminium matrix reinforced with non-metal carbides (silicon carbide, boron carbide, etc.) or carbon fibres, aluminium carbide often forms as an unwanted product. In case of carbon fibre, it reacts with the aluminium matrix at temperatures above 500 °C; better wetting of the fibre and inhibition of chemical reaction can be achieved by coating it with e.g. titanium boride.

Applications

Aluminium carbide particles finely dispersed in aluminium matrix lower the tendency of the material to creep, especially in combination with silicon carbide particles.[11]

Aluminium carbide can be used as an abrasive in high-speed cutting tools.[12] It has approximately the same hardness as topaz.[13]

See also

List of compounds with carbon number 1

References

Mary Eagleson (1994). Concise encyclopedia chemistry. Walter de Gruyter. p. 52. ISBN 978-3-11-011451-5.
Gesing, T. M.; Jeitschko, W. (1995). "The Crystal Structure and Chemical Properties of U2Al3C4 and Structure Refinement of Al4C3". 50. Zeitschrift für Naturforschung B, A journal of chemical sciences: 196–200.
Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 297. ISBN 978-0-08-037941-8.
Solozhenko, Vladimir L.; Kurakevych, Oleksandr O. (2005). "Equation of state of aluminum carbide Al4C3". Solid State Communications. 133 (6): 385–388. Bibcode:2005SSCom.133..385S. doi:10.1016/j.ssc.2004.11.030. ISSN 0038-1098.
qualitative inorganic analysis. CUP Archive. 1954. p. 102.
Barsoum, M.W.; El-Raghy, T.; Ali, M. (30 June 1999). "Processing and characterization of Ti2AlC, Ti2AlN, and Ti2AlC0.5N0.5". Metallurgical and Materials Transactions A. 31 (7): 1857–1865. doi:10.1007/s11661-006-0243-3. S2CID 138590417.
Deborah D. L. Chung (2010). Composite Materials: Functional Materials for Modern Technologies. Springer. p. 315. ISBN 978-1-84882-830-8.
Urena; Salazar, Gomez De; Gil; Escalera; Baldonedo (1999). "Scanning and transmission electron microscopy study of the microstructural changes occurring in aluminium matrix composites reinforced with SiC particles during casting and welding: interface reactions". Journal of Microscopy. 196 (2): 124–136. doi:10.1046/j.1365-2818.1999.00610.x. PMID 10540265. S2CID 24683423.
Guillermo Requena. "A359/SiC/xxp: A359 Al alloy reinforced with irregularly shaped SiC particles". MMC-ASSESS Metal Matrix Composites. Archived from the original on 2007-08-15. Retrieved 2007-10-07.
Jomar Thonstad; et al. (2001). Aluminum Electrolysis : Fundamentals of the Hall-Héroult Process 3rd ed. Aluminum-Verlag. p. 314. ISBN 978-3-87017-270-1.
S.J. Zhu; L.M. Peng; Q. Zhou; Z.Y. Ma; K. Kucharova; J. Cadek (1998). "Creep behaviour of aluminum strengthened by fine aluminum carbide particles and reinforced by silicon carbide particulates DS Al-SiC/Al4C3composites". Acta Technica CSAV (5): 435–455. Archived from the original (abstract) on 2005-02-22.
Jonathan James Saveker et al. "High speed cutting tool" U.S. Patent 6,033,789, Issue date: Mar 7, 2000

E. Pietsch, ed.: "Gmelins Hanbuch der anorganischen Chemie: Aluminum, Teil A", Verlag Chemie, Berlin, 1934–1935.

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Salts and covalent derivatives of the carbide ion
CH4
+H		 He
Li2C2 Be2C B4C
BnCm
+B		 C
C2
C4−		 CN−
(CN)2
+N		 CO
CO2
C3O2		 CF
CF4		 Ne
Na2C2 Mg2C Al4C3 SiC
+Si		 +P CS2
+S		 CCl4
+Cl		 Ar
K2C2 CaC
CaC2		 ScC
Sc3C4
Sc4C3
Sc15C19		 TiC VC Cr3C2 MnC2 Fe2C
Fe3C
Fe5C2		 CoC Ni2C CuC
CuC2		 Zn2C Ga +Ge +As CSe2 CBr4
+Br		 Kr
Rb2C2 SrC2 YC ZrC NbC MoC Mo2C Tc Ru2C Rh2C PdC2 Ag2C2 CdC InC Sn Sb Te CI4
+I		 Xe
Cs2C2 BaC2 * LuC2 HfC TaC5 WC Re2C Os2C Ir2C PtC Au2C2 Hg2C2 TlC ?PbC Bi Po At Rn
Fr Ra ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* LaC2 CeC2 PrC2 NdC2 PmC2 SmC2 EuC2 GdC2 TbC2 DyC2 HoC2 ErC2 TmC2 YbC2
** Ac ThC PaC UC NpC, Np2C3 PuC, Pu2C3 Am Cm Bk Cf Es Fm Md No
Aluminium compounds
Al(I)
  • AlBr
  • AlCl
  • AlF
  • AlI
  • Al2O
  • AlOH
Organoaluminium(I) compounds
Al(C5(CH3)5)
Al(II)
  • AlB2
  • AlB12
  • AlO
Al(III)
  • AlAs
  • Al(BH4)3
  • AlBr3
  • Al(CN)3
  • AlCl3
  • AlF3
  • AlH3
  • AlI3
  • AlN
  • Al(NO3)3
  • Al2(CO3)3
  • Al(OH)3
  • Al(OH)2OAc
  • Al(OH)(OAc)2
  • Al(OAc)3
  • Al2SO4(OAc)4
  • AlP
  • AlPO4
  • AlSb
  • Al(C5H7O2)3
  • Al(MnO4)3
  • Al2(MoO4)3
  • Al2O3
  • Al2S3
  • Al2(SO4)3
  • Al2Se3
  • Al2Te3
  • Al2SiO5
  • AlAsO4
  • Al4C3
  • AlOHO
  • Al(OH)2CO2C17H5
  • NaAlH2(OC2H4OCH3)2
  • LiAlH2(OC2H4OCH3)2
  • K2Al2B2O7
Alums
  • (NH4)Al(SO4)2
  • KAl(SO4)2
  • NaAl(SO4)2
Organoaluminium(III) compounds
  • Al(C3H5O3)3
  • C
    36H
    69AlO
    6
  • (Al(CH3)3)2
  • (Al(C2H5)3)2
  • Al(CH2CH(CH3)2)3
  • Al(C2H5)2Cl
  • Al(C2H5)2CN
  • Al(CH2CH(CH3)2)2H
  • Al(C2H5)2Cl2C2H5Cl
  • Ti(C5H5)2CH2ClAl(CH3)2

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