MAX phases

The MAX Phases are layered, hexagonal carbides and nitrides have the general formula: Mn+1AXn, (MAX) where n = 1 to 3, M is an early transition metal, A is an A-group (mostly IIIA and IVA, or groups 13 and 14) element and X is either carbon and/or nitrogen.

MAX Phase periodic table
Elements in the periodic table that react together to form the MAX phases. The red squares represent the M-elements; the blue are the A elements; the black is X, or C and/or N.
A list of the MAX phases known to date, in both bulk and thin film form:[1]
211 Phases 312 Phases 413 Phases
Ti2CdC, Sc2InC, Ti2AlC, Ti2GaC, Ti2InC, Ti2TlC, V2AlC, V2GaC, Cr2GaC, Ti2AlN, Ti2GaN, Ti2InN, V2GaN, Cr2GaN, Ti2GeC, Ti2SnC, Ti2PbC, V2GeC, Cr2AlC, Cr2GeC, V2PC, V2AsC, Ti2SC, Zr2InC, Zr2TlC, Nb2AlC, Nb2GaC, Nb2InC, Mo2GaC, Zr2InN, Zr2TlN, Zr2SnC, Zr2PbC, Nb2SnC, Nb2PC, Nb2AsC, Zr2SC, Nb2SC, Hf2InC, Hf2TlC, Ta2AlC, Ta2GaC, Hf2SnC, Hf2PbC, Hf2SnN, Hf2SC Ti3AlC2,

V3AlC2,
Ti3SiC2,
Ti3GeC2,
Ti3SnC2,
Ta3AlC2,

 Ti4AlN3,

V4AlC3,
Ti4GaC3,
Ti4SiC3,
Ti4GeC3,
Nb4AlC3,
Ta4AlC3,

History

In the 1990s, the ternary compound, Ti3SiC2, was synthesized and fully characterized for the first time by Dr. Michel Barsoum's research group at Drexel University. A year later they showed that this compound was but one of over sixty phases,[2] most discovered and produced in powder form in the 1960s by H. Nowotny and coworkers.[3] In 1999 they discovered Ti4AlN3 and realized that they were dealing with a much larger family of solids that all behaved similarly. Since 1996, when the first paper was published on the subject, tremendous progress has been made in understanding the properties of these phases and the 1996 article [4] has been cited over 650 times.[5]


Synthesis

The synthesis of the ternary compound, Ti3SiC2 has been realized by different methods, including combustion synthesis, chemical vapor deposition, arc melting, hot isostatic pressing, SHS, reactive sintering, and mechanical alloying. [6][7][8][9]

Properties

These carbides and nitrides possess unusual and, sometimes, unique chemical, physical, electrical, and mechanical properties that combine the best attributes of metals and ceramics [10][11][12][13] such as high temperature wear, corrosion resistance, and toughness. They are useful in technologies involving high efficiency engines, damage tolerant thermal systems, increasing fatigue resistance, and retention of rigidity at high temperatures.[14]

Electrical

The MAX phases are electrically and thermally conductive due to their metallic-like nature of bonding. Most of the MAX phases are better electric and thermal conductors than Ti. This is also related to the electronic structure [15]

Physical

While MAX phases are stiff, they can be machined as easily as metals. They can all be machined using a manual hacksaw, despite the fact that some of them are three times as stiff as titanium metal, with the same density as titanium. They can also be polished to a metallic luster because of their excellent electrical conductivities. They are not susceptible to thermal shock and exceptionally damage tolerant. Some are oxidation and corrosion resistant. Polycrystalline Ti3SiC2 has zero thermopower that is correlated to the anisotropic electronic structure.[16]

Mechanical

The MAX phases as a class are generally stiff, lightweight, and plastic at high temperatures. Some, like Ti3SiC2 and Ti2AlC, are also creep [17] and fatigue [18] resistant, and maintain their strengths to high temperatures. They exhibit unique deformation characterized by basal slip (evidences of out-of-basal plane dislocations and dislocation cross-slips were recently reported in MAX phase deformed at high temperature[19]), a combination of kink and shear band deformation, and delaminations of individual grains.[20][21][22] During mechanical testing, it has been found that polycrystalline Ti3SiC2 cylinders can be repeatedly compressed at room temperature, up to stresses of 1 GPa, and fully recover upon the removal of the load while dissipating 25% of the energy. It was by characterizing these unique mechanical properties of the MAX phases that kinking non-linear solids were discovered. The micromechanism supposed to be responsible for these properties is the Incipient Kink Band (IKB). However no direct evidence of these IKBs has been yet obtained, thus leaving the door open to other mechanism that are less assumption-hungry. Indeed, a recent study demonstrates that the reversible hysteretic loops when cycling MAX polycrystals can be as well explained by the complex response of the very anisotropic lamellar microstructure.[23]

Potential Applications

1. Ductile, machinable refractories

2. High temperature heating elements

3. Coatings for electrical contacts

4. Neutron irradiation resistant parts for nuclear applications [24]

5. Precursor for the synthesis of carbide-derived carbon [25]

6. Precursor for the synthesis of MXenes, a family of two-dimensional transition metal carbides and carbonitrides [26]

References

  1. ↑ Eklund, P., Beckers, M., Jansson, U., Högberg, H., & Hultman, L., The Mn+1AXn phases: Materials science and thin-film processing. Thin Solid Films 518, 1851-1878 (2010)
  2. ↑ Barsoum, M.W., Brodkin, D., & El-Raghy, T., Layered Machinable Ceramics For High Temperature Applications. Scrip. Met. et. Mater. 36, 535-541 (1997)
  3. ↑ Nowotny, H., Struktuchemie Einiger Verbindungen der Ubergangsmetalle mit den elementen C, Si, Ge, Sn. Prog. Solid State Chem. 2, 27 (1970)
  4. ↑ Barsoum, M.W. & El-Raghy, T., Synthesis and Characterization of a Remarkable Ceramic: Ti3SiC2. J. Amer. Cer. Soc. 79 (7), 1953-1956 (1996)
  5. ↑ Barsoum, M.W. & El-Raghy, T., Synthesis and Characterization of a Remarkable Ceramic: Ti3SiC2. J. Amer. Cer. Soc. 79 (7), 1953-1956 (1996)
  6. ↑ Yin, Xi; Chen, Kexin; Zhou, Heping; Ning, Xiaoshan (August 2010). "Combustion Synthesis of Ti3SiC2/TiC Composites from Elemental Powders under High-Gravity Conditions". Journal of the American Ceramic Society 93 (8): 2182–2187. doi:10.1111/j.1551-2916.2010.03714.x.
  7. ↑ Arunajatesan, Sowmya; Carim, Altaf H. (March 1995). "Synthesis of Titanium Silicon Carbide". Journal of the American Ceramic Society 78 (3): 667–672. doi:10.1111/j.1151-2916.1995.tb08230.x.
  8. ↑ Gao, N. F.; Miyamoto, Y.; Zhang, D. (1999). Journal of Materials Science 34 (18): 4385–4392. doi:10.1023/A:1004664500254. Missing or empty |title= (help)
  9. ↑ Li, Shi-Bo; Zhai, Hong-Xiang (8 June 2005). "Synthesis and Reaction Mechanism of Ti3SiC2 by Mechanical Alloying of Elemental Ti, Si, and C Powders". Journal of the American Ceramic Society 88 (8): 2092–2098. doi:10.1111/j.1551-2916.2005.00417.x.
  10. ↑ Barsoum, M.W., The Mn+1AXn Phases: a New Class of Solids; Thermodynamically Stable Nanolaminates. Prog. Solid State Chem 28, 201-281 (2000)
  11. ↑ Barsoum, M.W. Physical Properties of the MAX Phases in Encyclopedia of Materials Science and Technology, edited by K. H. J. Buschow et al. (Elsevier, Amsterdam, 2006)
  12. ↑ Barsoum, M.W. & Radovic, M., Mechanical Properties of the MAX Phases in Encyclopedia of Materials Science and Technology, edited by R. W. Cahn K. H. J. Buschow, M. C. Flemings, E. J. Kramer, S. Mahajan and P. Veyssiere (Elsevier, Amsterdam, 2004)
  13. ↑ Barsoum, M.W., The MAX Phases and Their Properties in Ceramics Science and Technology, Vol. 2: Properties,, edited by R. R. Riedel & I.-W. Chen (Wiley-VCH Verlag GmbH & Co, 2010), Vol. 2.
  14. ↑ Basu, Bikramjit; Kantesh Balani (2011). Advanced Structural Ceramics. Wiley. ISBN 0470497114.
  15. ↑ M. Magnuson et al. Electronic structure and chemical bonding in Ti2AlC investigated by soft x-ray emission spectroscopy; Phys. Rev. B. 74, 195108 (2006).
  16. ↑ The electronic-structure origin of the anisotropic thermopower of nanolaminated Ti3SiC2 determined by polarized x-ray spectroscopy and Seebeck measurements M. Magnuson, M. Mattesini, Ngo Van Nong, P. Eklund and L. Hultman; Phys. Rev. B 85 , 195134 (2012).
  17. ↑ Radovic, M., Barsoum, M.W., El-Raghy, T., & Wiederhorn, S.M., Tensile Creep of Coarse-Grained (100-300 µm) Ti3SiC2 in the 1000-1200 °C Temperature Range. J. Alloys and Compds. 361, 299-312 (2003)
  18. ↑ Gilbert, C.J. et al., Fatigue-crack Growth and Fracture Properties of Coarse and Finegrained Ti3SiC2. Scripa Materialia 238 (2), 761-767 (2000)
  19. ↑ Guitton, A.; Joulain, A.; Thilly, L. & Tromas, C. Evidence of dislocation cross-slip in MAX phase deformed at high temperature. Sci. Rep., 4 (2014)
  20. ↑ Barsoum, M.W. & El-Raghy, T., Room Temperature Ductile Carbides. Metallurgical and Materials Trans. 30A, 363-369 (1999).
  21. ↑ Barsoum, M.W., Farber, L., El-Raghy, T., & Levin, I., Dislocations, Kink Bands and Room Temperature Plasticity of Ti3SiC2. Met. Mater. Trans. 30A, 1727-1738 (1999)
  22. ↑ Guitton, A.; Joulain, A.; Thilly, L. & Tromas, C. Dislocation analysis of Ti2AlN deformed at room temperature under confining pressure. Philosophical Magazine,92, 4536-4546 (2012)
  23. ↑ Guitton, A.; Van Petegem, S.; Tromas, C.; Joulain, A.; Van Swygenhoven, H. & Thilly, L. Applied Physics Letters, 104, 241910 (2014)
  24. ↑ Tallman, Darin (2014). "Effect of neutron irradiation on select MAX phases". Acta Materialia. doi:10.1016/j.actamat.2014.10.068.
  25. ↑ Lukatskaya, Maria; Halim, Joseph (2014). "Room-Temperature Carbide-Derived Carbon Synthesis by Electrochemical Etching of MAX Phases". Angewandte Chemie. doi:10.1002/anie.201402513.
  26. ↑ Naguib, Michael (2011). "Two-Dimensional Nanocrystals Produced by Exfoliation of Ti3AlC2". Advanced Materials. doi:10.1002/adma.201102306.

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