Intermetallics: Crystal Structures

compounds, which have some potential as structural materials for commercial applications, mainly at elevated temperatures and hostile environments. Ordered intermetallics based on aluminides and silicides constitute a major group of intermetallics, which has been extensively researched since the early 1990s. Another important group of intermetallics are the Laves phases. They represent a huge group of binary intermetallic compounds, many of which have good combinations of high melting point, low density, and good oxidation resistance. Many ternary elements and, in particular, refractory elements, have large solid solubility in Laves phases for a potential improvement of mechanical properties. Last but not least, the crystal structures of some non-commercial intermetallic compounds (important from the standpoint of fundamental studies) will also be discussed. Traditionally, the crystallographic lattices of intermetallic compounds have been quoted according to the Strukturbericht designation. However, because this system cannot be conveniently and systematically expanded to cover the large variety of crystal structures currently being encountered, the system has gradually fallen into disuse. Nowadays, the system of Pearson symbols (Villars and Calvert 1991) has become more widely used. However, because the Strukturbericht designations are still quite popular, in the present article each crystallographic lattice of an intermetallic compound will be distinguished by the Strukturbericht designation and accompanied by the corresponding Pearson symbol in parentheses.

Intermetallics: Crystal Structures

The search for new high-temperature structural materials has stimulated much interest in ordered intermetallic compounds (Westbrook and Fleischer 1995, Williams 1997). Alloys based on the ordered intermetallic compounds constitute a unique class of metallic material that form a long-range ordered crystal structure (as opposed to a random solid solution) below a certain critical temperature, generally referred to as the critical ordering temperature (Tc). For most of the aluminides of nickel, iron, and titanium this Tc temperature is close to (usually above) the melting temperature of an intermetallic. A notable exception is Ti3Al, which disorders at 1100 1C but has a melting point around 16001C. Iron aluminide of the Fe3Al type passes through two ordered structures (D03 and B2) before becoming disordered (Vedula 1995). It must be pointed out that a perfect ordered crystallographic structure of an intermetallic compound exists only at the exact stoichiometry corresponding to its stoichiometric formula. However, quite a number of intermetallics, including the aluminides of nickel, iron, and titanium, exist over a range of compositions, but the degree of order decreases as the deviation from stoichiometry increases. Additional alloying elements can be incorporated without losing the ordered crystallographic structures. The possibility of alloying the ordered structures of intermetallic compounds opens up new avenues for development of novel high-temperature alloys to improve or optimize properties for specic applications. Therefore, a thorough understanding of how atoms are arranged in an ordered fashion in the crystallographic lattices of intermetallic compounds is a major prerequisite for further development of novel intermetallic-based high-temperature alloys and understanding their mechanical, physical, and chemical properties. This article presents a comprehensive view of the crystal structures of intermetallic

1.
1.1

Aluminides and Silicides

Generic Cubic Crystal Structures

Figure 1 shows hard-sphere models of the generic crystallographic unit cells of cubic aluminides and silicides. The term generic means that these crystal structures occur in aluminides and silicides naturally, for example upon congruent solidication from the melt without any change in composition. Intermetallic compounds such as Ni3Al, Zr3Al, and Ni3Si have an L12 (cP4) crystal structure (Fig. 1(a)), a derivative of the face-centered cubic (fcc) crystal structure. This unit cell contains four atoms, i.e., the same number as fcc. The nickel (Ni3Al, Ni3Si) or zirconium (Zr3Al) atoms occupy face-centered positions and the aluminum or silicon atoms occupy the corners of the unit cell. Both NiAl and FeAl possess a B2 (cP2) crystal structure a derivative of the body-centered cubic (bcc) crystal structure (Fig. 1(b)). The unit cell contains two atoms, i.e., the same number as bcc. In reality, it consists of two interpenetrating primitive cubic cells and is sometimes referred to as the CsCl type. The aluminum atoms occupy the cube corners of one sublattice and the nickel atoms occupy the cube corners of the second sublattice.

Intermetallics: Crystal Structures

arrangement of B (Si or Al) atoms (Fig. 1(d)). The A15 is considered the simplest of the so-called topologically close-packed (TCP) structures (Khantha et al. 1989). Finally, Fe3Al has the ordered cubic D03 (cF16) crystal structure (Fig. 1(e)). This unit cell contains eight bcc-type subcells and it may be thought of as being composed of four interpenetrating fcc lattices (notice that according to the system of Pearson symbols the D03 lattice is classied as cubic facecenteredcF). In each subcell the iron atoms occupy corners and as such each of them is shared with eight neighboring subcells, i.e., one eighth of the iron atom per subcell. Since there are eight subcells, the corner atoms provide eight iron atoms per unit cell. In addition, four iron atoms occupy the centers of four subcells, so altogether there are twelve iron atoms in the D03 unit cell. Including the four aluminum atoms, which also occupy the centers of four subcells, the total number of atoms per unit cell comes to sixteen. Fe3Al transforms from the D03 structure to a defective ordered cubic B2 (cP2) crystal structure at temperatures above the critical ordering temperature Tc of B814K (Vedula 1995). 1.2 Cubic Aluminides Stabilized by Alloying

Figure 1 Generic cubic lattices of aluminides and silicides. (a) L12 (cP4), (b) B2 (cP2), (c) C1 (cF12), (d) A15 (cP8), and (e) D03 (cF16).

Silicides such as Mg2Si, Co2Si, and Ni2Si possess a more complex C1 (cF12) crystal structure with 12 atoms per unit cell (Fig. 1(c)). The archetype of this structure is the ionic ceramic compound CaF2 (calcium uorite). This ionic structure can be viewed as built on an fcc lattice of small cations (Ca2 ) with eight bigger anions (F) forming a simple cubic 1 1 sublattice (at 1 positions) inside the fcc 4 4 4 etc. unit cell. There are (4Ca2 8F) ions per unit cell. Such a crystal structure is termed a uorite structure. If in some ionic compounds the fcc lattice is built on large anions, and smaller cations are located inside the fcc cell, then the C1 crystal structure is termed an anti-uorite structure. From the point of view of atomic size, Mg2Si (and its companion intermetallics Mg2Ge, Mg2Sn, and Mg2Pb) is regarded as uorite type whereas CoSi2 and NiSi2 are regarded as antiuorite type. The A15 (cP8) cubic structure with A3B stoichiometry (Cr3Si and Nb3Al) and eight atoms per unit cell consists of orthogonal chains of A (Cr or Nb) atoms along /100S directions criss-crossing the bcc 236

Low-density and highly oxidation-resistant titanium and zirconium trialuminide intermetallics, with respective stoichiometric formulas Al3Ti and Al3Zr (trialuminides), crystallize in tetragonal D022 (tI8) and D023 (tI16) crystallographic lattices, respectively (Fig. 2(b),(c)). Their crystallographic structures are closely related to the L12 structure (Fig. 2(a)). They can be essentially derived from the former by introducing an antiphase boundary (APB) with a displacement vector of a/2 /100S on every (001) plane in D022 and every second (001) in the D023 lattice (Fig. 2(a),(b),(c)). It must, however, be pointed out that a close examination of the close-packed planes and their respective order in the L12, D022, and D023 structures reveals that the order in these planes is distinctly different, being triangular (T) (Fig. 2(a)), rectangular (R) (Fig. 2(b)), and mixed (T-R) (Fig. 2(c)) in the L12, D022, and D023 structures, respectively. A close relationship between tetragonal and cubic structures in Fig. 2 allows transformation of tetragonal D022 Al3Ti into the L12 structure by alloying with approximately 810 at% copper, nickel, and zinc (Schubert et al. 1964a, Raman and Schubert 1965), chromium and manganese (Zhang et al. 1990), iron (Kumar and Pickens 1988), and palladium (Powers and Wert 1990). Similar transformation of the low-symmetry D023 Al3Zr into the L12 structure can be achieved by alloying with copper, nickel, and zinc (Schubert et al. 1964a, b), chromium and iron (Schneibel and Porter 1989), and manganese (Virk and Varin 1991, 1992). There is a general consensus

Intermetallics: Crystal Structures

Figure 2 The L12 structure in titanium and zirconium trialuminides, which can be stabilized by alloying of tetragonal D022 Al3Ti and D023 Al3Zr with Cr, Mn, Fe, Ni, Cu, Zn, and Pd. A hard-sphere model of the closepacked planes in each crystal structure is also shown. (a) Stabilized L12 structure of Al3Ti (X) where X is the appropriate alloying element; triangular (T) ordering, (b) D022 Al3Ti; rectangular (R) ordering, and (c) D023 Al3Zr; mixed triangularrectangular (T-R) ordering.

Figure 3 Hard-sphere models of crystalline unit cells of non-cubic aluminides and silicides. (a) L10 (tP4), (b) C11b (tI16), (c) D019 (hP8), and (d) D88 (hP16).

that the alloying element atoms substitute mostly for the aluminum atoms. It is to be pointed out that the rst case of systematic alloying-induced transformation to the L12 structure was reported for D022-structured Ni3V and hexagonal D019 (hP24)-structured Co3V by Liu (1984) (so-called long range-ordered (LRO) alloys). Both low-symmetry intermetallics are transformed to the L12 structure by partially substituting iron for cobalt and nickel, respectively. The crystallographic transformation to the L12 structure in the LRO alloys results in a dramatic increase in tensile ductility at room temperature as opposed to the same transformation in Al3Ti, which does not lead to any improvement in tensile ductility. 1.3 Noncubic Aluminides and Silicides

Commercially important aluminides and silicides such as D019 (hP8) Ti3Al, L10 (tP4) TiAl, C11b (tI6) MoSi2,

tetragonal tP32 (no Strukturbericht designation; PTi3 prototype) Nb3Si, and its counterpart the tetragonal D8l(tI32) a-Nb5Si3 (or D8m (tI32) b-Nb5Si3), do not possess cubic structures. Nb5Si3 belongs to a wider group of intermetallic compounds, so-called 5:3 silicides, having a general stoichiometric formula M5Si3 (M Nb, Ta, Mo, V, Ti, Zr, W). These compounds typically crystallize in either a tetragonal D8l (tI32) (e.g., Nb5Si3, Ta5Si3, Mo5Si3, V5Si3, W5Si3) or a hexagonal D88 (hP16) structure (e.g., Ti5Si3). However, the tetragonal M5Si3 can also crystallize with the D88 structure if they contain small amounts of interstitial impurities, in particular carbon (Sauthoff 1996). Figure 3 shows the hard-sphere models of selected noncubic crystallographic structures. The crystallographic unit cell of TiAl (Fig. 3(a)) is commonly referred to as a face-centered tetragonal (fct). The tetragonality is very small (c/a 1 02). The structure of MoSi2-type phases (Fig. 3(b)) has been described as a superstructure of the bcc or CsCl structure with three subcells stacked along the [001] direction. The c/a ratio for MoSi2 is 2.45. Ti3Al has a hexagonal structure (Fig. 3(c)) with eight atoms per unit cell. Finally, the hexagonal structure of Ti5Si3 is

Intermetallics: Laves Phases

Khantha M, Vitek V, Pope D P 1989 Twinning in A15 compounds. Mat. Res. Soc. Symp. Proc. 133, 99104 Kumar K S, Pickens J R 1988 Ternary low-density cubic L12 aluminides. In: Kim Y W, Grifth W M (eds.) Dispersion Strengthened Aluminum Alloys. TMS, Warrendale, PA, pp. 76386 Liu C T 1984 Physical metallurgy and mechanical properties of ductile ordered alloys (Fe, Co, Ni)3V. Int. Met. Rev. 29, 16894 Powers W O, Wert J A 1990 Microstructure, deformation and fracture characteristics of an Al67Pd8Ti25 intermetallic alloy. Metall. Trans. A 21A, 14551 . Raman A, Schubert K 1965 Uber den Aufbau einiger zu TiAl3 verwandter Legierungsreihen III. Untersuchungen in einigen TiNiAl und TiCuAl Systemen. Z. Metallkd. 56, 99101 Sauthoff G 1996 Intermetallics. In: Cahn R W, Haasen P, Kramer E J (eds.) Materials Science and Technology. VCH, Weinheim, Germany, Vol. 8, pp. 646766 Schneibel J H, Porter W D 1989 Microstructure and mechanical properties of L12-structure alloys based on Al3Zr. In: Liu C T, Taub A I, Stoloff N S, Koch C C (eds). Mater. Res. Soc. Symp. Proc. 133, 33540 Schubert K, Meissner H G, Raman A, Rossteutscher W 1964a Einige Strukturdaten metallischer Phasen (9). Naturwissenschaften 51, 287 Schubert K, Raman A, Rossteutscher W 1964b Einige Strukturdaten metallischer Phasen (10). Naturwissenschaften 51, 507 Vedula K 1995 FeAl and Fe3Al. In: Westbrook J H, Fleischer R L (eds.) Intermetallic CompoundsPrinciples and Practice. Wiley, Chichester, UK, Vol. 2, pp. 199209 Villars P, Calvert L D 1991 Pearsons Handbook of Crystallographic Data for Intermetallic Phases. ASM International, Metals Park, OH Virk I S, Varin R A 1991 Development of structure and porosity in cast Al5CuZr2 and Al66Mn9Zr25 intermetallic compounds. Metall. Trans. A 22A, 254552 Virk I S, Varin R A 1992 Mechanical behavior and microcracking of cubic ternary zirconium trialuminides. Metall. Trans. A 23A, 61725 Westbrook J H, Fleischer R L (eds.) 1995 Intermetallic CompoundsPrinciples and Practice. Wiley, Chichester, UK Williams J C 1997 Intermetallics for structural applications: potential, reality and the road ahead. In: Nathal M V, Darolia R, Liu C T, Martin P L, Miracle D B, Wagner R, Yamaguchi M (eds.) Structural Intermetallics 1997. TMS, Warrendale, PA, pp. 38 Zhang S, Nic J P, Mikkola D E 1990 New cubic phases formed by alloying Al3Ti with Mn and Cr. Scr. Metall. Mater. 24, 5762

Figure 4 The C15 unit cell characteristic of Laves phases.

built up by two atomic species which occupy three different crystallographic positions (Fig. 3(d)). The titanium(I) atoms are arranged in chains parallel to each other octahedrally surrounded by silicon atoms. In contrast, the titanium(II) atoms form columns of octahedrons connected along the c-axis. The octahedral interstices can be partially or completely lled by interstitials.

2.

Laves Phases

The binary Laves phases with an AB2 composition belong to the above-mentioned topologically closepacked (TCP) structures. In the group of TCP intermetallics, the Laves phases constitute the single largest group. They crystallize in the hexagonal C14 (hP12; MgZn2 prototype), the cubic C15 (cF24; Cu2Mg prototype) (Fig. 4), or the dihexagonal C36 (hP24; MgNi2 prototype) structures. The C14, C15, and C36 crystal structures differ only by the particular stacking of the same two-layered structural units, which allows structure transformations between these structures and twinning by synchroshear (Hazzledine et al. 1993). The stability of the three crystal structures is controlled by both the atomic size ratio of the A atoms and B atoms and by the valence electron concentration of the Laves phase (Sauthoff 1996). Some Laves phases have been regarded as promising for both functional and structural applications, such as superconducting C15 (Hf, Zr)V2, magnetic C15 TFe2 (where T Ti, Zr, Hf, Nb, and Mo), and materials for hydrogen storage C15 ZrV2, ZrCr2, and C14 ZrMn2 materials (Sauthoff 1996).

R. A. Varin University of Waterloo, Ontario, Canada

Bibliography
Hazzledine P M, Kumar K S, Miracle D B, Jackson A G 1993 Synchroshear of Laves phases. Mater. Res. Soc. Symp. Proc. 288, 5916