Institute of Metals Division - The Effective Atomic Radius of Silicon in Ternary Laves Phase Alloys

The approximate effective silicon radii in ternary Laves phase alloys with transition elements and silicon were found to range between 1.16 and 1.21A, i.e., considerably smaller than the atomic radius calculated for elemental silicon. The atomic radii were found to increase with the size of the transition element atoms in the structure. It has been noted by Aronsson1 that silicon in solid solution in iron, cobalt, and nickel has an effective CN 12 atomic radius of approximately 1.20Å, a value very much smaller than the CN 12 radius of 1.34Å derived from the interatomic distances in elemental silicon.7 The unusually short metal-silicon interatomic distances in transition element monosilicides and disilicides have been also pointed out by various investigators.1 A similar tendency was observed by Nevitt in Cr3O type silicides.2 Recent work on Laves phases in ternary systems of silicon with transition elements4"8 suggested that extensive Laves phase fields may occur in such systems.8 It has been pointed out by Laves7 that the MgCu2 and MgZn2 type structures lend themselves particularly well for the determination of the effective radii of the component atoms. In these AB2 phases the B atoms are arranged in close packed straight lines, and their distances are related in a simple manner to the lattice parameters.8 The present work was undertaken in order to find out whether or not the B transition element in such AB2 Laves phases can be replaced to an appreciable extent by silicon. In cases where extensive substitution proves to be possible, the "average atomic radius for the B site" at various silicon contents was to be determined, and the effective atomic radius of silicon calculated by extrapolation to complete replacement of the B component by silicon. The following ternary systems were studied: Ti-Mn-Si, Ti-Fe-Si, V-Co-Si, V-Ni-Si, Nb-Fe-Si, Nb-Co-Si, Ta-Fe-Si, Ta-Co-Si, and Mo-Fe-Si. In all of these alloy systems, the Laves phase solid solutions were found to extend over a considerable range of silicon content. As previously reported,4"8 in the V-Co-Si, V-Ni-Si, and Mo-Fe-Si ternary systems Laves phases do occur, even though there are no corresponding binary Laves phases. In stabilizing the Laves phase, silicon acts as if it were decreasing the effective electron concentration of the alloy.8 A more detailed study of the boundaries of the Laves phases in the V-Co-Si and V-Ni-Si systems has been made and will be published elsewhere. In both cases, the elongated Laves phase fields extend parallel to the B-Si side of the composition triangle, clearly showing that silicon is substituting for cobalt, respectively, nickel over a wide range of compositions. The binary Laves phases NbCo2 and TaCo2 have the cubic MgCu2-type structure. It was found that, in both ternary systems with silicon, again the MgZn2-type hexagonal Laves phase is stabilized and that this phase extends to high-silicon contents. In each ternary system at least three Laves phase alloys of the composition A(B1_xSix)2 were used, x here denoting the fractional substitution of the B-transition element atoms by silicon. The alloys, listed in Table I, were prepared by arc melting in argon. Each specimen was water quenched after a homogenizing anneal of 3 days at 110(FC, except for the Mo-Fe-Si alloys, which were annealed at 1200°C. Metallographic examination showed that most of the homogenized alloys consisted of a single phase, although some had minor amounts of a second phase, as shown in Table I. X-ray diffraction patterns were prepared using an asymmetrical focusing camera of large resolution and Fe Ka radiation. The patterns were indexed, and the lattice parameters of the hexagonal Laves phases were determined from the available diffraction lines of highest indices: (213), (205), and (313). The lat-