Institute of Metals Division - Intermediate Phases in Binary Systems of Certain Transition Elements (Discussion, p. 1412)

Thirty binary systems of vanadium and chromium group transition elements with second and third long period transition elements were explored in regard to the intermediate phases formed. It was found that the phases predominating in these systems are s, AB type with ordered a-tungsten or C8 structure, close-packed-hexagonal with small unit cell dimensions and, finally, phases isomorphous with 1-manganese. IN recent years, considerable information has become available concerning the intermediate phases in binary systems of the transition elements. Thus, the s phase has been found to occur in most of the binary systems of vanadium, chromium, and molybdenum with the group of elements manganese, iron, cobalt, and nickel.' It was observed that, while the rr phases formed by chromium with manganese, iron, or cobalt possess a considerable temperature range of stability, particularly in the Cr-Co system, the corresponding s phases with molybdenum are limited to a temperature range of less than 400" above about 1200°C. Goldschmidt' reported v phases of tungsten with iron and cobalt, and these are apparently stable only at (and above?) 1400°C." Exploratory work in this laboratory with Fe-W and Co-W alloys of approximately 60 atomic pct W annealed at 1300°C did not produce X-ray patterns suggesting the presence of a phase. It appears then that the phases of iron and cobalt with the chromium group elements decrease in stability as the two components are chosen from long periods further removed from each other. From the available information, it might be concluded that the controlling factor is the increasing difference in atomic radii between the components. In contrast to the a phase, the phases formed by iron and cobalt with chromium group elements' are stable only when the latter have large atomic radii (molybdenum and tungsten); the corresponding phases with chromium do not occur. When the difference in atomic size becomes still larger (r,/r,, approaching the ideal value of 1.225), the u and p phases are replaced by Laves phases (AB,), as in the alloys of iron and cobalt with columbium," tantalum." and titanium."-" However, atomic size certainly cannot be the sole determining factor, since, for instance, in contrast to the very stable (Mo, Co)p phase, no such phase occurs in the Mo-Ni system even though the atomic diameters of cobalt and nickel are nearly the same. Similarly, chromium and cobalt form a a phase in a wide temperature range," but the corresponding s phase in the Cr-Ni system is missing. It has been shown that the composition of the u phase in various binary and ternary systems of transition elements in the first long period may be correlated in a fairly quantitative manner with the number of electron vacancies. The influence of electronic structure is probably present also in binary and ternary phases' and to some extent, apparently, even in Laves phases." " Although the absence of phases in the Cr-Ni and Mo-Ni systems has not as yet been explained on the basis of electronic structure, it appears reasonable to suspect a connection. One of the great difficulties in arriving at well founded rules in regard to the alloying behavior of transition elements lies in the lack of reliable information concerning the details of their electronic structure in the metallic and alloy form. The theoretical penetration of this field appears to be beset by very considerable difficulties, even when the complications due to alloy formation are disregarded. Another great source of uncertainty is the scarcity of phase diagram information even for binary systems of the transition elements so that only a very limited basis is provided for generalizations as to the occurrence of intermediate phases. For instance, very few binary phase diagrams of second and third long period transition element systems have so far been published. The present work was undertaken in order to survey the various types of intermediate phases occurring in 30 binary systems of elements of the group vanadium, columbium, tantalum, chromium, molybdenum, and tungsten with the elements rhenium, ruthenium, rhodium, palladium, and platinum. For most of these binary systems phase diagrams are very incompletely or not at all known, as will be further reviewed.*