Institute of Metals Division - A Further Study of Ti2Ni-Type Phases Containing Titanium, Zirconium, or Hafnium

An experimental survey has determined the occurrence of Ti2 Ni-type phases in binary and ternary alloys of Ti, Zr, or Hf with first, second, or third long-period transition metals and also in ternary systems in which 0 is the third component. The existence of eleven previously unreported isomorphs is cited and some approximate phase boundaries are given. Lattice parameters are reported for the new phases. The periodic table relationships involved in the occurrence of the phase are discussed. A previous paper' reported the occurrence of a group of Ti2Ni-type phases (structure-type E93) containing Zr in combination with Rh, Ir, and Pt, and Hf in combination with Rh, Pd, Ir, and Pt, and cited evidence to show that all of the Zr phases and the Hf-Pd phase are not binary phases but occur only when 0 is present. More recently one of the present authors found that in the ternary systems of Ti and 0 with Cr, Mn, Fe, Co, and Ni the occurrence of the Ti2Ni-type phase could be correlated qualitatively with valency electron concentration, and that the role of 0 appeared to be that of an electron acceptor.' This paper describes the results of a broader investigation of the occurrence of Ti2Ni-type phases in binary and ternary systems containing Ti, Zr, or Hf. EXPERIMENTAL PROCEDURE Alloys were prepared by arc melting. The purity of the metals Zr, Rh, Hf, Ir, Pd, and Pt was given in the previous paper.' The additional materials used for this work were metals with a minimum purity of 99.9 pct and reagent grade ZrO2, TiO2, Cr2O3, and NiO. Chemical analysis of several alloys in each system indicated good agreement between intended compositions and cast-button compositions. For the heat treatment precautions were taken to avoid oxygen contamination. The specimens were wrapped in Mo foil and sealed in fused quartz tubes at a room temperature pressure of 1 x mm of Hg. These capsules were then annealed in a vacuum furnace at an external pressure of 5 X mm of Hg. Since the major constituent in most of the alloys studied was the brittle Ti2Ni-type phase, Debye-Scherrer patterns with sharp lines could be obtained with powder crushed from the annealed solid samples without being reannealed. Metallographic, X-ray diffraction, and density determination techniques previously described1, 2 were used. RESULTS AND DISCUSSION Zr-Rh-O, Zr-Ir-Oand Zr-Pt-O Systems-Figs. 1 through 3 show the approximate boundaries of the Ti2Ni-type phase fields at the temperatures indicated in the ternary systems Zr-Rh-O, Zr-Ir-O and Zr-Pt-0. In each isothermal section the Ti2Ni-type phase field is labeled E and the unidentified binary phase found in the previous work' is labeled ?. The dotted lines, which are not phase boundaries, correspond to the composition (Zr2 B)1-xOx. In each system the Ti2Ni-type phase field is displaced to the high-Zr side of this composition line. However, the departures from Zr2B stoichiometry for the metal components are not as high as Zr3B, as was inferred from the previous work. Lattice parameters of the Ti2Ni-type phases in the alloys shown as triangular data points in Figs. 1 through 3 are given in Table IA. The probable compositions of the Ti2Ni-type phases have been estimated from the isothermal sections. Although there are a few exceptions that probably result from uncertainties in phase boundary location and from the effect of variation of oxygen content, the generalization can be