Фазовая диаграмма системы Hf-V
К оглавлению: Другие диаграммы (Others phase diargams)
Hf-V (Hafnium-Vanadium)
J.F. Smith
The assessed diagram for the Hf-V system is based on [68Rud] and [69Rud]. The
diagram is closely related to the V-Zr diagram, except that the single
intermediate phase melts congruently rather than peritectically. Generally,
the existence of one intermediate phase in the system, at a stoichiometry of
HfV2 with a C15 MgCu2-type structure is accepted. Studies with higher-purity
materials confirmed the existence and structure of this phase an agreed that
it is without polymorphic transition above room temperature [61Ell, 77Min].
The assessed diagram shows (bHf) dissolving 23.5 at.% V at 1456 C in eutectic
equilibrium with liquid at 43 at.% Hf and HfV2 near 65 at.% V. (bHf)
disproportionates at 1190 C in eutectoidal equilibrium with (aHf) containing <
2 at.% V and HfV2 having composition also near 65 at.% V. On the V-rich side,
HfV2 has a maximum V content near 67 at.% V at 1520 ш C, where it is in
eutectic equilibrium with liquid at 69 at.% V and the terminal solution with
about 96 at.% V. HfV2 is indicated to melt congruently near 66 at.% V.
The HfV2 phase, like the V2Zr phase, has received considerable attention
because of the martensitic transformation in the region 100 to 120 K and the
superconducting transition near 8.4 to 9.6 K. The martensitic transition is
first order because there is both a volume discontinuity [76Iva] and a latent
heat effect [79Rap]. [82Bal2] showed that for V2Zr a number of structures are
competitive below the martensitic transition. Presumably, this also applies to
HfV2. There is some evidence that the martensitic transition actually is two
transitions [78Pan, 80Fin, 82Bal, 83Bal]. An initial second-order electronic
transition is followed at slightly lower temperature by a first-order
crystallographic transition. A variety of factors, including heat treatment,
stoichiometry, and chemical purity, affect the transition [78Pan]. Grain size
has a pronounced effect [79Koz, 81Gal].
In the Hf-V system, the superconducting transition temperature was reported to
reach a maximum at 80 at.% V [78Fin]. Because this was not a single-phase
alloy, the maximum was rationalized as a pressure effect from excess V acting
on the HfV2, but this was not proven. In contrast, the maximum transition
temperature in the V-Zr system was found at the ideal stoichiometry of V2Zr [
78Fin]. Measurements at high pressures [84Ber] show that the superconducting
transition temperature of HfV2 first increases with increasing pressure to
reach a maximum near 25 kbar and then drops monotonically to the highest
pressure of measurement at 220 kbar. The same report indicates that the
martensitic transition first becomes smeared at about 10 kbar and is not
detectable at 28 kbar and above.
Rapid quenching of Hf-rich alloys can produce multi-phase materials [80Ten].
However, at compositions near that of the Hf-rich eutectic, amorphous
materials with no detectable crystallinity can be obtained [80Ten, 82Gil].
61Ell: R.P. Elliot, Trans. ASM, 53, 321-329 (1961).
68Rud: E. Rudy and St. Windisch, J. Less-Common Met., 15, 13-27 (1968).
69Rud: E. Rudy, Compendium of Phase Diagram Data, U.S. Govt. Rep AFML-TR-65-2,
Part V, Air Force Materials Laboratory, Wright-Patterson AFB, 14-15 and 94 (
1969).
76Iva: V.E. Ivanov, V.A. Finkel', and E.A. Pushkarev, Dokl. Akad. Nauk SSSR,
Riz. Khim., 228, 119-122 (1976) in Russian; TR: Dokl. Phys. Chem., 228, 415-
417 (1976).
77Min: S. A. Minaeva and P.B. Budberg, Izv. Akad. Nauk SSSR, Met., (1) 206-
210 (1977) in Russian; TR: Russ. Metall., (1) 177-181 (1977).
78Fin: T.R. Finlayson and H.R. Khan, Appl. Phys., 17, 165-172 (1978).
78Pan: V.M. Pan, I.E. Bulakh, A.L. Kasatkin, and A. Shevchenko, J. Less-Common
Met., 62, 157-166 (1978).
79Koz: V.N. Kozhanov, Ye. R. Romanov, S.V. Verkhovskii, and A.P. Stepanov, Fiz.
Met. Metalloved., 48, 1249-1255 (1979) in Russian; TR: Phys. Met. Metallogr.,
48(6), 108-114 (1979).
80Fin: V.A. Finkl' and E.A. Pushkarev, Zh. Eksp. Teor. Fiz., 78, 842-846 (1980)
in Russian; TR: Sov. Phys. JETP, 51, 422-424 (1980).
80Ten: M. Tenhover, Appl. Phys., 21, 279-282 (1980).
81Gal: E.V. Galoshina, V.N. Kozhanov, S.V. Verkhovskii, M.A. Borozdina, Ye.P.
Romanov, T.S. Shubina, and K.N. Mikhalev, Fiz. Met. Metalloved., 52, 1205-1214
(1981) in Russian; TR: Phys. Met. Metallogr., 52(6), 68-76 (1981).
82Bal: A.S. Balankin, Fiz. Tverd. Tela (Leningrad), 24, 3475-3477 (1982) in
Russian; TR: Sov. Phys. Solid State, 24, 1977-1978 (1982).
82Gil: L. Gillott, P.N. Guile, N. Cowlam, and K.H.J. Buschow, Struct. Non-
Cryst. Mater., 10, 455-464 (1982).
83Bal: A.S. Balankin and D.M. Skorov, Izv. Akad. Nauk SSSR, Neorg, Mater., 19,
161-162 (1983) in Russian; TR: Inorg. Mater., 19, 142-144 (1983).
84Ber: I.V. Berman, N.B. Brandt, B.N. Kodess, I.E. Kostyleva, and V.I. Sidorov,
Fiz. Tverd. Tela, 26, 1812-1818 (1984) in Russian; TR: Sov. Phys. Solid State,
26, 1095-1098 (1984).
Published in Phase Diagrams of Binary Vanadium Alloys, 1989. Complete
evaluation contains 1 figure, 2 tables, and 33 references.
Special Points of the Hf-V System