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1. Introduction
The invar alloys, which are based on the composition Fe–36%Ni, have a near zero
thermal expansion coefficient over a substantial temperature range. Many other high
temperature properties and parameters (lattice parameter, electrical resistivity, magne-
tization and elastic moduli) show anomalies which have been found experimentally.
These observations indicate that there is a phase instability in the Fe–Ni phase system
at the invar composition. Several authors suggested the presence of a low temperature
miscibility gap to explain the anomalies and have proposed a variety of phase diagrams
for the Fe–Ni system.
The Fe–Ni phase diagram proposed by Romig and Goldstein in 1980 [1], showed
two major phases, α and γ, and a two phase α + γ region. Using this phase diagram,
for a typical invar alloy, heat treatment at 800◦ C occurs in the γ-phase. The alloy will
enter the two phase region at about 450◦ C during the cooling process.
The low temperature portion of the Fe–Ni phase diagram was recently revised
[2,3] based on meteoritical evidence and electron irradiation of laboratory FeNi alloys.
The authors concentrated on the composition range from 0 to 50 wt% Ni and on
temperatures below 450◦ C (figure 1). Both the stable and metastable phase boundaries
are defined. They observed an asymmetrical miscibility gap which is metastable below
390◦ C and is caused by the presence of a tricritical point which is produced by magnetic
interactions. One can apply this phase diagram directly to invar alloys of ∼ 36 wt%
Ni. This phase diagram is not simple and the low temperature phase transformations
are not still well understood.
Figure 1. FeNi phase diagram proposed by Reuter et al. [2] based on the investigation of meteoritic
metal. In this diagram the phases are represented by: α – low-Ni bcc phase; γ – high-Ni fcc phase; γ1
– low-Ni paramagnetic phase; γ2 – high-Ni ferromagnetic fcc phase; γ 0 – ordered FeNi3 ; γ 00 – ordered
FeNi. The dotted-dashed lines show the MS temperature and the Curie temperature Tc for γ1 phase.
Dashed lines show metastable extension of the miscibility gap from the tricritical point and the hatched
lines delineate the spinodal decomposition region.
The major experimental difficulty in studying these alloys is the slow diffusion
rate of the Fe–Ni system at these low temperatures. As cooling occurs, the diffusion
coefficient of Ni decreases, for example, from 1.5 × 10−16 cm2 s−1 at 600◦ C to 1 ×
10−21 cm2 s−1 at 500◦ C. At 300◦ C it takes more than 104 years for one atomic jump
to occur.
One of the ways in which we can study phase transformations which may be
responsible for invar behavior is to investigate materials of similar composition pre-
pared by non-conventional methods which are known to enhance diffusion, thus al-
lowing equilibrium to be reached in short times. So, to accelerate the approach to an
equilibrium-like state we studied samples prepared by non-conventional methods such
as: (i) Fe–Ni alloys in the form of fine particles prepared by mechanical alloying; (ii)
Fe–Ni multilayers in a very thin modulation ion bombarded with noble gas; (iii) Mete-
orites which contain Fe–Ni alloys slowly cooled after solidification in asteroidal bodies
for millions of years.
R.B. Scorzelli / A study of phase stability in invar Fe–Ni alloys 145
Figure 2. Mössbauer spectra at room temperature of 90 h milled Fe60 Ni40 alloy powders submitted to
annealing at 350◦ C for the indicated times. The subspectra correspond to: disordered magnetic phase
(dashed line); atomically ordered Fe50 Ni50 (crosses line); non-magnetic phase (dashed-dotted line) and
disordered magnetic phase (open diamonds line).
Table 1
Hyperfine parameters and relative phase area for samples: milled 90 h and annealed for 240 h; irradiated to
the doses 1017 Ne/cm2 ; Santa Catharina meteorite. IS = Isomer Shift relative to α-Fe; QS = Quadrupole
Splitting in mm s−1 ; H = Hyperfine Field in Tesla; A = Relative Area (%).
Samples Ordered Non-magnetic Disordered Magnetic
phase phase phase phase
H QS IS A IS A H IS A H IS A
Milled 90 h + 29 0.15 −0.07 10 −0.15 3 31 −0.09 80 20 0.09 7
annealing 240 h
Ion bombarded 29 0.20 −0.05 18 −0.18 41 30 −0.04 41 – – –
1017 Ne/cm2
Santa Catharina 29 0.18 −0.06 50 −0.19 38 30 −0.03 12 – – –
meteorite
R.B. Scorzelli / A study of phase stability in invar Fe–Ni alloys 147
Figure 3. CEM spectra of Fe–Ni multilayers: (a) as deposited; and Ne irradiated to the doses (b)
5 × 1015 Ne/cm2 ; (c) 1016 Ne/cm2 ; (d) 5 × 1016 Ne/cm2 ; (e) 1017 Ne/cm2 . The subspectra correspond to:
bcc α-Fe (dashed line); atomically ordered Fe50 Ni50 (crosses line); non-magnetic phase (dashed-dotted
line) and disordered magnetic phase (dotted line).
system is achieved, whereas for heavier ions (Ar, Xe and Kr) the mixing effect is
predominant.
4. Meteorites
Figure 4. Mössbauer spectrum at room temperature of the Santa Catharina meteorite. The sextet corre-
sponds to the atomically ordered Fe50 Ni50 phase and the singlet to the γLS phase.
observed in synthetic irradiated alloys, mechanically alloyed powders, and ion irra-
diated thin films, can be considered as indicative of the low-temperature equilibrium
state of Fe–Ni at the invar composition.
References
[1] A.D. Romig and J.I. Goldstein, Met. Trans. A 11 (1980) 1151.
[2] K.B. Reuter, D.B. Williams and J.I. Goldstein, Met. Trans. A 20 (1989) 719.
[3] C.W. Yang, D.B. Williams and J.I. Goldstein, J. Phase Equil. (in press).
[4] X. Sike, R.B. Scorzelli, I. Souza Azevedo, E. Baggio Saitovitch and A. Takeuchi, Mater. Sci. Forum
225–227 (1996) 453.
[5] A. Chamberod, D. Roth and J. Billiard, J. Magn. Magn. Mater. 7 (1978) 101.
[6] L. Amaral, R.B. Scorzelli, M.E. Brückman, A. Paesano, J.E. Schmidt, T. Shinjo and N. Hosoito,
J. Appl. Phys. 81 (8) (1997) 4773.
[7] A. Chamberod, J. Laugier and J.M. Penisson, J. Magn. Magn. Mater. 10 (1979) 139.
[8] J.F. Petersen, A. Aydin and J.M. Knudsen, Phys. Lett. A 62 (1977) 192.
[9] J. Danon, R.B. Scorzelli, I. Souza Azevedo, W. Curvello, J.F. Albertsen and J.M. Knudsen, Nature
277 (1979) 283.
[10] D.G. Rancourt and R.B. Scorzelli, J. Magn. Magn. Mater. 150 (1995) 30.