Journal of Non-Crystalline Solids 287 (2001) 329±333

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Mechanically alloyed low-nickel austenite Fe±Ni phase:

evidence of single-phase paramagnetic state
S.D. Kaloshkin a,*, V.V. Tcherdyntsev a, Yu.V. Baldokhin b, I.A. Tomilin a,
E.V. Shelekhov a
a
Department of Physical Chemistry, Moscow State Steel and Alloys Institute, Leninsky prosp. 4, 117936 Moscow, Russia
b
Institute of Chemical Physics, Russian Academy of Sciences, Kosygina str. 4, 117334 Moscow, Russia

Abstract
Fe100 x Nix alloys were obtained by a mechanical alloying technique (MA) from elemental metals. The alloys consist
of: single body-centered cubic phase (bcc) at nickel concentrations 6 22 at.%, single face-centered cubic phase (fcc) ± at
x > 28 at.% and two of these phases ± at 22 6 x 6 28 at.%. Annealing results in formation of single fcc phase structure in
the samples with x P 22 at.%. According to the M ossbauer spectrometry data these annealed alloys with 22±28 at.% Ni
were not ferromagnetic at room temperature. Cooling austenitic samples in liquid nitrogen as well as mechanical de-
formation stimulated austenite±martensite transformation accompanied by the appearance of ferromagnetism. Ó 2001
Elsevier Science B.V. All rights reserved.

1. Introduction their magnetic and mechanical properties. There

Mechanical alloying (MA) is a simple method
of the most severe mechanical treatment of mate-
rials at a relatively low temperature (0.4 Tm ) [1].
Since the MA method is used mostly for powders
and it is not necessary to retain a macroscopic
structure of the sample, the deformation degree of
material in this method is unlimited. Besides pro-
ducing new unstable phases in di€erent metallic
systems after such a severe treatment [2,3] the well-
known alloys and phases may attain new proper-
ties too [4]. Iron±nickel alloys are of interest due to
*
Corresponding author. Tel.: +7-095 230 4667; fax: +7-095
247 6001.
E-mail addresses: ksd@phch.misa.ac.ru (S.D. Kaloshkin),
vvch@phch.misa.ac.ru (V.V. Tcherdyntsev), iat@phch.misa.
ac.ru (I.A. Tomilin), sev@x-ray.misa.ac.ru (E.V. Shelekhov).
0022-3093/01/$ - see front matter Ó 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 1 ) 0 0 5 7 5 - 0
are several studies, where structure and properties
of MA Fe±Ni alloys were investigated [5±9]. It was
found that MA [5], as well as the ®ne grain
structure produced by rapid quenching of Fe±Ni
[10] results in a change in the transformation of the
face-centered cubic (fcc) phase into a body-cen-
tered cubic (bcc) one. Also it was shown that me-
chanically alloyed iron-based binary alloys
posseses wider single-phase concentration ranges
in comparison with those obtained by conven-
tional techniques [11±15]. And as expected [15]
annealing usually causes the decomposition of
supersaturated phases and narrowing of single-
phase concentration ranges. This tendency may
change in the case of non-di€usion austenite±
martensite transformation. As will be shown below
annealing may result in an increase of the con-
centration range of the metastable austenitic
phase. The aim of the present work is to study this
330 S.D. Kaloshkin et al. / Journal of Non-Crystalline Solids 287 (2001) 329±333
phenomenon and to show the possibility of pro-
ducing austenitic Fe±Ni alloys with <28 at.% Ni,
which in particular are not ferromagnetic.
2. Experimental techniques and materials
The MA of carbonyl iron (99.95%) and elec-
trolytic nickel (99.5%) powders was carried out in
a planetary ball mill (AGO-2U) with a rotation
speed of 675 min 1 . About 15 g of material and
150 g of steel balls with 8 mm diameter were loa-
ded into steel hermetic vials (160 cm3 ) for prepa-
ration of Fe1 x Nix alloys (10 < x < 90 at.%). Each
specimen was milled for 1 h at speci®c power of the
process about 20 W/g of material. To reduce
heating of the material the vials were water-cooled
and every 5 min operating time of processing was
interrupted with a 5 min pause. Such a processing
heated the material not more than 200°C. X-ray
di€ractometry and M ossbauer spectroscopy were
used to determine the structure and phase com-
position of the samples. Chemical composition of
samples after milling was measured by local X-ray
microanalysis method [16]. Deviation of chemical
compositions of samples from the nominal ones
was 61%. Contamination of about 0.3 at.% Cr
was found in samples because of the wear of Cr-
containing steel surfaces of vials and balls. An
analysis of gaseous impurities showed the presence
of about 1.0 wt% of oxygen and 0.05 wt% of ni-
trogen in four randomly selected powder samples.
As X-ray analysis did not detect oxide phases, we
concluded that gases were mainly adsorbed on
intergrain and intergranular surfaces of powders.
Annealing of samples was carried out in an argon
atmosphere.
3. Results
According to X-ray di€raction data Fe±Ni MA
samples contained bcc and fcc phases, but in the
concentration ranges di€ering from those of
equilibrium bulk alloys. As-milled Fe±Ni alloys
consist of: single bcc phase at nickel concentration
6 22 at.%, single fcc phase ± at x > 28 and mixture
of these two phases ± at 22 6 x 6 28 (Fig. 1, see
Fig. 1. Phase composition of MA Fe±Ni samples, as-milled and
after annealing at 650°C for 0.5 h.
also [17,18]). Fig. 1 shows that concentration
ranges of single-phase solid solutions on the base
of a-Fe and c-Ni(Fe) are larger in MA alloys
compared with the equilibrium phase diagram. In
contrast to the stable diagram, the FeNi3 com-
pound was not observed in MA alloys.
As reported in [18], a wide distribution of hy-
per®ne ®elds is typical for M ossbauer spectra of
most Fe±Ni alloys. For every as-prepared MA
sample the sextet component in the M ossbauer
spectra was observed. The average value of hy-
per®ne ®eld on iron atoms versus MA alloy com-
position is plotted in Fig. 2. These data are close to
those obtained for Fe±Ni alloys by other tech-
niques [5,7,20], where the correspondence of sextet
component to one or another ferromagnetic phase
in Fe±Ni alloys was shown. We suggest that the
hyper®ne ®eld depends only on the phase compo-
sition of an alloy and does not depend on the way
of its preparation. In the same ®gure the Curie
temperatures of bcc and fcc phases are plotted as a
function of the composition of each phase. These
data are extrapolated to larger concentration
ranges assuming identical atomic compositions of
coexisting phases, in agreement with data previ-
ously obtained for MA binary alloys [11±15].
Annealing of as-milled samples at 650°C
changes the phase compositions of several alloys.
 S.D. Kaloshkin et al. / Journal of Non-Crystalline Solids 287 (2001) 329±333
Fig. 2. Room temperature hyper®ne magnetic ®eld (experi-
mental points connected by the solid line) and corresponding
Curie temperature [19] of as-milled Fe±Ni samples (dashed
line).
As Fig. 1 shows after annealing the concentration
of Ni in single fcc-phase alloy at room tempera-
ture decreases to 22 at.%. Only the single para-
magnetic component was observed in the
M ossbauer spectra of alloys with 22 6 x 6 28 at.%
(Fig. 3). The fcc alloys change from paramagnetic
to ferromagnetic state with increasing Ni content.
For x ˆ 28 at.% broadening of the single com-
ponent, which corresponds to the appearance of
ferromagnetic interactions [21], was observed.
Martensitic transformation of annealed Fe±Ni
alloys with 22±26 at.% Ni may be induced by
cooling at liquid nitrogen temperature and by
mechanical deformation. M ossbauer spectroscopy
(Fig. 4) as well as X-ray di€raction analysis detects
martensite in the initially fully austenitic Fe78 Ni22
(b) alloy after cooling it in liquid nitrogen (c) or
crushing the powder in mortar (d). The same
procedure with an alloy containing 28 at.% Ni had
no e€ect.
Long-term annealing of the MA samples re-
sults in the appearance of the austenite±marten-
site transition at cooling to room temperature.
Experiments with Fe78 Ni22 MA alloy showed
that after annealing at 700°C for 12 h it became
almost completely martensitic at room tempera-
ture.
331
Fig. 3. Mossbauer spectra of MA Fe100 x Nix …x ˆ 20; 22; 24; 26;
28† alloys annealed at 650°C.
4. Discussion
It was rather unexpected to us to ®nd a com-
pletely paramagnetic state of alloys in binary
Fe±Ni system. Explanation of this phenomenon is
illustrated in Fig. 5. The alloys with x > 20 at.%
after annealing possess only one fcc phase. On the
other hand the Curie temperature of fcc phase
decreases with decreasing Ni content lower 6 35
at.%. At about x ˆ 28 at.% we expect the Curie
point to decrease up to room temperature. The
dependence of hyper®ne ®eld on phase composi-
tion also decreases with decrease of Ni in the same
concentration range. Because of the increase of the
single fcc phase concentration range, MA Fe±Ni
alloys with 22±28 at.% Ni are paramagnetic at
room temperature (Fig. 5).
As low-nickel (<28 at.% Ni) austenitic phase is
not thermodynamically stable at room tempera-
ture it has a tendency to transform into martensitic
phase. But the fact that an alloy with 28 at.% Ni
332 S.D. Kaloshkin et al. / Journal of Non-Crystalline Solids 287 (2001) 329±333
(a)
(b)
(c)
(d)
Fig. 4. M ossbauer spectra of MA Fe78 Ni22 alloy: (a) as-milled
alloys; (b) annealed at 650°C for 1 h; (c) annealed as (b) and
then cooled down to liquid nitrogen temperature; (d) crushed in
mortar.
did not transform into martensitic state shows the
decreasing tendency of Fe±Ni alloys to form
martensite phase with increase of Ni content (see
also [5,22]). On the other hand, the fact that long-
term annealing of austenitic samples caused an
increase of the temperature of martensite trans-
Fig. 5. Room temperature hyper®ne magnetic ®eld (experi-
mental points connected by the solid line) and Curie tempera-
ture [19] of MA Fe±Ni samples annealed at 650°C (dashed line).
formation shows that the depression of this
transformation in MA alloys is mainly caused by
the procedure of sample preparation. We conclude
that the mechanical treatment mainly suppresses
the austenite±martensite transformation. It seems
that the main cause of this suppression is grain size
of the MA fcc phase, but such structure defects as
dislocations, stacking faults and their interaction
also may a€ect the transformation.
5. Conclusion
The martensite transformation was suppressed
in Fe±Ni alloys prepared by MA technique. As a
result at room temperature non-ferromagnetic al-
loys with single-phased fcc structure were obtained
in the concentration range 22±26 at.% Ni. This
structure and magnetic state, however, may be
changed inducing martensite transformation by
low-temperature treatment or mechanical defor-
mation.
Acknowledgements
This work was supported by RFBR (00-03-
32529a) and INTAS (99-01741).
 S.D. Kaloshkin et al. / Journal of Non-Crystalline Solids 287 (2001) 329±333
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