Materials Letters 139 (2015) 194–196

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Amorphous phase decomposition in Al–Ni–RE system alloys

G. Abrosimova n, A. Aronin, A. Budchenko
Institute of Solid State Physics RAS, Chernogolovka, Russia

art ic l e i nf o a b s t r a c t

Article history: The structural changes in Al-based metallic glass at heating and deformation have been studied by X-ray
Received 15 September 2014 diffraction. It has been shown that the amorphous phase of Al–Ni–La and Al–Ni–Y alloys may decompose
Accepted 14 October 2014 at heating and deformation with formation of new amorphous phases with different chemical
Available online 23 October 2014
compositions. Both heating and deformation increase the parameters of diffusion mass transfer which
Keywords: facilitates the atomic redistribution processes.
Amorphous phase & 2014 Published by Elsevier B.V.
Decomposition
Deformation
Short range order

1. Introduction during low-temperature annealing: the initially homogeneous amor-

Amorphous alloys attract particular interest as materials with
unusual properties different from those of crystalline alloys of
similar composition and as systems far from equilibrium. Studies
on structure of amorphous alloys have been carried out over many
years [1–10], but the renewed interest to these materials is due to
the fact that they are precursors for fabrication of nanocrystalline
materials with diverse composition [11–15]. Research studies
[2,16–19] have also shown that the structure formed by crystal-
lization can undergo fundamental changes depending on the
processes or structural changes proceeding in the amorphous
phase prior to crystallization.
The structure of amorphous metallic alloys produced by rapid
quenching is usually homogeneous. It is known, however, that
sometimes immediately after production or as a result of some
influence, the amorphous structure changes or becomes inhomo-
geneous. For instance, formation of inhomogeneous amorphous
phases (co-existence of two amorphous phases) was observed in
Pd74Au8Si18 [20], Pd40.5Ni40.5P19 [21], Be40Ti24Zr36 [22] and some
other amorphous alloys. Such phases have generally no distinct
interface. As a rule, the presence of an inhomogeneous amorphous
structure is established by the data of electron microscopy analysis
or by deformation of the main diffusion maximum on X-ray
diffraction patterns. The process of structural changes of the
amorphous phase remains practically unstudied. Among the few
works one could mention [18] that reported observation of
continuous decomposition of the amorphous phase in Fe–Zr alloy
n
Corresponding author. Tel.: þ 7 496 5224685.
E-mail address: gea@issp.ac.ru (G. Abrosimova).
phous phase decomposed into regions with different component
concentrations which later crystallized into two solid zirconium
solutions in iron (zirconium–iron solutions) of different concentra-
tions. This produced a nanocrystalline structure in contrast to
annealing at higher temperatures when crystallization resulted in
significantly larger crystals. Decomposition of the amorphous phase
with formation and co-existence of several amorphous phases can
occur both before and during the crystallization process [23,24]. The
scale of the chemical composition change in the amorphous matrix
can be appreciably different. In the Fe–Zr system it is 10–30 nm; but,
for instance, in Ni–Mo–B system alloys decomposition occurs on a
scale of more than 50 nm [19]; in Cu–Zr–Ti system alloy it is 2–5 nm
[25]; in the latter case subsequent crystallization gives rise to very
fine nanocrystalline structure. Chemical decomposition of the amor-
phous phase and resulting formation of regions with different short-
range order types involve changes in the morphology and size of
crystallization precipitations and, in some cases, phase composition
changes [26]. Changes occurring within the amorphous state could
significantly influence the parameters of the crystal structure form-
ing upon subsequent heating [16]. The data available indicate that
decomposition of the amorphous phase prior to the onset of
crystallization brings about further formation of nanostructure even
in amorphous alloys that crystallize during conventional annealing
with formation of fairly large crystals.
Besides heating, deformation is another way of introducing
energy into the system. The most recent trends are application of
severe plastic deformation (SPD) and formation of novel struc-
tures. The use of the SPD method allowed formation of a
nanocrystalline structure in systems where it cannot be formed
by heat treatment [27–29]. Therefore, of interest is research on the
influence of various external actions on structural changes of the

http://dx.doi.org/10.1016/j.matlet.2014.10.076
0167-577X/& 2014 Published by Elsevier B.V.
 G. Abrosimova et al. / Materials Letters 139 (2015) 194–196 195

amorphous phase. The objective of the present work was this kind
of research in the course of low-temperature annealing and
deformation of amorphous Al–Ni–RE (RE ¼La or Y) alloys.
Alloy ingots of Al87Ni8La5 and Al87Ni10Y3 composition were
prepared by arc melting as preliminarily master alloys. Amorphous
ribbons about 30 мm thick and  20 mm wide were made by the
single roller melt spinning technique in a helium atmosphere. The
samples were heated and annealed at different temperatures.
Deformation was accomplished by the multiple rolling technique
using a VEB Schwermaschinenbau four-roll laboratory mill. The
deformation value (compression) varied from 10% to 30%.
The structure of the as-prepared and annealed samples was
studied by X-ray diffraction using a SIEMENS D-500 diffractometer
with Co Kα-radiation. Special computer programs were used for
smoothing and background correction.
The as-prepared quenched alloys were amorphous. The X-ray
diffraction patterns exhibited only wide halos typical of an
amorphous phase; no reflections from crystalline phases were
observed. According to DSC data, the onset temperature of the first
crystallization stage is 228 1С; aluminum nanocrystals thereby
start forming in the amorphous phase. Isothermal annealing
within the amorphous state was carried out at 150 1С, which is
appreciably less than the crystallization onset temperature.
The structure of the amorphous phase changes during anneal-
ing, which is revealed in the change of the diffusion maximum in
the X-ray diffraction patterns. The first diffusion maximum in the
X-ray diffraction pattern of the original amorphous ribbon is
symmetrical and after annealing it shows a shoulder on the large
angle side, the degree of the maximum distortion increasing with
annealing time. Fig. 1 presents the X-ray diffraction pattern of as-
prepared sample (a) and of the sample annealed for 25 h (first
diffusion peak region) (b). It is seen that subsequent to heat
treatment the diffusion maximum is a superposition of two
maxima. The positions of the scattering maxima are known to
determine the radius of the first coordination sphere R1,
R1 ¼ 7:73=ðS1 Þmax ¼ 14:06=ðS2 Þmax ¼ 20:46=ðS3 Þmax ……;

where (S1)max (S2)max (S3)max ¼4πsin θ/λ is the wave vector corre-
sponding to the first (second, third,…) maximum of the intensity
curve, θ the scattering angle, and λ the radiation wavelength [30].
Thus, the two diffusion maxima point to the presence of amor- Fig. 1. X-ray diffraction pattern of as-prepared amorphous Al87Ni8La5 alloy (a) and
phous matrix regions with different radii of the first coordination sample annealed at 150 1С for 25 h (b); 1 denotes the experimental spectrum, 2 the
sphere. The difference in the angular positions of the diffusion summary curve, 3 and 4 lines are the diffusion halos from the first and second
amorphous phases, respectively.
maxima is indicative of the formation of amorphous regions with
different chemical compositions of the two amorphous phases.
The maximum located at the smaller angles corresponds to the
amorphous phase with a large radius of the first coordination
sphere (or the largest interatomic distance in the amorphous
phase). Since in the system in question the largest atoms are
those of lanthanum (radii RNi ¼0.124 nm, RAl ¼ 0.143 nm, RLa ¼
0.188 nm), the amorphous phase is lanthanum-enriched. Hence,
the right halo corresponds to the amorphous phase with a smaller
radius of the first coordination sphere that is nickel-enriched or/
and lanthanum-depleted. The radius of the first coordination
sphere is determined by the position of the first diffusion peak
in the X-ray diffraction pattern using the Ehrenfest equation [30]
2R1 sin θ ¼ 1:23λ;

where R1 is the radius of the first coordination sphere, 2θ the angle

of reflection, and λ the radiation wavelength. Following annealing
for 25 h the radii of the first coordination sphere of the two
amorphous phases were equal to 2.98 Å and 2.54 Å.
Fig. 2 shows the difference in the angular position of the
diffusion maxima corresponding to the two amorphous phases
as a function of annealing time of the amorphous sample. It is seen Fig. 2. Difference in position of diffusion peaks as a function of annealing time of
that at the initial stage of annealing the decomposition of the amorphous Al87Ni8La5 alloy at 1501С.
196 G. Abrosimova et al. / Materials Letters 139 (2015) 194–196
Fig. 3. X-ray diffraction pattern of amorphous Al87Ni10Y3 alloy samples subsequent
to deformation; 1 denotes the experimental spectrum, 2 the summary curve,
3 and 4 lines are the diffusion halos from the first and second amorphous phases,
respectively.
amorphous phase proceeds more intensively (the difference in the
angular position of the peaks increases significantly), but after a
lapse of time (about 12 h) the decomposition process is finished
and there are no further changes in the positions of the maxima.
Thus, isothermal annealing of amorphous Al87Ni8La5, alloy
leads to decomposition of the amorphous phase: formation of
regions of different chemical compositions and, probably, with
different types of short-range order. As mentioned above the
result of heat-induced decomposition of the amorphous phase
was observed earlier, yet, here we report the first observation of
the decomposition process (time-related change of the coordina-
tion sphere radii).
Heat-induced decomposition of the amorphous phase was also
observed in the amorphous Al–Ni–Y system alloys. The alloy
samples were subjected to plastic deformation by way of multiple
rolling. Fig. 3 presents the X-ray diffraction pattern of the amor-
phous Al87Ni10Y3, alloy sample after 35% deformation. It is seen
that the first diffusion maximum is asymmetric and, as in the case
of heat treatment, it is a superposition of at least two maxima.
As is known, plastic deformation of amorphous alloys is
achieved by formation and propagation of shear bands. According
to the literature data [31], shear bands are oriented at an angle of
557 51 to the deformation direction. Another characteristic fea-
ture of plastic deformation of amorphous alloys is increasing
concentration of free band volume, i.e., increasing mean intera-
tomic distance. Since shear bands are distinguished by disordered
structure of the amorphous phase and low density regions in
which the mean interatomic distance is somewhat larger than in
the basic amorphous matrix, the structure of the deformed
samples can be regarded as “double-phase”, the first “phase”
being the original amorphous alloy and the other “phase” the
material in the shear bands. Then the diffusion peaks in the X-ray
diffraction patterns make up a superposition of two diffusion
maxima from each “phase”. It should be remembered, however,
that the share of the material in the shear bands is not large and,
hence, its contribution to scattering will be negligible. The follow-
ing variants of structural changes are feasible:
– deformation in shear bands (plastic flow localization regions),
– deformation of the whole sample (in shear bands as well as
shear-free zones).
According to our estimates [32], the share of the material in
shear bands is only several percent and their contribution to
scattering is insignificant. Therefore, though, in principle, scatter-
ing from shear bands could bring about broadening or distortion of
the diffusion maximum, yet such effects are not observed owing to
the small share of the regions. Hence, as in the case of heat
treatment, the discovered change in the shape of the diffusion
maximum revealed by the X-ray diffraction patterns is conditioned
by formation of regions with a type of short-range order and
composition different from those of the matrix. Naturally this does
not exclude a different structure of the material in shear bands
but, owing to the negligible contribution to scattering, its share
can hardly be estimated.
Thus, two amorphous halos testify that the sample contains
regions of different compositions. Analysis of the atom size and
composition of the metallic glass enables the conclusion that the
two diffusion maxima correspond to yttrium (and/or nickel)-
enriched and -depleted regions. As a result, deformation of amor-
phous Al87Ni10Y3 alloy involves a distinct decomposition of the
amorphous phase into regions of different chemical compositions.
From the results presented it follows that heating as well as
deformation of amorphous alloys can lead to decomposition of the
amorphous phase. Both processes increase the parameters of
diffusion mass transfer which facilitates the atomic redistribution
processes. Hence, under certain conditions temperature and defor-
mation can have similar effects on amorphous matrix structure.
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