Materials Science and Engineering A 449–451 (2007) 586–589

Physical properties of Al–R melts

V. Sidorov a,∗ , O. Gornov a , V. Bykov a , L. Son a , R. Ryltsev a , S. Uporov a , V. Shevchenko b ,
V. Kononenko b , K. Shunyaev c , N. Ilynykh c , G. Moiseev c , T. Kulikova c , D. Sordelet d
a Urals State Pedagogical University, Ekaterinburg, Russia
b Institute of Solid State Chemistry UD RAS, Ekaterinburg, Russia
c Institute of Metallurgy UD RAS, Ekaterinburg, Russia
d Iowa State University, Ames, IA, USA

Received 24 August 2005; received in revised form 26 January 2006; accepted 24 February 2006

Abstract
In this work, we present experimental data of physical properties (viscosity, surface tension, magnetic susceptibility and electroresistivity) studies
for Al–R (R = Ce, Pr, Sm, Gd, Dy, Ho, Yb and Y) alloys and first intermetallic compounds from aluminum side, Al11 R3 (Al3 R). All properties
were measured during heating up to 2000 K and the following cooling down under helium atmosphere. The main results are: (1) the electronic
characteristics of the objects are in good correlation with R positions in the periodic table, but rather lower than for pure elements. The conclusion
is that through all investigated temperature range, the rare-earth elements have partly covalent but not only metallic states; (2) all the melts remain
strongly microheterogeneous even at high overheatings above liquidus. The existence of associations with Al2 R type is highly probable here. Some
destruction of these associations takes place with increasing temperature above melting point at the composition of Al2 R compound. However, the
transformation into true solution state is somewhere above 1900 K. To check the idea, the thermodynamic modeling of the melts was performed.
It was shown that associates with Al2 R type are stable up to 2000 K.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Al–R alloys; Amorphous state; Viscosity; Magnetic susceptibility; Surface tension; Electroresistivity

1. Introduction this idea has to be checked experimentaly, especially for high

Al–R (rare-earth) alloys have been investigated long time due
to their interesting physical properties and possibility of com-
mercial application. Thus, the solubility of R in aluminum is very
low, the mixture of Al with Al3 R (Al11 R3 ) always takes place in
all important compositions [1]. These intermetallic compounds
show rather outstanding electrical and magnetic properties
themselves. For example, Al3 Ce and Al2 Ce are considered
to be model systems in investigations of “heavy fermions”.
Kondo effect and peculiarities in phase transitions of the second
order were found for these and similar Al–R compounds at
low temperatures [2–4]. It is a common place for many works
that rare-earth elements exist in R3+ or R2+ states in Al-based
alloys (see, for example [5]). It means that magnetic moment
per R-atom in alloys is the same as for pure R and 4f-electrons
are not involved into chemical bonds formation. However,
∗ Corresponding author.
E-mail address: sidorov@uspu.ru (V. Sidorov).
temperatures.
During last decades, these alloys were obtained in amor-
phous and quasi-crystal states by rapid quenching the melt.
Moreover, the light-weight aluminum-based glasses and bulk
metallic glasses were discovered recently. The nanostructures
obtained upon crystallization (devitrification) of these glasses
have considerably greater tensile strengths than do comparable
powder-derived nanocrystalline or conventional course-grained
materials, and exhibit other significant property improvements
[6]. It was found experimentaly that amorphization takes place
when R content is 7–14 at.% [7]. The reason of this effect is
not clear enough because this range is rather far from eutectic
composition [1].
Let us mention that not far from liquidus Al-based melts
remain strongly microheterogeneous systems and only overheat-
ing above specific temperatures initiate their transition to more
or less true solutions [8]. At the same time, it is known that
heat treatment of the melt before quenching influence greatly on
quality and properties of amorphous ribbons (see, for example
[9]).

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.02.437
 V. Sidorov et al. / Materials Science and Engineering A 449–451 (2007) 586–589 587

Thus, the aim of this work is to investigate physical prop-

erties of dilute Al–R alloys and intermetallic compounds Al3 R
(Al11 R3 ) in liquid state and specify the criteria determining their
tendency to amorphization.

2. Experimental

The samples of Al3 R or Al11 R3 (R = Ce, Pr, Sm, Gd, Dy,

Ho, and Yb) composition were prepared by arc-melting at
T = TL + 100 K (TL , melting point) from nominal purity of the
Al is (99.999%) and those of R are (>99.86%). Three times
re-melting was used for better homogenization. Phase check of
sample was made by X-rays. Oxygen content before and after
experiments was determined also.
Viscosity (ν) was measured by oscillating torsion method,
surface tension (σ), by sessile drop method, magnetic sus-
ceptibility (χ), by Faraday’s method, electroresistivity (ρ), by Fig. 1. Surface tension concentration dependencies at 1273 K.
contactless method in rotating magnetic field. The accuracy in
absolute values of mentioned properties determination was ±3, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Sc and Y by surface tension
±4, ±2 and ±3%, respectively. All experiments were performed measurements (see Fig. 1). It was found that all elements can
in BeO crucibles in inert gas atmosphere during heating and be divided into three groups according to their surface activity:
subsequent cooling with the step of 10–20 K and isothermal Ho, Dy, Sc, Lu, Y and Er are inactive impurities in aluminum,
exposition for 5–30 min at each temperature. Experimental tech- La, Pr, Ce and Nd decrease surface tension slightly, whereas the
nique and procedures are described in details in ref. [8]. Above influence of Tb, Gd, Sm, Eu and Yb is rather high. It seems that
1900 K, the strong interaction between the melt and the material R sublimation heat H could be taken as good criteria for their
of crucible was registered and that is why, we limit our experi- surface activity in liquid aluminium, the lower H the more
ments by 1900 K as a rule. active element is.
Experimental curves of kinematic viscosity ν, flow activa-
3. Results tion energy E, electroresistivity ρ and its temperature coefficient
dρ/dT for Al–La (Ce, Pr) are given in Figs. 2 and 3.
3.1. Intermetallic compounds The typical influence of R small additions on magnetic sus-
ceptibility of aluminum is shown in Fig. 4 for Al–Ce. Let us
It was found that magnetic susceptibility strongly decreases
mention that the oscillating shape of curves is identical both in
with increasing temperature from 300 to about 900 K; after
solid and liquid states. As for temperature dependences, they
this it becomes practically temperature-independent and above
look like those for intermetallic compounds. The main interest-
1750 K it begins to increase up again. The detailed descrip-
ing feature is the increasing of susceptibility above melting point
tion of Al3 R or Al11 R3 magnetic properties is given in [10].
of Al2 R compound.
Local extremes, changes of slope and “jumps” on χ(T) curves
(or χ−1 (T) and χ(T−1 )) can be correlated with phase transitions
in compounds. It makes one possible to check and correct tem-
peratures of transitions. For example, for Al3 Gd the temperature
of peritectic reaction Al3 Gd → L(Al) + Al2 Gd was found to be
for 70 K lower, whereas for Al3 Ho the temperature of similar
reaction Al3 Ho → L(Al) + Al2 Ho, for 50 K lower, than it come
from phase diagrams [1]. All melting points for these and other
compounds are in good agreement with literary data [1].
Kinematic viscosity for Al3 Ce and Al3 Sm was investigated
from melting point up to 2030 K. The growth of logarithmic
decrement of damping was fixed through all investigated range
and this fact means that the melts remain strongly heterogeneous
systems even at high temperatures. Some abnormal behavior of
viscosity was detected near 1920 K. However, the nature of these
anomalies needs additional investigations.

3.2. Dilute alloys

The surface activity of small additions of R (up to 2.5 at.%) Fig. 2. Concentration dependencies of viscosity and flow activation energy at
in liquid aluminum was investigated for La, Ce, Pr, Nd, Sm, 1273 K.
588 V. Sidorov et al. / Materials Science and Engineering A 449–451 (2007) 586–589

The main unsuspected result is rather small absolute values

of effective magnetic moments per rare-earth elements for all
compounds. It means that R atoms are not in the ion form R3+
here but in the other configuration with covalent bonds. A part of
4f-electrons is involved into covalent bonds formation and that
is why effective magnetic moment per R atom decreases. These
bonds strong enough remain in liquid state also. We think some
kind of quasi-molecules with Al2 R type exist in the melts. Above
melting point of Al2 R compound the volume fraction of such
quasi-molecules and the number of covalent bonds per R atom
begin to decrease with increasing the temperature. As a con-
sequence, magnetic susceptibility of the compound increases.
However, the transition into true solution state, i.e. without
any microheterogeneities is somewhere above 1900 K. Now the
question appears: is this situation typical for Al3 R (Al11 R3 ) com-
pounds only or it is universal for all Al–R melts containing up
to 30 at.% R.
Fig. 3. Concentration dependencies of electroresistivity and its temperature
The results in viscosity, electroresistivity, surface tension
coefficient at 1273 K.
and magnetic susceptibility investigations show that even dilute
Al–R melts are strongly microheterogeneous systems. Their
structure can be imagining as disordered matrix with acciden-
tally located microareas of Al2 R type. Different estimations give
the sizes of such microareas in the range 5–10 Å. When R con-
tent is rather small these microareas exist independently from
each other being prototypes of quasi-molecules. With increas-
ing of R concentration microareas begin to interact, building
different chains and nets, and above 5 at.% of R infinite cluster
(“skeleton”) of them appears in the melt. It is this “skeleton”
that provides high viscosity of the melt and its good tendency to
amorphization.
To justify this fact, the thermodynamic modeling in terms
of associated solution model was performed with the help
Fig. 4. Magnetic susceptibility of aluminum with different cerium content at of ASTRA software. The algorithm of multipurpose system
300 K.
ASTRA.4 is based on the universal method of determining
4. Discussion equilibrium characteristics of arbitrary heterogeneous systems,
which is based on thermodynamic fundamental principle of
For all compounds Al3 R or Al11 R3 , some parameters of elec- entropy maximum. This method provides a unique possibility
tron structure, i.e. effective magnetic moment per R atom, μeff , of a generalized description of any high-temperature state using
density of states at Fermi level, N(EF ) and paramagnetic Curie fundamental laws of thermodynamics only, irrespective to the
temperature, Θ were calculated from experimental χ(T) curves conditions and ways of obtaining the equilibrium. The method
using generalized Curie–Weiss law. The results are presented in requires minimum information about the system itself and its
Table 1. One can see that all parameters have maximum values in environment [11,12]. The equilibrium composition, activity of
the middle of R line. However, the largest μeff was obtained for components, excess partial and integral characteristics (Gibbs
holmium. It is quiet understandable because for light R, j = l − s, energy, entropy, and enthalpy) are calculated for temperature
and for heavy R, j = l + s. range 1773–2373 K in all interval of concentrations in starting
medium of argon at P = 1 atm. The results for Al–Ce system are
presented in Fig. 5. One can see that associations with Al2 R
Table 1
Electronic characteristics of Al3 R (Al11 R3 ) compounds in solid state type dominate even at high overheating above liquidus and this
situation is universal for al Al–R systems.
Compounds Electronic characteristic
Let us mention that Al2 R quasi-molecules can be considered
μeff (␮B ) N(EF ) (eV−1 ) Θ (K) as structural units (monomers) for the formation of different
Al11 Ce3 0.90 4 187 nets and chains (quasi-polymers) in liquid Al–R alloys. We
Al11 Pr3 1.33 9 189 think that the presence of such nets can explain a good tendency
Al3 Gd 3.84 46 229 to amorphization of Al–R alloys during rapid solidification.
Al3 Dy 5.61 66 151 With temperature increase the geometry and dimension of nets
Al3 Ho 6.49 35 85
change sometimes irreversibly. That is why melt heat treatment
Al3 Yb 2.02 7 50
before quenching can influence greatly on microstructure and
 V. Sidorov et al. / Materials Science and Engineering A 449–451 (2007) 586–589
Fig. 5. Equilibrium associations content for Al–Ce melt.
properties of solidified materials. We believe that the presence
of “skeleton” formed from associates with covalent bonds is
the necessary condition for all melts, which are going to be
amorphizated by rapid quenching.
5. Conclusion
Experimental investigation of physical properties together
with the thermodynamic modeling in terms of theory of
associated solutions demonstrate the fact that in Al–R alloys,
the rare-earth atoms form Al2 R quasi-molecules by rather
covalent bonding. This situation is being held both for dilute
alloys and intermetallic compounds in the extremely large
589
temperature region from room temperature up to ∼1800 K.
We believe that further aggregation of these quasi-molecules
provides high glass-forming ability of Al–R alloys.
Acknowledgements
The work is supported by RFBR (grants NN 06-08-01290
and 04-03-96110-Urals, 04-02-96095-Urals).
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