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The content of sodium in aluminium during electrolysis of the molten

systems Na3AlF6–NaCl–Al2O3 and NaF–NaCl

Article in Electrochimica Acta · April 2004

DOI: 10.1016/S0013-4686(03)00950-2

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 Electrochimica Acta 49 (2004) 1505–1511

The content of sodium in aluminium during electrolysis of the molten

systems Na3AlF6–NaCl–Al2 O3 and NaF–NaCl
P. Fellner a,1 , M. Korenko a , V. Danielik a,∗ , J. Thonstad b,2
a Department of Inorganic Technology, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37 Bratislava, Slovak Republic
b Department of Materials Technology, Norwegian University of Science and Technology, N-7491 Trondheim, Norway

Received 21 August 2003; received in revised form 13 November 2003; accepted 17 November 2003

Abstract

The content of sodium in molten aluminium during electrolysis of the molten system Na3 AlF6 –NaCl–Al2 O3 was investigated at the
temperatures 750, 890 and 1000 ◦ C. Simultaneously, the cathodic overvoltage was measured. It was found that the experimental data on the
cathodic overvoltage agree well with the values predicted on the basis of the concentrations of sodium in molten aluminium. Saturation of
molten aluminium with sodium was not achieved by electrolysis of a cryolite-based electrolyte.
To achieve saturation of sodium in liquid aluminium the eutectic mixture NaF–NaCl was used as electrolyte. The experiments were carried
out at the temperatures 710, 750, 800, 900 and 960 ◦ C, i.e. below and above the boiling temperature of sodium at atmospheric pressure. In
this case, saturation of the molten aluminium with sodium was reached. The obtained data are treated by a thermodynamic model.
© 2003 Elsevier Ltd. All rights reserved.

Keywords: Aluminium electrolysis; Cathodic overvoltage; Sodium in aluminium

1. Introduction [18]and recently by Thonstad et al. [19]. Knowledge of the

Sodium is always present as an undesired impurity in
aluminium produced by the so-called Hall-Héroult process
[1,2]. The content of sodium in aluminium is influenced by
the thermodynamics of the system (Al–Na)–cryolite-based
melt (cryolite: Na3 AlF6 ) and by the kinetics of electrode-
position of sodium into aluminium. The relationship be-
tween the composition of the cryolite-based electrolyte and
the equilibrium content of sodium in aluminium was in-
vestigated by Dewing [3–7], Tingle et al. [8], Peterson and
Tabereaux [9], Fellner and Lubyová [10], and Danielik and
Fellner [11]. The influence of polarization of the molten alu-
minium cathode on the content of sodium in aluminium was
described in papers by Thonstad and Rolseth [12], Vetyukov
and Borisoglebsky [13], Polyakov et al. [14], and Fellner and
co-workers [15,16]. The content of sodium in aluminium in
industrial cells was reported by Senin et. al. [17], Tabereaux
∗ Corresponding author. Fax: +421-2-52920171.
E-mail addresses: vladimir.danielik@stuba.sk (V. Danielik),
pavel.fellner@stuba.sk (P. Fellner).
1 Tel.: +421259325523; fax: +421252920171.
2 ISE Member.
thermodynamics is important also for the removal of impu-
rities from liquid aluminium.
The thermodynamic treatment of experimental data on the
equilibrium between Al–Na alloys and cryolite-based melts
[11,15,16,19] is based on the activities of sodium in molten
aluminium, recommended by Sigworth and Engh [20]. Re-
cently, however, Hansen and co-workers [21,22] published
data on the thermodynamics of sodium in liquid aluminium
alloys, differing remarkably from those recommended by
the previous authors [20,23–25]. This would influence the
calculation of the equilibrium content of sodium in alu-
minium in equilibrium with cryolite melts. Also the solu-
bility of sodium in molten aluminium found by Hansen and
co-workers [21,22] differs remarkably from the older data.
The work of Hansen and co-workers [21,22] was criticised
by Motzfeldt [26]. In this paper, we will present new ex-
perimental data that support this criticism. In addition, new
data on the solubility of sodium in liquid aluminium at tem-
peratures above the boiling point of sodium (883 ◦ C) are
presented.
On the basis of our experimental data, the thermodynam-
ics of Al–Na molten alloys below and above the boiling
point of sodium is discussed. In this paper, we will also

0013-4686/$ – see front matter © 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2003.11.011
1506 P. Fellner et al. / Electrochimica Acta 49 (2004) 1505–1511
discuss the relationship between the content of sodium in
aluminium and the cathodic overvoltage by the electrolysis
of NaF–AlF3 –NaCl–Al2 O3 melts.
2. Experimental
A sketch of the experimental apparatus used for the elec-
trodeposition of sodium into an aluminium cathode (or rather
electrodeposition of sodium as well as aluminium) is shown
in Fig. 1. The inner diameter of the graphite cell with a sin-
tered alumina lining was 55 mm, height 60 mm. Fifty grams
of aluminium and 100 g of electrolyte were weighed-in.
When the cryolite-based electrolyte was used, the electrolyte
was saturated with alumina at the beginning of the electrol-
ysis. Aluminium of purity 99.9% was used in the beginning
of the experiment. During the experiment, sodium was de-
posited into the aluminium. However, because of the molyb-
denum (or iron) plate at the bottom of the electrolytic cell,
a small amount of molybdenum was observed in the alu-
minium (less than 0.1%) at the end of the experiment.
The cathodic overvoltage, which is mainly concentration
overvoltage [1], was determined by a method based on fast
current interruption (ca. 50 ns). The potential decay of the
cathode voltage was monitored on an oscilloscope. Extrapo-
lation of the transient curves to zero time yielded the IR-free
cathode potential, referred to the aluminium reference elec-
trode . The experimental details can be found in [27].
Saturation of aluminium with sodium could not be
achieved by electrolysis of the NaF–AlF3 –NaCl–Al2 O3
Fig. 1. Sketch of the apparatus. (1) Anode current lead, (2) alumina tube,
(3) alumina lining, (4) quartz tube for sampling of aluminium, (5) graphite
crucible, (6) graphite anode, (7) Al reference electrode, (8) Al cathode,
(9) Mo plate, (10) crucible supporter, (11) cathode current lead.
melt. Therefore, in a subsequent series of experiments, an
electrolyte consisting of the eutectic mixture NaF + NaCl
(26.4 wt.% NaF + 73.6 wt.% NaCl, teut = 680 ◦ C) was used.
Electrolysis was carried out at the temperatures 710, 750,
800, 900 and 960 ◦ C. The temperatures 710 and 750 ◦ C were
chosen because the difference in the solubility of sodium
in liquid aluminium between the classical literature data
[23–25] and the results of Hansen and co-workers [21,22]
is high in that range. On the other extreme, the temperature
960 ◦ C is close to the temperature of electrowinning of
aluminium [1], and no data on the solubility of sodium in
aluminium at this temperature is available in the literature.
The electrolysis was carried out with cathodic current den-
sities (jc ) up to 0.625 A cm−2 . The cathode surface is curved.
The real cathodic current densities were determined accord-
ing to Zoriæ et al. [28]. At jc = 0.25 A cm−2 , the electroly-
sis could be carried out for several hours. The Al–Na alloy
was sampled every 15 min. For sampling a quartz tube (inner
Ø 4 mm) equipped with an attached syringe was used. The
sample was quenched in water mixed with ice. The cooled
metal sample was cleaned mechanically, dissolved in HCl
(diluted to 1:1) and analysed by AAS.
3. Results and discussion
3.1. Cathodic overvoltage
When the molten system NaF–AlF3 –NaCl–Al2 O3 is elec-
trolysed, the primary cathode reaction is the reduction of
Al(III) species. The chemistry of cryolite-based electrolytes
is rather complex [2]. Schematically the cathode reaction
can be written as
AlF3 + 3Na+ + 3e− = Al + 3NaF (1)
The electrical charge is transported mainly by Na+ ions
+
(tNa = 0.99 [1,2]). As a result of the ionic migration of
sodium cations and the cathode reaction, concentration gra-
dients of the species taking part in these processes arise at
the metal/electrolyte interface. The situation is illustrated
schematically in Fig. 2.
Concentration
NaF
AlF3
Boundary layer Bulk electrolyte
Distance from Al cathode
Fig. 2. Sketch of concentration gradients at the metal/electrolyte interface.
 P. Fellner et al. / Electrochimica Acta 49 (2004) 1505–1511 1507

250

200

150
ηcat/ mV

100

50

0.0 0.2 0.4 0.6 0.8 1.0

-2
jcat/A.cm

Fig. 3. The cathodic overvoltage vs. current density in the melt Na3 AlF6 + 5 wt.% NaCl + Al2 O3 (sat.) at 1000 ◦ C. Filled triangles: electrochemical
measurement of the cathodic overvoltage; full curve: data on the cathodic overvalotage described by the least squares method; open squares: calculated
from the contents of sodium in the aluminium cathode.

We may assume that the concentration overvoltage equals
the emf of the following concentration cell:
Al(Na)|NaF(I), AlF3 (I), NaCl(I)||NaF(II), AlF3 (II),
NaCl(II)|Al(Na)
Index II denotes the concentration of species at the
metal/electrolyte interface under cathodic polarization of
aluminium, while index I denotes the situation when no
current passes through the interface, i.e. the bulk compo-
sition. On the basis of this model, and taking reaction (1)
into account, the cathodic concentration overvoltage ηc
is related to the ratio of the concentrations of sodium in
non-polarized and polarized aluminium [1,27]. It holds:
RT c(Na, j = 0)
ηc = ln
F c(Na, j)
In Fig. 3, the cathodic concentration overvoltage mea-
sured at the temperature of 1000 ◦ C in the melt Na3 AlF6 +
5 wt.%NaCl + Al2 O3 (sat.) is plotted as a function of the
anode reaction was the evolution of chlorine. In neither case
could current densities higher than ca. 1 A cm−2 be used,
because of the occurrence of anode effect [2]. It can be seen
that Eq. (3) describes well the relationship between the con-
(2) tent of sodium in aluminium and the cathodic concentration
overvoltage, also in the case of the low melting electrolyte
containing a high concentration of NaCl. It also follows that
saturation of aluminium with sodium was not achieved in
these experiments, and the primary cathode process was al-
ways the electrodeposition of aluminium.
The results given in Figs. 4 and 5 show considerable
scatter. It is assumed to be due to losses of sodium during
sampling and quenching.
250
(3)
200
150
-η cat/ mV

cathode current density. The data are compared with the

overvoltage calculated according to relationship (3) from the 100

contents of sodium in polarized and unpolarized aluminium.

In Figs. 4 and 5, data on the cathodic overvoltage and the 50
content of sodium in liquid polarized aluminium are plotted
as a function of current density. In this case the electrolyte 0
consisted of 30 wt.% Na3 AlF6 +70 wt.% NaCl+Al2 O3 (sat.). 0.0 0.2 0.4 0.6 0.8 1.0
The melting point of this electrolyte is about 740 ◦ C. This j/ A.cm
-2

allowed us to carry out measurements at temperatures as low

as 750 ◦ C. Similar to the case of the melt Na3 AlF6 + 5 wt.%
NaCl + Al2 O3 (sat.), the primary cathode process was the
reduction of Al(III) species. However, because of low sol-
ubility of alumina in melts with high contents of NaCl, the
Fig. 4. The cathodic overvoltage vs. current density in the melt 30 wt.%
Na3 AlF6 + 70 wt.% NaCl + Al2 O3 (sat.) at 750 ◦ C. Filled triangles: elec-
trochemical measurement of the cathodic overvoltage; full curve: data
on the cathodic overvoltage described by the least squares method; open
squares: calculated from the contents of sodium in the aluminium cathode.
1508 P. Fellner et al. / Electrochimica Acta 49 (2004) 1505–1511

1200

1000

800 890 ˚C
x(Na)/ ppm

600

400
750 ˚C

200

-0.2 0.0 0.2 0.4 0.6 0.8 1.0

-2
j/ A.cm
Fig. 5. The content of sodium in polarised aluminium in the melt 30 wt.% Na3 AlF6 + 70 wt.% NaCl + Al2 O3 (sat.) at two temperatures, viz. 750 and
890 ◦ C. Full curves: data described by the least squares method.

3.2. Solubility of sodium in aluminium
The value of the saturation of liquid aluminium with
sodium is of both practical a theoretical interest, not only
for aluminum electrolysis but also for the refining and cast-
ing of aluminium. Recently published data by Hansen and
co-workers [21,22] suggest that a revision of the literature
data on this subject [23–25] has to be made. In order to pre-
pare saturated solution of sodium in liquid aluminium, we
electrolysed a melt consisting of 26.4 wt.% NaF +73.6 wt.%
NaCl (eutectic mixture). The electrolysis was carried out in
corundum crucibles, so a low content of alumina would be
present in the melt. The electrolysis was carried out at the
temperatures of 710, 750, 800, 900 and 960 ◦ C. This tem-
perature interval covers both the temperature of aluminium
electrolysis and the temperatures of refining and casting of
aluminium.
The results are shown in Figs. 6–8. The cathode current
density was 0.25 A cm−2 . When the current density was in-
creased up to 0.625 A cm−2 , the maximum concentration of
sodium in aluminium was not significantly different from
that obtained at a lower current density jc = 0.25 A cm−2

1800

1600

1400

1200
x(Na) / ppm

1000

800

600

400

200

0
0 50 100 150 200 250 300 350 400
τ / min

Fig. 6. The content of sodium in the liquid Al–Na cathode as a function of the duration of electrolysis at 710 ◦ C. Composition of the electrolyte:
26.4 wt.% NaF + 73.6 wt.% NaCl. Open squares: jc = 0.125 A cm−2 ; filled squares: jc = 0.25 A cm−2 .
 P. Fellner et al. / Electrochimica Acta 49 (2004) 1505–1511 1509

1800

1600
800 ˚C
1400
750 ˚C
1200
x(Na) / ppm

1000

800

600

400

200

0
0 50 100 150 200 250 300 350 400 450 500
τ / min

Fig. 7. The content of sodium in the liquid Al–Na cathode as a function of the duration of electrolysis. Composition of the electrolyte: 26.4 wt.%
NaF + 73.6 wt.% NaCl. Open squares: jc = 0.25 A cm−2 ; t = 750 ◦ C; cross: jc = 0.625 A cm−2 ; t = 750 ◦ C; filled squares: jc = 0.25 A cm−2 ; t = 800 ◦ C.
Horizontal lines: values of the content of sodium in aluminium determined by the regression analysis.

(see Fig. 7). The same limiting concentration of sodium
in aluminium was achieved even when the cathode current
density was lowered to 0.125 A cm−2 (see Fig. 6). At this
current density the electrolytic cell could be operated for
several hours without an anode effect. It can be seen that
after a certain time of electrolysis the content of sodium in
the Al–Na alloy reached a constant value. The amount of
deposited sodium was by two orders of magnitude higher
than that required for saturation of the Al–Na alloy with
sodium. The time dependence of the concentration of sodium
in aluminium can be explained by slow mixing of the de-
posited sodium with aluminium. Because of possible losses
of sodium during sampling and quenching, the highest con-
centrations of sodium in aluminium were considered to be
the most reliable. As shown in the following, the concentra-
tions of sodium in liquid aluminium saturated with sodium
agree reasonably well with the data published in the clas-
sical papers on this subject [23–25]. The high solubilities

1800

900 ˚C
1600

1400

1200
x(Na) / ppm

1000

800
960 ˚C
600

400

200

0
0 50 100 150 200 250 300 350 400
τ / min

Fig. 8. The content of sodium in the liquid Al–Na alloy as a function of the duration of electrolysis in the melt, 26.4 wt.% NaF + 73.6 wt.% NaCl,
at jc = 0.25 A cm−2 . Filled squares: t = 960 ◦ C; open squares: t = 900 ◦ C. Horizontal lines: values of the content of sodium in aluminium that were
considered as most reliable.
1510 P. Fellner et al. / Electrochimica Acta 49 (2004) 1505–1511
of sodium in aluminium reported by Hansen [21] have not
been confirmed.
The boiling point of pure sodium is 883 ◦ C. No experi-
mental data on the solubility of sodium in aluminium above
this temperature has been reported in the literature. From our
measurements it follows that at the temperature of 900 ◦ C
the solubility of sodium in aluminium reaches 1593 ± 80
ppm. At 960 ◦ C, the solubility of sodium in aluminium is
700 ± 80 ppm. As liquid sodium does not exist at atmo-
spheric pressure at these temperatures, the physical meaning
of this data has to be clarified. This can be done on the basis
of a thermodynamic model.
3.3. Thermodynamic model
At temperatures lower than 883 ◦ C (the boiling point of
sodium), the chemical potential of sodium in Al–Na alloys
saturated with sodium equals the chemical potential of pure
liquid sodium:
µ(Na in Al, satutared) = µ0 (Na, l)
As the concentration of sodium in liquid aluminium is
rather low (thousands of ppm) the Henry law can be applied.
In Henry’s approximation, the pressure of sodium vapours
over the liquid Al–Na alloy is proportional to the mole frac-
tion of sodium in the liquid Al–Na alloy:
p(Na) = kH (Na) · x(Na in Al)
where kH (Na) is Henry’s constant. For the dependence of
this constant on temperature, it holds:
∂ ln kH (Na) L̄(Na in Al)
=−
∂T RT2
where L̄(Na in Al) is the last differential heat of dissolution
of sodium in aluminium.
The pressure of sodium vapour over pure liquid sodium
can be described by the Clausius–Clapeyron equation:
d ln(p, Na) H ∅ (evaporation of sodium)
= (7)
dT RT2
The temperature dependence of the enthalpy of evapora-
tion of sodium was described on the basis of literature data
[29]. It follows:
H ∅ (evaporation) (J mol−1 )
= 109, 576 − 16.682T + 9.577 × 10−3 T 2
−3.545 × 10−6 T 3
For evaluation of the temperature dependence of Henry’s
constant we used the data on saturated content of sodium
in liquid aluminium obtained in this work. The temperature
dependence of the Henry constant can be described by the
following relationship:
(8960.1 ± 262.8)
ln kH (Na) = (25.591 ± 0.249) −
T calculated on the basis of data obtained in this work.
It follows that at 900 ◦ C kH (900 ◦ C) = 62.67 MPa; and at
960 ◦ C kH (960 ◦ C) = 90.87 MPa.
When we assume that the pressure of sodium vapour
over liquid Al–Na alloy saturated with sodium during
electrolysis of the NaF–NaCl mixture equals 105 Pa, it
follows from the thermodynamic model that the mole frac-
tion of sodium in aluminium saturated with sodium at
900 ◦ C is 1596 ppm, which is in excellent agreement with
the experimental value of 1593 ± 80 ppm. At 960 ◦ C the
calculated content of sodium in aluminium is 1000 ppm.
The experimental value obtained by the electrolysis is
700 ppm. With respect to approximations made and the
risk of loss of sodium during sampling and quenching,
this can be considered as an acceptable agreement. (It
should be stressed that the calculations made above the
boiling point of sodium (883 ◦ C) assume that the pres-
sure of sodium equals 105 Pa, while at temperatures lower
than 883 ◦ C, the Al–Na alloy is in equilibrium with liquid
sodium.)
The literature data on the content of sodium in liquid alu-
(4)
minium and the results obtained in this work are summarized
in Fig. 9. It follows that our results agree with the classical
literature data.
(5) 1000
950
(6)
900
850
t / ˚C
800
750
700
(8) 650
0.000 0.005 0.010 0.015 0.020 0.025 0.030
Al x (Na)
Fig. 9. The phase diagram Na–Al. Filled squares: this work; open squares:
Scheuer [23]; open circles: Fink et al. [24]; triangles: Ransley et al. [25];
crosses and plusses: Hansen and co-workers [21,22]; thin full line: phase
equilibria according to the Hansen and co-workers [21,22], dotted line:
calculated on the basis of data by Ransley et al. [25]; bold full line:
(9)
 P. Fellner et al. / Electrochimica Acta 49 (2004) 1505–1511
4. Conclusion
Data on the cathodic overvoltage in the system Na3 AlF6 –
NaCl–Al2 O3 are presented. It follows that the cathodic
overvoltage has its origin in concentration polarisation
at the aluminium cathode. The experimental data are in
good agreement with theory. However, when using the
Na3 AlF6 –NaCl–Al2 O3 electrolyte, saturated solution of
sodium in aluminium could not be obtained.
Al–Na alloys saturated with sodium at the temperatures
710, 750, 800, 900 and 960 ◦ C were prepared by electroly-
sis of a NaF–NaCl eutectic melt. A thermodynamic model
describing the saturation of molten aluminium with sodium
below and above the boiling point of sodium (883 ◦ C) is
presented. It is suggested that the data on saturation of alu-
minium with sodium presented by Hansen and co-workers
[21,22] are not suitable for a thermodynamic treatment of
Al–Na liquid alloys.
Acknowledgements
This work was supported by courtesy of the Slovak Grant
Agency (VEGA 1/9426/02) and by Professor Geir Martin
Haarberg, The Norwegian University of Science and Tech-
nology.
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