Electrochimica Acta 50 (2005) 5510–5517

Cathodic behaviour of samarium(III) in LiF–CaF2 media

on molybdenum and nickel electrodes
L. Massot ∗ , P. Chamelot, P. Taxil 1
Laboratoire de Génie Chimique UMR 5503, Département Procédés Electrochimiques et Matériaux,
Université Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex, France

Received 16 December 2004; received in revised form 16 March 2005; accepted 19 March 2005
Available online 4 May 2005

Abstract

The electrochemical behaviour of SmF3 is examined in molten LiF–CaF2 medium on molybdenum and nickel electrodes. A previous
thermodynamic analysis suggests that the reduction of SmF3 into Sm proceeds according to a two-step mechanism:
SmIII + e− = SmII

SmII + 2e− = Sm
The second step occurs at a potential lower than the reduction potential of Li+ ions.
Cyclic voltammetry, chronopotentiometry and square-wave voltammetry were used to confirm this mechanism and the results show that
it was not possible to produce samarium metal in molten fluorides on an inert cathode (molybdenum) without discharging the solvent. The
electrochemical reduction of SmF3 is limited by the diffusion of SmF3 in the solution. The diffusion coefficient was calculated at different
temperatures and the values obtained obey Arrhenius’ law.
For the extraction of the samarium from fluoride media, the use of a reactive cathode made of nickel leading to samarium–nickel alloys
is shown to be a pertinent route. Cyclic voltammetry and open-circuit chronopotentiometry were used to identify and to characterise the
formation of three alloys: liquid Sm3 Ni and a compact layer made of SmNi3 and SmNi2 .
© 2005 Elsevier Ltd. All rights reserved.

Keywords: Molten fluorides; Samarium; Cyclic voltammetry; Chronopotentiometry; Intermetallic compounds; Electrochemistry

1. Introduction minor actinides An (U, Pu, Cm, Am, Np, etc.) from the rest of
the fission products containing lanthanides Ln (Ce, Sm, Nd,
Partitioning and transmutation (P&T) concepts are ac- Eu, Gd, Dy). Success in the process requires reliable data on
knowledged as efficient ways to reduce the long-term ra- the electrochemical behaviour and thermodynamic data of
diotoxicity of nuclear waste by multi-recycling of actinides actinides and lanthanides in these media.
[1]. Electrochemical based methods (electrorefining, elec- Samarium is one of the most abundant fission products
trolysis) or reductive extraction are used as pyrochemical in nuclear reactors [1]. This work concerns the electrochem-
separation processes. Pyrochemical separation from molten ical behaviour of this element in molten LiF–CaF2 in the
salts (e.g. fluorides or chlorides) is considered as a suitable 810–870 ◦ C temperature range on inert (Mo) and reactive
alternative method to aqueous processes for the separation of (Ni) electrodes in order to examine the best conditions of
samarium extraction.
∗ Corresponding author. Tel.: +33 5 61 55 81 94; fax: +33 5 61 55 61 39.
As far we know in the literature, only LiCl–KCl media
E-mail address: [email protected] (L. Massot). have been used for samarium reduction studies at 723 K by
1 ISE member. Cordoba et al. [2] on an inert cathode and Iida et al. [3,4]

0013-4686/$ – see front matter © 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.03.046
 L. Massot et al. / Electrochimica Acta 50 (2005) 5510–5517 5511

with a reactive cathode, respectively. These authors found a The potentials were referred to a platinum wire (0.5 mm
two-step electrochemical reduction process, but only the first diameter) immersed in the molten electrolyte, acting as a
one, which is diffusion controlled, can be observed in molten quasi-reference electrode Pt/PtOx /O2− [9].
chloride on a molybdenum electrode: • Electrochemical equipment: all electrochemical studies
and electrolysis were performed with an Autolab PG-
SmCl3 + 1e− = SmCl2 + Cl− (1) STAT30 potentiostat/galvanostat controlled by a computer
using the research software GPES 4.9.
• Electrochemical techniques: cyclic voltammetry, chrono-
The reduction of SmCl2 into Sm metal was not observed potentiometry and square-wave voltammetry were the
by Cordoba because of the prior reduction of Li+ ions from electrochemical techniques used for the investigation of
the solvent, which hinders the extraction of bulk samarium. the samarium reduction process.
In contrast, Iida et al. [3,4] prepared some • Characterisation of reduction products: after the electroly-
nickel–samarium alloys by electrodeposition on a nickel sis runs, the surface of the cathode was examined by Scan-
surface in the same temperature range. But these authors ning Electron Microscope (LEO 435 VP) with an EDS
found that the composition of the layers obtained depended probe (Oxford INCA 200).
on the operating conditions (applied potential, temperature).
Borzone et al. [5] and Su et al. [6], using direct
calorimetry to calculate the enthalpy of formation of all the 3. Results and discussion
samarium–nickel alloys, showed that the alloy which has the
most negative enthalpy of formation is SmNi2 at the temper- 3.1. Analysis of the samarium E − pO2− diagram
ature of 1000 K.
These results in molten chlorides will be compared our The samarium E − pO2− diagram, shown in Fig. 1, ex-
own study in molten fluorides. In the first part of this article, hibits the stability zones of all the samarium species possi-
the reduction mechanism of SmF3 will be predicted theoret- bly involved in the electrochemical reduction process, as a
ically, using thermodynamic data of the potential-oxoacidity function of the potential and the oxide content in LiF–CaF2
diagram of samarium species. Then, the second part will de- bath. This diagram was made using HSC 4.1 software
tail the electrochemical reduction mechanism, compared with at T = 1100 K, with all soluble species activities equal to
previous works. Finally, the feasibility of samarium extrac- 0.1 mol/kg.
tion by alloying with nickel will be examined. First, this diagram shows that SmF3 should be electro-
chemically reduced into Sm metal in two steps:

2. Experimental SmIII + e− = SmII (2)

SmII + 2e− = Sm (3)
• The cell consists of a vitreous carbon crucible placed in a
cylindrical vessel made of refractory steel and closed by a Secondly, it indicates that at low O2− ion activities, the re-
stainless steel lid cooled by circulating water [7,8]. The in- duction potential of the second step is more negative than that
ner part of the walls was protected against fluoride vapours of Li+ (from the LiF–CaF2 ). So, according to this diagram, the
by a graphite liner. The experiments were performed under electrolytic production of samarium metal in fluoride melts
an inert argon (U-grade: less than 5 ppm O2 ) atmosphere, seems to be thermodynamically impossible without discharg-
previously dehydrated and deoxygenated using a purifi- ing lithium ions.
cation cartridge (Air Liquide). The cell was heated using
a programmable furnace and the temperatures were mea-
sured using a chromel–alumel thermocouple.
The electrolytic bath consisted of a eutectic LiF/CaF2
(Merck 99.99%) mixture (77/23 molar ratio). Before use,
it was dehydrated by heating under vacuum (10−2 mmHg)
from ambient temperature up to its melting point (762 ◦ C)
for 48 h. Samarium ions were introduced into the bath in
the form of samarium fluoride, SmF3 (Merck 99.99%),
powder.
• Electrodes: molybdenum and nickel wires (1 mm diam-
eter) were used as working electrodes. The area of the
working electrode was determined after each experiment
by measuring the immersion depth in the bath. The aux-
iliary electrode was a vitreous carbon (V25) rod (3 mm Fig. 1. E − pO2− diagram made using HSC 4.1 software at T = 1100 K and
diameter) with a large surface area (2.5 cm2 ). all soluble species activities equal to 0.1.
5512 L. Massot et al. / Electrochimica Acta 50 (2005) 5510–5517

Further information appearing from this diagram is that the

oxide content of the bath is a relevant parameter of stability
because SmF3 reacts with oxide ions to form the insoluble
oxide species Sm2 O3 when the O2− ion content is higher than
50 × 10−12 mol/kg.
Thus, the following part of the present article is concerned
with the electrochemical study of the SmF3 reduction pro-
cess.

3.2. Study of the SmF3 reduction mechanism

3.2.1. Cyclic voltammetry

Cyclic voltammetry was carried out on a molybdenum Fig. 3. Linear relationship between the SmF3 reduction peak current density
electrode in the LiF–CaF2 –SmF3 melt at 850 ◦ C. Molyb- and the SmF3 concentration in the melt.
denum was chosen because of its inertness with respect to
samarium in the working temperature range according the for reversible systems:
Mo/Sm binary diagram [10]. The electrochemical window is

nFD √
between the reduction of lithium ions and oxidation of the Ip = −0.4463nFSC◦ v (4)
RT
molybdenum electrode in the cathodic and anodic senses,
respectively. where S is the electrode area (cm2 ); C◦ is the solute concen-
The cyclic voltammogram obtained at 100 mV/s on a Mo tration (mol cm−3 ); D is the diffusion coefficient (cm2 s−1 );
electrode is shown in Fig. 2. It exhibits one peak (Ic ) in the F is the faraday (96,500 C); n is the number of exchanged
cathodic run at −1.3 V versus the platinum comparison elec- electrons; v is the potential scanning rate (V s−1 ) and T is the
trode. The shape of the associated anodic peak (Ia ) suggests absolute temperature (K).
that the cathodic product is a soluble compound arising from The linearity of Ip versus v1/2 is verified in Fig. 4, which
the reduction of SmIII (cf § 3.1). Furthermore, if the SmF3 indicates that the electrochemical reduction process is con-
concentration in the melt is varied for a given temperature, trolled by the diffusion of SmIII ions in the solution. The slope
we observe a linear relationship between the peak current of the straight line is:
density and the SmF3 concentration (Fig. 3). So, the cathodic
Ip
peak is attributed to the reduction of SmF3 , presumably into √ = −(0.134 ± 0.002)A s1/2 V−1/2 (5)
a divalent species of samarium. v
The reduction of SmII is not observed in this cyclic voltam- at T = 850 ◦ C and C◦ = 0.515 × 10−3 mol/ml.
mogram before the solvent reduction, as predicted by the
E − pO2− diagram. 3.2.2. Chronopotentiometry
Subsequently, the influence of the potential scan rate on In order to confirm the diffusion control of the elec-
the cyclic voltammograms was studied. The cathodic peak trochemical reduction process, several chronopotentiograms
intensity is correlated with the potential scanning rate by the were measured on a molybdenum electrode. Fig. 5 shows the
following relationship (Randles Sevcik equation) [11], valid evolution of the chronopotentiograms with the applied cur-
rent density. These curves exhibit a single plateau at about

Fig. 2. Typical cyclic voltammogram of the LiF–CaF2 –SmF3

(5.16 × 10−4 mol/ml) system at 100 mV/s and T = 1100 K. Working Fig. 4. Linear relationship of SmF3 reduction peak current density vs. the
El.: Mo (S = 0.315 cm2 ); auxiliary El.: vitreous carbon; quasi-reference El.: square root of the scanning potential rate at T = 1100 K. Working El.: Mo
Pt. (S = 0.315 cm2 ); auxiliary El.: vitreous carbon; quasi-reference El.: Pt.
 L. Massot et al. / Electrochimica Acta 50 (2005) 5510–5517 5513

Fig. 5. Typical chronopotentiograms with the intensity of the system Fig. 7. Reversal chronopotentiogram of SmF3 (5.15 10−4 mol/ml) in
LiF–CaF2 –SmF3 at 1100 K. Working El.: Mo (S = 0.315 cm2 ); auxiliary El.: LiF–CaF2 , I = 130 mA/cm2 at 1100 K. Working El.: Mo (S = 0.315 cm2 );
vitreous carbon; quasi-reference El.: Pt. auxiliary El.: vitreous carbon; quasi-reference El.: Pt.

3.2.3. Number of exchanged electrons

−1.3 V/Pt, corresponding to the reduction potential of SmIII
• Using the chronopotentiometry and cyclic voltammetry re-
into SmII . It can also be noted that the transition time (τ)
sults obtained successively in the same electrolyte, it is
decreases as the applied current density increases. This is in
possible to determine the number of electrons exchanged.
agreement with Sand’s law [12]:
The following relationship can be obtained:
√ √

I τ Ip / v n
= −0.5nFS(πD)1/2 = constant (6) √ = 53.85
C◦ I τ T
(8)
The data plotted in Fig. 6 prove that this equation is ver-
This procedure allows the incertitude on the electrolyte
ified. These experiments were repeated at various tempera-
concentration to be ignored.
tures and confirmed the validity of Eq. (6).
In the example of Figs. 4 and 6, 0.99 exchanged electrons
From these data, we obtain, at 850 ◦ C and
are found. The average of electrons exchanged was 0.99
◦
C = 0.515 × 10−3 mol/ml:
for the results of five experiments. Thus, the conclusion is
√ that one electron is exchanged, proving that the reduction
I τ = −(0.083 ± 0.002) A s1/2 (7)
peak observed actually can be attributed to the reaction:
Chronopotentiometric measurements confirm the results
SmIII + e− = SmII (2)
obtained by cyclic voltammetry: the electrochemical reduc-
tion process is limited by the diffusion of SmIII ions in the • Another electrochemical technique allows the number
solution. of exchanged electrons to be determined: square-wave
The reversal chronopotentiogram, shown in Fig. 7, reveals voltammetry [14,15]. In this technique, the scanning of
the formation of a soluble compound, in a reversible system potential proceeds stepwise with superimposition, on each
[13], at the Mo electrode during the cathodic run. The ca- step of the staircase, of two potential pulses, direct and re-
thodic transition time measured τ red (τ red = 0.36 s) is equal to verse, of the same intensity. Plotting the differential inten-
3τ ox (τ ox = 0.12 s). sity measured at each step between the successive pulses
versus the potential associated to each electrochemical re-
action provides a peak with a Gaussian shape. The math-
ematical analysis of the peak yields, in the case of a re-
versible system, a simple equation associating the half-
width of the peak W1/2 and the number of electrons ex-
changed:
RT
W1/2 = 3.52 (9)
nF
Fig. 8 shows a square-wave voltammogram of SmF3 in
LiF–CaF2 on a molybdenum electrode at 850 ◦ C. It exhibits
a symmetrical single peak at −1.1 V/Pt, corresponding to Ep/2
for the cyclic voltammogram.
The validity of application of Eq. (9) was verified by plot-
Fig. 6. Evolution of Iτ 1/2 vs. the intensity at 1100 K. Working El.: Mo ting the current density of the peak versus the square root
(S = 0.315 cm2 ); auxiliary El.: vitreous carbon; quasi-reference El.: Pt. of the frequency as reported in previous works [16,17]. In
5514 L. Massot et al. / Electrochimica Acta 50 (2005) 5510–5517

Fig. 9. Linear relationship of the logarithm of SmF3 diffusion coefficient

Fig. 8. Square-wave voltammogram of the LiF–CaF2 –SmF3 melt. Fre- vs. the reciprocal of the absolute temperature.
quency: 25 Hz, T = 1100 K. Working El.: Mo (S = 0.315 cm2 ); auxiliary El.:
vitreous carbon; quasi-reference El.: Pt.
3.3. Samarium electrodeposition on a reactive cathode
the present work, a linear relationship was observed in the (Ni)
9–100 Hz frequency range.
According to Eq. (8), the measurement of W1/2 leads to a 3.3.1. Preliminary discussions
number of exchanged electrons equal to 1.01 for eight voltam- The results obtained in the previous paragraph are only
mograms. This result confirms that the reduction of SmF3 in related to the reaction SmIII + e− → SmII . The reduction of
LiF–CaF2 melts yields a divalent samarium compound. SmII into Sm metal could not be observed because samarium
is more reactive than the solvent cations, lithium and probably
calcium [18]. Thus, the electrolytic extraction of samarium
3.2.4. Diffusion coefficient of SmIII ions
in these conditions is problematic because it should intervene
The diffusion coefficient of SmIII ions can be calculated
at a potential where the solvent cations are also discharged.
using Eq. (4) and/or (6).
To have a chance of achieving a successful elimination of
At T = 850 ◦ C and [SmF3 ] = 1.56 × 10−4 mol/ml, we
samarium ions from the molten salt mixture, the activity of
found the following average result:
the electrodeposited metal must be lowered. This is feasible if
DSmIII = (3.27 ± 0.05) 10−9 m2 /s the electroreduction of the samarium ions leads to the forma-
tion of an alloy with the cathodic substrate. The methodology
The calculation of D was repeated at several temperatures. was developed in our laboratory [19,20], and in other works
Table 1 reports the value of the diffusion coefficient obtained [21,22]. In the case where the cathode metal M reacts with
at different temperatures (830, 850, 870 and 900 ◦ C). These the electrodeposited metal N, to form an intermetallic com-
results obey the following relationship (Arrehnius’ law): pound MNx , the equilibrium potential is shifted in the anodic
  direction; the depolarisation term is equal to the emf of the
Ea
D = D◦ exp − (10) cell:
RT
MNx N ions
where Ea is the activation energy. , (12)
solvent N
The linearity of the evolution of ln D versus 1/T is observed
in Fig. 9. With these results, the Eq. (10) can be written: Nickel seems to be a good candidate for such a cathode
metal, since in previous works, it was shown that alloying
7.1811 nickel with rare-earth metals is particularly easy and rapid at
ln D = −3.9237 − (11)
T moderate temperatures [23–26].
where D is in cm2 /s and T in K.
From this relationship, the value of the activation energy 3.3.2. Nickel–samarium phase diagram
is found to be 59.7 kJ/mol. According to the Ni–Sm phase diagram, shown in Fig. 10
[10], samarium can form eight intermetallic compounds with
Table 1 nickel (Sm3 Ni, SmNi, SmNi2 , SmNi3 , Sm2 Ni7 , Sm5 Ni19 ,
Evolution of the SmF3 diffusion coefficient with the temperature SmNi5 , Sm2 Ni17 ). At the temperature of the experiments, one
T (◦ C) D × 105 (cm2 /s) compound is liquid (Sm3 Ni), and all the others are solid. The
830 2.96 identification and the characterization of these compounds
850 3.27 in the overall process of electrodeposition of samarium on
870 3.71 nickel were carried out by cyclic voltammetry and open-
900 4.34 circuit chronopotentiometry.
 L. Massot et al. / Electrochimica Acta 50 (2005) 5510–5517 5515

Fig. 10. Nickel–samarium phase diagram obtained by ASM binary alloys phase diagrams database.

3.3.3. Cyclic voltammetry solvent is associated with a reaction of the following kind:
Fig. 11 compares the cyclic voltammograms obtained at
850 ◦ C on molybdenum and on nickel electrodes at 100 mV/s. SmII + 2e− + xNi = SmNix (13)
The wave SmIII /SmII (at −1.3 V/Pt) is observed on each sub-
where x can take the values given by the binary diagram of
strate. Then, at more cathodic potentials before the solvent
Fig. 10.
limit, we notice a far higher current only in the case of the
nickel cathode, with cathodic and anodic peaks not well de-
fined. This current and these peaks are attributed to the for- 3.3.4. Open-circuit chronopotentiometry
mation of nickel–samarium alloys. The current measured in Cyclic voltammetry cannot be used to identify the in-
the potential range between the reduction SmIII /SmII and the termetallic compounds. A suitable technique is open-circuit
chronopotentiometry: after a short cathodic polarisation at
a high cathodic overpotential, the open-circuit potential of
the electrode is measured versus time. The evolution of the
potential consists of successive plateaux, of increasing po-
tential, each plateau being typical of equilibrium in the solid
state between two intermetallic compounds. The diffusion of
Sm within the substrate explains the increase at potential of
the cathode.
An example of an open-circuit chronopotentiogram ob-
tained after polarisation at −300 mA/cm2 for 15 s is shown
in Fig. 12. During this experiment, eight plateaux were ob-
served at about −0.76, −0.89, −1.00, −1.03, −1.25, −1.28,
−1.55 and −1.79 V/Pt. The potential is dictated by the dif-
ference of the samarium activity in the electrolyte (constant)
and at the surface of Sm–Ni alloy (variable). The samarium
Fig. 11. Comparison of the cyclic voltammograms of the LiF–CaF2 –SmF3 concentration decreases at the surface of the electrode as it
system on molybdenum and nickel electrodes at 100 mV/s and T = 1100 K. diffuses into the nickel. When a two-phase equilibrium in
Auxiliary El.: vitreous carbon; quasi-reference El.: Pt. the solid exists at the surface of the electrode, the samarium
5516 L. Massot et al. / Electrochimica Acta 50 (2005) 5510–5517

Fig. 12. Open-circuit chronopotentiogram of the LiF–CaF2 –SmF3 system

on nickel electrode at T = 1120 K. Auxiliary El.: vitreous carbon; quasi-
reference El.: Pt.

activity is equal in each phase and remains constant while

the Sm concentration at the surface decreases. This results
in a constant potential (plateau) for a given diffusion time.
The plateau obtained at −1.79 V/Pt is attributed to Sm3 Ni
because it is the compound containing the highest concentra-
tion of Sm, and so the last that would be reduced.

3.3.5. Observation and characterisation of the Sm–Ni

alloys
In order to characterise the intermetallic compounds ob-
tained, the electrodeposition of samarium–nickel alloys was
performed at 200 mA/cm2 at 850 ◦ C for 1 h. The cross sec-
tion of the sample obtained during this run was observed by
scanning electron microscopy. The micrograph is presented
in Fig. 13. An EDS probe allowed us to determine the com-
position of each phase present on the micrograph. Fig. 13. (a and b) SEM micrograph of the cross section of a nickel plate
Three different alloys were identified: after reduction of SmF3 at −200 mA/cm2 for 1 h and T = 1120 K.

(i) The first one was Sm3 Ni located in the micrograph of

the solvent layer outside of the electrode. This alloy was
ogy with Iida et al. [3] who only obtained a Ni2 Sm layer
obtained during the cooling of the sample. In effect, at
on nickel substrate by reduction of SmCl3 in LiCl–KCl me-
840 ◦ C, according to the phase diagram, only Ni–Sm liq-
dia, we can assume that, when the interdiffusion process
uid, falling down in the crucible, was produced. When
was reached equilibrium, only Ni2 Sm will be present in the
the sample was cooled, the Ni–Sm liquid produced, at
layer.
around 660 ◦ C, two compounds: Sm3 Ni and Sm. But Sm
The presence of Sm3 Ni in the electrolyte phase confirms
is not stable in the bath; it reacts with Li+ ions from the
that the compound is liquid at this temperature, and is par-
solvent, that’s why only Sm3 Ni is present on the micro-
tially removed from the electrode surface. This observation
graph.
suggests that at higher temperatures, with the same oper-
(ii) In the magnification in Fig. 13b, the compact layer at
ating current density, only Sm3 Ni would be formed at the
the nickel interface exhibits two phases: Ni3 Sm,closer
nickel surface and would fall down to the bottom of the cru-
to the nickel boundary and Ni2 Sm further away. This
cible.
feature could result from the interdiffusion process lead-
ing to (a) the compound with the higher Ni content, at
the nickel interface and (b) the most thermodynamically
stable compound within the layer. 4. Conclusion

This conclusion is in agreement with the data obtained The electrochemical behaviour of samarium was studied
by Borzone et al. [5] and Su et al. [6] who calculated the in the LiF–CaF2 medium using inert (Mo) and reactive (Ni)
free energies of formation of Sm–Ni alloys and determined electrodes. The results of the electrochemical techniques con-
that SmNi2 is slightly more stable than Ni3 Sm. By anal- firmed that the electrochemical reduction of SmIII occurs in
 L. Massot et al. / Electrochimica Acta 50 (2005) 5510–5517 5517

two steps with formation of SmII as an intermediate com- by SEM–EDX, and the GDR PARIS from the PACE program
pound. for financial support for this work.

Sm(III) + 1e− = Sm(II) and Sm(II) + 2e− = Sm(0) (14)

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