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Synthesis of Pb-Ca alloys by electrolysis of CaO solution in molten salt

Article · January 2002

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 SYNTHESIS OF Pb-Ca ALLOYS BY ELECTROLYSIS OF CaO SOLUTION IN MOLTEN SALT

E.B. Freidina and D.J. Fray

Department of Materials Science and Metallurgy, University of Cambridge,

Cambridge CB2 3QZ, UK

chlorine gas at the anode and this has lead to electrolytes that
eliminate this problem: molten salt solutions of calcium carbide
[5] and calcium carbonate [6] were suggested as electrolytes for
Abstract electrowinning of Ca.

Calcium is added to lead in order to remove bismuth from lead
bullion. At the present time, this is an inefficient and expensive
process and a possible alternative is to electrolyse calcium directly
from a molten salt. A solution of calcium oxide in calcium
chloride was used as the electrolyte and it was found that calcium
can be electrowon to the liquid lead cathode at the temperatures
below 650°C. Alloys containing up to 2 wt.% Ca were prepared
from CaCl2-NaCl-CaO fused mixture with current efficiency of
40-60%. There was a small amount of sodium co-deposition. The
effects of different parameters, such as temperature, current
density, time of the electrolysis etc. on the performance of the cell
and quality of the alloys were investigated.
In the present work calcium oxide was investigated as a source of
calcium as it has significant solubility in calcium chloride melts
[7]. The solubility of CaO in the CaCl2-NaCl melts has been
measured [8] and it was found that over a wide range of
compositions, where the mixture is liquid below 650°C (the
typical temperature of lead treatment), there is substantial
solubility.
CaO is less stable than calcium chloride and can be
electrochemically decomposed to calcium metal and oxygen gas
according to the reactions:

cathode: Ca2+ + 2e- = Ca (Pb-Ca alloy (1)

Introduction
anode: O2-= 2e- + ½O2 (gas) (2)
Calcium, in conjunction with magnesium, is added to lead bullion
for the removal of bismuth in the Kroll-Betterton process [1]. This
is normally achieved by direct addition and as calcium is overall: CaO = Ca + ½O2 (3)
considerably less dense than lead, it tends to float to the surface
and oxidise, wasting a significant fraction of the calcium and
causing the production of drosses, which have to be recycled since
they contain entrapped lead. Calcium will diffuse into the liquid lead cathode and form the
alloy, while oxygen will be evolved on the anode. One slight
Electrolysis of molten salts is an alternative approach to alloy problem might be the co-deposition of sodium as the electrode
preparation [2-6]. Calcium was deposited from molten CaCl2- potentials for the deposition of and sodium from chloride melts
NaCl [2,4] and CaCl2-KCl [3] on a liquid lead cathode. Much are very close[9].
better control of the process was obtained, compared to the direct
ion of calcium, with less calcium usage and dross production. A
considerable disadvantage of this technique is the generation of

Light Metals 2002

Edited by Wolfgang Schneider
TMS (The Minerals, Metals & Materials Society), 2002
 Experimental
60
Sodium chloride used was Aldrich A.C.S. reagent (99+% purity). 50

current efficiency/%
Calcium oxide was prepared by thermal decomposition of CaCO3
(Aldrich A.C.S. reagent, 99+% purity) at 1000°C. Anhydrous 40
calcium chloride was made from CaCl2·2H2O (Aldrich A.C.S.
reagent, 98+% purity). The salt was placed in alumina crucible 30
and heated at 0.2 degree/min to 300°C and, after being kept at this
20
temperature for 10 hours, it was mixed with other components
and melted at 800°C. 10

0
to the power 500 550 600 650 700 750
supply thermocouple
temperature/°C

electrode
lead
graphite
Figure 2. Current efficiency as a function of temperature at a
anode cathodic current density of 0.22 A/cm2.
furnace

As Alabyshev [2] showed the current efficiency also depends on

electrolyte lead cathodic current density as at high current densities more Ca is
cathode produced by the electrolysis than can diffuse in Pb away from the
lead. However, experiments at 650° varying the current density
showed that the current efficiency remained essentially constant
from 0.21 to 1.2 A/cm2 (figure 3).

Figure 1. schematic diagram of apparatus 70

The experimental set up is shown in Fig. 1. The electrolytic cell 60
current efficiency/ %

consisted of an alumina containing a liquid lead pool with a 50

molybdenum lead, protected from contact with the melt by a thin
alumina tube. The cell contained 75-80 g of electrolyte and about 40
200 g of lead. The anode was a Graphite rod of 1 cm diameter. 30
The melts were electrolysed under constant-current conditions
with the current being supplied by Wayne Kerr Electronics LS30- 20
10 Autoranging power supply and controlled by Black Star 4503 10
Intelligent Multimeter.
0
The alloys were analysed for calcium and sodium using ICP 0 0.2 0.4 0.6 0.8 1 1.2 1.4
emission spectrophotometer PERKIN – ELMER Plasma 1000. 2
current density/ A/cm

Figure 3. Current efficiency as a function of cathodic current

Results and Discussion density

Electrolysis of the melt CaCl2-NaCl-CaO demonstrated that

calcium was electrodeposited on to the liquid lead cathode and no
chlorine appeared in the anodic The temperature dependence of
the current efficiency is given in Fig. 2. The shape of the curve is
similar to the one reported in [2] and shows that the optimum
temperature, at this current density, is between 600° and 650°C.
As follows from the phase diagram of Pb-Ca alloy [7], with
addition of calcium to lead raises the melting point of the alloy
from 327° for pure lead to 660° for intermetallic compound
CaPb3. In these experiments, the intermetallic compound is solid
and, if formed, is likely to remain near the surface until it
dissolves. It was found that there was a limiting concentration of
calcium in lead, which can be obtained without loss of efficiency.
Figure 4 represents the dependence of yield on calcium content.
 70

60 12
current efficiency/%
50
10
40

Ca/Na wt. ratio

30 8

20 6
10
4
0
0 0.5 1 1.5 2 2.5 2
Ca content in the alloy/wt.%
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Figure 4. Current efficiency as a function of calcium content of
Ca content in the alloy/wt.%
lead

Figure 6 Ca/Na ratio as a function of Ca content in the alloy

A reason for low yield of the electrolysis may be due to the
solubility of calcium in the electrolyte. The solubility of calcium
in pure CaCl2 is as high as 5 mol.% at 775°C [10] and the 2Na + CaCl2 = 2NaCl + Ca. (4)
dissolved calcium can react with oxygen on the anode, again
forming CaO.
Combining optimum time of the electrolysis with low sodium
It was shown by previous work [2,4] that the sodium content in content in the electrolyte it should be possible to reduce the alloy
the alloy depends on the composition of the electrolyte and the contamination with Na even further.
electrolysis time. In these experiments, the melt compositions
ranged from 30.3 to 36.5 mol.% NaCl and attempts were made to
reduce the amount of sodium chloride by partially replacing it
with KCl which has more negative decomposition potential than Conclusions
NaCl and CaCl2. The results of the sodium analyses are shown in
the Figure 5. It should be noted that potassium was not detected Ca-Pb alloys were synthesised by electrolysis of molten mixture
in the lead. CaCl2-NaCl-CaO with current efficiency of 40-60%. The alloys
contained up to 2 wt.% calcium (9.5 mol.%) and the optimum
conditions of the electrolysis were found to be as follows:
temperature between 600° and 650°, cathodic current density 1–
12
1.2 A/cm2, calcium content in the final alloy about 0.7-1 wt.%
(2.5-5 mol.%). The yield can also be increased by using the same
Ca/Na wt. ratio in the alloy

10
electrolyte for longer time with the calcium oxide being
8
continually replaces as it is consumed.
Several factors can influence the sodium pickup, including
6 composition of the melt and duration of the electrolysis. The best
ratio between calcium and sodium concentrations in the alloys
4 obtained in this work was about 10. Higher values can be
achieved if optimum conditions are applied: final calcium content
2 in lead remains between 0.7 and 0.9 wt.% and the amount of
NaCl in the electrolyte is kept low, for instance by partially
0 replacing it with KCl.
0 10 20 30 40
NaCl content in the electrolyte/ mol.%
Acknowledgements
Figure 5 Ca/Na ratio as a function of electrolyte composition
The authors are grateful to the EPSRC for financial support and
for technical discussions with Mr A. Piper of Britannia Refined
The ratio between Ca and Na yields also appeared to depend on Metals Ltd.
calcium content. This is due to the sodium reaction with the
electrolyte [2]:
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