Influence of temperature and current density on oxygen

overpotential and corrosion rate of PbCo

3
O
4
, PbCaSn,
and PbSb anodes for copper electrowinning: Part I
A. Hrussanova
a,
*
, L. Mirkova
a
, Ts. Dobrev
a
, S. Vasilev
b
a
Institute of Physical Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 11, Sofia, Bulgaria
b
Central Laboratory of Electrochemical Power Sources, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., bl. 10, Sofia, Bulgaria
Received 19 February 2003; received in revised form 19 June 2003; accepted 1 July 2003
Abstract
The influence of temperature and current density on the oxygen overpotential and corrosion rate of PbCo
3
O
4
, PbCaSn,
and PbSb anodes during copper electrowinning were investigated. During prolonged electrowinning under galvanostatic
conditions, a rise in temperature leads to depolarisation of the reaction on all three anodes. At 45 jC, the potential of the Pb
Co
3
O
4
anode is about 40 mV lower than PbSb and about 70 mV lower than the PbCaSn anode.
Both at 1 and 5 A dm
2
, the potential of the PbCo
3
O
4
anode is lower than those on the other anodes under the same
conditions. Therefore, the use of a PbCo
3
O
4
anode under conditions similar to those used industrially (45 jC and 5 A dm
2
)
should cause a decrease in energy consumption.
At all temperatures and current densities examined, the corrosion rate of the PbCo
3
O
4
anode was the lowest of the three.
The rise in temperature has a greater effect on the corrosion rate of the PbCo
3
O
4
anode than increasing the current density.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Copper electrowinning; Oxygen evolution; Lead-based anodes; Composite PbCo
3
O
4
coating
1. Introduction
Recently, a new anodic material for metal electro-
winning has been developed on the basis of a PbCo
(13% Co) composite coating on a Pb substrate. It
has been shown that this anode has a low corrosion
rate and a considerable depolarising effect on the
anodic reaction during zinc electrowinning (Stefanov
et al., 2000). A comprehensive study on the behaviour
of the PbCo
3
O
4
composite anode in copper electro-
winning has been recently reported (Hrussanova et al.,
2001, 2002). It was found that the PbCo
3
O
4
com-
posite anode shows a considerable depolarising effect
on the oxygen evolution reaction compared to com-
monly used metallurgical PbSb 5.85% and PbCa
0.08%Sn 0.74% anodes. The corrosion rate of Pb
Co
3
O
4
anode during prolonged polarization (96 h)
under galvanostatic conditions is lower than that of
PbSb and PbCaSn anodes. The anodic layer on
the three anodes was composed mainly of PbSO
4
, a-
PbO
2
, and h-PbO
2
, although different morphologies
were observed. The layer was loose and coral-like on
0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2003.07.004
* Corresponding author.
E-mail address: antoanet@ipchp.ipc.bas.bg (A. Hrussanova).
www.elsevier.com/locate/hydromet
Hydrometallurgy 72 (2004) 205213
the PbSb anode, fibrous on PbCaSn, and was
dense and fine-grained on PbCo
3
O
4
.
Literature data concerning the effect of temperature
and current density on the anodic behaviour, particu-
larly on the corrosion rate of anodes for copper
electrowinning, are rather scarce.
This paper compares the influence of current
density and temperature on the corrosion rate and
Fig . 1. Dependence of the anode potential on time at a current density of 1 A dm
2
at 25, 35, and 45 jC and 5 A dm
2
at 45 jC. (a) PbCo
3
O
4
anode, (b) PbCaSn anode, and (c) PbSb anode.
A. Hrussanova et al. / Hydrometallurgy 72 (2004) 205213 206
oxygen overpotential of PbCo
3
O
4
anodes with Pb
CaSn and PbSb anodes.
2. Experimental details
The composition of the basic electrolyte (BE)
tested was as follows: 30 g L
1
Cu
2 +
(0.47 M
CuSO
4
5H
2
O) and 85 g L
1
(0.87 M) H
2
SO
4
. Three
anodes were investigated, PbCo
3
O
4
(3% Co) coating
on Pb, cast PbSb (Sb 5.85%), and hot rolled Pb
CaSn (Ca 0.081%, Sn 0.74%, Al 0.01%). The latter
two are commonly used in large-scale electrowinning
tankhouses. The preparation of the PbCo
3
O
4
com-
posite coating was previously described in detail
(Hrussanova et al., in press).
The PbSb, PbCaSn or PbCo
3
O
4
anode
(geometric area of 1 cm
2
) was subjected to galvano-
static polarization for up to 96 h at 25, 35, and 45 jC
and current densities of 1 and 5 A dm
2
. A copper
plate with an area of 1 cm
2
served as a cathode. The
reference electrode used was Hg/Hg
2
SO
4
(SSE).
Polarisation was interrupted for cyclic voltammetry
after 24 and 96 h. In order to avoid copper deposition
on the anode, the potential scanning was carried out in
the range from 0.4 to 2.0 V (SSE) at 10 mV s
1
.
Taking into account that the oxidation reactions of Pb
to PbSO
4
and PbSO
4
to PbO
2
, as well as the
corresponding reverse processes run through the con-
ductive PbO
2
layer, the height of corresponding
current maxima was used as a measure for the amount
of PbSO
4
and PbO
2
in the surface film.
The corrosion rate was determined by weighing an
anode of about 10 cm
2
and then polarising for 96 h.
The anode was washed with distilled water and treated
with a boiling solution of 180 g L
1
NaOH and 200 g
L
1
glucose in order to dissolve the anodic layer. The
anode was again washed with distilled water, dried,
and weighed. The corrosion rate of the anode was
determined using the following equation:
V
k

Dm
S
a
t
g m
2
h
1
;
where Dm= m
1
m
2
is the difference in the weight
of the anode (g) before and after polarization; S
a
is
the anode area (m
2
); t is the time of polarization
(hours).
After the polarization tests, samples of PbSb,
PbCaSn or PbCo
3
O
4
were rinsed and dried.
Using X-ray and SEM analysis, information about
the composition and the surface morphology of the
layer on anodes tested was obtained. X-ray measure-
ments were carried out using a Philips APD-15
diffractometer (Cu
Ka
radiation). Semiquantitative data
for the different lead compounds present in the anodic
layer are obtained using the area of the X-ray peaks.
The morphology of the surface layer on was investi-
gated using a scanning electron microscope (SEM)
(JEOL-Super-probe 733).
Fig. 2. Comparative relationship of the anode potential of PbCo
3
O
4
, PbCaSn, and PbSb anodes on temperature after 96 h.
A. Hrussanova et al. / Hydrometallurgy 72 (2004) 205213 207
Fig. 3. Cyclic voltammograms of PbCaSn anode at 25, 35, and 45 jC. (a) 0, (b) 24, and (c) 96 h.
A. Hrussanova et al. / Hydrometallurgy 72 (2004) 205213 208
3. Results and discussion
3.1. Effect of temperature and current density on the
anodic behaviour during prolonged polarization
The effect of temperature was studied by galvano-
static (potential time) and CV measurements. The
potential time dependencies of the PbCo
3
O
4
, Pb
CaSn or PbSb anodes are shown in Fig. 1. The
anode potentials were measured every 24 h. The anodic
potential sharply decreases between 0 and 24 h due to
formation of the anodic layer, but beyond is almost
constant. Fig. 2 shows the dependence of anode
potential on temperature after 96 h of polarization.
As can be expected, increased temperature leads to
depolarisation of the anode reaction on all three
anodes. After 96 h polarisation at 45 jC, the potential
of the PbCo
3
O
4
anode is about 40 mV lower than
that of PbSb and about 70 mV lower than that of the
PbCaSn anode.
Fig. 3 shows cyclic voltammograms of the Pb
CaSn anode at 0, 24, and 96 h polarization at 25, 35,
Fig. 4. X-ray spectra of the anodic film on (a) PbCo
3
O
4
formed after 96 h of polarization at current density 1 or 5 A dm
2
and temperature 25
or 45 jC. (b) PbCaSn and PbSb anodes at 45 jC and 5 A dm
2
.
A. Hrussanova et al. / Hydrometallurgy 72 (2004) 205213 209
and 45 jC. At the start time, temperature has a
negligible effect on the oxygen evolution reaction.
The height of the cathodic peaks decreases with
increasing temperature; hence, it seems that less
PbO
2
is formed at higher temperatures. After 24 h of
polarization, increased temperature leads to depolar-
isation of the oxygen evolution reaction (the part of
the CV curves corresponding to the oxygen evolu-
tion is shifted in a negative direction). The area and
height of the anodic peaks corresponding to the
formation of PbO
2
are increased, and the area of the
corresponding cathodic peak is also increased. The
same behaviour is observed after 96 h polarization:
the oxygen evolution reaction is also depolarised with
the rise in the temperature. Moreover, the amount of
the PbO
2
formed is greater than that after 24 h of
polarization (the corresponding anodic and cathodic
peaks are higher than that at 24 h). It can be concluded
that the rise in temperature leads to depolarisation of
the oxygen evolution reaction, as well as to formation
of a larger amount of PbO
2
and, as will be shown
subsequently, to a higher corrosion rate.
The effect of current density was studied by galva-
nostatic measurements performed at 45 jC using cur-
rent densities of 1 and 5 A dm
2
. The corresponding
potential time dependencies are shown on Fig. 1. The
anodic potential sharply decreases between 0 and 24
h as the anodic layer forms; beyond 24 h, the potential
is essentially constant. As would be expected, the rise
in current density leads to an increase in the potential of
the anodes. For both current densities, the potential of
the PbCo
3
O
4
anode is lower than both PbSb and
PbCaSn anodes. Therefore, at temperatures and
current density similar to those used in industrial
practice, the use of the PbCo
3
O
4
anode should lead
to a decrease in energy consumption.
3.2. Effect of temperature and current density on the
composition and structure of the anodic layer
According to X-ray data (Fig. 4a), the anodic film,
formed on PbCo
3
O
4
, at 1 A dm
2
and at 25 jC
contains PbSO
4
and PbO
1.57
, and h-PbO
2
, while the
film formed at 1 A dm
2
and at 45 jC contains
PbSO
4
, a-PbO, a-PbO
2
, and h-PbO
2
. The rise in
temperature does not noticeably affect the amount of
h-PbO
2
, but it does lead to a significant increase in
the amount of PbSO
4
. The comparison between the
X-ray spectra of the anodic layers on PbCo
3
O
4
at 1
and 5 A dm
2
shows that the rise in current density
leads to a negligible change in the amount of the lead
compounds.
The amount of a-PbO
2
formed on the PbCaSn
and PbSb anodes at 45 jC and 5 A dm
2
is about
three times greater than that formed on PbCo
3
O
4
Fig. 5. SEM micrograph of the anodic film on PbCo
3
O
4
, formed
after 96 h polarization at (a) 1 A dm
2
and 25 jC, (b) 1 A dm
2
and 45 jC, and (c) 5 A dm
2
and 45 jC.
A. Hrussanova et al. / Hydrometallurgy 72 (2004) 205213 210
(Fig. 4a and b). Therefore, the corrosion rate of Pb
CaSn or PbSb anode should be much higher than
that of PbCo
3
O
4
. Under these conditions, the corro-
sion rate should increase as follows: PbCo
3
O
4
< Pb
CaSn < PbSb.
Micrographs of the anodic film on PbCo
3
O
4
,
formed after 96 h of polarization at 1 A dm
2
and at
temperatures of 25 or 45 jC, are shown in Fig. 5a and b,
respectively. At both temperatures, the crystallites are
rounded, and smaller pyramidal-shaped crystallites are
also observed on them. The rise in temperature leads to
an enlargement of the crystallites and to the formation
of an anodic layer with a lower density. Therefore, an
increased corrosion rate could be expected.
The structure of the anodic film on PbCo
3
O
4
,
formed after 96 h of polarization at 5 A dm
2
and 45
jC is coral-like (Fig. 5c). It is evident that the increase
in current density from 1 to 5 A dm
2
leads to a
significant modification of the anodic structure and,
therefore, to a higher corrosion rate. It is known that
the presence of Co in the electrolyte inhibits the
growth of the anodic layer due to a specific catalytic
effect on the oxygen evolution reaction (Kiryakov and
Stender, 1952). For that reason, the corrosion rate of
PbCo
3
O
4
anode at 5 A dm
2
is slightly increased as
compared to that at 1 A dm
2
.
The structure of the anodic film formed on Pb
CaSn at 1 A dm
2
and 25 jC is fibrous Fig. 6a, but
the film formed at 5 A dm
2
and 45 jC is coral-like
(Fig. 6b). Thus, the increase in temperature and
current density leads to significant structural changes,
and it could be supposed that the corrosion rate will be
higher. Comparison of the anodic films on PbSb
(Fig. 6c and d) shows that in both cases, the structure
of anodic films is similar to coral, but the film
obtained at 45 jC and 5 A dm
2
is looser than that
obtained at 25 jC and 1 A dm
2
; hence, in this case,
higher corrosion rate could be expected.
Fig. 6. SEM micrograph of the anodic film on PbCaSn
,
formed after 96 h polarization at (a) 1 A dm
2
and 25 jC, (b) 5 A dm
2
and 45 jC;
on PbSb, formed after 96 h polarization at (c) 1 A dm
2
and 25 jC, and (d) 5 A dm
2
and 45 jC.
A. Hrussanova et al. / Hydrometallurgy 72 (2004) 205213 211
From the SEM micrographs of the anodic layers
formed at 5 A dm
2
and 45 jC on PbCo
3
O
4
, Pb
CaSn or PbSb, it can be seen that all three films are
coral-like, but the films on PbCo
3
O
4
and PbCa
Sn anodes are denser than that formed on the PbSb
anode. As a result, a higher corrosion rate of PbSb
could be expected.
3.3. Effect of temperature and current density on the
corrosion rate
The values of the corrosion rate of the three
anodes, measured at temperatures of 25, 35, and 45
jC and at current densities of 1, 3 and 5 A dm
2
are
given in Tables 1 and 2, respectively. It can be seen
that the corrosion rate of the three anodes increases
with both temperature and current density. The corro-
sion rate of PbSb is higher than that of PbCaSn,
in agreement with literature data (Bauer and Hein,
1996; Prengaman, 1984). At all temperatures and
current densities examined, the corrosion rate of the
PbCo
3
O
4
anode is the lowest. However, the increase
in the temperature from 25 to 45 jC causes a larger
increase in the corrosion rate for PbCo
3
O
4
than for
the other anodes. It has been found that the thickness
of the anodic layer increases with temperature (Asta-
hov et al., 1964). The increase in thickness is due both
to the increase in thickness of the dense part (PbO
t
,
PbO
x
, and a-PbO
2
) and in the loose part (h-PbO
2
) of
the layer, hence, the thickness above which spalling
due to internal stresses occurs more quickly at a
higher temperature. It is thought that Co decreases
the rate of the initial incorporation of oxygen in the Pb
crystal lattice and increases its passivity, whereas the
increase in temperature exerts an opposite effect
(Astahov et al., 1959).
It could be supposed that at 25 jC, only the dense
film is formed on the PbCo
3
O
4
anode, and as a
result, the corrosion rate is low. With the increase in
temperature to 45 jC, the corrosion rate is also
increased, and this effect predominates over the
inhibition effect of Co with an increased corrosion
rate. The increase in corrosion rate of PbCo
3
O
4
anode with increasing temperature shows that the
anode film is probably composed of two partsa
dense part and a loose part. The anodic layers on the
PbSb or PbCaSn anodes are composed of a
dense and a loose part. For that reason, no significant
change in the corrosion rate with the rise in temper-
ature was observed.
Table 2 shows that the increase in current density
from 1 to 5 A dm
2
causes a more pronounced
increase in the corrosion rate of PbSb or PbCa
Sn anode than that of the PbCo
3
O
4
anode. One
possible explanation of such a behaviour may be that
with increasing current density, the anode potential
increases into the region for intensive oxygen evo-
lution, and therefore, the formation of a dense anode
layer is impeded. That leads to an increase in
corrosion rate.
Table 2 shows that there is an increase in the
corrosion rate of a PbCaSn anode with increased
concentration of sulphuric acid and copper sulphate,
as expected (Gifuentes et al., 1999). A slight opposite
effect was observed in the case of PbCo
3
O
4
anode.
4. Conclusions
The rise in temperature from 25 to 45 jC leads
to depolarisation of the oxygen evolution reaction
on PbCo
3
O
4
, PbCaSn and PbSb anodes. At
45 jC, the potential on the PbCo
3
O
4
anode was
about 40 mV lower than on PbSb and about 70
mV lower than on PbCaSn.
Table 2
Corrosion rate at 45 jC as a function of current density
i
a
(A dm
2
) V
k
(g m
2
h
1
)
PbSb PbCaSn PbCo
3
O
4
1 2.62 1.58 1.6
3 4.18 3.51 (4.44) 1.69 (1.22)
5 10.17 3.94 2.04
The values in parentheses are for an electrolyte containing two times
higher concentrations of H
2
SO
4
and CuSO
4
.
Table 1
Corrosion rate of the anodes as a function of temperature after 96 h
at 1 A dm
2
T jC V
k
(g m
2
h
1
)
PbSb PbCaSn PbCo
3
O
4
25 1.93 1.2 0.52
35 1.32
45 2.62 1.58 1.6
A. Hrussanova et al. / Hydrometallurgy 72 (2004) 205213 212
Both at 1 and 5 A dm
2
, the potential values of
PbCo
3
O
4
are lower than those of the PbCaSn
and PbSb anodes under the same conditions. On the
basis of these results, it may be possible to decrease
the energy consumption by using PbCo
3
O
4
anodes
in industrial tankhouses.
At all temperatures and current densities examined,
the corrosion rate of the PbCo
3
O
4
anode is lower than
both PbCaSn or PbSb anodes. Increased temper-
ature had a more profound effect on the corrosion rate
of PbCo
3
O
4
than increased current density.
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