Hydrometallurgy 131–132 (2013) 144–157

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

The influence of alloying elements on the electrochemistry of lead anodes for

electrowinning of metals: A review
M. Clancy a,⁎, C.J. Bettles a, A. Stuart b, N. Birbilis a
a
ARC Centre of Excellence for Design in Light Metals, Department of Materials Engineering, Monash University, Clayton, VIC. 3800, Australia
b
Origma Pty Ltd., New Lambton, NSW 2305, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Lead (Pb) anodes are used in the electrowinning (EW) of metals. The performance of Pb-anodes is reviewed
Received 24 August 2012 herein, taking a holistic perspective, including metallurgy (i.e. solubility of metals in Pb) and the electro-
Received in revised form 1 November 2012 chemical impact of alloying. The review is general in its nature, however the application of copper (Cu)
Accepted 1 November 2012
EW is used illustratively to emphasise key points. The need for energy efficiency in the present era and future
Available online 7 November 2012
will dictate the use of anodes with low overpotential, hence warranting an appraisal of electrochemical per-
Keywords:
formance of Pb as altered by alloying.
Lead alloys/anodes © 2012 Elsevier B.V. All rights reserved.
Electrowinning
Corrosion
Oxygen overpotential

1. Introduction contaminating the metal deposited on the cathode (Tunnicliffe et

Lead (Pb) based anodes are currently the preferred choice for the
industrial electro-winning (EW) of many metals as they are conduc-
tive, economical and relatively stable at high potentials and low pH
(Tunnicliffe et al., 2012). Approximately 20% of the world's Cu is pro-
duced by the EW process (Moats and Free, 2007). EW anodes that are
used for the production of copper are required to be of good structur-
al and mechanical integrity, as well as experiencing a low rate of dis-
solution and/or corrosion (Prengaman et al., 2010). EW is nominally a
galvanostatic process, with industrial tank houses currently having an
average of 30% energy efficiency (Schlesinger et al., 2011). In an era of
increasing energy costs there is a need to make the EW process as en-
ergy efficient as possible. This may be achieved by design and produc-
tion of EW anodes that can offer significant energy savings.
The overpotential of the anode provides the most scope for reduc-
ing the overall cell voltage (Ivanov et al., 2000a). A high overpotential
results in an increased cell voltage and subsequently a reduced cell ef-
ficiency (Zhang and Houlachi, 2010). Overpotential in the context of
this review relates to the anode overpotential (also known as the ox-
ygen overpotential) arising from being held at a fixed anodic current
density during a galvanostatic process. It has been suggested that re-
ducing the anode potential promotes the formation of a denser oxide
layer, which consequently will have better adherence and lower dis-
solution. Insufficient adherence with the anode may cause the oxide
to detach, thus exposing the underlying Pb anode and potentially
⁎ Corresponding author. Tel.: +61 3 9905 4941; fax: +61 3 9905 1928.
E-mail address: marie.clancy@monash.edu (M. Clancy).
al., 2012).
The success of any new EW anodes may be assessed by the influence
on:
• Alloy workability
• Mechanical stability and durability
• Quality of the metallic cathode deposit
• Amount of sludge generated and subsequent cell maintenance
• Environmental effects and lead consumption (Nidola, 1989)
• And most importantly for this review; electrochemical and chemi-
cal stability.
Hrussanova discussed the influence of different Pb–X alloys on the
oxygen overpotential and this is displayed in Table 1 (Hrussanova
et al., 2001). However the electrochemical performance is not the only
parameter by which prospective anode alloys are rated and Ivanov
summarised that the critical qualities in a good anode are good electrical
conductivity (for energy efficiency), electrocatalysis (for high productiv-
ity) and stability (to minimise labour and maintenance costs) (Huang
et al., 2010; Ivanov et al., 2000b). The electrocatalytical properties have
the most scope for improvement and this could be achieved by altering
the surface of the Pb anode or the reaction mechanism, such that at a
constant current density the anode potential is reduced (Ivanov et al.,
2000a; Prengaman et al., 2010).
The electrical resistance of EW anodes is dependent on the
non-dissolution (in polarised conditions) and the non-corrosion
(in un-polarised conditions) of alloying elements. Anode integrity is
disadvantaged by the oxide (PbO2) layer being too thick or porous.
Elements for alloying should be chosen with these criteria in mind;

0304-386X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2012.11.001
 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157 145

Table 1
Alloy effect on oxygen evolution potential (Ivanov et al., 2000b).

Effect on oxygen evolution potential Alloys

Greatest reduction PbAg, PbCo, PbAgSnCo

Small reduction PbMn, PbCa, PbRh
No effect PbFe, PbC, PbPd
Increased PbAu, PbHg

namely to resist dissolution and aid in the growth of a dense layer of

PbO2. Known elements that fulfil this role are Sn, Ba, Sr or Ag and As
in the presence of Cl − ions (Ivanov et al., 2000b). The electronegativ-
ity of the alloying elements is also an important issue as elements
with a higher electronegativity will not passivate in H2SO4 and so
they are more susceptible to corrosion. To reduce the level of corrosion
the alloying element should be more resistant to corrosion than Pb
(Ivanov et al., 2000b). Passivation, and the potential at which it may
occur, must be monitored for Pb anodes as it should occur after installa-
tion and prior to EW.

2. The chemistry of EW and PbxOy formation

While this is a general review of the alloys used as anodes in the

EW system, the EW of Cu is used in this section illustratively to out-
line the key reactions that occur during the process. There are a num-
ber of critical oxidation processes that occur at the Pb anode (Ivanov
et al., 2000a). The first of these involves the reaction of the anode sur-
face with the sulphate ions in the electrolyte. The reaction, as outlined
in Eq. (1) results in the production of PbSO4. The reaction at the anode
during EW involves the decomposition of water and the subsequent
liberation of oxygen, as described by Eq. (1):
Pb þ SO4 2− −2e→PbSO4 E ¼ −0:356 V=SHE
Fig. 1. A breakdown of the key reactions that take place when Pb is exposed to a potential
in a sulphuric acid electrolyte, adapted from Hrussanova et al. (2001).
anode surface. This conductive layer offers a lower current density
and anode potential than its predecessor. It should be noted that the
formation of PbSO4 is reversible, and its formation depends on the
compactness of the oxide layer, which will affect diffusivity through
the discharge product, nature of this product and the thickness of the
oxide layer (Nikoloski and Nicol, 2008). The progression of Pb is
ð1Þ shown in the Pourbaix diagram in Fig. 2 (Nikoloski and Nicol, 2010;

The next reaction involves the decomposition of water and the

subsequent liberation of oxygen, as in Eq. (2).

4OH− −4e ¼ O2 þ 2H2 O E ¼ þ0:401 V=SHE

ð2Þ

As the PbSO4 layer that forms is non-conductive, areas adjacent to

it, where it has not formed, will have a higher potential and current
density. A high overvoltage enables the reaction described by
Eq. (3) (Ivanov et al., 2000a) and within Fig. 1, to take place. This re-
action will occur before that outlined with Eq. (2) has an opportunity
to take place.

PbSO4 þ 2H2 O−2e→PbO2 þ H2 SO4 þ 2Hþ E ¼ þ1:685 V=SHE ð3Þ

The electrolyte contains sulphate ions and the overall reaction can
be written as Eq. (4). For completeness, the net result of this reaction
is that oxygen is liberated at the anode and pure metal deposits at the
cathode (Schlesinger et al., 2011).

CuSO4 + H2O → Cu + ½ O2 + H2SO4

The growth of PbO2 on the surface of the anode is a positive develop-

ment as this conductive oxide prevents over-oxidation of the anode
(Prengaman, 1984a) and dissolution of the anode (Shervedani et al.,
2007). The formation of this oxide layer is important as it passivates
the Pb anode from attack (Nikoloski et al., 2010). The oxidation of Pb
has been and still is the focus of extensive research as it can occur by dif-
ferent mechanisms, depending on the environmental conditions
(Canagaratna et al., 1977a, 1977b; Casson and Hampson, 1977, 1978a, Fig. 2. Pourbaix diagram for Pb in the presence of sulphate ions at 25 °C, as adapted
1978b). Continued reaction of the PbSO4 with water eventually pro- from Maksymiuk et al., Lead, Elsevier, 2009 (Maksymiuk et al., 2009). The potential
duces a layer of α-PbO2 with a good electrical conductivity on the has been scaled against a Saturated Calomel Electrode (SCE).
146 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157

Nikoloski et al., 2010). Both PbSO4 and PbO2 are semi-permeable and
will allow for transport of select ion species through them (Slavkov
et al., 2002). The inflections that correspond to the reactions described
are presented in the voltammogram in Fig. 3 (Maksymiuk et al., 2009;
Taguchi and Sugita, 2002). PbO2 is an electrocatalytically active
layer with a high overpotential during the evolution of oxygen. The
overpotential is deemed high as it occurs at a voltage approximately
300 mV above that where oxygen is evolved. This is based on Eq. (3)
and Fig. 2.
The denser and more adherent the initial oxide layer is, the lower
the risk of oxide delamination and spallation, which could otherwise
leave the anode surface exposed and vulnerable to yet more corrosive
attack. Also, the denser and thicker the oxide layer is the more diffi-
cult it is for Pb 2 + to diffuse through to the electrolyte. This promotes
the oxidation of Pb 4+ ions and so PbO2 results from hydrolysis of the
aforementioned ions. This process takes place at the surface of the
anode and in the initial pores of the oxide layer (Ivanov et al.,
2000b). However, the main diffusing species are the sulphate ions
and oxygen. These have a greater mobility and can move inwards to-
wards the anode surface.
It should be stated at this point that there is more than one type of
PbO2. The growth of different types is attributed to the electrochem-
ical process altering as the pH changes. The oxide layer that forms on
the anode surface plays an essential role as it is the part of the anode
that is electrochemically active and the steps required for the forma-
tion of this oxide have already been presented (Ivanov et al., 2000a).
The two typical forms of PbO2 are rhombic (α) and tetragonal (β).
The former of these has a slightly higher density and is harder (Ivanov
et al., 2000a). β-PbO2 has a lower potential and rate of corrosion than
α-PbO2 (Zhang and Houlachi, 2010). The deposits of α-PbO2 oxide
are stronger and larger (~ 1 μm) than those of β-PbO2 (~0.5 μm).
α-PbO2 is the result of interaction between a complex and a hydroxyl
ion while β-PbO2 is the result of the complex containing SO42−. There-
fore, some researchers have claimed that α-PbO2 can only form in al-
kaline or neutral solutions and that β-PbO2 only forms by oxidation of
PbSO4 in an acidic environment (Ho et al., 1994). However, other re-
searchers have derived α-PbO2 from oxidation of PbSO4 (Ivanov et al.,
2000a). There is conflict with these proposed mechanisms, as α-PbO2
can also be formed in an acidic solution and Pb 4+ compounds are
only dissolved in H2SO4 with a concentration greater than 15 M.
This conflict may be resolved by appreciating that the surface of the
PbO2 crystals can undergo different adsorption processes and this is
why the alloying material can play a crucial role.
Oxygen diffuses through the oxide layer from the boundary be-
tween the oxide and the solution to form a thin layer of β-PbO2
from the sulphate. Due to further oxidation of the Pb above the equi-
librium potentials more oxygen gets entrained in the β-PbO2 layer
and so this evolves to α-PbO2 at the surface. Should the oxide contin-
ue to grow, and the distance from the anode-oxide boundary in-
crease, the fresh oxide will not be as rich in oxygen and so the
α-PbO2 becomes tetragonal PbO + Pb. Should the duration of passiv-
ation of the Pb anode exceed a critical point the oxide will surpass a
thickness limit, where internal stresses will cause oxide delamination
and spallation. Ideally the oxide layer should be a hard, thin, adher-
ent, dense and compact layer of pure PbO2 (Prengaman et al., 2010).
If the environment is conducive to continuous growth of the oxide
layer, small cracks will nucleate parallel to the anode surface. These
cracks, coupled with oxygen evolved underneath will allow for the
non-adherent overlying oxide flakes to spall away from the oxide.
3. Influence of alloying lead on the electrochemical performance
in EW
When the anode is polarised the alloying elements provide protec-
tion by altering the PbO2 layer on the anode surface. Should the surface
of the anode not be polarised, passivation is increased (Ivanov et al.,
2000b). This is attributed to the electrochemical processes generated
by the galvanic pairs (the Pb and alloying elements), the growth of a
dense oxide layer that contains the oxidised alloying elements and the
altered microstructure due to alloying.
Over the years there have been significant advances made in the
development and applications of Pb alloy anodes. Ivanov reviewed
the work of Kiryakov, who divided suitable alloying metals into
three categories (Ivanov et al., 2000b) and these are outlined in
Table 2 (Ivanov et al., 2000a). The information in this table illustrates
why there are so many quaternary Pb alloys investigated, as Pb is
alloyed with one metal from each of the above categories. Ivanov stat-
ed that alloys containing Ag or Co show the most promise with
regards to low oxygen evolution potential and low corrosion
(Ivanov et al., 2000a). PbAgSnCo could be considered to be in the
same performance category. Figs. 4 and 5 have been constructed
from data presented by Ivanov et al. (2000a). They show the influence
of current density and composition on the resultant anodic potential.
With respect to the alloys, the best performer is Pb–1%Ag–0.3%Sn–
0.02%Co while the alloy with the highest anodic potential is Pb–1%Au.
3.1. The Pb–Sb alloy system
Prior to PbCaSn, which is nowadays the most common anode alloy
for EW of copper, PbSb was widely used (Bagshaw, 1995). This is due
to the excellent strength and creep resistance of PbSb (Shervedani
et al., 2007). Sb must be added in relatively high amounts for it to
have any marked effect on the mechanical properties—however this
is possible since Sb displays solid solubility in Pb. Initially PbSb alloys

Table 2
Categories of Pb alloying elements as compiled from Ivanov, (Ivanov et al., 2000b).

Category Element Reason

1 Ag, Co, Pt or Au, Cu, Ni and Fe to a These have electrochemical–

lesser extent.
2 Tl, In, Sn, Bi, Sb……
3 Elements belonging to either
Category 1 or 2; mainly alkaline or crystallisation of the melt. To be
rare earth metals such as Ca.
Fig. 3. Voltammogram for Pb electrode in 4.5 kmol/m3 H2SO4 at 25 °C, adapted from
Taguchi, 2002, to show just the third cycle (Taguchi and Sugita, 2002).
catalytical effects and they reduce
the anodic corrosion of Pb.
These offer structural effects by
altering the alloy's microstructure.
This in turn has a positive effect on
how and what type of surface
PbO2 layer forms.
Influence is determined during the
effective the concentration of the
alloying element must remain low
enough that it does not alter the
phase structure of the anode,
otherwise it may be more
susceptible to corrosion.
 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157
Fig. 4. Potential (VSHE) of different pure metals in 1 M H2SO4 when polarised galva-
nostatically at 50 °C at current densities as listed and adapted from Ivanov et al., 2000a.
contained about 11 wt. % Sb. This has reduced to between 6 and 9 wt.
% due to the poor castability of the binary alloy prior to the addition of
ternary Sn being added to improve melt fluidity (Bagshaw, 1995).
During manufacture of PbSb alloys care needs to be taken to avoid
elongated dendrites which can form during solidification, causing
premature cracking along grain boundaries. PbSb alloys offer high
mechanical strength and hardness due to the presence of a eutectic
phase and the possibility for precipitation hardening (due to the for-
mation of PbSb precipitates) enhanced by the presence of other func-
tional elements in trace amounts, e.g. As. It is noted however, that as
with other alloys, there is a trade-off between strength and ductility,
such that increasing the volume fraction of precipitates reduces duc-
tility. Creep resistance of PbSb is substantially better than that of PbCa
(Prengaman, 1997) as Sb can segregate to the interdendritic regions
(Prengaman, 2001); however, this makes the alloy more vulnerable
to corrosion.
Fig. 5. Anodic potential (VSHE) of different Pb-alloys in 1 M H2SO4 at 25 °C, adapted from
Ivanov et al., 2000a.
147
PbSb alloys are susceptible to leaching/dissolution of the Sb from
the anode by the sulphuric acid solution. This may occur during
cycling (Prengaman, 1997) and over time the Sb is leached from the
positive to the negative grid. While this is mentioned here in refer-
ence to the lead acid battery system rather than the lead anode sys-
tem, the same situation could develop; if/when there is a short
circuit in the EW system. Formation of any intermediate, undesirable
species during this interruption to the EW process could have a neg-
ative influence on the proceeding performance of the anode and the
system as a whole (Burbank, 1971). Leaching may also occur during
discharge (Prengaman, 2005); whereby the positive and negative ac-
tive materials in the anode react with the sulphuric acid electrolyte to
form lead sulphate and as such it is unacceptable, particularly for high
purity Cu cathodes that have very low contamination thresholds.
3.2. The Pb–Ca–Sn alloy system
Prengaman developed the first rolled PbCaSn anode in the 1980s
(Prengaman et al., 2010) and by the 1990s there was a marked tran-
sition from PbSb to PbCaSn alloys. A key advantage of these alloys is a
reduced level of cathode contamination by Pb (Nikoloski and Nicol,
2010). The PbCaSn anodes are strong with a good level of homogene-
ity and the alloy is free of cracks or dross. The composition of these
anodes is approximately 0.08% Ca and 1.5% Sn, with trace amounts
of Bi, Al and Ag. The anodes have an average operating life of between
4 and 5 years and they corrode at a rate of 0.5 mm/year (Camurri et
al., 2001). The exact composition of the anode may vary from manu-
facturer to manufacturer, with some using purer lead than others,
thus increasing the level of additives e.g. Ag or Al in the anode.
While binary PbCa alloys could offer high mechanical strength, as
the Ca content was increased, so too was the rate of corrosion. PbCa
alloys have a grain structure that is more prone to corrosion and
their chemistry is not ideal for high performance environments
(Prengaman, 1997). PbCa alloys can be susceptible to accelerated cor-
rosion and creep due to ageing. This is attributed to Pb3Ca precipitat-
ing from the bulk solid solution, where its function is to provide
strengthening. It precipitates from the solid solution by means of cel-
lular precipitation reactions. This is an undesirable development and
will continue to occur as the grain boundaries react and move when
stressed, thus increasing corrosion and creep.
Sn in PbSn alloys is known to reduce corrosion (thanks to the
unique microstructure that Sn containing Pb alloys produce on
rolling). The favourable properties which Sn can offer may also be
discussed in terms of ion transportation and conductivity (Xu et al.,
2006). The PbCaSn alloy was a natural progression as PbCaSn alloys
could offer an alloy with the best properties of both of the binary al-
loys (Prengaman, 1997), i.e. the alloy can offer a lower corrosion
rate (lower oxygen evolution) while promoting the growth of PbO2
instead of other transient and deleterious oxides (Prengaman et al.,
2010).
PbCaSn alloys are by far the most popular choice today for Pb al-
loys used in EW of copper. In all cases, rolling the alloys increased
their mechanical strength and this is a standard step in the anode
manufacturing process. Rolling results in a higher yield strength
thanks to elongated grains. The ratio of Sn to Ca is critical to the suc-
cess of the alloy (Xu et al., 2006) as they form an intermetallic Sn3Ca
compound which translates to 0.01 wt. % Ca and 0.09 wt. % Sn. In
some cases, the required weight ratio of Sn to Ca may be as high as
22:5. Due to their different segregation behaviours the Sn: Ca ratio
is important for determining the stability of the alloy. The lower the
Ca content, the less Sn is required to form the oxide layer. This also re-
sults in a lower rate of corrosion. Increasing the Ca content reduces
the grain size, which increases corrosion while an increased Sn con-
tent will increase the grain size and so reduce corrosion (Rand et al.,
2002; Xu et al., 2006). Coarser grains are known to be less susceptible
to corrosion as there are less cellular boundary areas, which are high
148 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157
energy zones (Osório et al., 2009). One must bear in mind that the
grain size alone will not dictate the material's susceptibility to corro-
sion as this will also be influenced by processing and environmental
aspects. Should an alloy have a finer grain size it will be more reactive
which could mean that the passive oxide layer forms at a faster pace,
thus protecting the underlying alloy (Ralston and Birbilis, 2010).
The optimum Ca content was shown to be 0.07 wt. % as the yield
strength decreased beyond this amount, as in Fig. 6(a) (Prengaman,
1999). The addition of Sn has a very evident and positive influence
on the yield strength and this is economically feasible up to a content
of 1.0 wt. %. Adding any more than this does not yield a significant
enough increase in the yield strength to justify greater additions,
see Fig. 6(b) (Prengaman, 1999). When the Sn content is maintained
at this level ion transportation is the controlling step in the corrosion
process (Xu et al., 2006). The percentage volume of second-phase in-
termetallics in Sn doped PbCa alloys is increased, since (PbSn)3Ca oc-
cupies a slightly larger volume than its Sn-free equivalent. No matter
what the Ca content is of the alloy, the addition of Sn will always im-
prove the mechanical properties. Not only that but the Sn3Ca precip-
itate is more dimensionally stable, it has better mechanical properties
and is less susceptible to creep than the alternative Pb3Ca (Nguyen
et al., 2008; Prengaman, 2001). Introducing the intermetallic Sn3Ca
compound is a good way of strengthening areas in the matrix that
are deficient in Sn or Ca, thus enhancing the resistance to bending
and deformation.
Fig. 6. Influence of alloy composition and processing on the yield strength of PbCaSn
alloys, showing (a) Pb–Ca–1.5Sn and (b) Pb–0.07Ca–Sn, as adapted from Prengaman,
1999.
Segregation and/or preferential segregation are highlighted here
as another way of assessing an alloy's susceptibility to corrosion. Seg-
regation, in conjunction with the cooling rate applied during solidifi-
cation could both be important in influencing the time available for
preferential segregation and also the grain size. When choosing dif-
ferent alloying elements it is important to be aware of how they seg-
regate. For example, the majority of segregation in PbCa alloys occurs
during the solidification phase. The material that is first to freeze/
solidify will have a higher Ca content than the material that is last
to freeze, which will be the grain boundaries (Prengaman, 2001). Ca
segregates to the interdendritic sub-grain centres, away from the
grain boundaries where Sn is concentrated (Rand et al., 2002). This
is indicative of the grain boundaries being mechanically weaker but
more resistant to corrosion. During the solidification phase some of
the Sn is displaced from the solidifying sub-grain into the liquid
ahead of the solidification front. Sn preferentially segregates to the
grain boundaries and the interdendritic regions. These examples of
contrasting segregation behaviour show how important it is to be
aware of different elements' segregation preferences. For this reason,
extra Sn may be required, to ensure that the Sn3Ca precipitate forms.
It is widely accepted that Sn has a positive influence on the elec-
trochemistry of the alloys (Prengaman, 1997). Sn is a popular com-
plementary addition with Ca as it is responsible for reducing the
rate of corrosion and it also aids (Prengaman, 1999) in the formation
of the conductive PbO2 layer. Above the critical content of 1 wt. % Sn
there is a notable drop in the corrosion rate. Only a small quantity of
Ca is required for its positive influence to be adapted by the alloy. If
the quantity exceeds a certain level it actually accelerates alloy corro-
sion, especially at elevated temperatures.
Further research has been conducted on this ternary alloy to ex-
plore possible ways of further reducing the anode potential. An
array of methods involves altering the parameters of the EW process
in some way and of course, adding a ternary element to this well
established alloy is another possibility. Nguyen summarised a num-
ber of methods to reduce the anode potential of PbCaSn and these in-
cluded: increasing the Co ion concentration, increasing temperature,
increasing rotational speed, decreasing the acid concentration and fi-
nally decreasing the current density (Nguyen et al., 2008). The role of
Co is a matter that warrants special attention and it is dealt with in
Section 3.5.
3.3. Effect of processing/rolling
Whether or not the alloy is subjected to rapid cooling is almost
irrelevant in terms of grain size as the alloy will be subjected to
rolling and here the grain structure will be enlarged and elongated
to reduce corrosion. However, attention must be paid to how the
alloy is cast as this will set up a number of conditions in the eutec-
tic, should one exist. These conditions concern grain boundaries,
dislocation motion and subsequent mechanical properties. The
structure of the grain boundary is critical to the overall strength
and (electrochemical) performance of the alloy. If the grain bound-
aries occupy a large area the grain size is subsequently reduced,
which in turn improves the mechanical strength. However, at ele-
vated temperatures greater grain boundary areas mean an increas-
ing susceptibility to creep (Rand et al., 2002). The preference for
larger grains with smaller grain boundary regions is due to a re-
duced level of corrosion. The grain boundaries are more chemically
active than the grain itself, so attention must be given to elements
that show a preference for grain boundary segregation. The matter
of grain size is critical to the electrochemical performance of the
alloy and it is dictated by the composition of the alloy, the cooling
rates during casting, environmental and processing parameters
(Ralston and Birbilis, 2010).
Rolled alloys will have better mechanical properties than the
as-cast form (Albert et al., 1997), with rolled alloys also offering
 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157
uniform thickness and ductility (Prengaman, 1997). Often the effects
of rolling are dictated by the stability of precipitates present in the
alloy, and ultimately these control the positive/negative effects of
rolling. The addition of an extra element can alter the alloy's sensitiv-
ity to rolling. For example, the addition of Ag can prevent sliding of
the grains over one another. Without Ag, PbCaSn alloys that have a
high Sn:Ca ratio can suffer intergranular cracking, which makes
them unsuitable for many applications. In terms of corrosion, a cast
alloy that has been rolled is more resistant to corrosion as the grains
are orientated in the direction of rolling and the PbO2 layer that forms
has good adherence, which is better than that of an alloy that has not
been rolled (Zhang and Houlachi, 2010). This was proven to be the
case for PbAgCa alloys with Ca and Ag contents of 0.03–0.08 wt. %
and 0.3–0.4 wt. % respectively (Prengaman and Siegmund).
3.4. Alloys researched to date
Table 3 provides a synopsis of the Pb-based alloys that have been
investigated to date, in an effort to offer improved protection from
corrosion at a lower anodic potential, thus improving the longevity
of the anode, making it more energy-efficient and cost-effective.
Table 4 shows the periodic table of elements, highlighting those
that have been researched in relation to Pb alloys for the EW
process.
3.5. Synopsis of chemical effects
3.5.1. Ag
Ag has a 0.1 wt. % solubility limit in pure Pb (Okamoto, 2010). Ag
acts in a protective manner and aids in the growth of a dense oxide
layer (Ivanov et al., 2000b; Zhong et al., 1996). A minor addition of
Ag can offer improved control of the manufacturing process, the
alloy composition and the grain structure. By improving these aspects
the resultant alloy is of a higher mechanical strength and is more re-
sistant to creep. This effect of Ag holds true not just for PbCaSn alloys
but also for PbSb, PbAg and others (Bagshaw, 1995). An Ag addition of
0.5–1.0 wt. % helps to reduce corrosion (Ivanov et al., 2000b; Zhang
and Houlachi, 2010) and the anodic overpotential by as much as
120 mV (Ivanov et al., 2000a; Tunnicliffe et al., 2012). However, if
more than this could be added it could potentially reduce the amount
of Pb contamination in the deposit on the cathode.
Ag is similar to Sn in that it segregates to the sub-grain and the
grain boundaries, and therefore while areas such as the grain bound-
aries and interdendritic regions are more resistant to corrosion be-
cause of Sn/Ag enrichment, they may also be more susceptible to
deformation due to their lower Ca content. While Ag offers numerous
advantages, a cost-benefit analysis normally results in a reduced Ag
addition (Ivanov et al., 2000a).
During the dissolution of Ag in Pb the anodic surface area in-
creases, and therefore the anodic current density and the corrosion
rate decrease. Ag + has the same beneficial effect as Co 2+ when
added to the electrolyte (Ivanov et al., 2000b). Ag enables a lowering
of the rate of (Pb) oxidation in the sub-grain and grain boundary sites.
Ag decreases the activation energy for oxygen evolution (Monahov
et al., 2000), reduces anodic oxidation (Azim et al., 1977) and con-
verts the α-PbO2 to β-PbO2, which has a lower potential and corro-
sion rate than the former (Zhang and Houlachi, 2010). Ag delays
passivation of the oxide layer and the closing of pores in the PbSO4
layer. Ag coarsens the grain size in the eutectic structure (Azim et
al., 1977), while improving mechanical properties by increasing the
resistance to deformation and creep. Ag also reduces corrosion in
PbCaSn alloys (Albert et al., 1997; Prengaman, 1997). Depending on
the metal being extracted, the presence of Ag can also influence the
role of Mn, whereby the potential of a PbAg anode is reduced in the
presence of Mn (Ivanov et al., 2000a).
149
3.5.2. Al
Al additions of 0.01 to 0.08 wt. % refine the grain structure of Pb
alloys and reduce the rate of grain boundary movement (Bouirden
et al., 1991). Al is also a useful additive as a sacrificial oxidiser in
PbCa and PbCaSnCe alloys as it reduces the oxidation of Ca and or
Ce respectively (Li et al., 2007; Prengaman, 2010).
3.5.3. As
As can reduce corrosion in PbAg alloys increase the thickness of
the oxide layer and reduce the anodic electrical resistance. Additions
of this element do not cause any significant increase in the anodic po-
tential. When added to PbSb alloys As acts as a grain refiner (Rand
et al., 2002).
3.5.4. Au
Au has a 0.19 wt. % solubility limit in pure Pb (Okamoto, 2010). Au
causes an abrupt reduction in electrical resistance (Ivanov et al.,
2000b). This may be due to the production of an oxide with a low
electroconductivity, which does not act as a Pb protector.
3.5.5. Ba
Ba greatly improves the mechanical properties and stabilises the
grain structure, thus avoiding over-ageing (Bagshaw, 1995). By
stabilising the structure these alloys could avoid recrystallisation,
grain boundary movement, microstructural instability and subse-
quent high temperature corrosion. Additions of this element do not
cause for any significant increase in the anodic potential.
3.5.6. Bi
Bi has a 25.16 wt. % solubility limit in pure Pb (Okamoto, 2010). Bi has
various speculated effects on corrosion and oxygen evolution, with little
agreement on any of these (Koop et al., 1993; Li et al., 2006) but there are
suggestions that it is slightly more beneficial than damaging (Zhong
et al., 1996).
3.5.7. Ca
Ca has many influences and for that reason it is present in the cur-
rently used commercial anodes, PbCaSn. Ca improves the mechanical
properties and reduces the anode potential (Osório et al., 2009;
Schlesinger et al., 2011). While it can increase corrosion if the amount
added is too much (Albert et al., 1997), additions of just 0.08 wt. %
will increase the mechanical strength. The beneficial effects of Ca
can taper off with time due to dissolution of Ca from the surface
layer (Ivanov et al., 2000b). Ca aids in minimising Pb contamination
of the cathode in PbAgTl alloys (Ivanov et al., 2000b) and in PbAg al-
loys (Prengaman, 1984a; Zhang and Houlachi, 2010). Ca promotes the
conversion of α-PbO2 to β-PbO2 (Zhang and Houlachi, 2010). The
higher the Ca content the more refined the grain structure (Rand
et al., 2002).
3.5.8. Cd
Cd has a 3.29 wt. % solubility limit in pure Pb (Okamoto, 2010). Cd
reduces corrosion by modifying the nucleation of oxide in the PbSO4
pores. During this step in the anodic polarisation phase there is a sub-
sequent 50% reduction in the electricity consumed, due to the pres-
ence of Cd and its influence on the formation of PbSO4 (Azim et al.,
1976). Cd results in a microstructure with smaller dendrites; it may
also refine the eutectic structure while preferentially segregating to
Sb-rich areas in PbSb alloys (Azim et al., 1977). The oxide formed is
denser than the oxide formed on Cd-free PbSb. Increasing the Cd con-
tent moves the oxygen evolution potential in a more noble direction.
It has been suggested that the protective nature of Cd is based on it
blocking the pores in the PbSO4, such that it promotes further oxide
nucleation. This suggests that the Cd effects are transient and will
taper off with time.
150 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157

Table 3
A synopsis of different alloys that have been made and researched with applications for the EW industry.

Alloy Reference Properties

PbAg (Ivanov et al., 2000b; These anodes have been developed with modified microstructures, e.g. coarse grained and/or porous. A coarse
Zhang and Houlachi, structure offers 50% lower rates of corrosion and an overpotential that is 25 mV lower than conventional anodes.
2010) Porous anodes have significantly less corrosion, less MnO2 generated, less Pb contamination at the cathode and
an overpotential that is lower by 57–83 mV (in Zn electrowinning).
PbAu (Ivanov et al., 2000b)
PbBa (Bagshaw, 1995) These are inferior to PbCa alloys and have diminished age-hardening.
PbBi (Li et al., 2006) When compared against PbAg the anode potential was negligible. Bi is not high impact and even with 7.33 wt. % Bi
the potential is only 30 mV less than that of pure Pb. If Bi content is >0.1% the rate of the oxygen evolution reaction
increases. This is due to dissolution of Bi (during anodic polarisation) from the alloy and its subsequent adsorption
onto the PbO2 surface.
PbCa (Prengaman, 1984a) Both of these binary additives strengthen the Pb anode by precipitation hardening. The precipitates are very small
PbSr (Prengaman, 1984a) and form they form by a cellular precipitation mechanism.
PbLa (Li et al., 2009) Unsuitable as it has a high overpotential for oxygen evolution reaction.
PbLi (Bagshaw, 1995) Better mechanical properties than PbCa but poorer corrosion resistance.
PbRh (Ivanov et al., 2000a) Offers a significantly reduced anode potential with v. low Rh.
PbSb (Prengaman, 1997) PbSb has excellent strength and creep resistance. The high mechanical strength and hardness are due to the
presence of a eutectic phase and the alloy undergoing precipitation hardening.
PbSm (Chen et al., 2007) Unsuitable as it has a high overpotential for oxygen evolution reaction.
PbTe (Guo et al., 2009) Unsuitable due to insignificant reduction in anode potential.
Pb–TiO2 (Stefanov and These do operate at a lower overpotential than a Pb anode, but the anode potential is 15 mV higher than that of a
Dobrev, 2005) Pb–1Ag anode. These anodes are sensitive to corrosion in H2SO4 and the oxide formed has poor adhesion.
PbTl (Cifuentes et al., 2011; Good corrosion properties, similar to that of PbAg.
Ivanov et al., 2000b)
Pb–1Ag (Ivanov et al., 2000b) From their studies they found these three alloys to be the most resistant. Should NO3ˉ or Clˉ be present in the
PbAgSn (Ivanov et al., 2000b) electrolyte, then a Pb alloy with 2–4% Tl was most resistant.
PbAgAs (Ivanov et al., 2000b) PbAgSn has good chemical but poor mechanical strength (Casson and Hampson, 1978b).
PbSbAs (Bagshaw, 1995) The two main effects of As in this alloy are an increased rate at which age-hardening occurred and also the creep
resistance was improved, which had a positive knock-on effect on durability. In fact this alloy experiences less creep
than PbCaSn.
PbCaSn (Prengaman, 1999) Sn added to reduce corrosion and aid in formation of passive layer. Ca is added to improve the mechanical
properties.
PbAg–MnO2 (Barker et al., 2008) These anodes produce 50% less oxide scale that PbAg anodes and the overpotential could be reduced by as much
as 250 mV.
PbAgBi (Zhong et al., 2008a) When the Bi content of this alloy is increased the anode potential does reduce, with 5 wt. % Bi resulting in a potential
(Lai et al., 2009) lowered by 60–80 mV. However the Bi needs to be kept below 1 wt. % if corrosion is not to be accelerated. Optimum
composition was decided at: Pb–0.8Ag–0.8Bi.
PbBaSn (Bagshaw, 1995) Poor castability and Ba corrodes away, thus the active material is lost.
PbSrSn (Bagshaw, 1995) Much the same properties as its PbCaSn equivalents and as Sr can be expensive it was futile to explore its application
any further.
PbAgTl (Ivanov et al., 2000b) Tl helps to more evenly distribute Ag, therefore allowing this alloy to offer good protective characteristics and
resistance.
Pb(0.5)Ag(1.0)Tl (Ivanov et al., 2000b) This alloy is five times more resistant than its Pb(1.0)Ag equivalent.
PbAgSe (Ivanov et al., 2000b) PbAg alloys with a high quantity of Se will experience low corrosion. However this effect tapers with time.
PbAgTi (Ivanov et al., 2000b) This alloy has good resistance. The Ag helps to reduce Pb solubility in H2SO4 1.5 times. The best corrosion resistance
was for Pb–(0.75)Ag–(0.5)Ti.
PbAgCa (Ivanov et al., 2000b) Offers good resistance but this tapers off after time.
(Zhang and Houlachi, 2010)
PbBaAg (Ivanov et al., 2000b) These show promising initial results in terms of weight loss but a lot of slime is generated. On removal there are
PbSrAg (Ivanov et al., 2000b) signs of considerable alloy damage.
PbAgSb (Ivanov et al., 2000b) All three of these ternary alloys were designed by Tomas (1984) in an attempt to reduce the Ag content of the alloy
PbAgCu (Ivanov et al., 2000b) while also reducing the corrosion of Pb. Various functions of Ag have been proposed, such as: it prevents selective
PbAgMn (Ivanov et al., 2000b) dissolution of the Sb phase, it catalytically decomposes the persulphate ions and it helps the PbO2 layer to remain
adherent during corrosion (Canagaratna et al., 1977b).
PbCdSb (Azim et al., 1976) The Cd in this alloy is responsible for reducing steady state corrosion through alteration of the nucleation rate in the
former PbSO4 pores.
PbCaSn with Ag (Prengaman, 1999) Ag is known to improve the deformation and creep resistance of PbCaSn alloys markedly, whether the alloy is in a
cast or rolled state. It also reduces the corrosion rate in these alloys.
PbCaSn with Ba (Prengaman, 1999) Ba improves the mechanical properties and stabilises the grain structure, thus avoiding over-ageing or creep. By
stabilising the structure these alloys could avoid recrystallisation, grain boundary movement, microstructural in
stability and subsequent high temperature corrosion.
PbCaSn with Bi (Bialacki et al., 1984) The addition of Bi does not enhance the electrochemical properties of this alloy.
PbCaSn with Co (Prengaman, 2010) The Co addition reduces the anodic potential by 100 mV. This has potential to be a favourable additive, however
there are problems relating to alloying and homogeneity.
PbCaSn with Li (Shervedani et al., 2007) The Li additive reduces the rate of corrosion and prevents growth of the anodic Pb2+ film.
PbAgCaSr (Zhong et al., 2008b) Possible application was electrowinning of Zn but did not rate well in terms of operating potential and corrosion
(relative to PbAg). Oxide that formed was flaky and not well adhered to anode surface.
Pb–(3.5–5)Tl–(0.003–0.03) (Bray and Morral, 1941)
Te–(0.05–1.0)Ca
PbAgSnCo (Ivanov et al., 2000b) Showed the least corrosion in comparison to PbAg, PbAgBaAs, PbAgSr, PbAgAs, PbAgSn (in 1 M H2SO4 at 400 A/m2).
Pb–(1)Ag–(0.05) (Ivanov et al., 2000b) Both of these alloys produce an oxide that is twice as thick as that on PbAg anodes. The oxide is also denser.
Co–(0.04)Sb However corrosion is not significantly reduced.
Pb–(1)Ag–(0.05) (Ivanov et al., 2000b)
Co–(0.25)Sn
Pb–(0.4–0.5)Ag–(0.7–1.0) (Ivanov et al., 2000b) Proposed as an ideal alloy. Anode resistance is increased four times. Pb dissolution reduced five times.
Tl– (0.1)Ca
 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157 151

Table 4
Periodic table with respect to solubility in Pb in wt. %. The value beneath each element is the maximum solubility, e.g. the solubility of Cd is 3.29 wt. %. (Data adapted from Okamoto, 2010).

H Legend He
0 No Pb-X phase diagram available 0
Li Be 0 < wt.% soluble in Pb < 0.5 B C N O F Ne
0.1 0 0.5 < wt.% soluble in Pb 0 0 0 0 0 0

Na Mg Insoluble in Pb AI SI P S CI Ar
1.59 0.74 0 0 0 0 0 0

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0 0 0 0 0 0 0 0 0 0 0 0 0.15 0 0 0 0 0

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0 0 0 0 0 0 0 0 0 0 0.1 3.29 57.9 18.3 3.49 0 0 0

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Bi Po At Rn
0 0 0 0 0 0 0 0 0 0 0.19 26.4 90.1 Pb 25.2 0 0 0

Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Uub
0 0 0 0 0 0 0 0 0 0 0 0

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
0 0 0 0 1.09 0 0 0 0 0 0 0 0 0
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
0 0 0 0 0 0 0 0 0 0 0 0 0 0

3.5.9. Ce
Ce promotes a fine crystal grain structure (Liu et al., 2001;
Shervedani et al., 2007). When added to PbCaSn alloys Ce may offer
improved hardness, mechanical strength and possibly corrosion resis-
tance by preventing growth of the anodic Pb(II) or PbO2 film (Liu
et al., 2001).
3.5.10. Co
The addition of Co is a significant step in reducing the energy re-
quirements of the EW process and subsequently it has drawn consid-
erable attention from researchers. The favourable influence of Co in
Pb-based anodes was investigated as early as 1917 (Nikoloski and
Nicol, 2010).Technically, Co is not soluble in Pb and so a binary
PbCo anode is not possible. Various methods have been investigated
to develop a Pb–Co anode alloy. These include firstly alloying Co
with the like of Sn, Sb or Bi before alloying that with Pb. Other
methods include mechanical alloying or high temperature melting
of Pb and Co, followed by fast cooling. These have been met with
varying degrees of success and the introduction of new issues.
However, should Co be added in even a very small amount, it can
have a notable effect and the influence of Co can be realised by as lit-
tle as 50–300 ppm of Co (Koop et al., 1993). A 200 ppm addition to a
PbCaSn anode reduced the oxygen evolution potential by 150 mV
(Prengaman et al., 2010). A Pb-anode covered with a spray rolled-
(3 wt. %) Co containing surface layer reduced the oxygen evolution
potential by 90 mV (Keshavarz Alamdari et al., 2012). This was said
to be the equivalent effect as to adding 1% Ag.
Ideally, the Co would be added to the alloy itself, either as part of a
surface coating or embedded on/in the anode surface. RSR Technolo-
gies have designed a new PbCaSnCo rolled anode, where the Co is
continuously renewed at the anode surface. This means that the Co
is not lost due to bleeding of the system and so it remains on the
anode surface where it plays a positive role during PbO2 develop-
ment. This has notable economic benefits as the cost reduction can
be as much as $80,000 per tank house per year (Prengaman et al.,
2010). It should be noted that these projected savings are just that,
and have not been proven in industry to date. However, Prengaman
has patented a PbCaSnCo bulk alloy that is the most preferable option
as the homogenous distribution of Co within the alloy itself means
that Co will always be present at the surface (Prengaman, 2010).
While there is good agreement amongst researchers about the
positive influence of Co, the nature of the reaction mechanisms is
still unclear. Clarification is needed in relation to: the effect of adsorp-
tion of intermediate species that contain Co on the anode surface,
identification and characterisation of the active surface area of the
PbO2 layer and finally the role played by the Co redox couple
(Co 3+/Co 2+) in the catalytic reaction (Nikoloski and Nicol, 2010).
The advantages of Co are attributed to how it oxidizes on the
anode surface. The compounds that result from this process are
again catalytically decomposed throughout the anode surface. This
continuous process removes more of the current at the low Co 2+
levels. The protectiveness of this microsystem is due to the electro-
negative metals in the alloy acting as the anode, thus Pb is protected.
Nikoloski and Nicol suggest that Co alters the porosity of the PbO2
film to allow for better transfer of electric current to the underlying
anode (Nikoloski and Nicol, 2008). The positive attributes of Co were
suggested to be related to: Co catalysing the decomposition of Pb
persulphates, Co aiding the discharge of sulphate ions via Co2O3
which acts as an oxygen carrier and finally Co assisting in the produc-
tion of a presently unidentified impermeable film on the anode surface.
However, it is quite difficult to maximise the positive effects of Co
in Pb anodes as it is difficult to alloy due its low solubility in Pb. Not
only that but Co is prone to segregation to Sn-rich areas in the alloy,
so an even distribution cannot be guaranteed. It has been reported
that an increase in the Co content altered the morphology of the
PbO2 layer that formed and produced a thinner layer that was less
dense. This affirms the role of Co, i.e. that Co reduces Pb anode corro-
sion by increasing passivation. Therefore it is important that the Co
152 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157
influence is optimised but not exaggerated such that its net effect is
negative.
Once PbO2 has formed to any degree, the rate of Co3+ hydrolytic re-
duction is accelerated. The redox couple of Co3+ and Co2+ is adsorbed
at active sites of the Pb anode. The process that takes place is described
using Eqs. (5) and (6). The culmination of the reactions is reduced oxy-
gen potential.
2þ 3þ
CoðadsÞ −e↔CO ð5Þ
3þ 2þ þ the presence of Cu actually refined the grain structure or simply re-
4CoðadsÞ þ 2H2 O ¼ 4CoðadsÞ þ 4H þ O2 ð6Þ
The mechanism of oxygen evolution from the Co redox couple is fur-
ther explained with Eqs. (7)–(9), where either Eqs. (8) or (9) are said to
control the rate of the process.
Co
3þ
þ OH↔CoOH
2þ
ð7Þ
2þ 2þ
CoOH ↔2Co þ H2 O þ O ð8Þ
O þ O↔O2 ð9Þ
The addition of Co allows for the oxygen evolution to occur more
readily and at a lower potential (Nikoloski and Nicol, 2008). This
event, coupled with the concurrent oxidation of PbSO4, hides the ef-
fect of any mutations of the PbSO4/PbO2 interface (Koch, 1959).
Ivanov claimed that the reduced potentials could be attributed to Co
concentration at the anode surface (Ivanov et al., 2000a). During elec-
trolysis Co is deposited on to the Pb anode surface. This might only
take place to a small degree at certain potentials and it may also be
a reversible process. However, should it occur, it allows for the Co
to go into solution and the Co concentration at the anode surface to
rise.
Another interesting effect of Co, as alluded to by Koch, is that in
the absence of Co the final potential depends on the current density
at which the PbO2 layer forms (Koch, 1959). However when Co is
present the current density has less/no influence on the anode
potential.
Use of the Co3O4 compound is another means of maintaining a Co
presence at the anode surface, such that it can aid in reduction of the
anodic potential and oxygen evolution. Hrussanova has conducted
extensive research on these with regards to their anodic behaviour
(Hrussanova et al., 2001, 2004a, 2004b). These studies show that
use of this composite anode (with 3 wt. % Co) can result in a corrosion
rate that is 6.7 times lower than that of a PbSb alloy. This is due to the
Pb–Co3O4 anode having a depolarising effect on the oxygen evolution
reaction. The oxide formed on this composite anode is dense and
fine-grained, which is a marked improvement in comparison to the
loose oxide on the PbSb anode and the fibrous oxide on the PbCaSn
anode (Hrussanova et al., 2004a).
3.6. Summary of Co effect
To summarise the effect of Co: it reduces the anode overpotential
while catalysing the evolution of oxygen at the anode surface. Not
only does it reduce the level of anode corrosion but also PbSO4 forma-
tion and cathode contamination. The latter of these is due to the elec-
trocatalytic activity of the Co oxide (Pavlov and Monahov, 1998). The
oxide formed is thinner, more adherent and less sensitive to transfor-
mation to PbSO4. PbO2 formation is promoted over other potentially del-
eterious oxides. The cathode is less contaminated with Pb (Nikoloski and
Nicol, 2010) and the deposit is smoother, brighter and has a reduced
nodular size (Panda et al., 2009). Finally, corrosion at the anode may be
reduced by effective addition of Co3O4 on to the PbO2 layer.
3.6.1. Cr
Cr has a higher conductivity than Pb but still has a negative effect
on corrosion (Ivanov et al., 2000b). This must be due to a higher level
of chemical activity, perhaps involving anodic potential and current
distribution.
3.6.2. Cu
When 0.04 wt. % Cu is added to a Pb–(2–5 wt. %)Sb alloys there is a
notable grain refinement effect (Bagshaw, 1995; Rand et al., 2002)
due to the formation of a Cu2Sb compound. It is not definite whether
tarded grain growth (Barak, 1980).
3.6.3. Hg
Hg has a 26.37 wt. % solubility limit in pure Pb (Okamoto, 2010). Hg
causes an abrupt reduction in the electrical resistance of the anode
(Ivanov et al., 2000b). Like Au, it produces an oxide with a low
electroconductivity and so it does not act as a Pb protector.
3.6.4. La
La inhibits the oxygen evolution reaction, such that it prevents
growth of the protective oxide film (Li et al., 2009). However as a
rare earth metal, it has been shown to offer some favourable proper-
ties, e.g. grain refinement and reduced corrosion. La also reduces the
resistivity of the PbO2 surface layer.
3.6.5. Li
Li has a 0.1wt. % solubility limit in pure Pb (Okamoto, 2010). Li,
when added to PbCaSn reduces corrosion and prevents the growth
of the surface oxide layer. Li improves the crystal grain structure
without decreasing the hydrogen overpotential (Liu et al., 2001;
Shervedani et al., 2007).
3.6.6. Mg
Mg has a 0.743 wt. % solubility limit in pure Pb (Okamoto, 2010).
Mg increases the Pb oxidation rate (Prengaman, 2005).
3.6.7. Mn
Mn can often be present in the electrolyte in the form of Mn 2+
ions. In the EW of Zn it is deliberately added when there is not enough
of it present in the ore. However for Cu EW it is highly undesirable
and avoided as much as possible. Whatever the application is, the
amount of Mn present must be limited such that it does not negative-
ly influence the physicochemical properties of the electrolyte, i.e. the
conductivity, density and viscosity (Subbaiah and Das, 1994). Mn will
oxidise to MnO2 at potentials above 1.7 V (Tjandrawan and Nicol,
2010) and the amount oxidised will increase as the potential in-
creases. Should Mn react with PbO2, it can reduce it to PbSO4 as in
Eq. (10).
2þ þ
Mn þ PbO2 þ H2 SO4 ¼ MnO2 þ PbSO4 þ 2H ð10Þ
If the PbSO4 converts back to PbO2 the oxide will not have the
same morphology as the original oxide produced and this can intro-
duce structural weaknesses, in terms of the oxide being thicker, less
adherent, less stable and more likely to spall (Prengaman et al., 2010).
The positive effect of Mn 2+ is dependent on the alloy composition
and in some instances (on pure Pb), it cannot be realised without the
presence of Co (Nikoloski and Nicol, 2008). For Zn EW, the presence
of Mn 2+ ions reduce the oxygen overpotential and rate of anode cor-
rosion (Cachet et al., 1999). With respect to Cu EW, the corrosion rate
is three or four times higher in the presence of Mn 2+ ions in compar-
ison to no Mn 2+ ions in the electrolyte (Siegmund, 2007).
The dense, thin layer of MnO2 that can form on the surface of the Pb
anode can have good adherence and as it is non-conductive, it protects
 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157
the underlying anode (Tunnicliffe et al., 2012; Zhang and Houlachi,
2010). An anode that is coated in MnO2 has a significantly lower oper-
ating voltage than typical anodes (Eggett and Naden, 1975). However,
if excessive MnO2 forms on the anode surface it may not be sufficiently
adhered and it may spall from the surface, allowing it to contaminate
the deposit on the cathode or to form sludge in the tank, which would
reduce the cell efficiency. Also, if the anode is not polarised the MnO2
is soluble in the electrolyte and there could be contamination of the de-
posit at the cathode (Ivanov et al., 2000b).
3.6.8. Mo
While Mo additions to Pb reduce the corrosion of the alloy, the an-
odic film produced is an unstable flaky Pb oxide layer and so is unde-
sirable (Ivanov et al., 2000b).
3.6.9. Na
Na has a 1.588 wt. % solubility limit in pure Pb (Okamoto, 2010)
and can, according to Zhong, refine the grain size as the Na content
is increased (from 0.08 to 0.1 wt. %) (Zhong et al., 1996).
3.6.10. Nb
Nb has good mechanical strength but poor conductivity.
3.6.11. Nd
A 0.03 wt. % Nd addition to a Pb–Ag alloy can enhance the tensile
strength by ~ 21.8% and inhibit PbSO4 formation, thus reducing anode
corrosion. Nd also reduces the oxygen overpotential (Hong et al.,
2012).
3.6.12. Sb
Sb has a 3.492 wt. % solubility limit in pure Pb (Okamoto, 2010). Sb
offers great mechanical strength and creep resistance. Not only that,
but Sb increases the rate of oxidation of Pb at the grain boundaries
and at the surface (Prengaman, 2005). Sb promotes the growth of
hard, dense, glassy α-PbO2 (Prengaman, 1984a). An increase in the
Sb content increases the rate of corrosion (Tshimwanga et al., 2011)
and increases the thickness of the oxide layer (Ivanov et al., 2000b).
When used in acid battery cells Sb is known to leach out from the
anode, thus diminishing the performance of the anode while contam-
inating the electrolyte and possibly the cathode (Venugopalan, 1994).
3.6.13. Se
Se is a popular choice as a grain refiner (Bagshaw, 1995; Lyon, 2010;
Rand et al., 2002). It also increases the resistance of PbAg(Ca/Se) alloys
but this effect tapers with time due to dissolution of Ca/Se from the sur-
face layer (Ivanov et al., 2000b).
3.6.14. Sm
Sm has a 1.093 wt. % solubility limit in pure Pb (Okamoto, 2010).
The influence of Sm appears to be dependent on the amount that is
added to the Pb. Pb alloys with b0.1 wt. % Sm additions produce a
thicker oxide film with higher electrochemical impedance than that
of pure Pb. Sm has negligible influence on the conversion of PbSO4
to PbO2 during charging. Should more than 0.1% Sm be added howev-
er, the oxide film on the alloy surface is thinner and Sm promotes the
conversion of passive PbSO4 to conductive PbO2. A high Sm content
inhibits growth of the passivation layer and decreases its electro-
chemical impedance (Chen et al., 2007).
3.6.15. Sn
Sn has an 18.29 wt. % solubility limit in pure Pb (Okamoto, 2010)
and has many beneficial properties. Sn additions to Pb can reduce the
susceptibility to passivation, reduce corrosion and increase mechani-
cal properties, e.g. yield strength (Prengaman, 1984b; Rand et al.,
2002; Schlesinger et al., 2011). Additions of Sn reduce the anodic po-
tential and increase the grain size (Prengaman, 1997). Sn decreases
153
Fig. 7. Effect of increasing temperature and current density on the overpotential in 1 M H2SO4
as adapted from Ivanov et al., 2000a.
the thickness of the PbO2 passivation layer (Miraglio et al., 1995;
Rand et al., 2002; Shervedani et al., 2007) and improves the conduc-
tivity of the aforementioned layer (Albert et al., 1997). In PbCaSn al-
loys the Sn can help to inhibit PbSO4 formation, thereby promoting
growth of the more conductive PbO2 layer (Slavkov et al., 2002; Xu
et al., 2006). The Sn concentration aids in regulation of O 2− diffusion
by limiting PbO growth and reducing O2 release (Rocca et al., 2006).
Sn improves the castability of PbSb alloys (Bagshaw, 1995), promotes
more homogenous distribution of elements that have low/negligible
solubility in Pb, e.g. Ag and Co, and then offers subsequent better pro-
tection (Ivanov et al., 2000b).
3.6.16. Sr
Sr additions do not cause for any significant increase in the anodic
potential. Sr helps to reduce the amount of oxide spallation, which in-
creases the lifetime of the anode while improving the cathode purity
(minimising Pb contamination). Sr improves the crystal grain struc-
ture without decreasing the hydrogen overpotential (Liu et al.,
2001; Shervedani et al., 2007).
3.6.17. Te
A 0.01–1.0 wt. % addition of Te to Pb can offer grain refinement,
corrosion resistance and an accelerated oxygen evolution reaction
(Guo et al., 2009).
3.6.18. Ti
Ti has good mechanical strength but a conductivity that is five
times lower than that of Pb and so it increases the rate of Pb corrosion
(Ivanov et al., 2000b).
3.6.19. Tl
Tl has a 90.08 wt. % solubility limit in pure Pb (Okamoto, 2010). Tl
results in a finer grained Pb microstructure. Tl helps to more evenly
distribute Ag, such that it can provide better protection (Ivanov
et al., 2000b). The rate of Tl dissolution in acids is practically indepen-
dent of acid concentration. Tl helps to improve the mechanical
strength of the anode.
3.6.20. W
W produces an unstable flaky Pb oxide layer. It has the required
mechanical properties but low conductivity (Ivanov et al., 2000b).
3.6.21. Zr
Zr offers excellent corrosion resistance in acid sulphate solution as
it forms its own oxide layer (Zhang and Houlachi, 2010).
154 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157
3.7. Other influencing factors
For completeness, the operating temperature and current density
are considered with respect to optimising the performance of the Pb
anode. Currently, there is growing demand for tank houses to be
able to operate at higher current densities as this offers a higher
space-time yield performance (Nieminen et al., 2010). However,
higher current densities demand higher power consumption (Das
and Krishna, 1996), which is further reinforcement of the need for
improved anode design. Irrespective of the demand to operate a cell
with an equal number of anodes and cathodes at a higher current
density, an increase in the current density in the cell is inevitable
when a third of the cathodes are routinely removed for stripping
the metal deposit, and so the current supplied to each anode in the
cell increases by approximately 33% until the cathodes are returned.
An increase in the current density could jeopardise the quality of
the deposit on the cathodes, and so it must be done in a carefully con-
trolled manner, so that the quality and quantity of the output is not
threatened. Very high current densities (over 800 A/m 2) are involved
in high impurity concentrations at the cathode. As higher current
densities are applied the risk of short-circuiting and anode passiv-
ation increases (Stelter and Bombach, 2010). The current density
can be increased, once care is taken to decrease the diffusion bound-
ary layer (δ) of the metal ions, by increasing the rate of agitation
around the cathode. Another option is to increase the rate of ion dif-
fusion. Cifuentes et al. have done extensive research on ways to in-
crease the current density and these methods have been based
primarily around better, more energy efficient cell design (Cifuentes
and Simpson, 2005; Cifuentes et al., 2004, 2006, 2007). It was
suggested that to reduce the energy requirements the anode needs
to be made of a more catalytic material, such that the reaction at
the anode would be less energy-intensive.
Maintaining the alloy microstructure at elevated temperatures is
critical to the anode success. In the case of the PbCaSn alloys this is
achieved by ensuring that the alloy contains enough Sn to react
with all of the Ca present, thus converting it to Sn3Ca as opposed to
Pb3Ca. It is widely accepted that increasing the temperature will
cause the rate of corrosion to rise but the exact relationship between
temperature and corrosion is dependent on the alloy composition
(Ivanov et al., 2000b). Prengaman has estimated that a 20 °C rise in
the temperature of the electrolyte can lead to a doubling of the corro-
sion rate (Prengaman, 1999). Regardless of the anode composition,
an increase in cell temperature will result in lower power consumption
(Das and Krishna, 1996) and a lower anodic overpotential (Cifuentes
et al., 2008; Panda and Das, 2001) and this is shown in Fig. 7 (Ivanov
et al., 2000a).
The rate at which the anode corrodes is directly related to the
temperature of the electrolyte and the current density that the cell
is operating at (Prengaman et al., 2010). An increase in either of
these parameters will result in a rise in the corrosion rate. The rise
in the temperature depolarises the oxygen evolution reaction and
causes more PbO2 to form. The temperature setting can also influence
the structure of the oxide that forms, with a temperature increase
contributing to looser oxide growth (Hrussanova et al., 2004a). An in-
crease in the temperature will have the same effect as increasing the
current density. At current densities in the range of 100 to 500 A/m 2
the PbCo3O4 anode experienced the least corrosion, followed by the
PbCaSn anode and finally the PbSb anode which experienced the
most corrosion (Cifuentes et al., 2011).
4. Summary and going forward
For new and improved alloys to be designed a holistic approach
such as that described in Fig. 8 needs to be taken. To consider any
changes to the conventional systems used in the tankhouses the ener-
gy consumption warrants concern as energy costs are increasing, and
Fig. 8. After reviewing the literature available on the design and electrochemical perfor-
mance of Pb-based alloys this figure has been constructed to illustrate what are deemed
to be key parameters to be considered when designing optimised Pb anodes.
in some countries, e.g. Australia, the introduction of a carbon tax
means that the costs of running an EW tankhouse are only increasing.
For a new anode to be worthy of serious attention it must have a
lower level of Pb dissolution in the electrolyte as this in turn could re-
duce Pb contamination of the cathode (Morimitsu et al., 2010). The
solubility of the anode in the electrolyte must also be considered as
should it be dissolved it could potentially get bled from the system
at some point and so the high performance effects are lost.
Of course, the first place to start with designing a new Pb alloy is
with materials that are already soluble in Pb. The periodic table,
with respect to this is presented in Table 5 with data that has been
added from Okamoto (2010). There are just 14 elements that are sol-
uble in pure Pb and in descending order of solubility there are: Tl, In,
Hg, Bi, Sn, Sb, Cd, Na, Sm, Mg, Au, Ga, Li and Ag. If any of these can/do
provide favourable characteristics they can be employed as potential
hosts for alloying other materials that have a positive influence on the
electrochemical performance of the alloy, but are not themselves sol-
uble in Pb. Solubility in Pb is not critical to the success of a new anode.
Co is a perfect example of an element that can offer improved perfor-
mance with only trace (ppm level) additions. However, these poten-
tial energy savings are still only in the early stages and to date, no
large-scale tests have been conducted on a commercial PbCaSnCo
anode alloy material. It should be re-iterated that these are very diffi-
cult alloys to produce with homogenous distribution of Co in the
alloy.
Any alternative anode must offer a reduced oxygen evolution po-
tential. While noble (precious) metals are an obvious choice for im-
proved design, they come with significant cost penalties. However,
should the energy savings be substantial this could outweigh the
cost of actually manufacturing the new anode. Other materials
worth researching further are the likes of Ce and indeed many other
of the rare earth metals groups. Ce has an electrode potential close
to that of Ca and it offers improved hardness, mechanical strength
and could possibly improve corrosion resistance (Liu et al., 2001).
Ni deserves further investigation as in other alloy systems Ni and Co
have a strong relationship, and they preferentially substitute for one
another. They are adjacent to each other on the periodic table and
as such are quite similar. At the moment, Co has only really been
assessed as an additive to the PbCaSn anode but the influence of Co
is very dependent on the anode composition (Panda et al., 2009) so
 M. Clancy et al. / Hydrometallurgy 131–132 (2013) 144–157 155

Table 5
Periodic table with respect to Pb alloys (highlighted in black) that have previously been manufactured and researched.

H He

Li Be B C N O F ne

Na Mg AI Si P S CI Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sh Te I Xe

Cs Ba la Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn

Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg Uub

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

it warrants further research for any other alloys that may show po-
tential for improved efficiency.
It is preferable if the element that can reduce the anode potential
segregated to the grain boundaries, which are known to have higher
level of chemical activity than the grain itself. In the grain boundaries
the element can offer heightened electrochemical performance and
subsequent protection of the anode via a number of methods such as
lowering the anode overpotential and favourably influencing growth
of an anodic film with a low electrical resistivity, while maintaining
good mechanical strength and creep resistance.
In an effort to better understand the influence of the alloy compo-
sition on the electrochemical performance of the anode more efforts
need to be made to characterise the morphology, density and thick-
ness of the oxide that grows on the anode and also the microstructure
of the underlying Pb-based alloy. At present this information is severely
lacking. Also, the most popular data presented in the literature reviewed
is cyclic potentiodynamic polarisation curves but chronopotentiometry
(galvanostatic) assessments need to be included in an effort to validate
any findings. This is critical as some alloying elements, such as Se, suffer
a tapering effect, with initial benefits diminishing to such an extent that
they become negligible over a prolonged period of time. Longer term
galvanostatic tests are a more true representation of the cell and as
such this test is critical for determining what alloys are worth pursuing
as potential alternatives.
Given the almost infinite number of Pb alloys that could be pro-
duced, the void in terms of microstructural data in the scientific do-
main and the massive impact that elements added in trace amounts
can have on the electrochemical performance, there is definite
scope for design and characterisation of new and improved alloys
for the EW industry.
Acknowledgements
The financial assistance of BHP Chile and the Australian Research
Council (LP100200140) is gratefully acknowledged.
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