Hydrometallurgy 54 2000.

91106
www.elsevier.nlrlocaterhydromet

Continuous electrowinning of zinc

A.E. Saba ) , A.E. Elsherief
Electro Metallurgy Lab. Central Metallurgical R&D Institute, P.O. Box 87, Helwan, Cairo, Egypt
Received 1 March 1999; accepted 1 August 1999

Abstract
Synthetic and pure zinc solution produced from laboratory leached oxidised zinc ores, under
controlled temperature and pH were subjected to continuous elctrowinning operations until the
least possible zinc concentration was reached. Conventional DC electrolysis technique, PC and
PCR procedures were examined. The effect of organic additives and some of the impurity foreign
cations were also investigated. Current efficiencies of more than 95% were obtained from acid
sulphate solutions electrolysed at 45 mA cmy2 and 258C for DC and PC techniques. Electrowinning of zinc from relatively concentrated solutions 160 g dmy3 . could be achieved, successively,
with acceptable current efficiencies down to a concentration of 40 g dmy3. Copper additives were
found to decrease the current efficiency and worsen the quality of the cathode deposits.
Manganese and silica were found to have limited effects on both current efficiency and
morphology of the deposit. Iron was found to have a deleterious effect on both the current
efficiency and the deposit features. Organic additives, gelatine and thiourea, have good leveling
effects on the cathode deposits. Gelatine was found to improve the current efficiency especially in
the presence of a mixture of foreign cations. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Zinc; Electrowinning; Current efficiency

1. Introduction
Zinc ores, present at Um Gheig, in the eastern desert of Egypt, are found mainly as
oxidised ore containing willemite ZnSiO4 ., hemimorphite ZnSi 2 O 7 OH. 2 P H 2 O. and
smithsonite ZnCO 3 .. This ore was leached by sulphuric acid in a two-step technique
under controlled temperature and pH w13x. The coagulated silica produced by this

Corresponding author. Fax: q20-202-5010639; e-mail: rucmrdi@rusys.eg.net

0304-386Xr00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 9 9 . 0 0 0 6 1 - 4

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

92

treatment was filtered off. The leached liquor obtained contains, besides zinc, different
amounts of Cu, Fe, Mn, Mg, Co and SiO 2 . Many of these cations were removed by the
normal purification techniques w3x but traces of Fe, Cu, Mn and SiO 2 are still present.
Some of these impurities, i.e., Cu and Fe are more noble than zinc, and will be
co-deposited with zinc during electrolysis and serve as micro-cathodes upon which
hydrogen is evolved w48x. They affect negatively the cathodic current efficiency C.E..
and the quality of the electro-deposited zinc w9x. Winand w10x showed that the quality and
type of the deposits depend on many factors such as the current density, temperature,
pH, the presence of impurity cations and anions, inhibitors and type of substrate used.
Das et al. w11x, showed that a considerable energy saving in the electrowinning processes
could be achieved if the operating current density is increased, whilst maintaining high
current efficiency C.E.. and cathode quality. During electrowinning operations, zinc is
depleted in the electrolyte solution, while acid is increased; this will affect badly the
quality of the cathode deposit and greater acid mist formation, especially when using
high current densities. Many types of organic additives have been investigated w6,1217x
by several authors, to improve the cathode quality and to prevent the acid mist formation
w12,16,18x. Some of these additives were used as leveling agents. Appropriate amounts
of these additives w6,8,14,19x were found to be necessary for the formation of fine
grained, smooth and compact deposits.
Usually the current density applied to the electrolysis process is restricted by the
limiting current, beyond which serious deterioration in the quality of the cathode deposit
is achieved. Pulsating current PC. and periodic current reversal PCR. are two
techniques developed to permit the possibility of increasing the current density while
decreasing the concentration of the metal-bearing solution during electrowinning, without affecting the cathode quality w20x. The interruption of the current flow, in PC, and
the change of polarity, in PCR, greatly decrease the concentration gradients at the
electrodeelectrolyte interface, The effective current density with PC and PCR are equal
to:
i eff s i = TrT q T X
for PC; and
i eff s i = T y T XrT q T X
for PCRwhere: i s current density, A my2 ; i eff s effective current density, A my2 ;
T s forward time, seconds; T X s dead period or duration of reversal current, seconds.
The factors and relations governing the different variables like the period of pulse,
dead and reversal periods, concentrations, rate of diffusion, etc., have been thoroughly
investigated w20x.
The aim of this article is to study the continuous electrowinning of zinc from
concentrated solutions, and the determination of the reduced zinc concentration at which
electrowinning has to be stopped and the electrolyte has to be recycled as a leach
solution. Also, a study of the effect of the presence of copper, iron, manganese and silica
impurities, and gelatine and thiourea additives on the efficiency and morphology of the
cathodic zinc deposits was made.

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

93

2. Experimental
The electrolysis cell consisted of a Pyrex 500 ml beaker with a Perspex cover holding
the electrodes and powder feeder w3,20x. Aluminum strips, 40 cm2 surface area, were
used as cathodes. Two platinum sheets, measuring 4 = 5 cm were used as anodes placed
on either side of the cathode, sheathed in bags of polypropylene cloth to prevent MnO 2
sludge from contaminating the bath, when manganese salts were added to the electrolyte. All experiments were performed at 25 " 18C at constant stirring. The electrolyte
used, 250 ml, was prepared by the double leaching of Egyptian oxidised zinc ore,
purified by air, to oxidise the iron content, and then with the zinc powder addition
technique. The solution obtained after the purification steps usually contains iron, 25 mg
dmy3 , copper, 0.2 mg dmy3 , manganese, less than 0.1 mg dmy3 and silica in negligible
amounts. Sulphuric acid and distilled water were added to get the desired electrolyte
composition. Foreign cations i.e., iron, copper and manganese, as the sulphate salts
while silica as SiOH. 2 were added to the purified solution to get the desired composition. Gelatine and thiourea were dissolved in the electrolyte before experiments. All the
chemicals used were of analytical grade.
During electrolysis, the concentration of zinc was adjusted by the addition of
prepared ZnOH. 2 through the feeder, at intervals of time, so that the concentrations of
zinc and sulphuric acid in the electrowinning cell were kept constant.
An electronic pulse-control unit was used w20x which provides pulse duration from 1
to 180 s for on and off or reversal intervals.
Cyclic voltammetry measurements were carried out by the aid of a Wenking
Potentioscan POS 73. They were conducted in a Pyrex glass cell employing a carbon rod
counter electrode. The working electrode was an aluminum wire mounted in epoxy
resin, with a cross-section area of 0.049 cm2 . Potentials were measured relative to a
mercurymercurous sulphate electrode using Luggin capillary and a bridge filled with
the working solution. The voltage and current changes were followed through a system
connected to the potentioscan.
Prior to the electrolysis experiments, the electrodes were degreased with acetone and
washed thoroughly with distilled water.
The cathodic current efficiency was determined as the ratio of weight of metal
actually deposited by passing a definite quantity of electricity W X . to the theoretical
weight that would be deposited by that quantity of electricity according to Faradays law
W .:
W s I = t = 32.69r26.8 A h
where I s electric current passed in amperes; T s time in hours; 32.69 s equivalent
weight of zinc; 26.8 s quantity of electricity needed to produce an electro-chemical
change of 1 g-equivalent of a substance.
If W X is the weight of the metal actually deposited at the cathode, then
Current efficiencys W XrW . = 100.
The surface morphology and microstructure of the electro-deposited samples were
examined by scanning electron microscope SEM..

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A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

3. Results and discussions

3.1. Cyclic oltammetry
Cyclic voltammetry experiments of zinc electro-deposition from 120 g dmy3 Zn and
50 g dmy3 H 2 SO4 solution, on aluminum substrate, were carried out. The cathodic
potential was varied in the range from y900 to y1700 mV at a scan rate of 20 mV sy1 .
The linear sweep curves that represent the onset of cathodic deposition and redissolution
of the deposited zinc are shown in Fig. 1. The cathodic curve can be attributed to both
zinc deposition and hydrogen evolution reactions. Zinc deposition commences at y1550
mV. The crossover potential, the point of zero net current, is reached at y1435 mV,
representing the equilibrium potential. The anodic curve, on the other hand, corresponds
to the dissolution or stripping of the deposited zinc. When stripping is complete, the
anodic peak reaches the original starting potential. The region BCD is properly called a
nucleation hysteresis loop w21x.
Cyclic voltammogram due to current sweep, at a scan rate of 16 mA sy1 , with the
same conditions is given in Fig. 2. The difference in the potentials of zero current in the
cathodic and anodic direction of the sweep reflects the changes in the potentials due to
changes in zinc concentration near the aluminum substrate. Also the change in the

Fig. 1. Potentialsweep cyclic voltammograms for zinc deposition and stripping on Al electrode 0.049 cm2 .,
from 120 g dmy3 Znq50 g dmy3 H 2 SO4 solution at 258C scan rate 20 mV sy1 ..

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

95

Fig. 2. Currentsweep cyclic voltammograms for zinc deposition and stripping on Al electrode 0.049 cm2 .,
from 120 g dmy3 Znq50 g dmy3 H 2 SO4 solution at 258C scan rate 16 mV sy1 ..

character of the aluminum substrate due to the deposition of zinc and the changes in its
behavior to the evolution of hydrogen is considered.
3.2. Potentiostatic
Fig. 3 shows typical results obtained by the potentiostatic method. Three different
curves were obtained by maintaining the cathode potential constant at y1400, y1500
and y1600 mV. The results obtained show that as long as the response current is
smaller than the limiting current, i l , its value does not change with time. A continuous
steady value was obtained at y1400 mV. A gradual increase in current was recorded at
y1500 mV, at the first stage of electrolysis, and then semi-steady state was reached. A
sharp increase in current was recorded at y1600 mV, showing that the response current
is in the region of the limiting current. This sharp increase in the current was related to
the progressive formation of a rough deposited zinc, with a large surface area.

Fig. 3. Currenttime curves for zinc deposition and stripping on Al electrode 0.049 cm2 ., from 120 g dmy3
Znq50 g dmy3 H 2 SO4 solution at 258C, at constant potential of: 1. y1400, 2. y1500 and 3. y1600 mV.

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A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

3.3. Galanostatic
The cathodic polarization of zinc electrowinning on aluminum substrate when being
subjected to different polarizing currents, ranging from 30 to 60 mA cmy2 , were
recorded as a function of time. Experiments were performed under two sets of
conditions, without stirring and with moderate stirring of the solutions. The results are
depicted in Fig. 4.
With stirred solutions, at 30, 45 and 60 mA cmy2 , curves I, II and III were obtained,
respectively, representing continuous potential plateaus at y1590, y1700 and y1720
mV, respectively. With non-stirred bath, at 45 mA cmy2 , the recorded potential plateau
is found at y1710 mV and lasts after 65 s, curve IV, followed by a sharp increase in the
cathodic polarization. This can be explained on the premise that the diffusion layer is
rapidly increased due to the slow zinc cation replenishment near the electrode surface as
a result of the decrease in convection of the ions in the solution. Also, the accumulation
of hydrogen bubbles on the electrode surface results in a sudden increase in the cathodic
overpotential.
3.4. Current efficiency
The change in cathodic current efficiency with variable applied current densities,
ranging from 30 to 60 mA cmy2 , was studied with electrolytes containing different
concentrations of zinc ions and free sulphuric acid. The concentration of zinc and acid
were kept constant. Experiments were performed for 3 h. The results obtained are
summarised in Table 1.
The above results show that the current efficiency is high, within the current densities
applied, for a wide range of concentrations for both zinc and sulphuric acid. The highly
convenient results were achieved with a current density of 45 mA cmy2 . The current

Fig. 4. Potentialtime curves for zinc deposition on Al electrode at: 1. 30, 2. 45, 3. 60 mA cmy2 with
stirred solution and 4. 45 mA cmy2 with non-stirred solution.

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

97

Table 1
Current density,
mA cmy2

Efficiency
%

Bath composition
g dmy3 Zn

g dmy3 H 2 SO4

30
45
60
30
45
60
30
45
60
30
45
60
30
45
60
30
45
60

94.5
96.1
97.2
95.8
96.6
96.9
96.3
97.2
97.0
92.3
92.8
92.1
83.1
88.3
87.5
61.5
63.2
64.2

160
160
160
120
120
120
65
65
65
50
50
50
40
40
40
40
40
40

40
40
40
50
50
50
90
90
90
150
150
150
80
80
80
270
270
270

efficiency decreased dramatically when zinc content in the electrolyte decrease to less
than 40 g dmy3 , and especially when sulphuric acid increases ) 80 g dmy3 . in these
experiments.
A long term experiment, using a fixed volume and one electrolyte, with a starting
composition of 120 g dmy3 zinc and 50 g dmy3 H 2 SO4 , was performed to determine
the minimum zinc concentration solution suitable for electrowinning, with acceptable
current efficiency. The electrolyte composition, Zn and H 2 SO4 , were analysed and
determined, at different intervals, during the experiment. The results obtained are
summarised in Table 2.
This experiment shows that continuous removal of zinc from the electrolyte, down to
around 40 g dmy3 , were achieved with current efficiency of more than 85%. Beyond
this concentration a very low current efficiency was obtained. Accordingly, solutions
with this range of zinc concentration - 40 g dmy3 . should be transferred to the
leaching vessel, to make use of its high acid content, for further dissolution of the ore.

Table 2
Current density,
mA cmy2

Period,
hour

Efficiency
%

45
45
45
45

3
4
4
3

96.6
93.4
86.3
53.1

Bath composition
Zn g dmy3
H 2 SO4 g dmy3
start
end of experiment
end of experiment
end of experiment

120
99.2
69.2
41.2

50
98.4
140.4
181.6

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A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

From the results of the above table, the variation of the zinc ion concentration with
time is depicted in Fig. 5. This figure reveals that at high concentrations the depletion
rate of zinc is approximately linear and tails off as the concentration of zinc reaches 40 g
dmy3 . After this the concentration decays near exponentially according to the well-known
expression for a reactor with a diffusion-limited reaction w22x.
3.4.1. Morphological examinations
The surface morphology of the deposits electrowon from different concentrated
electrolytes, at a current density of 45 mA cmy2 , were inspected by SEM. These
pictures show that zinc occurs mainly in acicular crystalline form parallel to the
substrate. At moderate concentrations 160 g dmy3 Zn and 40 g dmy3 H 2 SO4 . mossy
structures were seen around the edges. By changing the concentration, i.e., lowering zinc
and increasing acid concentrations, these features were changed, where the mossy-like
structures predominate. Fig. 6a shows that the acicular and needle-like platelets are still
present beside the mossy structure. As the zinc concentration decreases and the acid
increases, more fine deposits, composed of the same features, but in finer form were
obtained.
On increasing the applied current density to 60 mA cmy1 , Fig. 6b, coarser platelets
were obtained. This can be related to the absorption and adsorption of the evolved
hydrogen, a process which increases with the increase of the applied current density on
the active sites and thus preventing the formation of increased number of nucleation
sites. This enables the zinc to be deposited on lesser number of nuclei that cause the
deposited crystals to grow.
The above mentioned morphology can be explained according to Winand w10x who
shows that in the absence of organic additives, the inhibition intensity may be charac-

Fig. 5. Concentration variations of zinc and sulphuric acid in the bulk solution during a long term electrolysis
experiment c.d.s 45 mA cmy2 ..

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

99

Fig. 6. Scanning electron micrographs of zinc deposits from: a. 40 g dmy3 Znq80 g dmy3 H 2 SO4 at 45 mA
cmy2 ; b. 50 g dmy3 Znq150 g dmy3 H 2 SO4 at 60 mA cmy2 . =1000.

terised by the relation between the exchange current density, which is a function of the
apparent cathodic current density J and the diffusion limiting current density Jdl . He
showed that the lower the J, the higher the inhibition intensity and the smaller the
crystals deposited. He also showed w13x that, with high concentrated electrolytes, the
value of Jrc where c is the concentration. is low, and the crystals formed are FI
field oriented isolated crystals. and BR oriented repeated crystals.. With the

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A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

decrease of zinc concentration, Jrc increases, and FI begins to predominate with

dendritic powder; and hydrogen evolved in much larger amounts, consuming electricity
and decreasing current efficiency.
3.4.2. Gelatine additions
Different ratios of gelatine from 50 mg dmy3 to 2 g dmy3 were added to different
electrolytes with zinc concentration ranging from 160120 and 50 g dmy3 H 2 SO4 . The
addition of gelatine at such concentrations was found not to affect the current efficiency
obtained, agreeing with that obtained with electrolytes free of gelatine. On the other
hand, gelatine was found to smoothen the electrodeposited zinc, Fig. 7. This effect is
highly pronounced with gelatine concentration of 50 mg dmy3 . The deposited zinc
become fine grained with much smaller crystals. The positive effect of gelatine on the
structure of the cathodic zinc is related to its nature, which is a protein high polymer of
amino acids linked by peptide chain CONH . w15x. Small amounts of gelatine are
enough to improve the quality of the cathodic deposit. Such long chain peptide forms
adsorbed layers which increase the cathodic polarisation of zinc and thus improve the
quality of the metal deposit. This polarising effect of gelatine was studied by the same
authors w3x by cyclic voltammetry using acidified zinc sulphate electrolytes and in the
presence of different ratios of gelatine ranging from 50 to 2000 mg dmy3 . The results
obtained showed that the addition of gelatine to the acid sulphate zinc solution caused a
marked progressive polarisation. The polarisation was very pronounced at 50 mg dmy3
gelatine addition. On further increase of the gelatine additions, the rate of increasing
polarisation was found to decrease. This high polarisation was related, on the same basis

Fig. 7. Scanning electron micrographs of zinc deposits electrowon from 50 g Znq150 g H 2 SO4 q50 mg
gelatine Iy1 at 45 mA cmy2 , X s1000.

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

101

mentioned before, to the build up of adsorbed layers of gelatine at the electrode surface,
which hinders the further diffusion of zinc ions.
3.4.3. Thiourea addition
As gelatine is reported w13x to have no influence on preventing the nodulation growth
of electrodeposits, thiourea, which has been reported to decrease nodular growth w14x,
was added in addition to gelatine in a concentration of 0.01 g dmy3 . The surface
morphology of the zinc precipitate was found to be good, as with gelatine alone. The
current efficiency was not affected with experiments up to 19 h under conditions of
constant zinc and acid concentration.. Thiourea was expected to lower the possibility of
nodular formation for long-run industrial scale processes.
3.4.4. Effect of PC and PCR
As PC and PCR techniques are used to improve the morphology of the electrodeposits, especially at high current densities, these two techniques were tested with the
electrodeposition of zinc.
A time span of 50 s forward current and 5 s for cut off or reversing the current
polarity for the PC and PCR techniques were selected and used. This pulse duration, 50
s, was chosen as less than the time required to reach the transition time, with non-stirred
solution, determined earlier i.e., 65 s, Fig. 4.
Galvanostatic electrowinning experiments were studied using the PC and PCR
techniques. The potential-time relationship obtained, on applying 45 mA cmy2 for the
forward period, are given in Fig. 8a. and b. for the PC and PRC, respectively.
With PC technique, Fig. 8 curve a., on passing the current the cathodic polarisation
is increased to a sufficiently negative value forming a plateau at about y1720 mV. On
switching off the current, the potential rapidly reaches the ZnrZn2q equilibrium value,
y1480 mV, determined earlier Fig. 1.. It was found that the 5 s off period is sufficient

Fig. 8. Potentialtime curves for zinc deposited on Al electrode 0.049 cm2 ., from 120 g dmy3 Znq50 g
dmy3 H 2 SO4 at 45 mA cmy2 , with pulse cycles of 50:5 s. a. PC and b. PCR.

102

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

to restore the equilibrium potential of zinc. By repeating the above cycle, semi-steady
cathodic potential of y1720 mV was reached in subsequent pulses.
Results obtained with PCR technique, Fig. 8 curve b., show that when the polarity of
the cathode was reversed, for 5 s the potential rapidly passed the crossover potential
y1480 mV. and reached y1250 mV. Cathodic polarisation values remained almost
constant, ; 1720 mV, with repeated cycles.
The two techniques were then examined for both the current efficiency and precipitate morphology. Experiments were conducted for 3 h. The results obtained with
different bath compositions are summarised in Table 3.
These results show that the current efficiencies obtained, with all the experiments
conducted, are high with the PC technique, even compared with those obtained with the
DC experiments. PCR, as expected, gives lower efficiencies. This is related to the
re-dissolution of the cathodic zinc electrodeposited during the reverse cycle, which
represents a negative use of current and energy.
A long-term experiment with PC technique was performed, under the same conditions applied before, to determine the lowest concentration at which electrowinning of
zinc should be stopped, when applying the PC technique. The results obtained are
summarised in Table 4.
The table shows similar general trend to that obtained with DC experiments, Table 2.
Solutions with ; 65 g Zn dmy3 and high acid concentrations of about 130 g dmy3 ,
should not be subjected to further electrowinning, otherwise very low current efficiencies will be obtained. Such solutions should be returned for the second stage of leaching
of the ore.
3.4.4.1. Morphological examinations. The main advantage of using PC and PCR
techniques is their production of highly compact zinc deposits. These deposits are found
to be more homogeneous and adherent than those obtained with the DC experiments.
The morphological features obtained are the same for both PC and PCR. The zinc
deposits obtained were found to have smaller crystals with smooth edges than those
obtained with DC technique and can be compared with those obtained with the presence
of gelatin, Fig. 7. This can be related to the chemical dissolution effect acting on the
crystal edges during the cutting off or reversing the current. Also, during electrolysis, the

Table 3
Current density,
mA cmy2

Technique

Period,
hour

Efficiency
%

Bath composition
g dmy3 Zn
g dmy3 H 2 SO4

60
60
60
45
45
60
60
60

DC
PC
PCR
DC
PC
DC
PC
PCR

3
3
3
3
3
3
3
3

96.0
98.75
81.27
96.6
97.0
63.2
72.8
48.14

160

40

120

50

40

270

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

103

Table 4
Current density,
mA cmy2

Period,
hour

Current
efficiency %

Starting bath composition

g dmy3 Zn
g dmy3 H 2 SO4

45

3
4
4
4

98.7
94.4
86.5
55.2

120.0
96.3
65.7
38.0
E a 20.4

50
84.9
129.2
170.0
196.0

E s End of experiment.

HSO4y and SO42y anions are strongly adsorbed at the cathode surface during the off
time, in the PC technique. This blocks the growth centers at the cathode and forces the
creation of new nuclei at each new pulse, with the formation of fine-grained deposits
w14,20x.
3.4.5. Effect of foreign cations
3.4.5.1. Effect of copper. Three different copper concentrations namely 6.2, 12.5 and 20
mg dmy3 Cu were made up in a solution containing 120 g dmy3 zinc and 50 g dmy3
H 2 SO4 in order to determine their effect on the efficiency and quality of electro-deposited zinc. Electrolysis was performed for 4 h, at a current density of 45 mA cmy2
and at 258C.
The current efficiencies were 96%, 91% and 88%, respectively. Cathodic polarisation
of zinc in the presence of copper was found by the authors w3x to decrease with the
copper concentration in the solution. In addition, copper was found to activate the
dissolution of electrodeposited zinc. This explains the decrease in efficiency obtained
with the increase of copper content in the electrolyte.
The morphological examination of electrodeposited zinc in the presence of copper,
shows that the deposit is dull and dark. This effect is more pronounced with the increase
of copper content in the electrolyte. This can be explained on the basis that copper is
reduced to the metallic state, electrolytically, prior to zinc and co-deposited with it.
Copper was found to decrease the grain size of the electrodeposited crystals of zinc.
3.4.5.2. Effect of iron. The voltammograms obtained for zinc electrodeposition, in the
presence of different proportions of iron ranging from 50 to 150 mg Fe dmy3 as were
studied earlier w3x, show that the cathodic current efficiency of zinc deposition decreases
with the increase of the iron concentration in the electrolyte. With 50 mg dmy3 Fe, the
current efficiency obtained was 82%, under the same conditions applied with copper
additions. A more dramatic decrease in efficiency was obtained with 150 mg dmy3 Fe,
where an efficiency of 53% was obtained. This decrease in efficiency was related to the
reverse redox system of Fe 2qrFe 3q taking place at the two electrodes, consuming high
amounts of electricity.
Iron was found to have a pronounced effect on the morphology of the electro-deposited zinc. Coarse crystalline deposits of large separate polyhedral needles and

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A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

upward-growing zinc pyramidal dendrites were obtained, Fig. 9. This worsening of the
properties of the zinc deposit, in addition to the decrease in the current efficiency, shows
that iron should be removed, if possible, from the electrolyte during the leaching step of
the ore.
3.4.5.3. Effects of manganese and silica. The presence of manganese, 0.9 and 1.8 g
dmy3 Mn, caused little increase in the polarisation of zinc in sulphate solutions w3x. This
effect may be attributed to the accumulation of the manganese cations near the cathode
surface, which hinder the approach of zinc cations. The proportions of manganese added
were found to have no effect on the current efficiency of the electrodeposited zinc, under
the conditions applied. The presence of manganese, on the other hand, in the range of
1.53 g dmy3 , was reported to be required in the electrolyte to minimise the lead anode
corrosion w8x.
Colloidal silica, in the proportions of 33 to 165 mg dmy3 SiO 2 , was added and found
to give little decrease in cathodic polarisation w3x. It was found to have nearly no effect
on the current efficiency in the range studied.
The presence of manganese was found to decrease the size of zinc grains electrodeposited. Zinc platelets with random orientations were clearly observed.
The presence of 33 mg dmy3 silica gave compact, smooth and round edges of the
electro-zinc precipitate obtained.
3.4.5.4. Effects of mixture of foreign cations. A mixture containing 10 mg Cu, 1.8 g Mn
and 165 mg dmy3 silica was added to the electrolyte. This mixture was found to have a

Fig. 9. Scanning electron micrographs of zinc electrodeposits in presence of Fe cations at different current
densities, electrowon from 50 g dmy3 Znq150 g dmy3 H 2 SO4 q40 mg dmy3 Fe at 80 mA cmy2 . =1000.

A.E. Saba, A.E. Elsheriefr Hydrometallurgy 54 (2000) 91106

105

decreasing effect on the current efficiency 82.5%.. The electrodeposit obtained was full
of cavities and holes. Small fine-grained, scattered nodules and spongy dendrites were
also found.
Addition of gelatine, 50 mg dmy3 , improves the current efficiency of the electrodeposited zinc 88.3%.. The deposit obtained becomes continuous and covers the whole
electrode surface, with small grain sizes. A transition from dendritic to boulder type and
the marks of dendritic growth disappear.
Using the PC technique yields very fine, smooth and compact Zn deposits. Moss
formations formed with free electrolytes, or powdery and dendritic and nodules deposits
obtained with the presence of mixtures of foreign cations were suppressed.

4. Conclusions
The effects of zinc, free sulphuric acid concentrations and current density on the
current efficiency and morphology of electrodeposited zinc were studied. The minimum
zinc concentration at which electrowinning should be stopped was determined and found
to be in the range of 40 gm dmy3 with a sulphuric acid content of ) 150 gm dmy3 .
Addition of gelatine, in the range of 50 mg dmy3 was found to improve the quality of
electrodeposited zinc. PC and PCR techniques were examined. PC was found to be more
suitable for the electrowinning of zinc than the PCR, as it improves both the current
efficiency and quality of the deposit. The effect of the presence of Cu, Fe, Mn and silica
in the electrolyte media was studied. Copper and iron, even at low concentrations, were
found to decrease the current efficiency and worsen the quality of the electrodeposited
zinc. Both of them should be removed during the purification steps to avoid their
harmful effect.

Acknowledgements
The authors gratefully acknowledge the considerable assistance of Mrs. N. Elhusseiny
in the experimental work.

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