Hydrometallurgy 133 (2013) 5863

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Hydrometallurgy
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Effect of additives on monovalent copper electrodeposition in ammoniacal

alkaline solutions
T. Oishi a,, M. Yaguchi a, K. Koyama a, 1, M. Tanaka a, J.-c. Lee b
a
Metals Recycling Group, Research Institute for Environmental Management Technology, National Institute of Advanced Industrial Science and Technology (AIST),
16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan
b
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 124 Gwahang-no, Yuseong-gu, Daejeon 305-350, Republic of Korea

a r t i c l e

i n f o

Article history:
Received 23 August 2012
Received in revised form 19 November 2012
Accepted 29 November 2012
Available online 6 December 2012
Keywords:
Monovalent copper electrolysis
Additive
Surface roughness
Copper recycling
Ammoniacal solutions

a b s t r a c t
In order to reduce the surface roughness of a copper deposit from cuprous ions in ammoniacal alkaline solutions, optimization of the electrolytic conditions was attempted, and the surface roughness was somewhat
improved. Because the improvement was insufcient, the addition of gelatin or polyethylene glycol (PEG)
to the electrolyte was then examined. It was revealed that both additives effectively polarized during copper
electrodeposition and that the extent of the polarization increased with the molecular weight of the additives. As a result, both surface roughness and crystal size of the copper deposit were reduced. In the case of
PEG, however, nodules tended to form and gelatin was concluded to be superior to PEG as an additive for
the present electrolysis. The inuence of gelatin on the impurity content of the copper deposit was also investigated, and the addition of gelatin was found to have a positive effect on reducing the lead content. This is
important because lead is the most important impurity in the authors' copper recycling process employing
the present electrolysis.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Our research group has been developing a copper recycling process
from used appliances (secondary resources) using monovalent copper
ions (Cu(I)) and ammoniacal alkaline solutions (Alam et al., 2007;
Koyama et al., 2006; Oishi et al., 2006, 2007, 2008). In this process,
metallic copper in secondary resources such as printed circuit boards
is recovered via the following steps: (1) metallic copper is leached as
monovalent copper ions (Cu(I)) using divalent copper ions (Cu(II)) as
the oxidizing reagent in an ammoniacal alkaline solution, (2) impurities
including lead and zinc are removed from the solution by solvent extraction or other techniques, and (3) the puried solution is subjected to an
electrowinning step in which metallic copper and Cu(II) are formed on
the cathode and anode, respectively, from Cu(I). The Cu(II) formed is
then reused as the oxidizing reagent at the rst leaching step. The advantages of this process are the low electric power requirement during
the electrowinning step due to the use of monovalent copper electrolysis and the low cell voltage (Koyama et al., 2006), as well as the potential
to obtain a high-purity copper directly from the secondary resources
such as printed circuit boards (Oishi et al., 2007). In addition, the ammonia/ammonium chloride solution is regarded as one of the alternative

Corresponding author. Fax: +81 29 861 8481.

E-mail address: tetsuo.oishi@aist.go.jp (T. Oishi).
1
Present address: Department of Mechanical Science and Engineering, Faculty of
Engineering, Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba
275-8588, Japan.
0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2012.11.015

solution candidate for copper electrorening (Brown et al., 1981) because

of the low electric power requirement. Although these researchers
concluded that a sodium chloride/hydrochloric acid solution, which is
another examined candidate, is superior to an ammoniacal solution, the
copper deposit obtained from the ammoniacal solutions was smooth,
coherent, and incorporated no dendrites. Their observation concerning
the copper deposit is consistent with that of the present authors (Oishi
et al., 2007), and these characteristics are advantageous for practical
application to both copper recycling and electrorening processes.
In our preliminary examination, however, it was found that the
copper deposit became rough under harsh conditions, i.e., weak convection, long-term electrolysis, and high current density. Because these
conditions are generally preferable for a commercial operation from
the perspective of reducing running costs and maximizing productivity,
it is important to nd solutions that yield a smooth deposit even under
such harsh conditions. During the conventional copper electrorening
process using copper sulfate/sulfuric acid solutions, additives such as
glue, thiourea, and chloride ions are used in order to improve the
surface morphology of the deposit. These additives are used for a
prolonged period; however, the way in which these additives function
during the electrolysis is not fully understood. Thus, a number of fundamental and/or systematic studies have been undertaken by several
researchers (e.g., Alodan and Smyrl, 1998; Ando et al., 2002; Nakano
et al., 2003), as well as research into alternative additives (Stelter et
al., 2002; Varvara et al., 2001) and similar studies into zinc electrowinning (e.g., Karavasteva and Karaivanov, 1993; Kerby et al., 1977; Ohgai
et al., 1999). In addition, leveling and brightening effects are among the

T. Oishi et al. / Hydrometallurgy 133 (2013) 5863

2. Experimental
The copper electrodeposition was conducted in a rectangular vessel
(50 mm130 mm90 mm [h]), which was divided into two components by an anion exchange membrane (Tokuyama Company, Ltd.,
ACM) xed at the center of the vessel. The typical composition of the
electrolytic solution was 5 kmol m3 NH3, 4 kmol m3 NH4Cl, and
0.5 kmol m3 Cu2O. The typical Cu2O concentration, 0.5 kmol m3,
corresponds to a copper content of 64 kg m3, which is slightly higher
than that used in conventional copper electrorening, 4050 kg m3.
These concentration ranges were selected on basis of the results of our
past study reported previously (Oishi et al., 2006). Gelatin (Nippi, Inc. or
Wako Pure Chemical, MW=2.11021.1105) and PEG (Wako Pure
Chemical, MW=21022104) were used as additives at concentrations of 10 or 100 g m3. In order to evaluate the inuence on the impurity content, lead oxide (Wako Pure Chemical) was also added to the
electrolytic solution depending on the objective of the experiment. The
prepared solution was then stirred for 20 h with copper particles of
1 mm diameter along with Ar gas owing into the solution in order to
reduce the generation of divalent copper ions (Cu(II)), which were
formed by the unavoidable oxidation of Cu2O or Cu(I) during the solution preparation. Ar gas was also used to prevent the oxidation of
Cu(I) during the experiment. The anolyte contained 5 kmol m3 NH3

10

Surface roughness (Ra) / m

most important topics in the eld of electroplating from previous

years. Therefore, there are a number of papers concerning the use
of additives in these circumstances, and general aspects of this
process are described in books on electroplating (e.g., Kanani,
2004). According to a literature survey, however, most of the studies
concerning copper electrodeposition focus on acidic solutions such
as copper sulfate/sulfuric acid solutions, and the information about
ammoniacal solutions are quite limited. The paper by Ibrahim
(2000) is probably the only such paper available in the literature,
which describes the addition of sodium dodecylbenzenesulfonate
to an ammoniacal copper sulfate solution to yield a bright copper
deposit. This additive, however, is not a familiar one for copper
electrodeposition and has a certain level of toxicity.
On the basis of this background, we rst investigated the inuence of
the bath composition and current density on the surface roughness of
the copper deposit in order to obtain a smooth deposit without any
additives. Because the effects of the optimization of these variables
were found to be insufcient, we examined gelatin (puried glue) and
polyethylene glycol (PEG; one of the most viable potential alternatives
to glue) as additives (Nakano et al., 2006; Stelter et al., 2002). The
effectiveness of these agents was evaluated through electrochemical
measurements, observations of the surface morphology, and examination of the impurity content of the copper deposit.

(a)2.0
(b)4.0

(c)5.0

100

1000

Charge passed / C cm-2

Fig. 2. Surface roughness of the copper deposits obtained from the electrolytic
solutions containing 5 kmol m3 NH3, (a) 2.0, (b) 4.0, and (c) 5 kmol m3 NH4Cl and
0.5 kmol m3 Cu2O at 1000 Am2 under agitation.

and 4 kmol m 3 NH4Cl without any copper-ion sources. The cathode

was a copper or platinum plate (10 mm20 mm) in which the back surface was covered with a resin tape to prevent electrodeposition. A platinum plate (45 mm50 mm) and an Ag/AgCl electrode immersed in a
3.33 kmol m3 KCl solution were used as the anode and reference electrode, respectively, but all potentials in this paper are given with reference
to the normal hydrogen electrode (NHE). The electrochemical measurements and electrolysis were initially carried out by an electrochemical
measurement system (Hokuto Denko Co., HZ-5000) at room temperature, approximately 25 C, without articial agitation. In this condition,
however, stripes in the vertical direction were formed on the surface of
the copper deposit on account of the convection near the electrode
surface caused by a decrease in the solution density. Because such a
macroscopic roughness signicantly decreased reproducibility, the electrolytic solution was agitated using a magnetic stirrer during the electrodeposition for the surface roughness measurement described below. A
long-term electrodeposition was also conducted in order to observe the
additive effect under conditions similar to commercial ones. In this case,
a rectangular vessel (50 mm115 mm90 mm [h]) was used without
any membrane, and copper plates (45 mm50 mm1 mm [t] and
40 mm80 mm5 mm [t]) were used as the cathode and anode,
respectively. The bath volume was approximately 4104 m3, corresponding to a depth of 70 mm in the present vessel, and the distance
between the surface of the electrodes was set at approximately
110 mm. The copper deposit was measured using a surface roughness
meter, observed by scanning electron microscope (SEM) and/or
dissolved in nitric acid solutions for the inductively coupled plasma

10
C(NH3) / kmol m

Surface roughness (Ra) / m

Surface roughness (Ra) / m

-3

CNH4Cl / kmol m

10
-3

(a)3.0
(b)5.0

(c)10

59

-3

1000

Charge passed / C cm-2

Fig. 1. Surface roughness of the copper deposits obtained from the electrolytic
solutions containing (a) 3.0, (b) 5.0, and (c) 10 kmol m3 NH3, 4 kmol m3 NH4Cl,
and 0.5 kmol m3 Cu2O at 1000 Am2 under agitation.

(a)0.25
(b)0.50

(c)1.0

0
100

CCu2O / kmol m

100

1000

Charge passed / C cm-2

Fig. 3. Surface roughness of the copper deposits obtained from the electrolytic
solutions containing 5 kmol m 3 NH3, 4 kmol m 3 NH4Cl and (a) 0.25, (b) 0.5,
and (c) 1 kmol m 3 Cu2O at 1000 A m 2 under agitation.

T. Oishi et al. / Hydrometallurgy 133 (2013) 5863

Surface roughness (Ra) / m

60

10

A)

-3

CCu2O / kmol m
(a)0.25

40

(a)0.25

30

(b)0.50

B)

-3

CCu2O / kmol m
(b)0.50

(c)1.0

(c)1.0

20
4
10

2
0

100

1000

100

1000

Charge passed / C cm-2

Charge passed / C cm-2

Fig. 4. Surface roughness of the copper deposits obtained from the electrolytic solutions containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl, and (a) 0.25, (b) 0.5, and (c) 1 kmol m3
Cu2O at a current density of (A) 500 and (B) 2000 Am2 under agitation.

atomic emission spectroscopy (ICP-AES) measurement, after successive rinsing in a NH3(2.5 kmol m 3)NH4Cl(2 kmol m 3) solution,
tap water, and deionized water. The surface roughness was measured
using a contact-type roughness meter (Tokyo Seimitsu Co., SURFCOM
480A) at a scan rate of 0.06 mm s1 for 4.0 mm in the vertical direction.
The values in this paper are given as the average of three measurements
at different positions near the center of the cathode. The average roughness (Ra) was selected as the parameter of the surface roughness,
because some of the samples had heterogeneous regions such as nodules
on a sub-mm scale. Average roughness, which reects the roughness of
both the microscopic and macroscopic scale to a certain extent, is appropriate for the evaluation of such samples.

3. Results and discussion

3.1. Inuence of bath composition and current density on surface roughness

respectively (Oishi et al., 2006). The result shown in Fig. 2 seems to

conict with the concept of the Wagner number, which is an important
parameter for the determination of the homogeneity of the deposit in
the eld of electroplating (e.g., Goodenough and Whitlaw, 1989;
Wagner, 1951) and is proportional to the slope of the polarization
curve at a given current density (d/di) and conductivity of the solution.
Because these parameters have a positive effect on the uniformity of the
current density distribution on an electrode surface, an increase in Wagner number results in a smooth deposit. According to this concept, one
would expect any positive effect of the NH4Cl concentration, which is
nearly proportional to the solution conductivity; however, it showed
no signicant effect as described above. This apparent contradiction
might be attributed to the leveling effect of Cu(II) in the solution.
Cu(II) is reduced by Cu metal, but it still exists at a concentration in
the order of 0.01 kmol m3 on account of the unavoidable oxidation
or equilibrium among Cu(I), Cu(II), and Cu metal.

2CuNH3 2 CuNH3 4 Cu
The inuence of the concentration of each electrolyte on the surface
roughness at a current density of 1000 Am2 is shown in Figs. 13,
where the basic bath composition was selected to be 5 kmol m3
NH3, 4 kmol m3 NH4Cl, and 0.5 kmol m3 Cu2O, and the concentration of each electrolyte was varied with xed concentrations of the
others. The cathodic current efciency calculated from the weight gain
of the cathode on the assumption of one electron reaction was in the
range 7696%, which was controlled by the Cu(II) concentration as the
authors reported elsewhere (Oishi et al., 2006). As shown in Figs. 1
and 2, the NH3 and NH4Cl concentrations seem to have no signicant
inuence on the surface roughness, although increases in the NH3 and
NH4Cl concentrations cause a slight increase in the kinematic viscosity
and a signicant increase in the electric conductivity of the solution,

Current density / A m-2

1000

100
Gelatin free

10

MW=

2,100

MW=

3,700

MW= 14,000
MW= 110,000

1
-0.2

-0.3

-0.4

-0.5

Because Cu(II) is reduced to Cu(I) on the surface of the cathode

and this reaction is diffusion limited in the examined current density
range, Cu(II) has a certain effect in reducing the surface roughness.
On the other hand, a low Cu(I) concentration led to a high surface
roughness, as shown in Fig. 3. This tendency became clearer at the
higher current density of 2000 A m 2, as shown in Fig. 4(B), while
no signicant effect was observed at the lower current density of
500 Am 2, as shown in Fig. 4(A). According to Winand (1975), the electrodeposition type (e.g., unorientated deposition, eld-orientated isolation, and basis-orientated reproduction type) is signicantly controlled
by the extent of the inhibition and the ratio of the passed current versus
the diffusion-limited current. Although there is no one-to-one correspondence between the electrodeposition type and surface roughness,
the electrodeposition type signicantly inuences the surface roughness. In the present cases, the inuence of the latter factor was clearly
observed; that is, a dramatic change in the surface roughness was
observed when the Cu(I) concentration (which is nearly proportional
to the diffusion-limited current) and current density were varied
(Figs. 3 and 4). In other words, the former factor denoting the extent
of inhibition seemed to be independent of, or very weakly affected by,
the other variables (ammonia and ammonium chloride concentrations).
On the basis of these results, it was concluded that there is a certain
limitation in reducing the surface roughness without the addition of
an additive(s) in the present system. Thus, the use of some additives
was then examined.

-0.6

Potential vs. NHE / V

Fig. 5. Cathodic polarization curves on a copper plate electrode in the electrolytic solutions containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl, and 0.5 kmol m3 Cu2O with
and without 100 g m3 of gelatins having different molecular weights with no articial agitation.

3.2. Polarization by additives

The inuence of the average molecular weights of gelatin and PEG on
the polarization curve for the copper electrodeposition is shown in
Figs. 5 and 6, respectively, in which 100 g m3 of the additives was

T. Oishi et al. / Hydrometallurgy 133 (2013) 5863

added to the electrolyte. Each electrode potential was measured after

applying a given current density 3 min. The shoulder in the low polarization region is due to the reduction of Cu(II) to Cu(I). As shown in these
gures, the extent of the polarization increased with the average
molecular weight of the additives in both cases. In addition, the polarization became more signicant as the concentration of the additives increased. These tendencies are close to those observed in the copper
sulfate/sulfuric acid solution by Stelter et al. (2002) and Nakano et al.
(2003) and are attributed to the increasing number of lone pairs of electrons working as the active sites for the adsorption to the copper surface.
The inuence of the molecular weight on the availability of gelatin to adsorb to the copper surface was experimentally conrmed by Nakano et
al. (2003) using the absorbance at a 190-nm wavelength. The consistency between the present results and those reported by other researchers
suggests that the behavior of gelatin and PEG in the ammoniacal alkaline
solution (of which the pH is 910) is nearly the same as that in the
strongly acidic solutions, and that these additives effectively reduce
the surface roughness of the copper deposit even in the present electrolysis. Although the difference between the effects of gelatin and PEG is
difcult to recognize from the polarization curves shown in Figs. 5 and
6, the current density dependence of the extent of polarization was
slightly different. That is, the polarization by gelatin was greater than
that of PEG in the relatively low current density region (approximately
100 Am2 or less), while the inuence of PEG became signicant in
the higher current density region, when the molecular weights of the
gelatin and PEG were close to each other. This tendency is believed to reect the kinetic difference in the adsorption/desorption process of gelatin and PEG on the copper surface, but further investigation is needed in
order to understand this phenomenon.
3.3. Inuence of additives on the morphology of the deposit
On the basis of the preliminary experiment, the PEG having molecular weight of 2 103 was chosen for further investigation. As shown in
Fig. 6, polarization during the copper electrodeposition became more
signicant when the molecular weight of PEG was 2 104, and these
conditions appeared suitable for obtaining a smooth deposit. In this
case, however, the copper deposit tended to be black and fragile,
which suggests an increase in the carbon content in the deposit that is
attributable to the strong adsorption of PEG on the copper surface. In
the case of the gelatins, similar disadvantages were not observed.
Thus, the molecule having highest molecular weight (MW= 1.1 105)
was chosen among the examined gelatins.
The surface roughness of the copper deposit obtained from the
10 g m3 of gelatin or PEG added electrolyte is shown in Fig. 7. In both
cases, the surface roughness dramatically decreased with the use of
additives, and this was more signicant in the case of gelatin. This is

61

attributable to the polarization by the additives during the copper

deposition, which makes nucleation easier, decreases the grain size,
and consequently contributes to forming a smooth surface. The current
efciency was approximately 90% in both cases and was nearly the
same as that of the additive-free conditions. Then, in order to conrm
the effectiveness of these additives, long-term electrolysis was carried
out with no articial agitation. Photos of the copper deposits obtained
by galvanostatic electrolysis at 300 Am2 for 50 h are shown in Fig. 8.
On account of the convection near the electrode surface, the deposits
had stripes in the vertical direction, especially in the case of the
gelatin-added solution. As shown in this gure, the appearance of the
deposit was signicantly improved by the addition of gelatin, as the
surface roughness measurement suggested (Fig. 7). In the case of PEG,
many nodules were formed on the surface, while the surface also became
smooth to a certain extent. These deposits were further observed by
SEM. As shown in Fig. 9(a), the grain size was of the order of several
hundred m to mm, and the grains appeared to consist of relatively
large crystals in the case of the additive-free solution. When gelatin
was added, the surface became smooth, but the grain size itself appeared
similar to that from the additive-free solution (Fig. 9(a-1) and (b-1)). The
difference between these deposits was seen in the size of the crystals
forming the grains, as shown in the SEM images at higher magnications
(Fig. 9(a-2) and (b-2)). In the case of PEG, the grains were not visible at
the observed magnications, and each crystal was difcult to recognize
even at the higher magnication (Fig. 9(c)). Although PEG appears
superior to gelatin based on the SEM observations, the addition of PEG
to the electrolyte tended to cause nodule formation as shown in
Fig. 8(c), and a similar tendency was reported by Stelter et al. (2002) in
acidic sulfate solutions. This might be caused by the strong interaction
between the PEG and copper surface, which was suggested by the results
of the preliminary experiment mentioned in the rst paragraph of this
section. Because the formation of nodules frequently leads to unfavorable results, such as short circuits and contamination, it was concluded
that PEG is unsuitable as an additive for the present electrolysis. As for
gelatins, almost the same deposits as those shown in Fig. 8(b) were
obtained when other gelatins having molecular weights less than
1.1105 were employed. This indicates the effectiveness of the gelatin
or glue in obtaining smooth and bright deposits from the present electrolytic solutions. The cathodic current efciency, average cell voltage, and
power consumption during the electrolysis were approximately 90%,
1.0 V, and 470 kWh ton1, respectively. These values were nearly independent of the existence of the additives because of the lower additive
concentrations than those in the cases of Figs. 5 and 6, as well as a high
IR drop in the solution. The measured IR drop in the solution was approximately 0.7 V, which accounted for most of the cell voltage.

Surface roughness (Ra) / m

Current density / A m-2

1000

100

PEG free

10

MW=

200

MW= 2000
MW= 20000

Additive free

PEG added
Gelatin added

0
-0.2

-0.3

-0.4

-0.5

-0.6

Potential vs. NHE / V

Fig. 6. Cathodic polarization curves on a copper plate electrode in the electrolytic solutions
containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl, and 0.5 kmol m3 Cu2O with and without 100 g m3 of PEGs of various molecular weights with no articial agitation.

100

1000

Charge passed / C cm-2

Fig. 7. Surface roughness of the copper deposits obtained from the electrolytic solutions containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl, and 0.5 kmol m3 Cu2O with
and without 10 g m3 of additives at a current density of 500 Am2 under agitation.

62

T. Oishi et al. / Hydrometallurgy 133 (2013) 5863

a) Additive free

c) PEG

b) Gelatin

1cm

1cm

1cm

Fig. 8. Appearance of the copper deposits obtained by galvanostatic electrolysis at 300 A m2 for 50 h in the electrolytic solutions containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl,
and 0.5 kmol m3 Cu2O with and without 10 g m3 of additives with no articial agitation.

3.4. Inuence of gelatin on the impurity content

As mentioned above, gelatin was found to be effective in generating a
smooth copper deposit, and this phenomenon was attributed to the
polarization during the copper electrodeposition. A high polarization,
however, generally tends to emphasize the contamination by impurities
during the electrodeposition. On the other hand, one would expect
a similar polarization effect for the electrodeposition of impurities,
which might reduce the impurity content of the copper deposits. Thus,
the inuence of the gelatin addition on the impurity content of the
copper deposit was further investigated. During the copper recycling

process that we proposed, lead was reported as the most important

impurity (Oishi et al., 2007). In general, the lead concentration at
pH =910, which is the typical pH of the solution used in the present
process, is of the order of 1 105 kmol m3 or less, owing to the low
solubility of PbO or Pb(OH)2 (Delahay et al., 1951). In concentrated
ammonia solutions, however, Pickering and Pidgeon (1969) reported
that up to 0.5 kmol m 3 of Pb(II) could be dissolved under ambient
conditions. In fact, the solubility of the Pb(II) compound increased
with the ammonia concentration in the present solutions (Oishi et al.,
2008), and the copper deposit recovered from the actual printed circuit
boards contained a signicant amount of lead if the electrolytic solution

b) Gelatin

a) Additive free
(a-1)

c) PEG

(b-1)

200 m

(a-2)

(c-1)

200 m

(b-2)

10 m

200 m

(c-2)

10 m

10 m

Fig. 9. SEM images of the copper deposits obtained by galvanostatic electrolysis at 300 A m2 for 50 h in the electrolytic solutions containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl,
and 0.5 kmol m3 Cu2O with and without 10 g m3 of additives with no articial agitation.

Partial current density / A m-2

T. Oishi et al. / Hydrometallurgy 133 (2013) 5863

103
10

10

Cu

100

Pb

10-1
10-2
Additive free

10-3
10-4

Gelatin added

-0.26

-0.28

-0.30

-0.32

-0.34

-0.36

63

1) The surface roughness decreased to a certain extent when the Cu(I)

concentration was relatively high and the current density was low,
whereas the NH3 and NH4Cl concentrations seemed to have no
signicant effect.
2) The addition of gelatin and PEG decreased the surface roughness
of the copper deposit, which is attributable to their polarization
effects during the copper electrodeposition.
3) Gelatin was found to be superior to PEG as the additive for the
present solutions from the perspective of reducing the surface
roughness and the probability of nodule formation.
4) The addition of gelatin also suppressed the electrodeposition of lead,
and consequently reduced the lead content of the copper deposit.

Potential vs. NHE / V

Acknowledgment
Fig. 10. Partial current density for Cu and Pb electrodeposition during the potentiostatic
electrolysis in solutions containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl, 0.5 kmol m3
Cu2O, and 2.4 mol m3 PbO with and without 100 g m3 of gelatin (MW=1.1105)
with no articial agitation.

The authors wish to acknowledge Nippi, Inc., for supplying the gelatins
of various molecular weights.
References

was not puried in advance (Oishi et al., 2007). To evaluate the inuence
of gelatin on the impurity content, a potentiostatic electrolysis was
carried out in a solution in which 2.4 mol m3 PbO was added as the
Pb(II) source. On the basis of the amount of copper and lead deposited
on the cathode, the average partial cathodic current density for copper
and lead electrodeposition was calculated and plotted in Fig. 10 as a
function of the cathode potential. The number of electrons required for
the copper and lead electrodeposition was assumed to be 1 and 2,
respectively. From this gure, it was recognized that the lead electrodeposition was also suppressed by the addition of gelatin as well as the
copper electrodeposition. Because there is a certain difference between
the extents of polarization for the copper and lead electrodeposition,
the addition of gelatin consequently reduced the lead content at most
of the potentials applied in this study, as shown in Fig. 11. Although
we have no denite information to explain this result, our previous
study suggested that lead was electrodeposited on copper via a similar
mechanism of under-potential deposition (Oishi et al., 2008). Thus, the
decrease in the lead content by the addition of gelatin (Fig. 11) might
be caused by the adsorption of gelatin molecules on the active sites of
the copper surface for the lead electrodeposition or adsorption.

4. Conclusions

Lead content of the deposit / ppmw

The reduction of the surface roughness of the deposited copper by

additives or optimization of the electrolytic condition was examined in
ammoniacal alkaline solutions, and the following results were obtained:

Additive free
Gelatin added

1000

500

-0.26

-0.28

-0.30

-0.32

-0.34

-0.36

Potential vs. NHE / V

Fig. 11. Lead content of the copper deposit obtained by the potentiostatic electrolysis in
solutions containing 5 kmol m3 NH3, 4 kmol m3 NH4Cl, 0.5 kmol m3 Cu2O, and
2.4 mol m3 PbO with and without 100 g m3 of gelatin (MW=1.1105) with no articial agitation.

Alam, M.S., Tanaka, M., Koyama, K., Oishi, T., Lee, J.-C., 2007. Electrolyte purication in
energy-saving monovalent copper electrowinning process. Hydrometallurgy 87,
3644.
Alodan, M., Smyrl, W., 1998. Effect of thiourea on copper dissolution and deposition.
Electrochim. Acta 44, 299309.
Ando, K., Tsuchida, N., Komi, H., 2002. Control of additives in copper electrorening by
using the Hull Cell test. J. MMIJ 118, 8690.
Brown, A.P., Loutfy, R.O., Cook, G.M., Yao, N.-P., 1981. The electrorening of copper
from a cuprous ion complexing electrolyte. J. Met. 33, 4957.
Delahay, P., Pourbaix, M., Rysselberghe, P.V., 1951. Potential-pH diagram of lead and its
applications to the study of lead corrosion and to the lead storage battery.
J. Electrochem. Soc. 98 (2), 5764.
Goodenough, M., Whitlaw, K.J., 1989. Studies of copper deposition for high aspect ratio
printed circuit boards. Trans. Inst. 67, 5762.
Ibrahim, M.A.M., 2000. Copper electrodeposition from non-polluting aqueous ammonia baths. Plat. Surf. Finish. 87, 6772.
Kanani, N., 2004. Electroplating, 1st ed. Elsevier, Science, Amsterdam . (Chapter 3).
Karavasteva, M., Karaivanov, St, 1993. Electrowinning of zinc at high current density in
the presence of some surfactants. J. Appl. Electrochem. 23, 763765.
Kerby, R.C., Jackson, H.E., O'keefe, T.J., Wang, Y.-M., 1977. Evaluation of organic additives for use in zinc electrowinning. Metall. Trans. B 8B, 661668.
Koyama, K., Tanaka, M., Lee, J.-C., 2006. Copper leaching behavior from waste printed
circuit board in ammoniacal alkaline solution. Mater. Trans. 47 (7), 17881792.
Nakano, H., Oue, S., Ohgai, T., Izumi, K., Akiyama, T., Fukushima, H., 2003. Effects of
polymer additives on copper electrorening (in Japanese). J. MMIJ 119 (10, 11),
663667.
Ohgai, T., Fukushima, H., Akiyama, T., Baba, N., 1999. Effects of polymer additives on
zinc electrowinning (in Japanese). J. MMIJ 115 (9), 700704.
Oishi, T., Koyama, K., Tanaka, M., Lee, J.-C., 2006. Inuence of electrolyte on an energysaving copper recycling process using ammoniacal alkaline solutions. Mater. Trans.
47 (11), 28712876.
Oishi, T., Koyama, K., Alam, S., Tanaka, M., Lee, J.-C., 2007. Recovery of high purity copper cathode from printed circuit boards using ammoniacal sulfate or chloride solutions. Hydrometallurgy 89, 8288.
Oishi, T., Yaguchi, M., Koyama, K., Tanaka, M., Lee, J.-C., 2008. Effect of phosphate on
lead removal during a copper recycling process from wastes using ammoniacal
chloride solution. Hydrometallurgy 90, 161167.
Pickering, R. W., Pidgeon, J. S., 1969. Extraction and recovery of metals from ores,
concentrates and residues. U.S. Patent 3,440,155.
Stelter, M., Bombach, H., Nesterov, N., 2002. Using polyethylene glycols as alternative
inhibitors in copper electrorening. JOM 54, 3236.
Varvara, S., Muresan, L., Nicoara, A., Maurin, G., Popescu, I.C., 2001. Kinetic and morphological investigation of copper electrodeposition from sulfate electrolytes in the presence
of an additive based on ethoxyacetic alcohol and triethyl-benzyl-ammonium chloride.
Mater. Chem. Phys. 72, 332336.
Wagner, C., 1951. Theoretical analysis of the current density distribution in electrolytic
cells. J. Electrochem. Soc. 98 (3), 116128.
Winand, R., 1975. Electrocrystallization of copper. Trans. Inst. Min. Metall. 84, C67C75.