Examination of copper electrowinning

smoothing agents. Part IV: Nucleation

and growth of copper on stainless steel
A. Luyima, W. Cui, C. Heckman and M.S. Moats*
Postdoctoral research fellow, graduate research assistant, undergraduate research assistant and
associate professor, respectively, Materials Research Center, Missouri University of Science
and Technology, Rolla, MO, USA
*Corresponding author email: moatsm@mst.edu

Abstract
Nucleation and growth of copper on 316L stainless steel from synthetic acidified copper sulfate was studied in the absence
and presence of chloride ions and/or organic additives HydroStar 4208, DXG-F7 and Cyquest N-900 using a
potentiostatic technique. The currenttime data obtained at 0.16V versus the SHE were analyzed using nucleation and
growth models. Scanning electron microscope (SEM) images of deposits produced at 300 A/m2 show that the addition
of 20 mg/L chloride ions increased the size and reduced the number of copper nuclei. Potentiostatic currenttime data
from the electrolyte without organic additives, and confirmed by SEM images, indicate progressive nucleation with
two-dimensional growth under diffusion control. None of the organic additives studied at a concentration of 2.5 mg/L
with 20 mg/L chloride changed the nucleation and growth mechanism, but the additives increased the number and
reduced the size of copper nuclei, leading to more uniform coverage of the stainless steel substrate.

Minerals & Metallurgical Processing, 2016, Vol. 33, No. 1, pp. 39-46.
An official publication of the Society for Mining, Metallurgy & Exploration Inc.
http://dx.doi.org/10.19150/mmp.6465

Key words: Copper, Electrowinning, Additives, Nucleation, Growth

Introduction perature and copper concentration, small amounts of organic

Electrowinning of copper is an important process smoothing agents traditionally, guar products are added to
in the manufacture of high-purity copper metal. Ap- copper electrowinning electrolytes. Moreover, these additives
proximately 20 percent of the worlds refined copper inhibit the growth of copper nodules and lead to improved de-
is produced from acidified copper sulfate solutions posit quality by producing bright, smooth and dense cathodes.
by electrowinning (Schlesinger, Sole and Davenport, Recently, the use of polysaccharides, such as HydroStar 4208
2011). In many plants, copper is electrodeposited and DXG-F7, and polyacrylamides, such as Cyquest N-900,
on AISI 316L stainless steel substrates for a period has been reported in commercial electrowinning tankhouses
of 6-7 days, after which the copper is stripped from as replacements for guar (Ashford, Clayton and Sandoval,
the blanks. Even though the deposition time for a 2012; Robinson et al., 2013; Sandoval, Morales and Bernu,
commercial copper electrowinning circuit is around 2010). However, little information has been published on the
one week, it is critically important to control the effect of these new organic additives, especially regarding the
nucleation, growth and nature of the initial deposit nucleation and growth mechanisms of copper electrodeposits
(Sun and OKeefe, 1992). in their presence.
Deposit morphology and structure are influenced The current density versus time relationships for potentio-
by the real current density at the electrode surface. static nucleation and growth in one dimension (needles), two
The real current density across the cathode surface is dimensions (cylindrical shape), and three dimensions (hemi-
made uniform by proper design of the electrowinning spherical shape) are provided in Table 1 (Thirsk and Harrison,
cell and electrodes and careful operational practice. 1972). The measured current density, i, is proportional to time
Even with good design and control, some current to the nth power, tn (n = 0.5, 1, 1.5, 2 and 3). These relation-
maldistribution occurs. The outcome of severe current ships have been used to examine the mechanism of copper
maldistribution is poor deposits that affect product electrodeposition on stainless steel and titanium substrates
quality and/or increase energy consumption. To (Sun and OKeefe 1992; Dutra and OKeefe, 1999) and other
combat current maldistribution and create a larger systems (Hills et al., 1974).
operating window in terms of current density, tem- The electrochemical characterization of the effects of
Paper number MMP-15-027. Original manuscript submitted April 2015. Revised manuscript accepted for publication October
2015. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. prior
to Aug. 31, 2016. Copyright 2016, Society for Mining, Metallurgy & Exploration Inc.

MINERALS & METALLURGICAL PROCESSING 39 Vol. 33 No. 1 February 2016

chloride and organic additives using cyclic voltammetry, stainless steel coupons obtained from T.A. Caid, titanium mesh
electrochemical impedance spectroscopy and galvanodynamic, coated with a mixed metal oxide of iridium oxide (IrO2) and
chronopotentiometric and chronoamperometric techniques tantalum pentoxide (Ta2O5), and a double-junction reference
was presented in Parts II and III of this series (Luyima et electrode with electrode potential of 0.218 V versus the standard
al., 2016; Cui et al., 2016). In this final installment, an ex- hydrogen electrode (SHE) were used as the working (cathode),
perimental study of the effects of chloride, HydroStar 4208, counter (anode) and reference electrodes, respectively.
DXG-F7 and Cyquest N-900 upon the nucleation and growth
mechanisms during copper electrowinning from synthetic Electrolyte solution. Synthetic electrowinning solutions
sulfate electrolytes on stainless steel cathodes is presented. were prepared using cupric sulfate pentahydrate and concen-
Current transients from potentiostatic experiments together trated sulfuric acid to produce a base electrolyte with a room-
with scanning electron microscope (SEM) images were used temperature composition of 40 g/L copper (Cu) and 160 g/L
to determine these mechanisms. sulfuric acid (H2SO4). The organic additives were predissolved
in water at a concentration of 3.5 g/L and added to each 250-mL
test electrolyte solution to obtain the desired concentration 30
Experimental minutes prior to the application of electricity.
Materials. The base electrolyte chemicals copper sulfate
pentahydrate and sulfuric acid were ACS grade reagents Apparatus setup. The three-electrode cell used was pre-
purchased from GFS Chemicals. Distilled deionized water viously described in detail in Parts II and III of this series. A
was used in all solution preparation. The organic additives Gamry Reference 3000 Potentiostat/Galvanostat/ZRA con-
are commercial products and were provided by copper mining nected to a computer and controlled by Gamry Framework
companies. HydroStar 4208 and DXG-F7 are saccharide-based software was used to control the potential and current and
chemicals produced by ChemStar Products Company and record the potential and current measurements.
Mosaic Commerce, respectively. Cyquest N-900 is a polyacryl-
amide produced by Cytec Industries. In each experiment, 316L Nucleation experiments. A short, 5-sec potential pulse of
0.16 V versus the SHE was applied to the cell and the current
density versus time data were recorded. Following the test, the
Table 1 Current density versus time relationships current density data were examined versus (t t0)n, where t is
for potentiostatic nucleation and growth (Thirsk and the nucleation time, t0 is the induction time observed before
Harrison, 1972). copper crystallization occurs, and n is equal to 0.5, 1, 1.5, 2
or 3 (Sun and OKeefe, 1992).
Mod- Rela- Nucleation Growth Control Chronopotentiometry tests were conducted with constant
el tionship type type regime current control at 30 mA/cm2 to produce 10-sec and 30-sec
1 i = f(t1/2) instantaneous 3D diffusion copper deposits for analysis in a scanning electron microscope.
It is worth mentioning that industrial cells run in constant current
2 i = f(t) progressive 1D kinetic
mode during copper deposition and that is why experiments
3 i = f(t) progressive 2D diffusion
for SEM analysis were carried out in that mode.
4 i = f(t) instantaneous 2D kinetic
5 i= f(t3/2) progressive 3D diffusion

6 i = f(t2) progressive 2D kinetic

Results and discussion
Potentiostatic tests. The data from the potentiostatic experi-
7 i = f(t2) instantaneous 3D kinetic ments were examined using the models in Table 1. The model
8 i = f(t3) progressive 3D kinetic that produced the highest linear correlation coefficient, R2, was
chosen as the correct mechanism.

(a) (b)

t (sec) t (sec)

Figure 1 Current density versus time relationship for the nucleation and initial growth of copper on 316 L stainless
steel in base electrolyte of 40 g/L Cu and 160 g/L H2SO4, at 40C with no external agitation, at the applied potential of
0.16 V versus the SHE. (a) Induction period (b) nucleation period.

February 2016 Vol. 33 No. 1 40 MINERALS & METALLURGICAL PROCESSING

 Table 2 Model fitting for the nucleation of copper
at 0.16 V versus the SHE without additives.

Model # Nucleation type R2

2, 3 and 4 t t0 1.000
1 (t t0)0.5 0.956
5 (t t0)1.5 0.980
6 and 7 (t t0)2 0.938
8 (t t0)3 0.840

No additive. The current transient recorded for copper elec-
trodeposition on 316L stainless steel at 0.16 V versus the SHE in
the absence of chloride or organic additives in the electrolyte is
shown in Fig. 1. There are three possible characteristic regions
in the transient. The first region corresponds to an initial pulse
and is related to double-layer charging. This period exists for
just a few milliseconds (Bijani et al., 2011; Sun and OKeefe,
1992). This pulse was not revealed in these experimental tests.
The second region is one where current density is essentially
constant and is known as the induction period. The induction
time, t0, was determined to be 0.11 sec for this experimental
setup and was constant for each experiment (see Fig. 1a). No
copper was observed on the electrode at the end of this induc-
tion period (Sun and OKeefe, 1992). As the copper nucleated
and grew, the current density increased with time, and this is
the third region in Fig. 1b.
The experimental data after the induction period (t t0) were
fitted to the various models and the results plotted and shown
(t t0)n (secn)
Figure 2 Current density versus time relationships for
the base electrolyte without any additives at the applied
potential of 0.16 V versus the SHE.
in Fig. 2. The modeling outcomes are summarized in Table 2.
The results suggest that the nucleation and growth follow one
of the models with n = 1 (models 2, 3 and 4), as denoted by
the highest linear regression coefficient.
SEM micrographs of copper electrodeposits at 300 mA/cm2
in an electrolyte without additives are shown in Figs. 3a-d,
where copper nucleation on the 316L stainless steel appears
to occur preferentially along the polishing lines, as observed
by Dutra and OKeefe (1999). The images reveal differently
sized nuclei with mostly two-dimensional growth appearance.

(a) (b)

(c) (d)

Figure 3 SEM micrographs of copper nuclei on 316L stainless steel in base electrolyte of 40 g/L Cu and 160 g/L H2SO4
at 40oC without additives: (a) and (b) after 10 sec at 30 mA/cm2, (c) and (d) after 30 sec at 30 mA/cm2.

MINERALS & METALLURGICAL PROCESSING 41 Vol. 33 No. 1 February 2016

 t t0 (sec) t t0 (sec)

Figure 4 Current density versus time relationship for
copper electrodeposition on stainless steel from base
electrolyte of 40 g/L Cu and 160 g/L H2SO4 at 40oC with
addition of 20 mg/L Cl but without organic additives at
the applied potential of 0.16 V versus the SHE.
Figure 6 Current density versus time relationships at the
applied potential of 0.16 V versus the SHE for electrolytes
with and without 2.5 mg/L of a given organic additive and
without added chloride.

Therefore, the copper nucleation in an electrolyte without
additives appears to be progressive nucleation with two-
dimensional growth. This finding is different from that of Sun
and OKeefe (1992), who found that copper electrodeposition
occurred with progressive nucleation with three-dimensional
growth on stainless steel. It is important to note that Sun and
OKeefe used a more cathodic potential for their 1992 study.
A similar study by Dutra and OKeefe (1999) revealed that at
less cathodic potentials the nucleation and growth mechanism
could change from three-dimensional to two-dimensional for
copper deposited on a titanium substrate.
Chloride ions. The current density versus time plot after
an applied potential step of 0.16 V versus the SHE for an
electrolyte with 20 mg/L Cl added is shown in Fig. 4. At 20

(a) (b)

(c) (d)

Figure 5 SEM micrographs of copper nuclei on 316L stainless steel in base electrolyte with the addition of 20 mg/L
chloride without organic additives: (a) and (b) after 10 sec at 30 mA/cm2, (c) and (d) after 30 sec at 30 mA/cm2.

February 2016 Vol. 33 No. 1 42 MINERALS & METALLURGICAL PROCESSING

mg/L Cl, an increase in initial current was observed. This is
known as depolarization and has been reported by Sun and
OKeefe (1992) and many others, including in Part III of this
series. Moreover, the current density was more than 35 percent
higher than without Cl ions. There was no obvious change in
the nucleation and growth models (Fig. 4), as a linear current
response versus (t t0) was observed.
SEM micrographs (Figs. 5a-d) of deposits produced at 30
mA/cm2 in the presence of 20 mg/L Cl indicate differently
sized nuclei and three-dimensional growth after 10 and 30 sec.
The short-term deposits were produced at a current density that
is more similar to industrial operation. The apparent change in
growth mechanism between the potentiostatic data in Fig. 4 and
the constant-current deposits in Fig. 5 is probably caused by the
more cathodic potential imposed by the constant current. This
observation follows the earlier discussion regarding Sun and
OKeefes results. A more cathodic potential in the absence of
organic additives appears to foster three-dimensional growth.
It can also be seen that the size of the copper nuclei produced
from the base electrolyte without Cl ions (Figs. 3a-b) is ap-
proximately half that of the copper nuclei produced from the
base electrolyte with 20 mg/L Cl. The presence of chloride
promotes growth of existing nuclei, resulting in a decreased
number of copper nuclei, which hinders the formation of a
deposit that completely covers the stainless steel blank.
HydroStar, DXG-F7 and Cyquest N-900. Organic addi-
tives are used as smoothing agents in copper electrowinning.
Recent operating data from modern tankhouses indicate the
preferred smoothing agents are HydroStar, DXG-F7 and Cy-
quest N-900 (Robinson et al., 2013). Previous research in the
presence of 20 mg/L chloride indicated that HydroStar does
(a)
(c)
Figure 7 SEM micrographs of copper nuclei on 316L stainless steel in a base electrolyte with addition of 2.5 mg/L
Cyquest N-900 and with no chloride: (a) and (b) after 10 sec at 30 mA/cm2, (c) and (d) after 30 sec at 30 mA/cm2.
MINERALS & METALLURGICAL PROCESSING 43
not polarize or depolarize the reaction while Cyquest N-900
polarizes the copper deposition reagent (Helsten and Moats,
2013; Moats, Luyima and Oliveria, 2014). Apart from the fun-
damental study of DXG-F7 presented in Part II of this series,
the authors are unaware of any public fundamental reports on
the electrochemical effects of DXG-F7.
Figure 6 shows a plot of current density versus time for
potentiostatic experiments with electrolytes containing either
no additive or 2.5 mg/L of a given organic additive and in the
absence of added chloride to the solution. The data indicate
the addition of 2.5 mg/L of HydroStar depolarizes (that is, ac-
celerates) the copper deposition reaction. However, 2.5 mg/L
of DXG-F7 and Cyquest N-900, respectively, had minimal
polarizing effects. The current density versus time curves
obtained from those electrolytes with organic additives also
indicate linear relationships for current density versus (t t0).
Table 3 is a summary of the models with the highest linear
regression coefficients for the current density versus time data
at different electrolyte compositions. SEM images (Figs. 7-9)
appear to confirm progressive nucleation (variance in nuclei
size) with two-dimensional growth for these three organic
additives when no chloride was added.
Moreover, comparing Fig. 3 with Figs. 7-9, the SEM images
for electrolytes containing HydroStar, DXG-F7 and Cyquest
N-900 appear to show increased rates of nucleation and retarda-
tions of overall growth. Figures 7-9 show reduced nuclei size,
increased nuclei number, and more uniform coverage on the
stainless steel substrate compared with the deposits produced
in the base electrolyte.
Chloride and organic additives. The interactions between
chloride ions and the organic additives during potentiostatic
copper electrodeposition are depicted in Fig. 10. The current
(b)
(d)
Vol. 33 No. 1 February 2016
 (a) (b)

(c) (d)

Figure 8 SEM micrographs of copper nuclei on 316L stainless steel in a base electrolyte with addition of 2.5 mg/L
DXG-F7 and with no chloride: (a) and (b) after 10 sec at 30 mA/cm2, (c) and (d) after 30 sec at 30 mA/cm2.

(a) (b)

(c) (d)

Figure 9 SEM micrographs of copper nuclei on 316L stainless steel in a base electrolyte with addition of 2.5 mg/L
HydroStar and with no chloride: (a) and (b) after 10 sec at 30 mA/cm2, (c) and (d) after 30 sec at 30 mA/cm2.

February 2016 Vol. 33 No. 1 44 MINERALS & METALLURGICAL PROCESSING

 Table 3 Model fitting for the nucleation of copper at 0.16 V versus the SHE.

Additive concentration
Additive Equations R 2 values Mechanisms
(mg/L)
None 0 i = 3.44(t t0) + 3.11 1.00
Chloride 20 i = 2.95(t t0) + 5.46 1.00
HydroStar 2.5 i = 4.74(t t0) + 6.72 1.00 Progressive nucleation,
DXG-F7 2.5 i = 2.20(t t0) + 3.40 1.00 2D growth,
Cyquest N-900 2.5 i = 2.43(t t0) + 4.53 1.00 diffusion control
HydroStar + chloride* 2.5 i = 3.45(t t0) + 7.74 1.00
DXG-F7 + chloride* 2.5 i = 3.71(t t0) + 7.9 1.00
Cyquest N-900 + chloride* 2.5 i = 3.19(t t0) + 8.08 0.99
*The electrolyte contained 2.5 mg/L organic additive and 20 mg/L chloride.

density versus time curves obtained from these electrolytes with

organic additives and Cl ions also give linear relationships of
current density versus (t t0), as shown in Table 3 and Fig. 10.
As mentioned earlier, the addition of 2.5 mg/L HydroStar
depolarized the copper deposition reaction, and the addition of
20 mg/L chloride does not change this behavior. Similar results
have been reported by Cui (2014) and in Part III of this series.
The addition of 20 mg/L Cl to an electrolyte containing 2.5
mg/L DXG-F7 appeared to depolarize the reaction of copper
deposition. Similar results were observed for Cyquest N-900.
The Cyquest N-900 results appear to contradict results presented
in Part III of this series. However, the technique and time scales
of our previous experiments (cyclic voltammetry with 1 mV/
sec scan rate and electrochemical impedance spectroscopy)
were much longer than those of this study. The nucleation of
copper is also heavily influenced by the surface state of the t t0 (sec)
stainless steel, which may have caused some of the variation
between the different types of experiments. The difference Figure 10 Current density versus time relationships at
warrants further investigation. the applied potential of 0.16 V versus the SHE with addi-
SEM images of copper deposits from electrolytes contain- tion of both 20 mg/L Cl and 2.5 mg/L organic additive(s).
ing a combination of Cl ions and organic additive (Cl with
HydroStar, and Cl with Cyquest N-900) show that they
appear to have produced rougher surfaces with larger nuclei
(Figs. 11 and 12) when compared with the electrolytes with no 1992). With that said, the addition of chloride and Cyquest
Cl (Figs. 7 and 9). This is probably because of faster growth N-900 produced large areas of complete coverage of copper
rates observed when Cl ions are present (Sun and OKeefe, on stainless steel in 30 seconds at 300 A/m2.

(a) (b)

Figure 11 (a) and (b) SEM micrographs of copper nuclei on 316L stainless steel in a base electrolyte with addition of
2.5 mg/L HydroStar and 20 mg/L chloride after 30 sec at 30 mA/cm2 (magnification 1000x).

MINERALS & METALLURGICAL PROCESSING 45 Vol. 33 No. 1 February 2016

 (a)
Figure 12 (a) and (b) SEM micrographs of copper nuclei on 316L stainless steel in a base electrolyte with addition of
2.5 mg/L Cyquest N-900 and 20 mg/L chloride after 30 sec at 30 mA/cm2.
It is worth mentioning that: (1) Cyquest N-900 produced the
best deposition coverage at the concentration examined among
the additives used and (2) DXG-F7 was the fastest additive to
dissolve during the preparation of the aqueous stock solution.
Conclusions
A nonstirred three-electrode cell setup was used to conduct
potentiostatic measurements to elucidate the nucleation and
growth mechanisms during the initial phases of copper elec-
trowinning using stainless steel blanks in the presence of addi-
tives consisting of chloride, HydroStar, DXG-F7 and Cyquest
N-900. Based on the theoretical nucleation and growth models,
good agreement was achieved between theory and the SEM
micrographs of deposits produced at the commercially relevant
current density of 30 mA/cm2. The dominant mechanism for
copper nucleation and growth on 316L stainless steel in a 40
g/L Cu and 160 g/L H2SO4 electrolyte at 40C appears to be
progressive nucleation with two-dimensional growth under
diffusion control. SEM analysis also pointed to possible three-
dimensional growth at more cathodic potentials in the presence
of chloride without organic additives.
Addition of small 2.5-mg/L quantities of the organic addi-
tives Hydrostar, DXG-F7 and Cyquest N-900 did not appear
to affect the nucleation and growth mechanism. However, the
smoothing agents resulted in a reduction in size and increase in
number of nuclei, leading to more uniform distribution across
the stainless steel substrate. At the concentrations evaluated,
Cyquest N-900 produced the best coverage.
Acknowledgments
The authors thank the Materials Research Center, Missouri
S&T, for supporting this work and the copper mining companies
for supplying the organic reagents.
February 2016 Vol. 33 No. 1 46
(b)
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