Canadian Metallurgical Quarterly

The Canadian Journal of Metallurgy and Materials Science

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The Role of Electrolyte Additives on Passivation

Behaviour During Copper Electrorefining

Michael S. Moats & J. Brent Hiskey

To cite this article: Michael S. Moats & J. Brent Hiskey (2000) The Role of Electrolyte Additives
on Passivation Behaviour During Copper Electrorefining, Canadian Metallurgical Quarterly,
39:3, 297-306, DOI: 10.1179/cmq.2000.39.3.297

To link to this article: https://doi.org/10.1179/cmq.2000.39.3.297

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 297

Canadian Metallurgical Quarterly, Vol 39, No 3, pp 297-306, 2000

© Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

THE ROLE OF ELECTROLYTE ADDITIVES ON PASSIVATION

BEHAVIOUR DURING COPPER ELECTROREFINING
MICHAEL S. MOATS and J. BRENT HISKEY

Copper Research Center, Department of Materials Science and Engineering,

University of Arizona, 4717 E. Fort Lowell, Tucson, Arizona, 85719, USA

(Received July 1999; in revised form January 2000)

Abstract — Additives, such as chloride, thiourea and glue, are commonly added to electrorefining elec-
trolyte to control deposition structure and morphology. Very few studies have been performed to observe
their effects on anode passivation. Chronopotentiometry was utilized to observe the passivation behav-
iour of commercial copper anodes in synthetic electrolyte. The effect of chloride, thiourea and glue were
investigated individually. A simulated electrolyte containing all three additives was used in conjunction
with twenty commercial copper anode samples to determine possible interactions between additives and
anode composition.

Résumé — Des additifs, tels que du chlorure, de la thiourée et de la colle, sont généralement ajoutés à
l’électrolyte de raffinage électrolytique afin de contrôler la structure et la morphologie du dépôt. Il existe
très peu d’études de leur effet sur la passivation de l’anode. On a utilisé la chronopotentiométrie pour
observer le comportement de passivation d’anodes commerciales en cuivre dans un électrolyte
synthétique. On a étudié individuellement l’effet du chlorure, de la thiourée et de la colle. On a utilisé un
électrolyte simulé contenant tous les trois additifs en conjonction avec vingt échantillons d’anode
commerciale en cuivre afin de déterminer les interactions possibles entre les additifs et la composition
de l’anode.

INTRODUCTION al. demonstrated that passivation time decreased with

Anode passivation in copper electrorefining has received
increasing attention as industry pushes to higher current
densities which can accentuate this detrimental behaviour.
Most of the recent research focuses on the role of anode
impurities on the passivation mechanism. This has been
accomplished through microstructural [1-22] and electro-
chemical [23-45] investigations. The role of the electrolyte
composition has not received as much focus.
From the studies that have occurred, it is readily shown
that electrolyte composition and temperature have a signif-
icant impact on passivation phenomena. Anode passivation
has been shown to be aggravated by increasing the copper
concentration, the sulfuric acid concentration, or decreas-
ing the temperature[23,39,44-46]. These factors all
increase the likelihood of copper sulfate precipitation
which can act as a passivating film. Noguchi et al. showed
that time to passivation decreased with increasing Sb3+,
As3+, Bi3+ in the electrolyte [42]. The accelerated passiva-
tion was attributed to an increase in slime formation. Abe et
increasing nickel added as nickel sulfate [23]. The nickel
addition also aggravates copper sulfate precipitation by the
increased sulfate and increased viscosity which lowers the
diffusivity of copper ions [49].
Several recent studies have focused on the effect of
additives on passivation in laboratory experiments. Hiskey
and Cheng showed that thiourea has a strong influence on
the time to passivation of a commercial copper anode [47].
For a small addition, 1-5 ppm, thiourea improves the passi-
vation behaviour, but for a large addition, greater than 15
ppm, the tendency towards passivation increases. Jin et al.
showed that the addition of amino acid chelating agents can
inhibit passivation. In particular, ethylenediaminete-
traacetic acid (EDTA), diethylenediamine-pentaacetic acid
(DTPA) and triethylenediaminehexaacetic acid (TTHA)
show some benefit. All three exhibit an optimal concentra-
tion for extending passivation times[48]. Jin and Ghali
studied the effects of several aromatic nitro compounds.
The most beneficial toward inhibiting passivation were 3, 5
- dinitrosalicylic acid and 3, 5 - dinitrobenzoic acid.

CANADIAN METALLURGICAL QUARTERLY

298 MICHAEL S. MOATS and J. BRENT HISKEY

In this current investigation, a more systematic evalua-
tion of the three most common electrorefining additives,
thiourea, glue and chloride, is performed with a focus on
their effects on anode passivation. Each additive was inde-
pendently and collectively investigated to determine possi-
ble interactions. Other experiments were conducted with
several anodes to observe interactions between additives
and anode composition.
EXPERIMENTAL
Electrolyte
A synthetic electrolyte was utilized for all electrochemical
testing. The electrolyte was prepared by using ACS reagent
grade chemicals with no further treatments (except glue
which was obtained from BHP Copper) and 18.2 MΩcm
deionized water. A standard electrolyte composition of 40 g
l-1 Cu (0.63 M) and 160 g l-1 H2SO4 (1.66 M) was used at a
temperature of 65 °C +/- 0.5 °C. The copper source chem-
ical was CuSO4•5H2O. Additives that are known to decom-
pose with time in the electrolyte, such as thiourea and glue,
were added just prior to heating the electrolyte.
There were two categories of experiments performed:
1) single variable and 2) additives versus anode composi-
tion. In the single variable experiments, chloride, thiourea
and glue were investigated individually using a minimal
number of anode samples. A simulated electrolyte (con-
taining all three additives) was used in conjunction with 20
different anode samples to determine interactions between
additives and anode composition.
Chronopotentiometry
Chronopotentiometry (CP) was performed to observe the
effect of compositional and electrolyte variables on the pas-
sivation response during anodic dissolution. The CP tests
were performed in a one liter three-electrode cell purchased
from EG&G Instruments Inc. The working, auxiliary and
reference electrodes were a cylinder from an anode sample,
a length of high purity copper rod and a saturated mer-
curous sulfate electrode (MSE), respectively. The working
and counter electrodes were prepared by polishing with sil-
icon carbide paper from 180 grit to 600 grit and cleaning
with 18 MΩcm deionized water in an ultrasonic bath for
five minutes. The electrodes were rinsed with a copious
amount of deionized water and transferred to the elec-
trolytic cell containing one liter of synthetic electrolyte
held at 65.0 °C +/- 0.5 °C.
The electrodes were allowed to equilibrate with the sys-
tem by being held in the electrolyte at open circuit potential
for five minutes. A constant current density of 3820 A m-2
was then applied using an EG&G model 273
Potentiostat/Galvanostat controlled by HEADSTART soft-
ware for the duration of the test. A selection of 3820 A m-2
was used based on previous work by Cheng and Hiskey[29]

Table I – Selected Impurity Concentrations (ppm) for Commercial Copper Anodes

Anode Se Te Pb Ni As Sb O Ag

MCCA-2 20 16 387 3456 654 1069 1548 352

MCCA-3 623 108 140 1188 815 179 474 1280
MCCA-5 372 137 432 3353 717 348 2516 1740
MCCA-9 404 124 659 3904 656 353 3518 1700
MCCA-17 154 30 8 24 2413 173 1572 398
MCCA-18 100 25 693 1033 103 59 1108 257
MCCA-21 910 38 809 2835 590 89 2129 837
MCCA-23 901 39 749 2824 579 87 2076 822
MCCA-25 113 17 104 178 778 879 1795 511
MCCA-28 1705 569 2516 1389 1257 933 1883 1937
MCCA-35 457 41 39 124 210 39 2177 342
MCCA-40 455 38 114 183 1050 61 889 357
MCCA-42 565 181 691 1651 497 166 3598 1074
MCCA-45 779 389 1927 776 1576 712 1752 1853
MCCA-48 345 47 989 819 681 282 2083 344
MCCA-50 350 37 1259 978 479 216 1544 284
MCCA-54 577 76 580 2834 2521 467 3496 511
MCCA-57 538 71 610 2884 2430 440 2084 520
MCCA-65 303 26 88 74 801 182 3046 333
MCCA-72 404 25 49 59 826 201 2995 334

CANADIAN METALLURGICAL QUARTERLY

 THE ROLE OF ELECTROLYTE ADDITIVES ON PASSIVATION BEHAVIOUR DURING COPPER ELECTROREFINING 299

which illustrated that this current density results in enough

sensitivity to observe the effect of anode composition on
passivation in an acceptable time frame. Other current den-
sities were employed to study the effect of that parameter
on passivation characteristics of anodes and pure copper.
Potential-time (E-t) responses were collected as averages of
two-second intervals. The experiments were typically run
for 3600 seconds. All tests were conducted in air under sta-
tic conditions.

Small approximately cubic sections were removed from

the body of commercial copper anodes to furnish the sam-
ples for research. Working electrodes were carefully
machined from these sections into cylinders of 1.1 cm in
diameter and at least 1 cm in height. If possible, each elec-
trode was taken from the “set” side of each sample.
Electrical contact was provided by soldering a copper or
aluminum wire to the back surface (away from the “set”
side) of the cylinder using a lead-tin low temperature melt-
ing alloy. The electrode was then mounted to a length of
glass tubing (1.2 cm ID) with epoxy resin. The resin also
protected the copper piece from electrolyte contact except
for the circular face of the cylinder. This exposed face had
a surface area of 1 cm2. The glass tubing provided rigidity
and protection from the electrolyte for the contact wire.
Selected chemical analyses for the twenty commercial
copper anodes utilized in this investigation are presented in
Table I.
Fig. l. The Effect of Chloride in the Electrolyte on Time to Passivation
for Two Selected Anodes. 40 g l-1 Cu, 160 g l-1 H2S04, 65 °C, 3820 A m-2
no agitation, atmospheric conditions.
sivation was observed in the one hour time frame of a nor-
mal chronopotentiogram. To conserve the working elec-
trode from MCCA-25, these experiments were not repeat-
ed for longer times.
Several other anodes were tested with electrolyte con-
taining chloride. Anodes exhibiting a positive response to
chloride are shown in Figure 2, while those indicating min-
imal or slightly negative effect are in Figure 3.

RESULTS
Additives are commonly introduced to copper refining
electrolytes to control the cathode deposit characteristics.
The most common additives are chloride, thiourea and glue
[50]. These reagents were evaluated at various concentra-
tions using two anodes MCCA-23 and MCCA-25. These
two anodes were selected because of their short and long
passivation times in the standard electrolyte which were
measured to be 1015 and 2375 s, respectively. Other anodes
were also examined to provide supplementary information
concerning the effect of thiourea and chloride.
Thiourea
The effect of thiourea on tp for MCCA-23 and MCCA-25 is
displayed in Figure 4. Thiourea appears to have a positive
effect at low concentrations and a negative effect at high
concentrations. These results confirm those of Hiskey and
Cheng [47] as shown by the curve for MCCA-23 in Figure
5. A similar response indicating a slight increase in tp at low
thiourea concentration and a pronounced decrease at high

Chloride
Chloride is typically the only non-organic electrolyte addi-
tive used in electrorefining. Chloride levels of commercial
tankhouses vary between 20 and 70 ppm. Experiments
were performed with in electrolytes containing 0, 10, 30, 50
and 75 ppm chloride. Figure 1 illustrates the positive effect
of chloride on time to passivation for MCCA-23 and
MCCA-25. Anode MCCA-23 exhibited a slight increase in
tp up to about 50 ppm chloride and then a sharp increase to
75 ppm. Anode MCCA-25 displayed a noticeable increase
in time to passivation with the addition of 10 ppm chloride.
Experiments were also conducted with MCCA-25 in elec- Fig. 2. Anodes Exhibiting a Positive Effect to Chloride in the Electrolyte.
trolyte containing 30, 50 and 75 ppm chloride, but no pas- 40 g l-1 Cu, 160 g l-1 H2S04, 65 °C, 3820 A m-2, no agitation, atmospheric
conditions.

CANADIAN METALLURGICAL QUARTERLY

300 MICHAEL S. MOATS and J. BRENT HISKEY
Fig. 3. Anodes Exhibiting a Neutral to Negative Effect to Chloride in the
Electrolyte. 40g l-1 Cu, 160 g l-1 H2S04, 65 °C, 3820 A m-2, no agitation,
atmospheric conditions.
concentration was also observed for anodes MCCA-35 and
MCCA-28.
Previously Hiskey and Cheng [47], using the same pro-
cedure as the current investigation, detected cycles of pas-
sivation and reactivation prior to Region IV of chronopo-
tentiograms for a commercial copper anode in synthetic
electrolytes containing 15, 50 or 100 ppm of thiourea. The
tendency towards cyclic passivation-depassivation was
accentuated by allowing the electrolyte to stand for 24
hours before initiating the CP test. This behaviour was not
detected for any of the four anodes tested at any of the
thiourea concentrations utilized. The role of thiourea in
reactivation is not fully understood; it may be related to
thiourea degradation products.
Fig. 4. The Effect of Thiourea in the Electrolyte on Time to Passivation
for Two Selected Anodes. 40 g l-1 Cu, 160 g l-1 H2S04, 65 °C, 3820 A m-2,
no agitation, atmospheric conditions.
CANADIAN METALLURGICAL QUARTERLY
Fig. 5. Comparison of Effect ofThiourea on Time to Passivation for
Anode MCCA-23 and a Commercial Anodes Tested by Hiskey and
Cheng [47] Under Similar Conditions.
Glue
The influence of glue concentration on passivation time for
anodes MCCA-23 and MCCA-25 is summarized in Table
II. Both anodes appear to exhibit a maximum tp around 1
ppm. Higher concentrations appear to have little or no
effect. Interestingly, potential oscillations were observed
for both anodes in Region IV as shown in Figure 6 for
anode MCCA-23 in an electrolyte containing 20 ppm glue.
Interestingly, the large oscillations occur after a “stable”
beginning in Region IV. This is significantly different than
the passivation to reactivation potential behaviour observed
by Hiskey and Cheng [47] for electrolytes containing
thiourea which clearly showed that the oscillations were
prior to Region IV. The cause for the potential behaviour in
Region IV caused by electrolytes containing glue is not
fully understood at this time.
Simulated Industrial Electrolyte
An electrolyte of 40 g l-1 Cu, 160 g l-1 H2SO4, 30 ppm Cl,
1 ppm thiourea and 1 ppm glue was used to study the
effect of a simulated industrial electrolyte on twenty dif-
ferent anodes. The times to passivation for each anode in
standard electrolyte (40 g l-1 Cu and 160 g l-1 H2SO4) and
Table II – Time to Passivation as a Function of Glue
Concentration
Glue Concentration Time to Passivation
(ppm) (sec)
MCCA-23 MCCA-25
0 1015 2675
1 1426 >3600
5 916 2143
20 1290 2177
 THE ROLE OF ELECTROLYTE ADDITIVES ON PASSIVATION BEHAVIOUR DURING COPPER ELECTROREFINING 301

Table III – Time to Passivation for Selected Anodes in Standard and Simulated Electrolyte at 65 °C with a
Current Density of 3820 A m-2

Response to Additives Anode Standard tp (sec) Simulated tp (sec)

MCCA-17 2253 4111

MCCA-18 1846 2463
MCCA-23 1015 3015
MCCA-28 770 1154
MCCA-45 846 1044
Increase
MCCA-50 1525 1828
MCCA-54 1233 1804
MCCA-57 1221 2229
MCCA-65 1874 2839
MCCA-72 1363 1648

MCCA-2 977 956

MCCA-5 1014 1148
MCCA-9 939 1174
No Measurable MCCA-21 1034 1036
Difference MCCA-25 2675 2480
MCCA-35 1358 1422
MCCA-40 2120 1924
MCCA-48 1128 1108

Decrease MCCA-3 1673 1044

MCCA-42 1319 1020

simulated electrolyte are listed in Table III. Of the twenty is that anodes with high As (>1200 ppm) experienced
anodes tested, ten indicated a definitive increase in passi- large increases in tp. If the high arsenic and high nickel
vation time, eight remained about the same and two (>2800 ppm) anodes are removed from consideration, the
exhibited a significant decrease. remaining data reveals a negative trend with increasing
silver as shown in Figure 8.
The effect of anode composition interacting with the
additives in the electrolyte was examined. The fractional
change was calculated according to the following formu-
la

(SIM - STD) / STD (1)

where SIM is the tp in the simulated electrolyte (40 g l-1

Cu, 160 g l-1 H2SO4, 30 ppm Cl-, 1 ppm thiourea and 1
ppm glue) and STD is the tp in the standard electrolyte (40
g l-1 Cu and 160 g l-1 H2SO4). The fractional change was
compared to each significant impurity identified by mul-
tiple linear regression for STD. The best correlation
between fractional change and composition for all of the
Fig. 6. Reactivation Detected in Region ~V in the Presence of 20 ppm
data was found with arsenic. That trend is plotted in
Glue in the Electrolyte for MCCA-23. 40 g l-1 Cu, 160 g l-1 H2S04, 65 °C,
Figure 7. The most significant observation from this trend 3820 A m-2, no agitation, atmospheric conditions.

CANADIAN METALLURGICAL QUARTERLY

302 MICHAEL S. MOATS and J. BRENT HISKEY
Fig. 7. The Effect of Arsenic Concentration of the Anode on the Change
of Time to Passivation with the Introduction of 30 ppm C1-, 1 ppm
Thiourea and 1 ppm Glue to the Electrolyte. 40 g l-1 Cu, 160 g l-1 H2S04,
65 °C, 3820 A m-2, no agitation, atmospheric conditions.
Fig. 8. The Effect of Silver Concentration of Anodes with on the Change
of Time to Passivation with the Introduction of 30 ppm C1-, 1 ppm
Thiourea and 1 ppm Glue to the Electrolyte. 40 g l-1 Cu, 160 g l-1 H2S04,
65 °C, 3820 A m-2, no agitation, atmospheric conditions.
DISCUSSION
While organic additives, such as thiourea and glue, exhib-
ited a positive effect at low levels, higher concentrations of
these compounds tend to accelerate passivation. Thiourea is
especially harmful at high concentrations (i.e. 20 – 50
ppm). This phenomenon is thought to be caused by the
adsorption of these compounds or their degradation prod-
ucts on the anode surface. The adsorbed film would block
active surface sites just like slimes or copper sulfate lead-
ing to passivation. In the case of thiourea, it is believed that
formamidine disulfide (FDS) and ultimately elemental sul-
fur act as the blocking species. However, for glue and its
degradation products, it is unclear at this time how the
adsorption occurs or what species are responsible for the
CANADIAN METALLURGICAL QUARTERLY
passivating effect. There does appear to be an optimal con-
centration at which passivation is delayed for both glue and
thiourea, but exceeding that level can be detrimental.
Interactions Between Anode and Electrolyte Compositions
The experiments conducted with twenty different anode
samples in simulated electrolyte illustrated that interactions
occur between anode composition and electrolyte addi-
tives. This was shown in Table III by the fact that some
anodes experienced an increase in time to passivation while
others decreased. The fractional change in tp, (SIM-
STD)/STD, was compared to each impurity element. The
strongest correlation was found for arsenic. High arsenic
anodes, MCCA-17, MCCA-54 and MCCA-57, exhibited
the largest normalized increase. This seems to indicate that
anodes with arsenic respond favorably to additives in the
electrolyte. Excluding these anodes high in arsenic, most of
the remaining anodes show a decreasing trend in time to
passivation with increasing silver. The few anodes that do
not exhibit this behaviour are those with high nickel.
At this time, it is not fully understood why anodes with
higher arsenic respond so favourably to the introduction of
additives to the electrolyte. In pure electrolyte the effect of
arsenic has been related to possible changes in localized pH
at the anode surface. While the change in pH could affect
the complexing equilibrium between the additives and
cuprous ions, arsenic could also have an effect by provid-
ing a beneficial redox couple. Thiourea (Tu) which com-
plexes cuprous ion according to the following reaction
[ ]
+
Cu + + 4 Tu → Cu(Tu) 4 K f =2.44 × 1015 (2)
can also oxidize and form formamidine disulfide (FDS)
around 0.5 V vs NHE.
2 Tu → [ FDS]2+ + 2 e - E O ≅ 0.5 V (3)
The structures of thiourea and FDS in the fully protonated
form are shown in Table IV.
The dissolution of arsenic involves several reactions
depending on the phase present within the anode.
Regardless, the terminal species of arsenic in the highly
acidic electrolyte will be arsenate in the form of H3AsO4
which is generated from arsenite with a reduction standard
potential of 0.575 V.
 THE ROLE OF ELECTROLYTE ADDITIVES ON PASSIVATION BEHAVIOUR DURING COPPER ELECTROREFINING 303

CONCLUSIONS
+ (4)
H 3 AsO 4 + 2 H + 2 e → -
This investigation studied the effect of common electrore-
H 3 AsO 3 + H 2 O E O = 0.575 V fining additives on anode passivation behaviour. The major
conclusions from this research are:

The arsenic oxidation coupled with the reduction of
FDS could result in more Tu present at the anode. This
would increase the amount of cuprous ion complexed by
thiourea and extend the time to passivation.
[FDS]2+ + H 3 AsO 3 + H 2 O →
H 3 AsO 4 + 2 Tu + 2 H +
1. For most anodes tested, chloride had a significant posi-
tive effect by extending the times to passivation.
2. Both glue and thiourea appear to be an optimal concen-
tration (approximately 1 ppm) at which an increase in tp
observed. If the glue or thiourea concentration significant-
ly exceeds the optimal concentration, then a decrease pas-
(5) sivation time is observed.

3. Two relationships were detected between a electrolyte

The detrimental effect of silver on the response to addi-
tives in the electrolyte is believed to be related to its influ-
ence on the cuprous ion concentration. Impedance spec-
troscopy of the passive surface indicated that the resistance
of the adsorbed intermediate (cuprous ions) decreased with
increasing silver content within the anode. The addition of
75 ppm chloride to the electrolyte had minimal effect on
containing all three additives at normal industry concentra-
tions (simulated) and twenty commercial copper anodes of
varying composition.
4. The first observation was that anodes with high arsenic
(>1200 ppm) exhibited a significant increase in time to pas-
sivation when tested in the simulated electrolyte versus the
standard electrolyte (no additives).

Table IV – The Structures of Thiourea and Fully 5. The second relationship was that anodes with arsenic
Protonated Formamidine Disulfide less than 1200 ppm and nickel less than 2800 ppm dis-
played a negative response to the additives in the elec-
trolyte with increasing silver.
Compound Structure

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