Fundamental Studies of Copper Anode Passivation

During Electrorefining Part I. Development of Techniques

XUAN CHENG and J. BRENT HISKEY

Anode passivation is an extremely important phenomenon in commercial copper electrorefining op-

erations. Due to the electrochemical nature of the refining process, various electrochemical techniques
have been applied to examine anode passivation behavior. In this investigation, cyclic voltammetry,
linear potential sweep, and chronopotentiometry measurements were carried out on several com-
mercial copper anodes, as well as on pure electrowon (EW) copper cathode, in synthetic electrolytes
simulating the primary constituents for industrial operations. The important parameters associated
with anode passivation were identified and compared for the three electrochemical techniques. Chron-
opotentiometry is an extremely sensitive technique and proved to be the most suitable for analyzing
and characterizing copper anode passivation.

I. INTRODUCTION tiodynamic polarization measurements with pure copper

COPPER electrorefining in acidified copper sulfate elec-
trolytes has been widely used for over a century to produce
high-purity copper. Knowledge of the basic principles and
theories were well understood near the turn of the century;
however, some operating problems still remain unsolved.
Prominently among them is anode passivation, frequently en-
countered in commercial copper electrorefining operations.
Passivation results in a reduction of refinery output and an
increase of power consumption. A major cause of passiva-
tion is impurities in copper anodes which usually contain
notable amounts of Se, Te, As, Bi, Sb, S, Ni, and precious
metals such as Ag and Au. Although total impurity concen-
tration in commercial copper anodes is less than 1 wt pct,
the small amount of certain impurities can have a dominant
effect on the anode behavior and the refining process.
The effects of individual anode impurities such as arsenic,
antimony, silver, nickel, and selenium on passivation have
been previously recognized and extensively studied. [~-~~ Due
to the electrochemical nature of the copper refining process,
various electrochemical techniques (i.e., cyclic voltammetry,
potentiodynamic polarization, and galvanostatic measure-
ment) have been considered as complementary and powerful
approaches for studying copper anode passivation.
Kucharska-Giziewicz and MacKinnonttOl identified five
distinct regions in the cyclic voltammograms of silver-rich
(0.1 pct Ag) anodes. The five regions consist of (1) initial
dissolution, (2) formation of the first peak, (3) development
of the second peak, (4) current oscillations, and (5) regular
dissolution which occurs after surface films have formed on
the electrode. The formation of peaks corresponded to the
accumulation of reaction products on the anode surface.
The oscillations in region 4 were related to the detachment
of surface product layers. The shape of the second peak
was claimed to be related to the nature and composition of
product layers which were associated with the accumulation
of metallic silver on the electrode surface. Based on poten-
XUAN CHENG, Research Associate, and J. BRENT HISKEY,
Professor, are with the Copper Research Center, University o f Arizona,
Tucson, AZ 85721.
Manuscript submitted May 17, 1995.
and three silver-rich anodes, Compare et al.t8] observed dif-
ferent current maxima depending on the silver content of
anode samples. They observed two well-defined maxima at
the highest silver level (0.87 pct Ag) and peak current den-
sities considerably below that of pure copper. Passivation
times of pure copper and impure copper anodes were ob-
tained by Abe et al.tq and Compare et al.tS] through gal-
vanostatic measurements. The previous studies have
focused primarily on single element effects, notably, As,
Sb, Ag, Ni, and Se. In most instances, experimental anodes
were modified by adding large amounts of individual ele-
ments to amplify their effect on passivation. Unfortunately,
no explicit relationship between passivation behavior and
anode composition has been established. Furthermore, the
combined effects due to multiple element interactions have
not been thoroughly studied. In particular, little attention
has been paid to oxygen and its interaction with other im-
purities.
The work presented here attempts to improve on these
shortcomings. Cyclic voltammetry, linear potential sweep
(potentiodynamic polarization), and chronopotentiometry
(galvanostatic) measurements were carried out to study the
passivation behavior of commercial copper anodes contain-
ing multiple impurities. The aim of this work was to de-
velop an electrochemical method sensitive enough to
accurately determine multiple element effects. Analysis and
interpretation of the individual chronopotentiograms are
presented for several commercial copper anodes. This study
establishes the correlation between anode composition and
passivation for a limited number of commercial copper an-
odes. Future work will apply these techniques to a larger
number of anode samples.
II. EXPERIMENTAL
A. Materials
Chemical analyses for the several copper samples used
to make experimental electrodes are given in Table I. The
electrowon (EW) copper cathode representing pure copper
contained less than 16 ppm total impurities. Four commer-
cial copper anodes were used in this study. The synthetic

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 2713, JUNE 1996---393

 Table I. Chemical Analyses of Copper Samples

Element (ppm)
Sample Se Te Bi Sb As Pb S Sn Ni Fe Ag Au O2
EW Cu cathode 0.4 - - <0.1 <1 <1 0.3 3 <1 <1 7 <1 -- --
ER Cu rod 0.8 <1 0.4 <1 <1 0.5 4 <1 <1 2 9 -- --
Anode A1 411 38 52 37 136 33 26 2 92 9 302 7 930
Anode A2 415 41 54 42 148 33 35 2 78 14 313 6 1997
Anode A3 464 41 47 45 414 79 33 47 94 7 239 13 1673
Anode A4 418 35 41 84 620 117 30 84 109 4 335 8 2033

7000 , , i i
(also obtained from EG&G Instruments, Inc.). For each
6th cy'cle 23rd cycle

f
5000
>,
9~ 4000
3000 7~/
2000 t /
i 000
0 i
0.2 0.4 016 0.2 0.4 0.6 0.2 0.4 0.6
Potentiol (V, vs. SHE)
Fig, 1--~Cyclic v o l t a m m o g r a m s obtained with the pure copper at a scan
rate o f 2 mV/s.
electrolyte contained 40 g/L Cu 2§ and 160 g/L H2SQ. Cu-
pric sulfate (CuSO4"5HzO) and sulfuric acid (H2SO4) o f an-
alytical reagent grade were used for the preparation o f
electrolyte. Electrolyte solutions were made up using dis-
tilled deionized water o f 18 Mf~-cm purity.
Individual copper anode samples were furnished as cast
and quenched shapes referred to as "spikes." Working
electrodes were prepared from these samples and from the
EW copper cathode. Cylinders measuring 1.13 cm in di-
ameter and approximately 1 cm in height were carefully
machined from these materials. A copper wire was soldered
to the back surface o f each specimen to provide the nec-
essary electrical contact. The copper specimen including the
contact wire was mounted into a section o f glass tubing
(1.2-cm i.d.) with epoxy resin. A counter or auxiliary elec-
trode measuring 1 cm in diameter and 19.3 cm in length
was prepared from the high-purity ER copper rod. The ex-
posed areas o f the working and counter electrodes were
approximately 1 and 22.8 c m 2, respectively.
measurement, the working electrode was polished with a
silicon carbide paper, from 200-grit down to 600-grit, and
cleaned with deionized water in a ultrasonic bath for 5
minutes. The electrode was immediately transferred to the
electrolyte cell and then left at an open circuit potential for
5 minutes. Both the working and counter electrodes were
vertically placed in the cell. All potentials in this article are
quoted in volts with respect to the standard hydrogen elec-
trode (SHE), although they were measured against the mer-
curous sulfate electrode (0.62 V vs SHE).
Cyclic voltammetry (CV), linear potential sweep (LPS),
and chronopotentiometry techniques were employed in the
present investigation. For CV measurements, potential
scans started from the rest potential and progressed in the
anodic direction to 0.62 V, and then reversed in direction
back to the rest potential at a scan rate o f 2 mV/s. Voltam-
mograms were recorded for a total o f 23 cycles. For LPS
measurements, polarization curves were obtained from the
rest potential to 1.82 V at a scan rate o f 0.05 mV/s. This
slow scan rate was used to measure "steady-state" poten-
tial-current curves. Chronopotentiometry measurements
were performed by applying constant current densities of
1910 and 3820 A/m 2 to the working electrode. The current
densities higher than those operated in industrial processes
were chosen to collect passivation data more conveniently.
Potential-time (E-t) responses o f up to 1 hour were recorded
for each electrode tested. The repeat tests were performed
for pure copper and impure copper anodes. Under constant
conditions, the experiments were extremely reproducible
with a variation within 20 seconds.
llI. RESULTS
A. Cyclic Voltammetry Studies

B. Electrochemical Measurements
A conventional three-electrode cell, a model 273 poten-
tiostat/galvanostat (both obtained from EG&G Instruments,
Inc., Princeton, N J), and an IBM* PS/2 model 55 SX com-
*IBM is a trademark o f International Business Machines Corp.,
A r m o n k , NY.
puter were used for electrochemical measurements. The
electrolyte was maintained at 65 ~ -4- 0.5 ~ in a constant
temperature water bath. All the tests were conducted under
air atmosphere without agitation. The working electrode
was a sample o f an impure copper anode or pure EW cop-
per. The auxiliary electrode was a length of copper rod.
The reference electrode was a mercurous sulfate electrode
The cyclic voltammograms obtained with the pure cop-
per in a synthetic electrolyte at 65 ~ are shown in Figure
1 for the 1st, 6th, and 23rd cycles. As depicted in these
voltammograms, there were no peaks or oscillations ob-
served for the pure copper, even after 23 cycles, although
Kucharska-Giziewicz and MacKinnont~O} observed minor
current oscillations in the reverse scan for the 1st cycle but
none for the 23rd cycle.
The CV responses with the four commercial copper an-
odes are presented in Figures 2 through 4 for the different
polarization cycles. It is obvious that the polarization re-
sponse for the commercial copper anodes is considerably
more complicated than for pure copper. The voltammo-
grams o f the four copper anodes for the 1st cycle are not
significantly different from each other. The slopes in the

394--VOLUME 27B, JUNE 1996 METALLURGICAL AND MATERIALS TRANSACTIONS B

 70001A
~-~-~-I ] -'2 A3 ' ' A4
, ,~
[
4000 -- ~ ,
6000 [- /[
E / I 1
<
v 5000
/ ,'
i t At "J"

4000
ce
A2~: ,1~''
d3
3000 .
E
2000
2000
s
1000 i/ J)
0
0.2 0.4 0.6 0.2 O.4 0.6 0.2 0.4 0.6 O.2 0.4 O.6
Potential (V, vs, SHE)

through (d) Cyclic voltammograms obtained with the

Fig. 2 - - ( a ) 0 .....
commercial copper anodes for the I st cycle at a scan rate of 2 mV/s. 0.0 0.5 1.0 1.5 2.0

P o t e n t i a l (V, vs. SHE)

7000 , ,

t
A1 A2' A3 A4 Fig. 5--Polarization curves for pure copper and four commercial copper
6000 anodes at a scan rate of 0.05 mV/s.

~
E

4000
/)
5000 1
A4 were not significantly affected by repeated potential cy-

I?
cling.
o 3000

2000 B. Linear Potential Sweep Studies

o 1000 Polarization curves of pure copper and four commercial
0 (I copper anodes obtained from LPS measurements are com-
0.2 0.4 0.6 0.2 0.4 0.6 0.2 0.4 0.6 0.2 0.4 0.6 pared in Figure 5. Pure copper remained virtually unpas-
Potential (V, vs. SHE) sivated throughout the potential sweep, as indicated by the
absence of significant decrease in current density. There
Fig. 3 - - ( a ) through (d) Cyclic voltammograms obtained with the was a slight tendency toward passivation indicated by the
commercial copper anodes for the 6th cycle (A2 is the 4th cycle) at a
scan rate of 2 mV/s.
peak at 0.55 V. However, the electrode returned to active
dissolution with continuous current oscillations to the end
of the sweep. The appearance of the peak at 0.55 V is
7000 A1 ~ ' i i
A2 ' ' A,3 ] A4 ' associated with the formation of surface film. The contin-
6000 uous oscillations indicate that the surface film formed is

I
E
5000
unstable. Polarization curves of the four commercial copper
k>, anodes all showed typical activation-passivation behavior
4000 I and showed only one current density maximum. Transpas-
to
g I
sivation behavior was not observed for copper anodes. The
co9
3000 ~(21 magnitude and locations of current density maxima varied
2000
slightly for each anode.
(D
1000
)
0 f I [' C. Chronopotentiomeny Studies
0.2 0.4 0.6 0.2 0.4 0.6 0.2 0.4 0.6 0.2 0.4 0.6
Potential (V, vs. SHE) The typical chronopotentiometric response of pure cop-
per was obtained in a synthetic electrolyte at 1910 and at
Fig. 4 - - ( a ) through (d) Cyclic voltammograms obtained with the 3820 A/m 2. The results are shown in Figure 6. As can be
commercial copper anodes for the 23rd cycle at a scan rate of 2 mV/s.
seen from this figure, anode potentials increased very
slightly with time. No apparent passivation was observed
region of active dissolution are all approximately the same. at either current density for 1 hour.
Anodes A2 and A4 (high oxygen concentration, Table I) Typical E-t curves for the commercial copper anodes in
exhibited noticeably lower peak current densities. Oscilla- synthetic electrolyte at 1910 and at 3820 A/m 2 are presented
tions were observed for A1 and A2 starting with cycles 6 in Figure 7. At 1910 A/m 2, the anode did not experience
and 4, respectively. The appearance of oscillations is gen- any passivation. However, at 3820 A/m 2, all anodes became
erally associated with the formation of unstable surface passivated with time as indicated by the significant increase
films. All anodes experienced a reduction in peak current in potential. In brief, the E-t curves of anodes at 3820 A/m 2
density with increasing number of cycles. A1 and A2 dis- exhibited a slight increase in potential from the rest poten-
played well-defined peaks labeled as "1" and "2". These tial to the onset of passivation. Minor potential oscillations
results are similar to and contain all the features described started to occur prior to passivation. A sharp increase in
by Kucharska-Giziewicz and MacKinnon.V~ Although the potential indicates the onset of passivation. Finally, severe
current density maxima decreased with increasing potential and persistent oscillations continued to the end of the test.
cycling, in general, the electrochemical responses of A3 and Chronopotentiograms for pure copper and the four corn-

METALLURGICAL AND IvlATERIALS TRANSACTIONS B VOLUIvlE 27B, JUNE 1996--395

 0.5 I I ~ l I is clear that the passivation time t~, varied considerably tbr
3820 A/m 2 these electrodes.
0.4 1910 A / m 2
Ld
T
U3
IV. DISCUSSION
d
> 0.3
Cyclic voltammetry, linear potential sweep, and chron-
>.E
opotentiometry all provided potentially useful information
-6 0.2 regarding the anode passivation, although each method dis-
Pure Copper
played different sensitivities to variations in anode com-
O
o._ 0.1 position. Current density maxima (i,,,.) from cyclic voltam-
metry, peak potentials (E~) and peak current densities (i,,)
from linear potential sweep measurements, and passivation
0.0 i i I i i times (tp) from chronopotentiometry are summarized in Ta-
0 600 1200 1800 2400 3000 3600
ble II. The CV current density maxima decrease with in-
Time (Second) creasing number of cycles for all anodes. Accumulation of
Fig. 6---Typical chronopotentiograms tbr a pure copper electrode at 1910
reaction products on the electrode surface accounts for this
and 3820 A/m-'. decrease. The LPS measurements approximate steady-state
conditions and yield peak current density (i,) values varying
from 2770 to 3170 A/m 2. Peak potentials (Ep) vary by ap-
proximately 25 mV for the four commercial anodes. This
3.0 j I I I I I is considered a fairly insensitive technique. In contrast, pas-
Copper Anode 3820 A/m 2 sivation time (tp) values obtained by chronopotentiometry
2.5 A4 t
range from 857 to 1382 seconds. This technique appears to
he the most sensitive one and provides the best quantitative

"--iI
n-
0'I
2.0 measure of anode passivation.
d
> A complete inspection of the CV curves for the four
>"
1.5
commercial copper anodes reveals important information.
A1 and A2 exhibit five distinct regions in the voltammo-
-5
gram after 23 cycles. These results are similar to those of
1.0
0 Kucharska-Giziewicz and MacKinnon ['~ and even include
0
13- 1910 A/m 2 the reactivation region marked " 3 " in Figure 4(b). A3 and
0.5 ~-.----~- -~ A4 do not contain these features after extended cycling. The
difference in these patterns appears to be related to the ar-
0.0 I I I I I
senic content of the electrode. As given in Table I, A1 and
6O0 1200 1800 2400 3000 3600
A2 contain 136 and 140 ppm, respectively; whereas A3 and
Time ( S e c o n d ) A4 contain 414 and 620 ppm, respectively. Clearly, higher
Fig. 7--Typical chronopotentiograms for commercial copper anodes
concentrations of arsenic in those anodes reduce the ten-
(sample A4) at 1910 and 3820 A/mz. dency toward passivation.
A close examination of the major impurities besides ar-
senic shows that oxygen concentration also varies consid-
~.0 I I I I
erably in the anodes. Other impurities that show some
A2 A4 A3 AI variation include lead, nickel, and tin. In previous investi-
2.5 3820 A / m 2
gations of single element effects, arsenic was shown to have
a remarkable influence on anode slime adhesion, as well as
I
m 2.0 a depassivating effect on anodes531 Minotas et al.F] dem-
d> onstrated that arsenic could be beneficial to the electrore-
> 15
fining process in the presence of oxygen in solutions.
O
However, Noguchi et al.tgJ reported that high arsenic con-
1.0 centrations in anodes accelerated the passivation times, in
o
particular, at high anode oxygen content. Oxygen itself was
iX.
0.5 ~ cu also found to promote passivation.m When various types
and amounts of impurity, elements are present simultane-
0.0 I I i I I ously in anodes, the effect on anodic slimes becomes more
0 300 600 900 1200 1500 complex.
Time (Second) The LPS measurements indicate only minor variations in
passivation response tbr the four anodes investigated. Peak
Fig. S--Potential-time response for a pure copper electrode and
commercial copper anodes at 3820 A/m-~showing variation in passivation
potentials (E~) and current densities (it) are listed in Table
time (tp). II for these experiments. The LPS technique may provide
meaningful data for anodes with gross compositional dif-
ferences; however, for the commercial copper anodes ex-
mercial copper anodes are displayed in Figure 8 to indicate amined, LPS proved to be of minor significance. On the
the difference in relative time t,, elapsed to passivation. It other hand, tf, values are a useful measure of anode passi-

396---VOLUME 27B, JUNE 1996 METALLUR(IICAL AND MATERIALS TRANSACTIONS B

 Table II. Summary of Electrochemical Measurement Results
Cyclic Voltammetry Chrono-
(at 2 mV/s) Linear Potential Sweep potentiometry
/max (.&'m~) (at 0.05 mV/s) (at 3820 A/m2)
Copper
Anode
Number I st cycle 6th cycle 23rd cycle (V vs SHE) i~, ( A / m 2) tp (S)
Pure Cu 6720 5350 4790 0.584 2520
A1 6890 4670 3760 0.467 3170 1382
A2 6220 3900* 3110 0.455 2770 857
A3 7390 5610 4450 0.480 2810 1051
A4 5310 4820 4270 0.466 2890 992
*4th cycle

3.0 i i i
for impure copper anodes. These regions are illustrated in
5 8 2 0 A/m 2 t, q; Figure 9 and are discussed in detail subsequently.
2.5 Copper Anode
-r"
co A. Region I: Active Dissohttion (0 --+ tp')
2.0
&
> The potential increases sharply from the rest potential to
>- a value just below 0.5 V upon imposition of 3820 A/m 2.
1.5
The following region is characterized by active dissolution
1.0 of the copper anode and a slow increase in potential with
time.
eL 0.5 ~ ~ Chronopotentiograms of pure copper and the four copper
I II III IV anodes are plotted on an expanded scale in Figure 10 for
0.0 I T I l this region. It is obvious that pure copper dissolves at a
0 300 600 900 1200 1500 much lower slope (zXE/At) than the impure copper anodes.
Time (Second) At low arsenic, AE/At and 6' appear to be influenced by
anode composition. However, at high arsenic, the response
Fig. 9--Chronopotentiogramfor commercialcopperanodes (sample A2) in this region is nearly the same for A3 and A4. zXE/At is
showing four distinctive regions and passivationtime (6).
related to the concentration gradient of copper released
from the anodes according to the Nemst equation. When
0.55 2rE~At gets very large, the change of surface concentration
RegionI / is no longer sufficient to maintain active copper dissolution,
and other reactions may set in. The diffusion of copper ions
I from the electrode surface is controlled by either the for-
mation of surface films or impurity slime emanating from
the anode.

5 3 B. Region II: Pre-Passivation (t,' ~ tp)

*~ 0 . 4 5
o Potential oscillations characterize this region. The am-
0.40 f i
0 300 600
Time (Second)
Fig. 1 0 ~ E x p a n d e d scale potential-time response in region I for a pure
copper electrode and four commercial copper anodes at 3820 A/m 2.
ration. Furthermore, these values are sensitive to the type
and concentration of impurities present in the anodes.
Compared to the voltammograms and polarization
curves, the chronopotentiograms of commercial copper an-
odes at 3820 A/m 2 show many distinguishing features as-
sociated with anode passivation. Changes in E-t response
indicate alternations in surface layer properties, and anal-
ysis of these features can provide meaningful information
directly linked to the passivation phenomena. Four distinc-
tive regions can be identified from the chronopotentiogram
plitude of these oscillations gradually increases with time.
This behavior is related to the formation and stability of
i surface films. This appears to be periodic deposition and
900 1200 dissolution of surface products. These products are critical
to the development of passivation.
C. Region IlL" Passivation Onset (tp --4 tp")
Potentials increase abruptly at 6, but immediately drop
back to about 1.4 V, and then increase almost linearly with
time until 6"' The E-t response at t --- tp is characteristic of
the formation of a nonconducting layer, as described by
Kortum,[' u which leads to anode passivation. The values of
tp provide a quantitative measure of the tendency toward
passivation and are sensitive to anode composition. A linear
increase in potential is generally observed in the passivation
onset region (6 ~ tp"), which is related to the growth of
passivating surface layers. This region follows the ion-con-
ducting mechanism, discussed by Kortum.t' q

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 27B. JUNE 1996--397

D. Region IV." Passivation (t > tp")
Continuous potential oscillation is observed in this re-
gion. The persistent oscillation in region IV is strong and
irregular. Cheng et al.t~zl have identified massive layers of
copper selenides and copper sulfate coating on the outer
anode surface. However, in region IV, copper oxide films
formed in intimated contact with the electrode surface are
considered the main factor causing the passivating phenom-
ena.
It is apparent from the preceding analysis that the de-
tailed features of each region are diagnostic for the passi-
vation response of commercial copper anodes. Furthermore,
the passivation time (tp) provides the most sensitive param-
eter for determining compositional effect.
V. CONCLUSIONS
In this investigation, cyclic voltammetry, linear potential
sweep, and chronopotentiometry were used to examine the
passivation behavior of commercial copper anodes. Most
significant information was obtained from the examination
of chronopotentiograms. Cyclic voltammetry could distin-
guish certain impurity element effects such as arsenic and
oxygen on the copper anode behavior. However, it was not
sensitive enough to study multiple element effects. For the
anodes investigated, the linear potential sweep technique
could only indicate the general tendency of anode passi-
vation. It did not provide any electrochemical features as-
sociated with the passivation. However, chronopotentiom-
etry provided detailed features which are closely related to
passivation phenomena and was considered to be a more
powerful method to distinguish multiple elemental inter-
actions.
Four distinctive regions were identified from the analysis
of chronopotentiograms for commercial copper anodes: (1)
active dissolution, (2) pre-passivation, (3) passivation onset,
and (4) passivation. Characteristic values for the passivation
time (tp) were readily obtained for these commercial copper
anodes. Preliminary results indicate that high concentra-
tions of arsenic (400 to 600 ppm) in the anode reduce the
tendency toward passivation. However, at low concentra-
398---VOLUME27B, JUNE 1996
tions of arsenic, high oxygen concentrations appear to pro-
mote anode passivation.
ACKNOWLEDGMENTS
The financial support of the Copper Research Center,
University of Arizona, under the United States Defense Lo-
gistics Agency, Defense National Stockpile Center, Grant
No. DN-004, is gratefully acknowledged. The authors also
wish to thank the Magma Copper Company for partial fi-
nancial support.
REFERENCES
1. S. Abe, B.W. Burrows, and V.A. Ettel: Can. Metall. Q., 1980, vol.
19, pp. 289-96.
2. T.T. Chen and J.E. Dutrizac: in The Electrorefining and Winning of
Copper, J.E. Hoffmann, R.G. Bautista, V.A. Ettel, V. Kudryk, and
R.J. Wesely, eds., TMS, Warrendale, PA, 1987, pp. 499-525.
3. J.P. Demaerel: in The Electrorefining and Winning of Copper, J.E.
Hoffmann, R.G. Bautista, V.A. Ettel, V. Kudryk, and R.J. Wesely,
eds., TMS, Warrendale, PA, 1987, pp. 195-209.
4. T.T. Chen and J.E. Dutrizac: Metall. Trans. B, 1989, vol. 20B, pp.
345-61.
5. T.T. Chen and J.E. Dutrizac: JOM, 1990, vol. 42, pp. 39-44.
6. T.T. Chen and J.E. Dutrizac: Hydrometallurgy and Electrometallurgy
of Copper, Proc. Copper 91 Int. Syrup., W.C. Cooper, D.J. Kemp,
G.E. Lagos, and K.G. Tan, eds., Pergamon Press, New York, NY,
1991, vol. III, pp. 369-89.
7. J.C. Minotas, H. Djellab, and E. Ghali: J. Appl. Electrochem., 1989,
vol. 19, pp. 777-83.
8. C. Compare, E. Fr~chette, and E. Ghali: Hydrometallurgy and
Electrometallurgy of Copper, Proc. Copper 91 Int. Syrup., W.C.
Cooper, D.J. Kemp, G.E. Lagos, and K.G. Tan, eds., Pergamon Press,
New York, NY, 1991, vol. III, pp. 355-67.
9. F. Noguchi, N. lida, and T. Nakarnura: Hydrometallurgy and
Electrometallurgy of Copper, Proc. Copper 91 Int. Syrup., W.C.
Cooper, D.J. Kemp, G.E. Lagos, and K.G. Tan, eds., Pergamon Press,
New York, NY, 1991, vol. III, pp. 391-404.
10. E.A. Kucharska-Giziewiez and D.J. MacKirmon: CANMET, Internal
Report No. MSL 92-47 (TR), 1992.
11. G. Kortum: Treatise on Electrochemistry, Elsevier, New York, NY,
1965, pp. 513-27.
12. X. Cheng, J.B. Hiskey, and T.F. Krusmark: Hydrometallurgy and
Electrometallurgy of Copper, Proc. Copper 95 Int. Symp., 1995, vol.
III, pp. 225-40.
METALLURGICALAND MATERIALSTRANSACTIONSB