A mineralogical study of nodulated copper cathodes

J.E..Dutrizac and T.T. Chen

CANMET
555 Booth Street
Ottawa, Canada KIA OGI

ABSTRACT
Mineralogical studies were carried out on nodulated copper cathodes from three
primary refineries to characterize the nodular growths and to elucidate the causes of the
nodulation. Nodulation is often initiated at the surface of the starter sheet or the stainless
steel plating blank, although a layer of smooth copper sometimes is deposited before
nodulation commences. In some instances, the "roots" of the nodules exhibit a pronounced
dendritic texture that is associated with an abundance of cavities. Slimes particles are not
usually associated with these growth features which lead to a globular surface deposit. The
globules sometimes develop into larger nodules, and this type of nodulation is likely caused
by improper addition agent concentrations. The nodules on most cathodes, however, exhibit
"roots" at the contact with the substrate that are associated with microcavities and large
clusters (>40pm) of slimes particles. The slimes constituents are commonly Ag powder,
PbSO, and Cu,(Se,Te) but not AgCu(Se,Te) or Ag,(Se,Te). The size of the slimes clusters,
rather than their composition, appears to be the important factor causing the copper to grow
into nodules. Tiny individual slimes particles themselves do not appear to cause cathode
nodulation.

Proceedings of
Copper 99-Cobre 99 International Conference
Volume III-Electrorefining and Electrowinning of Copper
Edited by J.E.Dutrizac J. Ji and V. Ramachandran
The Minerals, Metals & Materials Society, 1999

INTRODUCTION
The Inco Copper Cliff Copper Refinery has a capacity of 170,000 t!y, andplates onto
conventional copper starter sheets (1). The Kidd Metallurgical Division of Falconbridge
Limited produces 145,000 t/y of copper by deposition onto stainless steel plating blanks (2).
Although the CCR Refinery of Noranda Inc. traditionally plated onto copper starter sheets,
the company has recently adopted stainless steel plating blank technology for its entire
t ofcathode (3). All three refineries normally produce high purity
production of 360,000 !y
copper having a good physical appearance. Occasionally, however, varying degrees of
cathode nodulation occur in all three operations, and the nodulation can affect all parts of the
cathode deposit. The nodules sometimes grow to several centimeters in size and the
presence of such large surface features makes the handling and stacking of the cathodes more
difficult. The formation of nodules fiequently traps quantities of electrolyte and slimes
particles, thereby reducing the purity of the copper product. Furthermore, the nodulation
also causes an uneven distribution of the current density, a reduction in current efficiency,
and hence, an increase in the operating cost of the refinery.
Several mechanisms have been postulated to explain cathode nodulation; these
include insufficient mass transfer, improper concentrations of the addition agents, and
suspended conducting particles. In an electrolyte fiee of additives, nodulation may be caused
by insufficient mass transfer (4); in this case, gas sparging sometimes reduces the degree of
nodulation. An improper ratio of thiourea, glue and chloride in the electrolyte can also
produce nodulation, and it is known that the optimum concentrations of the addition agents
change as the current density increases (5,6,7). Nodulation is also reported to be caused by
suspended conductive particles, such as anode slimes (8,9). Consequently, those parameters
which enhance the suspension of particulate matter, such as increased electrolyte density or
viscosity, the evolution of gases at the anode and a high slimes fall, could indirectly promote
cathode nodulation. It is believed that once a nodulated surface develops, the localized
current density, and hence the copper deposition rate, increases abruptly resulting in the
further rapid growth of the nodules.
Cathode nodulation is clearly undesirable, and all three.copper refineries would.like
to 'eliminate the nodulation problem. A first step towards the. elimination of cathode
nodulation is a clear identification of its causes. To this end, CANMET recently carried out
detailed mineralogical investigations of nodulated copper cathodes from the three refineries
to elucidate the various causes of the nodulation and to suggest possible means to resolve
the nodulation problem. The results .of those studies are sumrnariied in this report.

ELECTROREFINING AND ELECTROWINNING OF COPPER

EXPERIMENTAL
Samples
Two nodulated copper cathodes were supplied by Inco's Copper Cliff Copper
Refinery. The first sample (Inco-4) was a severely nodulated cathode obtained after 5 days
of plating at a current density of 180 AM,and1the second sample (Inco-2) was a similar
cathode collected after 6 days of plating. Nodulated areas from the tops and mid-sections
of both cathodes were chosen for study. To provide complementary information, a sample
of the suspended slimes was collected from about 2 cm below the electrolyte surface prior
to the removal of the Inco- 1 sample from the cell.
Three cathode deposits from the Kidd Metallurgical Division of Falconbridge
Limited were studied. The first sample (Kidd-1) was obtained after 16 h of plating onto a
stainless steel blank at a current density of about 250 A/m2. Many 100-500 pm nodules were
dispersed over an otherwise smooth and fine-grained copper deposit. The Kidd-2 sample
was collected after 24 h of plating. This deposit was generally smooth, but contained several
1-2 mm nodules dispersed randomly over the surface. The Kidd-3 sample was obtained by
plating copper for 36 h onto a piece of a milled and polished Kidd anode. The -0.9 mm thick
cathode copper deposit was smooth and fine grained; no nodulation was evident although
several pin holes -1 mm in diameter were detected in the deposit.
Four samples were provided by 'the CCR Refinery of Noranda Inc. Two of the
samples (CCR-1 and CCR-2) were starting sheets produced using -22 h plating cycles and
conventional copper plating blanks. Both samples were extensively nodulated and multiple
nodule growth was common. The nodules on the CCR- 1 sample were 2-3 m m in diameter
and were often loosely attached to the copper matrix; those on the CCR-2 sample were 1-2
mm in diameter and were firmly adherent. The CCR-3 sample was another copper starter
sheet made on a copper plating blank; several sinall nodules were present near the solution
level, although most of the deposit was smooth. The fourth sample (CCR-4) was a copper
starter sheet made by plating for -22 h at about 260 A/m2 onto a stainless steel blank. The
deposit was relatively uniform but contained numerous tiny semi-globules and many pin
holes dispersed over the entire surface.

Mineralogical Techniques
Special efforts were necessary to prepare the nodulated cathodes for study. After
direct examination of the nodulated samples using an optical stereomicroscope andlor the
scanning electron microscope (SEM) to select the areas for study, the samples were sawed
to a convenient size. The sawn pieces were mounted at right angles to the deposit surface
using liquid epoxy, and were ground and polished to expose the contact zone between the
nodule and the underlying copper. The sections were examined using optical microscopy
and scanning electron microscopy with backscattered electron (BSE) or secondary electron
images to determine whether any slimes particles or impurity phases were present at the
"roots" of the nodules or inside the nodules. The sections were then lightly ground to

VOLUME 111

remove -100 pm of the surface and were repolished; these sections were re-examined with
the SEM. Repeated grinding and polishing of the samples were carried out across the
"roots" of the nodules to increase the possibility of detecting any impurity particles around
the contact zones. When impurity particles were detected, the sections were analyzed in
detail using the scanning electron microscope with energy dispersive X-ray analysis (EDX)
and the electron microprobe.
The suspended anode slimes sample, which was collected using a suction device, was
filtered, water washed and dried at room temperature. The slimes were studied initially by
X-ray diffraction analysis to identify the major crystalline phases. Polished' sections were
prepared and ,thesamples were examined with a scanning electron,microscope equipped with
an energy dispersive X-ray analyzer to determine the chemical species and their
morphologies. In this regard, extensive use was made of backscattered electron (BSE)
images to differentiate the various chemical species. Details of the mineralogical procedures
have been reported elsewhere (10).

RESULTS AND DISCUSSION

Suspended Slimesin the Inco Refinery

. .

Figure 1 illustrates the morphologies of the suspended slimes in the Inco refinery that
are generally similar 'to those detected in the Kidd and CCR operations. In general, the
slimes occur as large clusters or agglomerates which are composed of a diversity of species.
The tiny bright grains are Ag powder, the ring-like particles are selenides, the triangularshaped particle is an octahedral crystal of NiO and the matrix is the oxidate phase,
(Cu,Ni)SO,.nH,O or Cu-Sn arsenate. Some of the bright particles are PbSO,, but Cu20 is
rare or entirely absent. Figure 2 shows another view of the suspended slimes particles. The
tiny bright grains are mostly Ag powder, the spheroidal and ring-like particles'are selenides,
the platy hexagonal-shaped crystal is Cu-Sn-Ni oxide, the matrix is mainly
(Cu,Ni)SO,.nH,O, and the two largedark grains are K-AI silicate. It is apparent from both
photomicrographs that Ag powder is an important constituent of the suspended slimes, and
the silver is believed to form mostly by the reaction of low concentrations of silver ion with
the abundant cuprous ions present in the electrolyte (1 1,12).
Ag'

+ Cu'

Ago + Cu2'

(1)

Overall, the suspended solids contain major amounts of Cul(Se,Te),(Cu,Ag),,(Se,Te),

PbSO,, Ag powder and NiO, as well as minor or trace amounts of AgCu(Se,Te), Cu-Sn-Ni
oxide, K-Ca-AI silicate, Al silicate, K-A1 silicate, Cu-Sn arsenate, Ni-Fe-Sn oxide, BaSO,,
Cu-Pb-As-Bi oxide and an oxidate phase of Cu-Ag-Se-Pb-Ni-As0,-SO, composition.
Significantly, the Ag-rich selenides, which are a major constituent of;the bulk anode slimes
fiom the Inco refinery (139, are but a minor species in the suspended slimes. The implication
is that the suspended slimes were recently generated and released from the anode surface.
If the suspended slimes had been in contact with the electrolyte for a prolonged period of

ELECTROREFINING AND ELECTROWINNING OF COPPER

Fig. 1 - Morphology of the suspended

slimes in the Inco electrolyte. 1,NiO, 2- Ag, 3- selenide, 4oxidate phase (matrix), 5PbS04.6- (Cu,Ni)SOd.nHzO

Fig. 2 - Morphology of the suspended

slimes in the Inco electrolyte. 1Ag, 2- selenide, 3- Cu-Sn-Ni
oxide,
4NiO,
5(Cu,Ni)S04.nH20, 6- K-A1
silicate

Fig. 3 - Secondary electron .micrograph

show,ing the general morphology of the copper nodules in
the Kidd-31 sample.

Fig. 4 - BSE micrograph showing the

general' morphology of a
nodule in the Kidd-1 sample.
1- copper matrix, 2- plating
blank (removed$, 3- slimes
particles

VOLUME I11

.time, as would 'bethe case if thezsuspended slimes originated from the bottom of the refining
cell, the selenides would ,have been enriched in silver,. as, suggested by .the following
equations:

- AgCu(Se,Te) + Cu'
Ag' + AgCu(Se,Te) - Ag,(Se,Te) + Cut
Cu,(Se,Te)

+ Ag'

(3)

On the other:hand; the suspended slimes musthave been in contact with the electrolyte long.
,enough for the.Cu,O .phase,which is a minor species in the slimes attached to the ,faceof the
Inco anodes (13), to dissolve according to the following reactions:

As will be discussed in detail later, the constituents of the suspended slimes are
similar to those found at the "roots" of many of the cathode nodules. The Ag powder, Curich selenides and PbSO, particles are abundant in the suspended slimes, and'these are the
common constituents of the "roots" of the cathode nodules.
Slimes-Related Cath~de~Nodulation
The Kidd-1 sample, which was obtained after 16 h of plating, represents the earliest
stage of nodulation considered in this investigation, and was studied to try to characterize
the "root" responsible for nodule growth. Figure 3 shows the typical morphology of the
nodules which developed on the fine-grained and flat copper matrix. The nodules are 100200 pm in size, and seem to occur randomly on the copper matrix. Multiple growths of the
nodules are common, and many of the nodules in this sample exhibit a somewhat irregular
form. Figure 4 shows a cross-section of one of the nodules, and illustrates a common
morphology. The nodule and the copper matrix appear to exist as a single mass; no physical
boundary is discemable between them. A cluster of slimes particles, however, is present at
the base or "root" of the nodule. The slimes particles, typically Ag powder, Cy(Se,Te) and
PbSO,, are randomly embedded in a compact copper matrix. Significantly, no cavities are
detected in the copper mass, although abundant cavities are often associated with the
nodules. The thickness of the copper deposit is about 450 pm; the slimes particles are
detected approximately 150 pm from the start of the copper deposit and they extend into the
nodule itself. It appears that the attachment of a cluster of slimes particles to a pre-existing
smooth copper deposit caused the development of the nodule in this sample.
Figure 5 shows another common morphology of the nodules in the Kidd- 1 sample..
A cluster of slimes particles, approximately 40pm in size, occurs at the beginning of the
copper deposit and near the contact between the copper deposit.and the stainless steel;plating
blank. No other slimes particles aredetected in the nodule or in the copper deposit adjacent

ELECTROREFINING AND E,LECTROWINNINGOF COPPER

Fig. 5 - BSE micrograph of another

nodule in the Kidd- 1 sample.
1- copper matrix, 2- plating
blank (removed), 3- slimes
particles

Fig. 6 - ;BSE micrograph illustrating the

morphologies of the slimes
particles shown in Figure 5. 1copper, 2- Cuz(Se,Te), 3- PbS04,
4- Ag

Fig. 7 - Secondary electron micrograph

showing the morphology of the
copper deposit of the ,Kidd-3
sample and the presence of
holes at the surface. 1- copper
matrix, 2- 'hole, 3- groove, 4striation

Fig. 8 - BSE micrograph of the interface

between the cathode deposit, the
anode copper.plating blank and a
hole in the 'Kidd-3 sample. 1hole, 2- cathode copper, 3anode copper (plating blank, 4-

Cu20+Cu2(Se,Te)+(Cu,Pb,As)
oxide inclusions, 5-.interface.

VOLUME HI

to the nodule. The nodule and the copper deposit occur as a single mass; no boundary can
be discerned between them and no cavities are present. It appears that the slimes particles
occur at the "root" of this nodule. Figure 6 shows the detailed morphology of the slimes
cluster illustrated in Figure 5. The slimes cluster, approximately 40 pm in size, appears to
be a single entity, with PbSO, and Ag particles closely associated with the larger Cu,(Se,Te)
structure. The slimes particles seem to be embedded in a compact copper matrix, which
superficially resembles a fragment of Kidd anode copper (14).
The Kidd-3 sample was generated by plating copper onto a smoothly milled Kidd
copper anode. This test was done to ascertain whether individual slimes particles, on an
otherwise flat copper surface, caused cathode nodulation. In this experiment, the deposited
copper was consistently smooth and nodul'e-free,although numerous pin holes were evident
in the deposit. Figure 7 illustrates the morphology of two of these holes which are nearly
circular in cross-section; they seem to start as a tiny point and gradually expand with
prolonged plating thickness. Therhorizontal striations.onthe interior walls of the holes likely
imply an irregular release of gas during copper deposition. A groove originating from the
hole and pointing vertically upward (the sample is shown 'upside down in Figure 7) is
commonly present on the surface of the copper deposit. The orientation of the groove and
the shell-like morphology of the hole with the larger>dimensionpointing upward imply that
these are gas vent holes. No impurity or slimes particles are detected in any of the holes.
Figure 8 shows the detailed morphology of a hole near the surface of the plating blank. The
lower-right portion of the photomicrograph is the anode copper plating blank and the left
oxide particles
portion is the deposited copper. Clusters of Cu,O-Cu,(Se,Te)-(Cu,Pb,As)
occur along the grain boundaries of the anode copper. The pin hole developed from the
surface of the polished anode copper plating blank; that is, the gas is released from the
beginning of electrolysis and at the contact between the anode copper starter sheet and the
cathode deposit. An impurity cluster in the anode copper is exposed at the polished surface
of the plating 'blank. Based on the morphology of the copper deposited on the surfaces of
the impurity clusters and that on the surface of the inclusion-free metal, it is concluded that
the tiny individual slimes particles embedded in the surface of the plating blank do not affect
the morphology of the cathode deposit and do not cause cathode nodulation.
Figure 9 provides a general view of the cross-section of a copper nodule formed at
the solution level of an Inco cathode (Inco-1). Numerous slimes particles and tiny cavities
are detected at the "root" of the nodule, and these features are shown in greater detail in
Figures 10 and 11. Numerous tiny Ag grains are embedded in the "root" of the nodule, and
many (Cu,Ag),(Se,Te) particles are present on the surfaces of the cavities which are
otherwise totally enveloped by thelmass of the nodule. Figure 12 illustrates the cross-section
of another cathode nodule occuning at the solution level of the Inco cathode (lnco-1). The
"root" of this nodule contains several tiny cavities, which are totally enveloped by the mass
of electrodeposited copper. Numerous slimes particles, such as Ag powder, selenides,
PbSO,, Cu-Sn-Ni oxide, NiO and Cu,(Se,Te) particles with Cu-Pb-As-Bi oxide cores are
present in the cavities (Figure 13). The morphologies of these slimes particles are very
similar to those of the suspended slimes collected from near the surface of the Inco

ELECTROWFINING AND EZ,ECTROWINNING OF COPPER

Fig. 9 - Cross-section of a cathode nodule

occurring at ,the solution level of
an Inco cathode (lnco-1). 1nodule, 2- cathode, 3- impurity
particles, 4- cavity

Fig. 10 - Detailed morphology of the

"root" of the cathode nodule
shown in Figure 9. 1- cavity,
2- Ag, 3- Cu2(Se,Te) +
FbS04, 4- copper

Fig. 1.1 - Detailed morphology of the

cavity at the "root" of the
cathode nodule shown in
Figure 9. 1- Cu2(Se,Te), 2Ag, 3- PbSO., or Cu-Pb-As-Bi
oxide

Fig. 1'2 - Cross-section of a cathode

nodule occurring at the
solution, level of the Inco
cathode (Inco- 1). 1- nodule,
2- cavity, 3- cathode

392

VOLUME III

Fig. 13 - Detailed motpho'logy of a cavity

in the cathode nodule shown in
Figure
12. 1- Ag, 2Cu2(Se,Te),3- Cu-Sn-Ni oxide
+ NiO, 4- ,PbS04.5- copper

Fig. 14 - Cross-sect.ion of a nodule

occurring ,at the middle of
the Inco cathode (Inco-2). 1nodule, 2- cathode, 3- slimes
particles + tiny cavities

Fig. 15 - Detailed morphology of the

"root" of the nodule shown in
Figure 14. 1- NiO + Cu-Sn-Ni
oxide, 2- Ag, 3- cavity, 4copper, 5- porous copper

Fig. 16 - BSE micrograph of a nodule at

the solution, level of the CCR-3
sample. 1- cavity, 2- plating
blank, 3- slimes particles, 4copper dendrites

ELECTROREFINING AND ELECTROWINN1N.GOF COPPER

electrolyte (Figures 1 and 2). In fact, the association of Cu-Pb-As-Bi oxide with Cu,(Se,Te),
and not with AgCu(Se,Te) or Ag,cSe,Te), implies that the "root" consists of a cluster of
slimes particles spalled relatively recently from the anode surface. In the bulk anode slimes
on the bottom of the refining cells, the selenide species are significantly Ag-rich; e.g.,
AgCu(Se,Te), (Cu,Ag),(Se,Te), or Ag,(Se,Te).
Figure 14 illustrates a cross-section of another cathode nodule occurring at the
middle portion of an Inco cathode (Inco-2). The "root" of this nodule, which is shown in
Figure 14, contains several'cavities and many tiny impurity particles. The cavities are totally
enclosed by the nodule. Detailed examination of the "root" revealed the presence of Ag
powder, crystals of NiO associated with Cu-Sn-Ni oxide and Cu,(Se,Te) particles with CuPb-As-Bi oxide cores embedded in the copper matrix, whereas the cavities appear to be free
of impurity particles (Figure 15). The presence of Cu,(Se,Te) particles with Cu-Pb-As-Bi
oxide cores in the copper matrix and the association of many Ag particles suggests that the
slimes cluster, which' appears to serve as the nucleus for the growth of the nodule, was
freshly liberated fiom the anode surface.
Figure 16 shows the tiny copper nodules present.at the solution level of the CCR-3
sample. The nodules exhibit distinctivebanding and radiating growth textures. Numerous
cavities arepresent at the "roots" of the nodules, and the "roots" occur at the contact between
the deposit .and the copper plating blank. The radiating copper texture seems to have
developed fiom the very inception of electrodeposition. Slimesparticles such as Ag powder,
Cu,(Se,Te), AgCu(Se,Te), PbSO,, a Pb-Sb-Bi-Cu-S-0 phase, Cu,O and ,(Cu,Ni)SO, are
present in the cavities or are.embedded in the copper deposit. Figure 17 illustrates a cluster
ofslimes particles detected at the:"root" of one.ofthe nodules. Silver powder and various
selenides are abundant, but Cu,O, PbSO, Sn0,and (Cu,N,i)SO,.are .also detected:: The
implication is thata largecluster of floating slimes particles became attached to the,top of
the copper starter sheet very early in the re'fining cycle and caused the observed nodulation
The adhesion of "large" clusters of slimes particles on the cathode surface results in
enhanced localized copper deposition that can lead to cathode nodulation. Large clusters of
slimes particles, suspended in the electrolyte or floating on the surface of the electrolyte, can
be transported to the cathode surface by the electrolyte flow or by gas bubbles. Flloating
slimes clusters may lead to nodulation at the solution level, whereas suspended slimes
clusters may cause nodulation anywhere on the face of the cathode . The cavities at the
"roots" of the nodules may indicate that the slimes clusters were transported by gas bubbles,
or they may indicate copper deposition around the porous slimes clusters. There is little
evidence that individual slimes species, such as discrete particles of Cu-Ag selenide, isolated
grains of Ag powder or crystals of PbSO,, cause cathode nodulation. In fact, many such
slimes particles are present as individual grains, and even as tiny agglomerated grains, on the
surfaces of the cavities, but copper nucleation and growth did not occur on such particles.
Likewise, the cross-sections of the nodules show no evidence of the development of
individual nodules or radiating copper features fiom the individual slimes particles. Rather,
a single nodule seems to develop from the entire slimes cluster.

. .... ,,.
,

.* ..

..

. ...,.:

. .. ,...
,...
..

..,":
.?:

. . .-I:

._ ,...+>
,.......
.,.

394

VOLUME IIJ

Fig. 17 - BSE micrograph of a slimes

cluster at the "root" of a
nodule in the CCR-3 sample.
1- Ag in (Cu,Ni)S04, 2- Ag in
Cu20, . 3 SnOz,
4Cu2(Se,Te), 5- PbS04, 6copper, 7- cavity, 8- Ag

Fig. 18 - General morphology of a

cathode nodule on the Kidd2 sample.

Fig. '$9 - BSE micrograph showing the

contact zone between a
nodule and the initial c.opper
deposit for the Kidd-2
sample. 1- slimes particles, 2cavity zone, 3- nodule, 4initial copper deposit, 5stainless steel plating blank
(removed)

Fig. 20 - Detailed :morphology of the

slimes particles shown ,in
Figure 19. 1- Cuz(Se,Te), 2Ag powder, 3- PbS04, 4cavities

ELECTROREFTNING AND ELECTROWINNING OF COPPER

The nodules obtained from different parts of the cathode or from different cathodes
exhibit the same general morphology and contain the same impurity species. Often, the
arrangement of the slimes particles at the "roots" of the ilodules (e.g., Figures 10 and 55) is
superficially similar to that of the grain-boundary inclusions in an uncorroded copper anode
(cf. Figure 8). In fact, it was initially postulated that sinall fragments of the copper anode
were transported to the cathode and contributed to the nodulation. This belief was further
strengthened by the abundance of silver powder and Cul(Se,Te), rather than AgCu(Se,Te),
particles at the "roots" of the nodules; these species are prevalent in the anode and at its
surface, but are relatively rare in the bulk slimes. Subsequent studies, however, did not
support this hypothesis. Firstly, the slimes particles in the "roots" are smaller than those in
the grain-boundary inclusions in the anodes, and the copper grains which they appear to
delineate are also smaller than the copper crystals in the anode. Secondly, the slimes particles
detected in the "roots" of the nodules are generally devoid of Cu,O whereas copper oxide
is an abundant constituent of the grain-boundary inclusions. Lastly, the electron microprobedetermined composition of the copper metal, even at points between the individual slimes
particles, is not that of anode copper. Specifically, low Ni contents (<0.03% Ni) were
detected in the Inco samples despite the high (-0.5% Ni) solid solution nickel content of Inco
anode copper. The overall conclusion is that large clusters of slimes particles, and not
fragments of the copper anode, are responsible for cathode nodulation. In this regard,
however, it is believed that relatively large clusters are required to initiate nodulation and
that the physical dimensions of the slimes clusters, rather than their composition, are the
principal cause of cathode nodulation.
Nodulation Possibly Caused by Anode Slimes
The Kidd-2 sample illustratesthe extent of cathode nodulationafter 24 h of plating
0n.a stainless steel blank. Figure 18 shows the typical morphology of the nodules and the
multiple-growth texture illustrated is common at this stage of nodule development. Most
of the nodules are -1 mrn in,diameterand rest on a relatively fine-grained and smooth copper
matrix.
Cross-sections of 16 nodules from the Kidd-2 sample were prepared and examined
in detail. Seven of these contained slimes particles (typically Ag powder, Cu,(Se,Te) and
PbSO,), near the contact zone between the nodule and the copper deposit; no impurity
particles were observed in the other nodules, although potential inclusions may have been
"missed" by the sample preparation technique. Figure 19 shows the contact zone between
the nodule and the copper deposit. The dark spotty zone is composed of cavities which
presumably represented,the surface of the nodule at an earlier stage of its growth. Slimes
particles (bright) are present in the cavity zone, suggesting an original occurrence at the
surface of the nodule. Figure 20 illustrates the detailed morphology of the slimes particles
shown in Figure 19. The dark spots are cavities presumbly located at the surface of the
nodule in an earlier stage of its development. The irregular or ring-shaped grains are
Cu,(Se,Te), the tiny bright particles are Ag powder, and the round grains are PbSO,. It is
worth noting that the selenide species is Cu,(Se,Te), not AgCu(Se,Te) or Ag,(Se,Te): The

VOLUME 111

close association of the slimes particles with the cavities, and hence an earlier surface of the
nodule, 'may imply that these slimes particles were simply trapped on the surface of the
nodule. On the other hand, they may represent part of a larger cluster of slimes particles
which initiated the growth of the nodule.
Figure 21 illustrates the general' morphology of the CCR-I sample, which is a starter
sheet formedon a copper blank. The surface of this deposit is extensively covered with 2-3
m m nodules and many of the nodules consists of multiple growths. Most of the nodules sit
in "craters" formed in the starter sheet, and inany of the nodules appear to be only loosely
attached to the starter sheet.
More than 70 nodules in the CCR- 1 sample were examined, and many of them
contain slimes particles at the contact zone between the nodule and the copper matrix or
between the nodule and the plating blank. Figure 22 illustrates the typical morphology of
these nodules as seen in cross-section. Multiple growths of the nodules are evident. The
dark region with the sharp straight boundary at the bottom of the figure represents the
original location of the copper plating blank from which the starter sheet was stripped. The
dark spaces between or within the nodules are voids originally present during electrolysis,
and such cavities are common in this sample. The nodule in the center developed directly
on the surface of the copper plating blank. Slimes particles are commonly present on the
surfaces of the cavities, but are rare within the nodules themselves. Theldetailedmorphology
of a cavity which is located near the contact zone between the nodule and the copper plating
blank is shown in Figure 23. The dark regions are cavities near the surface of the nodule; the
tiny bright particles are Ag powder, the bright grains are PbSO, and the ring-like particle is
Cu,(Se,Te). The slimes species are similar to those identified in the Kidd and Inco cathode
nodules. Based on the mozphology, it appears that the slimes particles may have been
trapped on the surfaces of the nodules, especially in the cavities between the surfaces of the
nodules and the copper starter sheet. On the other hand, the nodule may have developed
from a large slimes cluster part of which remained on the surface of the nodule. There is no
indication that any of the individual slimes particles caused the nucleation and growth of the
copper nodules, despite the obvious abundance of such individual slimes particles on the
surface of the copper during the early stages of copper deposition.
Non-Slimes Related' Nodulation
The CCR-2 sample is extensively nodulated. The surface of this sample is covered
by nodules which are 1-2 mrn in diameter, and are similar in habit to those shown in Figure
21. In contrast to the nodules on the CCR-1 sample, however, these nodules adhere firmly
to the starter sheet and no "craters" are evident. Figure 24 shows the general morphology
of this sample, and the multiple growth of the nodules is evident. Nodules grow on top of
other nodules, creating spaces (betweenthein. In contrast to the CCR-1 sample, where most
of the nodules developed directly from the sudace of the plating blank, nodulation in the
CCR-2 sample began after a small amount of smooth copper deposition had taken place. In
most cases, a layer of copper approximately 50- 100 pm thick was plated before nodulation

ELECTROREFINING AND EIEECTROWINNf.NG OF COPPER

Fig. 21 - General morphology of the

cathode nodules on the CCR1 sample.

Fig. 22 - .BSE micrograph showing the

typical morphology of the
nodules in ihe CCR- 1 sample.
1- nodule, 2- copper plating
blank (removed), 3- open
space, 4- slimes particles in
cavity zone

Fig. 23 - Detailed morphology of the

cavity zone shown in Figure
22. 1- copper, 2- cavity, 3- Ag
powder,, 4- Cu2(Se,Te), 5PbS04

Fig. 24 - BSE micrograph showing the

typical morphology of the
nodules in the CCR-2 sample.
1- nodule, 2- open space, 3copper
plating
blank
(removed), 4- beginning of
the nodular growth

occurred. Despite repeated grinding and polishing of this sample to try to expose the "roots"
of the nodules on the copper matrix, no impurity particles were detected in this sample.
More than 60 such nodules were examined in detail, but no slimes particles were detected
in any of them.
The CCR-4 sample was plated onto a stainless steel blank. In this instance, the
copper surface is more or less smooth; it exhibits a uniform globular morphology with -0.5
mm globules covering the entire surface. Numerous~circularpin holes are present (cf. Figure
7) and these originate both from the plating blank and from the deposited copper itself. No
inclusions or slimes particles are detected in any of the holes. It is believed thatthe pin holes
represent vents which allow the escape of the gases evolved at the cathode during
commercial electrolysis.
Figure 25 illustrates the globular morphology of the nodules on the surface of the
CCR-4 sample. In the vicinity of the globule (left half of photo) there are abundant cavities
and an extensive radiating-dendritic copper texture, which is characteristic of this type of
growth in the vicinity of the plating blank. Small copper globules are present in the cavities
and also in the nodulated matrix. Particles of Fe-Cu-Cr-Ni sulphate and Cu-Ni sulphate are
detected in some of the cavities; the presence of Fe and Cr in the sulphate phase implies the
superficial leaching of the stainless steel plating blank. The non-nodulated part of the
deposit (right side of the photomicrograph) is compact and more uniform; the surface in
contact with the plating blank is smooth. Figure 26 illustrates the morphology of the globule
in greater detail, and its radiating-dendritic texture is evident.
Figure 27 shows the surface of the deposit in the CCR-4 sample which was in direct
contact with the stainless steebplating blank. Abundant tiny radiating sphemles are evident,
and the implication is that excessive copper nucleation occurred at the surface of the
stainless steel. The result is a globular-dendritic texture with abundant cavities between the
growing copper sphemles and dendrites. Although trace amounts of Fe-Cu-Cr-Ni sulphate
or Cu-Ni sulphate are present in the cavities, significantly no anode slimes particles such as
Ag powder, PbSO, or Cu,(Se,Te), were detected in this sample. Occasionally, particles of
Cu,O were evident, and in this regard, Figure 28 shows a semi-globular copper growth with
a strongly dendritic texture. Patches of Cu,O are present between some of the copper
dendrites, but the morphology of the Cu,O is very different from that detected in either the
CCR anodes or CCR anode slimes 615). The conclusion is that the Cu,O formed directly at
the cathode, presumably by the reaction of electrochemically produced cuprous ions with
water.

The extensive radiating dendritic copper growth, the abundant cavities and the
heterogeneous copper growth morphologies at and near the contact with the stainless steel

ELECTROREFINING AND ELEClXOWINNING OF COPPER

Fig. 25 - Cross-section of the copper

deposit (CCR-4 sample)
showing its semi-globular
morphology. 1- cavity, 2radiating dendritic copper, 3plating blank (removed), 4particles of Fe-Cu-Cr-Ni
sulphate

Fig. 26 - Cross-section of the copper

nodule (CCR-4 sample)
showing radiating dendrites.
1- cavity, 2- radiating
dendrites, 3- Fe-Cu-Cr-Ni
sulphate, 4- plating blank
(removed), 5- tiny copper
spherule

Fig. 27 - BSE micrograph showing the

morphology of the copper
originally in contact with the
stainless steel' plating blank of
the CCR-4 sample. 1- .Fe-CuCr-Ni sulphate, 2- tiny copper
grains, 3- radiating copper
spherules. 4- organic, 5- cavity

Fig. 28 - BSE micrograph of Cu20

particles in a semi-globular
copper mass of the CCR-4
sample. 1- Cu20, 2- cavity,
3- Fe-Cu-Cr-Ni sulphate, 4copper dendrites, 5- plating
blank (removed)

VOLUME TtI

plating blank indicate that the globular morphology commences fiom the very beginning of
electrolysis. Slimes particles were not detected in this sample, and this observation c o n f i m
that the uniform globular morphology which extensively covers most of the surface of the
copper deposit is likely caused by variations in the electrolysis conditions, such as improper
ratios of the addition agents, locally high current densities, poor electrolyte circulation or
even the superficial corrosion of the stainless steel plating blank.

CONCLUSIONS
Mineralogical studies, carried out on nodulated cathodes from three primary copper
refineries, suggested two causes of cathode nodulation. The more prevalent is the
attachment of large clusters of slimes particles on the surface of the cathode; the second and
less common cause seems to be related to improper ratios of the addition agents. Nodulation
is often initiated at the surface of the copper starter sheet or the stainless steel plating blank,
although less commonly a thin layer of smooth copper is /deposited before nodulation
commences.
The nodules on many of the cathodes show a "root" at the contact with the substrate
that is associated with micro cavities and large clusters of slimes particles. In these
instances, it is concluded that the'nodulation is initiated by the slimes clusters. For example,
a deposit fiom the Kidd Metallurgical Division of Falconbridge Limited, obtained after only
16 h of deposition ontotstainlesssteel blanks in the commercial circuit, showed the presence
of clusters of Ag powder, Cu,(Se,Te) and PbSO, particles at the roots of the nodules.
Likewise, two nodulated cathode samples fiom Inco's Copper Cliff Copper Refinery, after
5 or 6 days of plating onto copper starter sheets, consistently exhibitedl micro cavities and
large slimes clusters at the roots of the nodules. The slimes particles are Ag powder, NiO,
Cu,(Se,Te), 'PbSO,, Cu,(Se,Te) with Cu-Pb-As-Bi cores and Cu-Sn-Ni oxide. One of the
CCR deposits obtained after 22 h of plating showed several' nodules at the solution level
which seem to have originated fiom large clusters of slimes particles. The individual slimes
particles in the clusters were Ag powder, Cu,(Se,Te), PbSO,, Cu,O, (Cu,Ni)SO, andl SnO,.
Significantly, Ag-rich selenides and Cu,O, which are abundant in the slimes h m the bottom
of the refining cells, are not detected at the "roots" of the nodules. In fact, the compositions
and morphologies of the slimes particles at the "roots" of the nodules are similar to those of
the slimes clusters suspended in the electrolyte that were sampled at the time the cathode
deposits were obtained. The occurrence of micro cavities and large clusters of slimes
particles at the "roots" of the nodules implies that this type of nodulation is caused by
nucleation and growth on the large clusters. That is, the size of the slimes clusters, rather
than their composition, appears to be the more important factor leading to nodule growth.
Tiny individual slimes particles likely do not cause nodulation, and this conclusion is
supported by the observation that smooth deposits are formed on milled anode copper plating
blanks despite an abundance of individual slimes particles at the surface of this material.
In other instances, however, the nodulation does not seem to be caused by the
presence of slimes particles or large clusters of slimes particles. In'this regard, one of the

ELECTROREFINING AND ELECTROWINNING OF COPPER

starter sheets provided by the CCR Refinery of Noranda Inc. contained abundant globule-like
surface growths.and circular pin holes dispersed across the surface. Although more than 60
globules were examined, no slimes particles were detected, and no slimes particles were
found in the.tiny holes: In the regions of the.globular morphology, the.copper surface in
contact with the stainless steel plating blank is rough, and.there amabundant cavities. The
texture of the copper is that of radiating dendrites or micro spherules, and it is believed that
the dendrites initiated,theglobular growths. Nodulation starts from the plating blank, and
no slimes particles are detected in the deposit, effectively excluding the possibility of
nodulation initiated by suspended slimes. Another starter sheet provided by the CCR
Refinery was extensively covered by tiny nodules up to 3 m m ,in size. Multiple nodule
growths are common and the nodules adhere firmly to the copper sheet. For this.sample, a
small amount of uniform copper deposition occurred prior to the development of the
nodulation. Although over 50 nodules were examined, no slimes particles were detected,
and the conclusion is that the nodulation in this .sample is caused by variations in the
electrolysis conditions, such as improper ratios of the addition agents.

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1.

J.M. Schloen and W.G. Davenport, "Electrolytic Copper Refining - World

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e r - Cobre '95: Electrorefinine and
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J. Lenz, Personal communication. Kidd Metallurgical Division of Falconbridge

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T.T. Chen and J.E. Dutrizac, "A Mineralogical Study of the Deportment and
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