Paper -1
Paper presented at the seminar on
Quality Control of Copper
Cathodes: An overview
by Balachandran.P.Kamath, B. Latchhayya,
Kiran Prasad Shetty *
Introduction:
Copper Electro refining has been established
as an industry since 1871 at Nevark, in United
States. The basic operating process has
remained the same, but there has been
tremendous improvement in its application. All
operations have become automated. The
permanent cathode technology has been one
of the largest single factors responsible for
improvement of quality.
The main driving force for improvement of
cathode quality has been the market demand
for better quality of rods. Till the first half of the
century, a copper with a purity of 99.95 % was
considered good. Today, the copper quality is
not decided by the purity level, but by the type
and level of individual impurities
This paper discusses some basic aspects,
which are important to a Refinery operator. It
also dwells into certain critical facets of
electrorefining, which although well known are
not felt important by the production personnel.
It may be emphasized that in refinery the
problems get out of hand over a period of time
and it takes equally long time to bring back the
operations to normalcy. The initial indications of
problems are innocuous but suddenly they take
a turn in the form of poor efficiency, poor quality,
high scrap percentages or higher power
consumption.
Mechanisms affecting Cathode
Quality:
Theoretically, the cathodes produced should be
absolutely pure under ideal conditions. This is
because the impurities which are more reactive
than copper dissolve but do not deposit.
Impurities which are less reactive than copper
do not dissolve at all and settle at the bottom of
the cell as slimes. In real practice, however, the
ideal conditions do not prevail under industrial
*THE AUTHORS ARE WITH STERLITE INDUSTRIES (I) LTD.,COPPER DIVISION,SILVASSA.
1
“Testing & Quality Control of
Copper & Copper Alloy Products”
held at Mumbai on 8-9 December, 1999.
conditions and the quality is affected. The
primary reasons are as under:
a) Co-deposition with copper
b) Entrapment of electrolyte
c) Entrapment of slimes.
Co deposition of impurities:
It is well known that each element has an
electrode potential for deposition. The Electro
deposition potential for copper is much higher
than the impurities with the exception of Silver.
Co deposition of impurities along with copper
takes place under the following set of
conditions:
• Very low copper content in electrolyte
• Presence of silver in electrolyte in
dissolved form
• High voltage conditions due to passivation
etc.
Lowering copper concentration of electrolyte to
less than 20 gms/ Litre causes deposition of
impurities. This may take place in De
copperising or Liberator cells but not in Electro
refining cells.
Silver dissolves to a small extent in Electrolyte
and gets electro deposited since it’s electrode
potential is higher than Copper. This however
is limited to below 10 ppm normally. Chlorine
ion causes the Silver to precipitate as Silver
Chloride which is highly insoluble in aqueous
electrolyte.
Entrapment of electrolyte:
Entrapment of electrolyte is another parameter
causing deterioration in Cathode quality.
Nickel, Arsenic and Iron are some of the entrapments are also visible. Figure – 1 gives
impurities, which get entrapped along with the the microscopic structure of fine grain copper
electrolyte. Entrapment is enhanced due to deposit.
rough and spongy cathode deposit. To prevent
this occurrence, one should keep the level of
these impurities below certain limits. Also, the
deposition condition in cells should be such that
spongy and nodular deposits are not formed.

Entrapment of slimes.

Presence of suspended particles in electrolyte

causes the cathode to deteriorate. Besides,
slime causes nodulation in cathodes, which
causes entrapment of more slimes and
electrolyte. The entrapment of slimes also
causes more nodules to form unless the
reagent addition is satisfactory.

Measurement of Cathode Quality

Parameters: Fig – 1: Microscopic structure of
fine grain copper deposit.
1. Visual Inspection :

The first and simplest method is to carry out 3. Analysis :

regular visual inspection of cathodes during
production. In case of ISA process, observing
the operation of the Cathode Washing and
stripping machine would give the best indication
to the process operator.
It is well known that use of certain addition
agents give striations on cathode surface. Flow
pattern has a big bearing on the deposit, which
can be to some extent seen by looking at the
striations. Daily inspection of cathodes while
stripping can give clear indications of flow
patterns in cells, problems of deposition if any
and even some indications about the
consistency of addition agent presence in cells.
It is absolutely essential that all persons
connected with electrorefining inspect the
stripping on a day to day basis and correct
various operating parameters regularly, albeit
making very small changes.
2. Metallographic Examination
To have a better control over the cathode
growth, the crystal structure of the cathode can
be viewed using microscope. A sample is taken
at right angles to the direction of growth,
polished and etched to reveal the grain
structure. The structure will indicate whether the
reagents are added at correct level and if the
reagent delivery system is functioning correctly.
Power interruption lines, slime and electrolyte
Several methods of analysis are used for
cathodes. However, the segregation of
impurities in cathodes has made it very difficult
to get a representative sample of the cathode
lot. The distribution of impurities is not uniform,
tending to concentrate at top, bottom and
edges. Different impurities show bias at
different locations. Many methods have been
suggested but none of them have been
accepted universally. The problem is in getting
a representative sample and not of analysis.
Hence the method of sampling cathode will
influence the level of impurities found.
The instrument for analysis which are adopted
are:
1. DC Arc spectrometer
2. Spark Spectrometer.
3. ICP
4. Atomic Absorption Spectrophotometer
The two most commonly used sources for
detection of impurities in copper cathodes are
low voltage DC arc spectrometer and high
voltage AC spark spectrometer

2
DC arc spectrometer continuous to be an
important spectroscopic technique for solid
samples, while other techniques such as ICP
and Atomic absorption work well for liquid
samples. The digestion necessary to put the
solid sample in to a liquid will in many cases
dilute the sample beyond the detection limits
obtainable with these techniques. In addition,
some sample resists digestion even in strong
acids.
a) DC Arc Spectrometer
Principle:
The essential parts of a spectrograph are a slit,
an optical system and a camera for recording
the spectrum. The light from the source of
radiation passes through the slit, which is a
narrow vertical aperture, then through the
optical system, which includes a prism or
grating. An image of the slit is produced by
means of lenses at the point where the light is
recorded. One such image is produced for each
radiation having a specific wavelength, and the
result is a series of vertical line images, which
constitute the spectrum of the element being
investigated. The optical system may be either
of glass or quartz; the latter transmits in the
ultraviolet region, where many useful lines
occur, as well as in the visible region
The holders for arc and spark excitation are
housed in a metal box fitted with a safety shield.
b) Atomic Emission Spectrometer
Principle:
In atomic emission spectroscopy, a minute part
of the sample is vaporized and thermally
excited to the point of atomic emission. An
electric arc or spark supplies the energy
required for these processes, or more recently
by a laser or plasma composed of inert gas.
The atomic spectrum emitted by the sample is
used to determine its elemental composition.
The wavelength at which the intensity
measurement is made identifies the element,
whereas the intensity of the emitted radiation
quantifies its concentration.
The instrument may be divided into three major
components.
1. The sampling device and source
2. The spectrometer.
3
3. The detector and reader.
The Sampling device and the source depend
on the type of the sample and the analytical
data desired. As the emission spectrum
emerges from the source it is focussed on to
the spectrometer’s entrance slit, where it is
dispersed in to its component wavelengths. The
optical elements permit site selection within the
source discharge and thus eliminate the need
to move the entire source assembly. The use of
mirrors, properly placed also eliminates the
chromatic & spherical aberrations encountered
with lens optics. At the exit slits of spectrometer,
the radiation is sensed by a photodetector.
No single source is best for all applications.
Factors that influence the selection of an
excitation source are the concentration of the
elements being determined, the vapor
pressures or volatility’s of these elements, the
excitation potentials of the atomic lines used in
the analysis and the physical condition of the
sample. For solid samples, arc excitation is
more sensitive, while spark excitation are more
stable. Plasma sources are choices for
solutions and gaseous samples.
Factors governing the cathode
quality.
1. Anode composition and behavior
of impurities during electrolysis:
Copper anodes of different origins will have
different chemical compositions, thereby
different behavior during electrolysis. Major
impurities in copper anodes are Ag, As, Au, Bi,
Fe, Ni, Pb, S, Sb, Se, and Te apart from
oxygen. The accumulation of these impurities
can lead o serious complications in
electrorefining. Typical anode composition is
given below( Table-1).
Table-1 : Typical Anode composition
Element Concentration
Cu 99.3 % - 99.7 %
Oxygen 1200–1500 ppm
Sulphur < 20 ppm
Iron < 20 ppm
As, Ag, Bi, Sb, Pb, Ni Should be as consistent as
possible from cast to cast.
Ag/Se Molar ratio >1
 As (Bi+Sb) molar >2 washing of electrolyte from the cathodes. Fig–
ratio 2 gives the microscopic structure of cathode
Anode composition plays a vital role in cathode deposit entrapped with electrolyte.
quality. The approximate distribution of the
principal elements contained in anode between
cathodes, electrolyte and slime is given below
in %. ( Table-2).

Table – 2 : Distribution of anode impurities in copper

electrorefining .( in %)

Element Cathod Electrolyte Slime

e
Gold 1-1.5 - 98.5-99
Silver 2-3 - 97-98
Copper 98 1.9 0.1
Se & Te 1-2 - 98-99
Lead 1-5 - 95-99
Nickel 15 75 10
Sb 20-30 20 5-60 Fig – 2: Microscopic structure of Cathode
Sn 20-30 20 50-60 deposit entrapped with electrolyte.
S 3-5 - 95-97
Fe 10-20 80 10-20 When the electrolyte contains large amount of
Zn 2 94 4 nickel, iron and zinc sulphates, the solubility of
Al 3 77 20 copper sulphate decreases, and the solution
becomes supersaturated with copper sulphate;
Bi - 22 79
as a result its crystal may separate.
AS 10 70 20 Consequently the concentration of copper ions
in the layer of electrolyte adjacent to the
cathode may become too low and hydrogen will
Impurities can be divided into following groups be released at the cathode together with the
according to their behavior in the electrolysis copper. The current efficiency will consequently
process. decrease and the quality of cathode deposit will
deteriorate.
Ni, Zn, Co, Fe :
It is necessary to ensure that the electrolyte
These are the metals that are more contains little of the these metals
electronegative than the copper and pass
almost completely in to the solution, thereby
gradually accumulating in the electrolyte. Ag, Se, Te, Au:
During the electrolytic refining of copper, nickel
accumulates in the electrolyte faster than the
other impurities, since its content in the anodes These metals are more electropositive than
is always greater than the content of any copper and almost completely pass on to the
elements of this group. Nickel, iron and zinc slime. Metals which do not dissolve in sulphuric
contained in the electrolyte in comparatively acid solution (Pb, Sn) and also relatively week
large quantities do not affect the composition of electrochemically active compounds of Cu2Te,
the cathodes but may give rise to unfavorable Cu2Se and Cu2S also belongs to this group. .
effects in the electrolysis of copper. Sometimes Analysis of slime indicates predominately silver
small amount of iron and nickel do nevertheless bearing compounds Ag2Se, (AgCu)2Se and
appear in the cathode copper. This is explained their analogous tellurides. To prevent physical
by the fact that iron and nickel sulphates remain inclusion of these compounds in copper
in the cathode either with the electrolyte in the cathode, it is required to maintain the atomic
form of inclusions in the pores and inter ratio Ag / (Te+Se) at more than 2.
crystalline cavities or on account of the poor

4
For silver contamination of cathode there exists
the possibility of electrolyte deposition at the
cathode limited by the solubility of silver in the
electrolyte. When the anode contains a large
amount of silver some of it can pass in to the
solution in the form of AgSO4. In order to
prevent silver from accumulating in the
electrolyte and possibility of codeposition along
with the copper, it is precipitated in slime as
AgCl by adding Chloride Ion Cl-.
Factor affecting the level of selenium
contamination level in cathode copper is the co
deposition of selenium. Normally the
concentration of Se is low (<O.2ppm), but care
should be taken to avoid any contamination,
particularly by silver refinery leach liquors.
Selenium forms complex with thiourea in the
ratio Se (IV) : CS (NH)2::1:4 particularly when
there is insufficient silver in anodes to
precipitate silver as Ag2Se. Formation of these
compounds could increase the solubility of
certain selenides and at the same time is
absorbed on the cathode surface. High
concentrations of Te in the electrolyte result in
contaminated copper with poor drawing
properties.
Gold does not dissolve in the electrolyte and
completely goes to the slime.
As, Bi, Sb:
These metals have potentials very near to the
copper and are most harmful, as they readily
pass on to the solution and remains in the
solution and co deposits with the copper under
conditions of the low copper concentration, high
concentration of these metals in the electrolyte
and high current density. The presence of these
impurities reduces the electrical conductivity,
ductility and malleability of copper. The
incorporation of As, Sb and Bi in cathode can
be due to one or more of the following: anode
slime occlusion, electrolyte occlusion, direct
precipitation of impurities from solution apart
from co deposition(3).
Arsenic presents in electrolyte as AsO43-. When
the concentration of bismuth and animony in
electrolyte is low arsenic does not have
appreciable effect on the electrolytic process.
But if the electrolyte contains higher
concentration of Bi and Sb , then it forms
insoluble compounds Bi2O3.As2O5, and
5
arsenates BiAs04, SbAsO4 which separates
from the electrolyte in the form of fine particles,
forming floating slime. This slime adheres to top
of the cathode forming top nodules and
contaminates them.
0.5
Float slime
0.4 SbSo4
Conc. of Sb, GPL
saturation
0.3
Optimum operating
0.2 range
0.1
0
0.1 1 10
Conc. os As, GPL
Fig – 3: Solubilities of As and Sb in electrolyte.
The Sb in the anode dissolves in the electrolyte
in the trivalent state. . Then in the presence of
dissolved oxygen in the electrolyte, Sb (III)
oxidises in to Sb (V) State. Studies reveal that
Sb (V) contributes significantly in floating slime
formation. The floating slime formation could be
controlled, if As/(Sb+Bi) molar ratio is
maintained at more than 2. The solubility of
arsenate compounds is strongly influenced by
temperature. One investigation has shown that
a temperature decrease from 60OC to 50OC
results in 20% decrease in the solubility product
for antimony arsenate.(5).
Ideally cathode quality will be enhanced by
maintaining low Sb concentration and by
maintaining an electrolyte well under the
saturation limit of arsenates. Fig - 1 shows the
solubilities of Sb and As in electrolyte
One method for controlling the floating slime is
the Bolidens process. The Bolidens process for
eliminating the float slimes is based on
preventing the oxidation of Sb (III) to Sb (V). It
was found that oxidation of, As (III) to As (V) is
more rapid than is Sb oxidation. Thus addition
of As (III) to electrolyte will minimise the
formation of Sb (V) preventing float slime
formation. The arsenic additions will have a
similar effect on Bi concentrations. Increasing
content of arsenic in anodes also helps.(5)
Other processes for removing Sb and Bi are
detailed in Electrolyte purification section.
 OXYGEN: 3.
Oxygen present in the anode as copper oxide
(Cu2O). This chemically dissolves by
electrolyte, as opposed to the electrochemical
dissolution of metallic copper.
Cu2O + H2SO4 CuSO4 + H20 + Cu
This copper which is accumulated in the
electrolyte must be removed, so that copper
concentration remains constant and passivation
of anodes is avoided. This is achieved by using
liberator cells. More on oxygen and passivation
is discussed in coming sections.
SULPHUR:
Although anode sulphur content does not have
any direct effect on the cathode sulphur,
sulphur content in the anode should be
prevented for any spewing at the desired
oxygen level.
2. Current Density 4. Electrolyte composition
Current density (CD) is an important parameter
in copper electrorefining as operating at higher
current densities lead to decrease in purity of
copper deposit. CD should be optimized to get
higher production rate and at the same time
higher copper cathode purity. The affect of CD
on electrorefining can be explained as below(2).
• At higher CD, copper deposition at cathode
increases, but at the same time it could lead to
dendritic growth at cathode surface. This
causes slime and electrolyte to get entrapped
on the cathode and lowers cathode purity.
• Also at higher CD , chances of anode
passivation are more. The anodes produce
Cu++ ions at faster rate then they convect away
leading to a higher concentration of Cu++ ions at
anode surface resulting in a layer of copper
sulphate. The passivation of anodes having
higher oxygen and low As/(Sb+Bi) ratio can be
partially overcome by operating at lower current
densities.
• At higher CD, chances of impurities such as As,
Bi and Sb , co depositing with the copper is
more.
6
Electrode Alignment
Electrode alignment has a significant effect on
cathode purity as it determines the current
density across electrodes. If the electrodes are
not spaced equally, more current passes
through the section where the distance
between anode and cathode is less, due
comparatively lesser resistance and less
current through the section where distance is
more. This result in uneven distribution of
current across cell and localized high current
density areas are formed resulting in the
detrimental effects as discussed in previous
section. It is important to keep the anode and
cathode contacts with the busbar cleaner, as it
is another cause for uneven distribution of
current.
Also presence of any bent plates can entrap
slime deteriorating cathode purity.
Copper refining electrolyte normally has
following composition
Table – 3 : Electrolyte Composition
Concentrations
Copper 40-50 gpl
Sulphuric acid 160-180
gpl
Total Sulphates < 300 gpl
Nickel <15 gpl
Arsenic < 15 gpl
Iron < 3 gpl
Sb < 500 ppm
Bi <300 ppm
Chloride 25-50 ppm
And various other impurities dissolved from
anodes. Apart from this they also contain
additives added for facilitating smooth
deposition of copper. The temperature is
maintained AT 62-66OC and continuously
circulated at required rate. It is essential that
electrolyte composition be maintained at
optimum level and impurities at as low as
 possible to avoid any harm to the electrorefining
and thereby cathode contamination.
• The copper concentration in electrolyte during
copper refining is primarily depends on the
anode oxygen content. Copper ions in solution
must be maintained to ensure copper is always
available for deposition at cathode surface, at
content in the electrolyte. This rapid change
suggests that, in an electrolyte already
saturated with Bi, a drop in acid
concentration will induce precipitation of Bi.
0.7

Bi in electrolyte , GPL
level far in excess of impurities. Using liberator 0.6
cells controls copper concentration in 0.5
electrolyte. 0.4
0.3
If copper concentration is lowered, the
0.2
impurities start depositing along with the copper
and contaminate the cathode. Too high 0.1
concentration of copper ions results in 0
crystallization of copper sulfate and chances of 0 100 120 140 160 180 200 220
anode passivation also increases. This also Acid concentration , GPL
increases power consumption.
Fig – 4: Solubility of Bi in electrolyte.
 Acid concentration is maintained in the
electrolyte as the electrical resistance of
cell depends to a considerable degree on The average impurity levels in the cathodes at
the concentration of sulphuric acid in the various acid concentrations in the electrolyte
electrolyte. If the acidity of electrolyte is too are given in Fig –5 & 6 for Se, Sb, Bi, Pb & Ni.
high then following unfavorable processes
occurs 16
Conc. in cathode , ppm

Pb
 The dissolution of anode increases and 12
consequently copper ion concentration in Ni
electrolyte increases. This leads to an
8
increase in number of cells with insoluble
anodes, which is undesirable since in these
cells the cathode purity is low and power 4
consumption increases. The chemical
dissolution at the top of cathode also 0
increases and this leads to broken cathode 0 100 125 150 175 200

 The passage of silver in to the solution 2

increases and some of it may be deposited 1.8
Conc. in cathode , ppm

Se Sb
on the cathodes. 1.6
1.4 Bi
 The concentration of As3+ in solution 1.2
increases. 1
0.8
 Studies(5) reveal that the solubility of Bi in 0.6
the electrolyte is strongly dependent on the 0.4
sulphuric acid concentration. . The variation 0.2
in the concentration of bismuth in the 0
electrolyte as function of acid concentration 0 100 125 150 175 200
is given in Fig - 4 . Acid conc. in electrolyte,gpl

Fig–5 & 6 : Variations of cathode impurities at

different electrolyte acid concentrations.
An increase in the acidity of electrolyte by
only 20gpl (from 150 gpl to 170 gpl) may The figure indicates that for most of the cases
result in the sharp increase of the Bi the impurity levels in the cathode pass through

7
a minimum at an acid concentration in the
vicinity of 160 gpl. This trend appears to apply
both to the elements which contaminate the
cathode mainly by slime occlusion such as Se
and Pb, and for which the contamination occurs
to a greater extent by electrolyte entrapment.
The contamination of the cathodes at low
acidities (100-125 gpl) appears to have been
caused by the poor morphology of deposits.
The tendency for increasing contamination of
cathode at higher acidity values of 175 –200 gpl
can be attributed to increased viscosity and
density of the electrolyte, causing a decrease in
the limiting current density and in the rate of
slime settlement. Acid level is maintained by
adding concentrated sulphuric acid to the
system.
• Chloride concentration is maintained in the
electrolyte due to following reasons.
 It prevents the passing of silver to the
solution by precipitating it as silver chloride.
 Chloride ions work in combination with the
thiourea to reduce the grain size of copper
deposit via a copper-chloride-thiourea
complex.
 It also precipitate out antimony and arsenic
as antimony oxychloride and arsenic
chloride and pass these impurities in to
slime
Low chloride levels causes soft cathodes due to
grain refinement. High chloride levels causes
large columnar based crystals and pile of
relatively long, needle like crystals resulting in
increase in shorts. Chloride level in electrolyte
is monitored daily and are maintained by
adding hydrochloric acid.
• The another important parameter to be
monitored is the total sulphates (total
concentration of sulphates associated with
the dissolved metals in electrolyte.). If the
total sulphate levels go above 300 gpl,
there is a strong chance for passivation.
Passivation occurs when copper is prevented
from coming off the anode because of copper
sulfate barrier at anode surface. This is most
undesirable as Passivation causes severe short
growth apart from higher power consumption.
This leads to areas of high current density and
therefore poor cathode quality. Anode affected
8
by passivation will have scrap with uneven
surface.
Passivation can be controlled only by reducing
sulphates, either by dilution or removal. A slight
increase in temperature also increases
solubility of copper sulphte, thereby reducing
passivation. One more solution for this problem
is the periodical reversal of refining current.
• Apart from this electrolyte contains major
impurities such as nickel, arsenic and iron.
Higher the concentration of these impurities
higher is the chances of their inclusion in
copper deposit. Electrolyte also contains
other impurities such as Bi, Sb. In order to
keep the level of these impurities it is
important to go for electrolyte purification.
5. Electrolyte temperature:
Electrolyte temperature is one important
parameter to be controlled in electrorefining.
Higher the temperature, higher is the mobility of
ions in the electrolyte and, consequently the
conductivity increases. Apart from this
temperature control is necessary for the
following reasons (1)
 At higher temperatures the cathode deposit
crystal structure becomes much coarser,
and the density of cathode decreases.
 Too high temperature results in increased
solubility of silver in electrolyte and silver co
deposits in cathode along with the copper
contaminating the copper and silver loss.
 High temperature decomposes glue at
faster rate and could lead to glue shortage
at cathode surface resulting in rough
growth.
 Low temperature lowers solubility of
copper, thereby increasing chances of
anode passivation.
 Low temperature also increases electrolyte
density, so anode slimes have a tendency
to float increasing chances of slime
inclusion in cathode deposit.
 Lower the temperature, higher is the
electrolyte viscosity, so electrolyte moves
unevenly in cells and anode slime gets
entrained in the electrolyte.
 Low surface temperature of the electrolyte
resulting due to uncovering of cells may
result in protruding horizontal growth at
solution line.
Considering the above facts it is desirable to
maintain the temperature in the range of 62-
66OC.It is worthy to note here that a section is
be cut in, only when the electrolyte temperature
is at minimum 550C to avoid any precipitation of
impurities at cathode mother blank surface.
6. Electrolyte circulation and flow
Electrolyte circulation plays a vital role in
electrorefining of copper. Any major variation in
this could lead to cathode deposit
contamination. The continuation circulation of
electrolyte at desired rate is necessary to:
 Maintain optimum electrolyte temperature
 Low flow rates provide insufficient reagents
and mixing, thereby contributing to rough
growth at cathode surface. Also circulation
of electrolyte helps in replenishing addition
reagents which have been consumed /
degraded.
250
200 Grainy deposition
Current Density , A/M2
150
Semi grainy deposition
100
50 Flat deposition
0 necessary to have all the cells be aligned
0 5 10 15
Flow rate , LPM
Fig – 7 : Effect of flow rate on deposit at various
current densities.
 During electrorefining of copper, the
solution near the anode is constantly being
enriched with copper ions, while that near
the cathode is being depleted. Eventually
the time arises when the amount of copper
ions becomes insufficient for normal
electrolysis; the deposition of antimony and
arsenic may begin resulting in cathode
contamination.
 Higher flow rates disturb the slime layer at
cell bottom and chances of slime inclusion
in the cathode increases. Attempts are
therefore made to maintain a circulation
rate where the electrolyte is well mixed but
the slime is not disturbed.
Hence, given the importance of flow rate,
following points be followed to ensure target
flow rates are achieved and maintained
8
Amount of slime , mg/sq.cm.hr
7
Adhering slim e
6
Floating slim e
5
4
3
2
1
0
0 5 10 15 20 25
Flow Rate ,LPM
Fig – 8 : Change of amount of slime in
electrolyte with flow rate
 It is important for operating personnel to
have a constant watch on electrolyte
circulation and flow rate and always be
maintained at optimum rate of 25 LPM. A
V-notch provision at cell outlet will enable to
have a proper control over flow rate.
 A look at the cathode deposit and the
direction of striations gives complete
picture of flow pattern in the cells.
 Apart from this as the electrolyte is fed to
cells from a common head tank, it is
20 25 and kept at same level, so that each cell
could experience similar electrolysis
conditions.
 It is advisable to cut off the current,
whenever circulation is stopped or variation
in flow rate is observed. Analysis of
cathodes taken from the cell where flow is
stopped indicates higher contamination
due to Bi, Sb, and As. especially at cathode
top with dark spots
9
7. Colloids addition and control
The grain refining and leveling agents (Colloids)
are added to the electrolyte as they assist in
smooth, dense deposition of copper deposit.
These colloids act as grain refining and leveling
agents, without which cathode deposits would
be dendrite and soft, entrapping electrolyte and
anode slimes.
They most often act as inhibitors. They adsorb
on the cathode surface, where they take part in
the electrochemical deposition of copper. Some
of these additives restrict the growth of existing
crystals and thus force the deposition to take
place via the formation of new nuclei. The
amount of colloids added depends on various
parameters such as composition of electrolyte,
the current density and others. As said earlier
regular look at the physical appearance and
quality of copper deposit gives good indication
of colloids addition.
Addition rates may vary at different refineries
according to the cathode deposit morphology. If
the continual delivery of reagents stops, coarse
crystal growth occurs after about 4 hrs. If the
stoppage is remedied within that time, fine
equipped growth resumes, with no discernible
loss of cathode quality(4).
Glue {Gelatin}:
Glue consists of large protein molecules and
possesses a strong positive charge and gets
adsorbed in to the areas in cathode surface,
where there is a strong negative charge or high
spots. These spots occur where there is a high
current flow and copper deposition rate is more.
Being a poor conductor of electricity it acts as a
inhibitor, preventing any further deposition on
these high spots thus enabling cathode to a
smoother surface and less shorts. This
eliminates entrapment of slime or electrolyte in
these areas. Glue is also consumed by
hydrolysis in the presence of acid and at high
temperature especially during the first half hr of
addition. . It is necessary to have a continuous
dosing of glue. Inefficient glue supply results in
pyramidal copper deposits. However
oversupply of glue makes it less effective in
cathode surface leveling apart from increasing
power consumption.
An instrument called COLLAMAT (practiced in
Norddeutsche Affinerie) could monitor glue
content in the electrolyte. Using COLLAMAT it
10
is possible to optimize the glue addition rate,
and to have knowledge about flow conditions
and glue supply in the cell
Thiourea {C (H2N)2S} :
It is a white crystalline material and dissolves
readily in water and helps in smooth deposition
of copper by reducing the grain size, increasing
hardness, brightness and cathode density. It
gets adsorbed to the cathode surface and
controls the size and shape of crystals. Studies
also reveal that thiourea acts in conjunction with
the chlorine ions forming a complex and thus
facilitating smooth cathode surface. Thiourea is
also capable of prohibiting the polarising effect
of gelatine on the deposition mechanism of
copper. It is likely that thiourea acts as a solvent
for gelatine.
Striations on the cathode surface are the best
indication for the thiourea addition rate.
Striations are the series of small ridges on the
cathode and follow the same direction as
electrolyte flow. Excess thioure addition causes
deep striations and can entrap slime or
electrolyte, thus reducing the cathode purity.
Thiourea does not decompose, but it is
apparently consumed in connection with the
deposition of copper.
Since thiourea is a sulphur bearing compound,
higher addition rate could lead to sulphur
contamination of cathode. Cathode flexing
sound and its strippability gives a good
indication for thiourea addition. Thiourea in
electrolyte can be monitored by reatrol system
Avitone:
It is a sulphonate surfactant and enhances the
action of gelatin by allowing the protein to
uniformly spread out and adsorb over greater
area.
8. Suspended solids and electrolyte
filtration
The solid particles contaminating the cathodes
are either anode slimes containing elements or
compounds which are not dissolved during the
electrolytic process or are formed in the bulk of
electrolyte through the increasing concentration
of insoluble compounds. The extent of cathode
contamination due to the occlusion of anode
slimes may depend on various electrorefining
parameters such as anode composition, the
morphology of the cathode deposit, anode
passivation and the characteristics of the slime
i.e. its specific gravity and particle size.
Insoluble solids formed in the bulk of
electrolyte are generally rich in As, Bi and Sb.
Depending on their respective concentration in
electrolyte; these elements can for from wide
range of insoluble compounds such as
antimony and bismuth arsenate (floating
slimes). These compounds may have a
detrimental effect on the quality of copper
deposit.
Floating slime can also be formed by
contamination of electrolyte with oil, lubricants
or any other petroleum products.
Apart from floating slime there exist suspended
particles. The particulate can be classified in to
two groups as follows.
Nodule producers: Cu, C, Sb, Se, Ag
Non producers of nodules : characteristics. In some refineries flocculent
PbSO4, PbO2,
Cu2Se, CaSO4.
Electrically conducting and semi conducting
particulates causes nodules on copper
cathodes whereas non-conducting particulates
do not. Surface characteristics of deposits
grown at various temperatures and with various
paticulates present at standard conditions is
given below in Table – 4.
Table – 4: Effect of various particulates on Cathode deposit.
Increasing temperature decreases solution
density and viscosity, thereby enabling slime to
settle at the bottom.
Continuous filtration of the electrolyte helps in
reducing the total suspended solids content in
the electrolyte. It is desirable to filter 100 % of
the electrolyte entering the electrolytic cells to
maintain the suspended solids well within the
limit of less than 2 ppm. It is important for the
production personnel to monitor the efficiency
of polishing filter, the filter cloth conditions etc.
on regular basis and to take the corrective
actions immediately as any negligence on this
part could lead to increase in suspended solids
in the system thereby reducing the cathode
purity due to slime entrapment. The efficiency
of the filter is monitored by measuring the
suspended solids at inlet and out let of polishing
filter.
One more possible method for decreasing the
suspended solids content in the electrolyte is
the addition of flocculating agents. Flocculating
agents consists of large organic molecules,
which have anionic, cationic or non-ionic
such as Prercol-351 (Colloids Canada Inc),
Superfloc-210 (Cyanamid Canada Inc.) are
used to settle down the suspended solids to
bottom slime layer. For flocculating agents to be
successful, it is essential that its addition does
not have any affect on cathode morphology.
The suspended solid content in electrolyte need
to be analysed daily to have a better control
over their content in the electrolyte. Fig-9
shows the microstructure of copper deposit with
slime entrapment.

Particulate 500C 700C

Cu Moderately Very few nodules
smooth nodules
C Very rough Round and
nodules moderately rough
nodules
Sb Moderately rough Quite smooth and
nodules rounded nodules
Se Round and Round and
smooth nodules smooth nodules Fig – 9: Microscopic structure of cathode
Ag No nodules No nodules deposit with slime entrapment

The extent of entrapment of particulate

depends much more on the deposit quality than
on the availability of contaminating particulate.

11
9. Other factors.
Power disturbances: - Cathode quality may
deteriorate if there occurs frequent power
interruption, resulting in formation of electrolyte
layer on the cathode surface and further
deposition taking place over the this layer. It is
advisable to increase the current in increments
to avoid any drastic changes taking place. Also
temperature of the electrolyte to be maintained
to avoid precipitation of impurities at the
cathode surface whenever the current is
switched off. Fig - 10 shows the power out lines
in cathode deposit microstructure.
Fig – 10 : Microscopic structure of cathode
deposit with “power out” lines.
Electrolyte volume shrinkage and drastic
changes in electrolyte parameters could also
result in poor quality of cathode. Volume
shrinkage will result in increase in concentration
of impurities thus harming the electrorefining
process.
Cathode washing is important, as it is
necessary to remove the adherent electrolyte
salts on the cathode surface. Also sometimes
dilute suplphuric acid is added to the wash
water to maintain the level at 2 gpl as it helps in
removing the oxide layer. Also cathode mother
blanks should have minimum temperature of
65oC before placing in electrolyte, as there is
chances of electrolyte impurities precipitating
out at surface, when cold plates are put in to
the electrolyte.
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Electrolyte Purification
Many impurities pass on to the electrolyte when
anode dissolves and over a period of time they
accumulate in the electrolyte and when the
concentration of these impurities exceeds the
limiting concentration, they deteriorate the
electrorefining process leading to poor cathode
quality. Following methods are used in
controlling the impurities.
1. Electrolyte Bleeding
Bleeding of electrolyte, low in copper helps in
removing major soluble impurities of copper
(derived from soluble Cu2O), arsenic, nickel,
iron, antimony and bismuth. This can be
achieved by:
Copper – Electrodeposited in liberator cells
using insoluble lead anodes (Electrowinning) in
three stages.
Arsenic - Co deposited with the copper during
second and third stages of Electrowinning. A
major proportion of it could be removed by
solvent extraction. The arsenic is recovered in
solution, which is then combined with copper
sulphate to produce copper arsenate byproduct
for sale.
Antimony/Bismuth – Co deposited with the
copper during second and third stages of
Electrowinning. A significant portion of this also
precipitates out on cell walls and pipes, from
where it could be removed. Also some selective
removal processes are available for removing
Sb and Bi, which are discussed in coming
section.
Nickel/iron - Crystallised in the form of crude
hydrated nickel sulphate by evaporating the
decopperised electrolyte in evaporating pans.
The concentrated black acid is sent back the
electrolyte circuit to maintain the acid balance. A
small of this is discard to prevent a gradual
build up of Ca, K, Mg and Na ions.
Surface electrolyte bleeding process.(6)
At the top 10 mm layer below the surface of
electrolyte inside the cell, the copper
concentration diminishes very suddenly to
about 35 gpl. The difference between this
portion and the bottom portion is nearly 10 gpl.
However impurity concentration is same at all
layers. This enables us to take the surface
electrolyte from the rest of the solution, which
has already been decopperised by 15 –20 %. If
this surface electrolyte, low in copper is sent to
the purification section, the quantity of
electrolyte purified would be increased by
around 20 % and the impurity removal quantity
will also be higher.
Acid recovery and neutralization process
Electrolyte is bled for electowinning cells at less
than 2 gpl copper and around 250 gpl acid
concentration. The electrolyte is passed
through sorption chamber containing ion
exchange resins, where acid is adsorbed in
resins and resultant electrolyte is sent to
neutralisation section. The acid could be
recovered from the resins by desorption.
The electrolyte from sorption chamber is then
neutralised in a mixing tank using caustic or
Soda ash. The pH is maintained at 10-11.
During neutralisation most of the impurities are
converted to their respective hydroxides or
carbonates and precipitates out from solution.
The tank content is filtered in a filter press. The
impurity sludge collected from filter press is
bagged. The clear liquid is then subjected to
evaporation, to recover sodium sulphate
sludge.
2. Selective removal Processes.
.(6)
a) Chelating Resin Adsorption Process
Since antimony & bismuth are the main
component of the scales present in the pipes
and of floating slimes, it can be called as the
most troublesome impurity in electrorefining.
Unitica Co. developed a chelating resin (UR-
3300) which removes Sb and Bi effectively by
adsorption (proposed by Tamano refinery of
Hibi Kyodo Smelting Company). As the
electrolyte passes through the packed column
of chelating resin, Sb and Bi are selectively
removed. They are then desorbed by means of
hydrochloric acid, and then recovered in the
form of a highly concentrated antimony chloride
solution by means of evaporation. Purified
electrolyte is then sent back to the circulation
section.
This process doubles the capacity for removing
antimony from electrolyte..
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b) Activated carbon solvent adsorption
Activated carbon is known and is widely used
as adsorbent, but this is rarely utilized in strong
acid solution such as copper electrolyte.
Sumitomo Copper refinery developed a
technique for separation of antimony from
electrolyte using activated carbon under
specific conditions. The presence of As plays a
major role in this adsorption as antimony gets
adsorbed in the form of Sb AsO4.
c) Solvent extraction
Zeneca Inc. has developed a reagent called
SBX-50, which is suitable for selective removal
of bismuth and antimony through solvent
extraction method. Sbx-50 is a long chain alkyl
ester of phosphoric acid. BHP copper uses this
method for Sb and Bi removal.
d) Norddeutsche Process(5)
It is based on the selective adsorption of As, Sb
and Bi from electrolyte with stannic acid. The
process not only helps in eliminating float slime
formation by reducing the Sb concentration but
the SbAsO4 and Bi AsO4 equilibrium are
broken. The resultant electrolyte becomes
undersaturated and arsenate precipitation is
eliminated.
e) Barium Carbonate Treatment(7).
This process to remove bismuth in electrolyte
was developed in Outokumpu’s Pori Copper
refinery. The process is based on the co-
precipitation of bismuth from the electrolyte by
means of poorly soluble barium sulphate.
The feed electrolyte is fed to a mixing tank; in to
which barium carbonate is added. Barium
sulphate precipitates, when barium carbonate
decomposes under the effect of the acid
content in the electrolyte. The forming
sulphates co precipitates bismuth and part of
antimony . The precipitate is separated by
filtration and the filtered electrolyte is sent back
to the circulation tank.
The disadvantage of this method is the disposal
of barium sulphate, which contains Bi and
unreacted barium carbonate. (Salts of heavy
metals Pb, Sr can also be used instead of Ba
salt.)
f) Detellurisation
High concentrations of Te in the electrolyte
result in contaminated copper, which has poor
drawing properties. If the refinery operates with
the near zero discharge bleeds, the Te which is
dissolved in the decopperising operation of
slimes (leaching) could return to the refinery.
The tellurium is removed by cementation on Cu
at 950C in up flow fixed bed reactor.
Apart from above other processes used for
selective removal of impurities whenever
impurity level in electrolyte exceeds specified
limit are
 Combined solvent extraction of As, Sb and
Bi using hydroxamic acid and stripping
using H2S.
 Removal of Bi from electrolyte using
Superlig materials ( Superlig 83)involving
macrocyclic affixed to silica supports,
 Addition of SO2 to reduce pentavalent Sb
to trivalent state and the addition of
chelating agents for Sb and Bi removal
(Hitachi process).
Conclusion
From the above discussions, it can be
concluded that the high cathode quality can be
obtained if following parameters are
maintained.
 Cu++ irons constant availability at cathode
surface
 Optimum current density and electrode
alignment
 Availability of appropriate quantity of
additives over cathode surface constantly
 Low concentration of impurities
electrolyte.
 Uniform electrolyte temperature and flow in
electrolytic cells
 Absence of slime particles in electrolyte.
Acknowledgement:
The authors wish to express their deep sense
of gratitude to the management of Sterlite
Industries (I) limited, for giving total support to
us with our endeavor to improve quality of our
cathode and wire rods to international
standards. We also grateful to them for granting
the permission to attend this seminar and
present the papers.
References:
1. A.K.Biswas and W.G.Davenport,
“Extractive metallurgy of copper”,
Pergamon Press, 1976.
2. C.L.Mantell.”Electrochemical Engineering”
3. T.B.Braun, J.R.Rawling, and K.J.Richards,
“Factors affecting the quality of
electrorefined cathode copper.
4. 0.Forsen, L.Zhu and A.E.Antila.,”
Electrochemical Characterization of
gelatine , thiourea and chloride ions in the
electrorefining of copper”.
5. V.Baltazar and P.L.Claessens, “Factors
affecting the cathode purity during copper
electrorefining” (AIME, Las Vegas, 1976).
6. T.Shibata, M.Haschiuchi, and T.Kato,
”Tamano refinery’s new processes for
removing impurities from electrolyte”.
7. Olli V.J.Hyarinen, “Process for selective
removal of bismuth and antimony from an
electrolyte especially in electrolytic refining
of copper”.
in
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