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Examination of copper electrowinning

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Article in Minerals and Metallurgical Processing · February 2016

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 Examination of copper electrowinning
smoothing agents. Part I: A review
M.S. Moats*, A. Luyima and W. Cui
Associate professor, postdoctoral research fellow and graduate research assistant, respectively, Materials
Research Center, Missouri University of Science and Technology, Rolla, MO, USA
*Corresponding author email: moatsm@mst.edu

Abstract
Organic smoothing additives are used to produce dense, thick, high-quality cathodes in copper electrowinning. Glue had
been used traditionally and is still used in operations that do not employ solvent extraction to produce the electrowinning
electrolyte. With the advent of solvent extraction–electrowinning, guar started to be used and remained in use for many
years as it does not affect the phase disengagement in solvent extraction. Recently, however, guar has been replaced by
less-expensive saccharide- and polyacrylamide-based additives. This paper is the first of a series of four papers that
examine saccharides and polyacrylamides as new additives for copper electrowinning. A review of previous research
related to copper electrowinning additives is presented here, along with a selected review of additives in other copper
electrodeposition systems.

Minerals & Metallurgical Processing, 2015, Vol. 33, No. 1, pp. XXX-XXX. (tbd)
An official publication of the Society for Mining, Metallurgy & Exploration Inc.

Key words: Copper, Electrowinning, Chloride, HydroStar, Cyquest N-900, Cyclic voltammetry, Electrochemical
impedance spectroscopy

Introduction
The recovery of copper from solution by electro-
winning was first practiced in the early 1900s, but it
was the combination of solvent extraction with elec-
trowinning (SX-EW) in March 1968 at the Ranchers
Bluebird Mine (Kordosky, 1992) that changed the
landscape for the electrowinning process. Most cop-
per electrowinning capacity is now associated with
solvent extraction, though some copper is still won
directly from leach solutions (Robinson et al., 2013).
The ability to produce high-purity copper cathodes
from SX-EW has taken the continued improvement of
SX-EW technology over the past more than 40 years.
One of the technologies that has seen improvement
is that of the organic smoothing agents used during
the electrodeposition of copper in the tankhouse.
These organic additives are added to the acidic copper
sulfate electrolyte during electrowinning to improve
the smoothness, brightness and density of the copper
cathodes. The organic additives that are presently in
use are different from those used in 1999 (Jenkins et
al., 1999). Over the past decade, many tankhouses
have replaced the use of guar-based organic additives
with those derived from other saccharides. Until now,
there has been no comprehensive publication in the
open literature on the behavior of these additives
during copper electrowinning.
Our research group at the Missouri University of
Paper number MMP-15-024. Original manuscript submitted April 2015. Revised manuscript accepted for publication August
2015. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. prior
to Aug. 31, 2016. Copyright 2016, Society for Mining, Metallurgy & Exploration Inc.
Science and Technology has been studying these new additives
and present our findings in a series of four papers. The purpose
of this series is to explore and gain further understanding of
these new organic smoothing agents. Part I furnishes a review
of previous work published on copper electrowinning organic
additives, while Parts II-IV present recent research findings on
the fundamental electrochemical characterization of the effects
of three new organic additives (DXG-F7®, HydroStar® and
Cyquest® N-900), the interaction with chloride ions, and the
nucleation and growth of copper on stainless steel cathodes
in the presence of these three additives.
Copper electrodeposition
A fundamental discussion of the electrodeposition of cop-
per and the role of additives in acidic copper sulfate plating
systems is presented first of all.
Copper predominantly exists as a divalent cation in aqueous
acidic sulfate solutions obtained from leaching-purification
unit processes. During electroreduction, copper (II) ions in
solution diffuse to the negative electrode (cathode) surface
from the bulk of the solution. As copper (II) ions get close to
the surface of the cathode, their hydration sheath is removed.
The cupric ion is reduced to the cuprous state by the transfer of
a single electron, as shown in the reaction depicted by Eq. (1).
The cuprous ion is transformed into a neutral copper atom by
either electron transfer, as in Eq. (2), or comproportionation,
as in Eq. (3). The copper adatom will then diffuse along the

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

surface until it combines with other copper adatoms to form
a new nucleus or add to an existing grain:
(1)
(2)
(3)
During copper electrodeposition, the cupric to cuprous re-
duction is the rate-limiting step (Mattsson and Bockris, 1959).
Even so, a small amount of cuprous ions exist on or near the
cathode electrode surface due to the equilibrium established
by the reaction in Eq. (3).
To grow a thin film or thick cathode of electrodeposited
copper, the reactions in Eqs. (1)-(3) need to be driven from the
equilibrium state. Energy in the form of an applied potential
drives the reactions toward the formation of copper metal.
The extra energy or potential required to promote the forward
reactions at the intended rate is called overpotential. The rate
of the reaction is measured in terms of current per unit area of
the electrode and is known as current density. The relationship
between overpotential and current density is described empiri-
cally by the Tafel equation, given as Eq. (4), or more funda-
mentally by the Butler-Volmer equation (Bard and Faulkner,
1980), presented as Eq. (5). More details about fundamental
electrochemistry can be found in numerous textbooks, includ-
ing the one by Bard and Faulkner (1980).
(4)
(5)
where η is overpotential, i is current density, a and b are em-
pirical constants, i0 is the exchange current density, α is the
transfer coefficient, n is the number of electrons transferred, F
is Faraday’s constant, R is the gas constant and T is temperature.
The amount of overpotential required to drive the reaction
rate depends on the metal being deposited, the electrolyte
composition, and the surface upon which the deposition occurs.
The presence of cuprous ions affects the polarization behavior
of copper and the behavior of electrowinning additives. Ver-
eecken et al. (2005) demonstrated a correlation between the
copper deposition potential and the cuprous ion concentration
near the surface using a rotating-ring disc electrode technique.
They showed that copper deposited faster in cuprous-rich
conditions than in cuprous-depleted conditions for the same
applied potential. The increased presence of cuprous ions near
the cathode surface leads to acceleration of the copper plating
reaction. Moreover, additives can “polarize” or “depolarize”
copper electrodeposition by increasing or decreasing the activ-
ity of cuprous ions.
Copper-electrodeposition additives Lakshmanan, Mackinnon and Brannen (1977a) studied
The effect of an electrowinning additive is determined by
measuring the rate of reaction (current density) or potential
for a given reaction. If the rate of reaction is enhanced at a
fixed potential or the needed potential to drive a certain rate
decreases, the reaction is said to be depolarized. For example,
when chloride ions are added to acidic copper sulfate baths,
they depolarize or catalyze the copper reduction process (Ilgar
and O’Keefe, 1997). If the rate of reaction decreases at a fixed
potential or the needed potential to drive a certain rate increases,
the reaction is said to be polarized. Glue, in the form of gelatin,
and thiourea are known to polarize copper electrodeposition
February 2016 • Vol. 33 No. 1 2
(Stankovic, 1985; Veilleux, Lafront and Ghali, 2002). Addi-
tives that inhibit or polarize the reaction are believed to adsorb
onto the cathode surface, which increases the effective current
density and results in an increase in overpotential as indicated
by the Tafel equation or Butler-Volmer equation.
It is also known that certain compounds affect the electro-
chemistry, structure, properties and appearance of electrode-
posited copper. These compounds have been classified into
four categories (Vereecken et al., 2005):
• Brighteners or accelerators.
• Levelers.
• Suppressors or inhibitors or carriers.
• Chlorides.
A summary of selected additives and the categories to which
they have been assigned is given in Table 1.
Brighteners help produce a bright and shiny copper cathode
surface. They are typically sulfur (S)-bearing compounds that
interact with the copper (Cu) surface to form Cu-S bonds.
Thiourea and bis(sodium sulfopropyl) disulfide (SPS) are
commonly used brighteners. They are typically incorporated
into the copper deposits. Brighteners tend to refine the grain
structure by catalyzing the copper reaction and promoting the
formation of new grains.
Levelers help produce a smooth surface by inhibiting the
growth of protrusions or edges. Levelers are nitrogen-containing
compounds such as glue, polyacrylamide compounds, thiourea,
benzotriazole (BTA) or Janus Green B (JGB). Levelers and
brighteners usually work well in conjunction with each other.
For example, glue and thiourea are typically used in copper
electrorefining.
Suppressors, inhibitors or carriers are believed to affect
both copper dissolution and deposition. They are described
as polarizers or current suppressors. Examples of suppressors
are polyethylene glycol (PEG) and polyalkylene glycol (PAG).
Glue or gelatin is also known to act as a polarizer. These ad-
ditives have been shown to interact with the cathode surface
and influence plating in through holes and vias in circuit-board
and microelectronic plating. They also produce deposits with
tighter grain structures.
Chloride ions are not only known to depolarize or acceler-
ate the copper-plating process but also assist in interactions
between the copper surface and suppressors (Shao, Pattanaik
and Zangari, 2007). The interaction between glue, thiourea and
chloride in copper electrorefining is well documented (Knuutila,
Forsen and Pehkonen, 1987; Suarez and Olson, 1992; Sun and
O’Keefe, 1992). Thus, electrorefineries control the addition of
each of these compounds to obtain copper cathodes of desired
quality and density. These compounds can also affect anode
passivation in copper electrorefining (Moats and Hiskey, 2000).
The interaction between chloride and PEG in microelectronic
plating has also been established (Vereecken et al., 2005).
the effect of chloride on the electrowinning of copper from
solutions of 20 g/L Cu and 150 g/L sulfuric acid (H2SO4)
at 35oC. In their study, the effect of chloride ions depended
upon the current density. Chloride ions at a concentration of
10 mg/L depolarized copper electrodeposition and promoted a
(022)-oriented deposit. Increasing chloride content especially at
430 A/m2 promoted pyramidal growth, that is, (111) preferred
orientation. The interactions between chloride and thiourea
(Lakshmanan, Mackinnon and Brannen, 1977b) and chloride
and glue (Mackinnon, Lakshmanan and Brannen, 1978) during
copper electrowinning had been reported. However, the inter-
MINERALS & METALLURGICAL PROCESSING
 Table 1 — Summary of copper electrodeposition organic additives by category.
Brightener/accelerator Leveler
Polyacrylamides
Glue
Thiourea
Thiourea
Bis(sodium sulfopropyl) disulfide (SPS)
Benzotriazole (BTA)
Janus Green B (JGB)
actions between modern copper electrowinning additives have
not been reported in the open literature and will be discussed
in Part III of this series (Cui et al., 2016).
All of these additives either adsorb onto the copper surface
or linger near the surface in the electrical double layer. The
adsorption of electrorefining additives was examined by Hope
and his group using surface-enhanced Raman spectroscopy
(Brown and Hope, 1995, 1996; Brown et al., 1995).
While the roles of organic additives in copper electrorefining
and the electroplating of microelectronics, circuit boards and
copper foil have been studied fairly extensively, the roles of
modern additives in copper electrowinning have received less
attention. This review will examine what has been reported in
the open literature and lay the foundation for the experimental
work reported in Parts II-IV of this series (Luyima, Moats et
al., 2016; Cui et al., 2016; Luyima, Cui et al., 2016).
Copper electrowinning before solvent extraction
Early references to copper electrowinning indicate the use
of low current densities and the use of wooden staves in pipes
and cells, with no reference found as to whether or what organic
additives were used. Ellingham and Moore (1931) indicated
current densities of 140-160 A/m2 were being used in copper
electrowinning facilities. They also indicated the effect of glue
on polarization at the cathode in copper electrorefining. Later,
Grunenfelder (1954) described the hydrometallurgy of copper,
including electrowinning. In his descriptions, no discussion of
organic additives was given. In the same monograph, Eichrodt
and Schloen (1954) provided the addition rates of glue and
Goulac, or sodium lignin sulfonate, at 20 copper electrorefiner-
ies. Later, McArthur and Ledeboer (1960) revealed that glue
was added to the Chuquicamata tankhouse at a rate of 60-125
g/t. It is supposed that early electrowinning tankhouses either
used glue or did not add smoothing agents because of the low
current densities employed and/or organics leached from the
contained wood products.
Solvent extraction and guar
Guar or guar gum eventually became the standard smoothing
agent for copper electrowinning for several decades. The cou-
pling of solvent extraction and electrowinning, while elegant and
transformative for copper hydrometallurgy, placed constraints
upon the organic additives that could be used in a tankhouse.
As Hiskey (1999) indicated, colloidal addition agents such as
glue produce smooth, dense fine-grained deposits in copper
electrorefining but are not used in electrowinning “because of
the potential problems associated with the formation of cruds
in the solvent extraction circuit.” It is not clear, however, when
it was realized that glue could not be used with solvent extrac-
tion. Hopkins, Eggett and Scuffham (1973) indicated that glue
MINERALS & METALLURGICAL PROCESSING 3
Suppressor/inhibitor/carrier
Polyethylene glycol (PEG)
Polyalkylene glycol (PAG)
Glue
Gelatin
Polyacrylamides
and Goulac are not compatible with solvent extraction. Readett
and Mark (1989) reconfirmed that glue “is not compatible with
the solvent extraction organic extractant reagents.” Vereecken
and Winand (1976) studied polyacrylamides for use in copper
electrowinning and compared their results with “those obtained
with the commonly used guar gum.”
The open literature does not indicate why some additives
are compatible with solvent extraction and others are not. It is
believed industrially that glue inhibits phase disengagement
and facilitates crud formation while guar, polysaccharides
and some polyacrylamides do not. The underlying cause for
this is likely the charge of progeny compounds caused by
acid hydrolysis of the additive. All organic additives undergo
acid-catalyzed hydrolysis in copper electrowinning electro-
lytes, resulting in shorter organic molecules. Natural animal
glues, which are primarily labile proteins, decompose by
acid-catalyzed hydrolysis in sulfuric acid to produce amino
acids oligomers. Amino acids contain an amine group, which
in the strong sulfuric acid solution are protonated and thus
are positively charged. When the spent electrolyte mixes
with the organic phase in solvent extraction, the positively
charged molecules would be attracted to the negatively
charged extractant. This interaction could change the surface
tension of the organic/aqueous interface and inhibit phase
disengagement. Guar, polysaccharides and polyacrylamides
also undergo acid-catalyzed hydrolysis to form compounds
with hydroxyl or carbonyl groups. These compounds would
not be attracted to the extractant at the organic/electrolyte
interface during mixing and thus do not change the surface
tension or inhibit phase disengagement. Additional work
would be needed to verify this hypothesis.
In their 2003 survey of copper electrowinning facilities,
Robinson et al. (2003) indicated that 34 electrowinning fa-
cilities were using guar or a similar product while only eight
were using something different such as Cyquest, poly(acrylic
acid), N-100/FA920, M351 and OPT43. The median addition
rate for guar was 250 g/t at a median current density of 275
A/m2. Even though guar was widely used in copper electro-
winning, there is very little literature related to its effect on
copper electrodeposition. Stantke (1999) indicated that guar
is a galactomannan, which is a polysaccharide. Guar gum’s
molecular structure consists of a mannose backbone with ga-
lactose side groups at a mannose:galactose ratio of ~2:1 with
molecular weight of 50,000-8,000,000 (Food and Agriculture
Organization of the United Nations, 2008).
Vereecken and Winand (1976) compared the copper quality
obtained with polyacrylamide against guar in electrowinning.
Their research only indicated guar was superior without giv-
ing many details.
Miller (1995) indicated that Guartec, a guar derivative, was
used as a flocculating agent to help settle suspended solids in
the cell. The removal of suspended solids reduced nodular
Vol. 33 No. 1 • February 2016
growth and crud formation in solvent extraction.
Stantke (1999) presented information on the measurement
of guar using the CollaMat system. The electrochemical ac-
tivity of different amounts of guar was demonstrated. Using
the CollaMat system, response rates versus time as functions
of temperature and acid concentration were examined. The
results are summarized in Table 2 for temperature and in Table
3 for acid concentration. In all tests, the guar did not reach
maximum activity for some time. The maximum activity and
the degradation time were dependent on the temperature and
acid concentration. From these results, Stankte concluded “that
the most active species (molecules) of guar are generated by
hydrolysis reaction” and that guar was a weak polarizer.
Fabian (2005) examined the effect of guar, using Guarfloc
66, on the electrochemical behavior of copper depositing on
preplated copper and bare 316L stainless steel in solutions of
36 g/L Cu, 160 g/L H2SO4 and 25 mg/L chloride ions (Cl−)
at 45oC. Cyclic voltammetry and electrochemical impedance
spectroscopy (EIS) revealed that guar depolarized (reduced
the overpotential of) the copper deposition reaction. The de-
polarization increased with residence time until a maximum
was reached. Again, the hydrolysis product of guar appeared
to influence copper deposition. To explain the depolarizing
behavior, Fabian et al. (2009) proposed that guar acted as an
electrolyte inhibitor by residing at or near the outer Helmholtz
plane and interacted with the metal surface through long-range
electrostatic forces.
Fabian, Ridd and Sheehan (2007) examined guar and an acti-
vated polyacrylamide (APAM). They performed laboratory-scale
electrowinning experiments and found that guar plus chloride
was not as effective in smoothing the cathode as the APAM plus
chloride created in the laboratory at the same concentration.
Aragón and Camus (2011) examined the interaction of guar
and chloride on the crystal structure of copper deposits and
found that guar in concentrations of 15-30 mg/L with 30 mg/L
Cl− improved the quality of the deposit.
Table 2 — Effect of temperature on activity of guar measured by the CollaMat system – 35 g/L Cu, 160 g/L H2SO4,
2 ppm guar (Stantke, 1999).
Temperature Maximum activity Time to reach maximum
(oC) (mV/min)
40 7.7
45 5.7
50 4.6
60 3.4
70 0.8
Table 3 — Effect of acid on activity of guar measured by the CollaMat system – 35 g/L Cu, 45oC, 2 ppm guar (Stantke,
1999).
Maximum activity Time to reach maximum
Acid concentration (g/L)
(mV/min)
120 4.5
160 5.7
200 7.0
February 2016 • Vol. 33 No. 1 4
Moats and Derrick (2012) examined guar, consisting of
Guartec and Guartec S1, using a galvanodynamic method to
determine the nucleation overpotential of copper on stainless
steel or copper and the growth overpotential of copper from
solutions of 40 g/L Cu, 180 g/L H2SO4 and 20 mg/L Cl− at
room temperature and pressure. At concentrations from 2 to
30 mg/L, guar did not affect the nucleation or growth over-
potential. It should be noted that in their study, the organics
were added 30 minutes prior to the approximately 45-minute
experiments. The low temperature and short residence time
may have affected the results, given the previous discussion
on guar becoming more active by hydrolysis.
Other saccharides
Sandoval, Morales and Bernu (2010) revealed that a large
copper producer had tested and converted its tankhouses from
guar to a modified polysaccharide smoothing agent. This product
is sold under the trade name HydroStar. The smoothing agent
was reported to produce a denser cathode with lower sulfur
content than three different guar products and did not affect the
solvent extraction circuit, cell voltage or cathode lead content.
Comparisons of bench-scale data collected in the presence of
HydroStar and guar are presented in Table 4. During the plant
trial, the addition rate of this smoothing agent was 44 percent
higher than that of guar but was still considered cheaper due
to its lower cost.
Examination of the most recent electrowinning survey data
(Robinson et al., 2013) reveals that many SX-EW tankhouses
have switched from guar to either HydroStar or DXG-F7,
which are a modified polysaccharide and an oligosaccharide,
respectively. An oligosaccharide is defined as a few monosac-
charides covalently linked. A polysaccharide consists of a chain
of monosaccharide and disaccharide units. Unfortunately, these
compounds have not been characterized in the open literature.
A summary of the additives used in the SX-EW tankhouses
Time to reach 50% degradation
(min) (min)
320 680
210 615
150 375
50 170
40 50
Time to reach 50% degradation
(min) (min)
540 650
210 545
115 380
MINERALS & METALLURGICAL PROCESSING
 Table 4 — Comparison of physical characteristics of cathodes produced in bench-scale copper electrowinning with
different additives (Sandoval et al., 2010).

Additive Lead (ppm) Sulfur (ppm) Density (g/cm3) Porosity (%) Grain structure
HydroStar 0.14 4.8 8.852 1.21 FT-BR*
Guar 0.00 30.8 8.702 2.88 BR*
*FT = field-induced texture, BR = basis reproduction. See Winand (1992) for more details.

from the 2013 survey data is given in Table 5. Table 5 — Summary of additives used in copper
Similar to guar, published investigations of saccharide ad- tankhouses (Robinson et al., 2013).
ditives in copper plating are limited. Dextrin has been used
in commercial acid sulfate copper plating for many decades Additive No. of tankhouses
(Winkler, 1941). Turner and Johnson (Turner and Johnson, HydroStar 7
1962; Johnson and Turner, 1962) indicated that “dextrin is
Guar 5
generally used with thiourea and enhances brightening.”
Dextrin at concentrations up to 100 mg/L in 1 M copper (II) DXG-F7 3
sulfate (CuSO4) and 1 M H2SO4 at 25oC had no effect on the Guar/starch 1
polarization curve using a stationary electrode. The results Guar/HydroStar 1
with dextrin and thiourea were erratic and not reproducible.
Cyquest N-900 1
Taft and Bingham (1932) used gum arabic to understand
copper–additive interactions. Moats and Derrick (2012) exam- Polyacrylamide/
1
ined the polarization behavior of gum arabic and gum locust. polysaccharide
Gum locust was found to have a depolarizing effect, while None 1
gum arabic had a polarizing effect. Unknown 8
With the revelation that HydroStar is being used com-
mercially, several investigations were conducted to study
this additive on copper electrodeposition. Moats and Derrick
(2012) indicated that HydroStar did not affect polarization
in their conditions, which included the presence of chloride of HydroStar and guar had decreasing roughness (average and
ions. Helsten and Moats (2013) examined HydroStar at a variation) with increasing additive concentration (Fig. 1). A
more industrially relevant temperature (40oC) and found the fundamental investigation of HydroStar was recently presented
same results as Moats and Derrick. Helsten and Moats also using traditional electrochemical methods, namely, cyclic
examined a 50/50 weight percent mixture of modified poly- voltammetry and EIS (Moats, Luyima and Oliveira, 2014).
saccharide and guar. The mixture did cause a slight change in HydroStar again did not polarize the copper deposition reaction.
the plating polarization, but the magnitude of this change was To date, no published reports exist on the behavior of DXG-
not large, for example, 10 mV. Using a 60-minute plating test, F7. As such, the second paper in this series (Luyima, Moats et
deposits produced in the presence of HydroStar or the mixture al., 2016) will be devoted to this topic.
(μm)

Figure 1 — Smoothing effect of selected additives after 1 hr of electrodeposition in a

laboratory-scale copper electrowinning cell.

MINERALS & METALLURGICAL PROCESSING 5 Vol. 33 No. 1 • February 2016

Polyacrylamides
Besides polysaccharides, such as guar, HydroStar or DXG-
F7, some copper electrowinning tankhouses use compounds
originally designed to be flocculants. The 2003 electrowinning
survey (Robinson et al., 2003) indicated several plants used
flocculants. Recently, a polyacrylamide (Cyquest N-900) has
been reported in commercial electrowinning tankhouses as a
replacement for guar (Ashford, Clayton and Sandoval, 2012).
The polyacrylamide has been reported to produce high-quality
cathode while removing manganese dioxide (MnO2) from
coated titanium anodes (Sandoval et al., 2013).
Vereecken and Winand (1976) investigated several poly-
acrylamides. The compounds were found to polarize the copper
electrodeposition reaction but produce inferior deposits to guar.
Fabian and others (Fabian, 2005; Fabian, Ridd and Sheehan,
2006, 2007; Fabian et al., 2009) developed APAM by modify-
ing a nonionic polyacrylamide with chemical treatment, and
then discussed its effects in several publications. Their results
indicated the activated polyacrylamide polarized the surface
during copper electrodeposition and produced a superior deposit
to guar. APAM affected the charge transfer resistance detected
by EIS measurements. It appeared to interact with chloride, and
Fabian proposed an APAM-copper (I) chloride (CuCl) complex
similar to the CuCl-PEG complexes reported in damascene
copper plating baths (Hebert, 2005; Vereecken et al., 2005).
Moats and Derrick (2012) investigated a polyacrylamide
using a galvanodynamic method at room temperature in the
presence of 20 mg/L chloride and indicated that it polarized
the copper reduction reaction. Helsten and Moats (2013)
produced similar polarization results at 40oC with a different
polyacrylamide and revealed that this polyacrylamide was more
effective at low concentrations than HydroStar or a HydroStar/
guar mixture at smoothing a copper deposit, as shown in Fig. 1.
A study of Cyquest N-900 revealed similar responses to
polarization and EIS as the previous works by Fabian and his
colleagues (Moats et al., 2014). Cyquest N-900 polarized the
copper deposition but not the nucleation of copper on stainless
steel. It also increased the measured charge transfer resistance.
Other additives
A few studies of other organic additives in copper electro-
winning had been reported. Muresan et al. (2000) investigated
a horse-chestnut extract (HCE) and a mixture of ethoxyacetic
alcohol and triethyl-benzyl-ammonium chloride (IT-85). They
reported that IT-85 produced a fine-grained, leveled deposit
with a strong (110) texture. HCE had a smaller leveling effect.
Varvara et al. (2004) evaluated Ferasine and indicated that it
also promoted a (110) texture deposit, acted as a leveling agent
and polarized copper deposition. Yu et al. (2008) examined
gelatin in combination with several other compounds, includ-
ing thiourea, polyacrylamide, hexadecylpyridinium bromide
(HDPBr), polyethylene glycol and cetyltrimethylammonium
bromide. Their study is relevant to direct electrowinning but
not SX-EW operations because of the problematic interaction
of gelatin, or glue, with SX. Their results indicated gelatin plus
HDPBr had the strongest inhibiting effect of the combinations
examined. Recently, Zhang et al. (2015) reported on the effects
of using quaternary-ammonium-based ionic liquids as additives
for copper electrodeposition. The ionic liquids promoted the
formation of fine-grained and level deposits.
Discussion on electrowinning additives
Most commercial copper electrowinning smoothing agents,
February 2016 • Vol. 33 No. 1 6
including guar, HydroStar and DXG-F7, are polysaccharides.
The use of these compounds or similar ones is dictated by the
interface of solvent extraction with electrowinning. These
compounds are weak polarizers at best and in some cases do
not appear to polarize at all. There is evidence that guar needs
a considerable amount of time to become fully active and the
hydrolysis products are the influencing species. The lack of
an adequate amount of time to allow saccharides to hydrolyze
may have influences on the results of some groups.
Saccharides can have many configurations. They can be
linear or branched or contain carbon rings. All contain carbox-
ylic acid groups and may contain aldehydes or ketone groups.
Thus, they have some chemical similarities to PEG, which
is a known suppressor that polarizes copper electrodeposi-
tion especially in the presence of chloride. The commercial
saccharides have been shown to smooth copper deposits in
electrowinning, but the mechanism involved still needs to be
determined. This led to our investigation of the nucleation and
growth of copper under simulated electrowinning conditions
in the presence of HydroStar, DXG-F7, Cyquest N-900 (a
polyacrylamide) and chloride, which is Part IV of this series
(Luyima, Cui et al., 2016).
Summary
Copper electrowinning has been practiced for more than
a century. We found minimal discussion during the first 50
years on the use of organic additives to control the plated
copper structure. It appears that either glue was used or no
additives were used, possibly due to low current densities or
the leaching of natural compounds from used wooden electro-
winning structures. The combination of solvent extraction and
electrowinning in 1968 opened the door to a new era in copper
hydrometallurgy and eventually resulted in 20-25 percent of
the world’s refined copper being produced by this process.
The combination of solvent extraction and electrowinning
also eliminated the ability to use glue and resulted in the use
of guar as the common additive for the next 30-40 years. In
the past decade, guar has been replaced in many tankhouses
by other saccharide products. A few tankhouses have used and
continue to use polyacrylamides as their smoothing agents.
While considerable research has been undertaken on the
additives used in microelectronic and circuit-board plating,
for example, in the damascene process, and copper electrore-
fining, little research has been reported on the contemporary
additives used in copper electrowinning. Saccharides and
polyacrylamides have been shown commercially to be able
to produce smooth, dense deposits. The saccharides appear
to be weak polarizers or nonpolarizers, so the mechanism by
which they work still needs to be determined. Polyacrylamides
are not well understood either and should be investigated fur-
ther. Parts II-IV of this series add to the body of knowledge
regarding how modern organic additives affect the copper
electrowinning process.
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