Minerals Engineering 6668 (2014) 152156

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Effect of electrolytes on the flotation of copper minerals in the presence

of clay minerals
Shengli Zhao a,b,, Yongjun Peng a,
a
b

School of Chemical Engineering, University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia
ALS Metallurgy, 39 River Rd, Wivenhoe, Tasmania 7320, Australia

a r t i c l e

i n f o

Article history:
Received 24 December 2013
Revised 29 April 2014
Accepted 30 April 2014
Available online 20 May 2014
Keywords:
Copper minerals
Chalcocite
Kaolinite
Flotation
Electrolyte

a b s t r a c t
Clay minerals have a deleterious effect on otation. In a previous study (Peng and Zhao, 2011), the
authors found that the otation of secondary copper minerals such as chalcocite was more affected by
clay minerals than the otation of primary copper minerals such as chalcopyrite due to stronger surface
oxidation resulting in an electrostatic attraction to clay particles. In this current study, the intention was
to use electrolytes to mitigate the adverse effect of clay minerals on chalcocite otation. A copper ore
mainly containing chalcocite was examined. In fresh tap water, kaolinite signicantly depressed chalcocite otation. However, with an increase in the electrolyte concentration, the recovery of chalcocite was
increased. It is concluded that the electrolytes reduce the electrostatic attraction between kaolinite and
chalcocite so that the surface coating of kaolinite on chalcocite surfaces may be mitigated leading to
improved chalcocite otation. It is interesting to nd that anions and cations with a greater atomic size
had a more benecial effect which may be associated with their tendency to modify surface
hydrophobicity.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The mining industry is well aware of the difculty in treating
copper ores in the presence of clay minerals. In a previous study,
Peng and Zhao (2011) investigated the effect of bentonite on the
otation of chalcopyrite (a primary copper sulde mineral) and
chalcocite (a secondary copper sulde mineral) in terms of slime
coating. They found that as a result of the different extent of mineral surface oxidation, chalcopyrite remained negatively charged
but chalcocite became positively charged after grinding leading
to the different interactions of copper minerals with bentonite particles. The surface of chalcocite after grinding was electrostatically
attracted to bentonite resulting in bentonite slime coating and the
depressed otation of chalcocite. Unlike chalcocite, chalcopyrite
exhibited an electrostatic repulsion to bentonite. Zhao and Peng
(2012) conrmed the occurrence of bentonite slime coating on
chalcocite but not on chalcopyrite by Cryo-SEM measurements.

Corresponding authors. Address: School of Chemical Engineering, University of

Queensland, St. Lucia, Brisbane, QLD 4072, Australia (S. Zhao). Tel.: +61 7 3365
7156; fax: +61 7 3365 3888.
E-mail addresses: Shengli.Zhao@alsglobal.com (S. Zhao), yongjun.peng@uq.edu.
au (Y. Peng).
http://dx.doi.org/10.1016/j.mineng.2014.04.024
0892-6875/ 2014 Elsevier Ltd. All rights reserved.

Other researchers have also reported clay slime coating on

galena, coal and bitumen surfaces through the electrostatic
attraction reducing surface hydrophobicity and then depressing
the otation signicantly (Arnold and Aplan, 1986; Gaudin et al.,
1960; Liu et al., 2005a,b). In pentlandite otation, serpentine minerals also depress otation due to slime coating. Edwards et al.
(1980) found that pentlandite otation was depressed in the presence of lizardite or chrysotile. By using electrophoresis and Scanning Electron Microscopy (SEM) measurements, they identied
slime coating of serpentine minerals on the pentlandite surfaces
which contributed to pentlandite otation depression. This mechanism was also identied by Bremmell et al. (2005) using otation,
zeta potential measurements, SEM and Atomic Force Microscope
(AFM) analysis on a mineral system consisting of pentlandite and
lizardite. A similar phenomenon was observed by Peng and
Bradshaw (2012) when they oated pentlandite in the presence
of lizardite in de-ionised water. However, Peng and Bradshaw
(2012) found that bore water with a high ionic strength increased
pentlandite otation recovery. They proposed that the reduction of
electrical double layer forces between particles in bore water mitigated the coating of lizardite particles on pentlandite surfaces
resulting in the improved pentlandite otation. For the same reason, the clay slime coating on copper mineral surfaces may be mitigated by electrolytes.

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S. Zhao, Y. Peng / Minerals Engineering 6668 (2014) 152156

The effect of electrolytes on mineral otation has been studied

by other researchers from a different perspective. Paulson and
Pugh (1996) investigated the otation of model hydrophobic
graphite particles in a series of electrolytes. Based on otation
recovery, they classied the electrolytes into three distinct groups
as shown in Fig. 1. Group A electrolytes (LaCl3, MgCl2, MgSO4,
Na2SO4, etc.) gave high otation and group B electrolytes (NaCl,
LiCl, KCl, CsCl, NH4Cl, etc.) gave intermediate otation, but group
C electrolytes (NaAc, NaClO4, HClO4, HCl, H2SO4, LiClO4, etc.) produced low otation. Paulson and Pugh (1996) proposed that the
increased otation performance of the hydrophobic graphite in
electrolytes was linked with the dissolved gas concentration gradients in the electrolyte solutions. Higher otation recoveries were
attributed to an increase in the collision probability with higher
concentration of smaller non-coalescing bubbles and a reduction
in the electrostatic interactions between particles and bubbles.
In fact, Craig et al. (1993) studied the inhibition of bubble coalescence in electrolyte solutions. By empirically assigning ions a
value of either a or b an electrolytes coalescence inhibition behaviour could be described using simple combining rules as shown in
Table 1. A cation or an anion is assigned as a or b. Only aa or bb
electrolytes result in a bubble coalescence inhibition (indicated
by a tick) and ab or ba electrolytes result in no inhibition (as indicated by a cross). Researchers have not found any exceptions to
these simple predictive rules. Currently it is unclear precisely what
properties make an ion a or b ion.
In addition, Hancer et al. (2001) classied certain ions as structure breaking ions. These ions are large inorganic ions, such as Cs+
and I. On the other hand, small inorganic ions, such as Li+, Mg2+,
F, and Cl are referred to as structure making ions. Table 2
shows some structure maker and breaker ions. Hancer et al.
(2001) proposed that for a collector molecule to adsorb at the salt
interface it had to displace interfacial water or penetrate through
the structure of water. If the structure of water was strongly hydrogen bonded due to the presence of structure making anions and
cations, then collector molecules could not reach the surface and
be adsorbed. Those ions that had a tendency to destroy the structure of water could create a condition for the adsorption of collector molecules and subsequently allow the otation of soluble salt
minerals.
In this study, the effect of clay minerals on chalcocite otation
was examined in electrolyte solutions. It is expected that electrolytes may mitigate slime coating and therefore improve chalcocite
otation. Meanwhile, electrolytes may also affect otation through

Table 1
Combining rules for effects of electrolytes on bubble coalescence inhibition Craig et al.
(1993).

a
a
a
a
b

a
b
b

Anions
OH
Cl
Br
NO
3
ClO
3
2
SO4
ClO
4
CH3COO
Oxlate2

H+





Mg2+
I.Sol
p

Na+

Ca2+
I.Sol
p

K+
p
p
p
p

NH+4

Cs+

Me4N+

Li+


p
p


p
p
p


p



I.Sol



I.Sol

p
l
I.Sol

I.Sol

p
p

I.Sol

p
I.Sol

I.Sol

p

I.Sol




I.Sol

p
p

Table 2
Structure makers and breaker ions (Hancer et al., 2001).

Li
Structure makers
Na
K
Cs
Structure makers
Rb

Cl

Br

NF

NF

NF

NF
NF
NF

NF
F
F

NF
F
F

NF
F
F

NF

the inhibition of bubble coalescence and modication of surface

hydrophobicity which were examined in this study as well.
2. Experimental
2.1. Materials and reagents
A copper ore sample obtained from an Australian copper plant
was crushed to a size of 1.70 mm and stored in a freezer before
grinding and otation. The copper grade of the ore is about 2.9%.
Quantitative XRD analysis indicates that the copper ore contains
0.1% chalcopyrite, 0.4% cuprite, 4.7% chalcocite, 40.6% hematite,
16.4% muscovite, 33.8% quartz. About 91% Cu originates from chalcocite. A kaolinite sample was purchased from Sibelco Australia
Limited Company to study the effect of clay minerals on chalcocite
otation. It contains 70.3% kaolinite, 18.8% muscovite and 6.8%
quartz based on quantitative XRD analysis.
Tap water was used throughout the study. Table 3 shows the
chemical compositions of the water analysed by ICP. The pH of
the water was 7.0.
Potassium amyl xanthate (PAX) and methyl iso-butyl carbinol
(MIBC) of industrial grade were used as collector and frother,
respectively.
To investigate the effect of electrolytes on the otation of chalcocite in the presence of kaolinite, sodium chloride (NaCl), lithium
chloride (LiCl), sodium uorite (NaF), potassium chloride (KCl) and
sodium Iodide (NaI) of analytical grade were used to make different strengths of solutions. These electrolytes vary in both anion
and cation size.
2.2. Grinding and otation
600 g Crushed copper ore was ground in a laboratory stainless
steel ball mill at 60% solids to obtain 80% particles passing
38 lm. The mill discharge was then transferred to a 2.5 L Agitair
Table 3
Chemical compositions of tap water used in this study (mg/L).

Fig. 1. Flotation recovery of model hydrophobic graphite in different groups of

electrolytes (Paulson and Pugh, 1996).

TDS

EC

Cl

SO2
4

CO2
3

Ca

Mg

Na

52

110

11

24

7.9

0.6

2.8

7.4

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S. Zhao, Y. Peng / Minerals Engineering 6668 (2014) 152156

Fig. 2. Chalcocite otation in the absence and presence of kaolinite in tap water.

otation cell for otation using an agitation speed of 700 rpm. The
solid density in the otation was 25%. When kaolinite was tested,
some copper ore slurry was replaced by the same amount of dispersed kaolinite slurry. In this study, different ratios of kaolinite
to the copper ore were tested, but the solid density in the otation
remained the same. During the conditioning, collector (25 g/t) and
frother (110 g/t) were added. Flotation was performed for 7 min
and 3 concentrates were collected after cumulative times of 2.5,
5 and 7 min.
3. Results
3.1. Chalcocite otation in tap water
Fig. 2 shows chalcocite otation response in the absence and
presence of kaolinite in tap water. In the absence of kaolinite, chalcocite displayed a good otation behaviour with 50% Cu grade and
96% Cu recovery at the end of otation. The presence of kaolinite
decreased chalcocite otation. Both Cu grade and Cu recovery were
decreased when 20% or 30% kaolinite was added and copper otation kinetics was also decreased. At 30% kaolinite Cu grade and
recovery were reduced to 33% and 63%, respectively at the end of
otation.
In a separate study where the effect of kaolinite on chalcopyrite
otation was investigated, kaolinite had little effect on chalcopyrite otation. Nor did 30% weight of kaolinite change the pulp rheology in otation. In the previous study, Peng and Zhao (2011) also
found that bentonite did not affect chalcopyrite otation but did
inuence chalcocite otation. In that study, both chalcopyrite
and chalcocite were ground to 38 lm. Peng and Zhao (2011)
attributed the depression of chalcocite otation by bentonite to
the oxidation of the chalcocite surface which was attracted to bentonite resulting in bentonite slime coating. This may explain the
depression of chalcocite otation by kaolinite in the current study
using tap water.

Fig. 3. Chalcocite otation in the presence of 30% kaolinite in NaCl solutions.

kaolinite. Obviously, the addition of NaCl mitigated the negative

effect of kaolinite on chalcocite otation.
3.3. Effect of cations on chalcocite otation in the presence of kaolinite
Fig. 4 shows the effect of different cations on chalcocite otation in the presence of 30% kaolinite. For a comparison, Cu grade
and recovery from chalcocite otation in tap water and NaCl solutions were also included in the gure. As can be seen, like NaCl, LiCl
and KCl mitigated the negative effect of kaolinite on chalcocite otation. However, the three cations (Na+, Li+ and K+) affected the otation differently. 0.47 mol/L LiCl and 0.34 mol/L NaCl produced
almost identical Cu grade-Cu recovery curves suggesting that Li+
may be inferior to Na+ in mitigating the negative effect of kaolinite
on chalcocite otation, reaching similar otation results but at
higher concentration. Meanwhile, 0.27 mol/L KCl produced the
best chalcocite otation with the best Cu grade-Cu recovery results
despite the moderate concentration. As a result, K+ is superior to
Na+ and Li+ in mitigating the negative effect of kaolinite on chalcocite otation.
3.4. Effect of anions on chalcocite otation in the presence of kaolinite
Similarly, the effect of different anions on chalcocite otation in
the presence of 30% kaolinite was investigated. The results are
shown in Fig. 5. Cu grade and recovery from chalcocite otation
in tap water and NaCl solutions were also included in Fig. 5 for a
comparison. Again, the three anions, F, Cl and I mitigated the
negative effect of kaolinite on chalcocite otation. As can be seen
from Fig. 5, F improved chalcocite otation response the least
despite the highest concentration, 0.48 mol/L tested. 0.48 mol/L
NaF increased Cu recovery from 63% in tap water to 78% without

3.2. Effect of NaCl addition on chalcocite otation in the presence of

kaolinite
Fig. 3 shows chalcocite otation response in the presence of 30%
kaolinite in NaCl solutions. With the addition of NaCl, chalcocite
otation was improved. The higher the NaCl concentration, the
better the chalcocite otation response. As shown in Fig. 3, the
addition of 0.08 mol/L NaCl increased Cu grade and recovery to
38% and 80%, respectively, at the end of otation. The addition of
0.34 mol/L NaCl increased Cu grade and recovery to 42% and 90%,
respectively, which are close to 50% Cu grade and 96% Cu recovery
achieved from the otation of the chalcocite ore in the absence of

Fig. 4. Effect of cations on chalcocite otation in the presence of 30% kaolinite.

S. Zhao, Y. Peng / Minerals Engineering 6668 (2014) 152156

Fig. 5. Effect of anions on chalcocite otation in the presence of 30% kaolinite.

changing the Cu concentrate grade at the end of otation. Cl produced better otation than F even at a lower concentration. For
example, 0.17 mol/L NaCl produced chalcocite otation concentrate with 39% Cu grade and 89% Cu recovery. I improved chalcocite otation the most. 0.13 mol/L NaI produced a otation
concentrate with 42% Cu grade and 91% Cu recovery.
4. Discussion
In the previous study, it was demonstrated that the surface of
chalcocite tends to be oxidised during grinding with stainless steel
media producing oxidising conditions (Zhao and Peng, 2012). After
grinding, chalcocite exhibited a pH isoelectric point at around 9.5
and was positively charged at pH values less than the pH iso-electric point. It has been reported that the edges and faces of clay minerals carry a negative charge in alkaline pH (Luckham et al., 1999;
Zhao et al., 2008). Therefore, oxidised chalcocite is strongly
attracted to kaolinite at otation pH 9.0 resulting in kaolinite slime
coating on chalcocite surfaces. This explains the otation results
obtained in the current study that chalcocite displayed good otation but kaolinite substantially depressed chalcocite otation.
With the addition of NaCl in otation, chalcocite otation in the
presence of kaolinite was improved signicantly. As shown in
Fig. 3, the high NaCl concentration was favourable to the otation
response. Apparently, NaCl mitigated the negative effect of kaolinite in chalcocite otation. The possible reason for the improved
chalcocite otation by NaCl is that the surface of both kaolinite
(negatively charged) and chalcocite (positively charged) are neutralised by the cations and anions in NaCl solutions. As reported
by Rattanakawin and Hogg (2001) and Liang et al. (2007), electrolytes compress electrical double layers and therefore reduce the
surface charges on particles. The compression of electrical double
layers may mitigate kaolinite slime coating on chalcocite surfaces
resulting in improved chalcocite otation even in the presence of
high kaolinite concentrations. This is in agreement with Peng and
Bradshaw (2012) demonstrating that pentlandite otation in the
presence of lizardite was improved in saline water.
Besides NaCl, LiCl, NaF, KCl and NaI all mitigated the negative
effect of kaolinite on chalcocite otation to some extent. Figs. 4
and 5 show the following order that the cations and anions mitigated the negative effect of kaolinite:

155

cations and anions affect chalcocite otation differently is not clear

but the underpinning mechanism may be discussed against published research outcomes.
Based on the combining rules for the effect of salts developed by
Craig et al. (1993), improvements in otation may be predicted by
the presence of the salts examined in this study, due to the inhibition of bubble coalescence. In other words, the use of these salts
may result in smaller bubbles that improve bubble-particle collision efciency and increase froth stability so that the drainage of
minerals from froth to pulp is reduced. However, Craig et al.
(1993) did not compare the ability of cations and anions in inhibiting bubble coalescence. Similar to Craigs theory, Paulson and
Pugh (1996) attributed the improved otation of hydrophobic
graphite in salt solutions partially to an increase in the collision
probability with higher concentration of smaller non-coalescing
bubbles. Based on the classication of salts by Paulson and Pugh
(1996), the salts examined in this study fall into group B electrolytes which gave intermediate otation of graphite. This is different from the observation in this study where these salts had a
wide range of effect on chalcocite otation in the presence of
30% kaolinite.
To further examine the possibility of bubble coalescence in salt
solutions resulting in smaller bubbles and subsequently improved
otation in this study, mass recovery and water recovery were
examined. The content of gangue minerals in the otation pulp
was more than 95% and the gangue recovery by entrainment
may be estimated by the mass recovery. Tao et al. (2000) and
Schwarz and Grano (2005) linked water recovery with froth stability in the otation and found that a more stable froth was accompanied by an increase in water recovery. As shown in Fig. 6, in tap
water, a linear relationship occurred between mass recovery and
water recovery with the extrapolation of the line passing the origin. This indicates the entrainment of ne gangue minerals in otation as demonstrated by Johnson (1972) and Laplante et al.
(1989). The addition of salts moved the mass recovery-water
recovery relationship upwards. At the same water recovery, these
salts yielded an additional 2% mass recovery. This suggests that
bubble coalescence may be inhibited by the addition of salts resulting in the higher mass recovery. However, the mass recoverywater recovery relationships produced by these salts were similar
although chalcocite otation produced by them was signicantly
different. Meanwhile, these mass recovery-water recovery relationships were not strictly linear. It is concluded that other factors
than the inhibition of bubble coalescence in salt solutions may play
an important role.
Attention was then turned to examine the theory from Hancer
et al. (2001) on water structure makers and breakers. In general

K > Na > Li ;


I > Cl > F :
0.13 mol/L NaI almost restored chalcocite otation even in the
presence of 30% kaolinite, whilst 0.48 NaF displayed a moderate
improvement. NaCl, the most populous salt in saline water
improved chalcocite otation signicantly. However, why these

Fig. 6. Mass recovery as a function of water recovery from chalcocite otation in

the presence of 30% kaolinite in tap water and different salt solutions.

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S. Zhao, Y. Peng / Minerals Engineering 6668 (2014) 152156

water structure breakers are larger size ions while water structure
makers are smaller size ions. The larger size the ion (i.e., K+ and I),
the weaker the bond formed with water molecules and the higher
the surface hydrophobicity. This presumption was conrmed by
contact angle measurements of KI, KCl, NaCl and NaF by Hancer
et al. (2001).This is consistent with chalcocite otation results produced with these ions in the current study. The larger the cation or
anion, the better the otation. It is expected that these ions may
also affect chalcocite otation in the absence of kaolinite through
the modication of surface hydrophobicity.
This study indicates that salts reduce the negative effect of kaolinite on chalcocite otation primarily by mitigating kaolinite slime
coating on chalcocite surface. However, salts may also modify surface hydrophobicity and therefore affect mineral otation to different extents.
5. Conclusions
The current study indicates that kaolinite slime coating on chalcocite otation may be mitigated by electrolytes. In tap water, the
kaolinite coating on the chalcocite surface occurs as a result of the
electrostatic attraction leading to the depression of chalcocite otation. With the addition of electrolytes to the otation system,
the otation of chalcocite may be improved due to slime coating
being mitigated as a result of electrolytes effects on the electrostatic interaction between particles. In addition, electrolytes may
modify the surface properties and therefore the otation behaviour. Larger size ions may improve chalcocite otation in the presence of kaolinite more than smaller size ions presumably due to
the increased surface hydrophobicity.
Acknowledgements
The authors wish to thank the experimental support from Tony
Button and John Glen from ALS Burnie Laboratory. The nancial
support from Dr. Yongjun Pengs New Start-up Grant awarded from
the University of Queensland is also appreciated.

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