Minerals Engineering 92 (2016) 2836

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

Adsorption of copper sulphate on PGM-bearing ores and its influence on

froth stability and flotation kinetics
W. Nyabeze , B. McFadzean
Centre for Minerals Research, Department of Chemical Engineering, University of Cape Town, Private Bag X3, Rondebosch 7701, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Copper sulphate is used as an activator in the flotation of base metal sulphides as it promotes the inter-
Received 26 November 2015 action of collector molecules with mineral surfaces. It has been used as an activator in certain platinum
Revised 1 February 2016 group mineral (PGM) flotation operations in South Africa although the mechanisms by which improve-
Accepted 15 February 2016
ments in flotation performance are achieved are not well understood. Some investigations have sug-
gested these changes in flotation performance are due to changes in the froth phase rather than
activation of minerals by true flotation in the pulp zone. In the present study, the effect of copper sul-
Keywords:
phate on froth stability was investigated on two PGM containing ores, namely Merensky and UG2
Froth flotation
Froth stability
(Upper Group 2) ores from the Bushveld Complex of South Africa. Froth stability tests were conducted
Copper sulphate using a non-overflowing froth stability column. Zeta potential tests and ethylenediaminetetraacetic acid
Copper activation (EDTA) tests were used to confirm the adsorption of reagents onto pure minerals commonly found in the
two ores. The results of full-scale UG2 concentrator on/off copper sulphate tests are also presented. The
UG2 ore showed a substantial decrease in froth stability in the order of reagent addition: no
reagents > copper > xanthate > copper + xanthate, while Merensky ore showed a slight decrease. It was
shown through zeta potential measurements that copper species were to be found on plagioclase, chro-
mite, talc and pyrrhotite surfaces and through EDTA extraction that this copper was in the form of almost
equal amounts of Cu(OH)2 and chemically reacted copper ions on the Merensky and UG2 ore surfaces. In
certain cases, the presence of copper sulphate and xanthate substantially increased the recovery, and
therefore the implied hydrophobicity, of pure minerals in a frothless microflotation device. It was, there-
fore, proposed that increases in hydrophobicity beyond an optimum contact angle for froth stability, were
the cause of instabilities in the froth phase and these were found to impact grade and recovery in a full-
scale concentrator. Differences in the extent of froth phase effects between the different ores can be
attributed to differences in mineralogy.
2016 Elsevier Ltd. All rights reserved.

1. Introduction sulphate is expected to enhance the bubbleparticle interaction in

In the flotation of sulphide minerals, collectors belonging to the
xanthate class are most commonly used. Activators are chemical
compounds usually added to promote the interaction of collector
molecules with the mineral surfaces (Rao, 2003). The most com-
mon activator used in the flotation industry is copper sulphate
and it was traditionally used as an activator for sphalerite (zinc sul-
phide). Copper sulphate has been used on some PGM operations to
improve the recovery of base metal sulphide (BMS) minerals, and
consequently PGMs, but certain ores, such as UG2, have very little
BMS minerals present and the mechanism of copper sulphate
interaction is poorly understood. In general, the addition of copper
Corresponding author.
E-mail address: nybwad001@myuct.ac.za (W. Nyabeze).
the pulp phase due to enhanced mineral surface hydrophobicity.
However, it has been noted that the addition of copper sulphate
may affect the froth stability (Ekmeki et al., 2006). The purpose
of this study was to investigate this observation in more detail.
Aktas et al. (2008) described froth stability as the time of persis-
tence of a froth. Froth stability affects the overall flotation
performance since the froth phase provides a zone where the
hydrophobic material is upgraded (Ekmeki et al., 2006). For unsta-
ble froth, breaking of bubbles results in hydrophobic particles pre-
maturely returning to the slurry which reduces the recovery
(Kawatra, 2002). If the froth is too stable, a large amount of gangue
could be entrained, reducing the grade of the concentrate
(Moolman et al., 1995). Chemical, operating and particle factors
may all affect the froth stability. Copper sulphate is a chemical fac-
tor that affects the particle properties, in particular the particle

http://dx.doi.org/10.1016/j.mineng.2016.02.004
0892-6875/ 2016 Elsevier Ltd. All rights reserved.
 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836 29

hydrophobicity. Increasing particle hydrophobicity beyond an Table 1

optimum contact angle (
65) has been shown to have a destabil- Comparison between UG2 and Merensky ores (Jones, 1999).

ising effect on the froth phase (Johansson and Pugh, 1992). Merensky
Most flotation processes occur at alkaline conditions due to the Dominated by orthopyroxene (
60%)
mineralisation of the ores and it is important to understand the and plagioclase (
20%)
reactions occurring at these conditions. The pH of the system will
affect the type of chemical species present and influences the
Cr2O3 (chromium (III) oxide) content
adsorption mechanism as well as the flotation efficiency (Ralston is about 0.1%
and Healy, 1980). For copper, the predominant species at pH values BMS make up to 3% of the ore-
lower than 6 are Cu2+ ions, whereas above pH 6 Cu(OH)2 is pre- chalcopyrite, pyrrhotite and
dominant (Fuerstenau, 1982). The majority of the work on copper pentlandite with pyrite in trace
amounts (<0.1%)
sulphate activation has been done on sphalerite (zinc sulphide)
Minerals found in a silicate substrate.
where the most widely accepted mechanism for copper sulphate Majority of the PGMs associated
activation at high pHs involves a direct ion exchange reaction with pentlandite, in either the
between Cu2+ ions and Zn2+ ions (Finkelstein, 1997) and subse- grains or along the pentlandite
quent electrochemical redox reaction involving the oxidation of gangue boundaries
PGM content in the reef ranges
sulphur on the mineral surface and the reduction of Cu(II) to Cu
between about 4 and 10 g/t
(I) (Gerson et al., 1999). Average PGM mineral grain size
The ores of interest to this study are platinum group mineral about 45 lm, concentrate milled
(PGM)-bearing ores hosted within the Bushveld Complex in South to about 55% passing 75 lm to
liberate the PGM minerals
Africa The three main PGM containing ores in the Bushveld Com-
Lower concentrate grade because for
plex are Merensky, Upper Group 2 (UG2) and Platreef a given quantity of ore, the mass
(Schouwstra et al., 2000). The mineralogical differences of the ores of concentrate is higher than in
require different processing approaches. Merensky and UG2 ores UG2 ore. The smelting costs are
were used in this study. The Merensky reef contains approximately thus higher than UG2
UG2
Dominated by chromite (
6090%),
with less silicate minerals
orthopyroxene (
525%) and
plagioclase (
110%)
Cr2O3 content is about 30%
BMS represent less than 0.1% of the
mass of the reef, the most abundant
being chalcopyrite, pentlandite and
pyrrhotite
Sulphide grains are generally finer
than those of the Merensky reef.
PGMs found in a chromite matrix
PGM content in the reef between 4.4
and 10.6 g/t
Average PGM mineral grain size
about 15 lm, concentrate finely
milled to about 80% passing 75 lm to
liberate the PGM minerals
The grades of UG2 concentrate are
higher than Merensky concentrate
(around 1.3% of the feed ore), hence
the amount of concentrate to be
smelted is smaller

1% base metal sulphide (BMS) minerals and these are strongly

associated with PGMs. On the other hand, the UG2 reef contains
less than 0.1% of BMS (Jones, 1999). The other difference between
the two ores is in the content of gangue minerals. Merensky ore is
dominated by orthopyroxene and plagioclase (silicate gangue min-
erals) whereas UG2 ore is dominated by chromite an oxide
gangue mineral and less silicate gangue minerals (Jones, 1999).
With regards to copper sulphate activation, the majority of the
studies have focussed on pulp phase effects (Nicol, 1984; Prestidge
et al., 1994; Trahar et al., 1997; Chen and Yoon, 2000; Fornasiero
and Ralston, 2005; Shackleton et al., 2007; Chandra and Gerson,
2009) and very few have focussed on the froth phase (Ekmeki
et al., 2006). This study aims to investigate the froth modifying
effects of copper sulphate when it is used as a pulp phase activator
for PGMs.
2. Experimental methods
2.1. Materials and reagents
2.1.1. Ore mineralogy and milling
A Merensky ore and a UG2 ore from the western limb of the
Bushveld Complex were used for the laboratory studies. Table 1
summarizes some of the key mineralogical differences between
the two ores.
2 kg portions of the Merensky and UG2 ores were milled in a
stainless steel rod mill with a diameter of 30 cm and it was charged
with 22 stainless steel rods of length 28.5 cm and diameter 25 mm.
Both ore samples were milled at 66% solids in synthetic plant water
to achieve a grind of 60% passing 75 lm. Copper sulphate (at a
dosage of 90 g/tonne) was added in the mill prior to xanthate addi-
tion to minimise interactions of the activator with xanthate in the
pulp (Chandra and Gerson, 2009).
2.1.2. Reagents and pure minerals
Copper sulphate pentahydrate (CuSO45H2O) was used as an
activator. Purified sodium isobutyl xanthate (SIBX) was used as a
collector. EDTA (Ethylenediaminetetraacetic acid) was used as a
complexant to extract metal hydroxides from mineral surfaces.
Di-sodium tetraborate (Na2B4O710H2O) was used as a background
electrolyte for zeta potential determinations. DOW 200, a propy-
lene glycol methyl ether was used as a frother. 0.1 M solutions of
sodium hydroxide and hydrochloric acid were used for pH adjust-
ment. Synthetic plant water was made by modifying distilled
water with the addition of various chemical salts to contain total
dissolved solids of 1023 ppm and an ionic strength of
2.4  102 M (Wiese et al., 2005). The composition of the synthetic
plant water is shown in Table 2. The synthetic plant water con-
tained key ions similar to those typically found in industrial flota-
tion circuits. All chemicals, except the flotation reagents, were of
analytical grade quality.
The pure minerals used in this study were pyrrhotite, plagio-
clase, chromite and talc. The minerals were carefully selected to
ensure a representative range of hydrophilic and hydrophobic min-
erals for the UG2 and Merensky ores. Pyrrhotite is the most abun-
dant BMS in Merensky ore and chromite is an abundant gangue
mineral in UG2 ore. Plagioclase and talc are hydrophilic and
hydrophobic gangue minerals respectively which are present in
both ores. Activation of these minerals by copper could reduce
the grade of the concentrate and affect the froth characteristics.
The surface areas for the pure minerals were determined using
the BET (Brunauer Emmett Teller) method and these were used
to calculate the surface coverages (in monolayers) of reagents by
assuming the surface area of the reactive thiol group of a xanthate
molecule to be 37 2 (Bradshaw, 1997) and the theoretical surface
area required per atom uptake of copper was taken to be 20.8 2
(Gaudin et al., 1959). Table 3 shows the BET surface area for each
pure mineral used in the zeta potential and microflotation tests.
2.2. Froth stability tests
The froth stability column was used to analyse the effect of cop-
per sulphate on the froth phase of the flotation system based on a
Table 2
Total ions present in synthetic plant water.
Ions present Ca2+ Mg2+ Na+ Cl SO2
4 NO2
3 CO2
3 TDS
Concentration 80 70 153 287 240 176 17 1023
(ppm)
30 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836

Table 3 lected at the end of each run. The experiments were conducted in
BET surface area for each mineral in each size class investigated. duplicate to minimise experimental error.
Mineral/ore Test Particle size (lm) BET surface area (m2/g)
Talc Zeta potential 25 5.95 2.4. Zeta potential tests
Pyrrhotite Zeta potential 25 0.949
Plagioclase Zeta potential 25 1.95
Zeta potential tests were carried out on dilute dispersions of
Chromite Zeta potential 25 0.872
Talc Microflotation 106 + 38 3.57 pure minerals of particle size less than 25 lm using a Malvern
Pyrrhotite Microflotation 106 + 38 0.114 Zetasizer 4. This measures electrophoretic mobility, which is used
to calculate the zeta potential via Smoluchowskis equation
(Hunter, 1993). Experiments were carried out in a 102 M di-
method of measuring froth stability developed by Bikerman sodium tetraborate solution (background electrolyte) at pH 2, 4,
(1973). A schematic flow diagram of the column is shown in 6, 8 and 10 at 25 C. The minerals were conditioned for 20 min to
Fig. 1. The milled slurry was diluted to 30% solids by addition of ensure constant pH. Xanthate and copper sulphate solutions were
synthetic plant water, conditioned for 5 min with 1.1  102 M of concentration 5  103 M. The experiments were conducted in
xanthate solution which corresponds to a dosage of 80 g/tonne. triplicate to minimise experimental error.
150 ppm of frother was added and the slurry was fed to the column
to the 30 cm mark. Air was introduced to the column at 6 l/min 2.5. Surface species analysis
which corresponds to a superficial gas velocity (Jg) of 1.27 cm/s.
The froth height relative to the pulpfroth interface was recorded EDTA (Ethylenediaminetetraacetic acid) is a strong complexant
as well as the maximum froth height, Hmax, which is a dynamic used to determine the amount of Cu(II) on the mineral surface pre-
equilibrium condition between the rate of formation and decay sent as Cu(OH)2 since it complexes strongly with hydroxides but
of the froth (Barbian et al., 2003). All tests were performed in trip- does not react with sulphides (Kant, 1997). A 0.03 M EDTA solution
licate to minimise uncertainty. of 250 ml volume was used with a 20 ml feed slurry sample to the
frothing column. The procedure developed and tested by Lange
2.3. Microflotation tests et al. (1997) was used for the tests using a closed vessel bubbled
through with nitrogen to purge the system of oxygen. The slurry
A microflotation cell was used to determine the flotation sample was filtered and the filtrate sent for copper analysis using
response of pure minerals in the absence of the froth phase and AAS Atomic Absorption Spectroscopy before and after reaction
under low solids densities. The microflotation cell developed by with EDTA.
Bradshaw and OConnor (1996) was used and the procedure devel-
oped by (Malysiak, 2003) was adapted. The test work was con- 2.6. Full scale flotation surveys
ducted using 3 g of talc or pyrrhotite samples at pH 9 using
synthetic plant water. Two monolayers were used for copper sur- Flotation surveys were performed on the rougher bank of a
face coverage and 0.5 monolayers for xanthate surface coverage South African UG2 ore concentrator. The rougher bank consisted
which gives an optimal coverage on the mineral surface of 6 flotation cells, but the fifth cell was not operational and was
(McFadzean et al., 2012). The number of monolayers was calcu- bypassed. The survey was conducted over 3 h, with samples taken
lated from the BET surface areas of the pure minerals and the sur- every 20 min. Feed and tails of the bank and concentrates from
face area of a xanthate thiol group or copper(II) ion. Concentrates each cell were sampled for assay. The flow rates of all concentrates
were collected for 2, 4, 6 and 8 min and a tailings sample was col- were also measured manually every 20 min. These were used to

Fig. 1. A schematic representation of the experimental setup for the froth stability column. The column is made of Perspex with a diameter of 10 cm and height of 100 cm.
 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836 31

help drive the mass balance since high confidence could be Talc, No Reagents Talc, Cu
Talc, X- Talc, Cu + X-
assigned to flow rates that were measured 10 times. The default No Reagents Model Cu Model
copper sulphate dosage to the roughers was 45 g/t, with 90 g/t X- Model Cu + X- Model
100
SIBX, and a number of surveys were conducted at this setting. A 90
single survey was conducted with copper sulphate dosing turned 80

Talc Recovery (%)

off. All the other reagent dosages remained the same. Control data
confirmed that the bank was operating in a stable condition over
the time of the surveys.
3. Results
3.1. Froth stability tests
The dynamic froth stability factor, R was used as a measure of
froth stability and this is defined as:
X V f A  Hmax
Q Q
where Vf is the volume of foam at equilibrium, Q is the gas volumet-
ric flow rate, Hmax is the equilibrium foam height and A is the cross-
sectional area of the column (Bikerman, 1973). Fig. 2 shows the
relationship between the dynamic froth stability factor and the
addition of reagents for UG2 and Merensky ores.
Generally, Merensky ore resulted in a more stable froth than
UG2 ore for all of the conditions investigated except for when no
reagents were added. The largest difference in froth stability of
the two ores was obtained when both copper sulphate and xan-
thate were present. The addition of copper sulphate had no effect
on the dynamic froth stability factor for Merensky ore. The addi-
tion of xanthate as well as both copper sulphate and xanthate
resulted in a slight destabilisation for Merensky ore. The UG2 ore
showed a more substantial decrease in froth stability with the
addition of reagents.
3.2. Microflotation tests
The microflotation data was fitted to the Klimpel flotation
model in order to assess the flotation kinetics by predicting the
flotation rate constant, k, as well as the maximum recovery, Rmax
(Klimpel, 1980). Fig. 3 shows the effect of reagent addition on talc
floatability in synthetic plant water at pH 9.
It is evident from Fig. 3 that the addition of reagents to talc in
synthetic plant water did not significantly affect floatability. The
highest talc recoveries were obtained when only copper sulphate
was added and when both copper sulphate and xanthate were
added. This is also evident in Table 4 as the highest Rmax values
are obtained at these conditions.
30
25 23.1
24.6
23.0
22.5
20.7
20 19.0
(s)
70
60
50
40
30
20
10
0
0 5 10 15 20 25
Time (min)
Fig. 3. Talc microflotation with synthetic plant water at pH 9. The error bars are
shown but they are obscured by the markers.
1
The effect of addition of reagents on the floatability of pyrrho-
tite in synthetic plant water at pH 9 is shown in Fig. 4.
The addition of copper sulphate alone slightly increased the
overall recovery of pyrrhotite. The addition of xanthate increased
the flotation kinetics and the overall pyrrhotite recovery slightly
as shown in Table 4. Both copper sulphate and xanthate in the sys-
tem resulted in the largest increase in pyrrhotite floatability as
shown in Fig. 4.
3.3. Zeta potential determinations
Zeta potential measurements were used to show the presence
of copper species on the surfaces of pure minerals since the pres-
ence of copper alters the surface charge of the mineral. The isoelec-
tric point pH (pHi.e.p) which is the pH where a mineral particle has
a neutral net charge was also used as an indication of the extent of
surface oxidation since a pHi.e.p close to that of the corresponding
metal hydroxide/oxide indicates that the surface is heavily oxi-
dised (Fullston et al., 1999). Fig. 5 shows the variation of zeta
potential with pH in the absence and presence of copper sulphate
(with xanthate absent).
It is evident that the presence of copper caused the zeta poten-
tial of the minerals to shift to more positive potentials at pH 9,
which is the pH of interest. Before copper sulphate activation,
the zeta potentials of the minerals were between 48 mV and
63 mV and these shifted to between 19 mV and 30 mV as rep-
resented by the broken lines in Fig. 5 below. The addition of copper
sulphate also shifted the isoelectric point pH (pHi.e.p) to higher pH
values for chromite and plagioclase. This is shown in Table 5.
The effect of copper sulphate on the four minerals investigated
in the presence of xanthate is shown in Fig. 6.
The zeta potentials of the minerals with copper activation in the
presence of xanthate lie in the range between 48 mV and
72 mV. This is significantly lower than the range of zeta potential
21.9
obtained when copper sulphate was added in the absence of xan-
thate which was between 19 mV and 30 mV. Since xanthate

15 14.0 MER
UG2 Table 4
Theoretical maximum recovery and flotation rate constant for talc and pyrrhotite in
10
synthetic plant water.

5 Condition Talc Pyrrhotite

Rmax (%) k (min1) Rmax (%) k (min1)
0 No reagents 97 0.369 28 0.218
No Cu Cu No Cu, Xanthate Cu, Xanthate
Copper 100 0.196 37 0.133
Xanthate 91 0.500 34 0.340
Fig. 2. Froth stability of Merensky versus UG2 ore in synthetic plant water at pH 9.
Copper + Xanthate 100 0.224 61 0.200
The copper sulphate dosage was 90 g/tonne and SIBX dosage was 80 g/tonne.
32 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836

Pyrrhotite, No Reagents Pyrrhotite, Cu was added after copper activation, the more negative zeta potential
Pyrrhotite, X- Pyrrhotite, Cu + X-
No Reagents Model Cu Model values obtained indicate adsorption of xanthate onto activated
X- Model Cu + X- Model
50
mineral surfaces.
45
40 3.4. Activation products analysis
35
Recovery (%)

30 The microflotation test work showed that the nature of the acti-
25 vation species influences the floatability of the minerals. The zeta
20 potential tests gave an indication of the extent to which the surface
15 charge was altered as a result of copper activation and xanthate
10 adsorption. In order to determine the nature of the activating spe-
5 cies on the mineral surfaces, analyses were done using EDTA, a
0 complexing agent.
0 5 10 15 20 25
Time (min) For the froth stability tests, the dosage of 90 g/tonne of copper
sulphate used is equivalent to 46 g/tonne of Cu and approximately
Fig. 4. Pyrrhotite microflotation with synthetic plant water results at pH 9. 10 mg/L (if all the copper was in solution). The following mass bal-
ance was used for the total copper in the system.

Talc, No Cu Talc, Cu Cutotal CuOH2;surface Cusolution Cusurface 2

Chromite, No Cu Chromite, Cu
Plagioclase, No Cu Plagioclase, Cu Cu(OH)2,surface is a non-selective copper hydroxide precipitate
Pyrrhotite, No Cu Pyrrhotite, Cu
30 that can be extracted from the surface using EDTA. Cusurface is Cu
20 (I) or Cu(II) that has chemically reacted with the mineral surface
10
and cannot be extracted with EDTA. Cusolution is the residual copper
Zeta Potential (mV)

0
-10 left in the solution.
-20 Fig. 7 shows the results for analysis of copper in the conditioned
-30 Merensky and UG2 pulp prior to the froth stability tests.
-40 The highest amount of Cu(OH)2, was observed when only cop-
-50
per sulphate was added in the absence of xanthate for both ores.
-60
-70 The surface copper was possibly in the form of copper(I) sulphide.
-80 When xanthate was present, the amount of copper extractable by
0 1 2 3 4 5 6 7 8 9 10 11
EDTA was lower than when no xanthate was added. For all of the
pH
No Xanthate
conditions investigated in Fig. 7, the amount of residual copper left
in solution was minimal.
Fig. 5. Effect of 5  103 M CuSO4 on minerals in the absence of xanthate in a
102M Na2B4O7 background electrolyte solution.
3.5. Full scale flotation surveys

Table 5 Fig. 8 shows the normalised platinum grade versus recovery

Shift of pHi.e.p values of pure minerals with the addition of copper sulphate in the curves for surveys of the rougher bank of a UG2 concentrator with
absence of xanthate. copper sulphate being dosed at dosage of 45 g/t (copper on) and
Mineral pHi.e.p before copper addition pHi.e.p after copper addition with no copper sulphate being dosed (copper off). This shows that
there was an improvement in grade on most of the cells in the
Talc 4.4 4.4
Chromite 5.5 7.3 rougher bank when copper was present. There was a slight
Plagioclase 6.2 7.2 decrease in the recovery of platinum under the same conditions.
Pyrrhotite 5.9 6.3 The grade and recovery were normalised by dividing by a common
value in order to protect the confidentiality of the data.
Fig. 9 shows Cr2O3 recovery as a function of water recovery for
three surveys in which copper sulphate was not dosed to the rougher
bank and for one survey in which copper sulphate was dosed at
Talc, Xanthate Chromite, Xanthate
Plagioclase, Xanthate Pyrrhotite, Xanthate Solution Cu Surface Cu EDTA Cu
Talc, No Xanthate Chromite, No Xanthate
100
Plagioclase, No Xanthate Pyrrhotite, No Xanthate
30
90
20
80
10
Zeta Potential (mV)

44 50
0 70 56 57
Cu % (mg)

-10 60
-20 50
-30
40
-40
-50 30
53 49
-60 20 43 42
-70 10
-80
0 2 4 6 8 10 12 0
pH MER MER UG2 UG2
Copper Cu Cu, Xanthate Cu Cu, Xanthate

Fig. 6. Effect of xanthate on copper activated minerals in a 102 M Na2B4O7 Fig. 7. Merensky and UG2 ore in synthetic plant water copper analysis by EDTA
background electrolyte solution. All reagent concentrations were 5  103 M. extraction.
 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836 33

1.0 below pH 56 as shown in Fig. 5, when compared to the conditions

with no reagent addition. This is in agreement with the findings by
Normalised cumulative grade

0.9 Fornasiero and Ralston (2005) and James and Healy (1972) who
found no adsorption of copper species on metal oxide surfaces at
0.8 acidic pHs. Thus, it appears that, below pH 56, no copper species
were adsorbing onto the talc, chromite or plagioclase. In the case of
0.7 pyrrhotite, Chang et al. (1954) found that at pH 5.1, there was a
direct ion exchange of Cu2+ for Fe2+ in the crystal lattice of pyrrho-
0.6 Copper ON tite. Thus, if Cu2+ exchanged for Fe2+ there would be no net change
Copper OFF in surface charge, which is what was observed for pyrrhotite.
0.5 From the speciation diagram of Cu(II) (Fuerstenau, 1982), the
predominant copper species above pH 6 is Cu(OH)2 and as seen
0.4
in Fig. 5, the zeta potential became less negative above pH 6 which
0.4 0.5 0.6 0.7 0.8 0.9 1.0
indicates precipitation or adsorption of the neutral Cu(OH)2 mole-
Normalised cumulative recovery
cule which shields the minerals negative charge. The addition of
Fig. 8. Normalised cumulative platinum grade versus recovery curves for surveys copper sulphate shifts the zeta potentials from between 48 mV
with copper on and copper off in the rougher bank of a UG2 concentrator. and 63 mV to between 19 mV and 30 mV at pH 9. The pHi.e.p
of all of the minerals shifts to higher values that are closer to the
2.5 pHi.e.p of Cu(OH)2 of 9.4 (Parks, 1965). This reinforces the assump-
Copper OFF tion that copper adsorbs on all the minerals in the form of Cu(OH)2
Cumulative Cr2O3 recovery (%)

Copper ON
2
Linear (Copper OFF)
Linear (Copper ON)
1.5
1 (2006) proposed the nature of the adsorption of copper species was
0.5
0 values was CuOH+ which was formed in solution. Positively
0 5 10 15
Cumulative water recovery (%)
Fig. 9. Cr2O3 versus water recoveries for multiple surveys with no copper present
(copper off) and a single survey with copper present at 45 g/t (copper on).
45 g/t. Chromite recovery has been successfully used as a tracer for
entrainment, since it is not naturally floatable, and the slope of the
chromite versus water curves is an indication of the entrainability
of those particular froth conditions (Ekmeki et al., 2003; Hay and
Roy, 2010; Alvarez-Silva et al., 2012). It is clear to see that, in this
study, the addition of copper sulphate has modified the froth condi-
tions such that the entrainability of chromite was significantly
altered compared to the condition when no copper sulphate was
present. The slope of the copper-off line is 7.59  102
0.11  102, while the slope of the copper-on line is
9.38  102 0.20  102. This may explain the differences in grade
and recovery data seen in Fig. 8 and will be discussed further below.
4. Discussion
In this section of the paper, the zeta potential results are anal-
ysed first to show the effect of reagents on the surface charge of
the pure minerals investigated. This is followed by a discussion
of the microflotation results to investigate copper sulphate activa-
tion in the absence of the froth phase. The EDTA extraction results
are then discussed which investigate the form of activation prod-
ucts on the mineral surfaces. Lastly, all of the pulp phase activation
results are linked to the froth stability tests and the full-scale plant
surveys.
4.1. Effect of copper sulphate and xanthate on zeta potentials of pure
minerals
For all of the minerals investigated, there was no substantial
change in the zeta potential with addition of copper sulphate
above pH 6. The shift in the zeta potential of pure minerals above
pH 6 shown in Fig. 5 suggests inadvertent activation of the miner-
als as the activation by copper is non-selective. This is similar to
the findings by Martinovic et al. (2005) in their studies on surface
properties of gangue minerals in PGM bearing ores. Ekmeki et al.
likely to be electrostatic.
Wesseldijk et al. (1999) showed that chromite can be activated
by the typical platinum concentrator reagent suite and that the
copper species adsorbed on the chromite surface at alkaline pH
20 25 30
charged complexes such as Cu(OH)+ could contribute to the less
negative zeta potential observed when the pH is increased. This
means that the minerals are most likely to be covered in copper
hydroxides in alkaline conditions. The presence and amounts of
copper hydroxides on the mineral surfaces were further investi-
gated using the EDTA extraction method in this study.
It can be seen from Fig. 6 that the addition of xanthate to
copper-activated minerals caused a decrease in the zeta potential
of all of the four minerals. Adsorption of the negatively charged
xanthate neutralises the more positive copper species and brings
the zeta potential back to similar values as those in the absence
of reagents. Fornasiero and Ralston (2005) saw similar results for
quartz activated with copper and nickel and using xanthate as a
collector.
4.2. Talc and pyrrhotite floatability
Adsorption of copper species at pH 9 was confirmed by the zeta
potential measurements. In the presence of collector, a more
hydrophobic copper xanthate species is expected to form on the
mineral surface increasing the contact angle and hence the recov-
ery of the particles through increased particle hydrophobicity.
Talc is a naturally hydrophobic mineral and the reagents (cop-
per and xanthate) were added to investigate their effect on the
minerals floatability. The microflotation results showed that the
floatability of talc did not substantially change with the addition
of reagents (Fig. 3). This is despite the fact that the zeta potential
tests showed that copper (and copper and xanthate) adsorb onto
the talc surface in alkaline conditions. However, the talc has a high
natural floatability and the addition of reagents may not be
expected to increase that floatability further.
It may have been expected for the floatability of the talc to
decrease in the presence of copper due to non-selective precipita-
tion of copper hydroxide at pH 9. The fact that this did not occur
may mean that the copper did not react with the talc hydrophobic
34 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836
basal planes but with the already hydrophilic edges (Burdukova
et al., 2008). Since talc floated at all of the conditions investigated,
a significant amount of talc is thus expected to report to the froth
phase during froth stability tests, since no depressant was used in
this study to reduce talc floatability.
The addition of copper sulphate alone did not enhance pyrrho-
tite recovery as seen in Fig. 4. Addition of xanthate (without copper
sulphate) resulted in a slight increase in the recovery of pyrrhotite.
Flotation experiments done in deionised water (not shown here)
showed no increase in floatability when xanthate was added in
the absence of copper sulphate. Therefore, it is proposed that the
charged ions in synthetic plant water may have adsorbed onto
the pyrrhotite surface, activating the surface and providing anchor
points for xanthate adsorption in much the same way that copper
activation does. The enhancement in the floatability of pyrrhotite
when both copper and xanthate were present could be due to
the formation of hydrophobic copperxanthate species. Some
researchers however claim copper activation is not possible at high
pHs since copper ions are essentially insoluble in alkaline solution
and thus not available for reaction (Buswell and Nicol, 2002). Con-
trary to these observations, the highest recovery of pyrrhotite was
observed with the addition of copper(II) prior to xanthate addition
at pH 9 which confirms activation of the pyrrhotite in alkaline con-
ditions possibly due to the conversion of hydrophilic Cu(OH)2 to
copperxanthate species.
4.3. Activation products analysis
For both Merensky and UG2 ores, the amount of EDTA extracta-
ble copper decreased when xanthate was present as shown in
Fig. 7. This is probably due to adsorption of copper onto the min-
eral surfaces and attachment of xanthate onto these sites resulting
in stable copper xanthate complexes on the mineral surface, which
were not extractable by EDTA. The copper hydroxide species are
known to act as sites for collector adsorption (Fornasiero and
Ralston, 2005). This would result in better floatability in the pres-
ence of xanthate since more collector molecules preferentially
adsorb onto the copper sites on the mineral surface increasing
the hydrophobicity as observed in Fig. 4 for pyrrhotite flotation.
The Merensky ore had a relatively large percentage of copper
hydroxide on the mineral surface (in the absence of xanthate) com-
pared to the chemically reacted copper as shown in Fig. 7. The sul-
phide minerals in the Merensky ore were expected to chemically
react with the copper to form stable complexes. Previous evidence
for the presence of copper hydroxide on sulphide mineral surfaces
comes from Gerson et al. (1999) who conducted secondary ion
mass spectrometry (SIMS) to determine the lateral distribution of
copper on individual sphalerite particle surfaces and their work
confirmed the formation of colloidal Cu(OH)2 (s) on the sphalerite
surface at pH 8.5. A similar reaction of the sulphide minerals in the
Merensky ore with copper sulphate at pH 9 may have occurred
instead of the bulk of the copper being electrochemically reduced
on the mineral surface as expected.
Fig. 7 showed that about half the surface copper on the UG2 ore
was chemically reacted copper. The formation of chemically
reacted copper on the UG2 ore surface was unexpected as the
amount of base metal sulphides in the ore are much lower than
in Merensky ore and it may have been expected that copper simply
precipitated on the UG2 ore surface as Cu(OH)2. However, in the
absence of sulphide minerals, the copper species must have
reacted with oxide minerals in the UG2 ore in order to remain
bound to the surface. There is evidence in literature of metal ions
chemically reacting with non-sulphide minerals (Mackenzie and
OBrien, 1969; Nagaraj and Brinen, 1996; Shackleton et al., 2003;
Al-Abadleh and Grassian, 2003). The formation of Cu(I)xanthate
complexes on the activated silicate mineral surfaces is illustrated
in Fig. 10.
The chemically reacted copper on the UG2 ore surface is
expected to promote the adsorption of xanthate which may
increase the particle hydrophobicity. This may then reduce the
froth stability due to an increase in contact angle beyond the opti-
mum angle to confer stability.
Fig. 7 also shows that the percentage of copper in the bulk solu-
tion was very low since most of the copper added to the system
was either chemically reacted on the ore surfaces or extracted in
the form of copper hydroxides. Therefore, there was no copper left
in solution to act as a froth modifier in its own right. Any effects on
the froth were through the coppers modifying effects on the par-
ticle surfaces.
4.4. Froth stability tests
Two parameters with respect to particle properties namely par-
ticle hydrophobicity and the amount of particles reporting to the
froth phase were found to be applicable to explain the changes
in froth stability. The same trend of decreasing froth stability with
addition of copper, xanthate and both copper and xanthate was
observed for the two ores investigated. It is assumed this is due
to the increase in hydrophobicity of the complexes formed as a
result of pulp phase interactions. Based on the microflotation
results discussed earlier, the increase in hydrophobicity of the
complexes formed is proposed below:
Mineral < MineralCu < MineralXanthate
< MineralCuXanthate
It is assumed that the decrease in the froth stability as a result
of the addition of reagents is due to an increase in contact angle
and increasing hydrophobicity which promotes coalescence of
bubbles. The destabilisation effects of the froth observed could
be due to increase in the contact angle beyond an optimum maxi-
mum (Johansson and Pugh, 1992), in this case the optimum point
being the condition when no reagents are added. In a review by
Hunter et al. (2008) it was agreed by a number of authors that
the range of contact angles in which particles stabilise froths is
small and there is a sudden drop, where particles begin to work
as destabilisers.
4.4.1. Copper sulphate
The addition of copper sulphate had little effect on the froth sta-
bility of the Merensky ore, but had a destabilising effect on the UG2
ore. For the Merensky ore, it was expected that the formation of
hydrophobic Cu(I) sulphide species on the mineral surfaces would
increase the contact angle and result in an increase in bubble coa-
lescence. There was a slight increase in floatability of pyrrhotite
upon addition of copper sulphate in the microflotation tests, which
suggests that the hydrophobicity increased slightly. However, in
the context of the full mineralogical composition of the Merensky
ore, this seems to have been insufficient to cause any changes in
O O Cu(I) X
Si
O OH
Fig. 10. Schematic representation of xanthate adsorption onto a copper activated
silicate mineral. Adapted from Malysiak (2003).
 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836 35

froth stability. The zeta potential tests showed adsorption of cop- also expected to react with xanthate resulting in the formation of
per onto all the mineral surfaces and there was Cu(OH)2 and chem- the hydrophobic copper(I)xanthate species resulting in the desta-
ically reacted copper present on the mineral surfaces as evidenced bilisation of froth observed.
by the EDTA tests. However, the net effect caused no change in the
froth stability.
4.4.4. Full scale flotation surveys
The UG2 ore, on the other hand, was destabilised upon the addi-
The flotation survey results shown in Fig. 9 shows that the froth
tion of copper (Fig. 2). The zeta potential results showed the addi-
structure is altered by the addition of copper sulphate and that the
tion of copper sulphate resulted in non-selective adsorption of
entrainability decreased when copper sulphate was added to the
copper onto the mineral surfaces. The EDTA results showed
system. This means that there was less hydrophilic gangue col-
adsorption of copper chemically onto the UG2 mineral surfaces
lected per unit water in the presence of copper sulphate than in
and this was unexpected for a UG2 ore with a very low sulphide
the absence of copper sulphate. Section 2.3 showed that the addi-
mineral content. Oxide minerals have been shown to form chemi-
tion of copper sulphate and xanthate resulted in negatively
cally reacted species with copper from previous studies. However,
charged particle surfaces. Charged particles in the thin films and
the higher froth stabilities observed for Merensky ore for most of
plateau borders of the froth will be subject to electrostatic repul-
the conditions investigated could be due more floatable sulphides
sion, resulting in the expulsion of some of these charged particles
in the ore which stabilise the froth more than activated oxide min-
from the froth relative to less charged particles, which would be
erals found in UG2 ore.
more aggregating. Aggregating particles are known to stabilise
the froth by showing an increase in packing efficiency (Hunter
4.4.2. Xanthate
et al., 2008). This explanation refers only to hydrophilic particles.
The addition of xanthate resulted in more destabilised froth
The effect of hydrophobic particles was discussed in Section 2.5.
than the condition with only copper addition for both the Meren-
In the present case, copper sulphate addition resulted in an
sky and UG2 ores, although destabilisation was minimal for the
increase in grade (due to less entrained material) and a small
Merensky ore. The decrease in froth stability was attributed to
decrease in recovery (due to a less stable froth). The possibility that
the increase in hydrophobicity of the complex formed on the min-
these grade and recovery differences were produced by pulp phase
eral surfaces. The zeta potentials of the pure minerals (talc and pla-
effects have been discounted for the following reasons: (1) An
gioclase) were slightly altered with the addition of xanthate
increase in grade and recovery would have been expected if copper
possibly indicating some adsorption. The floatability of talc was
sulphate activated the valuable minerals; (2) Even if copper sul-
not changed with the addition of xanthate as shown by the
phate also activated gangue minerals, an increase in valuable min-
microflotation tests although the zeta potential tests suggested
eral recovery would still have been expected along with a decrease
adsorption of xanthate onto the talc surfaces. The ions in the syn-
in grade; (3) It was shown that the addition of copper sulphate had
thetic plant water could have increased sites for collector adsorp-
an effect on froth structure through the entrainability function and
tion on the pyrrhotite surfaces. An increase in hydrophobicity
also by the decrease in froth stability shown in the laboratory tests.
increases the contact angle which in turn results in an increase
In general, the effect of copper sulphate addition on metallurgi-
in bubble coalescence which was observed with the addition of
cal recovery and grade may be complex. There may be opposing
xanthate as a collector to the two ores.
effects of copper sulphate addition. An increase in pulp phase valu-
able mineral recovery with copper sulphate addition, may be offset
4.4.3. Copper sulphate and xanthate
by a decrease in froth stability resulting in drop-back of valuable
The most destabilised froth was observed for the condition with
minerals. The overall recovery would be the net effect of these
both copper sulphate and xanthate present for both ores. The froth
two sub-processes. In the case of grade, inadvertent copper activa-
stability of the Merensky ore was slightly decreased whereas the
tion may result in the flotation of gangue minerals that dilute the
UG2 ore was substantially decreased. The zeta potential tests
grade. On the other hand, a less stable froth may result in a reduc-
showed the addition of xanthate after copper activation of the min-
tion in entrainment and drop-back of minerals to the pulp. In the
erals made the zeta potential more negative, which is indicative of
case under investigation, the grade was increased upon the addi-
xanthate adsorption after copper activation. The floatability of talc
tion of copper sulphate suggesting that inadvertent gangue activa-
was not changed significantly with the addition of both copper sul-
tion was not a major problem and that changes in grade were due
phate and xanthate. However, talc is very naturally hydrophobic
to the less stable froth. There was a relatively minor loss in plat-
and it is possible that reagent addition has no further effect on
inum recovery, upon addition of copper sulphate, which confirmed
hydrophobicity. Pyrrhotite floatability was highest in the presence
that froth instability was the overriding process, rather than acti-
of these two reagents. It is presumed that the addition of xanthate
vation and increased recovery of valuable minerals.
to copper activated sulphides in the Merensky ore increased the
hydrophobicity and contact angle of particles. The higher contact
angles promote bubble coalescence, resulting in the observed 5. Conclusions
decrease in froth stability.
The analysis of the mineral surface products using the EDTA From the preceding findings it is evident that froth stability is
extraction method revealed there was less Cu(OH)2 on the mineral dependent on the particle properties such as particle concentration
surfaces in the presence of both copper sulphate and xanthate than and particle hydrophobicity. These factors were found to be
when only copper was present. This was evidence of xanthate directly linked to activation by copper sulphate. The results
forming stable complexes with the copper since minimal copper showed the Merensky ore froth was not destabilised to a large
was left in the bulk solution. Besides the formation of copper xan- extent with the addition of copper sulphate although chemically
thate species via Cu(OH)2 reduction, significant amounts of chem- reacted copper species were found on the surface of Merensky
ically reacted copper were found on both ores. This was ore. The base metal sulphides were rendered more hydrophobic
unexpected for the UG2 ore since the sulphide content of the ore as shown by the microflotation tests for pyrrhotite. The increased
is very low. Earlier findings in literature have shown that oxide hydrophobicity was either at or below the optimum range for good
and silicate minerals can react chemically with copper which froth stability (
65), or the heavily mineralised Merensky ore
explains the presence of chemically reacted copper on UG2 sur- froth was not that susceptible to the destabilising effects of
faces. This chemically reacted copper on the UG2 ore surfaces is increased contact angle.
36 W. Nyabeze, B. McFadzean / Minerals Engineering 92 (2016) 2836
For the UG2 ore, froth stability decreased with addition of cop-
per sulphate which was not entirely due to non-selective hydro-
philic copper hydroxide coating as initially proposed. The
formation of chemically reacted copper was unexpected and it is
the first time that this has been shown for UG2 ore. It was postu-
lated that the copper also chemically reacted with the oxide min-
erals in the UG2 ore. The decrease in froth stability in the presence
of xanthate was attributed to the formation of hydrophobic cop-
perxanthate species, which have a destabilising effect in the spar-
sely mineralised UG2 froth.
The results of the surveys on a UG2 concentrator conducted
with the addition and without the addition of copper sulphate aug-
mented the results of the laboratory tests. Entrainability was
reduced upon addition of copper sulphate and this resulted in an
improvement in grade and a slight decrease in recovery presum-
ably due to a less stable froth. The extent of these changes in grade
and recovery will vary according to which of the pulp or the froth
sub-processes are dominant. Pulp phase sub-processes include
valuable mineral and/or gangue mineral activation resulting in
increased recovery of either mineral to the concentrate. Froth
phase effects include changes in amount or hydrophobicity of
solids reporting to the froth that will alter the froth stability.
Acknowledgements
The authors would like to thank the members of the Centre for
Minerals Research Reagent Research Group (Anglo American Plat-
inum, Impala, Lonmin and Nkomati) and the National Research
Foundation (NRF) for their financial support during this study
and for permission to publish this paper. They would also like to
acknowledge the work done by the 2012 graduates of the Anglo
Graduate Development Programme in acquiring the plant data.
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