Minerals Engineering 39 (2012) 89–98

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

Quantifying rheological and fine particle attachment contributions to coarse

particle recovery in flotation
D. Xu a, I. Ametov a, S.R. Grano b,⇑
a
Ian Wark Research Institute, The ARC Special Research Centre for Particle and Material Interfaces, University of South Australia, Mawson Lakes, SA 5095, Australia
b
Institute for Mineral and Energy Resources, The University of Adelaide, SA 5005, Australia

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

Article history: This study focused on the flotation behaviour of very coarse quartz particles in the presence of fine silica
Received 20 September 2011 and alumina, both of which were used as pulp viscosity modifiers. A decrease in the contact angle of the
Accepted 11 July 2012 coarse quartz particles, caused by the attachment of fine particles was believed to be the principal mech-
anism accounting for the noted depression. Only small surface coverage of attached fine particles may
dramatically decrease the quartz particle recovery because the flotation behaviour of the coarse particles
Keywords: was very sensitive to particle hydrophobicity, e.g. less than 5% surface coverage is able to decrease the
Desliming
contact of particles from 83° to 81° and causes a decrease in recovery from 60% to 20%. The effect of
Fine particle
Coarse particle
removing the fine particles from the pulp, by the process known as desliming, on the flotation behaviour
Rheology of coarse quartz particles was also investigated. The results showed that desliming is beneficial for the
recovery of coarse quartz particles. Furthermore, the recovery of coarse quartz particles attached with
fine particles can be restored by conducting flotation in high viscosity medium where glycerol was used
as the viscosity modifier.
Ó 2012 Published by Elsevier Ltd.

1. Introduction pulp viscosity in a viscous slurry resulted in a decrease in the bub-

Detachment of particles from bubbles is one of the key issues
responsible for the low recovery of coarse particles. For coarse par-
ticles attached to bubbles, the particle–bubble aggregates must
withstand the various forces which are operational in the flotation
cell to be successfully transported to the pulp/froth interface. A
property-based flotation model, developed at the Ian Wark Re-
search Institute (The Wark flotation model) (Duan et al., 2003;
Pyke et al., 2003) suggests that a key parameter which directly con-
trols the stability of a particle–bubble aggregate and which quan-
tifies the mean shear forces acting on the bubble–particle
aggregate is the mean turbulent energy dissipation. A decrease in
the mean turbulent energy dissipation throughout a flotation cell
may benefit the recovery of coarse particles due to the reduction
of shear forces acting on the particles attached to the bubbles,
increasing the stability of the bubble–particles aggregates. Other
studies have shown that increasing the viscosity of the pulp results
in a decrease in turbulent energy dissipation in a flotation cell
(Kitano et al., 1981; O’Connor et al., 1990).
It has also been suggested that slurry rheology is an important
factor for flotation due to its marked effect on cell hydrodynamics,
including gas dispersion throughout the cell (O’Connor et al., 1990;
Deglon et al., 2007). O’Connor et al. (1990) found that a decrease in
⇑ Corresponding author. Tel.: +61 0 8 83130626; fax: +61 8 8303 8030.
E-mail address: stephen.grano@adelaide.edu.au (S.R. Grano).
ble size due to increased turbulence in the cell. However, Deglon
et al. (2007) found the opposite trend for the change in bubble size,
in a study of Bindura nickel ore slurries. According to Deglon et al.
(2007), the bubble size decreases with an increase in the solids
concentration. Deglon et al. (2007) proposed that the decrease in
bubble size was due to the high yield stress in the slurry, which
caused a more concentrated energy dissipation near the impeller
and leads to the production of small bubbles. A decrease in the
gas hold up was also attributed to the high yield stress of the
slurry, which prevents the dispersion of bubbles through the cell
(Deglon et al., 2007).
An increase in slurry viscosity may be achieved by increasing
the percent solids, particularly using fine particles as the viscosity
modifier. An example of the effect of particle concentration on the
rheology of titanium dioxide suspensions was reported by Yang
et al. (2001). At relatively low volume fraction of the titanium diox-
ide (U = 0.109), the suspension shows Newtonian behaviour, i.e.
the viscosity is independent of the shear rate. An increase in the
solids volume fraction to U = 0.174 results in shear-thinning
behaviour, with the viscosity decreasing with an increase in shear
rate. With a further increase in the solids volume fraction the rhe-
ological behaviour of the suspension remained shear-thinning, but
the apparent viscosity values increase considerably by almost
three orders of magnitude at U = 0.431 (Yang et al., 2001). Similar
trends in rheological behaviour was observed for slurries of
dolomite (Deglon et al., 2007), galena (Gao and Forssberg, 1993;

0892-6875/$ - see front matter Ó 2012 Published by Elsevier Ltd.

http://dx.doi.org/10.1016/j.mineng.2012.07.003
90 D. Xu et al. / Minerals Engineering 39 (2012) 89–98

Wang and Forssberg, 1995), quartz (Prestidge, 1997a,b) and coal
(Tangsathitkulchai, 2003), though changes in flow behaviour occur
at different volume concentrations of the particles.
One of the drawbacks of using fine particles to modify the vis-
cosity is the possible interaction between coarse and fine particles,
which may cause a decrease in the flotation recovery of the coarse
particles by reducing the hydrophobicity of the coarse particles.
Thus, fine particles may modify the flotation behaviour of coarse
particles through both viscosity modification and fine particle
attachment to coarse particles. This paper investigates the effect
of fine particles on the flotation of coarse particles through rheo-
logical modification and/or fine particle attachment mechanisms.
(Malvern Instruments Ltd., Worcestershire, UK) in electrophoretic
light scattering mode for dilute particle suspensions.
Dilute silica and alumina suspensions were prepared at 0.5 wt.%
solids, in 103 M KCl and dispersed with a magnetic stirrer for
30 min. The suspension was allowed to stand for 5 min, and the
colloidal particles (<5 lm in size) in the supernatant were si-
phoned off for the zeta potential measurement. The suspension
pH was altered to a desired value with HCl and KOH solutions,
and allowed to equilibrate for 10 min before the samples were di-
rectly injected into a disposable capillary cell for zeta potential
measurements. The measurements were performed over the pH
range 5–9.5 for alumina. The zeta potential of the silica was inves-
tigated over pH range 3–9.

2. Experimental
2.2.2. Particle size distribution of alumina and silica
The particle size distribution of alumina and silica was deter-
2.1. Material
mined by laser diffraction using a Mastersizer 2000 (Malvern
Instruments Ltd., UK). The basic particle size sensor comprises an
Samples of quartz (GEO Discoveries, Australia) were ground and
optical measurement unit which supplies information to a com-
screened to two coarse size fractions of interest, namely 150–
puter to process data and perform the analysis.
300 lm and 600–850 lm. Each size fraction of ground quartz were
Ultrasonication for 5 min and a polyphosphate dispersant (i.e.,
cleaned using the procedure outlined by Pashley and Kitchener
Calgon) were used to achieve full dispersion of both alumina and
(1979). Namely, the particles were washed in concentrated hydro-
silica particles.
chloric acid three times (2 h each time) and then rinsed with copi-
ous amounts of Milli-Q water several times until the pH value of
2.2.3. Slime coating of fine particle on quartz surface
the Milli-Q water (5.6) was restored. The particles were then im-
Scanning electron microscopy (a PHILIPS XL-20 electron micro-
mersed in a 30% NaOH solution at 60 °C for 1 min, followed by
scope) was used to determine the adsorption of fine silica and alu-
the same rinsing procedure. The particles were then dried in a
mina particles on the surface of coarse quartz particles. The
clean oven at 110 °C overnight and stored in capped bottles in a
samples were mounted onto the sample holder using double-sided
desiccator under vacuum.
sticky tape and were coated with a thin carbon layer using a vac-
Trimethylchlorosilane (TMCS) solutions in cyclohexane were
uum evaporator.
used for particle methylation (Pashley and Kitchener, 1979). Since
TMCS readily reacts with water, the methylation reaction was per-
2.2.4. Slurry rheology
formed in a glove box under nitrogen atmosphere. Different con-
The rheological behaviour of the silica and alumina suspensions
centrations of TMCS were prepared by diluting the required
was investigated using a Haake RotoVisco RV1 rheometer (Thermo
volumes of TMCS in cyclohexane. The cleaned quartz were weighed
Electron GmbH, Germany) fitted with the concentric cylinder (Cou-
into a beaker and heated in an oven at 110 °C overnight to remove
ette) sensor.
the physisorbed moisture. Particles with various contact angles
Each slurry sample (100 cm3) was prepared by adding known
were obtained using solutions of different TMCS concentrations
weights of fine silica or alumina particles to known volumes of the
and reaction time. All glassware was cleaned and dried before use.
103 M KCl solution at pH 9. Prior to the rheology measurement,
Fine alumina (Hydral 710, Alcoa of Australia Limited) and silica
the suspensions were stirred for 1 h using an overhead stirrer. In
(Sigma–Aldrich Inc., USA) were used to adjust the pulp viscosity.
the measurement, the shear rate increased from 0 s1 to 1000 s1
The choice of these particles is based on the fact that at pH < 9, alu-
(an upward curve) and then decreased down to 0 s1 (a downward
mina is positively charged (Johnson et al., 2000), and may interact
curve) in 200 s. The rheological parameters were automatically re-
with coarse quartz particles. In contrast, silica has a negative zeta
corded by a computer. The percentage of fine alumina and silica is
potential in the 3–9 pH range (Ametov and Prestidge, 2004), and
shown as volume% in all cases using 2.65 g/cm3 and 3.95 g/cm3
is not expected to interact with quartz. The condition of pH 9,
density for silica and alumina respectively to convert the mass of
i.e., the pHIEP of alumina was used because particle interaction,
fine particles to corresponding volume.
and consequently viscosity, is most significant at this pH value.
The aggregates may facilitate the attachment. Thus, rheological
2.3. Methodology
and fine particle attachment contributions to flotation response
may be discerned. To contrast the effect of particle interaction in
2.3.1. Flotation
the case of the alumina particles, silica was also examined as a
Flotation tests on coarse quartz particles were carried out
model system that would exhibit lower particle interaction under
according to the flowsheet shown in Fig. 1. Quartz particles
these conditions. Therefore, using alumina and silica, the effect of
(60 g) of various mean contact angle values and particle sizes were
colloidal particles on the viscosity of the suspending medium and
floated in a 1.5 dm3 bottom driven flotation cell. All flotation tests
the flotation behaviour of the coarse quartz may be considered,
were carried out at an impeller speed of 600 rpm. Air was intro-
as a first approximation, as an investigation for the cases of inter-
duced into the flotation cell at a flow rate of 3.5 dm3/min
acting and non-interacting fine particles. Characterisation of fine
(Jg = 0.4 cm/s). Dowfroth 250 (170 g/t, 8 ppm in solution) was used
alumina and silica is presented in the next section.
as frother. Froth depth was 3 ± 1 cm. Quartz particles were hydro-
phobised to the target value of contact angle before the flotation
2.2. Characterisation of fine particles test. Four concentrates were collected, cumulatively at 0.5 min,
2 min, 4 min and 8 min. Make-up water was used to the cell to
2.2.1. Zeta potential of alumina and silica particles keep the interface at the same level during the flotation tests.
Zeta potential of silica and alumina was determined from the The viscosity of the suspending medium was increased by: (i)
particle dynamic mobility using the Nano-ZS Zetasizer instrument using glycerol (95% purity)/water mixtures instead of water and
 D. Xu et al. / Minerals Engineering 39 (2012) 89–98
Fine Size
Gangue Glycerol
Particles
Flotation Concentrates Tailing
Frother
0-0.5 min 2-4 min
0.5-2 min 4-8 min
Fig. 1. The schematic diagram of conventional flotation tests conducted on coarse
quartz particles.
(ii) by the addition of the colloidal alumina or silica particles at dif-
ferent volume concentrations. Flotation tests in water and the glyc-
erol/water mixtures were conducted at pH 7. In the case where fine
particles were used to increase the viscosity of the suspending
medium, 103 M KCl solution was used as a background electro-
lyte, and the pH of the slurry was maintained at 9.
To determine the recovery of coarse quartz particles in the flo-
tation tests in the presence of alumina and silica, the concentrates
and tailings were wet screened at 38 lm to remove the fine parti-
cles. To estimate the experimental errors, all tests were performed
in triplicate.
2.3.2. Experimental flotation rate constant
Assuming that froth flotation is a first-order kinetic process, the
flotation recovery, Rt, at time t may be described by the following
expression:
Rt ¼ Rmax ð1  expðktÞÞ
where k is the flotation rate constant and Rmax is the flotation recov-
ery at an infinite time.
A nonlinear least square regression was used to calculate k and
Rmax from the best fit of the curve of experimental flotation recov-
eries versus time using Eq. (1). These flotation rate constants are
referred to as the experimental flotation rate constants in the text.
Small variations in the flotation recovery versus time data may re-
sult in different values of flotation rate constant. To minimise er-
rors associated with the calculations of the rate constant, the
tests were carried out in triplicate and the average values of flota-
tion recovery at each time were used to calculate the rate constant.
Fig. 2. Experimental procedure used for desliming of coarse quartz particles.
91
2.3.3. Desliming
The flotation recovery of coarse quartz particles generally de-
creased in the presence of the colloidal silica and alumina particles,
presumably due to the adsorption of fine particles onto the surface
of the coarse quartz. To investigate whether the adsorption of fines
was reversible, a series of desliming tests was carried out. The des-
liming procedure is schematically presented in Fig. 2. Slurry, con-
taining coarse quartz and fine silica or alumina particles was
placed in the flotation cell as per the standard flotation procedure.
The coarse quartz particles were allowed to settle. The superna-
tant, containing fine particles was then decanted, the cell was re-
filled with the 103 M KCl solution and the flotation test was
performed. In a different test, the desliming procedure was re-
peated twice to increase the amount of removed fine particles.
The flotation test was also conducted following the procedure de-
scribed above.
2.3.4. Contact angle measurement
Advancing mean contact angles of the quartz particles in water
were measured using DCAT 11/DCAT 11EC, DataPhysics Instru-
ments (Germany). This instrument allows measurements of the
contact angle and surface energy of cylindrical samples in accor-
dance with the Washburn technique (Muganda et al., 2011). Eq.
(2) was used to calculate the contact angle for two-liquid systems.
c2 l1 q22 ðx2 =tÞ1
cos h1 ¼ cos h2 ð2Þ
c1 l2 q21 ðx2 =tÞ2
where c is the surface tension of the liquid, l is the viscosity of the
liquid, and q is the density of the fluids. The subscripts 1, 2 refer to
the liquid where the contact angle is determined and calibrating li-
quid respectively. The contact angle in water was measured using
cyclohexane as the calibrating liquid. Thus, in Eq. (2) cos h2 = 1. Gi-
ven other parameters (c, l, q, and x2/t which could be determined
during the measurement), the contact angle may be determined.
3. Results
3.1. Characterisation of the fine alumina and silica
3.1.1. Zeta potential of alumina and silica particles
ð1Þ Fig. 3 shows the zeta potential of alumina and silica particles as
a function of pH at ionic strength of 103 M KCl.
It is apparent that at pH 9, alumina is slightly positively charged
(+2 mV) and silica is negatively charged (40 mV). The results are
consistent with those reported elsewhere (Ametov and Prestidge,
2004; Johnson et al., 2000).
3.1.2. Particle size distribution of the fine alumina and silica
Fig. 4 shows the particle size distribution data for the fine par-
ticles of both alumina and silica. Evidently, a broader size distribu-
tion for the silica than the alumina particles is observed. The mass
mean size (D [4,3]) of the fine silica and alumina particles are
3.09 lm and 3.10 lm respectively. The size distribution shown to
92 D. Xu et al. / Minerals Engineering 39 (2012) 89–98

50 280
(a)
Alumina 210
25
Zeta Potential (mV)

Silica
6% v/v
10% v/v
140 14% v/v
0

70

Shear Stress (Pa)

-25

0
(b) 9% v/v
-50 20% v/v
100
2 3 4 5 6 7 8 9 10 36% v/v

pH
75
Fig. 3. Zeta potential of alumina and silica as a function of pH at ionic strength of
103 M KCl.
50

10
25
silica
alumina 0
8
0 200 400 600 800 1000
Shear Rate (1/s)
Volume (%)

6
Fig. 5. Shear stress as a function of shear rate and solid volume percentage for (a)
alumina and (b) silica suspensions at pH 9 in 103 M KCl solution.

0.6
2
0.5
Apparent Viscosity (Pa.s)

0
0.4
0.1 1 10 Alumina (mean size 3 µm)
Particle Size (µm) Silica (mean size 3 µm)
0.3
Fig. 4. Particle size distributions of alumina and silica particles.

characterise the fine particles may not be the actual particle size
distribution in the flotation cell due to aggregation or dispersion
effects under shear conditions.
3.1.3. Rheology of the fine alumina and silica suspensions
The flow curves for alumina and silica suspensions as a function
of solids percent (v/v) are presented in Fig. 5a and b respectively.
The measurements were performed at pH 9 in 103 M KCl solution,
at which pH the zeta potential of alumina and silica particles is
+2 mV and 40 mV, respectively (Fig. 3). Alumina suspensions ex-
hibit shear-thinning behaviour, i.e. the viscosity of the suspensions
decreases with an increase in the shear rate. At the low value of
zeta potential, the van der Waals attractive forces are dominant,
and alumina particles readily aggregate when the suspension is
at rest. Under shear, the large particle aggregates are separated
into smaller units and, at very high shear, into individual particles.
Such a process rheologically manifests itself as shear-thinning
behaviour.
Silica suspensions show Newtonian behaviour, i.e., the viscosity
of the suspension is independent of the shear rate. At pH 9 in 103
M KCl solution, the zeta potential of the silica particles is 40 mV,
and the electrostatic repulsion dominates the inter-particle
0.2
0.1
0.0
0 10 20 30 40 50
Percent Solids (vol. %)
Fig. 6. Apparent viscosity (at 500 s1) of fine alumina and silica suspensions as a
function solids volume percent in 103 M KCl solution at pH 9. The horizontal line
shows the viscosity of interest (30 mPa s) and the corresponding solids percent (v/
v) of silica and alumina.
interactions. The strong electrostatic repulsion ensures good dis-
persion of particles resulting in Newtonian behaviour.
The apparent viscosities (at a shear rate of 500 s1) of the silica
and alumina suspensions as a function of solids volume fraction
are shown in Fig. 6. Evidently, the apparent viscosity increases with
an increase in the solids concentration. In the case of alumina, the
increase in the apparent viscosity is much steeper than for silica,
also due to the nature of the inter-particle interactions in alumina
(the van der Waals attraction) and silica (the electrostatic repul-
sion) suspension. The aim of this investigation was to use two
 D. Xu et al. / Minerals Engineering 39 (2012) 89–98 93

30
(a)
100
(a)
2% v/v Alumina 75
20
4% v/v Alumina
Water only
50 Water only
10 2% v/v Alumina
Quartz Recovery (%)

3% v/v Silica
25

0
(b) 100
0
(b)
3% v/v Silica

Quartz Recovery (%)

30% v/v Silica 80
20
Water only
60

10 40

20
0
0 3 6 9 20
Flotation Time (min) (c)
Fig. 7. Recovery of coarse quartz particles (600–850 lm) as a function of flotation 15
time and the volume concentration of fine alumina (a) and silica (b) particles.
Coarse quartz particles with mean contact angle of 81° in the 600–850 lm size
range were used.
10

types of colloidal particles to increase the pulp viscosity, and then 5

to ascertain the effect of the higher viscosity on the flotation recov-
ery of coarse quartz. Of course, the value of the viscosity attained
by the addition of these types of particles is required to be compa- 0
rable. Two values of the viscosity were selected for investigation, 0 2 4 6 8
i.e., 12 mPa s and 30 mPa s. From Fig. 6, and 2% (v/v) alumina and Flotation Time (min)
3% (v/v) silica suspensions provide a viscosity of 12 mPa s. To ob-
Fig. 8. Quartz recovery as a function of flotation time in the presence of fine
tain a slurry viscosity of 30 mPa s, 4% (v/v) alumina and 30% (v/v)
alumina and silica. Quartz particles in these tests were in the 150–300 lm size
silica are required, respectively. range, with the contact angle of (a) 75°, (b) 50° and (c) 18°.

3.2. Effect of fine silica and alumina on coarse quartz flotation

The recovery of coarse quartz particles (600–850 lm, mean
contact angle 81°) in the presence of fine alumina and silica as a
function of flotation time is presented in Fig. 7. The recovery of
coarse quartz particles decreased dramatically, from 27% to 2%,
for tests in which the slurry contained 2% (v/v) alumina. A further
increase in the volume fraction of alumina, to 4%, did not affect the
outcome of the flotation tests. The effect of silica at 3% (v/v) was
less severe, i.e. the recovery of coarse quartz decreased to 13%.
Increasing the concentration of fine silica to 30% (v/v) resulted in
a further decrease in coarse quartz recovery to 3%.
Evidently, both types of fine particles negatively affected the
recovery of coarse quartz particles. In the case of alumina, which
is positively charged under the test conditions (pH 9, 103 M
KCl), some degree of interaction with the coarse quartz particles
was expected. Adsorption of hydrophilic alumina particles onto
the surface of hydrophobic quartz may lead to a decrease in the
mean contact angle of the coarse quartz surface, and therefore de-
crease coarse particle recovery. However, a decrease in the flota-
tion recovery of coarse quartz particles was observed in the
presence of fine silica, though to a lesser degree. This was not ex-
pected due to the surmised electrostatic repulsive force.
The effect of the fine silica and alumina on the flotation behav-
iour of the coarse quartz particles was also investigated as a
function of coarse quartz particle size range and mean contact
angle. The results of flotation tests for quartz particles in the
150–300 lm and 600–850 lm size ranges are shown in Figs. 8
and 9, respectively.
It is worth mentioning that the reason for using two different
hydrophobicity ranges for the two size fractions is that for coarser
particles, greater hydrophobicity is required to recover the parti-
cles. The contact angle ranges shown in the study is the range
where a reasonable recovery was obtained for the coarse particles
in water only. Thus we can investigate the effect of fine particles on
the recovery further.
For coarse particles with a reasonably high mean contact angle
(75° and 90° for quartz particles in the 150–300 lm and 600–
850 lm size ranges, respectively), the recovery of coarse quartz
was not affected by the presence of fine silica and alumina in the
pulp. The magnitude of the coarse quartz recovery remained as
high as the value obtained in water. In contrast, for quartz particles
with lower mean contact angle (50° and 18° in the 150–300 lm
size range and 83° for the 600–850 lm size range) the flotation
recovery of coarse quartz decreased in the presence of fine alumina
and silica. Notably, the effect of the fine alumina on the recovery of
quartz was much stronger compared to that of the fine silica
although the viscosity values in both cases were the same at
12 mPa s. It should be pointed out that in the case of coarse quartz
particles with a contact angle of only 18° (150–300 lm size range)
(Fig. 3.6c), the effect of alumina and silica was comparable, i.e., the
recovery of quartz decreased to a very low value of 3%.
94 D. Xu et al. / Minerals Engineering 39 (2012) 89–98

100
(a) 100 (a) water only
3% v/v silica
2% alumina
80 80

Quartz Recovery (%)

60 60

40 40
Water only
2 vol.% Alumina
20
Quartz Recovery (%)

20 3 vol.% Silica

0
100 10 20 30 40 50 60 70 80
(b) Contact Angle (Degree)

80
100 (b) water only
2% v/v alumina
60 3% v/v silica
80
Quartz Recovery (%)

40
60

20
40

0
20
0 2 4 6 8
Flotation Time (min)
0
Fig. 9. Quartz recovery as a function of flotation time in the presence of fine
68 72 76 80 84 88 92
alumina and silica. Quartz particles in these tests were in the 600–850 lm size
range, with mean contact angle values of (a) 90° and (b) 83°. Contact Angle (Degree)

In previous work (Xu et al., 2011), it was demonstrated that the
recovery of coarse particles increased with an increased medium
viscosity, controlled by adding certain amount of glycerol. Particu-
larly, when the medium viscosity is 7.6 mPa s, which is similar to
that investigated in this work, 12 mPa s, the recovery of quartz par-
ticles with a contact angle of 80° increased from 20% to 70%. It was
concluded that an increase in medium viscosity may benefit the
flotation recovery of coarse particles. However, in the presence of
fine particles, the flotation recovery of coarse particles decreased
even though the viscosity was similar. A possible mechanism is
discussed further below.
The recovery of coarse quartz particles after 8 min of flotation
as a function of mean contact angle in the absence and presence
of fine silica and alumina is shown in Fig. 10. Evidently, the recov-
ery of the coarse quartz particles in the 150–300 lm size range is
less sensitive to the presence of fine alumina and silica (Fig. 10a).
The flotation recovery of the quartz particles in the 150–300 lm
size range with a mean contact angle of 75° in the presence of fine
alumina or silica was as high as in the absence of fine particles, at
90%. For particles with a contact angle of 50° the recovery de-
creased to 22% in the presence of the fine alumina, and to 68% in
the case of fine silica. Particles with low hydrophobicity (h = 18°)
exhibited very low recovery (3%) in the presence of either fine sil-
ica or alumina.
Furthermore, the flotation response of very coarse quartz
particles (600–850 lm) to the presence of silica or alumina was
Fig. 10. Effect of fine particles on coarse quartz recovery, coarse particle size. (a)
150–300 lm, (b) 600–850 lm.
noticeably different. In the pulp containing silica particles (3%),
the recovery of quartz with mean contact angle of 90° remained
virtually the same as in water only (92%). The flotation recovery
of quartz particles with a mean contact angle of 83° was 60% in
water, and decreased to 50% in the presence of silica (Fig. 10b).
There was only 30% recovery at a lower mean contact angle of
81° even in water only. With fine silica added to the pulp the
quartz (81o) recovery decreased to 15%.
In the presence of fine alumina, the flotation recovery of coarse
quartz with a mean contact angle of 90° was as high as in water
only or as in the presence of silica (92% in both cases). In contrast,
the recovery of coarse quartz particles with mean contact angle of
83° decreased from 60% in water to 10% in the presence of fine alu-
mina (4%). Particles with a mean contact angle of 81° became
essentially unrecoverable in the presence of fine alumina particles.
It is also shown in Fig. 10 (water only) that the floatability of
very coarse particles is very sensitive to the hydrophobicity of
the particles. A small decrease in the contact angle (from 83° to
80°) results in a dramatic decrease in the flotation recovery (from
60% to 20%). Increasing the medium viscosity by fine particle addi-
tion failed to increase the quartz particle recovery may be due to
the adsorption of fine particles on the quartz surface, which
resulted in a decrease in particle contact angle. By assuming the
 D. Xu et al. / Minerals Engineering 39 (2012) 89–98 95

contact angle of fine hydrophilic particles adsorbed onto the quartz
surface is zero, only 4% surface coverage is sufficient to decrease
the contact angle of the quartz particles from 83° to 80° according
to Cassie’s equation (Cassie and Baxter, 1944). This may explain
why the flotation recovery of coarse particles decreased in the
presence of the fine particles, which in fact increase the pulp vis-
cosity. The attachment of fine particles may dominate the effect
of pulp viscosity for the flotation behaviour of coarse particles.
In the case of silica (3% v/v) suspension (Fig. 11b), the recovery
of quartz particles (80o) also decreased, from 20% to 13%. A single
stage of desliming did not improve the coarse quartz recovery.
However, two stages of desliming process successfully restored
the recovery of coarse quartz particles to the original value ob-
tained in water only.
3.4. Recovery of coarse quartz in glycerol/water mixture

3.3. Effect of removal of fine particles (desliming) on coarse quartz
particle recovery
Since the presence of fine particles had a negative effect on
quartz recovery, the effect of their removal in desliming was also
investigated. The desliming procedure was outlined in the experi-
mental section above. The effect of desliming on the coarse quartz
particles recovery on the size range of 600–850 lm is shown in
Fig. 11.
In the presence of alumina (2% v/v) (Fig. 11a) the flotation
recovery of quartz particles decreased from 60% to 10%. After a sin-
gle stage of desliming, the recovery of coarse quartz particles in-
creased from 10% to 50%. An additional desliming stage did not
result in an appreciable increase in coarse quartz recovery. It seems
reasonable to assume that, in the presence of alumina particles in
the pulp, the flotation recovery of coarse quartz may always be be-
low that of the original value achieved in the complete absence of
alumina particles.
80
(a) Contact Angle 83o
60
In the previous sections, it was shown that the recovery of
coarse quartz decreases in the presence of fine particles, particu-
larly in the case of alumina. It was also proposed that the loss of
recovery of coarse particles was due to the decrease in particle
hydrophobicity which resulted from the adsorption of fine hydro-
philic particles onto the quartz surface. Additionally in previous
work (Xu et al., 2011), it was demonstrated that the recovery of
coarse quartz particles could be increased by conducting flotation
in a high viscosity medium. Moreover, in high viscosity medium
coarse quartz particles with lower critical contact angle (Crawford
and Ralston, 1988) were able to be recovered (Xu et al., 2011).
Therefore, the question now becomes – Is it possible to restore
the flotation recovery of coarse quartz particles decreased in the
presence of fine alumina and silica by using a high viscosity med-
ium? – is logical and needs to be answered.
In this investigation, the coarse quartz particles were condi-
tioned in the presence the fine alumina (2% v/v) or silica (3% v/v)
following the flotation procedure described in the previous section.
A single stage of desliming was carried out using a flotation cell. In
the ‘‘control’’ test, 103 M KCl solution was used to increase the
pulp volume in the flotation cell to the required volume and the
flotation was conducted. In the test investigating the effect of a
high viscosity medium, the calculated amount of glycerol was
added to ensure a 50% glycerol/water mixture with the viscosity
of 7.6 mPa s, and the flotation test performed.

80
(a) Alumina, Contact Angle 83o
40
water
with 2% alumina 60
single stage de-sliming
two stage de-sliming
20
Quartz Recovery (%)

40

water only
Quartz Recovery (%)

20 Single stage de-slimed, in water

0
Single stage de-slimed, in 50% glycerol
(b) Contact Angle 80o

0
(b) Silica, Contact Angle 80o

20 water only
60 Single stage de-slimed, in water
Single stage de-slimed, in 50% glycerol

40

10
water
with 2% alumina 20
single stage de sliming
two stage de sliming
0
0 0 2 4 6 8
0 2 4 6 8
Flotation Time (min)
Flotation Time (min)
Fig. 12. Quartz particle recovery restored by increasing pulp viscosity using 50%
Fig. 11. Effect of desliming on the recovery of coarse quartz particles (600–850 lm) glycerol/water mixture for quartz particles in the presence of fine alumina (a) and
from alumina (a) and silica (b) containing slurries. fine silica (b).
96 D. Xu et al. / Minerals Engineering 39 (2012) 89–98
Table 1
Summary of flotation rate constants and recoveries (Rmax) and water recoveries (Rw) for coarse quartz particles in the 600–850 lm size fraction in the desliming tests.
Coarse quartz flotation conditions
Water (No fines)
Slime particles
Single stage de-slimed, floated in water
Single stage de-slimed, floated in 50% glycerol/water mixture
Fig. 13. SEM images of quartz particles in the flotation tailings (the contact angle of coarse quartz was 90°). Flotation tests were conducted in the presence of alumina (a) and
silica (b) at 2% v/v and 3% respectively. Arrows point to adsorbed particles coarse quartz size range (600–850 lm).
The recovery of quartz particles as a function of flotation time in
the ‘‘control’’ test (water) and in the test conducted in the 50% glyc-
erol/water mixture are presented in Fig. 12. The flotation data was
fitted using the first order kinetic equation (Eq. (1)). The flotation
rate constant and the maximum recovery at infinite time Rmax
are summarised in Table 1. It is apparent that the presence of fine
particles in the pulp resulted in a decrease in the recovery of coarse
quartz, an increase in the water recovery, as well as the flotation
rate constant (Table 1). The effect of the fine alumina on flotation
of quartz was more pronounced than that of the fine silica. A single
stage of desliming, followed by flotation in water, partially restored
the recovery of the coarse quartz particles. The flotation rate con-
stant in both cases (for the presence of fine alumina and silica) also
increased. It is notable that there is not much difference in water
recovery with desliming which indicates that the increase in recov-
ery with desliming is not due to increased entrainment. However,
for flotation tests after the single stage desliming but in the pres-
ence of the 50% glycerol/water mixture showed that the coarse
quartz recovery increased to a value higher than in the ‘‘control’’
tests. In fact, it was higher than the recovery of the coarse quartz
in water in the absence of fine particles, i.e. marginally higher for
fine alumina particles, and considerably higher in the case of the
fine silica (Table 1). In contrast, the flotation rate constant in the
tests conducted in the 50% glycerol/water mixture decreased, sim-
ilarly to what was observed and discussed in previous work (Xu
et al., 2011). Furthermore, highest water recovery was observed
in the 50% glycerol/water mixture for both cases (alumina and sil-
ica) due to the increased pulp viscosity.
4. Discussion
4.1. Effect of slime coating on quartz flotation
The flotation results indicate that fine particles in the pulp have
a negative effect on the flotation behaviour of the coarse quartz.
The fine particles were used to increase the pulp viscosity and, pos-
sibly, the flotation recovery of coarse quartz particles. However,
Slime alumina, 2% v/v ° Silica, 3% v/v
Quartz contact angle 83 Quartz contact angle 80°
k Rmax Rw k Rmax Rw
1.8 59 16 1.5 18 14
0.69 12 28 1.2 14 18
1.27 49 23 0.87 14 20
1.08 65 45 0.79 34 30
the flotation recovery of quartz decreased. The supposition that
the coarse particle recovery may increase in the presence of fine
particles is based on previous work that increased viscosity
(through addition of glycerol) increased coarse particle recovery
(Xu et al., 2011). That the fine particles actually caused depression,
while also increasing pulp viscosity, demonstrated that an addi-
tional mechanism was at play.
It was demonstrated in previous (Fig. 10 water only) and also in
previous work (Xu et al., 2011) that the flotation response of coarse
particles is very sensitive to the particle hydrophobicity. Calcula-
tions discussed previously, suggest that only very low surface cov-
erages of hydrophilic fine particles (of the order of 5%) are required
to reduce the contact angle below the critical value depressing flo-
tation. The decrease in the recovery of very coarse particles, even
though in higher pulp viscosity, may be due to the fact that hydro-
philic fine particles adsorbed on the quartz surface, and conse-
quently reduce the contact angle of the coarse quartz particles to
below the critical contact angle. More significant decreases of
recovery in the case of fine alumina than that of silica may be ex-
pected due to the different nature of surface charge and propensity
to adsorb onto the coarse quartz surface.
To elucidate the possible mechanism of the decrease in recovery
of quartz particles in the presence of fine alumina and silica, scan-
ning electron microscopy (SEM) was used. Coarse quartz particles,
collected from the tailings were gently washed with water and
studied by SEM. The SEM images of the quartz particles are pre-
sented in Fig. 13.
Evidently, both types of particles, i.e. alumina (Fig. 13a) and sil-
ica (Fig. 13b), adsorb onto the coarse quartz surface. Possibly, a
greater amount of alumina is present on the quartz surface com-
pared to silica. Moreover, the majority of the alumina particles ad-
sorb on edges or steps on the quartz surface. This may be due to the
higher surface energy of the edges, which are rougher compared to
the crystal planes, and possibly provide more adsorption sites. An-
other possible reason for greater quantities of alumina particles on
the quartz surface is the self-aggregation of alumina particles. At
pH 9, which is near the iso-electric point for alumina, the surface
charge of alumina is low (zeta potential is +2 mV), the attractive
 D. Xu et al. / Minerals Engineering 39 (2012) 89–98
van der Waals forces are dominant, and fine particles aggregate.
Decreasing the pH to values further away from the iso-electric
point may reduce the self-aggregation of alumina, but it may also
promote adsorption of alumina onto the coarse quartz surface due
to electrostatic interaction.
It was reported earlier that both silica and TMCS treated quartz
are highly negatively charged (the zeta potential is 40 mV) and,
due to the dominant electrostatic repulsion, may not interact un-
der the conditions of the experiment. However, the SEM image in
Fig. 13b showed that fine silica particles also adsorb onto the sur-
face of the coarse quartz, although to a lesser extent compared to
alumina. Similarly to the fine alumina, fine silica particles also ad-
sorb onto the edges and steps of the quartz surface. Although, the
mechanism of adsorption of fine silica on the surface of hydropho-
bic quartz is not understood, it is clear that only a small surface
coverage of either fine alumina or fine silica are required to de-
crease the contact angle of the coarse quartz particles below the
critical value necessary for stable bubble–particle attachment. As
previously outlined, the critical contact angle for 600–850 lm size
range is of the order of 85°, with decreases in contact angle below
80° able to effectively depress flotation completely. Surface cover-
age of hydrophilic fine particles less than 9% is able to decrease the
contact angle by 5° making the flotation recovery of coarse parti-
cles very sensitive to the surface coverage of fine hydrophilic par-
ticles. This gives rise to the often noted ‘knife-edge’ behaviour of
coarse particles in plant practice.
4.2. Effect of desliming on quartz recovery
As shown earlier, the removal of fine particles from the pulp is,
to some extent, beneficial for the flotation of coarse particles. A sin-
gle stage of desliming increased the recovery of coarse quartz par-
ticles in the presence of fine alumina, although in the presence of
fine silica, it was rather unsuccessful. In contrast, adding a second
stage of desliming for the alumina containing pulp was ineffective,
but appreciably improved the recovery of quartz in the pulp con-
taining fine silica. The positive effect of desliming may be attrib-
uted to detachment of fine particles from the surface of the
coarse particles, thus restoring the value of the contact angle. How-
ever, it seems that the success of the desliming process depends on
the type of the interaction between the fine and coarse particles, as
well as on the concentration of fine particles in the pulp and, pos-
sibly, turbulence and fluid velocity in the flotation cell (Edwards
et al., 1980; Bandini et al., 2001).
4.3. Restoring the recovery of quartz particles using high viscosity
medium (50% glycerol/water mixture)
In previous work (Xu et al., 2011) it was demonstrated that
much higher flotation recovery of coarse particles may be achieved
in the high viscosity medium. This effect was attributed to changes
in the hydrodynamic parameters in a flotation cell, such as an in-
crease in the mean bubble size, broadening of the bubble size dis-
tribution and a decrease in local turbulent energy dissipation and
fluid velocity. In addition, it was shown that the critical contact an-
gle, the minimum contact angle required for particles to float, is
lower in high viscosity medium. An increase in the medium viscos-
ity reduces the kinetics of the bubble–particle collection process,
but at the same time, increases the maximum recovery of coarse
particles. The decrease in flotation rate constant in the high viscos-
ity medium may be attributed to the decrease in turbulent energy
dissipation and fluid velocity, and consequently the decrease in
bubble particle collision frequency. Conversely, low energy dissi-
pation and fluid velocity are favourable for greater stability of bub-
ble–particle aggregates, and therefore the maximum recovery of
the coarse particles increases.
97
Adsorption of fines onto the surface of the coarse particles de-
creases the coarse particle contact angle. In the cases, where the
coarse particles become unrecoverable as a result of the adsorbed
fine particles, their contact angle decreases to a value lower than
the critical contact angle determined in water. Conducting the flo-
tation tests at higher viscosity is beneficial to the recovery of the
coarse particles in two ways: (i) the high viscosity medium de-
creases turbulent energy dissipation in the flotation cell, resulting
in an increase in the stability of bubble–particle aggregates and (ii)
the contact angle of coarse particles does not need to be as high for
the particles to be recovered. In practice, desliming is sometimes
used to remove fine particles from the pulp and to reduce the
amount of fine hydrophilic particles attached to the coarse parti-
cles. This is recognition of the controlling behaviour of the fine par-
ticles on coarse particle recovery, and the sensitivity of coarse
particles to changes in contact angle. Moreover, desliming may
also be accompanied by deliberate changes in pulp viscosity by
the introduction of high viscosity media. This combination of ap-
proaches has been used to successfully increase the recovery of
coarse composite particles from an ore (Farrokhpay et al., 2011).
5. Conclusions
The depression of coarse particle recovery was due the attach-
ment of fine hydrophilic particles, which resulted in a decrease
in particle mean contact angle. Increasing the pulp viscosity using
fine particles failed to benefit the coarse particle recovery due to
the dominant effect of fine particle attachment, which was attrib-
uted to the fact that the flotation recovery of coarse particle is very
sensitive to particle hydrophobicity. Desliming was successful in
restoring recovery to a degree probably due to detachment of fine
hydrophilic particles and an increase in the contact angle of coarse
particles. Further increases in the recovery of coarse particles were
apparent with the high viscosity medium using glycerol as a vis-
cosity modifier.
Acknowledgement
Financial support from AMIRA International, the Australian Re-
search Council and University of South Australia, is gratefully
acknowledged.
References
Ametov, I., Prestidge, C.A., 2004. Hydrophobic interactions in concentrated colloidal
suspensions: a rheological investigation. Journal of Physical Chemistry B 108,
12116–12122.
Bandini, P., Prestidge, C.A., Ralston, J., 2001. Colloidal iron oxide slime coatings and
galena particle flotation. Minerals Engineering 14, 487–497.
Cassie, A.B.D., Baxter, S., 1944. Wettability of porous surfaces. Transactions of the
Faraday Society 40, 546–551.
Crawford, R., Ralston, J., 1988. The influence of particle size and contact angle in
mineral flotation. International Journal of Mineral Processing 23, 1–24.
Deglon, D.A., Shabalala, N.Z.P., Harris, M.C., 2007. Rheological effects on gas
dispersion. Minerals Engineering International Conferences: Flotation 07 Cape
Town, Xstrata Process.
Duan, J., Fornasiero, D., Ralston, J., 2003. Calculation of the flotation rate constant of
chalcopyrite particles in an ore. International Journal of Mineral Processing 72,
227–237.
Edwards, C.R., Kipkie, W.B., Agar, G.E., 1980. The effect of slime coatings of the
serpentine minerals, chrysotile and lizardite, on pentlandite flotation.
International Journal of Mineral Processing 7, 33–42.
Farrokhpay, S., Ametov, I., Grano, S., 2011. Improving the recovery of low grade
coarse composite particles in porphyry copper ores. Advanced Powder
Technology 22, 464–470.
Gao, M., Forssberg, E., 1993. The influence of slurry rheology on ultra-fine grinding
in a stirred ball mill. In: 18th International Mineral Processing Congress.
Sydney, Australian.
Johnson, S.B., Franks, G.V., Scales, P.J., Boger, D.V., Healy, T.W., 2000. Surface
chemistry–rheology relationships in concentrated mineral suspensions.
International Journal of Mineral Processing 58, 267–304.
98 D. Xu et al. / Minerals Engineering 39 (2012) 89–98
Kitano, T., Kataoka, T., Shirota, T., 1981. An empirical equation of the relative
viscosity of polymer melts filled with various inorganic fillers. Rheologica Acta
20, 207–209.
Muganda, S., Zanin, M., Grano, S.R., 2011. Influence of particle size and contact angle
on the flotation of chalcopyrite in a laboratory batch flotation cell. International
Journal of Mineral Processing 98, 150–162.
O’Connor, C.T., Randall, E.W., Goodall, C.M., 1990. Measurement of the effects of
physical and chemical variables on bubble size. International Journal of Mineral
Processing 28, 139–149.
Pashley, R.M., Kitchener, J.A., 1979. Surface forces in adsorbed multilayers of water
on quartz. Journal of Colloid and Interface Science 71, 491–500.
Prestidge, C.A., 1997a. Rheological investigations of galena particle interactions.
Colloids and Surfaces A: Physicochemical and Engineering Aspects 126, 75–83.
Prestidge, C.A., 1997b. Rheological investigations of ultrafine galena particle slurries
under flotation-related conditions. International Journal of Mineral Processing
51, 241–254.
Pyke, B., Fornasiero, D., Ralston, J., 2003. Bubble particle heterocoagulation under
turbulent conditions. Journal of Colloid and Interface Science 265, 141–151.
Tangsathitkulchai, C., 2003. The effect of slurry rheology on fine grinding in a
laboratory ball mill. International Journal of Mineral Processing 69, 29–47.
Wang, Y., Forssberg, E., 1995. Dispersants in stirred ball mill grinding. Kona 13, 67–
77.
Xu, D., Ametov, I., Grano, S.R., submitted for publication. Effect of medium viscosity
on coarse particle flotation. International Journal of Mineral Processing.
Yang, H.-G., Li, C.-Z., Gu, H.-C., Fang, T.-N., 2001. Rheological behavior of titanium
dioxide suspensions. Journal of Colloid and Interface Science 236, 96–103.