Minerals Engineering 56 (2014) 136–144

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

Decoupling rehology and slime coatings effect on the natural flotability

of chalcopyrite in a clay-rich flotation pulp
E. Forbes ⇑, K.J. Davey, L. Smith
CSIRO Process Science and Engineering, Bayview Avenue, Clayton, VIC 3168, Australia

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

Article history: Clay minerals are a commonly occurring gangue in mineral beneficiation operations and occur in a vari-
Received 27 September 2013 ety of ore deposits, including porphyry copper ores. The presence of clays in mineral beneficiation circuits
Accepted 14 November 2013 can cause a wide range of different problems, including that of slime coatings on valuable minerals and
Available online 8 December 2013
elevated viscosities of flotation pulps. The aim of this work was to decouple and estimate the relative
magnitudes of the slime coatings and pulp rheology effects on the natural floatability of chalcopyrite
Keywords: in a model mineral system. It was found that the two phenomena can be partially isolated and that they
Flotation
both have a detrimental effect on flotation performance. It was also found that the level to which these
Rheology
Slime coatings
two phenomena affect chalcopyrite recovery is of a similar order of magnitude.
Kaolinite Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction als induces the production of a large amount of slimes. The pres-
ence of slimes has a negative impact on slurry rheology, with
Clay minerals are a commonly occurring gangue in mineral ben- detrimental effects on both flotation and comminution. As rheol-
eficiation operations and occur in a variety of ore deposits, includ- ogy describes flow properties of fluids it has a significant impact
ing porphyry copper ores (Bulatovic et al., 1998; Petruk, 2000), low on flotation cell hydrodynamics. Schubert (2008), argues that low
grade nickel ores (Senior and Thomas, 2005), platinum group metal pulp viscosity causes a reduction in turbulence damping, which in-
deposits (Visser et al., 1994) and diamond bearing ores (Boshoff creases the probability of particle/bubble attachment, while also
et al., 2007). In some rare cases, the proportion of clay minerals increasing the probability of detachment. This was verified by Xu
within such ores can reach as high as 80% (Burdukova et al., et al. (2011), who found that increased pulp viscosity resulted in
2008). Not only are high proportions of clay minerals in concen- an increased stability of the bubble/particle aggregates, thus
trates penalized by smelters, but the presence of these minerals decreasing detachment probability. The effect of increased pulp
in flotation and comminution pulps causes a wide array of prob- viscosity was also shown to have a detrimental effect on gas dis-
lems for the flotation operations, including higher reagent con- persion, through limiting the turbulent region of flotation cells to
sumption, poorer selectivity and impeded flotation kinetics a small ‘‘turbulent cavern’’ surrounding the impeller (Bakker
(Connelly, 2011). et al., 2009; Shabalala et al., 2011).
Clay minerals fall within the phylosilicate mineral family (Deer Another detrimental and well known effect of very fine particles
et al., 1978). Phylosilicate minerals are so named because they typ- on flotation is commonly referred by the generic term ‘‘slime coat-
ically display a platy/leafy habit, fylo meaning ‘‘leaf’’ in Greek. ings’’. In this phenomenon, relatively coarse valuable particles be-
There are a large number of different types of phylosilicates in come either completely or partially coated by a layer of hydrophilic
existence, with a variety of different properties. The faces and slimes, thereby rendering the valuables hydrophilic and inhibiting
edges of phylosilicates carry different electrical charges, making collector adsorption. The mechanism responsible for such coatings
these particles electrostatically anisotropic. The faces (or basal is widely believed to be the electrostatic attraction between oppo-
planes) tend to be negatively charged, while the edges carry a sitely charged mineral particles (Arnold and Aplan, 1986; Del
charge that alters from positive to negative as a function of pH Guidice, 1934; Edwards et al., 1980; Sutherland and Wark, 1955;
(Van Olphen, 1951). Trahar, 1981). Please note that for the sake of brevity, this electro-
The presence of clays in mineral beneficiation circuits can cause static interaction will be referred to as ‘‘slimes coatings’’ through-
a wide range of different problems. The soft nature of these miner- out the manuscript. However, very little is known on the relative
magnitude of the impacts that both of these effects have on flota-
tion recovery.
⇑ Corresponding author. Tel.: +61 03 9545 8588.
E-mail address: elizaveta.forbes@csiro.au (E. Forbes).

0892-6875/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.11.012
 E. Forbes et al. / Minerals Engineering 56 (2014) 136–144 137

The objective of this work was to study both the effect of slime the whole surface of the froth to be scraped with a paddle at a con-
coatings and pulp rheology on the recovery of chalcopyrite from a stant depth and rate. The froth was scraped every 2 s for the first
clay rich flotation pulp, with the aim of decoupling the two effects minute of flotation and every 5 s thereafter. The cell was fitted
and attempting to quantify their relative magnitudes. This was with a rubber diaphragm, sight tube and electronic sensor for auto-
achieved by studying a model batch flotation system in the ab- matic detection and control of the pulp level. A Radiometer PHM61
sence of reagents. The pulp rheology was manipulated by changing laboratory pH meter and pHC2401 combined pH electrode was
the proportion of clay material in the gangue component of the flo- used to measure the pH. Radiometer TTT80 titrators and ABU80
tation pulp, while the slime coatings were manipulated by altering burettes were used to add acid/base to set and maintain the pH.
the pulp pH. The rheological properties of the flotation pulps were Frother solution was added at a rate of 2 ml min1 continually
monitored by measuring the flow behaviour of flotation tailings. commencing 2 min before flotation and for the duration of the test.
An attempt was made to quantify the effect of slime coatings by The flotation gas was zero grade synthetic air used at a flow rate of
measuring the interaction between clay minerals and chalcopyrite 8 L min1. The flotation procedures used for the mineral-quartz
using zeta potential distribution measurements. mixtures followed a standard procedure developed by CSIRO. The
ground pulp was transferred to the flotation cell and the water le-
vel was raised to a preset level. The pH was then adjusted to the
2. Materials and methods
test value. The addition of frother commenced and after 2 min con-
centrate collection started. Concentrates were taken after 0.5, 1, 2,
2.1. Mineral samples
4 and 8 min. At the end of each test, while the pulp was still being
mixed in the flotation cell, two 50–60 ml sub-samples of the flota-
The chalcopyrite (CuFeS2) was handpicked high-grade mineral
tion tailings was collected using a polypropylene syringe for rheol-
from Mt Lyell, Tasmania. The stochiometric composition of chalco-
ogy measurements.
pyrite is 34.6% Cu, 30.4% Fe and 35.0% S and the chemical analysis
The flotation rate coefficients were calculated using the follow-
indicated that the sample was very high grade and contained neg-
ing expression, where f(t) is the fraction of chalcopyrite remaining
ligible impurities.
unrecovered after time t, g is the fraction of non-floating chalcopy-
The kaolinite (Al2Si2O5(OH)4) mineral sample was obtained
rite, u is the fraction of fast-floating chalcopyrite which has a flo-
from Wards Scientific. Chemical analysis indicated that the kaolin-
tation coefficient of kf and ks is the rate coefficient of the slow-
ite sample contained 22.1% Al, 17.7% Si and 0.94% Ti as the major
floating chalcopyrite, as shown in Eq. (1) (Frew and Trahar, 1982):
elements present while quantitative phase analysis (QPA) based
on X-ray diffraction (XRD) analysis indicated that the major com- f ðtÞ ¼ g þ u  eðkf tÞ þ ð1  u  gÞ  eðks tÞ : ð1Þ
ponents of the sample were kaolinite (72% with an additional
8% dickite) and gibbsite (17%).
The quartz (SiO2) mineral was a sample obtained from Creswick 2.4. Particle size measurement
Quartz, near Smeaton, Victoria. Chemical analysis indicated that
the quartz contained 46.3% Si, equivalent to 99% SiO2 based on a The particle size distribution of the flotation tailings was esti-
stochiometric composition of 46.7% Si for quartz, and the levels mated by light scattering, using a Malvern Mastersizer 2000. Sam-
of impurity elements detected in the sample were all less than ple aliquots were placed in an ultrasonic bath for 1 min before
0.03% confirming the high quality of the quartz sample. measurement. Each of the two tailings samples was sub-sampled
twice, with the particle size distribution of each sub-sample mea-
2.2. Reagents sured in triplicate. The aggregate of twelve resulting measure-
ments was used as an average particle size distribution curve.
The flotation tests were conducted in the absence of collector.
The frother was a commercial grade polypropylene glycol (Cytec 2.5. Zeta potential measurements
Aerofroth 65) prepared as 0.25% w/v solution in distilled water.
The flotation gas was bottled zero-grade synthetic air and the Zeta potential measurements were performed using the CAD
water used throughout the tests was distilled water. Dilute solu- Zeta compact instrument. A CCD camera captured the movement
tions of sodium hydroxide and sulphuric acid were added to set of charged particles within an electric field. This video footage
and maintain the pH during flotation tests. was then analysed for particle trajectories and output a range of par-
ticle mobilities. These mobilities were converted to zeta potentials
2.3. Flotation procedure using the Smoluchovski Equation (Dukhin and Derjaguin, 1976).
The mineral suspensions were conditioned at pH 11 for 2 h and
The composition of the flotation pulp was made with pure min- sonicated for 20 min. After sonication, the samples were allowed to
erals, with 2.5% valuable mineral and 97.5% gangue. The valuable stand for further 60 min. A small sample (0.1 ml) of the superna-
mineral phase was represented by chalcopyrite, which corre- tant was taken and diluted to 500 ml. The resultant dilute suspen-
sponded to a Cu head grade of 0.87%. The gangue phase was repre- sion was examined with the sample viewer of the zeta meter
sented by a mixture of quartz and kaolinite at a variety of ratios, instrument. Further 0.1 ml supernatant aliquots were added to
ranging from 0% to 100% quartz (100% to 0% kaolinite). the 500 ml dilute suspension until the concentration of particles
In order to ensure that the particle size distribution of chalcopy- (as seen in the instrument sample viewer) was sufficient for taking
rite remained consistent throughout the test series, the chalcopy- good measurements.
rite was ground separately in a 1.4 dm3 ceramic mill for 7 min. The extremely dilute nature of the supernatant suspension
The quartz and kaolinite (at a variety of proportions) were ground meant that its exact particle size distribution could not be experi-
in a 5.3 dm3 ceramic grinding mill for 30 min. The ground samples mentally determined by light scattering, due to insufficient obscu-
were transferred into a batch cell and made up to a volume of circa ration values. However a calculation of Stokes velocity (Bird et al.,
2750 ml for each test to give a flotation pulp density of 29 wt% 2007) required for the particles to remain in suspension after
solids. 60 min in 15 cm of liquid, determined that the average size of chal-
Flotation tests were performed in a 3 dm3 modified Denver cell copyrite and kaolinite particles had to be smaller than 2.5 and
(Guy, 1992) in which the impeller was driven from below to allow 3.5 lm respectively.
138 E. Forbes et al. / Minerals Engineering 56 (2014) 136–144

The dilute mineral suspension was gradually made more acidic,

allowed to equilibrate for 15 min, then a sample was withdrawn
for measurement. A portion of the sample was fed to the instru-
ment with a syringe, until a good visual cross-section of particles
was obtained, upon which time a measurement sequence was ini-
tiated. This was repeated at least 9 times per sample.
The measurements were performed in a pH range between 2
and 10. 1 M sodium hydroxide and 1 M hydrochloric acid solutions
were used for pH adjustment with a background electrolyte of
102 M KCl.

2.6. Rheology measurements

Rheology measurements were performed using a HAAKE

ViscometerÒ VT550 fitted with a MV2P measuring sensor. The
measurements were performed in a step-wise, logarithmic shear
rate ramp, ranging from 20 to 500 s1. In some cases, due to the
low slurry viscosity, the measurement was not reliable in the en-
tire measured shear rate range, and a more limited range was used.
The time between steps was set to 10 s. The obtained curves were Fig. 1. Cumulative copper recovery with time, as a function of different quartz/
analysed using the Herschel Buckley model (Barnes et al., 1989), kaolinite ratios in the gangue phase, at pH 8.

were s is the shear stress (Pa), c is the shear rate (s1), sHB is the
Hershel Buckley yield stress (Pa), gHB is the flow coefficient (Pas)
Meanwhile, the flotation rate coefficient for the slow floating mate-
and p is the Herschel Buckley flow index, as show in Eq. (2):
rial (ks), decreases steadily as the proportion of kaolinite in the
s ¼ sHB þ gHB  cp ð2Þ gangue phase increases.
The proportion of chalcopyrite in the flotation pulp, as well as
The sHB term is an estimate of the slurry yield stress, which is the pulp chemical conditions, remains constant between tests.
defined as the initial resistance to deformation. The flow coefficient Therefore the most likely explanation is that the detrimental flota-
(gHB) is a term that describes the rate the slurry’s resistance to tion performance stems from the effect that the increased propor-
deformation (a viscosity indicator), while the HB flow index (p) tion of clay material has on pulp characteristics.
indicates the deviation from Newtonian behaviour.
For a perfectly Newtonian fluid (e.g. water), the sHB term is zero, 3.1.2. Effect of pH
as such fluids have no yield stress, and the flow index approaches Once the floatability of chalcopyrite as a function of increasing
unity. In such cases the gHB term becomes equivalent to a Newto- proportion of kaolinite in the gangue phase was established, tests
nian viscosity (a constant). As the fluid deviates from Newtonian were performed to evaluate the effect of pulp pH in the presence
behaviour, the fluid gains a yield stress and becomes progressively of large quantities of clay material (30/70 quartz/kaolinite ratio).
more shear-thinning (i.e. the flow index decreases, causing the Once again, the flotation tests at pH 8 were performed in dupli-
flow curve to become increasingly non-linear). cate to establish good reproducibility. The results are presented
in Fig. 2, and show that while the copper recoveries remain rela-
3. Results and discussion tively high in the alkaline pH range (8–10), the recoveries drop in
the acidic range (4–6). Similar results can be seen when the
3.1. Flotation tests recovery curves are analysed for flotation kinetics, as shown in
Table 2. The results indicate that the flotation rate coefficient of
3.1.1. Effect of quartz/kaolinite ratios the slow floating material (ks) decreases steadily with decreasing
The results of flotation tests at a variety of quartz/kaolinite pH.
ratios in the gangue phase are presented in Fig. 1. All tests were The natural floatability of chalcopyrite is not affected by pH and
performed at pH 8. The tests at 30/70 quartz/kaolinite ratio were remains relatively high in the pH range 4–12 (Castro, 2012;
performed in duplicate to ensure good reproducibility. The results Chandraprabha et al., 2004). Therefore, it is likely that the notice-
show that when the gangue phase consists entirely of quartz (rep- able decrease in flotation performance stems from the effect that
resenting a baseline flotation condition), chalcopyrite exhibits a pH has on the gangue phase.
high level of floatability, achieving over 90% recovery. This result
is entirely expected as chalcopyrite is known to be a naturally 3.2. Slime coatings
floatable mineral (Heyes and Trahar, 1977). As the proportion of
kaolinite in the gangue phase increases, the recovery of chalcopy- As discussed in the introductory sections, one possible explana-
rite decreases dramatically. When the gangue phase consists tion for the detrimental effect of kaolinite on flotation performance
entirely of kaolinite, only 60% copper recovery is achieved. is the phenomenon of slime coatings, whereby the chalcopyrite
One of the most notable differences between test conditions in particles become coated with hydrophilic kaolinite particles, thus
not only the decrease in the overall recovery, but also the rate at decreasing their flotability.
which flotation takes place. As the residence time of a typical Slime coatings are typically driven by the attractive electro-
industrial flotation cell is 2–6 min (Deglon et al., 2000), the flota- static forces between the valuable particles and gangue
tion rate is an important indicator of flotation performance. Anal- particles, where slime coatings are at their worst in the pH region
ysis of flotation kinetics was performed in a manner described in where the two sets of particles carry opposing charges (Arnold
Section 2.3. The analysis results are summarised in Table 1. The and Aplan, 1986; Attia and Deason, 1989; Fuerstenau et al.,
results show that the fast floating fraction (u) of chalcopyrite 1958; Iwasaki et al., 1962). The surface charge of mineral parti-
disappears entirely as the quartz/kaolinite ratio reaches 30/70. cles is typically estimated using zeta potential measurements.
 E. Forbes et al. / Minerals Engineering 56 (2014) 136–144 139

Table 1 particle planes. Kaolinite specifically, carries three differently

Flotation kinetic analysis, as a function of different quartz/kaolinite ratios in the charged facets: a tetrahedral (T) face, an octahedral (O) face and
gangue phase, at pH 8.
a T–O edge, as illustrated in Fig. 3.
Quartz/Kaolinite Floating fraction Rate coefficient This means that the value one obtains from a zeta potential
ratio (min1) measurement represents an average, or aggregate, surface charge
Non (g) Fast (u) Slow (1  g  Fast Slow value. Furthermore, the Smoluchovski equation used for calculat-
(%) (%) u) (%) (kf) (ks) ing zeta potential from electrophoretic mobility was derived for
100/0 8 66 27 5.50 0.55 spherical particles. Kaolinite particles have a plate-like morphol-
70/30 12 57 31 3.20 0.43 ogy and their flow properties in solution differ substantially from
30/70 0 0 100 – 0.23
spherical particles. These issues highlight the fact that the use of
0/100 0 0 100 – 0.11
zeta potential measurements to estimate the surface charge distri-
bution of anisotropic minerals can be highly misleading and cer-
tain researchers advise to avoid it altogether when working with
anisotropic minerals (Burdukova et al., 2007; Hou et al., 2009;
Missana and Adell, 2000).
Nonetheless, there are ways in which zeta potential measure-
ments can be used to estimate the manner in which clay minerals
can interact with other minerals on the basis of charge. This is
specifically pertinent in determining whether or not clay minerals
are likely to cause slime coatings in flotation applications. This
method makes use of the distribution of zeta potential measure-
ments in a binary mineral system (Liu et al., 2002; Xu et al.,
2003).
The measurement involves obtaining the zeta distribution of
each individual mineral and then compares it to the zeta
distribution of a binary mineral mixture. This technique can give
an indication whether or not one of the minerals had been
effectively coated with another (a single distribution peak, vs. a
bimodal distribution). This method does not estimate the exact
nature of the clay surface charge, but it does provide a measure
that can predict the behaviour of that mineral in an industrial
Fig. 2. Cumulative copper recovery with time, as a function of pH, at a 30/70 setting.
quartz/kaolinite ration in the gangue phase. Fig. 4 shows the distributions of the zeta potential at each pH
value for kaolinite, chalcopyrite and the binary mixture of the
Table 2 two. Average values of the distributions are in line with zeta poten-
Flotation kinetic analysis, as a function of pH, at a quartz/kaolinite ratio of 30/70. tial results obtained by other authors for both chalcopyrite
(Fullston et al., 1999) and kaolinite (Johnson et al., 1998). The
pH Floating fraction Rate coefficient
(min1) graphs show that the distributions of the zeta potential are very
wide, covering the range from 0 to 70 mV. However, in each case,
Non (g) Fast (u) Slow (1  g  u) (%) Fast Slow
(%) (%) (kf) (ks)
the data show a uni-modal peak. The zeta distributions for kaolin-
ite and chalcopyrite completely overlap, which is consistent with
pH 4 0 0 100 – 0.12
pH 6 0 0 100 – 0.14
the two minerals having similar surface charge distributions. It is
pH 8 3 0 97 – 0.26 therefore not surprising that the zeta distribution similarly over-
pH 15 0 85 – 0.33 laps the two original distributions.
10 This result could possibly mean one of two things:

 The two minerals are not interacting, and there is no significant

slime coating taking place in the flotation system.
 The initial average distributions of zeta potential are too similar
to show significant differences between chalcopyrite and kao-
linite, meaning that this measurement is not adequate to pick
up the interaction.

Given that kaolinite edges and octahedral faces were estimated

to carry a positive charge in the acidic pH range (Johnson et al.,
1998), it is unlikely that no interaction is taking place. Therefore,
the most likely explanation is the second possibility.
Fig. 3. Crystallochemical structure of kaolinite, adapted from Flegmann and George
(1975).
If one assumes that slime coatings have a significant impact on
flotation performance in the tested system, one would expect it to
take place at the lower pH values (4 and 6), resulting in a decrease
in flotation performance. This was in fact the case (see Fig. 2). How-
The simple zeta potential measurements do provide an adequate ever, one should not ascribe the deterioration in flotation perfor-
description of the surface charge of chalcopyrite. However, the mance to slime coatings alone and the possibility of the flotation
same cannot be said for kaolinite. Kaolinite is an anisotropic performance being influenced by flotation pulp rheology must also
mineral, which means that it has distinctly differently charged be investigated.
140 E. Forbes et al. / Minerals Engineering 56 (2014) 136–144

Fig. 4. Zeta potential distributions for kaolinite, chalcopyrite and a binary mixture of the two as a function of pH.

3.3. Rheology effect

The samples of the tailings from each of the flotation tests were
analysed for their flow characteristics, in order to determine the ef-
fect of pulp rheology on flotation performance. The obtained data
were analysed using a Herschel Buckley model in order to obtain
flow characterisation indices, mainly the HB yield stress (sHB),
the flow coefficient (gHB) and the Herschel Buckley flow index (p).

3.3.1. Effect of quartz/kaolinite ratios

Fig. 5 and Table 3 show the effect of the increasing proportion of
kaolinite in the flotation pulp. As expected, in the absence of kao-
linite, the flotation pulp exhibits behaviour very close to that of a
Newtonian fluid, with minimal yield stress and HB indices (p)
approaching unity. Similarly, the flow coefficient (viscous parame-
ter) is relatively low. As the proportion of kaolinite in the flotation
pulp increases, the flow coefficient begins to increase and the sus-
pensions begin to deviate more significantly from Newtonian
behaviour. This is expected, as kaolinite particles have an irregular
(platy) shape, with larger effective particle volume fraction, which Fig. 5. Flow curves of flotation tailing samples at different quartz/kaolinite ratios in
leads to more viscous slurries. the gangue phase, at pH 8, fitted with the Herschel Buckley flow model.
In addition, due to the soft nature of the kaolinite mineral, the
increased proportion of kaolinite in the comminution stage results
in a significant decrease in the average particle size of the flotation Table 3
Regression parameters for the Herschel Buckley model fit, as a function of quartz/
pulp, as shown in Fig. 6. The significant shift towards fine particle
kaolinite ratios.
sizes further contributes to the increase in slurry viscosity (Farris,
1968). It must be noted at this point, that although the overall par- Quartz/kaolinite ratio 100/0 70/30 30/70 0/100

ticle size distribution of the flotation pulp markedly decreases in sHB (Pa) 0.07 0.13 0.05 0.28
the presence of kaolinite, this has no effect on the particle size dis- gHB (Pa s) 0.002 0.01 0.01 0.02
p 0.95 0.83 0.64 0.67
tribution of chalcopyrite particles, as this mineral was ground sep-
R2 1.00 0.86 0.99 0.99
arately for this very reason (see Section 2.3).
 E. Forbes et al. / Minerals Engineering 56 (2014) 136–144 141

Fig. 7. Flow curves of flotation tailing samples at different pH values, at a 30/70

Fig. 6. Cumulative particle size distributions of the flotation tailings samples at
quartz/kaolinite ratio, fitted with the Herschel Buckley flow model.
different quartz/kaolinite ratios in the gangue phase.

Table 4
Regression parameters for the Herschel Buckley model fit, as a function of pH.
The combined effect of the kaolinite particle shape and a fine pH 4 6 8 10
particle size has a profound effect of increasing slurry viscosity.
sHB (Pa) 0.60 0.52 0.13 0.04
The most extreme flow behaviour is observed when kaolinite com- gHB (Pa s) 0.14 0.05 0.01 0.002
prises 100% of the gangue, with a significant deviation from slurry p 0.46 0.60 0.83 1.01
Newtonian behaviour, which corresponds to the finest particle size R2 0.98 0.97 0.86 0.99
distribution (P80 of 15 lm) and 100% platy material in the gangue
phase.
Effect of pH This means that at pH 10, all the mineral surfaces present in the
Fig. 7 shows the effect of pH on the flow properties of the flota- flotation pulp carry a negative charge, which puts the suspension
tion pulp. Table 4 summarises the parameters of the Herschel in a state of dispersion. Similarly, at pH 8, the majority of surfaces
Buckley model fitted to the experimental data. The results show are still negatively charged, with the octahedral (O) faces of kaolin-
that at high pH (8 and 10) the flotation pulp has negligible yield ite approaching neutrality. This means that the mineral suspension
stress, with a very low flow coefficient (non Newtonian viscosity). remains largely dispersed.
The HB indices are very close to unity, indicating that the flow At lower pH values, quartz, chalcopyrite and kaolinite T faces
properties are close to Newtonian behaviour. This is indicative of remain negative, while the O faces and O–T edges of kaolinite
the fact that the suspension is in a state of dispersion, with little now carry a positive charge. This means that a significant amount
particle/particle interaction. of heterocoagulation is likely to take place, which is confirmed by
The situation changes dramatically in acidic pH, where the sus- the rheological measurements. Therefore, although the zeta poten-
pensions begin to deviate significantly from Newtonian behaviour. tial measurements presented in Section 3.3 have failed to show the
This is indicated by the HB indices deviating from unity and sus- degree of interaction between kaolinite and chalcopyrite, this
pensions now having a yield stress. Similarly, the flow coefficients interaction now becomes more obvious in light of the rheology
(indicators of fluid viscosity) increase by an order of magnitude measurements. This also serves as further indication of the pres-
compared to those obtained at alkaline pH conditions. This is ence of slime coatings at low pH values in the flotation pulp.
strongly indicative of the fact that the particles are interacting with
one another, forming an aggregated suspension network. 3.4. Correlations with flotation performance
This is consistent with what is known with regards to the sur-
face charge distribution of kaolinite, chalcopyrite and quartz. In The rheological parameters extracted from modelling flow
an alkaline pH range, both quartz and chalcopyrite carry a strong curves using the Herschel–Buckley model were used to identify
negative charge, with points of zero charge pH 2 (Smith and Scott, the correlations between flotation and rheological behaviour. The
1990) and 2.5 (Fullston et al., 1999) respectively. The surface two parameters used were the flow coefficient, gHB (viscous term)
charge distribution if kaolinite is more complex. It has been esti- and the HB index (deviation from Newtonian behaviour). Flotation
mated that the tetrahedral (T) face of kaolinite is negative in the takes place in high shear conditions, therefore the yield stress
majority of the pH range, while the octahedral (O) face, under- terms is not applicable, since it is only relevant to fluids that are
goes a change from positive to negative at approximately pH 9. close to a state of rest.
The (T–O) edge of kaolinite has been estimated to undergo a The flotation behaviour was characterised by the flotation rate
change from positive to negative at approximately pH 7 (Johnson coefficient pertaining to slow floating material (ks). Fig. 8 summa-
et al., 1998; Williams and Williams, 1977). It is important to note rises the effect that the change in both the pH (at 30/70 quartz/
that while these estimates are far from absolute, they nonetheless kaolinite ratio) and the proportion of quartz in the gangue (at pH
provide a sufficient guideline for gauging kaolinite coagulation 8) have on flotation performance. In this case the quartz/kaolin ra-
behaviour. tio is expressed as % quartz in the gangue phase. The figure shows
142 E. Forbes et al. / Minerals Engineering 56 (2014) 136–144

Fig. 9. Flotation rate coefficient for slow floating material as a function of Herschel
Fig. 8. Flotation rate coefficient for slow floating material as a function of pH and%
Buckley flow coefficient (gHB).
quartz in the flotation pulp.

that the best flotation performance was obtained at high quartz

concentrations at pH 8. The worst performance was obtained at
100% kaolinite in the gangue at pH 8, as well as at 70% kaolinite
at pH 4. It appears that the two effects are of the similar order of
magnitude.
This demonstrates that both pH and quartz/kaolinite ratio have
a strong effect on flotation performance; however, it needs to be
determined whether the change in performance can be attributed
to the increase in pulp viscosity or to slime coatings, or both.
Fig. 9 shows the effect of pulp viscosity (as expressed by the
flow coefficient, gHB) on flotation performance. It can be clearly
seen that a small change in pulp viscosity (0–0.03 Pas) results in
a dramatic decrease in flotation performance, when induced by a
change in the gangue composition (quartz/kaolin ratio effect). On
the other hand, a significantly larger variation in pulp viscosity
(0–0.1 Pas) results in a smaller change in flotation performance
when induced by a change in pH. In fact, two distinctly different
Fig. 10. Flotation rate coefficient for slow floating material as a function of the
viscosity conditions result in a practically identical flotation re- Herschel Buckley index.
sponse (30/70 quartz/kaolin ratio pH 4 and 0/100 quartz/kaolinite
ratio at pH 8). One of the major impacting factors will be pulp chemistry, spe-
Similar trends can be seen with the HB index, which indicates cifically the use of high ionic strength recycled water or even sea-
the deviation from Newtonian behaviour, as seen in Fig. 10. The water. Previous work has shown that the use of sea water actually
two effects (quartz/kaolinite ratio effect and pH effect) both result mitigates the detrimental effects of slime coatings in flotation of
in roughly linear relationships between flotation performance and nickel (Peng and Bradshaw, 2012). This was attributed to the com-
the HB index. However, the two relationships have distinctly dif- pression of the electrical double layers around particle surfaces,
ferent slopes and clearly arise due to two different effects. thus reducing the range of attractive electrostatic forces, prevent-
It has been demonstrated that the change in pulp pH has a ing coagulation. On the other hand, the reduction in double layer
strong effect on flotation pulp rheology. It has also been clearly repulsion also leads to an increase in the prevalence of attractive
demonstrated that pulp rheology has a strong effect on flotation van der Waals forces, in accordance with DLVO theory (Derjaguin
performance. However, pulp rheology alone cannot explain all and Landau, 1941; Verwey and Overbeek, 1948). This in turn leads
the differences seen in the test results. This means that the slime to an increase in particle/particle interactions, which leads to an in-
coatings are very likely present in this flotation system, and are crease pulp viscosity. It is not clear how these two effects would
at least partially responsible for a sharp decrease in flotation per- balance each other out in a clay-rich environment.
formance at low pH values. Another factor is the presence of composite mineral particles in
the flotation feed. The interactions between two fully liberated
3.5. Implications for practical flotation mineral particles are relatively easy to predict based on their sur-
face charge properties. However, how these interactions take place
The aim of the study was to decouple two specific flotation sub- within mineral composites which have highly irregular and non-
processes and attempt to enumerate their magnitudes. For this isotropic surface charge characteristics is a much more complex
reason the study was conducted using a highly controlled, artificial matter. A further complication is the additional effect of reagent
system, which consisted of pure minerals in a distilled water envi- coverage of mineral surfaces and how that affects their surface
ronment. In practical flotation applications, both the ore feed stock charge distribution and subsequent particle/particle interactions.
and pulp chemistry are likely to be substantially different. This These and a number of other factors need to be investigated further
leaves some interesting questions as to how these flotation sub- if one is to make the findings of this study more relevant to the
processes will be affected in an industrial setting. realities of flotation practice.
 E. Forbes et al. / Minerals Engineering 56 (2014) 136–144 143

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