Minerals Engineering 55 (2014) 190200

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

A preliminary rheological classication of phyllosilicate group

minerals q
Bulelwa Ndlovu a,b,, Elizaveta Forbes c, Saeed Farrokhpay a, Megan Becker b, Dee Bradshaw a,
David Deglon b
a
Julius Kruttschnitt Mineral Research Centre, University of Queensland, 40 Isles Road, Indooroopilly, 4068 QLD, Australia
b
Minerals to Metals Research Initiative, Department of Chemical Engineering, University of Cape Town, South Africa
c
CSIRO Process Science and Engineering, Clayton, Victoria, Australia

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

Article history: With the increased exposure to progressively complex ores, there is growing concern over the effects of
Available online 29 July 2013 phyllosilicate gangue minerals. These minerals present challenges during ore beneciation, with issues
such as reduced otation performance and complex tailings treatment arising. Often broadly classied
Keywords: as clays, the understanding of the distinct behaviour of phyllosilicates remains poor. This work focusses
Phyllosilicates on talc, illite and kaolinite, and forms part of an ongoing study which aims at investigating the entire
Iso-electric point phyllosilicate group, categorised as serpentine, micas; talc/pyrophillite, kaolinites, illites, smectites and
Point of zero charge
vermiculite. Using pure minerals belonging to each phyllosilicate type, a comprehensive surface charge
Illite
Kaolinite
and rheological analysis was conducted, incorporating their charge anisotropy and non-spherical mor-
Talc phology. The mineralogy was discussed, based on pre-existing knowledge of the minerals. Talc, kaolinite
and illite suspensions are characterised by high yield stresses and low viscosities, with differences in their
behaviour attributed to variations in charge anisotropy, aspect ratio and surface morphology. A compar-
ison with other phyllosilicates showed that muscovite (mica) results in the least rheologically complex
suspensions, while the brous nature of chrysotile (serpentine) leads to suspensions with the highest
yield stresses and viscosities. The other minerals demonstrate intermediate rheological behaviour. Such
a classication may be foundational to geometallurgical advances which can enable process performance
predictions based on mineralogy.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
With the rising global demand for minerals and the preferential
treatment of higher grade ores in previous years, the mining and
minerals processing industries are encountering progressively
complex, nely disseminated ores. These ores often require very
ne grinding in order to achieve sufcient liberation of the valu-
able minerals; rendering the recovery expensive given higher en-
ergy and capital costs. The processing of these ores is further
hindered by the presence of multiple phases of unwanted sur-
rounding phyllosilicate gangue material. Often broadly classied
as clays, this class of minerals is closely associated with several
processing issues such as reduced otation rates (Ralston and
Fornaserio, 2006), complex tailings treatment (de Krester et al.,
1997) and pumping challenges (Dunn, 2004). The extensive para-
genesis of phyllosilicates from weathering, sedimentation, diagen-
q
Paper was accepted for publication under the special issue Process Mineralogy.
Corresponding author at: Julius Kruttschnitt Mineral Research Centre, Univer-
sity of Queensland, 40 Isles Road, Indooroopilly, 4068 QLD, Australia. Tel.: +61 7
3365 5920; fax: +61 7 3365 5999.
E-mail addresses: b.ndlovu@uq.edu.au, ndlovu.bulelwa@gmail.com (B. Ndlovu).
esis and hydrothermal alteration, also means that they are
associated with a wide range of host rocks and mineral types.
These include volcanic volatile-rich carbonatites (e.g. smectites in
kimberlites along the Slave Cratons, Canada) (Boshoff et al.,
2007), ultrabasic nickel laterites (e.g. serpentinites in Norseman-
Wiluna Greenstone belt, Australia) (Senior and Thomas, 2005)
igneous intrusions (e.g. talc in the Bushveld Complex, South Africa)
(Schouwstra et al., 2000) and porphyry copper deposits (e.g. micas
in Escondida, Chile). Hence, the deleterious effects of phyllosilicate
minerals are ubiquitous throughout the minerals processing indus-
try, and an understanding of the specic effects of these minerals
on process performance is warranted.
The problems associated with phyllosilicate bearing ores are
physicochemical, and impact all facets of the mineral processing
circuit, with inefciencies arising during beneciation, dewatering
and disposal. The sticky nature of phyllosilicates renders the use
of conveyors, idlers and screens difcult, and the pump capacity
is signicantly reduced during materials handling. They also re-
strict percolation and limit recovery during leaching due to preg
robbing (Connelly, 2011a). In comminution, the grinding efciency
is lowered, making it necessary to operate the mill at lower
densities (Tangsathitkulchai, 2003). High phyllosilicate ores im-

0892-6875/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.06.004
 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
pede the otation kinetics, often manifest in higher reagent con-
sumption and poorer selectivity (Schubert and Bischofberger,
1978; Schubert, 2008; Bakker et al., 2009; Shabalala et al., 2011).
The risk of wall collapse and leakage is also enhanced during the
treatment of high phyllosilicate tailings, resulting from their poor
dewaterability (de Kretser and Boger, 1992).
Despite the abundance and adverse effects associated with phyl-
losilicate minerals, the industrys understanding of the processing
issues and potential solutions for treating phyllosilicate bearing ores
remains poor. In many cases, these problems are simply avoided by
either not processing the ores at all, or by some operations opting to
run at signicantly lower solids concentrations. Slurry dilution with
water is also frequently used to reduce medium viscosity through-
out the circuit (Connelly, 2011b). However, this puts a strain on an
increasingly scarce resource, particularly given many mines are
located in arid or desert regions. Indeed some operations have
approached the processing problems by nding chemical and engi-
neering solutions. These include the use of viscosity modiers such
as sodium pyrophosphate (TSPP) and caustic soda, as is done in
problematic Merrill Crowe gold plants (Connelly, 2011b). The
incorporation of multi-stage cyclones, scrubbers and hydrosizers
into the circuit is also used to remove the phyllosilicates upstream
(e.g. Mount Keith and Windimurra plants) (Senior and Thomas,
2005). However, such adjustments are not only highly capital inten-
sive, but they are also unsustainable as they may be unable to adapt
to variations in ore mineralogy. Other solutions include blending
phyllosilicate bearing ores with less problematic ores, but this ap-
proach is limited to concentrations below which the phyllosilicate
bearing ore starts to cause processing problems. This concentration
is strongly dependent on the phyllosilicate gangue minerals present
in the ore, and is the concentration beyond which those gangue min-
erals will cause problems. Such information has not been clearly de-
ned for each phyllosilicate mineral. A better fundamental
understanding, particularly of the rheological properties of the dif-
ferent phyllosilicates is required for long-term solutions to these
processing problems.
1.1. Rheology in the mineral processing industry
The importance of rheology in different aspects of the process-
ing circuit has been highlighted by several researchers (e.g. Yue
and Klein, 2004; Boger, 2009; Farrokhpay, 2012). The rheological
properties (simply dened as the suspension yield stress and vis-
cosity) are of great practical importance in many mineral process-
ing applications, as they are useful indicators of the degree of
aggregation and dispersion of particles within that suspension
(Luckham and Rossi, 1999; Johnson et al., 2000). Although the dis-
tinction between these two parameters is often difcult in practice,
they each represent different contributions towards overall sus-
pension behaviour. For example, the design and operation of
pumping systems of particulate suspensions are based on the vis-
cosity and yield stress values. In such applications, both the yield
stress and viscosity will have an impact on energy requirements,
with the yield stress having greater signicance in ensuring the
successful start-up and ow of a pumping system from a static
shut down condition (Sofr and Boger, 2002).
Most studies linking ore mineralogy and their rheological
behaviour in the mineral processing industry have been limited
to naturally occurring ores; creating an environment that is both
difcult to control and quantify, especially when studying the ef-
fects of the specic gangue minerals (Wiese et al., 2007; Burdukova
et al., 2008; Shabalala et al., 2011). Indeed, there has been an
extensive amount of research on the surface charge-rheology rela-
tionships of pure phyllosilicate minerals in the geotechnical, soil
and colloid science elds, with most studies conned to the clay
minerals kaolinite and montmorillonite. As a result, the analysis
191
of the surface charge properties of these minerals is well docu-
mented (Brandenburg and Lagaly, 1988; de Krester et al., 1997;
Greene et al., 2002; McFarlane et al., 2005; Tombcz and Szekeres,
2006; Vanerek et al., 2006; Bourg et al., 2007). However, most of
these studies have been angled towards other industries (e.g.
nanocomposite science, ceramic manufacturing, cosmetics, paper
making and soils decontamination), where the key issues are not
necessarily relevant within the minerals processing context. None-
theless, the research already conducted in these industries has
demonstrated the importance of the high surface area, asymmetric
particle shape, and anisotropic surface charge properties, to the
rheological properties of this group of minerals (Rand and Melton,
1977; James and Williams, 1982; Permien and Lagaly, 1994; John-
son et al., 1998; Luckham and Rossi, 1999; Tombcz and Szekeres,
2006). This forms a solid basis for the comprehensive analysis of
phyllosilicate mineral rheological behaviour within the minerals
processing industry, where to date, the study of these minerals in
their pure form is relatively new in its application.
1.2. Phyllosilicate mineralogy
Phyllosilicate minerals are built of varying proportions of tetra-
hedral (T) and octahedral (O) layers, resulting in minerals of rela-
tively similar structures but with different physical and chemical
properties. Consequently, there exist several different classica-
tions and denitions of the group in literature (e.g. Dixon and
Weed, 1989; Hurlbut and Sharp, 1998). The classication used in
the present work is in accordance with that by Deer et al. (1992),
and groups the minerals according to the proportion of T and O lay-
ers, as well as the interlayer connections that may occur between
successive structural units. This categorises the minerals into ser-
pentinite, talc/pyrophillite, mica, chlorite and clay mineral groups
as shown in Fig. 1. The clay minerals can be further classied into
non-swelling (kaolinites and illites), and swelling clays (smectites
and vermiculites). The rheological properties of suspensions of
pure chrysotile (serpentine group), muscovite (mica group) and
vermiculite (vermiculites) have previously been investigated, dem-
onstrating their complex ow behaviour relative to a non-phyllos-
ilicate mineral, quartz (Ndlovu et al., 2011a,b). The present study
now analyses the illite, talc and kaolinite groups.as part of an ongo-
ing study aimed at characterising the entire phyllosilicate group on
the basis of their rheological properties.
Illite exists as a common accessory mineral in many sedimen-
tary rocks, where it is commonly associated with micas and smec-
tites (Klein and Hurlbut, 1993). Studies in the oil sands industry
have demonstrated that the addition of illite does not have a signif-
icant effect on bitumen recovery (Kasongo et al., 2000). However, it
is through its characteristic degradation to smectites, and its occur-
rence as interstratied illitesmectite that it reduces bitumen
recovery (Wallace et al., 2004). Talc is a gangue mineral, commonly
encountered in complex sulphide ores and in ores of the platinum
group metals (e.g., the Bushveld Merensky, South Africa and the
Sudbury Igneous Complex, Canada) (Schouwstra et al., 2000; Hol-
well et al., 2006; Lotter et al., 2008). In the processing of these ores,
the reporting of MgO to the otation concentrate has been attrib-
uted to magnesium bearing minerals such as talc and pyroxene.
Being naturally hydrophobic, talc readily reports to the otation
concentrate, effectively increasing the viscosity in the froth phase
and altering the froth stability. This results in a reduction in both
pay metal grade and recovery. Furthermore, the alteration of
pyroxenites to talc often occurs by the formation of talc rims on
pyroxene, albeit in minor amounts, enhancing the oatability of
pyroxene and increasing the amount of natural otable gangue
(NFG) in the concentrate (Becker et al., 2009). Elevated quantities
of talc (and MgO) grades in the concentrate can cause furnace
operational problems during smelting and downstream processing.
192 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
Fig. 1. A classication of phyllosilicate group minerals.
This is due to increased liquidus temperatures, often resulting in
smelting penalties for mineral processing companies (Beattie
et al., 2006). Due to its high commercial use in the ceramics indus-
try, kaolinite has been mined for many years, with challenges such
as pumping difculties and adherence to conveyors occurring
(Connelly, 2011a). Kaolinite is also a common gangue mineral in
many porphyry copper deposits and Australian hematite/goethite
iron ores. The high alumina content in these ores is often detrimen-
tal to the blast furnace and sinter plant operations due to the prev-
alence of highly viscous slags and high coke rates (Ma et al., 2009)
requiring the furnace to operate at higher temperatures and short-
ening the campaign life of the furnace (Jung et al., 2004).
This study seeks to investigate and compare the surface charge
and rheological properties of suspensions of pure talc, illite and
kaolinite minerals. The surface charge properties are investigated
by comparing conventional electrokinetic zeta potential measure-
ments to potentiometric titrations. The morphological properties
of the minerals are also discussed, based on existing knowledge
of the minerals. The ow behaviour is investigated in terms of
the Bingham yield stress and Bingham viscosity values, with the
time dependent (thixotropic/rheopetic) properties not being eval-
uated in this case. The rheological properties of talc, kaolinite
and illite suspensions are then compared with the rheological
properties of other phyllosilicate mineral suspensions (chrysotile,
muscovite, vermiculite and montmorillonite), whose surface
charge and rheological properties have been previously analysed.
Such a comparison provides a preliminary rheological classication
of the phyllosilicate group.
2. Theory
2.1. The mineralogy of talc, kaolinite and illite minerals
The fundamental unit of illite [K2Al4(Si8Al2)O20(OH)4] is similar
to that of muscovite, in that it comprises an O (gibbsite (Al(OH)3)
layer, co-ordinated between two inward pointing T layers, in a T
OT conguration. Alternating TOT layers are held together by
layers of interlayer K+ ions, which balance a negative charge aris-
ing from to the isomorphous substitution of higher valence Si4+
cations with Al3+ ions of a lower valence in the tetrahedral layer.
However, illite contains fewer interlayer cations than muscovite,
such that bonding is weaker, and there is consequently less regu-
larity of stacking (Deer et al., 1992). Nonetheless, illite bears a
close resemblance to muscovite and tends to exist as extensive
sheets of high aspect ratio with molecularly smooth surfaces
(Deer et al., 1992). Talc [Mg6(Si8O20)(OH)4] is also comprised of
an O (brucite (Mg(OH)2)) layer, sandwiched between two T lay-
ers, with successive TOT units held together by van der Waals
interlayer bonds. This results in the stacking of layers and the
long, thin platy morphology of talc sheets. Unlike illite and talc,
kaolinite [Al4(Si4O10)(OH)8] consists of a T and gibbsite O layer
in a 1:1 ratio. Successive TO layers are superimposed and held
 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200 193

together by weak van der Waals forces, forming extended sheets.
Although kaolinite has a platy structure similar to talc and illite,
kaolinite platelets tend to have an increased thickness relative
to their lateral extent and are generally characterised by relatively
lower aspect ratios (Grim, 1968; Deer et al., 1992; Tateyama et al.,
1997; de Kretser et al., 1998).
p.z.c, however, is most likely a net point of zero charge,
representing a pH at which the positive charge on one basal plane,
balances out the negative charge on another plane in a particle. The
ambiguity around these parameters, for anisotropically charged
minerals, requires their combined use for a comprehensive estima-
tion of their degree of charge anisotropy.

2.2. The surface charge properties of phyllosilicates

3. Experimental methods

There is still much debate regarding the derivation of charges

3.1. Materials and mineral characterisation
on the edges and faces of phyllosilicate minerals. The edges are be-
lieved to carry a pH dependent charge, determined by the proton-
Illite, talc, kaolinite and quartz samples were used in this study.
ation and deprotonation of exposed aluminol and silanol
All samples were supplied in a pre-ground form. Talc from New
amphoteric groups (Rand and Melton, 1977; Luckham and Rossi,
York, USA and illite from Rochester, USA were both supplied by
1999; Nasser and James, 2006). Although the hydrolysis of silicon
Wards Minerals. Northern Queensland kaolinite Q38 was obtained
in the surface plane may result in a slight pH dependent charge
from Granville, NSW, provided by Unimin Australia Limited. The
on the basal T faces (Scales et al., 1990; Tateyama et al., 1997),
samples were screened and the 75 lm fraction used for all exper-
the charge is assumed to be largely due to the aforementioned iso-
imental work. This ensured that the illite, talc and kaolinite sam-
morphous substitution of higher valence ions with ions of a lower
ples fell within the same size range of previously studied
valence. This results in a charge imbalance in the T plane, leaving
phyllosilicates for a comparative analysis in which size was not a
the faces with a negative charge (van Olpen, 1951; van Olpen,
factor. This also served as a means to remove any coarse non-phyl-
1977; Okuda et al., 1969; Zhou and Gunter, 1992; Johnson et al.,
losilicate material which may have been present in the samples.
1998). This charge separation between the different planes results
The mineralogy of the minerals was determined using Powder
in the characteristic charge anisotropy of phyllosilicate minerals.
X-ray diffraction (XRD). Samples were micronized in ethanol and
The surface charge properties of kaolinite and talc have been
dried overnight at 40 C prior to measurement. XRD spectra were
studied extensively; with most studies using the electrokinetic
obtained using a PANalytical XPert Pro MPD powder diffractome-
zeta potential measurement as a sole means to characterise charge
ter (manufactured by PANalytical, Netherlands), equipped with an
(Johnson et al., 1998; Morris et al., 2002; Furstenau and Huang,
XCelerator detector. Samples were run with xed divergence and
2003; Bremmell and Addai-Mensah, 2005). However, the applica-
anti-scatter slits, using Co Ka radiation. PANalyticals HighScore
tion of this technique to phyllosilicate minerals is compromised
Plus Software (v3.0d) was used for phase identication and quan-
by its inherent assumption of uniform spherical morphology. It
tication using the Rietveld renement method. XRD mineralogy
has been acknowledged that extra precaution needs to be taken
showed that talc had a purity of 94 wt%, containing 4 wt% quartz
when analyzing the charge properties of these minerals (Rowlands
and trace amounts of serpentine and anatase. The illite sample
and OBrien, 1995; Rasmusson et al., 1997; Miller et al., 2007). The
contained 5 wt% muscovite, while kaolinite had a purity of
discrepancies between the true point of zero charge (p.z.c) (pH at
92.4 wt%, with 5 wt% quartz, 2.1 wt% illite/muscovite and trace
which the charge on the particle surface is zero) and the iso-elec-
amounts of anatase. In all cases, the impurities comprised mainly
tric point (i.e.p) (pH at which zeta potential is zero) for anisotropic
of quartz and muscovite. These minerals have previously been
particles have been demonstrated and discussed in greater detail
shown not to result in rheologically complex suspension behav-
by Alvarez-Silva et al. (2010) and Ndlovu et al. (2011a,b).
iour, particularly at such low concentrations (Ndlovu et al.,
Ideally, correction of the electrokinetic zeta potential measure-
2011a,b). Therefore, the colloidal behaviour could still be assumed
ment, and accurate estimation of the overall surface charge of
to be largely due to the bulk mineralogy i.e. talc, illite and kaolinite.
anisotropically charged minerals, would require knowledge of
A wet size analysis of each mineral was obtained using a Mal-
the relative charge density and surface area of the different planes.
vern Mastersizer (Malvern, UK). A summary of the P50 values of
Such information is attainable for minerals with a sheet-like struc-
the talc, kaolinite and illite samples, used in this study, is given
ture, allowing perfect cleavage into a molecularly smooth surface
in Table 1. The details of the other phyllosilicates, discussed and
for use in streaming potential measurements, as is often observed
used for comparison in this paper, are also given. These values
with illite and muscovite (Scales et al., 1990). However, this is
were considered adequately similar for the purposes of this study,
more complicated for other phyllosilicates of low crystallinity
and for comparison with the other phyllosilicates.
(e.g. poorly ordered stepped structures) or extreme morphology
The poor surface crystallinity of kaolinite Q38 has been studied
(e.g. brous chrysotile). Some researchers have also attempted to
using the Hinckley index calculation and SEM analysis and has
calculate the charge distribution of asymmetric particles from zeta
been reported previously (Zbik and Smart, 1998; Du et al., 2010).
potential data, using an estimation of the aspect ratio (Delgado
The poor crystallinity of this kaolinite has been shown to have a
et al., 1986; Williams and Williams, 1978; OBrien and White,
signicant effect on its settling and colloidal characteristics and
1978). However, these too have often relied on an assumption of
perfect planes, as well as the accurate estimation of the aspect ratio
Table 1
using scanning electron microscopy (SEM) analysis, which on its A summary of the P50 values for talc, kaolinite and illite. The p50 values of previously
own does not provide a sufciently adequate quantitative esti- studied phyllosilicates are also given.
mate. In the absence of the knowledge of these quantities, the elec-
Mineral Type P50 (lm) References
trokinetic measurement merely provides an average zeta potential
value which can be very misleading if viewed in isolation. Further- Talc Phyllosillicate 13.5 Present work
Kaolinite Phyllosillicate 14 Present work
more, it is not exactly clear what the nature of this average is Illite Phyllosillicate 11 Present work
since for anisotropically charged minerals, the iso-electric point Chrysolite Phyllosillicate 0.1  100 Ndlovu et al. (2011a)
(i.e.p) determined by electrophoresis and the point of zero charge Muscovite Phyllosillicate 14 Ndlovu et al. (2011b)
(p.z.c) determined by titration, are not the same. The i.e.p, in this Vermiculite Phyllosillicate 16 Ndlovu et al., 2011b
Montmorillonite Phyllosillicate 13 Ndlovu et al. (2011a,b)
case may merely represent an apparent i.e.p, dependent only on
Quartz Tectosillicate 12 Ndlovu et al. (2011b)
the plane of measurement and with no physical implication. The
194 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
this is likely to affect its rheological behaviour (Du et al., 2010).
SEM analysis was conducted to conrm that a smooth surface
structure could not be assumed for the kaolinite Q38 sample used
in this study. A Nova Nano scanning electron microscope (manu-
factured by FEI, Oregon, USA) was used to investigate the surface
morphology, with the SEM image shown in Fig. 2. Indeed Q38
has a poor crystallinity, with a high frequency of ragged, broken
nanosized edges across the basal planes. A smooth surface struc-
ture cannot be assumed for this kaolinite.
3.2. Rheology measurements
Rheological measurements were performed using an AR1500EX
(Thermal Analysis, Germany), with a standard 4-panel vaned rotor
geometry. This geometry is more suitable for the analysis of suspen-
sions within the minerals processing industry, as it is less suscepti-
ble to artefacts arising from large particle sizes, and results in less
sample disturbance and thixotropic breakdown during insertion
(Nguyen and Boger, 1987; Barnes and Carnali, 1990; Barnes and
Nguyen, 2001; Estelle et al., 2008). It also eliminates variable gap ef-
fects which commonly arise when dealing with non-Newtonian u-
ids with a yield stress (Keentok et al., 1985; Yan and James, 1997).
The rheological analysis of the pure mineral suspensions was con-
ducted as a function of solids concentration, within the limitations of
each mineral (1025% solids by volume for talc and kaolinite, 1035%
solids by volume for illite, and 1040% solids by volume for quartz).
The suspensions were prepared using 0.01 mol dm3 NaCl as a back-
ground electrolyte. Stress/strain tests were conducted in a shear rate
controlling regime, with an upward and downward ramp within the
range 0400 s1, over a 60 s time period. No signicant hysteresis
was observed between the upward and downward ramps.
The resulting rheograms demonstrated pseudo-plastic behav-
iour. The Bingham model was used to estimate the suspension
Bingham yield stress and plastic viscosity in each case. The Bing-
ham model is represented by Eq. (1), where s is the shear stress
(Pa), s0 is the Bingham yield stress (Pa), gp is the Bingham viscosity
(Pa s) and c is the shear rate (s1).
Bingham Plastic model : s s0 gpc 1
3.3. Zeta potential measurements
Zeta potential measurements were performed using a ZetaP-
robe Analyzer (Colloidal Dynamics, USA). For each mineral, a 5%
Fig. 2. High resolution SEM image showing the rough surface structure of Q38, with
the formation of micro-islands and exposed broken edges on the basal surfaces.
solids by weight suspension was prepared in 250 mL
0.01 mol dm3 NaCl solution. The suspension was stirred to ensure
homogeneity throughout the measurement. The pH was adjusted
using an automatic titration, with solutions of 0.2 mol dm3 and
0.2 mol dm3 NaOH and HCl used as pH modiers. The measure-
ments were taken through an upward and downward ramp, within
the range of pH 210. No signicant hysteresis was observed in
each case. The ZetaProbe Analyzer uses the electrophoretic mobil-
ity and Smoluchowskis equation (Dukhin and Derjaguin, 1976) to
calculate the zeta potential at each pH condition. The pH at which
the zeta potential is zero is the iso-electric point (i.e.p).
3.4. Potentiometric titration measurements
The point of zero charge (p.z.c) of each mineral was determined
using the RobertsMular potentiometric titration. This method
works on a principle of ion exchange, with the pH measured at dif-
ferent ionic strengths of the solution (Mular and Roberts, 1966).
Suspensions consisting of 1.00 g samples of each mineral in
50 ml of 0.001 mol dm3 NaCl were prepared, with each suspen-
sion adjusted to a different pH value (ranging from pH 3 to
pH 11). The ionic strength of each solution was then raised from
0.001 mol dm3 to 0.1 mol dm3 by the addition of the appropriate
amount of dry NaCl crystals. The pH of the resulting solution was
measured to give a nal pH. The difference in the initial and nal
pH values (DpH) is plotted against the nal pH. The pH value at
which DpH is zero indicates the point of zero charge (p.z.c) of each
mineral.
4. Results and discussion
4.1. The surface charge properties of talc, kaolinite and illite
The electrokinetic zeta potential measurements of talc, kaolin-
ite and illite were measured as a function of pH over the range
pH 2pH 10, with the results presented in Fig. 3. The results show
that all the minerals have an apparent negative zeta potential in
the majority of tested pH ranges, exhibiting a trend similar to that
of the negatively charged silica basal faces. This was expected for
talc and illite, whose silica T layer makes up two thirds of the min-
eral structure. Moreover, the typical high aspect ratio of talc and il-
lite enhances the likelihood of measurement along the faces
relative to the edges. In the case of kaolinite, which comprises T
and O layers in equal proportions, an equal contribution from both
layers, manifest in a gradual change from positive to negative zeta
potential, may be expected. However, this was not the case, with a
reported negative zeta potential throughout the tested range.
Nonetheless, this trend was similar to typical observations in pre-
vious studies on kaolinite (Williams and Williams, 1978; Kaya and
Yukselen, 2005; Miller et al., 2007).
The electrokinetic iso-electric points (i.e.p) were measured at
pH 2.2 and pH 2.3 for talc and illite respectively. This is within
the range of reported values i.e. pH 2pH 3 for talc (Steenberg
and Harris, 1984; Wang and Somasundaran, 2005; Burdukova
et al., 2007) and pH 2pH 4 for illite (Ohtsubo and Yoshimura,
1991). No i.e.p was detected for kaolinite, which is in agreement
with reported zeta potential curves for this kaolinite Q38 sample
(Du et al., 2010). However, i.e.p values of kaolinite from other
deposits have generally been reported in the range circa 3.5 (John-
son et al., 1998).
Potentiometric titrations were conducted over the range of pH
2pH 11, with the titration curves of talc, kaolinite and illite shown
in Fig. 4. The results show a net p.z.c. at pH 3.1 for kaolinite, pH 6.8
for illite, and pH 8.4 for talc. At these conditions, there exists an
equal charge balance between positively and negatively charged
planes. In each case, pH conditions below the p.z.c. represent the
 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
Fig. 3. The electrophoretic zeta potential curves of talc, kaolinite and illite. The
error bars represent the 95% condence interval of the average values.
range in which the particle surface carries an overall positive
charge, while conditions above the p.z.c are representative of a
negative particle surface charge.
A comparison of the i.e.p and p.z.c values of each mineral gives
an indication of the degree of charge anisotropy. For isotropically
charged minerals, the i.e.p and p.z.c are identical and occur at
the same pH value (Subanna et al., 1998; Johnson et al., 2000; Alva-
rez-Silva et al., 2010). A large divergence between the values is
indicative of a high degree of charge anisotropy and deviation from
isotropic mineral behaviour. In each case, there is a difference be-
tween the measured i.e.p and p.z.c values, demonstrating that the
minerals do indeed differ from isotropically charged minerals.
Although no i.e.p value was measured for kaolinite here, a compar-
ison of reported values (circa pH 3.5) shows similarity with the
Fig. 4. The potentiometric titration curves of talc, kaolinite and illite. The error bars
represent the 95% condence interval of the average values.
195
measured p.z.c (pH 3.1). This indicates that, although the faces
may carry a negative charge, it may only be slightly negatively
charged. In the case of illite, a clear disparity between the i.e.p
(pH 2.2) and p.z.c (pH 6.8) was observed, indicating that the faces
carry a stronger negative charge. This was also observed for talc,
with showed the largest deviation between the i.e.p (pH 2.3) and
p.z.c (pH 8.4). On this basis, the combined results suggest that
the degree of charge anisotropy decreases in the order
talc > illite > kaolinite.
4.2. Proposed particle interactions at natural pH (pH 8pH 9)
Contemporary approaches to phyllosilicate colloid and rheolog-
ical behaviour are based on the DLVO (Derjaguin and Landau,
1941; Verwey and Overbeek, 1948) theory, where net interaction
is assumed to be a result of competing electrical double layer
repulsion and van der Waals attractive forces. These determine
whether the mineral suspensions will be stabilised (in sol form)
or coagulated (in a gel form) (Nasser and James, 2006). Phyllosili-
cate particles with a platy morphology can have a number of com-
binations of orientation when in suspension. Although there has
been considerable research into this area, there has been no agree-
ment on the interpretation of the types of particle interaction, and
there exist differing schools of thought on the dominance of one
type of particle orientation over the other.
Conventional theories based on van Olpens original model (van
Olpen, 1951; van Olpen, 1977) suggest that platelets can associate
in edgeedge (EE), edgeface (EF) and faceface (FF) congurations,
with the formation of each dependent on the balance of electro-
static interaction between the planes of adjacent particles. Under
acidic conditions, positively charged edges and negatively charged
faces will mutually attract, giving rise to EF (card house) occula-
tion. At conditions close to the edge i.e.p, EE interaction is likely. Be-
yond this, both the edges and faces are negatively charged and the
particles are dispersed. High electrolyte concentrations (at acidic
and alkaline conditions) result in double layer compression or ion
shielding of the surface charges, causing particles to adhere to
one another along their basal faces in FF (card pack) ocs (James
and Williams, 1982; Luckham and Rossi, 1999; Nasser and James,
2006). FF association gives thicker aggregates of higher density,
whereas EF and EE associations lead to more rheologically complex,
lower density aggregates of larger volume (Rand and Melton, 1977;
Raveendran and Amirtharajah, 1989; Mahmood et al., 2001). This
theory is most valid for platy minerals with a low aspect ratio,
where the edge surface area is such that the edge charge contrib-
utes towards the overall charge. However, by considering differ-
ences in plate thickness, asymmetry and aspect ratios of
phyllosilicates, this cannot be assumed in all cases. For particles
with a high lateral extent relative to thickness (high aspect ratio),
the edge surface area is small compared to the face. In such cases,
it has been hypothesised that any charge development on the faces
spills over on the edges, effectively screening out and edge charge
effects. By this theory, the most important aspect of colloidal
behaviour is FF agglomeration, and the effective volume fractions
due to rotation are seen to be dominant (Scales et al., 1990 Tatey-
ama et al., 1997; de Kretser et al., 1998). Changes in rheological
behaviour with pH are attributed to subtle misalignment of FF
agglomeration. The assumption here is that the phyllosilicate parti-
cles exist as perfectly cleaved extensive, smooth, long, thin plates.
More recently, studies by Zbik and Smart (1998); Du et al.
(2010) and Zbik et al. (2010) have demonstrated the importance
of surface crystallinity towards particle interactions and colloidal
behaviour. In this case, the assumption of ideal long, thin platy
morphology is challenged; primarily due to the unpredictable nat-
ure of mineral formation such as sedimentation, fragmentation or
lateral intergrowth, rendering the formation of molecularly
196 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
smooth minerals less likely. This has given rise to a different school
of thought on the likely modes of particle interaction, where it can-
not be assumed that the extensive faces are at or that the edges
are insignicant. Instead, the rough surface structures with ex-
posed broken edges are thought to provide adsorption sites and
predominantly promote EE bridging occulation, with some EF
aggregation also likely (Du et al., 2010).
The authors consider all aspects as signicant to overall suspen-
sion behaviour, and this paper attempts to explain the rheological
behaviour of talc, kaolinite and illite using a combination of these
theories. Rheological tests on the pure mineral suspensions were
conducted at the natural pH which was in the range of pH 8pH
9. This is a common pH condition at which many otation opera-
tions are conducted.
The test pH (pH 9) is far from the measured p.z.c of kaolinite
(pH 3.1), which represents the pH at which there is an equal bal-
ance of positive and negative charges. The edge p.z.c of kaolinite
has been estimated using a variety of techniques, and has been re-
ported to be in the range pH 5.8pH 7.5 (Rand and Melton, 1977;
James and Williams, 1982; Gupta et al., 2011). Above this pH, the
edge (and the particle) carries an overall negative charge. There-
fore, at pH 9, it is less likely that both positive and negative charges
exist. Moreover, pH 9 lies above the measured p.z.c, which is also
indicative of an overall negative surface charge. If the effects of
charge anisotropy are signicant in this case, then the possible
modes of particle association are a combination of a dispersed sys-
tem (due to repulsive forces between negatively charged edges and
faces) and weak EE interactions (due to near neutral edges and
negative faces). This would result in suspensions with very low
yield stresses. However, it has been shown that kaolinite Q38 is a
low crystalline kaolinite with a high frequency of broken edges
on the rough surfaces (Fig. 2). This is likely to result in strong EE
bridging associations, with the possibility of some EF interactions
also occurring between exposed edges and faces. If the surface
crystallinity is indeed of importance to the colloidal behaviour, this
would result in suspensions of signicantly higher yield stresses
than in the dispersed state as would be dictated by the surface
charge properties.
Conversely, due to its structural similarity to micas, illite tends
to exhibit a smooth high aspect ratio sheet like structure (Deer
et al., 1992). It is this same property that makes these minerals
amenable to direct force measurements, in a manner in which less
ordered phyllosilicates cannot be used (Scales et al., 1990). By con-
sidering charge effects, the measured p.z.c (pH 6.8) is close to the
test pH. An overall negative charge is expected at pH 9, with a
likely combination of dispersed particles and weak EE aggregation
in suspension. However, due to its typical high aspect ratio, FF
agglomeration may be the most important aspect contributing to-
wards illite suspension behaviour, with the possible transition to
EE structures due to progressive FF layering and increasing thick-
ness of the edges at pH 9. For talc, on the hand, the test pH is close
to the measured net p.z.c (pH 8.4), indicating that there is a close
balance between positive and negative charges of faces and edges.
This is likely to result in a combination of EE and EF coagulation,
manifest in high yield stresses.
A summary of the measured iso-electric points, points of zero
charge and the inferred aggregation is given in Table 2.
Table 2
A summary of the measured iso-electric points, points of zero charge and the inferred
aggregation mechanisms of talc, kaolinite and illite.
i.e.p p.z.c Inferred aggregation at pH 89
Illite 2.2 6.8 Weak EE, FF, dispersion
Talc 2.3 8.4 EE and FF
Kaolinite 3.1 EE and FF
4.3. Pure mineral suspension rheology
Having estimated the possible particle interactions for each
mineral at usual process pH conditions, it is now possible to corre-
late this with the rheological properties (yield stress and viscosity)
to get a better understanding of the most likely type of particle
packing in the pure mineral suspensions at these conditions. The
suspension rheograms were modelled, using the Bingham approx-
imation, to estimate the Bingham yield stresses and viscosities.
Fig. 5 shows the typical pseudo plastic behaviour observed for talc,
kaolinite and illte suspensions at 20% solids by volume, with the
Bingham model tted in each case.
The rheological properties of pure suspensions of talc, kaolinite
and illite were compared with the rheological properties of pure
quartz suspensions. Quartz is a non phyllosilicate mineral, whose
isotropic charge and near spherical morphology makes its use, as
a mineral with contrasting properties, favourable. The benign rhe-
ological properties of quartz suspensions at pH 9 have been well
established. At these conditions, quartz particles are strongly neg-
atively charged and well dispersed. Such suspensions are charac-
terised by very low yield stresses, close to zero (Ndlovu et al.,
2011a,b).
A comparison of the Bingham yield stresses of talc, kaolinite, il-
lite and quartz suspensions, as a function of solids concentration, is
given in Fig. 6. To reiterate, the yield stress is indicative of the
strength and complexity of the free forming structures that would
be observed in suspension. It can be used to estimate energy
requirements in applications such as materials handling or ota-
tion, prior to pumping or agitation. Among other applications in
minerals processing, it can also be related to the particleparticle
and particle-occulant binding and settling rates which occur prior
to the raking process in settling beds and tailings dams. In this
application, it can be used to estimate settling rates, occulant
requirements and bed densities (Du et al., 2010).
The results show a characteristic increase in Bingham yield
stress with solids concentration. This is a result of an increasing
likelihood of particle interaction, which enhances the complexity
of structures formed in suspension (Prestidge, 1997). Talc and kao-
linite suspensions are characterised by higher Bingham yield
stresses than illite suspensions, which in turn have higher Bingham
yield stresses than quartz suspensions. This suggests that at
Fig. 5. Some typical rheograms that were observed for talc, kaolinite and illite
suspensions at 20% solids by volume. The Bingham model is tted to estimate the
Bingham yield stress and viscosity values in each case.
 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200 197

Fig. 6. A comparison of the Bingham yield stresses of talc, kaolinite, illite and quartz
suspensions. The error bars represent the 95% condence interval of the average
values.
Fig. 7. A comparison of the Bingham viscosities of talc, kaolinite, illite and quartz
suspensions. The error bars represent the 95% condence interval of the average
equivalent solids concentrations of each mineral, the degree of values.
complexity in the structures that form in suspension, may decrease
The results show that all the phyllosilicates are characterised by
in the order of talc = kaolinite > illite > quartz, under normal pro-
relatively low viscosities, as they fall within the range of quartz
cessing conditions. Based on the differences in their charge anisot-
suspensions. This indicates that at high shear conditions, talc, kao-
ropy, such behaviour is expected for talc and illite. The high degree
linite and illite are not likely to present viscous effects when pres-
of charge anisotropy in talc as derived by differences in the i.e.p
ent in suspension. Nonetheless, clear differences in the viscosity
and p.z.c (relative to illite and kaolinite) has already been dis-
values of the different minerals are observed. The differences can
cussed, and this corresponds to the proposed edgeedge and
be correlated to the ease of particle alignment in the direction of
edgeface interactions likely to occur in suspension. Illite has a
shear. The introduced shear force induces restructuring of the
lower degree of charge anisotropy, and while this may play a role
agglomerates into delaminated platelets. This property is used in
in the observed lower yield stresses, it is likely that the typical high
the raking process in assisting dewatering, by rearrangement of
aspect ratio and effective volume fraction of particles are impor-
EF and EE structures with high retention properties, to higher den-
tant factors in the formation of illite structures in suspension,
sity FF structures with improved settling rates (Du et al., 2010). The
based on knowledge of its typical smooth surface morphology. In
results show that the Bingham viscosities of talc and kaolinite are
this case, it is likely that the yield stresses are further depressed
similar, with few discernible differences. Both minerals have high-
by the re-alignment into faceface agglomerates which are less
er viscosities than illite suspensions. It is suggested that the reason
rheologically complex. Based solely on differences in charge
for these differences is that the resistance to collapse of pre-exist-
anisotropy, one would expect kaolinite suspensions to exhibit rhe-
ing EF and EE structures in kaolinite and talc suspensions is greater
ological behaviour more closely representing illite, as this would
than in illite, where it is likely that the alignment of proposed
likely result in dispersed suspensions. Lower yield stresses would
existing FF aggregates is merely improved. This resistance may
also be observed, if the assumptions of high particle asymmetry
be enhanced by poor mineral crystallinity.
and crystallinity were true, as this would result in a transition to
better faceface agglomeration as proposed for illite. However,
the elevated yield stresses observed indicate that kaolinite exists
in more complex structures than illite; a likely consequence of 4.4. Rheological classication of phyllosilicate group minerals
irregularities and poor crystallisation, promoting the formation of
structures which exist in several randomised alignments, including The rheological properties of talc, kaolinite and illite can now be
combinations of EE and EF agglomeration. compared to other phyllosilicates which have been previously ana-
A comparison of the Bingham viscosities of talc, kaolinite, illite lysed in a similar manner. Using minerals that are representative of
and quartz suspensions is given in Fig. 7. The efcient operation of each group, a preliminary rheological classication has been con-
many unit operations rests on the knowledge of medium viscosity. ducted. Fig. 8 gives a comparison of the Bingham yield stresses of
For example, grinding efciency, throughput, product neness and the phyllosilicate group of minerals. The details on the analyses
energy efciency can all be optimised through the monitoring of of the other minerals can be found in previous publications (Las-
viscous effects in stirred mills (Boger, 1999; Shi and Napier-Munn, kowski et al., 2010; Ndlovu et al., 2011a, b). Perhaps the most rel-
2002). In otation, the prediction of cell hydrodynamics is depen- evant outcome of such a comparison, to the minerals processing
dent on several factors including slurry viscosity (Schubert and industry, is the critical concentration of each phyllosilicate min-
Bischofberger, 1978; Furstenau and Huang, 2003; Schubert, 2008; eral. This is the concentration beyond which each mineral is likely
Bakker et al., 2009). Medium viscosity values are also important to present intractable processing problems, and can be estimated
in predicting the pumping conditions for the preferred semi-dry from the concentration beyond which exponential increments in
disposal and materials transportation during tailings treatment the suspension yield stress and viscosity are observed (shown for
(Nguyen and Boger, 1998). chrysotile in Fig. 8).
198 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
Fig. 8. A comparison of the Bingham yield stresses of phyllosilicate group minerals.
The error bars represent the 95% condence interval of the average values.
Chrysotile (serpentine group) results in suspensions with a crit-
ical concentration as low as 0.7% solids by volume, while montmo-
rillonite (smectite group) suspensions become problematic at
concentrations of circa 4% solids by volume. The pseudo plastic
behaviour observed at these unusually low concentrations can be
attributed to the brous morphology of chrysotile and the high
swelling capacity of montmorillonite. The other minerals, all with
different variations in platy morphology, have higher critical con-
centrations: kaolinite and talc 20% solids by volume; vermiculite
(vermiculites) 25% solids by volume; illite 30% solids; musco-
vite  > 35% solids by volume. The differences observed in this case
are related to variations in properties such as charge anisotropy,
swelling ability, crystallinity and surface morphology.
A comparison of the viscosities further demonstrates the dra-
matic effects of the brous morphology of chrysotile resulting in
signicantly higher suspension viscosities (Fig. 9a). Fig. 9b shows
the viscosities of the other minerals on a smaller scale. Although
the platy minerals do not result in suspensions with extremely
high viscosities, these are all higher than in quartz suspensions;
Fig. 9. A comparison of the Bingham viscosities of phyllosilicate group minerals. The error bars represent the 95% condence interval of the average values.
demonstrating the rheological complexity in phyllosilicate miner-
als relative to non-phyllosilicates.
It must be noted that aqueous dispersions of montmorillonite
exhibit unique thixotropic rheological properties (Barnes, 1997;
de Kretser et al., 1998; Kelessidis et al., 2007). The behaviour is
classical, in that a dramatic change from solid-like (gel) to liquid-
like (sol) state is observed on agitation, with reformation on rest-
ing. In the gelled (solid) state, the suspension exhibits a nite yield
stress and behaves as an elastic solid. In the liquid state, the sus-
pension behaves as a shear thinning liquid which can still exhibit
a yield stress, dependent upon solids concentration. Typically,
structural breakdown occurs at a rate dependent on the intensity
of the applied shear. Montmorillonite is also non-typical in that
the breakdown timescale is very rapid on the application of shear,
while the recovery process is orders of magnitude longer (de Kret-
ser et al., 1998). Therefore, the mechanical behaviour of montmo-
rillonite suspensions is much more complicated than other
phyllosilicates. Indeed, the thixotropic behaviour of montmorillon-
ite is of most relevance to the problems observed during the pro-
cessing of ores containing montmorillonite. It is also useful for a
wide variety of technological applications such as drilling muds,
paints, dyestuffs and cosmetics. For uniformity purposes, residence
times were minimised and thixotropic properties fell outside the
scope of the study. However, it is acknowledged that, in reality, dif-
ferent rheological behaviour could be observed, dependent upon
the applied shear and resting time.
5. Conclusions
The study has aimed at characterising the colloidal behaviour of
phyllosilicate minerals in terms of their surface charge (i.e.p and
p.z.c) and resulting rheological behaviour (yield stress and viscos-
ity). This has been done with a long term view of understanding
the impact of these minerals within the minerals processing
context.
Observed variations in the rheological behaviour of talc, kaolin-
ite and illite have been discussed in terms of conventional and non-
conventional perspectives on aggregation mechanisms, highlight-
ing the complexity of phyllosilicate behaviour. The study has
shown that the interpretation of phyllosilicate colloidal behaviour
may differ from mineral to mineral, and the analytical approach of
 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
these minerals should not be limited to one single school of
thought Indeed, the exclusion of certain factors such as surface
morphology and crystallinity can have a signicant impact on
interpretation. Phyllosilicate minerals have to be treated individu-
ally, and a detailed knowledge of the associated physical properties
(such as particle size, specic surface area, aspect ratio, surface
charge, surface morphology and crystallinity) is required for a
comprehensive understanding of the particle interactions. The pre-
dictions on talc, kaolinite and illite suspensions have been pro-
posed based on a combination of existing knowledge of the
minerals and the results of this study, There is a need for more
comprehensive characterisation efforts to isolate the causes of
the observed colloidal properties.
The rheological behaviour of phyllosilicate minerals is much
more complicated than that of simple isotropic minerals. This
has been demonstrated by the higher suspension yield stresses
and viscosities observed in pure talc, kaolinite and illite, relative
to pure quartz. In general, talc and kaolinite suspensions are char-
acterised by higher yield stresses than illite. However, the minerals
all form suspensions with relatively low viscosities, and they are
unlikely to present viscous effects during beneciation. It is worth
noting that while the study has assumed mono minerallic behav-
iour, based on the bulk mineralogy of the samples used, the effects
of the impurities must be evaluated for synergistic/ antagonistic
effects.
This study has facilitated the classication of the entire phyllos-
ilicate group in terms of suspension yield stress and viscosity.
Within the phyllosilicate group, suspensions containing chrysotile
are likely to present the most rheological difculties, while mica-
ceous and illite bearing ores are not likely to be problematic. Ores
containing vermiculite, kaolinite and talc are not likely to present
viscosity related issues at high shear conditions. The rheology of
suspensions containing smectites (such as montmorillonite) is sub-
ject to residence times and the thixotropic effects which exacer-
bate the rheological properties of such suspensions.
In reality, phyllosilicate minerals exist as composites in much
more complex mineral systems and there remains a large scope
for further investigation of phyllosilicates within the mineral pro-
cessing industry.
Acknowledgements
This has been a collaborative study, facilitated by the Minerals
to Metals Initiative at the University of Cape Town (UCT), with
nancial support from the SarChi Chair in Minerals Beneciation;
the Mineral Chemistry Research Alliance (MiCRA) at the Julius
Kruttschnitt Minerals Research Centre (JKMRC), University of
Queensland, and a UBC-UCT student exchange collaboration, with
funding from BHP.
References
Alvarez-Silva, M., Uribe-Salas, A., Mirnezami, M., Finch, J.A., 2010. The point of zero
charge of phyllosilicate minerals using the MularRoberts titration technique.
Minerals Engineering 23, 383389.
Bakker, C.W., Meyer, C.J., Deglon, D.A., 2009. Numerical modelling of non-
Newtonian slurry in a mechanical otation cell. Minerals Engineering 22,
944950.
Barnes, H.A., 1997. Thixotropy a review. Journal of non-Newtonian Fluid
Mechanics 70, 133.
Barnes, H.A., Carnali, J.O., 1990. The vane-in-cup as a novel rheometer geometry for
shear thinning and thixotropic materials. Journal of Rheology 34, 841866.
Barnes, H.A., Nguyen, Q.D., 2001. Rotating vane rheometry a review. Journal of
non-Newtonian Fluid Mechanics 98, 114.
Beattie, D.A., Huynh, L., Kaggwa, G.N., Ralston, J., 2006. The effect of polysaccharides
and polyacrylamides on the depression of talc and the otation of sulphide
minerals. Minerals Engineering 19, 598608.
Becker, M., Harris, P.J., Wiese, J.G., Bradshaw, D.J., 2009. Mineralogical
characterisation of naturally oatable gangue in Merensky Reef ore otation.
International Journal of Mineral Processing 93, 246255.
199
Boger, D.V., 2009. Rheology and the resource industries. Chemical Engineering
Science 64, 45254536.
Boger, D.V., 1999. Rheology and the minerals industry. Mineral Processing and
Extractive Metallurgy Review 20, 125.
Boshoff, E.T., Morkel, J., Vermaak, M.K.G., Pistorius, P.C., 2007. Kimberlite
degradation: the role of cation type. Minerals Engineering 20, 13511359.
Bourg, I.C., Sposito, G., Bourg, A.C.M., 2007. Modelling the acid-base surface
chemistry of montmorillonite. Journal of Colloid and Interface Science 312,
297310.
Brandenburg, H., Lagaly, G., 1988. Rheological properties of sodium
montmorillonite dispersions. Applied Clay Science 3, 263279.
Bremmell, K.E., Addai-Mensah, J., 2005. Interfacial chemistry mediated behaviour of
colloidal talc dispersions. Journal of Colloid and Interface Science 283, 1173
1182.
Burdukova, E., Becker, M., Ndlovu, B., Mokgethi, B., Deglon, D.A., 2008. Relationship
between slurry rheology and its mineralogical content. In: Wang, D.D., Xao, S.C.,
Wang, F.L., Cheng, Z.U., Long, H, (Eds.), Proceedings of the 24th International
Minerals Processing Congress. China Scientic Book Service Co., Ltd. Beijing, pp.
21692178.
Burdukova, E., Becker, M., Bradshaw, D.J., Laskowski, J.S., 2007. Presence of negative
charge on the basal planes of New York talc. Journal of Colloid and Interface
Science 315, 337342.
Connelly, D., 2011a. High clay ores a mineral processing nightmare. In: Australian
Journal of Mining, July/August edition: Mineral Processing-Flotation and
Separation, pp. 2829.
Connelly, D., 2011b. High clay ores a mineral processing nightmare Part 2. In:
Australian Bulk Handling Review: September/October edition, pp. 7881.
Deer, W.A., Howie, R.A., Zussman, J., 1992. An Introduction to Rock Forming
Minerals. Longman Scientic & Technical, Essex.
Delgado, A., Gonzalez-Caballero, F., Bruque, M., 1986. On the zeta potential and
surface charge density of montmorillonite in aqueous electrolyte solutions.
Journal of Colloid and Interface Science 113, 203211.
de Kretser, R.G., Scales, P.J., Boger, D.V., 1998. Surface chemistryrheology inter
relationships in clay suspensions. Colloids and Surfaces A: Physicochemical and
Engineering Aspects 137, 307316.
de Krester, R.G., Scales, P., Boger, D.V., 1997. Improving clay-based tailings disposal:
a case study on coal tailings. AIChE Journal 43, 18941903.
de Kretser, R.G., Boger, D.V., 1992. The compression, dewatering and rheology of
slurried coal mine tailings. In: Proceedings of the 5th Australian Coal Science
Conference, Newcastle, Australia, pp. 422429.
Derjaguin, B.V., Landau, L., 1941. Theory of stability of strongly charged lyophobic
sols and the adhesion of strongly charged particles in solution of electrolytes.
Acta Physiochem 14, 633662.
Dixon, J.B., Weed, S.B., 1989. Minerals in soil environments. Second ed., In: Dixon,
J.B.,Weed, S.B. (Eds.), Soil Science Society of America, Madison, Wisconsin, USA.
Du, J., Morris, G., Pushkarova, R.A., Smart, R.S.C., 2010. Effect of surface structure of
kaolinite on aggregation, settling rate and bed density. Langmuir 26, 13227
13235.
Dukhin, S.S., Derjaguin, B.V., 1976. Electrophoresis. Academy of Science, Moscow.
Dunn, F., 2004. A study of the relationship between various slurry material
characteristics and the ow behaviour of co-disposed Kimberlite tailings upon
deposition, MSc dissertation. University of Witwatersrand, Johannesburg, South
Africa.
Estelle, P., Lanos, C., Perrot, A., 2008. Processing the couette viscometry data using a
bingham approximation in shear rate calculation. Journal of non-Newtonian
Fluid Mechanics 154, 3138.
Farrokhpay, S., 2012. The importance of rheology in mineral otation: a review.
Minerals Engineering 3638, 272278.
Furstenau, D.W., Huang, P., 2003. Interfacial phenomena involved in talc otation.
In: Proceedings of the 23rd Int Minerals Processing Congress. Document
Transformation Technologies, Cape Town.
Greene, R.S.B., Eggleton, R.A., Rengasamy, P., 2002. Relationships between clay
mineralogy and the hardsetting properties of soils in the Carnarvon
horticultural district of Western Australia. Applied Clay Science 20, 211
223.
Gupta, V., Hampton, M.A., Stokes, J.R., Nguyen, A.V., Miller, J.D., 2011. Particle
interactions in kaolinte suspensions and corresponding aggregate structures.
Journal of Colloid and Interface Science 359, 95103.
Holwell, D.A., McDonald, I., Armitage, P.E.B., 2006. Platinum group mineral
assemblages in the Platreef at the Slandsloot Mine, in the Northern Bushveld
Complex, South Africa. Mineralogical Magazine 70, 83101.
Hurlbut, C.S., Sharp, W.E., 1998. Danas Minerals and How to Study Them (After
Edward Salisbury Dana), fourth ed. John Wiley & Sons, Inc., New York, pp. 248
257.
James, A.E., Williams, D.J.A., 1982. Flocculation and rheology of kaolinite/quartz
mixtures. Rheologica Acta 21, 176183.
Johnson, S.B., Franks, G.V., Scales, P.J., Boger, D.V., Healy, T.W., 2000. Surface
chemistryrheology relationships in concentrated mineral suspensions.
International Journal of Mineral Processing 58, 267304.
Johnson, S.B., Russell, A.S., Scales, P.J., 1998. Volume fraction effects in shear
rheology and electroacoustic studies of concentrated alumina and kaolin
suspensions. Colloids and Surfaces A: Physicochemical and Engineering
Aspects 141, 119130.
Jung, I.H., Decterov, S.A., Pelton, A.D., 2004. Critical thermodynamic evaluation and
optimisation of the FeOFe2O3MgOSiO2 system. Metallurgical and Materials
Transactions, B 35B, 877889.
200 B. Ndlovu et al. / Minerals Engineering 53 (2014) 190200
Kasongo, T., Zhou, Z., Xu, Z., Masliyah, J., 2000. Effect of clays and calcium ions on
bitumen extraction from Athabasca oil sands using otation. The Canadian
Journal of Chemical Engineering 78, 678680.
Kaya, A., Yukselen, Y., 2005. Zeta potential of soils with surfactants and its relevance
to electrokinetic remediation. Journal of Hazardous Materials 120, 119126.
Keentok, M., Milthorpe, J.F., ODonovan, E., 1985. On the shearing zone around
rotating vanes in plastic liquids: theory and experiment. Journal of non-
Newtonian uid mechanics 17, 2335.
Kelessidis, V.C., Christidis, G., Makri, P., Hadjistamou, V., Tsamantaki, C., Mihalakis,
A., Papanicolaou, C., Foscolos, A., 2007. Gelation of water-bentonite suspensions
at high temperatures and rheology with lignite addition. Applied Clay Science
36, 221231.
Klein, C., Hurlbut, C.S., 1993. Manual of Mineralogy (after J.D. Dana), 21st ed. Wiley
& Sons, New York.
Laskowski, J.S., Ndlovu, B., Kilickaplan, I., 2010. Rheology of aqueous suspensions of
needle-like mineral particles. In: Pawlik, M. (Ed.), Proceedings of the 8th UBC-
McGill-UA International Symposium on the fundamentals of mineral
processing: rheology and processing of ne particles. The Canadian Institute
of Mining, Metallurgy and Petroleum, Vancouver, pp. 193203.
Luckham, P.F., Rossi, S., 1999. The colloidal and rheological properties of bentonite
suspensions. Advances in Colloid and Interface Science 82, 4392.
Lotter, N.O., Bradshaw, D.J., Becker, M., Parolis, L.A.S., Kormos, L.J., 2008. A
discussion of the occurrence and undesirable otation behaviour
orthopyroxene and talc in the processing of mac deposits. Minerals
Engineering 21, 905912.
Ma, X., Bruckard, W.J., Holmes, R., 2009. Effect of collector, pH and ionic strength on
the cationic otation of kaolinite. International Journal of Minerals Processing
93, 5458.
Mahmood, T., Amirtharajah, A., Sturm, T.W., Dennett, K.E., 2001. A micromechanics
approach for attachment and detachment of assymetric particles. Colloid
Surfaces 177, 99110.
McFarlane, A., Bremmell, K., Addai-Mensah, J., 2005. Microstructure, rheology and
dewatering behaviour of smectite dispersions during orthokinetic occulation.
Minerals Engineering 18, 11731182.
Miller, J.D., Nalaskowski, J., Abdul, B., Du, H., 2007. Surface characteristics of
kaolinite and other selected two layer silicate minerals. The Canadian Journal of
Chemical Engineering 85, 617624.
Morris, G.E., Fornaserio, D., Ralston, J., 2002. Polymer depressants at the talcwater
interface: adsorption isotherm, microotation and electrokinetic studies.
International Journal of Minerals Processing 67, 211227.
Mular, A.L., Roberts, R.B., 1966. A Simplied method to determine isoelectric points
of oxides. Transactions of the Canadian Institute of Mining and Metallurgy 69,
438439.
Nasser, M.S., James, A.E., 2006. Settling and sediment bed behaviour of kaolinite in
aqueous media. Separation and Purication Technonology 51, 1017.
Ndlovu, B., Forbes, E., Becker, M., Deglon, D., Franzidis, J.P., Laskowski, J.S., 2011a.
The effects of chrysotile mineralogical properties on the rheology of chrysotile
suspensions. Minerals Engineering 24, 10041009.
Ndlovu, B., Becker, M., Forbes, E., Deglon, D., Franzidis, J.P., 2011b. The inuence of
phyllosilicate mineralogy on the rheology of mineral suspensions. Minerals
Engineering 24, 13141322.
Nguyen, Q.D., Boger, D.V., 1998. Application of rheology to solving tailings disposal
problems. International Journal of Mineral Processing 54, 217233.
Nguyen, Q.D., Boger, D.V., 1987. Characterisation of yield stress uids with
concentric cylinder viscometers. Rheological Acta 26, 508515.
Ohtsubo, M., Yoshimura, A., 1991. Particle interaction and rheology of illiteiron
oxide complexes. Clays and Clay Minerals 39, 347354.
OBrien, R.W., White, L.R., 1978. Electrophoretic mobility of a spherical colloidal
particle. Journal of the Chemical Society, Faraday Transactions II 74, 16071626.
Okuda, S., Inoue, K., Williamson, W.O. ,1969. Negative surface charges of
pyrophillite and talc. In: Heller, L. (Ed.), Proceedings of the International. Clay
Conference. Israel University Press, Tokyo, Japan, pp. 3141.
Permien, T., Lagaly, G., 1994. The rheological and colloidal properties of bentonite
dispersions in the presence of organic compounds IV. Sodium montmorillonite
and acids. Applied Clay Science 9, 251263.
Prestidge, C.A., 1997. Rheological investigations of ultrane galena particle slurries
under otation-related conditions. International Journal of Mineral Processing
51, 241254.
Ralston, J., Fornaserio, D. 2006. Effect of MgO minerals on pentlandite otation. In:
Onal, G., Acarkan, N., Celik, M.S., Arslan, F., Atesok, G., Guney, A., Sirkeci, A.A.,
Yuce, A.E., Perek, K.T. (Eds.), Proceedings of the 23rd International Minerals
Processing Congress. Promed Advertising Ltd., Istanbul, pp. 750755.
Rand, B., Melton, I.E., 1977. Particle interactions in aqueous kaolinite suspensions: I.
Effect of pH and electrolyte upon the mode of particle interaction in homoionic
sodium kaolinite suspensions. Journal of Colloid and Interface science 60, 308
320.
Rasmusson, M., Rowlands, W., OBrien, R.W., Hunter, R.J., 1997. The dynamic
mobility and dielectric response of sodium bentonite. Journal of Colloid and
Interface Science 189, 92100.
Raveendran, P., Amirtharajah, A., 1989. Role of short-range forces in particular
detachment during lter backwashing. Journal of Environmental Engineering
121, 860868.
Rowlands, W.N., OBrien, R.W., 1995. The dynamic mobility and dielectric response
of kaolinite particles. Journal of Colloid and Interface Science 175, 190200.
Scales, P.J., Greiser, F. And, Healy, T.W., 1990. Electrokinetics of the muscovite mica
aqueous solutioninterface. Langmuir 6, 582589.
Schubert, H., 2008. On the optimization of hydrodynamics in ne particle otation.
Minerals Engineering 21, 930936.
Schubert, H., Bischofberger, C., 1978. On the hydrodynamics of otation machines.
International Journal of Minerals Processing 5, 132142.
Schouwstra, R.P., Kinloch, E.D., Lee, C.A., 2000. A short geological review of the
Bushvelt complex. Platinum Minerals Review 44, 3339.
Senior, G.D., Thomas, S.A., 2005. Development and implementation of a new
owsheet for the otation of a low grade nickel ore. International Journal of
Mineral Processing 78, 4961.
Shabalala, N.Z.P., Harris, M., Leal Filho, L.S., Deglon, D.A., 2011. Effect of slurry
rheology on gas dispersion in a pilot scale mechanical otation cell. Minerals
Engineering 24, 14481453.
Shi, F.N., Napier-Munn, T.J., 2002. Effects of slurry rheology on industrial grinding
performance. International Journal of Mineral Processing 65, 125140.
Sofr, F., Boger, D.V., 2002. Environmental rheology for waste minimization in the
minerals industry. Chemical Engineering Journal 86, 319330.
Steenberg, E., Harris, P.J., 1984. Adsorption of carboxymethyl cellulose, guar gum
and starch onto talc, sulphides, oxides and salt type minerals. South African
Journal of Chemistry 37, 8590.
Subbanna, M., Pradip and Malghan, S.G., 1998. Shear yield stress of occulated
aluminazirconia mixed suspensions: effect of solid loading, composition and
particle size distribution. Chemical Engineering Science 53, 30733079.
Tangsathitkulchai, C., 2003. The effect of slurry rheology on ne grinding in a
laboratory ball mill. International Journal of Mineral Processing 69, 2947.
Tateyama, H., Scales, P.J., Ooi, M., Nishimura, S., Rees, K., Healy, T., 1997. X-ray
diffraction and rheology study of highly ordered clay platelet alignment in
aqueous solutions of sodium tripolyphosphate. Langmuir 13, 24402446.
Tombcz, E., Szekeres, M., 2006. Surface charge heterogeneity of kaolinite in
aqueous suspension in comparison with montmorillonite. Applied Clay Science
34, 105124.
Vanerek, A., Alince, B., van de Ven, T.G.M., 2006. Delamination and occulation
efceincy of sodium activated kaolin and montmorillonite. Colloids and
Surfaces A: Physicochem Engineering Aspects 273, 193201.
Van Olpen, H., 1951. Rheological phenomina of clay sols in connection with the
charge distribution on the micelles. Discussions of the Faraday Society 11, 82
84.
Van Olpen, H., 1977. Clay Colloid Chemistry, second ed.. John Wiley & Sons, New
York, pp. 318.
Verwey, E.J.W., Overbeek, J.T.G., 1948. Theory Stability of Lyophobic Solids. Elsevier,
Amsterdam.
Wallace, D., Tipman, R., Komishke, B., Wallwork, V., Perkins, E., 2004. Fines/water
interactions and consequences of the presence of degraded illite on oil sands
extractability. The Canadian Journal of Chemical Engineering 82, 678680.
Wang, J., Somasundaran, P., 2005. Adsorption and conformation of carboxymethyl
cellulose at solidliquid interfcaes using spectroscopic, AFM and allied
techniques. Journal of Colloid and Interface Science 291, 7583.
Wiese, J.G., Harris, P., Bradshaw, D.J., 2007. The response of sulphide and gangue
minerals in selected Merensky ores to increased depressant dosages. Minerals
Engineering 20, 886995.
Williams, D.J.A., Williams, K.P., 1978. Electrophoresis and zeta potential of kaolinite.
Journal of Colloid and Interface Science 65, 7987.
Yan, J., James, A.E., 1997. The yield surface of viscoelastic and plastic uids in a vane
viscometer. Journal of non-Newtonian uid mechanics 70, 237253.
Yue, J., Klein, B., 2004. Inuence of rheology on the performance of horizontal
stirred mills. Minerals Engineering 17 (1112), 11691177.
Zbik, M., Raftery, N.A., Smart, R.S.C., Frost, R.L., 2010. Kaolinite platelet orientation
for XRD and AFM applications. Applied Clay Science 50, 299304.
Zbik, M., Smart, R.S.C., 1998. Nanomorphology of kaolinnites: comparative SEM and
AFM studies. Clay and Clay Minerals 46, 153160.
Zhou, Z., Gunter, W.D., 1992. The nature of the surface charge of kaolinite clays.
Clays and Clay Minerals 40, 365368.