Minerals Engineering 114 (2017) 26–36

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

Slime coatings in froth flotation: A review MARK

a,b a b b,⁎
Yuexian Yu , Liqiang Ma , Mingli Cao , Qi Liu
a
School of Chemical & Environmental Engineering, China University of Mining & Technology (Beijing), Beijing 100083, China
b
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Slime coating is a significant phenomenon in froth flotation. The adverse effects of slime coating, by which a
Froth flotation value mineral is covered by slimes and prevented from direct contact with collectors and/or air bubbles, have
Slime coatings been recognized for decades. It happens ubiquitously in the flotation of various minerals, including sulfide
Heteroaggregation minerals (sphalerite, galena, chalcopyrite, pentlandite, etc.), oxide minerals (hematite, wolframite, scheelite,
Clay minerals
etc.), salt minerals (fluorite, potash, etc.), coal and bitumen. In this paper, an attempt was made to present a
comprehensive review of slime coatings in froth flotation including particle adhesion mechanisms, slime coating
measurement techniques, influencing factors, control methods and mitigation measures. It was shown that the
classical Derjaguin–Landau–Verwey–Overbeek (DLVO) theory, and the extended DLVO theory, are the main-
stream mechanisms underpinning slime coatings. According to their sources, the slimes can originate from
gangue minerals and value-gangue composite particles, or from colloidal compounds formed during ore dressing
due to grinding, mineral surface oxidation and chemical precipitation. The origin and property of the slimes, the
types and concentrations of electrolytes, and solution pH are the main factors influencing slime coatings. Current
techniques employed to study slime coatings are mainly focused on the interactions between two particles in a
static and ideal environment, which cannot account for slime coatings under commercial froth flotation con-
ditions. Physical mitigation methods such as ultrasonic treatment and high intensity conditioning are often more
effective than chemical mitigation methods that usually entail the use of dispersants. Gaps in the existing lit-
erature are discussed and potential research directions are suggested.

1. Introduction
With decreasing grade and increasing complexity of mineral dis-
semination, ores have to be ground to very fine sizes to liberate value
minerals for recovery. In the process, large quantities of fine gangue
minerals are generated due to either the fine grind or the clayey nature
of the ore (Kusuma et al., 2014; Liu and Peng, 2014; Wang et al.,
2015a). These fine gangue mineral particles are collectively called
“slimes”, and they exert many detrimental effects on froth flotation, a
mineral separation technique most widely used today. The slimes in-
crease reagent consumption and pulp viscosity, and are liable to entrain
into froth product (Arnold and Aplan, 1986a; Brown and Smith, 1954;
Burdon et al., 1976; Forbes et al., 2014; Mishra, 1978; Wang et al.,
2015b; Yu et al., 2015). The slimes can also coat the surfaces of value
minerals and significantly change the flotation behavior of the latter.
Intuitively, the slimes coated on value mineral surface form a hydro-
philic “armor” preventing the value mineral from direct contact with
collectors and/or air bubbles, lowering flotation recovery (Arnold and
Aplan, 1986a, 1986b; Bandini et al., 2001; Forbes et al., 2014; Jorjani
et al., 2011; Jowett et al., 1956; Liu et al., 2002; Tabatabaei et al., 2014;
Wang et al., 2015b; Yao et al., 2016a; Zhang and Peng, 2015).
A search of open literature shows that slime coatings are ubiquitous
in the flotation of various minerals, including sulfide minerals (spha-
lerite, galena, chalcopyrite, pentlandite, etc.), oxide minerals (hematite,
wolframite, scheelite, etc.), salt minerals (fluorite, potash, etc.), coal
and bitumen. In most cases, the slimes are composed of kaolinite,
montmorillonite, illite, serpentine, quartz, dolomite, and smithsonite.
In the early days, researchers attributed slime coatings to electrostatic
attraction because the slimes and value minerals carried opposite
charges (Bankoff, 1943; Fuerstenau et al., 1958; Iwasaki et al., 1962;
Sun, 1943). However, the ensuing research showed that slimes could
coat the value mineral surface even when they carried the same sign of
charges (Oats et al., 2010; Wang et al., 2013; Yao et al., 2016b; Yu
et al., 2015). The classical Derjaguin–Landau–Verwey–Overbeek
(DLVO) theory has been used to understand the slime coating phe-
nomenon from a chemical standpoint (Chen et al., 1999a; Oats et al.,
2010; Yao et al., 2016a; Yu et al., 2015), although some attributed slime
coatings to grinding (Bandini et al., 2001; Holuszko et al., 2008). Much

⁎
Corresponding author.
E-mail address: qi.liu@ualberta.ca (Q. Liu).

http://dx.doi.org/10.1016/j.mineng.2017.09.002
Received 9 January 2017; Received in revised form 26 July 2017; Accepted 14 September 2017
0892-6875/ © 2017 Elsevier Ltd. All rights reserved.
Y. Yu et al.
of the reported research on slime coatings was focused on identifying
slime coatings, but few studies confirmed the existence of slime coat-
ings unequivocally. Furthermore, the purpose of studying slime coat-
ings is to control it, but so far, few effective ways have been reported
and implemented to minimize the adverse effects caused by slime
coating either in laboratory or in commercial flotation operations.
It is therefore imperative to understand and consequently to control
slime coatings in froth flotation. In the following, the open literature on
slime coatings in froth flotation is reviewed with an objective to provide
a comprehensive overview of the slime coatings in froth flotation and to
seek measures that can be taken to mitigate the slime coatings problem
in mineral flotation.
2. Mechanisms of slime coatings
2.1. DLVO theory
The classical DLVO theory, which sums the universal van der Waals
interaction with electrostatic interactions, has been widely used to ex-
plain the aggregation and dispersion of colloidal particles. In the mi-
nerals industry, researchers used DLVO theory to explain the interac-
tion between mineral particles in water (Behrens et al., 2000; Celik and
Bulut, 1996; Elimelech et al., 2013; Yoon and Mao, 1996). Oats et al.
(2010) calculated the interaction forces between coal and clay particles
using DLVO theory and reported that the calculation could account for
the experimental observations in the coal and clay particles suspen-
sions. Their results showed that the van der Waals attraction governed
the clay coatings. Similarly, Chen et al. (1999a) proposed that van der
Waals force was the dominant force of adhesion for gangue slimes at-
tachment to coarse particles.
There are two methods to calculate the Hamaker constant for the
van der Waals interaction of mineral 1 with mineral 2 across a water
medium. One is the Hamaker approach (microscopic), and the other is
the Lifshitz approach (macroscopic). The Hamaker approach is based
on the assumption of molecular pairwise additivity and gives a good
approximation for gases and often for media interacting across a va-
cuum or low-pressure gas, but it often fails to predict interactions across
condensed phase media like water. In the latter case, the Lifshitz theory,
which is based on quantum physics, is more applicable and it often
predicts values of the Hamaker constant significantly higher than the
Hamaker approach (Berg, 2010). DLVO energy curves between coal and
clay particles calculated by the two methods are different and even
contradictory (Oats et al., 2010; Zhang et al., 2009). For example, the
total DLVO energy between coal and clay particles calculated by Zhang
et al. (2009) and Yu et al. (2015) using the Hamaker approach was
positive in the whole range of separation distance, so the coal and clay
particles repelled each other, which could not explain the clay coatings
on coal surface. However, the DLVO calculation based on Lifshitz ap-
proach by Oats et al. (2010) showed that the van der Waals attraction
was strong enough to overcome the electrical double-layer repulsion,
resulting in a net attraction between coal and clay particles at a close
separation distance.
When calculating the electrostatic force between particles, zeta
potentials obtained from experimental measurements are often used.
However, clay particles have a plate-like structure with basal and edge
surfaces that carry different charges (Gupta et al., 2010). The measured
overall zeta potentials are misleading because they are not a true
measure of either the basal face potential or the edge potential. In ad-
dition, it is recognized that the classical DLVO theory fails when the
surfaces are very hydrophilic or very hydrophobic, necessitating con-
sideration of additional interaction forces such as hydration and hy-
drophobic force (Derjaguin and Churaev, 1989). The summation of
electrostatic interaction, van der Waals interaction and other interac-
tions such as hydration and hydrophobic interactions results in the
extended DLVO theory (EDLVO) (Lyklema, 2005), and it is often con-
sidered to better represent particle interactions. For instance, Yao et al.
27
Minerals Engineering 114 (2017) 26–36
(2016a, 2016b) reported that the interaction behaviors between mag-
nesite, dolomite and quartz are better explained by the EDLVO theory
than by the classical DLVO theory.
2.2. Deposition of colloidal compounds formed during grinding
Comminution of ores is almost always carried out before froth flo-
tation. Researchers noticed that slime coatings may be a result of
comminution (especially grinding), through the formation of a hydro-
philic colloidal slime layer on the value mineral surface during com-
minution. For example, sphalerite can be heavily oxidized during dry
grinding when the mill is open to air, forming smithsonite (ZnCO3)
slime coating on the surface of sphalerite, depressing the hydro-
phobicity of sphalerite (Holuszko et al., 2008). Steel grinding media are
routinely used in flotation circuit, and the formation of colloidal iron
oxide/hydroxides originating from the grinding media can form slime
coatings on galena surface through van der Waals and electrostatic
interactions governed by DLVO theory, exerting a significant detri-
mental effect on the flotation performance of galena (Bandini et al.,
2001; Learmont and Iwasaki, 1984). The compounds formed during
grinding are often reported as colloidal particles, and the colloidal
particles may experience a stronger attraction to the mineral surface
due to the compaction or impact caused by the grinding media. Fayed
and Otten (2013) reported that plate-like agglomerates can be formed
due to the compaction action caused by grinding media. From a prac-
tical perspective, more attention should be focused on slime coatings
caused by deposition of colloidal compounds during grinding as it is a
common step preceding flotation.
2.3. Chemical precipitation
Some researchers reported that slimes were bound to the mineral
surfaces through a chemical reaction (Dorenfeld, 1953; Taggart et al.,
1934). Ma et al. (2014) reported that calcium ions released by the
hydrolysis of gypsum reacted with Na2CO3 to form calcium carbonate
which coats the surface of a molybdenum-tungsten mineral, resulting in
a lower flotation recovery (Ma et al., 2014). Through solution specia-
tion modeling, Wang et al. (2013) proposed that precipitation of
chrysotile, dolomite, hydroxyapatite and chrysotile may have occurred
on the surface of coal particles. These are hydrophilic precipitates and
likely have a negative effect on coal flotation (Wang et al., 2013). The
type of the chemical precipitation is closely related to the solution
chemistry of the pulp, and the conditions for precipitate formation and
its coating mechanism need further research.
3. Slime coatings detection and quantification techniques
It is suggested that slime coatings can be detected by indirect
macroscopic methods such as a reduction of flotation recovery, a
change in particle settling rates, and a change in rheological properties
of slurry. However, these methods may not give an accurate account of
true slime coatings (Arnold and Aplan, 1986a; Xu et al., 2003; Zhang
et al., 2016), as there can be more than one reason for the observed
macroscopic behaviors. For example, clay minerals can affect froth
flotation through slime coating but also through other ways, such as
affecting froth stability, changing pulp rheology and covering bubble
surfaces, that also lower flotation recovery of value mineral (Cruz and
Peng, 2016; Farrokhpay and Bradshaw, 2012; Forbes et al., 2014;
Ndlovu et al., 2015; Ndlovu et al., 2014). Thus, it can be misleading
simply attributing a lowering in flotation recovery of value minerals to
slime coatings. Similarly, the settling of value mineral particles may
have a “mopping” effect that can trap clay particles even when hetero-
aggregation does not occur. In addition, the solid concentration and the
particle network structure in a slurry can significantly affect its rheo-
logical properties and transform a Newtonian fluid to a non-Newtonian
fluid even when aggregation does not occur (Cruz et al., 2013; Cruz
Y. Yu et al.
et al., 2015). Therefore, direct visual observation of slime coating, or
direct measurement of interaction forces of two particles may be more
accurate to pinpoint slime coating. Belonging to these categories are
some of the frequently used techniques such as scanning electron mi-
croscopy, electrokinetic measurements, induction time measurement,
atomic force microscopy, and quartz crystal microbalance with dis-
sipation.
3.1. Scanning electron microscopy (SEM)
SEM is one of the most versatile instruments available for the ex-
amination and analysis of the microstructural characteristics of solid
objects. The primary reason for the SEM’s usefulness is its higher re-
solution than optical microscope (Goldstein, 1977). It permits the ob-
servation and characterization of heterogeneous organic and inorganic
materials and surfaces (Goldstein et al., 1992). Energy dispersive X-ray
spectroscopy (EDS) is an analytical technique that is often coupled with
electron-beam based techniques including SEM, transmission electron
microscopy (TEM) and scanning transmission electron microscopy
(STEM) (Koshihara et al., 1999). When combined with these imaging
tools, EDS can give the elemental composition of individual sample
points or to map out the lateral distribution of elements from an entire
imaged area (Solé et al., 2007). Since the elemental compositions of the
value mineral and gangue mineral are different, SEM coupled with EDS
can distinguish clay minerals from value minerals.
Many researchers observed slime coatings of flotation products by
SEM-EDS analysis (Edwards et al., 1980; Oats et al., 2010; Peng and
Bradshaw, 2012; Song et al., 2006; Yao et al., 2016a, 2016b; Zhang
et al., 2013). This is a direct observation of slime coatings; however, it
is not an in-situ technique which often renders the validity of the ex-
istence of slime coatings questionable. The observed slime coating
could be due to the natural sedimentation and attachment of clay
particles onto coal surfaces during filtration and drying of the samples.
Although the loosely deposited particles can be rinsed off by using
particle-free water, traditional scanning electron microscopy (SEM)
analysis involves drying and evacuating samples which would almost
certainly alter the surface properties. Wang et al. (2013) exploited
cryogenic-SEM and verified the existence of slime coatings in coal flo-
tation as shown in Fig. 1. In the cryogenic-SEM analysis, the samples
were taken from the coal slurry and quickly submerged into liquid ni-
trogen after washing by deionized water at pH 9.0. The flash-freezing
process dropped the temperature at a rate of > 800 °C per minute vi-
trifying the water without crystallization to ice, thus preserved the
structure of the sample. This procedure overcame the aforementioned
deficiencies in sample preparation. As shown in Fig. 1(b), small clay
particles were seen to coat the coal surface, and EDS detected their
compositions and verified them to be gangue slimes. Indeed cryogenic-
SEM is an objective and direct confirmation of slime coatings, but this
method is not really in-situ since this method does not detect slime
coatings inside the flotation pulp. Besides, the cryogenic-SEM cannot be
used to measure the degree of slime coatings quantitively.
3.2. Electrokinetic measurements
A method based on zeta potential distribution measurement to study
heteroaggregation was reported by Xu et al. (2003). The working
principles of this method are depicted in Fig. 2. If two minerals pos-
sessing different surface charges do not aggregate under a given sus-
pension condition, a bimodal zeta potential distribution can be ob-
served showing the zeta potential of each mineral. Under conditions of
a full surface coverage of clays on value minerals, the zeta potential of
the value mineral will be replaced by that of the clay minerals.
This is a useful technique to detect the interaction of binary parti-
culate component suspensions. The interactions of coal-clay, alumina-
quartz, montmorillonite-fluorite and bitumen-clay in aqueous media
have been studied by this technique (Chen et al., 2017; Liang et al.,
28
Minerals Engineering 114 (2017) 26–36
2017; Marjan et al., 2015; Xu et al., 2003). However, this method does
not work for two types of particles having very similar zeta potentials.
The measured zeta potentials would overlap whether aggregation oc-
curs or not (Forbes et al., 2014).
3.3. The induction time measurement
The induction time is a measure of the time required for a particle to
attach to a bubble (Forbes et al., 2014; Nguyen and Schulze, 2004;
Svennilsson, 1934). It depends on the surface chemistry, particle shape,
particle and bubble sizes, bubble and particle trajectories, and their
relative velocities (Verrelli et al., 2014; Verrelli and Koh, 2010). The
induction time of value minerals becomes longer when coated by hy-
drophilic clay minerals. Thus, the measured induction time can be used
as an indication whether slime coatings have occurred or not.
There are several different methods to measure the induction time
for bubble-particle attachment, such as microflotation, atomic force
microscope, induction timer, integrated thin film drainage apparatus
and Milli-Timer (Verrelli and Albijanic, 2015). Oats et al. (2010)
showed that clay slime coatings increased the induction time of coal-
bubble attachment. As shown in Fig. 3, the clay coatings on the coal
surface made the coal particle difficult to attach to the bubble surface. It
is worth noting that in the induction time measurement experiments of
Oats et al. (2010), the particle slurry was allowed to settle overnight
prior to the measurements, so that the bubbles were most likely not
coated by the slimes while the coal particles were.
The general observation is that the longer the induction time, the
more severe the clay coating. Therefore, this is a sensitive and semi-
quantitative way to measure slime coatings. It is only semi-quantitative
since it cannot measure the mass of the coated clays.
3.4. Interaction force measurement by atomic force microscopy (AFM)
Atomic force microscopy (AFM) is a powerful tool which can be
used to directly measure the interaction forces between two objects
such as particle-particle and particle-bubble (Gui et al., 2016; Kusuma
et al., 2014; Liu and Peng, 2015; Nguyen and Schulze, 2004). AFM
measurement may be carried out in air, vacuum or liquid (Berg, 2010),
making it suitable for in-situ determination of interaction forces be-
tween value minerals and clay particles in aqueous suspension under
different solution chemistry conditions (e.g. different pH, different
electrolytes and electrolyte concentrations). The measurement principle
is briefly described as follows (Gui et al., 2016; Xing et al., 2016). An
AFM uses a cantilever with a sharp tip to scan over a sample surface. As
the tip approaches the surface, the close-range attractive force between
the surface and the tip causes the cantilever to deflect towards the
surface. However, as the cantilever is brought even closer to the sur-
face, such that the tip makes contact with it, increasingly repulsive
force takes over and causes the cantilever to deflect away from the
surface. The cantilever deflections towards or away from the surface
can be detected by a reflected laser beam, which is converted to the
interaction forces using the Hooke’s Law once the spring constant of the
cantilever is determined.
The interaction forces between value minerals and clay particles
have been measured by AFM, and it is shown that there is an attractive
force between clay particles and many minerals under flotation pulp
conditions. For instance, coal and kaolinite attracts each other in water
in the presence of 3–10 mmol/L calcium ions at pH 7.0. This was ex-
plained on the basis that the electrostatic repulsive force between coal
and kaolinite was decreased due to the compression of electric double
layer caused by the calcium ions (Gui et al., 2016; Xing et al., 2016);
The partially hydrophobic fine solids in poor processing oil sands ores
show strong attractive forces to bitumen surface in process water which
contains high concentrations of calcium and magnesium ions, causing
problems in the extraction of bitumen by flotation from oil sands (Liu
et al., 2005). The attractive hydrophobic force coupled with reduced
Y. Yu et al. Minerals Engineering 114 (2017) 26–36

Fig. 1. SEM images and EDS spectra of the flotation concentrate (a) and tailings (b) taken from the flotation circuit. The SEM image shows that the coal surface of the concentrate is very
clean (a), but the surface of tailings solids is covered by small particles suggesting that slime coatings occurred on coal surfaces (b). The EDS spectra show the point composition indicated
by the arrows. A very strong signal from C element and other clear signals from O and Au were detected from the small particles on coal surface of the concentrate (a) indicating the small
particle (indicated by the arrow) is coal. In contrast, on the small particles of the tailings, the signal from C is very weak, but clear signals from Si, O, Al, and Mg were detected (b)
confirming that slime coatings occurred on coal surface as clay minerals are mainly composed of Si, O, Al, and Mg. The Au signal is from the gold coating (Wang et al., 2013).

electrostatic repulsive force due to the presence of Ca2+ and Mg2+
between the fine solids and bitumen are responsible for this enhanced
interaction. Since AFM can directly measure the interaction forces be-
tween two particles, it is an indispensable tool to investigate slime
coatings.
3.5. The quartz crystal microbalance with dissipation technique (QCM-D)
in simple static binary mineral-clay system. The complex flotation
conditions (e.g., the presence of multiple minerals, electrolytes and
flotation reagents, and the turbulent hydrodynamic conditions) may
have a significant impact on particle interactions. Therefore, the in-
teraction forces observed in those simple binary systems by such
methods may not represent the true situation in actual flotation en-
vironment, and therefore need to be used and interpreted with caution.

Quartz crystal microbalance with dissipation monitoring (QCM-D)
is an ultrasensitive tool that has been used to study microcosmic solid-
solid and solid-liquid interactions (Alagha et al., 2011; Fatisson et al.,
2009; Ivanchenko et al., 1995; Notley et al., 2005). The QCM-D works
by monitoring the resonance frequency and dissipation of a piezo-
electric quartz crystal sensor. When slime particles coat value mineral
surface immobilized on the quartz sensor, the increased mass of the
sensor changes its resonance frequency and dissipation. Therefore, by
monitoring the resonance frequency, it is possible to detect the de-
position of slime particles on the mineral-immobilized sensor. Recently,
Marjan et al. (2015) used QCM-D to study the interaction of mon-
tmorillonite, kaolinite and illite with bitumen surface, showing that
QCM-D is an effective technique to study the slime coatings. Moreover,
the QCM-D can quantify the mass of clay particles deposited on the
bitumen surface. For instance, the mass of montmorillonite deposited
on bitumen surface was found to be 8.80 μg/cm2 in 1 mM KCl solution
with 40 ppm of Ca2+ (1 mM CaCl2) at pH 8.5 (Marjan et al., 2015).
However, the immobilization of a mineral particle onto the quartz
sensor is a key challenge.
All the measurement techniques discussed above are reported only
4. Principal factors affecting slime coatings
4.1. Solution chemistry
4.1.1. The pH of the slurry
Pulp pH controls the activities of hydrogen ions (H+) and hydroxide
ions (OH−), the two most important counter-ions of the mineral sur-
face. The mineral surface charges can be changed by adjusting the pH of
the pulp. When the pH of the solution is lower than the isoelectric point
(IEP), the minerals charge positively; on the contrary, when the pH is
above IEP, the minerals charge negatively. As pH changes away from
IEP in both directions, the absolute value of zeta potential also increases
gradually (Franks, 2002; Parks, 1967). Therefore, changing the pH of
the pulp can result in a shift of zeta potential of the mineral surface,
with consequent changes in the electrostatic force between the value
mineral and clay particles, affecting the dispersion and aggregation of
the particles (DoymuŞ, 2007). If the signs of the zeta potential of value
mineral and clay mineral surfaces are opposite at the same pulp pH, the
electrostatic interaction force will be attractive. Coupled with the at-
tractive van der Waals forces, the clay mineral and value mineral

29
Y. Yu et al. Minerals Engineering 114 (2017) 26–36

Fig. 2. Schematic zeta potential distributions for a binary particulate

component system. In this figure, the black and white circles represent
mineral matter (M) and coal (C) particles, respectively. (a)
Superimposed zeta potential distribution of the two components
measured separately; (b) a binary mixture without heteroaggregation;
(c) weak attraction (coal partially covered by mineral matter with
some remnant free mineral matter particles); (d) strong attraction
(coal fully covered with mineral matter particles); (e) strong attraction
(coal partially covered with some but not sufficient mineral matter
particles available for full surface coverage) (Xu et al., 2003).

Fig. 3. The attachment of the coal particles onto air bubbles in the absence (left figure) and presence of (0.1% by weight) fine clay particles (middle figure) under the same conditions.
The left bubble surface is firmly attached by the fresh coal particles. By contrast, in the presence of fine clay particles, the coal surface is clay-like and difficult to attach to the bubble
firmly. As to the bubble-particle contact time (right figure), the presence of fine clay particle requires a longer time to achieve a 100% attachment (Oats et al., 2010).

30
Y. Yu et al.
Fig. 4. Adsorption isotherms for iron oxide slimes on galena particles (25–38 μm)
(Bandini et al., 2001).
attracts each other and slime coating occurs. In contrast, the two par-
ticles may repel each other if the two carry the same signs of charges,
offsetting the van der Waals force and experiencing dispersion.
The effect of pH on the attachment of oxide slimes on galena sur-
faces are shown in Fig. 4. As can be seen, with the increase of pH, the
quantity of iron oxide slimes coated on galena particles significantly
decreases (Bandini et al., 2001). The mean IEP of iron oxide is about 8.4
according to the reported literature (Carlson and Kawatra, 2013).
Therefore, as pH increases from 4 to 8, the magnitude of the positive
zeta potential of the iron oxide slimes decreases. Consequently, the
electrostatic attraction force between iron oxide and galena, which is
negatively charged from pH 4 to 10 (Vergouw et al., 1998), decreases
between pH 4 and 8. When pH continues to rise to 10, the zeta potential
of iron oxide slimes turns negative and an electrostatic repulsion occurs
between the iron oxide and galena. As a result, the quantity of iron
oxide slimes attached to galena decreases further.
4.1.2. The addition of electrolyte
The added electrolytes can interact with mineral particles in one of
two distinct ways: (a) non-specific ion adsorption which has no effect
on the position of IEP (i.e., the sign of the charge) but can cause changes
of the magnitude of the zeta potential of the mineral particles. (b)
Specific ion adsorption which can change the position of IEP and
sometimes give rise to charge reversal (Fokkink et al., 1987; Peter
Horsman and Yeager, 1985; Trefalt et al., 2015). In the case of non-
specific ion adsorption, the cations of the added electrolytes can com-
press the double layer of negatively charged mineral surfaces and shift
the zeta potential to less negative values. The higher the concentration
of the electrolyte, the lower the magnitude of the negative charges. For
example, the IEP of alumina is independent of the concentration of
NaNO3. With increasing concentration of NaNO3, the zeta potential
above IEP becomes less negative and the zeta potential below IEP be-
comes less positive (Reyes Bahena et al., 2002). In the case of specific
ion adsorption, the cations of the added electrolytes can enter the Stern
layer through specific adsorption, greatly compressing the double layer
at a very low concentration. With the increasing concentration of the
electrolyte, the specifically adsorbed cations can even change the sign
of the zeta potential. It is reported that multivalent cations are more
strongly adsorbed to clay particles than monovalent cations (Lagaly and
Dékány, 2013). For instance, AlCl3 changed the sign of zeta potential of
montmorillonite to positive at a concentration of 5 × 10−4 mol/L at pH
5.3. With further increase of the AlCl3 concentration, the positive zeta
potential rises rapidly. Specific adsorption is thought to have occurred
in the interaction between Al3+ and the montmorillonite surface (Saka
and Güler, 2006).
It has been reported in the literature that the addition of calcium
31
Minerals Engineering 114 (2017) 26–36
ions increased the positive charge of coal particles below the isoelectric
point (IEP) and decreased the negative charge above the IEP and
eventually shifted the IEP of coal particles (Arnold and Aplan, 1986b).
Base on the forementioned description, the adsorption of calcium ions
on coal surface should belong to specific adsorption. And this is in
agreement with the other authors’ findings (Celik and Somasundaran,
1986). Overall, if the cations of the added electrolytes does not show a
specific adsorption on negatively charged mineral surfaces, then they
only compress the electric double layer and shift zeta potential to less
negative values, and hence decrease the electrostatic repulsion between
the mineral particles and promote aggregation, aggravating slime
coatings (Chorom and Rengasamy, 1995; Gui et al., 2016; Vane and
Zang, 1997; Xing et al., 2016; Zhang and Liu, 2015; Zhang et al., 2013).
If the cations of the added electrolytes exhibit a specific adsorption on
mineral surfaces, even a low concentration of the electrolyte can cause
an apparent compression of the electric double layer, and a high con-
centration can lead to charge reversal.
Anions may also have an effect on zeta potential. For example, coal
particles exhibit a strong negative zeta potential in high concentration
of SO42− and CO32−, but not in the solution of the NO3− ions due to
greater adsorption of SO42− and CO32− ions (DoymuŞ, 2007). Other
authors also found that the presence of sulfate ions increased the ne-
gative charges of sphalerite and pyrite (Bulut and Yenial, 2016). In
general, the addition of electrolyte affects the magnitude and even the
sign of the zeta potential, which in turn changes the electrostatic in-
teractions between value mineral and clay particles.
4.2. Mechanical energy input
Mechanical energy input (such as mixing, agitation and high in-
tensity conditioning) exerts kinetic energy on particles and thus may
improve collision and adhesion of fine particles (Schubert, 1999; Yu
et al., 2017a). This is especially the case when a flotation collector is
present, which is usually the case in froth flotation. In fact, Warren
observed significant aggregation of ultrafine scheelite particles (90% by
weight of the particles were between 0.75 and 1.4 μm diameter) in the
aqueous solution of sodium oleate only when a certain minimum me-
chanical agitation energy was exerted, and he coined the phrase “shear
flocculation” to describe this phenomenon (Warren, 1975). This was
explained by an energy barrier in the DLVO interaction curve, and the
energy barrier must be overcome before particle aggregation or slime
coating occurs (Oats et al., 2010; Warren, 1975). Therefore, it can be
inferred that the mechanical energy input may provide external kinetic
energy to the suspension and render particles to overcome the energy
barrier more easily than that in the absence of mechanical energy input,
producing more serious slime coatings. However, the effect of me-
chanical energy input on slime coatings still need further study and will
be further discussed in Section 5.2.1.
4.3. Surface oxidation
Sulfide minerals are reactive and prone to oxidation in the presence
of air. Different sulfide minerals have different propensity to oxidation.
For example, the oxidation of chalcocite (a secondary copper sulfide
mineral) is faster than that of chalcopyrite (Peng and Zhao, 2011). Mild
oxidation results in a surface that is rich in polysulfides together with
some metal hydroxides (Buckley and Woods, 1984). Extensive oxida-
tion results in high quantities of metal hydroxides on the mineral sur-
face (Senior and Trahar, 1991). The surface oxidation may take place in
ambient air or in the grinding process, and sometimes this oxidation
can be accelerated by hydrogen peroxide generated during grinding
(Borda et al., 2003; Nooshabadi et al., 2013). The oxidation products
themselves have an influence on the floatability of the sulfide minerals.
For instance, the colloidal lead hydroxide particles formed by oxidation
reduce the kinetics of flotation recovery of galena (Bandini, 2000). Si-
milarly, metal hydroxides on the mineral surface decrease the flotation
Y. Yu et al.
of copper sulfides even in the presence of collector (Senior and Trahar,
1991). On the contrary, polysulfides on the surface as a result of mild
surface oxidation facilitate the collectorless flotation of copper sulfide
minerals due to the improved hydrophobicity by the formed poly-
sulfides (Ekmekçi and Demirel, 1997; Lekki and Drzymala, 1990).
However, the generated oxidation products may have different elec-
trochemical properties from the initial sulfide minerals. Unoxidized
sulfide minerals such as pyrite, sphalerite, chalcopyrite and galena are
negatively charged in a wide pH range and their IEP has been found
between 1 and 2 (Fornasiero et al., 1992; Fornasiero et al., 1994).
Oxidation of these sulfide minerals makes the sulfide minerals behave
like the corresponding metal oxides and shows distinct IEP of the metal
oxides (Fairthorne et al., 1997; Fornasiero et al., 1992; Fornasiero et al.,
1994; Fullston et al., 1999; Witika and Dobias, 1993). Therefore, this
sulfide to oxide conversion alters the electrostatic interactions between
sulfide minerals and clays. For example, Peng and Zhao (2011, 2012)
reported that bentonite slime coatings on oxidized chalcocite was more
severe than on unoxidized chalcocite, and depressed the flotation of
chalcocite due to the alteration of electrostatic forces before and after
surface oxidation (Peng and Zhao, 2011; Zhao and Peng, 2012).
4.4. Properties of the slimes
It is reported that at the same pH (9.0), the flotation of pentlandite
is more severely depressed by chrysotile than lizardite, possibly due to
the stronger electrostatic attraction between pentlandite and chrysotile
caused by the higher positive charge on the surface of chrysotile com-
pared with lizardite at this pH (Edwards et al., 1980). This indicates
that the electrical property of clay surface plays an important role in
slime coatings when it is governed by electrostatic interactions. Arnold
and Aplan (1986a) investigated the effect of clay type on coal flotation
and indicated that different clays influenced coal flotation differently.
They suggested that for this reason, slimes in a froth flotation system
should be well characterized. Kaolinite and illite clays were found to
cause little or no coal depression. The presence of as little as 2% ben-
tonite clay in the flotation feed, however, caused significant depression
of all but the most hydrophobic coals (Arnold and Aplan, 1986a). Xu
et al. (2003) also claimed that it was montmorillonite, the major con-
stitute clay mineral in bentonite, that significantly decreased coal re-
covery instead of kaolinite (Xu et al., 2003). Xu et al. (2003) reported
that the zeta potential of kaolinite was less negative than that of
montmorillonite at pH 5, and thus should be attracted to the coal more
than montmorillonite. It is puzzling that Xu et al. (2003) reported the
opposite coal flotation behavior. The montmorillonite coatings on coal
surface at pH 5 was confirmed by zeta potential distribution measure-
ment by Xu et al. (2003), but the same measurement technique could
not establish kaolinite coatings on coal surface at pH 5 due to the
overlapping of the zeta potentials of kaolinite and coal. It is interesting
to note that Gui et al. (2016) found that the overall forces between coal
and kaolinite at pH 4 measured by AFM was attractive. In Gui et al.’s
case, the zeta potentials of both of kaolinite and coal at pH 4 were more
negative than that reported by Xu et al. (2003) at pH 5. Therefore, in
the case of Xu et al. (2003), the kaolinite should have coated the coal
surface. It is possible that the kaolinite coating on coal surface did not
influence coal flotation but Xu et al. (2003) did not comment on this
possibility. The reason accounting for this discrepancy is still unclear
although it is noted that montmorillonite does have specific properties
that are different from kaolinite, such as higher cation exchange ca-
pacity and the tendency to swell in water.
Hou et al. (2016) extracted three fractions of slimes (< 74 μm) with
different densities (light, medium and heavy) from the original coal
slimes and artificially mixed them with coarse pure coal
(−710 + 74 µm) and then attempted to separate them by flotation.
They found that the medium density fraction which mainly contains
clay-coal composite particles greatly decreased the flotation recovery of
the pure coal, but the heavy fraction which mainly comprises clays only
32
Minerals Engineering 114 (2017) 26–36
Fig. 5. The EDLVO energy (van der Waals energy, electrostatic energy and interfacial
polar energy) of different sizes of kaolinite (radius = 1, 3 and 5 μm) with coal particle
(radius = 45 μm) at pH = 7 (Yu et al., 2015).
depressed the flotation to a much less extent. The authors proposed that
the great depression caused by the medium density fraction was due to
the partial hydrophobicity of the clay-coal composite particles. They
argued that the hydrophobic side of the composite particles could ad-
here to the coal surface by hydrophobic force, exposing the hydrophilic
side to water (Hou et al., 2016). Liu et al. (2005) reported that fine
solids (which were slightly hydrophobic) in poor processing oil sands
ores showed strong attractive forces to bitumen in process water than
those from good processing oil sands ores, causing problems in the
extraction of bitumen by flotation from oil sands. Thus, the coatings of
partially-hydrophobic composite particle play an important role in the
flotation of naturally hydrophobic minerals. Therefore, the different
properties of slimes such as crystallinity, cation exchange capacity,
swelling, and partial hydrophobicity (composite particles), etc. have a
significant contribution to slime coatings. In addition, it is also reported
that finer particles have a lower energy barrier in the total energy curve
as shown in Fig. 5, indicating that smaller clay particles are more likely
to attach to value mineral surface (Yu et al., 2015). However, this has
not been demonstrated experimentally yet.
5. Slime coating mitigation methods
5.1. Slime coating removal by chemical means
5.1.1. Dispersant
Dispersants are widely used to modify the colloidal interactions
between particles by modulating electrostatic and steric interactions
which offset the contribution of the van der Waals attraction to the total
net force (Oats et al., 2010). These dispersants are mostly anionic
polymers which adsorb on mineral surfaces, making them more nega-
tively charged. In froth flotation, sodium silicate (Na2SiO3) has been
widely reported to depress silicate and carbonate minerals by adsorbing
onto these gangue mineral surfaces and making them more hydrophilic.
Also, it is an effective dispersant due to the SiO32− and HSiO3− ions
which adsorb on the gangue mineral surface and enhancing the elec-
trostatic repulsion between negatively charged value minerals and
gangue minerals. Sodium silicate can also have different “module
number”, i.e., the SiO2/Na2O ratio, that alters its function (Taner and
Onen, 2016). However, sodium silicate does not significantly improve
the flotation performance of coal slimes (Oats et al., 2010). Carbox-
ymethyl cellulose (CMC), comprising a linear chain structure with β-D-
glucose as the basic unit, is another common anionic polymer which is
used to disperse gangue minerals. It is a typical dispersant which uti-
lizes the strong steric repulsion between particles with adsorption
layers of a long chain polymer, leading to a high stability of the col-
loidal dispersion. Edwards et al. (1980) reported that CMC can modify
the surface charge of serpentine slimes and reduce the detrimental
Y. Yu et al.
impact of the slime coatings on the flotation of pentlandite. Effective
dispersion results by CMC were achieved in fluorite–quartz/calcite
flotation separation. In this case, CMC chemically adsorbed on the
surfaces of fluorite and calcite at pH 9.0 through the formation of
calcium carboxylate (Crozier, 1992), and the adsorption made fluorite
and calcite negatively charged, and hence produced an electrostatic
repulsion force between fluorite and calcite. Meanwhile, since CMC is a
macromolecule, a strong steric repulsion between fluorite and calcite
was also present. The two repulsive forces overcame the van der Waals
attraction forces and mitigated the calcite coatings on fluorite surface.
In the case of fluorite/quartz flotation, although CMC could not adsorb
on the surface of quartz due to the strong negative charges on quartz
surfaces at pH 9.0, the strong electrostatic repulsion between quartz
and CMC-coated fluorite prevented the quartz coatings on fluorite
particles (Song et al., 2006). However, the effect of CMC may deterio-
rate when the water quality changes. For instance, in nickel plants using
fresh or low salinity saline water, CMC has a good performance in
controlling serpentine slime coatings on pentlandite surfaces. However,
CMC does not work in nickel plants using saline water. This difference
is attributed to the different ionic compositions of the water used during
flotation (Liu and Peng, 2015; Peng and Seaman, 2011). Recently, lig-
nosulfonate was reported to improve copper and gold recovery by
dispersing clay minerals in flotation using fresh water; this is attributed
to the enhanced electrostatic repulsion at the low dosage or steric re-
pulsion at the high dosage (Liu and Peng, 2015; Seaman et al., 2012;
Wei et al., 2013). However, high dosages of dispersants may depress not
only the gangue minerals but also value minerals due to the non-se-
lective adsorption of dispersants on both minerals (Huynh et al., 2000).
Thus, the selective adsorption of dispersants is the key to ensure the
success of dispersion.
5.1.2. Clay binder
Tao et al. (2007) developed a novel dispersant called “clay binder”
that reportedly significantly improved coal and phosphate flotation by
agglomerating clay minerals and removing them from the surface of
value minerals. It is a low molecular weight polymer that is the con-
densation product of urea and formaldehyde reacted under acidic
conditions. Depending on the application, the properties of the con-
densation polymers can be tailored to suit the specific application re-
quirements. The main factors affecting their performance are the molar
ratio of formaldehyde to urea, the addition of functional groups, the
degree of functionalization, molecular weight and crosslink density.
The two main adsorption mechanisms of the clay binders are dipole-
dipole interactions and strong hydrogen bond. Because of the amphi-
protic characteristics and multiple binding and chelating sites, binding
can be very selective (Taner and Onen, 2016; Tao et al., 2007). How-
ever, the authors did not clearly validate whether the “clay binder”
could really mitigate the slime coatings.
5.2. Slime coating removal by physical means
5.2.1. High intensity conditioning
Increasing energy input during conditioning has been shown to
substantially improve recovery and selectivity (Bulatovic, 1994;
Bulatovic and Salter, 1989; Chen et al., 1999b; Huang et al., 2016; Sun
et al., 2016). This energy input is termed “High Intensity Conditioning
(HIC)”. Previous studies demonstrated that the improvement derived
from selective collector adsorption, the fast diffusion of soluble col-
lectors, the emulsification of oily collectors and the creation of fine
mineral particle aggregates (Bulatovic and Salter, 1989; Huang et al.,
2016; Ma et al., 2013; Sun et al., 2008). However, the study from Chen
et al. (1999) showed that the “surface cleaning” of value minerals in-
duced by high intensity conditioning played an important role in this
improvement, removing the impurities from the mineral surface and
decreasing the slime coatings (Chen et al., 1999a, 1999b). Surface
cleaning was also reported by other researchers (Bandini et al., 2001;
33
Minerals Engineering 114 (2017) 26–36
Huang et al., 2016; Yu et al., 2017b). The hydrodynamic forces must be
responsible for the removal of slime coatings, which overcome the
adhesion force and remove particles from surfaces by rolling and
sliding. Chen et al. (1999a) indicated that the finer the slime particle,
the higher the critical shear velocity required for the slime to detach
from the surface. Overall, the high-intensity conditioning is proposed to
remove the coated slimes from the mineral surface, but certain energy
input is likely to increase slime coatings as discussed in Section 4.2, and
thus the intensity of conditioning is a key parameter that needs to be
determined to remove slime coatings. The successful industrial appli-
cation of HIC has been reported in Kailuan coal mining Ltd, China (Ma
et al., 2013). However, whether the detached slime particles after HIC
will re-attach onto mineral surface remains unknown.
5.2.2. Desliming before flotation
Since the slimes exhibit great detrimental effects on flotation effi-
ciency, it is desirable to remove the slimes before flotation (Taner and
Onen, 2016). Removing fine particles (which are mostly fine clay par-
ticles) from coal by sieving or classification (by a hyrocyclone) sig-
nificantly improved the coal flotation performance (Oats et al., 2010;
Quast et al., 2008). Desliming using a hydrocyclone also gave improved
flotation performance of pentlandite (Chen et al., 1999b). However,
desliming can only work when the slime fraction does not contain high
concentration of value minerals. If the slime fraction does contain high
concentration of value minerals, separate flotation circuits for slimes
and coarse fractions should be considered. Kienko and Voronova (2014)
treated fluorite ores by separate coarse and fine flotation at a cut size of
15 μm in laboratory tests, and the results showed that the overall re-
covery of fluorite increased by 18 percentage points. These separate
flotation circuits have been used in the Mt Keith nickel plant in Western
Australia (Peng and Seaman, 2012). In practice, the success of de-
sliming on subsequent flotation is still a matter of debate, i.e., it is still
unknown whether the improved flotation performance is only attrib-
uted to the reduction of reagent adsorption on slime particles, or
whether it is truly due to the removal of slime coatings from the value
mineral surfaces.
5.2.3. The ultrasonic treatment
Celik et al. (1998) reported that the ultrasonic treatment increased
the flotation recovery of the value minerals by removing the clay par-
ticles from boron minerals (Celik et al., 1998). Also, it was reported that
the rate of iron oxide removal from quartz surface in the presence of
Calgon was increased ∼5 times following ultrasonic treatment (Bandini
et al., 2001). Here the dispersant Calgon adsorbed on the surface of iron
oxide and reversed the surface charge to negative, and hence increased
the electrostatic repulsion between iron oxide and quartz. Meanwhile,
the sonication provided an extra mechanical force to expedite the re-
moval of iron oxide slimes. In China, the flotation of some problematic
coal slimes is suffering from slime coatings, it is found that ultrasonic
treatment increased the coal flotation recovery through removing the
fine slimes from coal surface (Kang and Lv, 2006). Gurpinar et al.
(2004) compared the SEM images of barite surfaces before and after
ultrasonic treatment and found that fine particles previously coated on
the surfaces were completely removed (Gurpinar et al., 2004). It was
proposed that, during ultrasonic treatment, a clean surface was created
by removing impurities from value mineral surfaces, which was then
followed by the formation of microbubbles on the hydrophobic solid
surface, leading to enhanced bubble-particle attachment (Celik, 1989).
These studies show that ultrasonic pre-treatment is an effective tech-
nique to remove slimes from mineral surfaces. However, the ultrasonic
treatment has not found use in commercial production.
5.2.4. Adding another mineral
Feng et al. (2012) described a method to mitigate the detrimental
effect of serpentine coatings on pentlandite. They reported that the
addition of quartz (−150 + 75 μm) to the suspension of pentlandite/
Y. Yu et al.
serpentine mitigated the serpentine coatings and improved the pen-
tlandite recovery significantly. They attributed this to the stronger at-
traction between serpentine slimes and quartz particles than between
serpentine and pentlandite since the quartz was more negatively
charged than pentlandite in the pH range of 4–11 in their tests. This
method provides a new concept to control undesired slime coatings.
However, this may meanwhile increase the entrainment of the new
mineral additives into the froth if their sizes are too small and lower the
grade of the concentrate (Liu and Peng, 2014; Wang et al., 2015a).
6. Summary
Slime coatings have long been recognized to have detrimental ef-
fects on froth flotation. The occurrence of slime coatings is attributed to
the interactions between particles which are interpreted by classical
DLVO or extended DLVO theories as well as chemical precipitation or
deposition of colloidal particles during grinding. According to the
sources, the coated slimes can be classified into two types: (1) original
particles such as associated gangue minerals and composite particles;
(2) secondary compounds caused by grinding, mineral surface oxida-
tion and chemical precipitation. Slime coatings are influenced by sev-
eral factors such as pH, electrolyte, mechanical energy input and slimes
properties. So far, much research has been focused on the factor of
solution chemistry. The literature reports many measurement methods
for slime coatings. However, these methods often have limitations and
lack general applicability.
A number of methods to control slime coatings were proposed
which can be divided into two categories, chemical means and physical
means. Considering the practical perspective, it is worth noting that
high intensity conditioning (HIC) should be highlighted. This is because
HIC not only mitigates slime coatings but also increases the diffusion of
soluble collectors and the collision of particles with oily collectors,
therefore, improves flotation recoveries.
Further studies are required to thoroughly understand slime coat-
ings and mitigate its detrimental effects:
(1) The study of slime coatings under actual flotation conditions
(complex slurries of polymetallic ores in the presence of flotation
reagents).
(2) In-situ technique to directly detect and quantify slime coatings in
laboratory scale and commercial scale flotation.
(3) Effective and applicable control methods to mitigate slime coatings
especially in commercial flotation circuits.
Acknowledgements
Financial support to the project was provided by National Natural
Science Foundation of China (No. 51604280) and Natural Sciences and
Engineering Research Council of Canada (NSERC). Yuexian Yu ap-
preciates a scholarship (Grant No. 201606430041) from the China
Scholarship Council (CSC) to carry out a visiting study at the University
of Alberta.
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