Advances in Colloid and Interface Science 150 (2009) 106–115

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Advances in Colloid and Interface Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c i s

A review of factors that affect contact angle and implications for flotation practice
T.T. Chau a, W.J. Bruckard a, P.T.L. Koh a,⁎, A.V. Nguyen b,⁎
a
CSIRO Minerals, Box 312 Clayton South, Victoria 3169, Australia
b
School of Chemical Engineering, The University of Queensland, Brisbane, Queensland 4072, Australia

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

Available online 12 July 2009 Contact angle and the wetting behaviour of solid particles are influenced by many physical and chemical
factors such as surface roughness and heterogeneity as well as particle shape and size. A significant amount
Keywords: of effort has been invested in order to probe the correlation between these factors and surface wettability.
Contact angle Some of the key investigations reported in the literature are reviewed here.
Wetting It is clear from the papers reviewed that, depending on many experimental conditions such as the size of the
Hydrophobicity
surface heterogeneities and asperities, surface cleanliness, and the resolution of measuring equipment and
Froth flotation
data interpretation, obtaining meaningful contact angle values is extremely difficult and such values are
reliant on careful experimental control. Surface wetting behaviour depends on not only surface texture
(roughness and particle shape), and surface chemistry (heterogeneity) but also on hydrodynamic conditions
in the preparation route. The inability to distinguish the effects of each factor may be due to the interplay
and/or overlap of two or more factors in each system. From this review, it was concluded that:
•
Surface geometry (and surface roughness of different scales) can be used to tune the contact angle; with
increasing surface roughness the apparent contact angle decreases for hydrophilic materials and increases for
hydrophobic materials.
•
For non-ideal surfaces, such as mineral surfaces in the flotation process, kinetics plays a more important
role than thermodynamics in dictating wettability.
•
Particle size encountered in flotation (10–200 μm) showed no significant effect on contact angle but has a
strong effect on flotation rate constant.

There is a lack of a rigid quantitative correlation between factors affecting wetting, wetting behaviour and contact
angle on minerals; and hence their implication for flotation process. Specifically, universal correlation of contact
angle to flotation recovery is still difficult to predict from first principles. Other advanced techniques and measures
complementary to contact angle will be essential to establish the link between research and practice in flotation.
© 2009 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2. Background of contact angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.1. The Young equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
2.2. The Wenzel equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
2.3. The Cassie equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3. Factors affecting contact angle measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1. Roughness factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1.1. Roughness characterisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1.2. The effect of dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1.3. The effect of roughness variation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1.4. Assigning the “true” apparent contact angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
3.2. Heterogeneity factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.3. The effect of particle size on penetration kinetics and contact angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.4. The effect of particle shape on contact angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

⁎ Corresponding authors.
E-mail addresses: peter.koh@csiro.au (P.T.L. Koh), anh.nguyen@eng.uq.edu.au (A.V. Nguyen).

0001-8686/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2009.07.003
 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115 107

4. Contact angles and their implication for flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

4.1. Contact angle and mineral floatability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
4.2. Contact angle and flotation kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.2.1. Contact angle and bubble–particle attachment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.2.2. Contact angle and bubble–particle detachment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.3. Beyond contact angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
5. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

1. Introduction
The flotation process has been widely used, for over a century, to
quickly and efficiently separate valuable minerals from gangue
minerals, based on the differences in their natural or induced
hydrophobicity. The process as a whole is very complex but can be
described as the overlap of three main principles: physical phenom-
ena, chemical control, and mechanical factors. Although the technol-
ogy is mature, the physical and chemical principles underlying the
flotation process have not yet been fully elucidated. Research into
froth flotation has been concerned mainly with the establishment of a
quantitative link between surface wettability and floatability. Such a
relationship is of fundamental importance not only to flotation science
but also can be used in the development of a model, which can
accurately predict the flotation behaviour. Such a model would
incorporate many physical and chemical parameters, including
contact angle, which is considered a quick and simple method to
quantify surface wetting. It is therefore necessary to understand
wetting and the key factors that influence wetting and contact angle,
in order to integrate these parameters into the model.
Contact angles have been studied intensively for more than one
century [1–3], and their implication for flotation process has been
delineated by Wark and Cox [4]. These investigators conducted a large
amount of work utilising contact angle measurements on flat mineral
surfaces to describe and explain the effects of modifiers as such
cyanide and hydroxyl and sulphide ion on sulphide mineral flotation.
However, the precise measurement and prediction of contact angles
for real mineral surfaces is extremely difficult due to the many factors
that influence wetting phenomena. On the experimental side, the
most important challenges seems to be the measurement of contact
angles locally at the lowest scale that permits a continuum view and
the measured relating this value to the larger scale. The main
theoretical problem is the analysis of three-dimensional situations
associated with rough or heterogeneous solid surfaces. In such cases,
the difficulties relate to the determination of the three phase contact
(TPC) line, which will be discussed in detail later. Although several
theories and approaches have been advanced so far, their applicability
and validity is still a matter of on-going debate. The well-known
Wenzel and Cassie equations are commonly used to quantify the
actual contact angle on rough and heterogeneous surfaces respec-
tively. They show that not only the chemical properties (hetero-
geneity) but also the physical properties (surface roughness, shape
and particle size) of the surface influence its wetting behaviour. A
large amount of experimental work, varying from nanometer scale to
millimeter scale, on a range of different surfaces has been reported. On
the microscopic scale, recent advances in the ability to manipulate
materials, at the molecular and atomic levels, have led to an upsurge of
interest in revisiting wetting phenomena based on the investigation of
carefully patterned surfaces, with the application of fabrication of
miniaturized devices.
The validity of the reported results for real mineral surfaces and
the manner in which they can be fitted into attachment models for
flotation, such as in computational fluid dynamics (CFD) modeling, is
questionable. The authors are aware that there are numerous studies
and recent reviews of wetting in general [2,3,5]. In this paper, the
wetting characteristics of mineral surfaces and those factors that
affect contact angle measurements and their implication to flotation
process are both consolidated. It provides a comprehensive review
defining the problems dealing with contact angle determinations on
real surfaces, i.e., investigating the influence of surface roughness,
heterogeneity, shape, and particle size, especially for powdered solids,
and consolidating the up-to-date understanding of the impact of these
factors on surface wettability. The ultimate goal is to clarifying
whether or not any of those factors have any significant impact on
mineral surface hydrophobicity. This knowledge can then be inte-
grated into a flotation model and/or be used as a feasibility study that
explores the means to enhance flotation efficiency.
2. Background of contact angle
The contact angle is a very common measure of the hydrophobicity
of a solid surface and is an important parameter in wet processing of
minerals such as froth flotation. The hydrophilic/hydrophobic balance
at the surface of the mineral can be evaluated in terms of the contact
angle developed between three phases: liquid, solid, and gas.
However, it is often difficult to find reproducible contact angles in
any system as the number of parameters is too large to control [2].
Hence, a variety of contact angles has been defined to address
different situations and some of these are outlined below.
2.1. The Young equation
The relationship between surface tension and contact angle was
first recognised by Young [6]. In principle, the contact angle of an air
bubble on a solid surface in aqueous solution, as shown in Fig. 1, is
determined by the mechanical equilibrium under the action of three
interfacial tensions, i.e., solid–air surface “tension” (γs/a), solid–liquid
interfacial “tension” (γs/l), and liquid–air surface tension (γl/a). The
contact angle determined by balancing the surface tension forces is
known as Young's contact angle, θY, and the relationship describing the
balance of surface forces is known as Young's equation as given in
Eq. (1).
γs = a = γs = l + γl = a cos θY : ð1Þ
Fig. 1. Contact angle between bubble and mineral solid surface in an aqueous medium.
108 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115

It is important to point out that the above relationship will not equation (Eq. (4)) for a porous surface, such as a mesh or screen
hold under conditions of inadequate contact angle measurement. surface:
Unfortunately, the literature on contact angle research contains a large
body of such uncertain data. Young's classical equation remains
supreme on the macroscopic scale only if all the conditions are met, cos θC = f1 cos θ1 −f2 : ð4Þ
though there have been a number of attempts to modify it or even to
discount it. The validity of Young's equation (Eq. (1)) requires that the
In this case, f2 is the fraction of air spaces (open area) which makes
solid surface is smooth, flat, homogenous, inert, insoluble, non-
cosθ2 = − 1, as θ = 180° for a non-wetting situation.
reactive, non-porous, and of non-deformable quality. These conditions
Originally, the Cassie-Baxter equation was proposed to described
are usually not met by real surfaces [7–10]. A surface, which meets all
wetting phenomena at porous surfaces, it can also be used for rough
the requirements of the Young equation, is referred to as an ideal
hydrophobic surfaces when liquid does not penetrate the surface
surface. However, most practical surfaces are non-ideal and the
structure. The advantage of the Cassie-Baxter model over Wenzel's
measurable contact angle values on such surfaces are referred to as
approach is that it describes real systems more accurately. However, in
the apparent contact angles, θapp. As a consequence, this value is not
the Cassie-Baxter equation, it is difficult to accurately determine the
unique but falls into a more or less wide interval between the
parameters f1 and f2 for randomly roughened surfaces.
advancing (largest) and the receding contact angle (smallest). The
The theories proposed by Cassie and Wenzel have been widely
difference between them is called contact angle hysteresis. It can be
used to predict the real (rough and heterogenous) surface behaviour,
quite large, as much as 50° for water on mineral surfaces [11]. The
especially in the past 5 years with the new area of research in
three main contributing factors relating to non-ideal surfaces are:
“superhydrophobic” surfaces. It has been assumed that equilibrium
contamination of either the liquid or the solid surface, surface rough-
interfacial free energies dictated wettability and that the Wenzel's and
ness, and surface immobility on a macromolecular scale.
Cassie's equations could be applied to predict or explain real surface
behaviour. The theories behind Eqs. (2) and (3) are generally
2.2. The Wenzel equation
consistent with the observed data for many surfaces that have been
studied over the past 50 or so years, but still many examples of where
Wenzel [12] may have been the first scientist to investigate the
they are inconsistent have also been reported [17] (and references of
effect of surface roughness on the static contact angle. He observed
such are cited in this paper). It has also observed that there is a
that surface roughness caused a hydrophobic fluid to behave as if it
transition between the Wenzel and Cassie regimes, which was first
were more hydrophobic and a hydrophilic fluid to behave as if it were
recognised by Johnson and Dettre [18]. This is shown in Fig. 2 and is
more hydrophilic. Wenzel also suggested that the geometry of the
discussed in detail later.
surface had a greater effect on the static contact angle than did the
The experimentally observed apparent contact angle, θ, may or
chemistry.
may not be equal to the Young contact angle, θY. In relation to this
On a rough surface, the apparent contact angle is related to the
matter, Li and Newman [19] have summarised the relevant thermo-
ideal contact angle according the Wenzel equation (Eq. (2)). This
dynamic studies and they conclude the followings:
modification is required when the drop size is sufficiently large
compared with the roughness scale, and if the liquid completely • On ideal solid surfaces, there is no contact angle hysteresis and the
penetrates into the roughness grooves on the solid surfaces. experimentally observed contact angle, θapp, is equal to θY.
• On smooth, but chemically heterogeneous solid surfaces, θ is not
cos θw = r cos θY ð2Þ necessarily equal to the thermodynamic equilibrium contact angle.

In this equation, θw is the Wenzel contact angle (the apparent

contact angle on a rough surface), θY is the ideal Young contact angle
on a smooth surface and r is the average roughness ratio, defined as
the ratio between the true and the apparent surface area of the solid.
The true surface area, A, can be determined by several measurement
techniques such as white light confocal microscopy (WLCM),
profilometry [13] and atomic force microscopy [14]. The apparent
surface area or geometric area, Ag, will be equal to the scan area
(product of the transversal and longitudinal scan-length) [15].
In Eq. (2), it is implicitly assumed that the surface features of the
substrate are insignificant compared to the drop dimensions and that
their geometry is of no consequence as long as it does not affect the
surface area. If this assumption is ignored, the use of Wenzel equation
may lead to incorrect conclusions and error on contact angles.

2.3. The Cassie equation

On a heterogeneous surface, the apparent contact angle is related

to the ideal contact angle by the Cassie equation. Cassie [16] derived
an equation (Eq. (3)) describing contact angle changes for two
component surfaces as follows.

cos θC = f1 cos θ1 + f2 cos θ2 ð3Þ

where f1 is the fractional area of the surface with contact angle θ1, f2 is Fig. 2. Static contact angle of water on wax substrates, as a function of the substrate
the fractional area of the surface with contact angle θ2, and θc is the roughness. Both the advancing angle (open symbols) and the receding ones (full symbols)
Cassie contact angle. The Cassie equation is reduced to Cassie-Baxter are displayed [18].
 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115 109

Nevertheless, the experimental advancing contact angle can be • The difficulty of assigning the “true” apparent contact angle.
expected to be a good approximation of θY. • The inability of distinguishing between variations in surface rough-
• On rough solid surfaces, no such equality between advancing ness and surface chemistry of heterogeneity and anisotropy.
contact angle and θY exists. Thus, all contact angles on rough
surfaces are essentially meaningless in terms of Young's equation. In 3.1.1. Roughness characterisation
other words, the apparent contact angle values of rough surfaces do The true surface area in Eq. (2) is normally measured by imaging,
not reflect the surface energy. and hence the average roughness ratio, is affected by the resolution
and the scan size. However, there is no clear understanding of the
It is noted that the first conclusion refers to the “classical”
relationship between the average roughness ratio and its dependence
consideration of contact angle hysteresis due to pinning and
on measurement parameters, as each study has looked at a particular
immobility of contact line [20]. However, for small contact angle
system using a particular instrument. Lai and Irene [26] reported that
(bb1 radian) there exists a thin wetting film around contact line and
there is no method that yields the true surface area for microscopically
disjoining pressure influences the contact angle hysteresis [21].
rough surfaces. The complete description of a surface is not possible
Kwok and co-workers [7,22] also concluded that the interpretation
due to limitations of the instrument and the discrete character (due to
of experimental contact angle values is difficult. They suggested that
discrete information collection by the instrument) of the topography.
meaningful contact angle experiments require considerable experi-
Therefore, the true roughness value is non-accessible experimentally
mental care and suitable methodology; the conventional goniometer
because it would require the acquisition of an infinite number of
technique does not qualify as such. The axisymmetric drop shape
points (i.e., a continuous topography). Characterising solid surfaces
analysis profile (ADSA-P) method provides more reliable contact
which include sub-microscopic roughness features are necessary to
angle values compared with other methods used for measurements
improve the correlation of the effects of roughness on spreading. More
on flat plates. The modified Washburn method, using a packed column
comprehensive experimental techniques for surface profiling, such as
of powder is considered to be the most suitable method for contact
atomic force microscopy, might provide images with higher resolution
angle measurements on powder surfaces, especially for real mineral
and precision. This is technically an area for future development in
particles [10]. Details of different experimental techniques for contact
instrumentation.
angle measurements have been reviewed in detail elsewhere [10].
The concerns regarding the validity of the Young, Cassie and
3.1.2. The effect of dimension
Wenzel equations and their applicability in various mineral systems is
Regarding the dimension, both the shape and size of the asperities
still an area of much scientific debate. As initiated by Pease [23], and
for a two dimensional or axisymmetric system, there exists a unique
then followed by many other researchers, these theories has been
correspondence between Young's definition and an experimentally
questioned and the fact that wettability as measured by contact angle
measured contact angle. However, for three-dimensional systems
is a one-dimensional issue has been raised and debated. More
with no special symmetry (i.e. non-uniform roughness), the apparent
complex and sophisticated models for rough and composite surfaces
contact angle may vary from point to point and, hence, may have
have also been proposed [17] but so far, there is no absolute theory
many values along the contact line. This leads to the fundamental flaw
that is robust enough to present a clear correlation between physical
of the Wenzel equation, which implies that there is a single apparent
surface properties, such as roughness, heterogeneity, particle shape
contact angle. From analysing four different, heavily structured
and size, and surface wetting properties. Some of the work relevant to
surfaces, Spori et al. [13] showed that the topographical influence on
this topic is reviewed here to consolidate the up-to-date results in this
contact angle cannot simply be predicted via a roughness factor, the
area from different research perspectives.
same roughness in the form of parallel grooves gives an entirely
different behaviour than one in the form of pits.
3. Factors affecting contact angle measurements
It has been reported that the three-phase structure at the contact
line, not the liquid–solid interface beneath the droplet, controls the
The wettability of real surfaces is subject to many factors, both
contact angle [17]. These findings are supported by the work of Gao
physical and chemical. For the flotation process, the effect of four main
and McCarthy [27] who directly questioned the Cassie and Wenzel
factors; surface roughness, heterogeneity, particle shape, and particle
theories in the publication titled “How Wenzel and Cassie were
size, on contact angle measurements are of importance and hence are
wrong”. They concluded that contact area plays no role in wettability
reviewed here.
and the contact angle and hysteresis are a function of contact line
structure such that the kinetics of drop movement, rather than
3.1. Roughness factor
thermodynamics, dictate wettability. It was suggested that the Wenzel
and Cassie equations should be used with the knowledge of their
Solid surface roughness has a significant effect on the macroscopic
inherent faults.
contact angle on flat surfaces and plays an important role in many
The influence of surface roughness on the kinetics of the bubble
practical wetting and spreading processes [11]. It is well-known that
attachment on Teflon plates was investigated by Krasowska and co-
surface roughness contribute to hysteresis in contact angle measure-
workers [28,29]. They found that the Teflon surface roughness was the
ments but the extent and quantitative correlation between contact
parameter of crucial importance for the attachment of the colliding
angle hysteresis and roughness is not obvious and the validity of
bubble. With increasing surface roughness from below 1 µm up to
Wenzel's equation is questionable. Bartell and Shepard [24] chal-
100 µm, modified by using abrasive papers, the static contact angle
lenged Wenzel's theory and showed that the contact angles of
increased from 99.6° to 128.8°, while the time needed for TPC
droplets on surfaces containing roughness within the contact line
formation and bubble attachment was significantly shortened.
were identical to those of smooth surfaces. Oliver et al. [25] proposed
some reasons behind the failures of the proposed theories, quantifying
3.1.3. The effect of roughness variation
the effects of roughness on contact angles as follows;
Most real solid surfaces, especially minerals and metals, are not
• Poor roughness characterisation. always homogeneous and clean. The intrinsically heterogeneous
• The theories (Wenzel (1936) equation and Cassie and Baxter (1944) characteristics are generally due to the composition of two or more
equation) only equated roughness with wetting hysteresis, which components with different surface properties. Such surface hetero-
only applies to idealised models of roughness, and therefore they geneity may also result from material anisotropy, or non-uniform
have limited practical applicability. dissociation of functional groups located at the surfaces. The adsorption
110 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115
of contaminants and/or the deposition of dust particles will turn many
intrinsically homogeneous surfaces into actually heterogeneous sur-
faces. Therefore, the selection of cleaning techniques and sample
preparation pathway will significantly influence the final surface hetero-
geneity obtained.
Busscher et al. [30] measured the effect of surface roughness
(created by polishing and abrasion and measured by profilometry) on
the wetting behaviour of at least 12 different commercial polymers,
and concluded that surface roughness values b 0.1 µm aid no influence
the wettability of the substrates. This finding is supported by other
workers [31–33], who reported that for surfaces with roughness less
than 0.1 µm, chemical interactions and heterogeneities were the
dominant factors affecting hysteresis.
However, contradictory results show that surface roughness
influences the wetting of the solids even at nano-scale. A study by
Veeramasuneni et al. [34] reported that an increase in surface
roughness, from 6 to 13 nm, will also increase the contact angles of
hydrophobic PTFE (poly-tetrafluoroethylene) surfaces and decrease
surface wettability. Extrand [35] proposed the explanation that
contact angles at rough hydrophobic surfaces are higher because the
drop edge is “arrested” by the border of the grooves and the liquid
does not penetrate the scratches.
Morrow [36] investigated the effect of surface roughness on
contact angle hysteresis through a study of capillary rise in PTFE tubes.
These tubes were roughened with dolomite powder to various
degrees, and capillary rise heights were recorded with various fluids
to cover a range of intrinsic contact angles. Roughness ratios were
shown to be a strong function of the intrinsic angle rather than simply
exclusive properties of the solid surfaces. From these results, it was
concluded that Wenzel's equation and his observations were some-
what inconsistent. Yang et al. [37] reported a positive correlation
between the surface roughness and advancing contact angle for crude
oil, although the degree of correlation depended strongly on the type
of crude oil used.
For hydrophobic surfaces the data of Johnson and Dettre [18],
reported in Fig. 2, show the effects of advancing θa (maximum static
angle) and receding θr (minimum static angle) contact angles of water
on surfaces of wax of variable roughness. As the roughness increases,
small variations in the angles, together with significant increases in
hysteresis, are observed. Then, both angles suddenly increase as the
hysteresis diminished. It was concluded that texturing a solid does not
only modify the hysteresis but it can also affect dramatically the value
of the mean contact angle itself.
Shibuichi et al. [38] confirmed that the contact angle can be tuned
by the solid roughness. Their data are summarised in Fig. 3 where the
effective contact angle on a rough surface is plotted against the Young
contact angle. This work showed the dramatical effect of roughness on
contact angle depending on different wettability conditions. In the
hydrophilic domain (cosθ N 0), the effective contact angle was found to
be smaller than the Young contact angle. In the hydrophobic region
(cosθ b 0), it is the contrary: the contact angle was observed to
increase largely if the substrate was rough enough. It was shown that
both hydrophobicity and hydrophilicity are reinforced by roughness,
in qualitative agreement with the different behaviours.
A recent theoretical model has been developed for rough surfaces
in the hydrophilic domain [39]. According to this model, fluids with a
static contact angle of θ b 45° will spread regardless of the surface
structure. If 45° b θ b 90° the condition of spreading or receding will
depend on the structure of the rough surface (i.e. the height, width
and separation of the rough bumps).
3.1.4. Assigning the “true” apparent contact angle
It is apparent that surface roughness has a significant impact on the
macroscopic contact angle of flat surfaces and this has been
intensively studied as mentioned above. However, there are few if
any studies relating the impact of surface roughness of real particles
Fig. 3. Cosine of the effective contact angle θ: as a function of the consine of the Young
angle θ (determined on a flat surface of the same material and varied using different
liquids)[38].
on their wettability, which makes it more difficult to obtain “true”
apparent contact angles.
Dang-Vu and co-workers [40,41] investigated the impact of
particle size and roughness on hydrophobicity of particles measured
by the modified Washburn method, also referred to as the “capillary
rise” method. This method is a comparative method in which the
contact angles of the liquids studied are calculated from the ratio of
the penetration rate of the reference liquid compared to that of the
studied liquid [10]. Therefore, variation in any factors, such as
roughness or particle size, may cause variation of the penetration
rate of all liquids, including the reference liquid. It is important to note
that the penetration rate is directly related to the kinetics, but is not a
true reflection of surface hydrophobicity, i.e., contact angle value. By
dipping glass beads in HF, the surfaces were roughened and the depth
of the grooves of the modified surface was determined to be in the
range of 5 to 15 µm. It was reported that the roughness of the surface
had a significant effect on the kinetics of liquid penetration of a
collection of particles but not on the contact angle (as determined by
the Washburn method). These results indicate that the hydrophobi-
city, unlike the kinetics of flotation, should not be influenced by the
roughness of particles.
From an engineering perspective, Ulusoy and Yekeler [42] reported
on the relationship between the surface roughness and wettability of
some industrial minerals (calcite, barite, talc, and quartz). The
minerals were ground in ball, rod, and autogeneous mills to produce
samples for roughness and wettability tests. The surface roughness
values of these minerals were determined on the pelleted surfaces of
the ground powders by an instrument called HB103-Surtronic 3+, the
operation of which was based on the mechanical sensing of surface
topography in combination with electronic amplification of the signal
obtained. The wettability parameter measured was the critical surface
tension, determined by a flotation method using a microflotation cell.
A linear correlation of surface roughness of the minerals with their
critical surface tension values was reported. The experimental results
revealed that the degree of hydrophobicity of these minerals
increased as the surface roughness decreased. In other words,
roughness adversely affects the flotability of these minerals as it
decreases the contact angle. These findings seem to qualitatively
support the Wenzel equation, since the contact angle of these
minerals are in the hydrophilic domain (θ b 90°). However, it is crucial
 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115
to note that the changes in surface wettability noted in this study [42]
were not solely due to roughness effects but also due to the chemical
reaction between the mineral samples and the media from the ball
and rod mills. In the autogeneous mills there was no such reaction. In
addition, the unique crystallographic structure of the mineral talc [43],
which contributes to its natural flotability, was completely neglected
in the paper.
Wotruba et al. [44] reported contradiction results from flotation
tests carried out on zircon samples before and after attritioning for
48 h in a planetary mill. It was noted that the particle shape remained
unchanged by the attritioning and only the particle surfaces were
roughened. It was shown that the freshly roughened material floated
in total far better than the original material. This indicates that either
the influence of the edge effect is marginal or that the change in edge
properties after attritioning was not sufficiently large. Further
investigations are required to elucidate the fundamental principles
behind these effects.
3.2. Heterogeneity factor
Surface heterogeneity is inevitable due to various reasons with one
such important factor relating to the presence of impurities. Crawford
et al. [45] reported that the advancing and receding contact angles for
water drops on methylated quartz plates varied with the area fraction
of trimethylsilane groups in a manner similar to that predicted by the
Cassie equation. Drelich et al. [46] investigated the wetting character-
istics of liquid drops at well-defined heterogeneous surfaces consist-
ing of hydrophobic and hydrophilic regions, prepared by patterning
self-assembled monolayers (SAMs). From their work, it was postu-
lated that the Cassie equation requires modification to account for the
contribution of the free energy associated with the three-phase
contact line. These modifications are important for heterogeneities of
small dimensions (several micrometers and less).
Bain et al. [47] studied SAMs of alkanethiols with different
functional groups adsorbed onto gold. They found that the Cassie
equation holds strictly only for systems where intermolecular forces
between surface functionalities and the probe liquid are dispersive.
When water was used as a probe liquid on surfaces where specific
hydrogen bonding effects were strong, the contact angle varied non-
linearly with surface composition. This non-linearity suggests a
limitation of the Cassie equation for some surfaces with molecular-
scale heterogeneities. Thermodynamic analysis of the Cassie equation
for three-phase systems shows that this equation should be applicable
to surfaces composed of macroscopically heterogeneous regions
[41,48], although the situation is less clear for molecular-scale
heterogeneities. The effect of heterogeneity (and roughness) on
contact angle is sometimes difficult to differentiate from the line
tension effect which has been used to describe the deviation from the
Young contact angle [49–51]. Theoretically, line tension of the air–
water–solid contact should be of the order of 100 pN which is the
product of the molecular size and the air–water surface tension [52].
Table 1
Type and size of particle bed used for capillary rise investigation (adapted from [40]).
Type of bed Particle size (µm)
Silica flour 0–123
Alkyl-silane treated silica flour 0–123
Glass b106 to 425
Quartz particles 37–46
Hydrophilic and hydrophobized quartz crystals 5–208
Siliconized beads 105–350
Glass beads 100–520
Glass beads 60–250
Limestone 0–500
Sphalerite particles 7.22–150
Galena particles 0–150
111
This theoretical order of magnitude for line tension is normally
smaller than the experimentally determined results for three-phase
liquid–solid–gas systems [50]. This difference in line tension was
attributed to the local roughness and heterogeneity and, therefore, the
pseudo line tension was introduced to describe the effect of bubble
size on contact angle and flotation of fine particles [53].
For practical purposes, properties of solid–liquid, solid–vapour and
liquid–vapour interfaces are controlled by adsorption of surfactants.
Consequently, contact angle and hysteresis depend not only on
chemical heterogeneity of mineral surfaces but also on the surfactant
adsorption. Specific examples for the adsorption effect on contact
angle obtained for flotation systems are given in Section 4.1.
Quantitatively, the effect of surfactant adsorption on contact angle
can be analysed through the change in the surface tension of the air–
water interface, γl/a, which is an important parameter of the Young
Eq. (1). The influence of surfactant adsorption at air–water interface
on contact angle, wetting and flotation in more general case is
reviewed in [5,21,54]. In addition to affecting contact angle, surfactant
adsorption under dynamic conditions, known as dynamic adsorption
layer or DAL, can influence hydrodynamic boundary conditions at the
air–water interface and the particle–bubble dewetting and attach-
ment [54]. In particular, if the bubble surface is retarded in solution of
high surfactant concentration, the adsorption and contact angle are
uniform along the bubble surface. If the surfactant concentration is
sufficiently low, the surfactant molecules adsorbed at the leading
surface of rising bubbles can be swept to the bubble rear by the liquid
flow, leaving the front bubble surface clean (free from surfactant) and
forming a stagnant cap of surfactant at the rear. As a result of the DAL
effect, in solutions of low surfactant concentration, the contact angle
between a particle and the front bubble surface is close to that in
surfactant-free water, while the contact angle on the rear stagnant cap
of the bubble can be different due to the rather high surfactant
adsorption. Evidently, the coupling between the contact angle and the
dynamic adsorption layer adds further to the complication of
analysing contact angle and hysteresis. This complicated aspect of
contact angle, surfactant and dynamic adsorption layer in flotation
theory deserves a separate review complementary to the interesting
topic of physicochemical hydrodynamics of rising bubbles [55].
3.3. The effect of particle size on penetration kinetics and contact angle
In mineral processing, size reduction by mechanical crushing and
grinding is required to decrease the size and consequently liberate the
valuable minerals from gangue minerals. A large number of particle
sizes and types have been used to study the effect of particle
properties on the penetration kinetics and wettability by the capillary
rise method as summarised in Table 1 [40]. By measuring the
penetration rate of various liquids into a packed beds of glass beads
of different size (60–520 um), it was reported that neither particle
size nor pore size distribution influence the values of contact angles,
but their influence on the penetration rate was reported [40].
The effect of particles References
The larger the particle size distribution, the higher the penetration rate [94,95]
The larger the particle size distribution, the higher the penetration rate [94]
The effect of particle size on the contact angle was not observed [96]
The effect of particle size on the contact angle was not observed [45]
The effect of particle size on the contact angle was not observed [97]
The larger the particle size distribution, the higher the penetration rate [98]
The larger the particle size distribution, the higher the penetration rate [95]
The effect of particle size on the contact angle was not observed [40]
The larger the particle size distribution, the higher the penetration rate [94]
The effect of particle size on the contact angle was not observed [99]
The effect of particle size on the contact angle was not observed [57]
112 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115

In relation to flotation, it was reported that for a given particle size,
there is a unique contact angle below which the particle will not float
[56]. The dependence of rate constant on particle size was found to be
essentially linear, which is contradicted to the independence of
particle size on contact angle as shown in Table 1.
To add in more complication, the contact angle values of untreated
galena particles was reported to be independent of particle size but to
be dependent on the preparation route [57]. Cyclosized galena
particles were reported more hydrophobic than sieved particles of
similar size, and hence floated better. While these findings are difficult
to interpret, they emphasize the importance of hydrodynamic
conditions in controlling the surface chemistry of sulphide minerals
and may partially explain the role of high intensity conditioning,
where high shear forces can reportedly enhance flotation selectivity. It
is clear that surface hydrophobicity depends on not only physical and
chemical properties of the surfaces but the influence of hydrody-
namics condition seems also to be critical.
were investigated by a two dimensional measuring technique based on
the particle projections obtained from SEM microphotographs. The
results showed that particles possessing higher elongation and flatness
properties were recovered better during column flotation, whilst
roundness and relative width had a negative effect on the flotation
behaviour of the talc mineral studied. Consequently, as the shape of the
particles produced by the mill deviated from the ideal sphere, their
floatability was increased. In other words, elongation and smoothness
helped to increase the hydrophobicity, while roundness and roughness
caused a decrease in hydrophobicity or floatability for the talc. It was
postulated that this was due to the stronger adhesion force of prismatic
particles resulting from larger contact areas and longer contact lines
compared with equivalent round particles. However, beside the shape
factor as an obvious reason, chemical and structural properties of the
material need be taken into consideration as possible causes to the
changes in wettability.

3.4. The effect of particle shape on contact angle 4. Contact angles and their implication for flotation

Particle shape, in the same way as particle size, is an important
powder physical property affecting powder packing and bulk density,
porosity, permeability, cohesion, flowability, attrition, interaction with
fluids, and the covering power of pigments. For real industrial
materials, most or nearly all particles are non-spherical. Shape
parameters are generally used to express some particle attributes,
such as elongation and roundness (Table 2). The effects of non-
sphericity on flotation may contribute to the cause of discrepancies
the predicted results.
Wotruba et al. [44] investigated the influence of particle shape on
floatability. Four main shape classes of zircon particles were selected;
prismatic-long, prismatic-short, elliptic, and round. From scanning
electron microscope images, it was shown that prismatic particles
mostly have a smooth, well-crystallized surface, while the surface of
the rounded particles is usually rough. The floatability of the prismatic
particles was found to be far better than that of the rounded ones. The
proposed explanations are as follows;
• The stronger adhesion force of the prismatic particles results from
larger contact areas and longer contact lines compared with
equivalent round particles.
• Better adhesion of prismatic particles is caused by the influence of
sharp edges.
• Differently structured surfaces can cause different adhesion forces.
The freshly roughened material, prepared by attritioning in a
planetary mill, floated in total far better than the original one, and the
prismatic particles showed still better floatability than the rounded
particles. These results indicated that either the influence of the edge
effect is marginal or that the change of edge properties was not
sufficiently large.
The effect of particle shape of talc ground in different mills on the
wettability and floatability was investigated by Kursun and Ulusoy [58]
and Ulusoy and co-workers [42,59]. Shape characteristics of the particles
4.1. Contact angle and mineral floatability
As there are a great number of factors which influence the
performance of a flotation machine and floatability of minerals in an
actual flotation process, starting with simplified and idealised
experimental systems is a logical approach in flotation research. Due
to that reason, contact angle on synthetic or ideal mineral samples
have been studied extensively to understand the fundamental basis of
the flotation process. Starting with a simple captive bubble device to
measure contact angle [4], many modern instruments have provided
revealing insights into wettability [60,61].
Fig. 4 shows a correlation between the results of early flotation
experiments and interfacial wetting properties measured in terms of
contact angle and adsorption density for the xanthate-galena system.
It is established that for sulphide flotation contact angle has to be
between 60 and 80° which can be achieved using either weak
xanthates (with 2–3 carbon atoms in the hydrocarbon chains) for
floating sulphides of base metals or strong xanthates (with six carbons
in the hydrocarbon chains) for floating sulphide minerals bearing gold
and other precious metals. Flotation of non-sulphide minerals
requires a similar range of contact angle which can be produced
using long hydrocarbon (12–18 carbon atoms) collectors (e.g., fatty
acids or their salts and amines). Fig. 5 shows a typical correlation
between the results for flotation recovery and interfacial wetting
properties for the amine–quartz system.

Table 2
The shape factors and shape coefficients.

Name and symbol Definition

Volume shape factor, ϕv v = ϕvL3
Surface shape factor, ϕs s = ϕsL2
Flatness ðperimeterÞ2
4πðareaÞ
Roundness
4πðareaÞ
ðperimeterÞ2
Elongation
length
width
Fig. 4. Correlation between flotation recovery and contact angle vs. adsorption density
Adapted from [100]. for the xanthate-galena systems [101].
 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115
Fig. 5. Correlation of contact angle, adsorption density, flotation response and zeta
potential for quartz as a function of dodecylammonium acetate (DDA) concentration at
pH = 6 to 7 [102].
Solution pH is another important parameter of mineral floatability
as flotation normally works better under slightly alkaline condition,
which also prevents corrosion of metal equipment and breakdown of
xanthates and many other collectors in acidic environment. Typical
correlation between flotation response, contact angle and other
interfacial wetting properties versus pH is shown in Fig. 6.
4.2. Contact angle and flotation kinetics
As the air bubbles rise in a flotation cell, they collect particles and
carry them out of the cell. The overall process of particle collection by air
bubbles is closely linked with flotation kinetics as shown in a number of
Fig. 6. Correlation between contact angle, adsorption density, flotation response and
zeta potential for quartz as a function of pH in the presence of 4 × 10− 5 M DDA [103].
113
papers and books, e.g., [62–64]. The bubble–particle collection is a
balance between two competing effects, those of particle collision and
attachment, and those of detachment. The bubble–particle collision is
determined by hydrodynamics and mechanics of particle and bubble
motions, and is independent of contact angle. The bubble–particle
attachment and detachment are determined by the interfacial proper-
ties, and can be a function of contact angle.
4.2.1. Contact angle and bubble–particle attachment
Successful particle–bubble attachment involves three steps, viz., 1)
thinning of the intervening liquid film to a (critical) thickness where
the film ruptures, 2) rupture of the intervening liquid film and
formation of a three-phase contact (tpc) nucleus (a hole of a critical
wetting radius) and 3) expansion of tpc line from the critical radius to
form a stable wetting perimeter.
In the 1930s, Frumkin et al. [65–67] considered the thinning
kinetics of the intervening liquid film between an air bubble and a
mineral surface, and suggested the film thinning process as a means of
interpreting froth flotation. A thermodynamic theory that defined the
region of stability and the conditions for the formation of a definite
contact angle between a bubble and a particle was developed. It was
shown that the liquid film could be thermodynamically unstable and
would therefore rupture. Deryagin et al. [68,69] further elucidated the
process of the film thinning and experimentally showed that surface
forces arose and operated in the film. The disjoining pressure, П, was
introduced to describe the action of the surface forces in the
intervening film. The Frumkin-Derjaguin equation shows the depen-
dence of the surface hydrophobicity, described in terms of the
thermodynamic contact angle, on the disjoining pressure as [70,71]
∞
1
cos θY = 1 + ∫ ∏ðhÞdh ð5Þ
γg = l h
e
where h and he describe the actual and equilibrium film thicknesses,
respectively. The Frumkin-Derjaguin equation can be used to determine
the contact angle as a function of the electrical potentials of the bubble
and particle surfaces, the Hamaker constant and the parameters of
hydrophobic attraction. The calculation confirms that typical contact
angle for flotation of quartz using amine is about 50–60° [72].
The expansion of tpc line to form stable bubble–particle aggregates
is also a function of the interfacial wetting properties, including the
particle surface hydrophobicity [73]. The kinetics of tpc expansion, as
predicted using the molecular-kinetic model, strongly depends on the
Young contact angle [74,75].
4.2.2. Contact angle and bubble–particle detachment
Detachment can be a problem when floating coarse particles or
middling particles with decreased hydrophobicity. The forces that held
the bubble and particle together are a complex function of different
angles which describe the polar position of the contact points on the
particle surface (Fig. 7). The force that detaches particles from the
bubble surface is due to the effect of stresses induced by shear or
turbulence. In a mechanical flotation cell, the region surrounding the
impeller and stator is highly turbulent. Therefore, a number of
investigations have related the particle–bubble interactions and the
maximum floatable particle size to the properties of the turbulent field.
Most usually, the results are expressed in terms of a “machine
acceleration” bm or the mean energy dissipation rate ε [76,77]. The
works of Schulze [77] and Schubert [78] were combined and improved
by Nguyen [79] who showed that for most purposes, the following
simple equation could be used to represent the maximum particle size
that could remain attached to a bubble as a function contact angle:


3γg = l ð1− cosθÞ 1 = 2
dp max = ð6Þ
Δρðg + bm Þ
114 T.T. Chau et al. / Advances in Colloid and Interface Science 150 (2009) 106–115
Fig. 7. Stable contact area between a bubble and a particle is a complex function of the
interfacial properties, including contact angle, θ, and surface tension σ. The picture is
exaggerated to show the details of the contact point.
where g is the acceleration due to gravity, θ is the particle contact
angle and Δρ is the particle density less the water density. The energy
dissipation in a flotation cell also controls the bubble size through the
splitting process. Accordingly, the value of bm in Eq. (6) is bounded as
the bubble size increases and can be determined from the maximum
in the size of bubble that can be stable in a flow field and the mean
energy dissipation rate, giving [80]
2 31 = 2
6=5
γg = l ð1− cosθÞ
dp max = 1:534 5 ð7Þ
1=5
Δρε4 = 5 ρl
where it is assumed that the acceleration due to gravity can be
neglected and ρ l is the liquid density. Making some realistic
assumptions for chalcopyrite particles with the contact angle of 60°,
Eq. (7) gives a maximum floatable particle size of 512 µm, which is
quite within the range of expectations [80].
Knowing the maximum floatable particle size, the efficiency, Es, of
the bubble–particle aggregate stability in the turbulent field can be
determined by:
( !2 ) ( )
dp max 2:34ðγg = l Þ6 = 5 ð1− cosθÞ
Es = 1− exp 1− = 1− exp 1−
dp d2p Δρε4 = 5 ρl
where dp is the particle diameter. Eq. (8) is valid when the hysteresis
of contact angle, Δθ = θA−θR, where θA and θR are the (maximum)
advancing and (minimum) receding contact angles, is smaller than θR.
If the contact angle hysteresis is significant (i.e., Δθ N θR), Eq. (8) is
replaced by [64,80]:
( 6=5
)
1:17ðγg = l Þ sinθR sinΔθ
Es = 1− exp 1− 1=5
d2p Δρε4 = 5 ρl
The latest theory evidently shows the importance of not only the
contact angle but also of both the advancing and receding contact
angles and the contact angle hysteresis in determining the bubble–
particle detachment and the aggregate stability.
Eqs. (8) and (9) are derived when the turbulent tensile stresses are
dominant. If the turbulent shear stresses or the vibration of bubbles
rising to the pulp-froth interface are the dominant forces causing the
particle detachment, the two equations are modified, as shown by
Nguyen and Schulze [64]. It is noted further that the contact angle in
Eqs. (6)–(9) is also influenced by the dynamic adsorption of
surfactants onto rising bubbles which is discussed in Section 3.2.
The equations will require extension and improvement by considering
the DAL effect on contact angle.
4.3. Beyond contact angle
Despite of the rapid expansion of our knowledge both in theory
and experiment of contact angle, the important role of contact angle in
flotation research is undeniable but the universal correlation of
contact angle to flotation recovery is still difficult to establish and
predict theoretically.
It was reported that contact angle is not the sole criterion responsible
for mineral recovery, but is rather one of the important contributing
factors [56]. A critical contact angle in certain conditions, below which
flotation will not occur, may be sufficient to delineate floatability of a
mineral sample. Or a range of contact angle, instead of single advancing or
receding value, may be more useful in predicting the floatability of
mineral samples. The progress for colloid chemistry in flotation is moving
forward to more sophisticated instrumentation for probing other
contributing factors in flotation, such as critical film thickness [81–84],
induction time [85–87], measurements with atomic force microscopy
[88–90] and adsorption mechanisms of reagents and salt ions [91–93].
Toward the understanding of a complex flotation process, all key
factors; such as contact angle, induction time, electrochemical, chemical
as well as mechanical, have to be taken into consideration and a
correlation of those key factors and flotation recovery is essential to
establish the link between research and practice in flotation.
5. Summary
Wetting behaviour can be quantified by contact angle measure-
ment. However, obtaining meaning and reproducible contact angle
values of real samples is difficult, due to its sensitivity to a variety of
influencing factors such as surface roughness, heterogeneity, particle
size, and particle shape. Wenzel's and Cassie's equations are generally
used to account for roughness and heterogeneity of the real surfaces
but recently it has been revealed that they are applicable only in
certain conditions. Therefore, it is suggested that the key to under-
standing wetting phenomena of real surfaces is probably not in trying
to fit experimental data to idealised models, but in examining the
detailed nature of the surfaces and characterising the surfaces to the
smallest scale possible, where assumptions are minimal. Then, it may
be possible to scale upwards to extract macroscopically verifiable data.
1=5
In flotation, the derivation of a robust model that works for
ð8Þ different conditions, mineral compositions, and scales is the key
challenge for such on-going research. So far, there is no rigid
quantitative correlation of contact angle on flotation rate recovery.
Such correlation will contribute to strengthen the correlation of
colloid chemistry and mineral processing. The exploration journey is
nowhere near its destination.
Acknowledgements
ð9Þ The authors wish to acknowledge Mr J.T. Woodcock, Mr G. Heyes
and Ms J. Bear for their help during the preparation of this manuscript.
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