Minerals Engineering 22 (2009) 213–219

Contents lists available at ScienceDirect

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

A review of techniques for measurement of contact angles and their applicability

on mineral surfaces
T.T. Chau *
CSIRO Minerals, Box 312 Clayton South, Vic. 3169, Australia

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

Article history: Knowledge of the wetting characteristic of mineral surfaces is paramount in enhancing the efficiency of
Received 26 May 2008 separation of valuable minerals from gangue using froth flotation. The contact angle value is a useful indi-
Accepted 27 July 2008 cator providing the hydrophobic characteristic of the solid mineral surfaces due to a close relationship
Available online 6 September 2008
between this parameter and the floatability of minerals.
In this paper, techniques for contact angle measurements and their applicability on mineral surfaces
Keywords: are reviewed. Two main groups of techniques for contact angle measurements are available; one group
Contact angle
is applicable to flat and smooth surfaces while the other one has been especially developed for non-ideal
Hydrophobicity
Froth flotation
surfaces or particles. Capillary penetration methods have been found to be more applicable than the other
methods cited in measuring contact angles on real mineral surfaces. The major challenge with this tech-
nique is the modification required to overcome the difficulties in the experimental packing technique
needed, and more importantly, to obtain the receding contact angle values. The coupling of accurate con-
tact angle measurements with real (batch) flotation data would seem to be area which has had limited
attention.
Crown Copyright Ó 2008 Published by Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
2. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
3. Contact angle measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
3.1. Flat surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
3.1.1. Drop profile. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
3.1.2. Drop dimensions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
3.1.3. Axisymmetric drop shape analysis-profile (ADSA-P) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
3.1.4. Wilhelmy method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
3.1.5. Capillary rise at a vertical plate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
3.1.6. Microscopy methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
3.2. Non-ideal surfaces and particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.2.1. ADSA-D method for non-ideal surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
3.2.2. Capillary penetration methods for particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218

* Tel.: +61 3 9545 8915; fax: +61 3 9562 8919.

E-mail address: Tammy.Chau@csiro.au

0892-6875/$ - see front matter Crown Copyright Ó 2008 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2008.07.009
214 T.T. Chau / Minerals Engineering 22 (2009) 213–219
1. Introduction
In mineral processing, after grinding the ore to liberate the min-
erals, flotation is widely used to quickly and efficiently separate
valuable minerals from the gangue minerals based on the differ-
ences in their natural or induced hydrophobicity. Hydrophobic
mineral particles are more readily attached to air bubbles and
floated to the top of the pulp, whereas the hydrophilic gangue
are not and report to the tailing.
Overall, the flotation process can be divided into three major
sub-processes; particle–bubble collision, adhesion of the mineral
particles to the air bubble, and detachment. The whole process is
complicated further by the addition of numerous reagents to the
pulp to control surface properties of particles and the pulp chemis-
try. The primary requisite for flotation is the replacement of water at
the mineral surface by an air bubble and this can be quantified by a
receding contact angle value. It is clear that a fundamental under-
standing of surface chemistry and wettability plays a crucial role
in controlling the bubble/mineral adhesion sub-process (Wark,
1984). However, there is a gap in this area which requires further
investigation to make improvements to the flotation process. Seri-
ous efforts based on different approaches, including modeling, the-
oretical and experimental studies are being conducted to bridge this
gap. At CSIRO, a computational fluid dynamics (CFD) model is cur-
rently being developed for mechanically stirred flotation cells where
contact angle is one of a number of very important input parameters,
that affects the accuracy and applicability of the model (Koh and
Schwarz, 2003, 2006). The success of this model may offer significant
cost savings in modifications to existing equipment and operations
to improve flotation performance. Therefore, achieving realistic con-
tact angle values for real mineral samples and precisely quantifying
the impact of various factors on these values is important.
The contact angle is a useful indicator in providing data on the
wetting characteristic of solid mineral surfaces due to the close
relationship between the contact angle and the floatability of min-
erals. Over the years, many different techniques have been devel-
oped for the measurements of contact angles. However,
controversy still reigns in the literature on the accuracy and quality
of the data reported and its suitability for use in the Young equa-
tion, as discussed later. For real mineral systems, only a few of
the available techniques can offer precise, meaningful and realistic
contact angle values without unreasonable requirements and/or
assumptions.
This paper is aimed at reviewing available contact angle mea-
surement techniques, especially those that are applicable to min-
eral surfaces, accessing their pros and cons, and identifying
possible methodologies for improvement and adaptation to real
mineral surfaces to gain further understanding on their practical
application in froth flotation. Details of most of the major contact
angle measurement techniques and their experimental set-ups
have been described by Adamson and Gast (1997), Hunter
(2001), Ralston and Newcombe (1992) and Kwok and Neumann
(1999). The methods can be generally divided into two main
groups; one group is applicable to flat and smooth surfaces while
Air
θ Air
Water
Mineral surface
Fig. 1. Contact angle (h) formation of water droplet in air (left) and air bubble in water on a solid surface (right).
the other one can be used for non-ideal surfaces or particles, which
is arguably more relevant for real mineral surfaces. An up-to-date
critical review of the proposed techniques is presented here.
2. Background
Two procedures are available for studying contact angles at the
three-phase contact line of solid surface/water/air: a drop of water
can be placed on a solid surface as shown in Fig. 1(left); alterna-
tively, a submerged air bubble can be used to probe the surface
of a solid immersed in water as shown in Fig. 1(right). The latter
procedure is more relevant and almost obligatory in studying the
surface reactions involved in mineral flotation where suitably sized
minerals are produced by grinding in water. In principle, these two
contact angles are the same.
As illustrated in Fig. 1(right), contact angle h of a bubble on a
mineral solid surface in an aqueous medium is defined as the
mechanical equilibrium of the bubble under the action of three
interfacial tensions: solid–air (cs/a) solid–liquid (cs/l) and liquid–
air, (cl/a). This equilibrium relation is known as Young’s equation
and is shown in Eq. (1)
cs=a ¼ cs=l þ cl=a cos h ð1Þ
The validity of Young’s equation requires that the solid surface is
smooth, flat, homogenous, inert, insoluble, non-reactive, non-por-
ous, and of non-deformable quality. Those conditions are usually
not met by real surfaces (Kwok et al., 1998; Lam et al., 2002; Tavana
et al., 2004). The difference between an ideal surface for contact an-
gle measurement and a real mineral surface and some proposed
solutions to prepare mineral surfaces to make them suitable for
measurement are recommended in Table 1. It is noted that surface
roughness and chemical heterogeneity are present to some extent
in all real mineral samples. As a result, the contact angle may
change from one point to another along the contact line and will
be differentiated into three definitions as shown in Fig. 2 (Marmur,
1996). The ‘‘intrinsic contact angle” as shown in Fig. 2(left) is ex-
pected for an ideal solid surface. The usual optical methods for mea-
suring contact angles, presented in Section 3, yield the ‘‘apparent
contact angle”. This is the angle between the direction of the tan-
gent to the ‘‘smoothed” solid surface and the direction of the tan-
gent to the air–water interface as shown in Fig. 2(right). On
perfectly smooth solid surfaces, the apparent contact angle is iden-
tical with the actual contact angle. On real mineral surfaces, those
two values may be very different.
The apparent contact angle of a real surface is not unique, but
falls into a more or less wide interval between the advancing (larg-
est) and receding (smallest) contact angle. The difference between
these two values is called the contact angle hysteresis. Butt et al.
(2006) reported that the hysteresis value is typically between 5°
and 20° but sometimes can also be significantly higher. Adamson
and Gast (1997) proposed three main reasons that cause hystere-
sis; contamination of either the liquid or the solid surface, surface
roughness, and surface immobility on a macromolecular scale.
Unfortunately, there is no independent means of distinguishing
Water
θ
Mineral surface
 T.T. Chau / Minerals Engineering 22 (2009) 213–219
Table 1
Comparison between an ideal surface for contact angle measurement and a real mineral surface and some proposed solutions to prepare mineral surfaces to make them suitable
for measurement
Ideal surface property Real mineral surface property
Smooth Rough
Flat Irregular shape
Homogenous Heterogeneous
Inert, insoluble, non-reactive Variable
Non-porous Variable
Non-deformable Non-deformable
Water
Air
θin
Mineral surface
Fig. 2. Differentiation between contact angle values: the intrinsic contact angle (left) and the apparent contact angle (right).
the source of reasons that cause contact angle hysteresis. There-
fore, there is a particular interest in producing surfaces that are
as close to perfect as possible so that there will be minimum and
negligible contact angle hysteresis.
In flotation, if the contact angle of a mineral is nil, this means
that water wets the mineral in preference to air and air–mineral
contact is impossible. A contact angle of 0° represents nonfloatabil-
ity. Conversely, a contact angle of 180° would represent complete
wetting of the mineral by air to the exclusion of water. No mineral
surface is known to give an air–water contact angle larger than
about 110°, so that the condition of a 180° angle cannot be realised
experimentally.
3. Contact angle measurements
In general, contact angle measurement techniques can be di-
vided into two categories; measurement on flat plates and mea-
surement on non-ideal surfaces or particles.
3.1. Flat surfaces
Several techniques exist to measure contact angle on a flat sur-
face horizontally or vertically. The most common method of con-
tact angle measurement involves the usage of low-magnification
optical devices to observe the drop or bubble image. It is quite dif-
ficult to obtain a clean and flat mineral surface that can give repro-
ducible results due to the difficulties in keeping such a surface
uncontaminated in an open-air laboratory environment. The
experimental procedure for surface preparation proposed by Wark
and Cox (1934), i.e., abrasion and/or polishing under water using
scrupulously controlled condition, has been found to give repro-
ducible and characteristic equilibrium angles. The success of the
contact angle measurements on flat surfaces rely heavily on the
surface quality and its cleanliness, and the value obtained may
lie somewhere between the advancing and receding angle, ha and
hr. In general, measurements of contact angles on flat surfaces
are difficult and uncertain when the angle is under 20° (due to
its high sensitivity to experimental error) (Gaudin, 1957).
3.1.1. Drop profile
For flat solid surfaces, the most widely used technique for con-
tact angle measurement is a direct measurement of the angle by
215
Proposed solutions
Polish as suggested by Wark and Cox (1934)
Use cutting saw, but a mineral sample of sufficient size is difficult to obtain
Use synthetic samples but these are not comparable to real mineral samples
Prepare and store samples under suitable conditions/ solutions
Not required for most metallic minerals
Not required for most metallic minerals
Water
Air
θ ap
Mineral surface
viewing the drop profile. Bigelow et al. (1946) showed that a tele-
scope goniometer can be used to view a drop placed on a polished
surface and measure the profile of the contact. An image of the
resting drop or of the adhering bubble can be projected onto a
screen and the outlines traced, whereupon the angle is measured
by a protractor. Alternatively, a photograph can be taken for per-
manent record as proposed in Leja and Poling (1960). The accuracy
is enhanced by the use of relatively high magnifications (up to 50
times) that permit the detailed examination of the intersection of
the drop profile and the solid surface. Hunter (2001) showed that
the angle formed by a sessile drop or, alternatively, an adhering
gas bubble can be determined to an accuracy of ±2° for contact an-
gles greater than about 20°.
The captive-bubble method introduced by Taggart et al. (1930)
is another variant of the profile method. It differs from the others
in that the bubble is not placed under the polished surface, but
above it, the supporting force of surface tension being used to keep
the system together, exactly as in a flotation system. Wark and Cox
(1934) demonstrated that the contact angle is the same whether
the air bubble is freely suspended or held by a glass holder.
The drop profile technique can be used to measure advancing
and receding contact angles by increasing and decreasing the drop
size, respectively. In addition, the observed contact angle may
change depending upon whether or not equilibrium with respect
to adsorption of surface active agents is attained.
There are two advantages of using this technique: only very
small quantities of liquid are required and solid surfaces as small
as a few square millimeters can be used. However, this advantage
is also the downside of this technique due to the higher risk/impact
of impurities. Another limitation of this technique is that the cam-
era or imaging device will be focused on the largest meridian sec-
tion, and hence reflect only the contact angle at the point in which
the meridian plane intersects the three-phase line. Surface hetero-
geneity and/or roughness could well cause variations of the contact
line along the three-phase line. In addition, the dependence of con-
tact angle on drop size causes a systematic problem. In general,
this is considered as the most convenient technique if high accu-
racy is not required.
3.1.2. Drop dimensions
Contact angles may be obtained through the measurement of
the drop dimensions when a sessile drop rests on a surface. The
216 T.T. Chau / Minerals Engineering 22 (2009) 213–219
drop may not need to have perfect axial symmetry, but a spherical
shape offers the advantage that the surface tension of the wetting
liquid can be determined simultaneously with the contact angle.
These methods consist of measuring parameters that determine
the entire profile of an axially symmetrical drop, starting with the
Laplace equation (Eq. (2)) describing the shape of fluid interfaces
 
1 1
c þ ¼ DP ð2Þ
R1 R2
where R1 and R2 are the two principal radii of curvature and DP is
the pressure difference across the interface.
Bashforth and Adams (1883) were the first to make the efforts
in using the Laplace equation to describe droplet shape from a the-
oretical perspective. Fisher (1979) developed a relationship be-
tween contact angle, radius, and volume in order to measure
small contact angles for sessile drops. An analytical balance was
used to determine mass and, with a known density (q, volume.
The radius was determined from a photograph of the drop. This
method has been improved by other researchers and developed
further based on the conjunction with, either or both of, the
numerical integration of the Laplace equation, and the tables of
Bashforth and Adams (1883).
Despite the progress in approach, there are several deficiencies
in the algorithm of this method. The error function is computed by
summing the squares of the horizontal distances between the mea-
sured points and calculated curve. This measurement may not be
adequate, particularly for sessile drops whose shapes are strongly
influenced by gravity and achieving the best fitting-curve plays a
crucial role in obtaining an accurate contact angle value. Thus this
technique has gone through modification, to overcome these defi-
ciencies, to the next level called the axisymmetric drop shape anal-
ysis-profile (ADSA) technique.
3.1.3. Axisymmetric drop shape analysis-profile (ADSA-P)
ADSA is a technique to determine liquid–fluid interfacial ten-
sions and contact angles from the shape of axisymmetric menisci,
i.e., from sessile as well as pendant drops. This technique was first
developed by Rotenberg et al. (1983) and was then improved by
Spelt et al. (1987) and Cheng et al. (1990). The two main assump-
tions are that the experimental drop is Laplacian and axisymmet-
ric, and the gravitational force is the only external force. ADSA-P
finds the theoretical profile that best matches the drop profile ex-
tracted from the image of the real drop, from which the surface
tension, contact angle, drop volume, and surface area can be com-
puted. The strategy employed is to fit the shape of an experimental
drop to a theoretical drop profile according to the Laplace equation
of capillarity (Eq. (2)), by using the surface or interfacial tension as
an adjustable parameter. The best fit identifies the correct surface
or interfacial tension and contact angle. It is worth mentioning that
this method is very different from the drop profile method: the
drop profile method puts a tangent to the drop profile, whereas
ADSA fits the best Laplacian shape to the entire profile of the drop.
Therefore, a complete and undisturbed drop profile is required in
the ADSA technique and having a needle immersed into the drop,
as mentioned in the drop profile technique, is not recommended.
Del Rio et al. (1998) reported that ADSA-P is a more reliable and
less sensitive to surface heterogeneity and/or roughness and there-
fore more suitable for mineral surfaces. Rodriguez-Valverde et al.
(2002) reported that the captive-bubble method in conjunction
with the ADSA-P technique allows comfortable, automatic and
reproducible measurements of contact angle on porous stones.
3.1.4. Wilhelmy method
This simple method is attributed to and named after Wilhelmy
(1863). When a thin, smooth, vertical plate, such as a microscope
cover glass or piece of platinum foil, is brought into contact with
a liquid, if the contact angle is less than 90° a downward force,
WF, is exerted on the plate (Eq. (3))
W F ¼ pcLV cos h ð3Þ
where p is the perimeter of the line of contact. If the depth of
immersion is not equal to zero then a volume V of liquid will be dis-
placed. Consequently, the effect of buoyancy must be taken into ac-
count when considering the force exerted on the plate, as shown in
Eq. (4)
W F ¼ pcLV cos h  V Dqg ð4Þ
Thus, if the surface tension is known, the contact angle can be read-
ily calculated. By moving a smooth plate of a known perimeter up or
down, an advancing or receding contact angle can be established.
While the Wilhelmy method at first seems to be an ideal method,
it has several drawbacks. A high sensitivity electrobalance is re-
quired. The solution must not swell too much and its vapour should
not adsorb onto the plate. The plate must have a constant perime-
ter, the same composition and morphology at all surfaces: front,
back and both edges. Sharp edge corners are required to minimize
the edge/corner effect. These conditions altogether may be difficult
to meet, especially with real mineral specimens.
3.1.5. Capillary rise at a vertical plate
The Wilhelmy plate technique may be modified so as to mea-
sure the capillary rise, h, at a vertical plate. When a liquid comes
in contact with a vertical and infinitely wide plate it will rise and
the height which it attains can readily be determined by the appli-
cation of the Laplace equation, yielding Eq. (5)
2
Dqgh
sin h ¼ 1  ð5Þ
2cLV
Knowing the density difference Dq between liquid and vapour, the
acceleration due to gravity g, and the liquid surface tension cLV, the
contact angle h can be obtained from a measurement of the capil-
lary rise h. For practical purposes, plates that are about 2 cm wide
satisfy the theoretical requirement of ‘‘infinite” width. The task of
measuring a contact angle has thus been reduced to a measurement
of a length, which can be performed optically, e.g., with a cathetom-
eter. This measurement has been automated by Budziak and Neu-
mann (1990) and Kwok et al. (1995) and is used to perform
various dynamic advancing and receding contact angle measure-
ments. This method has proved to be particularly suitable for mea-
suring the temperature dependence of contact angles. The
corresponding uncertainty in the value of h for a typical liquid is
about 0.1°. The disadvantage of this method and the Wilhelmy
method is that the surface tension cLV of the liquid must be known
and there may be a serious uncertainty if the solutions contain sur-
face active agents. In such systems, adsorption of the surface active
material at various interfaces may change the surface tension and
the contact angle simultaneously. The joint use of the Wilhelmy
method and the capillary rise allows the determination of contact
angle and liquid surface tension at the same time by solving Eqs.
(2) and (5) with the aid of the identity sin2h + cos2h = 1.
3.1.6. Microscopy methods
Some efforts have been put into measuring the contact angle of
a single colloidal particle in aqueous solution thanks to the use of
advanced microscopy methods such as atomic force microscopy
and confocal microscopy.
By measuring the interaction forces between a spherical colloi-
dal particle and a bubble in an aqueous solution by employing the
atomic force microscope (AFM), contact angles of individual parti-
cles can be determined as reported by Ducker et al. (1994), Preuss
and Butt (1999) and Ralston et al. (1999). However, there are sev-
 T.T. Chau / Minerals Engineering 22 (2009) 213–219
eral assumptions and ambiguities in the analysis as well as a com-
plicated experimental setup and calibration; hence it is an unpop-
ular method for contact angle determination as explained by
Johnson et al. (2006). In addition, the change of shape of particles
during compaction and the elastic bubble deformation caused in
them may change their wetting behaviour (Preuss and Butt,
1999). Nguyen et al. (2003) reported that as the position of the
three-phase contact relative to the particle was not known, it
was difficult to decide whether or not the measured contact angle
can be used as a measure of the extent of hydrophobicity of the so-
lid particle surfaces. These works indicate that AFM appears to be a
useful tool for determining the contact angle for single particles
and can provide valuable insight into intermolecular forces. How-
ever, the interpretation of AFM force measurements at deformable
surfaces is very convoluted and more studies are required in this
area.
A confocal microscopy technique, which was used for contact
angle measurement of individual microglass spheres with diame-
ter of 3–10 lm, was developed by Mohammadi et al. (2003). How-
ever, the results seem to be overestimated compared to those
obtained from the pendant drop method. The plausible reasons
for the discrepancy between the two methodologies are the effect
of fluorescent dye and/or low accuracy associated with pendant
drop technique.
3.2. Non-ideal surfaces and particles
The measurement of contact angles on non-ideal surfaces and
particles is extremely relevant for mineral applications, but is quite
challenging and frequently produces highly unreliable results. For
the sake of a complete review, methods to measure the contact an-
gle of non-ideal surfaces are first presented in Section 3.2.1. For
powdered solids, contact angle values obtained on compressed pel-
lets of the solids are smaller that that on a smooth specimen of this
solid due to surface roughness and porosity. Hunter (2001) com-
mented on the method of contact angle determination on com-
pressed disc as ‘As best, useless. At worst, positively misleading’.
The reliability and applicability of contact angle measurements on
a flat plate are questionable and suspect in an actual mineral con-
text because the measurement on a single surface cannot be repre-
sentative of minerals particles in a pulp. In addition, clean cleaved
mineral surfaces of sufficient size for making flat plate are seldom
available. The measurement of a contact angle for one colloidal par-
ticle is uncommon due to extreme experimental difficulties as men-
tioned in the microscopy method above; normally an average for
many particles is obtained instead. Therefore, methods to quantify
wettability of irregular particles in packed beds have been devel-
oped and found to be more applicable to a flotation context, in
which the floatability characteristic of irregularly shaped mineral
particles in the size range from 10 lm to 200 lm are of more inter-
est. Contact angle measurements on powders in a packed bed, re-
ferred to as capillary penetration methods, can reduce the
problems associated with single-surface studies. Details of capillary
penetration methods for particles are presented in Section 3.2.2.
3.2.1. ADSA-D method for non-ideal surface
For non-ideal surfaces (e.g., rough surfaces), contact angles are
generally difficult to obtain due to morphological and energetic
imperfections, leading to irregularities in the three-phase contact
line or a small contact angle in some cases. It is difficult to measure
contact angles in these cases by finding a tangent of the drop pro-
file due to the absence of a clear three-phase contact point.
Axisymmetric drop shape analysis-diameter (ADSA-D), another
branch of ADSA, can provide accurate and consistent contact angles
by viewing the drop from above, i.e., obtaining top-view of the
drop. In the ADSA-D program, when the contact diameter, liquid
217
surface tension, and volume of the drop are known, the contact an-
gle can be determined from a numerical integration of the Laplace
equation of capillarity, Eq. (3). This method is suitable for measur-
ing small contact angles, less than 20°, and may be also useful for
measuring contact angles on imperfect solid surfaces, such as
wood and stone although further improvements are required.
Rodriguez-Valverde et al. (2002) reported that the quantification
of surface roughness effect in contact angle is difficult and contro-
versial. They asserted that the equilibrium contact angle cannot be
measured due to the existence of metastable states and a strong
dependence of contact angle on drop size. This technique to date
seems only suitable for dynamic contact angle measurement on
non-ideal surface.
3.2.2. Capillary penetration methods for particles
Numerous qualitative penetration techniques are used with the
majority of the methods dealing with compressed powders. Dy-
namic techniques popularised by Washburn (1921), developed
theoretically by Levine et al. (1980) and Good and Lin (1976) have
been carefully validated for narrow capillaries by Fisher and Lark
(1979). This latter technique, mainly used for determining powder
contact angle, is based on the use of capillary pressure to drive
fluid at an observable rate through a packed bed of the powder
in a capillary tube.
Static measurements were originally proposed by Bartell and
Osterhof (1927), Bartell and Whitney (1932), and Bartell and Wal-
ton (1934). The theory underlying this method has been signifi-
cantly extended by White (1982). The wetting liquid rises in a
column of the packed powder to a certain height at which gravita-
tional forces on the column of liquid balance the capillary pressure.
Alternatively, an external pressure differential can be applied to
oppose the capillary pressure and measure the pressure difference
DP which just stops the capillary rise.
The Laplace pressure, which drives liquid into a capillary bed,
can be described by the Laplace equation (Eq. (6))
2cLV cos hp
DP ¼ ð6Þ
r eff
White (1982) defined the effective capillary radius reff the following
way (Eq. (7)):
2ð1  /Þ
reff ¼ ð7Þ
/q A
where u is the volume fraction of solid in the packed bed, q is the
density of the solid material and A is the specific surface area per
gram of solid. Combining Eqs. (6) and (7) yields the Laplace–White
Eq. (8), which is a strict thermodynamic expression for DP in porous
media:
cLV cos h/Aq
Dp ¼ ð8Þ
ð1  /Þ
Dunstan and White (1986) used a capillary method to test White’s
approach and broad agreement between theory and experiment
was obtained for cleaned and chemically treated smooth glass
ballotini. Direct determination of reff is problematic because the
specific wetted area of the particles may be different to that mea-
sured by techniques such as gas absorption.
This problem can be overcome by using a second fluid that is
known to perfectly wet the powder as reported by Diggins et al.
(1990) and Diggins and Ralston (1993). Their approach for deter-
mining contact angle is to compare the wetting behaviour of the li-
quid of interest with that of a perfectly wetting liquid, h = 0°, and
this step is sometime referred to as calibration. The requirement
is that the surface tension of the reference liquid must be below
the critical wetting surface tension of the solid. Cyclohexane
(c = 25.5 mN/m) is the most commonly used reference liquid. The
218 T.T. Chau / Minerals Engineering 22 (2009) 213–219
contact angle of the reference liquid, h2, is equal to zero and thus its
capillary pressure studies probe the geometry of the particle bed.
Prestidge and Ralston (1995) reported that the success of the
method relies on the correct choice of a reference liquid.
It is important to note that while the contact angles obtained on
such surfaces are not normally the Young contact angles, it is in-
deed this contact angle that will, together with the liquid surface
tension, determine the Laplace pressure DP, and hence the capil-
lary penetration (Kwok and Neumann, 1999).
Subrahmanyam et al. (1999) compared the contact angles of
quartz by capillary penetration of liquids and captive-bubble tech-
niques and it was concluded that the capillary penetration method
showed better correlation with floatability than the captive-bubble
method. The advantage of the capillary penetration method is
thought to be that its operation is simpler and quicker, enabling
multiple measurements to be taken with a corresponding improve-
ment in reliability.
The main experimental challenge of this method is to obtain a
constant and homogeneous powder packing in the capillary tubes.
The disadvantage of this method is that only advancing water con-
tact angle is obtained whereas the receding contact angles are usu-
ally quoted for flotation process because these contact angles are
supposed to correlate better with the actual flotation response
(Laskowski, 1994; Lam et al., 2002). Methods to overcome experi-
mental difficulties and modification, required to obtain receding
contact angle values, will make a crucial step closer to develop a
contact angle device that applicable to real mineral surfaces.
4. Conclusions
Contact angle measurements and techniques, especially those
applicable to mineral surfaces have been reviewed. Contact angle
measurements have been studied extensively and applied broadly
in many areas to allow a quick indication of surface hydrophobic-
ity. In mineral processing, techniques of contact angle measure-
ments on flat mineral surfaces are not competitive to capillary
penetration methods for particles in a flotation context. The draw-
back of the former technique is the extreme difficulty in obtaining
a mineral surface that satisfies all the requirements for optimum
measurements. Heterogeneity appears to be the biggest issue in re-
spect to optimum of the Young–Laplace equation.
It is concluded that the capillary penetration method for parti-
cles is the most suitable method for contact angle measurement on
real mineral samples. The goal is to be able to obtain an accurate
contact angle value of real mineral particles quickly and easily.
The challenge for the future is to be able to quantify the contact an-
gle value obtained, as a function of particle size, particle shape, het-
erogeneity, roughness, and amount of surface active agents. A new
robust model is required to incorporate all of these parameters into
the relationship between the ideal and the apparent contact angle
values. If reliable contact angle measurement data can be readily
obtained in real system, and correlated with the appropriate
(batch) flotation data, then the use and application of such mea-
surements may transferred from fundamental flotation studies to
practical flotation applications.
Acknowledgements
The author wishes to acknowledge Dr. B. Follink, Mr. J.T. Wood-
cock and Mr. W.J. Bruckard of CSIRO Minerals for their help during
the preparation of this manuscript.
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