Int. J. Miner. Process.

72 (2003) 215 – 225

www.elsevier.com/locate/ijminpro

Attraction between hydrophobic surfaces studied by atomic

force microscopy
Anh V. Nguyen a, Jakub Nalaskowski b, Jan D. Miller b,*, Hans-Jürgen Butt c
a
Department of Chemical Engineering, The University of Newcastle, University Drive, Callaghan, NSW 2308, Australia
b
Department of Metallurgical Engineering, University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114, USA
c
Max Planck Institute for Polymer Research, Ackermannweg 10, D-55021 Mainz, Germany
Received 28 December 2002; received in revised form 11 March 2003; accepted 30 June 2003

Abstract

Attraction between hydrophobic surfaces, known as the hydrophobic force, is critically important for attachment of particles
to air bubbles in flotation. However, the origins and models for this attractive force between hydrophobic surfaces have been a
source of debate since the first direct measurements of this force in the early 1980s. Using an atomic force microscope (AFM)
we studied the attraction between an AFM hydrophobic probe and a flat hydrophobic surface in water, in water – ethanol
mixtures, and in water saturated by gases with different solubility. The strong attractive force with long-range jump-in
attachment positions decreases with an increase in the ethanol content and disappears in pure ethanol. The size of steps on the
force curves depends on the gas solubility. However, the measured forces do not depend on the gas solubility significantly. The
influence of surface roughness and heterogeneity appear to be significant. Experimental results indicate the role of surface
stabilized submicron-sized bubbles in the hydrophobic attraction. This is in line with recent direct and indirect evidences for the
presence of gaseous bubbles at hydrophobic surfaces as well as with the early insights of flotation scientists.
D 2003 Elsevier B.V. All rights reserved.

Keywords: hydrophobic forces; submicroscopic bubble; bubston; AFM; flotation

1. Introduction exists between a particle and an air bubble at short

separation distances during their contact in water. This
In flotation, van der Waals (Nguyen et al., 2001) and theoretical consideration was illustrated by Kitchener
electrical double-layer (Nguyen et al., 2002) interaction and collaborators. Laskowski and Kitchener (1969)
forces between a mineral particle and an air bubble are demonstrated that the macroscopic wetting properties
usually repulsive. Thus particle – bubble attachment of a silica surface after methylation are drastically
indicates that there exists some additional, attractive changed. The wetting prediction by the Derjaguin-
force, termed the hydrophobic (attractive) force, which Landau-Verwey-Overbeek (DLVO) theory for these
surfaces also becomes inconsistent according to Pash-
ley and Kitchener (1979). Since the van der Waals
* Corresponding author. Tel.: +1-801-581-5160; fax: +1-801-
interaction and electrical double layer interaction were
581-4937. not significantly changed after the surface methylation,
E-mail address: [email protected] (J.D. Miller). these authors concluded that hydrophobic attraction

0301-7516/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0301-7516(03)00100-5
216 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225

operating between the methylated surfaces had to exponential function. The short-range exponential de-
extend to some greater distance in order to overcome cay length was from 2 to 3 nm for both surfaces. At
van der Waals and double-layer repulsions. Another longer distances the hydrophobic attraction decayed
elegant estimation of the magnitude and range of the exponentially with a decay length of 13 nm for hydro-
hydrophobic attraction was given by Blake and Kitch- carbon and 16 nm for fluorocarbon.
ener (1972) who estimated the range of the hydropho- It should be noted that all of the above-described
bic attractive force to be about 64 nm by observing the measurements were carried out with the Surface Force
rupture of an aqueous intervening film produced by Apparatus of Israelachvili (Israelachvili and Adams,
compressing an air bubble against a planar methylated 1976). Measurements with a different type of appara-
silica surface. tus (Derjaguin et al., 1977) also showed the existence
Measurement of hydrophobic attractive force has of a very long-range hydrophobic attractive force
been possible only during the last two decades. The between hydrophobic methylated silica filaments with
first direct measurements of the hydrophobic attraction an advancing water contact angle of 100j (Rabino-
forces between macroscopic surfaces were reported in vich and Deryagin, 1987, 1988). However, a triple-
1982 (Israelachvili and Pashley, 1982). These measure- exponential function with decay lengths of 3, 12.2,
ments with highly charged and a moderately hydro- and 13.5 nm was used to fit the experimental data in
phobic surface having an advancing water contact the separation distance ranges of 0 –20, 20 –60, and
angle of about 60j (Israelachvili and Pashley, 1982, 20 – 80 nm, respectively. In recent years the long-
1984) showed that the hydrophobic attractive force was range hydrophobic force has also been measured with
long-range (over 10 nm) and much stronger than van other non-interferometric surface force techniques
der Waals interaction, and that the force decayed (Froberg et al., 1999), of which the atomic force
exponentially with separation distance. A single expo- microscope (AFM) colloidal probe technique (Butt,
nential function with a decay length of 1 nm was used 1991; Ducker et al., 1991, 1992) is the most popular.
to fit the experimental data. Mica surfaces made hy- Since the first direct experimental evidence
drophobic by adsorption of cetyltrimethyl (also hex- reported in 1982, there has been no consensus on
adecyltrimethyl-) ammonium bromide (CTAB) were the explanation of the hydrophobic attractive force
used. The next measurements (Pashley et al., 1985) despite a number of proposed mechanisms, which
between hydrophobic surfaces, made by adsorption of include:
dihexadecylmethylammonium acetate, showed that the
hydrophobic attractive force had a longer range (about
Entropic origin, arising from configurational re-
15 nm). The hydrophobic attractive force versus sep- arrangement of the (vicinal) water molecules
aration distance was again described by a single expo- between the hydrophobic surfaces (Israelachvili
nential, but with larger decay length of 1.4 nm. The and Pashley, 1984; Claesson et al., 1986; Eriksson
surfaces were more hydrophobic with an advancing et al., 1989),
water contact angle of about 94j. In 1986, more
Separation-induced phase transition (cavitation)
hydrophobic surfaces were obtained by depositing a (Rabinovich et al., 1982; Yaminskii et al., 1983;
monomolecular layer of dioctadecyldimethlammo- Christenson and Claesson, 1988; Claesson and
nium bromide onto the mica surface; long-range decay Christenson, 1988; Berard et al., 1993),
length was 5.5 nm for the measurement in water and 4.5
Hydrodynamic fluctuating correlation (Rucken-
nm in 0.01 M KBr solution, respectively. Other experi- stein and Churaev, 1991),
ments with uncharged Langmuir – Blodgett films of
Charge-fluctuation correlation (Podgornik, 1989;
hydrocarbon and fluorocarbon surfactants (Claesson Podgornik and Parsegian, 1991),
and Christenson, 1988) showed some quite startling
Electrostatic origin (Attard, 1989; Rabinovich
results. The hydrophobic attractive force was measur- et al., 1993),
able out to a separation distance of 90 nm. The
Anomalous polarization of vicinal water molecules
advancing water contact angle was 113j and 93j for (Rabinovich and Deryagin, 1987, 1988), and
the fluorocarbon and DDOA surfaces, respectively.
Bridging submicron bubbles (Parker et al., 1994;
The hydrophobic force was again fitted by a double Attard, 1996).
 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225 217

The detailed experiments (Christenson et al., 1990, piezoelectric transducer. The deflection of the canti-
1992; Parker and Claesson, 1994) have shown that the lever due to the interaction between the surface and
hydrophobic attractive force is measurable at extreme- the particle is measured with a laser light, which is
ly high electrolyte concentrations, which conclusively focused onto the back of the cantilever spring. The
rules out any electrostatic mechanism in those partic- reflected laser light is directed onto a split photodiode
ular systems. The proposed mechanism, that the detector, which produces a voltage signal. The ap-
hydrophobic attractive force is due to the coalescence proach speed and relative bubble-particle position are
of preexisting submicron-sized bubbles at the hydro- controlled by the applied voltage across the piezo-
phobic surfaces that bridge the two approaching electric transducer. This results in accurate expansion
hydrophobic surfaces (Ishida et al., 2000; Tyrrell and contraction of the piezoelectric tube both tempo-
and Attard, 2002), is gaining increasing acceptance rally and spatially.
(Christenson and Claesson, 2001; Vinogradova et al., The surface interaction force is determined by
2001). In this paper, this mechanism due to bridging multiplying the cantilever deflection by its spring
sub-micrometer bubbles is examined and its impor- constant. The cantilever deflection is determined from
tance for flotation system is rationalized. the voltage signal of the photodiode employing a
scaling procedure, which uses the measured linear
displacements of both the cantilever and the piezo-
2. Experimental electric transducer at (physical) contact. The separa-
tion is then determined from the cantilever deflection
2.1. Methods and apparatus and the displacement of the piezoelectric transducer.

Surface forces between a spherical particle and a 2.2. Materials and preparation
flat surface were measured with a Digital Instruments
(Santa Barbara, CA) AFM (Nanoscope II and Nano- The initial measurements were carried out with a
scope IIIa) equipped with a silicone ring liquid cell. glass sphere (Polysciences) and a glass microscope
The AFM colloidal probe technique (Butt, 1991; slide (Assistent, Kühn und Bayer, Nidderau, Ger-
Ducker et al., 1991) was used. In this technique, a many). Both the particle and surface were made
micrometer-sized particle is glued to the end of a hydrophobic by a silanation process with trimethyl-
microfabricated cantilever with the triangular shape chlorosilane in the gas phase. After silanation, both
(Fig. 1). The flat surface is mounted to a xyz piezo- the particle and surface were rinsed with distilled
electric transducer and is moved upwards and down- water to remove any residual surfactants and contam-
wards relative to the particle with low constant speeds, inants and gently exposed to a nitrogen stream for
at which the hydrodynamic interaction is insignificant. drying. The (macroscopic) contact angle measured
This movement is driven by an applied voltage to the with a sessile drop apparatus (Krüss, Germany) was
about 62j. The contact angle on particles was not
measured, but it could be larger than the contact angle
of 62j measured with the glass microscope slide due
to microscopic heterogeneities and the line tension
effect (Yakubov et al., 2001).
Other measurements in degassed solutions were
carried out with a hydrophobic polyethylene (PE)
sphere and two different hydrophobic surfaces (PE
and silanated silica). The PE particles were obtained
using a procedure (Nalaskowski et al., 1999a), which
Fig. 1. Typical images, taken with a scanning electron microscope, involves suspending PE powder in glycerol, heating
of an 18 Am diameter sphere glued to a triangular cantilever. The
triangular shape minimizes possible twisting motions. The left the suspension above the melting point of the poly-
image is a side view showing the thinness of the cantilever. The mer, and then solidification of the dispersed poly-
right image shows the plan view. meric droplets at a reduced temperature. After
218 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225

appropriate filtration and drying, this procedure was withdrawn with a syringe and immediately used for
found not to change the surface properties of PE AFM measurements.
particles, which retained a high degree of hydropho- The prepared spherical particles were glued to the
bicity. The silica surface was made hydrophobic by AFM cantilever using a small amount of epoxy resin
silanation in the liquid phase with octadecyltrichor- following a procedure described by Ducker et al.
osilane. The PE surface was prepared by melting PE (1991). The AFM cantilevers were fixed at an angle
powder at a mica surface at about 120 jC. Melted PE of about 30j on a holder placed on a three-dimen-
was pressed against mica surface using a glass sional stage of a microscope fitted with long working
microscope slide. After cooling, mica was removed distance lenses. A small amount of resin was placed
from the PE surface manually and by a nitrogen on a tungsten wire attached to another three-dimen-
stream. All the surfaces and particle were rinsed with sional micromanipulator, which was used to transfer
glycerol, and then with distilled water several times the required amount of resin to the cantilever under
in order to remove surface contaminants. The ad- microscopic observation. Finally, a prepared sphere
vancing contact angle measured with a sessile drop was picked up with a cantilever, and the resin and the
was greater than 90j. glued particle were allowed to dry for about 24 h. In
All the chemicals used were of analytical grade. this way spheres with a diameter down to 1 Am could
The water was deionized with a Millipore facility. For be precisely positioned and glued to the end of the
the measurements with dissolved gases, water was AFM microfabricated cantilever as shown in Fig. 1.
outgassed by subsequent boiling/freezing under low
pressure several times. About 100 ml of degassed 2.3. Surface force measurement
water was placed into the gas-washing bottle and the
required gas was introduced through a coarse porous The particle on the cantilever was initially posi-
glass frit at the bottom at a flow rate of 1 l/min for tioned, under microscope control, roughly a few
about half an hour. The gas-saturated water was hundred nanometers above the flat surface using the

Fig. 2. Experimental results obtained for the scaled force, F/R, between silanated glass sphere (R = 4 Am) and plate in pure water, in 17% (by
volume) ethanol – water solution and in 100% ethanol.
 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225 219

AFM step motor. The deflection of the cantilever

versus the position of the piezoelectric translator
was measured following the standard AFM force
measurement procedure. The conversion of deflection
curves to normalized force versus separation distance
plots was carried out employing the AFM Analysis
Program from the University of Melbourne, Australia,
developed following the known procedure (Ducker
et al., 1991).

3. Results and discussion

3.1. Influence of ethanol

The results of the surface force measurements

between silanated glass surfaces in water and in
ethanol are shown in Fig. 2. In pure ethanol no
attractive force was measured. In pure water, a strong
and long-range attractive force was obtained and is
compatible to the force measured with similar sila-
nated surfaces (Rabinovich and Yoon, 1994). Ap-
pearance of the step in the force curve is the
characteristic of the measurements between surfaces
in pure water and has been attributed to the bridging
of submicroscopic gas bubbles at the hydrophobic
surfaces (Attard, 1996). The bridging is considered as
Fig. 4. Force amplitude, A, and ‘decay’ length, k, in Eq. (1) as a
the cause of the measured long-range attractions
function of ethanol content. Filled and unfilled circles represent two
between macroscopic hydrophobic surfaces. The the- sets of data obtained with different experiments.
oretical consideration (Attard, 1996) shows that the
attractive force due to the bridging of submicroscopic mental data shown in Fig. 2. The addition of ethanol
gas bubbles is proportional to the vapour – liquid to water increases the separation distance, referred to
interface tension. Thus, ethanol, which decreases as the jump-in distance, where the step in the force
the liquid – vapour surface tension, decreases the curve occurs (Fig. 3) and decreases the strength of
attractive force. This is confirmed with the experi- the measured force, to the extent that for mixtures
with a high content of ethanol the step is difficult
to measure.
It is important to note that in place of the known
power dependence derived for the bridging force of
submicroscopic gas bubbles (Yaminsky, 1997, 1999),
the measured force versus separation distance, D,
obeys the empirical single exponential dependence

F=R ¼ AexpðD=kÞ ð1Þ

The force amplitude, A, and the ‘decay’ length, k, as

a function of the ethanol content are shown in Fig. 4.
Fig. 3. Jump-in separation distance versus ethanol content. With an increase in the ethanol content, the force
220 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225
 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225 221

Fig. 5. Scaled force, F/R, between a PE sphere and a PE plate versus separation distance in water saturated by argon, nitrogen, and
helium.

amplitude decreases and the length scale increases. the gas used to saturate water. The higher the solubil-
Clearly, the data in Fig. 4 for kin Eq. (1) is significantly ity, the larger the size of the steps. However, the
larger than molecular decay lengths and represents a strength and the range of the attractive force in the
characteristic feature associated with long-range hy- water saturated by the gases appear to be the same,
drophobic force. indicating that the gas solubility is not a significant
controlling factor.
3.2. Influence of dissolved gases Other results obtained for the attractive force
between a PE sphere and a silanated silica plate in
The formation of bridging gas bubbles between the water saturated by nitrogen and helium are shown
hydrophobic surfaces can be observed and monitored in Fig. 6. In these cases, the steps on the force curves
by the step(s) in the force curves. Since the bridging are so pronounced that the steps in helium-saturated
gas bubbles cause the strong hydrophobic attractive water are now visible. It is important to note that
force, the influence of solubility of gases on the surface roughness and heterogeneities control the
hydrophobic force should be considered. Fig. 5 shows formation and stability of submicroscopic gas bubbles
the measured force versus separation distance ob- at the solid –liquid interface (Ryan and Hemmingsen,
tained with a PE sphere and a PE flat surface in the 1993) and, hence, the attractive force (Mahnke et al.,
presence of argon (solubility in water 34.2 ml/l), 1999; Nalaskowski et al., 1999b). Due to the presence
nitrogen (solubility in water 15.8 ml/l), and helium of PE crystallites, the PE surface is rough on the
(solubility in water 8.6 ml/l). The size of the observed microscopic scale. The silanated surface is also patchy
steps on the force curves depends on the solubility of due to the adsorption of surfactants (Flinn et al., 1994;
222 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225

Fig. 6. Scaled force, F/R, between a PE sphere and a silanated silica plate versus separation distance in water saturated by nitrogen and helium.
 A.V. Nguyen et al. / Int. J. Miner. Process. 72 (2003) 215–225 223

Nalaskowski et al., 1999b). It appears that the patchy 4. Conclusions

morphology of the silanated silica promoted the
formation of the gas bubbles and the pronounced The measurements of attractive forces between a
steps on the force curves in the helium-saturated water hydrophobic particle and a hydrophobic surface were
shown in Fig. 6. carried out in water, in water – ethanol solution, and in
water saturated by argon, nitrogen, and helium using
3.3. Implication for flotation the AFM colloidal probe technique. In the case of
ethanol added to water, the strong, long-range attrac-
The results obtained for the attractive surface force tive forces were measured with the presence of steps/
in water –ethanol mixtures as well as water saturated discontinuities on the force curves at very large
by different gases clearly demonstrate the role of the separation distances and decreased with an increase
submicroscopic gas bubbles at hydrophobic solid– in the ethanol content. The strong, long-range attrac-
liquid interfaces. The importance of the gas bubbles tive force disappeared in pure ethanol. These steps
‘precipitating’ at solid surfaces in enhancing mineral suggest that the mechanism of the hydrophobic at-
flotation, in particular in vacuum flotation, was well tractive force is due to the bridging of the preexisting
known to flotation chemists (Taggart, 1927; Gaudin, submicroscopic gas bubbles. In water saturated by
1957; Klassen and Mokrousov, 1963; Laskowski, argon, nitrogen, and helium, the appearance of steps
2001). The key feature of these investigations in on the force curves depends on the gas solubilities and
bubble formation is the significant role played by surface roughness and heterogeneities. However, the
the solid surface (Ralston et al., 2001). Dissolved strength and range of the measured forces do not
air and gasses can exist in water in the form of tiny strongly depend on the gas solubilities. It appears that
bubbles, down to nanometer dimensions called the nature of the hydrophobic attractive forces is
bubstons (i.e. bubbles stabilised by ions) (Bunkin, related to surface roughness and chemical heteroge-
1997). The formation of larger bubbles from the neities, which act as sites where gas can be trapped.
preexisting sources of the gas bubbles can therefore
occur without the need for a nucleation step, which
is not energetically favourable. Acknowledgements
In flotation, solid particles generally are in con-
tact with air before contact with water. Air and AVN gratefully acknowledges the Alexander von
gases which are trapped at particle surfaces, espe- Humboldt Foundation for a Research Fellowship
cially at hydrophobic surfaces, are not easy to be awarded in 1994 under which part of this research
displaced by the surrounding liquid water phase and was carried out, and Hans Joachim Schulze for
these gas bubbles are the preexisting sites for the invaluable assistance. The authors also gratefully
‘bridging’ of gas bubbles during the particle – bubble acknowledge the Australian Academy of Science,
interaction. Particle surface geometry and chemistry the Australian Research Council, the Department of
are important. Surface geometric defects can act as Energy (DE-FG-03-93ER14315), and the National
sites where gas can be trapped. Surface asperities Science Foundation (INT-0096920 and INT-0111248)
can stimulate rupture of the intervening liquid film for financial support.
during the bubble – particle attachment and enhance
flotation (Anfruns and Kitchener, 1977). Flotation
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