Int. J. Miner. Process.

78 (2005) 11 – 21
www.elsevier.com/locate/ijminpro

Nanobubbles, hydrophobic effect, heterocoagulation

and hydrodynamics in flotation
Heinrich Schubert
TU Bergakademie Freiberg, D-09596 Freiberg, Germany
Received 14 March 2005; received in revised form 15 July 2005; accepted 16 July 2005
Available online 2 September 2005

Abstract

It has been shown in recent years that the long-range attractive interaction forces between hydrophobic surfaces in aqueous
systems are caused by the capillary forces of gas bridges which form at the coalescence of nanobubbles adhering on the
surfaces. The coalescence of nanobubbles on selectively hydrophobized particles with coarser bubbles initiates the jump into the
three-phase contact at the attachment events in flotation. Therefore, one should no longer speak of hydrophobic forces in these
events but of hydrophobic effects because they are caused by capillary forces. However, in the selective hydrophobization of
particles by long-chain collectors (surfactants), there is another situation. Here, the association of nonpolar groups in the
adsorption layers plays an important role in the energy balance of adsorption. This association is caused by btrulyQ hydrophobic
interactions, which support the spotty distribution of the adsorbed collector ions on the particle surfaces and promote the
formation of nanobubbles. This paper is intended to show to what extent the results obtained by basic research on the
nanobubble formation as well as the force–distance dependence of collision events can be applied to flotation processes. This
particularly requires the consideration of the highly turbulent flow conditions in the impeller stream of the flotation machines, in
which the attachments almost exclusively occur. Various phenomena which occur in these machines and affect the reagent
regime and the hydrodynamics point to the fact that nanobubbles can form, exist and even grow into microbubbles in that
region. Therefore, so-called combined attachment events should predominate as already imagined several decades ago. The
highly turbulent pressure fluctuations in the impeller stream in addition to the dispersion of the bubbles effect also their
oscillations in size and shape, so that adsorption equilibria in the interfaces liquid/gas cannot be supposed. However, the
pressure fluctuations present the possibility to overcome potential barriers in the wetting films at attachment events.
D 2005 Elsevier B.V. All rights reserved.

Keywords: flotation; nanobubbles; hydrophobic effect; collector association; hydrodynamics; particle–bubble attachment

1. Introduction

The interpretation of the physical nature of the

interactions between hydrophobic particles in aqueous
E-mail address: schuberh@mvtat.tu-freiberg.de. systems has been increasingly taken up recently. The
0301-7516/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2005.07.002
12 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21
difficulties of their explanation resulted from their
relatively long-range character (Ninham, 1999). The
recent results of several research teams have provided
an explanation of the phenomena such that it is appro-
priate to speak of a hydrophobic effect instead of a
hydrophobic force. These facts also have conse-
quences for the interpretation of the heterocoagulation
between hydrophobic particles and bubbles inclusive
of the hydrodynamic conditions, in that they occur in
flotation processes, too.
2. Hydrophobic effect
When two particles in an aqueous suspension
approached closely, the resulting interaction force
always includes the van-der-Waals force and an elec-
trostatic component. The theoretical basis for this is
given by the DLVO-theory (Derjagin–Landau–Ver-
wey–Overbeek theory). If hydrophilic particles come
very close to each other, these interactions are aug-
mented by a steric hindrance which is caused by the
structurization of their hydration layers. In the case of
hydrophobic and hydrophobized particles relatively
strong and long-range attraction forces can be noticed.
The first direct force measurements between two
hydrophobic surfaces were reported in the early eigh-
ties of last century (Israelachvili, 1991; Israelachvili
and Pashley, 1982; Pashley and Israelachvili, 1981).
But only the development and application of the
atomic force microscopy (AFM) combined with
respective periphery made it recently possible to mea-
sure the force–distance dependence between interact-
ing surfaces as well as to analyze the surface states. In
this way the physical character of the long-range
attractive interactions could be elucidated on the one
hand, and the knowledge about the course of bubble
attachments on hydrophobic solid surfaces could be
broadened on the other hand (Attard, 2003; Ishida
et al., 2000, 2002; Nguyen et al., 2003; Preuss and
Butt, 1998, 1999; Tyrrell and Attard, 2001, 2002;
Sakamoto et al., 2002; Snoswell et al., 2003; Steitz
et al., 2003; Yang et al., 2003; Stöckelhuber et al.,
2004). The most important result of these investiga-
tions is the finding that in aqueous systems hydropho-
bic solid surfaces are in general coated with
nanoscopic bubbles which can coalesce and form gas
bridges at the approach of surfaces.
While for the first force measurements crossed
cylinders were used as contacting solids (Israelachvili,
1991; Israelachvili and Pashley, 1982; Pashley and
Israelachvili, 1981), for the AFM studies mainly the
solid plate/solid sphere (Ishida et al., 2000, 2002;
Nguyen et al., 2003; Sakamoto et al., 2002; Tyrrell
and Attard, 2001, 2002) and solid sphere/bubble (Pre-
uss and Butt, 1998, 1999) systems were studied. As
materials silicates were predominantly used, initially
mica, later on, above all, SiO2, glass, Si-wafer with
oxidized surface (Christenson and Claesson, 2001;
Ishida et al., 2000, 2002; Nguyen et al., 2003; Preuss
and Butt, 1998, 1999; Sakamoto et al., 2002; Tyrrell
and Attard, 2001, 2002; Yang et al., 2003), but also
plastics (Christenson and Claesson, 2001; Nguyen et
al., 2003) and occasionally other materials. The sili-
cate materials were made hydrophobic either by che-
mical preparation (methylation or silanation) (Attard,
2003; Christenson and Claesson, 2001; Ishida et al.,
2000, 2002; Nguyen et al., 2003; Snoswell et al.,
2003; Tyrrell and Attard, 2001, 2002; Yang et al.,
2003) or by adsorption of cationic surfactants, parti-
cularly quaternary alkylammonium salts (Preuss and
Butt, 1998, 1999; Sakamoto et al., 2002). The majo-
rity of the investigations were carried out with
relatively strong hydrophobicities (macroscopic
advancing contact angles N808). Furthermore, besides
the chemical heterogeneity of the solid surfaces their
physical heterogeneity (above all roughness) was
found to be an essential parameter and, therefore,
varied (Nguyen et al., 2003; Snoswell et al., 2003;
Yang et al., 2003).
By means of the tapping mode of the atomic force
microscopy the existence of nanobubbles on hydro-
phobic surfaces can be indirectly determined by scan-
ning the position of the liquid/gas interface, and as a
result a visual representation of the surface coverage
with nanobubbles is generated (Hansma et al., 1994;
Johnson, 1999). Further indications of their existence
can be derived from the force–distance dependence.
The figures of the surface coverage known up to now
can be subdivided into two groups, namely those
where single bubbles, which have approximately the
shape of spherical segments, exist at more or less large
distances (Sakamoto et al., 2002; Steitz et al., 2003;
Yang et al., 2003), and others where the nanobubbles
form a close-packed network (Attard, 2003; Tyrrell
and Attard, 2001, 2002). These differences may
 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21 13

reflect the respective hydrophobicity state as well as

the heterogeneity of the surfaces and/or the composi-
tion of the aqueous phase.
The existence of nanobubbles on hydrophobic
solid surfaces in aqueous systems can be considered
omnipresent. Even under very careful experimental
conditions it is hardly possible to preclude them com-
pletely (Sakamoto et al., 2002).
On close approach of interacting partners coated
with nanobubbles, the coalescence of colliding nano-
bubbles occurs as shown in Fig. 1 schematically. Each
step in the force–distance curve indicates such a coa-
lescence event and demonstrates a sharp rise of the
attractive capillary force caused by forming or grow-
ing gas bridges. Fig. 2 represents a force–distance
dependence having several coalescence events from
one of the first measured examples (Attard, 2003). Fig. 2. Force–distance dependence between hydrophobic surfaces
If, as in flotation, one of the colliding partner is a coated with nanobubbles (Attard, 2003; Parker et al., 1994).
coarser air bubble, this can result in heterocoagulation,
i.e. the attachment of the hydrophobic particle onto trolled by the DLVO-regime, if necessary supple-
the bubble. Up to now only a few experimental results mented by steric hindrance, and a hydrophobic
are available about the respective force–distance attraction. After the three-phase contact a relatively
dependences (Ralston et al., 2001). Because of the strong capillary force is effective. In these measure-
deformability of a bubble, the correct distance mea- ments normally the first sharp rise caused the jump
surement represents a severe problem. For the force– into the three-phase contact. But in some cases, there
distance measurement between a spherical particle of have also been noticed smaller rises which did not
few micrometers in diameter and an air bubble of yet lead to the three-phase contact (Preuss and Butt,
few hundreds of micrometers in diameter, Preuss and 1998). Important for the attachment events are also
Butt (1998, 1999) developed an experimental set-up the findings by Preuss and Butt that potential barriers
which is similar to AFM and has measuring instru- in the water film can be overcome by external forces
ments adjusted to the specific demands. They have similarly to flocculation. Therefore, in flotation the
interpreted their results on the force–distance depen- flow forces can play an indispensable role for colli-
dence in the following way. Before the three-phase sion events resulting in attachment.
contact and apart from external forces, the approach Recently Stöckelhuber et al. have presented model
of the hydrophobic particle to the bubble is con- developments which can explain the destabilizing

Fig. 1. Formation and rupture of gas bridges between solid surfaces coated with nanobubbles.
14 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21
effect of nanobubbles at the collision of hydrophobic
particles with air bubbles (Stöckelhuber, 2003; Stöck-
elhuber et al., 2004; Slachachov et al., 2005). When
nanobubbles exist in the contact region (Fig. 3), this
situation controls the stability and rupture, respectively,
of the water film and because of that the jump into the
three-phase contact and consequently the attachment.
The water film which has now to be considered is no
more the wetting film between the hydrophobic particle
and the air bubble but the bfoam lamellaQ between the
air bubble and the nanobubble (Fig. 3). Its stability is
controlled by the DLVO-regime exclusively within the
lamella, capillary forces (note the high capillary pres-
sure within the nanobubble!), and by strong flow forces
in flotation process. Therefore, in general the prerequi-
sites for heterocoagulation should be met.
From the findings about the nanobubble formation
published up to now, the following conclusions can be
derived:
! The formation of nanobubbles on solid surfaces
requires a minimum hydrophobicity as well as
roughness and increases with further increase of
the hydrophobicity and roughness (Christenson
and Claesson, 2001; Sakamoto et al., 2002; Yang
et al., 2003).
! Physical and chemical heterogeneity further the
formation of nanobubbles. The heterogeneous
nanobubble nucleation takes place in roughness
cavities. The roughness state is, therefore, a deci-
sive parameter (Brennen, 1995; Nguyen et al.,
2003; Yang et al., 2003; Ralston et al., 2001).
! The macroscopic contact angle of a hydrophobic
surface differs from the microscopic contact angles,
i.e. the angles determined by AFM at the nanobub-
Fig. 3. Water film between a hydrophobic solid surface coated with
a nanobubble and an air bubble.
bles. The latter angles are much larger and, therefore,
the nanobubbles show flatter shapes of their approxi-
mately spherical segments (Yang et al., 2003).
! Nanobubbles form only in aqueous systems. In
H2O/C2H5OH-systems the disposition to their for-
mation decreases with increasing alcoholic content,
and disappears completely at high alcohol concen-
trations (Christenson and Claesson, 2001; Nguyen
et al., 2003).
A question which is not yet solved sufficiently
concerns the stability (better: metastability) of the
nanobubbles. All observations made under the respec-
tive experimental conditions give evidence of their
existence over at least several tens of minutes without
discernible alterations (Attard, 2003; Yang et al.,
2003). This is particularly remarkable because the
capillary pressure p k of nanobubbles should be high.
For a spherical nanobubble of radius R = 50 nm in
water of surface tension of c lg = 0.072 N/m, for
instance, on the basis of the Laplace equation a capil-
lary pressure of p k = 2c lg / R c 29 bar results. Even if
one considers that a nanobubble which shows a dia-
meter of 2R = 100 nm in the AFM image, has a mean
curvature radius R m H 50 nm because of the large
microscopic contact angle on the one hand, and that
the surface tension c lg can be b0.072 N/m because of
adsorption in the liquid/gas interface and/or supersa-
turation of the liquid phase on the other hand, a con-
siderable capillary pressure would still remain. The
following possible explanations which can be only
briefly discussed here were given by (Attard, 2003):
! The nanobubbles are not in equilibrium with the
gas–supersaturated liquid phase.
! The difference between macroscopic and micro-
scopic contact angle is the consequence of the
fact that the line tension j in the three-phase con-
tact cannot be neglected for nanobubbles. There-
fore, the Young equation must be modified by an
additional term, and it follows for the microscopic
contact angle # (Yang et al., 2003):
j
cos # ¼ cos #Y  ð1Þ
clg r
#Y contact angle according to Young equation
1/r local curvature of the bubble base on solid
surface.
 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21
! There are also doubts if the Laplace equation is
generally applicable to nanobubbles. This is ex-
plained by the effect of the solid surface on their
volume and the gas/solid interface.
The question about the stability of the forming gas
bridges with regard to their capillary pressure does
not arise because their two radii of curvature have
different signs.
3. Hydrophobization of solid surfaces by surfactant
adsorption
The selective hydrophobization of hydrophilic
solid surfaces plays a process-determining role in
flotation processes. The reagents used for this pur-
pose have a polar–nonpolar molecule structure and
belong, apart from some reagents having short chains
(e.g. xanthates), to the ionic surfactants, which show
in aqueous solutions the ability to form micelles and
other associations.
The polar surfactant groups promote dissolution in
water as well as cause direct bonding to solid surfaces
by physisorption (electrostatic adsorption) and in
some applications also by chemisorption.
The nonpolar groups try to bescapeQ from sur-
rounding water molecules. If a nonpolar group pene-
trates an aqueous solution, hydrogen bonds must be
broken. But the interaction forces between nonpolar
groups and surrounding H2O molecules are much
smaller than those of the hydrogen bridges between
water molecules. The consequence of this situation
is described as hydrophobic bonding and results
from the fact that the nonpolar groups associate in
order to reduce their contact area with water mole-
cules as far as possible (hydrophobic solvation)
(Brezesinski and Mögel, 1993; Israelachvili, 1991).
At the surfactant adsorption on solid surfaces from
aqueous solution, the interaction W P which is caused
by the polar group (or groups) can be differentiated
from the interaction WA which the nonpolar group
contributes (Fig. 4). The interaction of adsorption,
W y , is given by:
Wy ¼ WP þ WA ð2Þ
W P includes the interactions of the polar group with
the solid surface or its electric double layer (chemi-
15
Fig. 4. Interactions at surfactant adsorption.
or physisorption), those between the polar groups in
the adsorption layer as well as the dehydration
effects connected with adsorption. The nonpolar
group contributes by its association with neighbour-
ing nonpolar groups within the adsorption layer to
the energy balance (Gaudin and Fuerstenau, 1955).
For the interaction of association per surfactant ion
(in the following termed association energy), it can
be written on the basis of the monolayer model of
adsorption (Schubert and Baldauf, 1967; Schubert,
1972, 1996):
WA ¼ uðm  1ÞskT ð3Þ
u change of the free enthalpy per –CH2– group
at complete association
m equivalent or effective chain length
s association grade (0 b s b 1)
k* pre-association coefficient (1 z k* N 0).
In solutions of low ionic strength, one can put
u =  1.39 kT, i.e. the amount which is equivalent to
a complete transfer of a –CH2– group from sur-
rounding water molecules into surrounding saturated
nonpolar groups (Mukerjee, 1967). But this amount
could only be realized if it would lead to the forma-
tion of a complete surfactant layer having an ideal
arrangement, and on the additional condition that
before adsorption no pre-associations (dimerization,
micellation, self-association) have taken place. For
straight-chain surfactants the actual chain length
agrees with the effective chain length. Chain branch-
16 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21

ing, double bonds, non-terminal polar groups and the
like impede the association. Under the condition that
the adsorption density C y and W P are constant, the
association energy su can be determined from the
adsorption isotherms of homologous series as fol-
lows (Schubert and Baldauf, 1967; Schubert, 1972,
1996):
Blnc su
¼ :
Bm kT
In Fig. 5 two examples of such series are
represented. Fig. 6 shows the respective associa-
tion energies su, calculated by Eq. (4), as a func-
tion of the surface coverage. It can be seen that su is
already considerable at very low surface coverages
(b 3%) and increases with the surface coverage up
to a limit. In solutions of low ionic strength this
limit amounts to about  1 kT for straight-chain
surfactants with one terminal polar group (curves
1, 2, 3 and 6 in Fig. 6). This means that on the
condition of u =  1.39 kT, the association grade s
ð4Þ in complete monolayers does not exceed about
0.7. By comparison of the curves 1 and 2 in
Fig. 6, one can note that on adsorption of n-alkane
carboxylic ions on carborundum as result of the
hydrolysis at pH 4.5 coadsorption of alkane car-

Fig. 5. Adsorption isotherms of homologous surfactant series: (a) n-alkyl ammonium chlorides on quartz (200–250 Am) at 25 8C and pH 6; (b)
n-alkane carboxylates on corundum (160–200 Am) at 60 8C and pH 4.5; (c k critical micelle concentration); (Schubert and Baldauf, 1967;
Schubert, 1972, 1996).
 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21 17

Fig. 6. Association energy su of surfactant layers as function of surface coverage (Schubert, 1996): (1) quartz (200–250 Am), n-alkyl
ammonium chlorides, 25 8C and pH 6; (2) corundum (160–200 Am), n-alkane carboxylates, 60 8C and pH 4.5; (3) quartz (200–250 Am), n-alkyl
ammonium chlorides, 10 g/l KCl, 25 8C; (4) quartz (200–250 Am), n-alkyl ammonium chlorides, 100 g/l KCl, 25 8C; (5) sylvite (200–250 Am),
n-alkyl ammonium chlorides, saturated KCl-solution, 25 8C; (6) cassiterite (40–63 Am), Na-n-alkane carboxylate, pH 6, 20 8C; (7) cassiterite
(40–63 Am), 1,1-n-alkane carboxylate, pH 6, 20 8C.

boxylic molecules has occurred. Such a coadsorp-
tion improves the association in a surfactant layer.
Furthermore, a comparison of the curves 1, 3, 4 and
5 in Fig. 6 suggests the conclusion that with
increasing ionic strength, and beyond that at con-
stant conditions, both u and s grow because of the
salting-out effect. In the case of 1,1-alkane dicar-
boxylates the limit of su reaches only about 0.6 su.
This must be the effect of an association hindrance
caused by the second polar group, but also points to
specific characteristics of the adsorption layer for-
mation (Schubert, 1996).
4. Heterocoagulation and hydrodynamics in the
flotation process
Now the question arises, as to what extent the
findings discussed above can be applied to indus-
trial flotation processes with the hydrodynamic
conditions in mind? For flotation machines having
impeller–stator systems which supply the energy
required for the realization of the microprocesses
into the aerated suspension (Schubert, 1999; Schu-
bert and Bischofberger, 1998), the following spe-
cial features must be emphasized:
One has to start from the fact that the selective
hydrophobization prevailingly occurs only in the flo-
tation cells. Because of the energetical heterogeneity
of the particle surfaces, the surfactant (collector) ions
are adsorbed in a spotty distribution. This has been
directly shown by microautoradiographic methods
(Boudriot et al., 1977; Plaksin, 1960; Schlesier,
1965; Schubert, 1996). With long-chain surfactants
– above all straight-chain ones – the association of
the nonpolar groups furthers the spotty distribution
already at very low surface coverages and in that way
the formation of nanobubbles, too. The necessary
surface coverage for flotation, however, depends on
several parameters (solid surface properties, surfactant
type, character and intensity of the adsorption mecha-
nism, size and structure of the nonpolar group, parti-
cle size and others). Based on available results, one
can assume that it is mainly between 10% and 50%
(Schubert, 1996). This means that the macroscopic
contact angles should be smaller than found in the
AFM studies. This has an unfavourable effect on the
formation of nanobubbles, whereas the essential
18 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21
increase of the physical heterogeneity (irregular,
rough particle shapes!) as well as chemical heteroge-
neity (inclusive of the surfactant association) should
further the nanobubble formation substantially.
According to the results of our own investigations,
the microprocesses of air dispersion and particle–bub-
ble attachment almost exclusively occur in the impeller
streams of the flotation machines. These streams make
up only a small percentage of the total volume of a
flotation cell (Schubert, 1999; Schubert and Bischof-
berger, 1998). This fact is in accordance with physical
considerations which suggest that the microprocesses
occur where the energy required for them dissipates.
Visually, one can get an idea of the position and
extension of the zone of high dissipation rate from
its small-bubbly (bmilkyQ) state as seen in Fig. 7,
where air bubbles were used as tracer (only a small
air concentration was used in water without surfactant
addition) (Schubert, 1999; Schubert and Bischofber-
ger, 1998). Furthermore, from stirring operations as
well as own studies it is known that the energy dis-
sipation rate e R in the impeller stream is a multiple of
the mean dissipation rate ē = P / m ( P power input into
the mass m of the multi-phase system). Values of (e R /
e )max c 5 to 200 are quoted for stirring equipment, and
¯ higher ones are valid for impeller–stator systems
the
(Schubert, 2003). In industrial flotation processes the
mean specific power input P / V S (V S aerated volume
of the suspension) is mainly in the range 1 to 2 kW/m3.
Fig. 7. Position of the impeller stream of a double-finger impeller (Schubert, 1999).
On the condition that ē = 1.5 W/kg, as an example one
can assume that the energy dissipation rate e R in the
impeller stream at least amounts to 30ē c 45 W/kg.
High stresses are the consequence in air dispersion,
because for the bubble diameter d B in the inertial sub-
range of microturbulence it is valid d B ~ 1 / e R0.4 as
well as high collision rates Z between bubbles and
particles for which one can correspondingly apply
Z ~ e R4/9(Schubert, 1996, 2003).
It has been demonstrated by high-speed photo-
graphs in a specially designed flotation cell that the
kinetics of flotation processes are determined primar-
ily by the conditions in the impeller stream (see Figs.
7 to 9 in Schubert and Bischofberger (1998)). Because
of the highly turbulent flow conditions in the impeller
stream, it was impossible to identify attachment
events there. Notwithstanding the careful analysis of
about 1400 m film, attachment events could also not
be detected outside of the impeller stream but only
already completed ones.
The specific volume flow rate of air q L = V̇ L / V S
(V̇ Lvolume flow rate of air; V S suspension volume)
amounts to about 0.5 to 1.5 m3/(m3 min) and the air
flow number c L = V̇ L / (nD 23) to about 0.07 to 0.3 (D 2
impeller diameter; n rotational speed of impeller)
(Schubert, 1996). From these, the prerequisites for
supersaturation of the liquid phase with air can be
derived. Air dispersion proceeds in the regions at the
downstream side (wake) of the impeller elements
 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21
(blades, bars, fingers etc.) at peripheral speeds of the
impeller which are generally between 6 and 9 m/s.
Under these conditions the liquid flow around an
impeller element breaks away at the edges of the ele-
ment and a cavity forms, which is air-loaded, extended
in the flow direction and whose surface pulsates (Fig.
8). The latter is caused by the large eddies, which detach
themselves on the flow around the element, periodically
tear off parts from the cavity and transport them down-
stream, in the course of these events they are further
dispersed. In the wake of such cavities one can observe
bubbles which are deformed as shreds, extended in the
flow direction and progressively further dispersed.
Furthermore, the turbulent pressure fluctuations in
the impeller stream have to be considered. Their
RMS-value (root-mean-square value) in the inertial
sub-range can be written (Schubert, 2003):
qffiffiffiffiffiffiffiffiffiffiffiffi
P P
DpV2 cð1 to 2Þq1 DuV2 c2q1 ðeR DrÞ2=3 ð5Þ
qP ffiffiffiffiffiffiffiffiffiffiffiffi
DpV2 =RMS-value of turbulent velocity fluctua-
tions which appear between two points at a dis-
tance Dr in the microturbulence field (Dr = K);
K=macroscale of turbulence.
Although the frequencies of the pressure fluctua-
tions in the impeller streams are smaller than those in
the ultrasound range, it can be deduced from test
results obtained with the latter in air-saturated water
that they further the heterogeneous nucleation as well
as the growth of already existing nanobubbles into
microbubbles (Brennen, 1995).
One can proceed from the fact that in the wakes
downstream of the impeller elements both the air
dispersion and the events of particle–bubble attach-
ment occur and that they more or less run parallel. In
this case appears that the attachment events occur
between particles coated with nano- and/or microbub-
Fig. 8. Air dispersion in the wake of an impeller element (Charčenko, 1986; Grainger-Allen, 1970; Schubert and Bischofberger, 1996).
19
bles and coarser bubbles, i.e. so-called combined
attachment events. The occurrence of such events
was already imagined by Taggart (1951) in the mid-
20th century and has been proved by Klassen (1960)
and Klassen and Mokrousov (1959) theoretically and,
later, experimentally. Eventually the pressure stresses
in the inertial sub-range according to Eq. (5) contri-
bute to overcome potential barriers in the water films
which have been found by Preuss and Butt in some of
their force–distance measurements.
5. Conclusions
All respective phenomena in flotation machines
which concern the reagent regime and the hydrody-
namics support the assumptions that nanobubbles can
form on hydrophobic particle surfaces, exist there and
even grow into microbubbles. Therefore, so-called
combined attachment events should predominate in
the impeller stream.
On account of the highly turbulent flow conditions
in the impeller stream and the consequent high fre-
quency velocity and pressure fluctuations, bubbles are
subjected to continuous alterations of their size and
shape as well as oscillations. The consequence is that
adsorption equilibria in the interfaces liquid/gas can-
not be supposed. This particularly affects the transfer-
ability of model calculations on the stability of
wetting films during particle collisions. However,
the pressure fluctuations in the impeller stream open
the chance to overcome existing potential barriers.
It would be welcome if future further research
work on particle–bubble attachment would approach
the real situation in flotation processes more closely,
including, above all, consideration of the hydrody-
namic conditions.
20 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21

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k Boltzmann constant Langmuir 16, 5681 – 5687.
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m Mass
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