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Nanobubbles, Hydrophobic Effect, Heterocoagulation and Hydrodynamics in Flotation
Nanobubbles, Hydrophobic Effect, Heterocoagulation and Hydrodynamics in Flotation
Nanobubbles, Hydrophobic Effect, Heterocoagulation and Hydrodynamics in Flotation
78 (2005) 11 – 21
www.elsevier.com/locate/ijminpro
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
difficulties of their explanation resulted from their While for the first force measurements crossed
relatively long-range character (Ninham, 1999). The cylinders were used as contacting solids (Israelachvili,
recent results of several research teams have provided 1991; Israelachvili and Pashley, 1982; Pashley and
an explanation of the phenomena such that it is appro- Israelachvili, 1981), for the AFM studies mainly the
priate to speak of a hydrophobic effect instead of a solid plate/solid sphere (Ishida et al., 2000, 2002;
hydrophobic force. These facts also have conse- Nguyen et al., 2003; Sakamoto et al., 2002; Tyrrell
quences for the interpretation of the heterocoagulation and Attard, 2001, 2002) and solid sphere/bubble (Pre-
between hydrophobic particles and bubbles inclusive uss and Butt, 1998, 1999) systems were studied. As
of the hydrodynamic conditions, in that they occur in materials silicates were predominantly used, initially
flotation processes, too. 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
2. Hydrophobic effect and Butt, 1998, 1999; Sakamoto et al., 2002; Tyrrell
and Attard, 2001, 2002; Yang et al., 2003), but also
When two particles in an aqueous suspension plastics (Christenson and Claesson, 2001; Nguyen et
approached closely, the resulting interaction force al., 2003) and occasionally other materials. The sili-
always includes the van-der-Waals force and an elec- cate materials were made hydrophobic either by che-
trostatic component. The theoretical basis for this is mical preparation (methylation or silanation) (Attard,
given by the DLVO-theory (Derjagin–Landau–Ver- 2003; Christenson and Claesson, 2001; Ishida et al.,
wey–Overbeek theory). If hydrophilic particles come 2000, 2002; Nguyen et al., 2003; Snoswell et al.,
very close to each other, these interactions are aug- 2003; Tyrrell and Attard, 2001, 2002; Yang et al.,
mented by a steric hindrance which is caused by the 2003) or by adsorption of cationic surfactants, parti-
structurization of their hydration layers. In the case of cularly quaternary alkylammonium salts (Preuss and
hydrophobic and hydrophobized particles relatively Butt, 1998, 1999; Sakamoto et al., 2002). The majo-
strong and long-range attraction forces can be noticed. rity of the investigations were carried out with
The first direct force measurements between two relatively strong hydrophobicities (macroscopic
hydrophobic surfaces were reported in the early eigh- advancing contact angles N808). Furthermore, besides
ties of last century (Israelachvili, 1991; Israelachvili the chemical heterogeneity of the solid surfaces their
and Pashley, 1982; Pashley and Israelachvili, 1981). physical heterogeneity (above all roughness) was
But only the development and application of the found to be an essential parameter and, therefore,
atomic force microscopy (AFM) combined with varied (Nguyen et al., 2003; Snoswell et al., 2003;
respective periphery made it recently possible to mea- Yang et al., 2003).
sure the force–distance dependence between interact- By means of the tapping mode of the atomic force
ing surfaces as well as to analyze the surface states. In microscopy the existence of nanobubbles on hydro-
this way the physical character of the long-range phobic surfaces can be indirectly determined by scan-
attractive interactions could be elucidated on the one ning the position of the liquid/gas interface, and as a
hand, and the knowledge about the course of bubble result a visual representation of the surface coverage
attachments on hydrophobic solid surfaces could be with nanobubbles is generated (Hansma et al., 1994;
broadened on the other hand (Attard, 2003; Ishida Johnson, 1999). Further indications of their existence
et al., 2000, 2002; Nguyen et al., 2003; Preuss and can be derived from the force–distance dependence.
Butt, 1998, 1999; Tyrrell and Attard, 2001, 2002; The figures of the surface coverage known up to now
Sakamoto et al., 2002; Snoswell et al., 2003; Steitz can be subdivided into two groups, namely those
et al., 2003; Yang et al., 2003; Stöckelhuber et al., where single bubbles, which have approximately the
2004). The most important result of these investiga- shape of spherical segments, exist at more or less large
tions is the finding that in aqueous systems hydropho- distances (Sakamoto et al., 2002; Steitz et al., 2003;
bic solid surfaces are in general coated with Yang et al., 2003), and others where the nanobubbles
nanoscopic bubbles which can coalesce and form gas form a close-packed network (Attard, 2003; Tyrrell
bridges at the approach of surfaces. and Attard, 2001, 2002). These differences may
H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21 13
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 bles. The latter angles are much larger and, therefore,
particles with air bubbles (Stöckelhuber, 2003; Stöck- the nanobubbles show flatter shapes of their approxi-
elhuber et al., 2004; Slachachov et al., 2005). When mately spherical segments (Yang et al., 2003).
nanobubbles exist in the contact region (Fig. 3), this ! Nanobubbles form only in aqueous systems. In
situation controls the stability and rupture, respectively, H2O/C2H5OH-systems the disposition to their for-
of the water film and because of that the jump into the mation decreases with increasing alcoholic content,
three-phase contact and consequently the attachment. and disappears completely at high alcohol concen-
The water film which has now to be considered is no trations (Christenson and Claesson, 2001; Nguyen
more the wetting film between the hydrophobic particle et al., 2003).
and the air bubble but the bfoam lamellaQ between the
air bubble and the nanobubble (Fig. 3). Its stability is A question which is not yet solved sufficiently
controlled by the DLVO-regime exclusively within the concerns the stability (better: metastability) of the
lamella, capillary forces (note the high capillary pres- nanobubbles. All observations made under the respec-
sure within the nanobubble!), and by strong flow forces tive experimental conditions give evidence of their
in flotation process. Therefore, in general the prerequi- existence over at least several tens of minutes without
sites for heterocoagulation should be met. discernible alterations (Attard, 2003; Yang et al.,
From the findings about the nanobubble formation 2003). This is particularly remarkable because the
published up to now, the following conclusions can be capillary pressure p k of nanobubbles should be high.
derived: For a spherical nanobubble of radius R = 50 nm in
water of surface tension of c lg = 0.072 N/m, for
! The formation of nanobubbles on solid surfaces instance, on the basis of the Laplace equation a capil-
requires a minimum hydrophobicity as well as lary pressure of p k = 2c lg / R c 29 bar results. Even if
roughness and increases with further increase of one considers that a nanobubble which shows a dia-
the hydrophobicity and roughness (Christenson meter of 2R = 100 nm in the AFM image, has a mean
and Claesson, 2001; Sakamoto et al., 2002; Yang curvature radius R m H 50 nm because of the large
et al., 2003). microscopic contact angle on the one hand, and that
! Physical and chemical heterogeneity further the the surface tension c lg can be b0.072 N/m because of
formation of nanobubbles. The heterogeneous adsorption in the liquid/gas interface and/or supersa-
nanobubble nucleation takes place in roughness turation of the liquid phase on the other hand, a con-
cavities. The roughness state is, therefore, a deci- siderable capillary pressure would still remain. The
sive parameter (Brennen, 1995; Nguyen et al., following possible explanations which can be only
2003; Yang et al., 2003; Ralston et al., 2001). briefly discussed here were given by (Attard, 2003):
! The macroscopic contact angle of a hydrophobic
surface differs from the microscopic contact angles, ! The nanobubbles are not in equilibrium with the
i.e. the angles determined by AFM at the nanobub- 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
ing, double bonds, non-terminal polar groups and the tion of the surface coverage. It can be seen that su is
like impede the association. Under the condition that already considerable at very low surface coverages
the adsorption density C y and W P are constant, the (b 3%) and increases with the surface coverage up
association energy su can be determined from the to a limit. In solutions of low ionic strength this
adsorption isotherms of homologous series as fol- limit amounts to about 1 kT for straight-chain
lows (Schubert and Baldauf, 1967; Schubert, 1972, surfactants with one terminal polar group (curves
1996): 1, 2, 3 and 6 in Fig. 6). This means that on the
condition of u = 1.39 kT, the association grade s
Blnc su
¼ : ð4Þ in complete monolayers does not exceed about
Bm kT 0.7. By comparison of the curves 1 and 2 in
In Fig. 5 two examples of such series are Fig. 6, one can note that on adsorption of n-alkane
represented. Fig. 6 shows the respective associa- carboxylic ions on carborundum as result of the
tion energies su, calculated by Eq. (4), as a func- 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- bert and Bischofberger, 1998), the following spe-
tion improves the association in a surfactant layer. cial features must be emphasized:
Furthermore, a comparison of the curves 1, 3, 4 and One has to start from the fact that the selective
5 in Fig. 6 suggests the conclusion that with hydrophobization prevailingly occurs only in the flo-
increasing ionic strength, and beyond that at con- tation cells. Because of the energetical heterogeneity
stant conditions, both u and s grow because of the of the particle surfaces, the surfactant (collector) ions
salting-out effect. In the case of 1,1-alkane dicar- are adsorbed in a spotty distribution. This has been
boxylates the limit of su reaches only about 0.6 su. directly shown by microautoradiographic methods
This must be the effect of an association hindrance (Boudriot et al., 1977; Plaksin, 1960; Schlesier,
caused by the second polar group, but also points to 1965; Schubert, 1996). With long-chain surfactants
specific characteristics of the adsorption layer for- – above all straight-chain ones – the association of
mation (Schubert, 1996). the nonpolar groups furthers the spotty distribution
already at very low surface coverages and in that way
the formation of nanobubbles, too. The necessary
4. Heterocoagulation and hydrodynamics in the surface coverage for flotation, however, depends on
flotation process several parameters (solid surface properties, surfactant
type, character and intensity of the adsorption mecha-
Now the question arises, as to what extent the nism, size and structure of the nonpolar group, parti-
findings discussed above can be applied to indus- cle size and others). Based on available results, one
trial flotation processes with the hydrodynamic can assume that it is mainly between 10% and 50%
conditions in mind? For flotation machines having (Schubert, 1996). This means that the macroscopic
impeller–stator systems which supply the energy contact angles should be smaller than found in the
required for the realization of the microprocesses AFM studies. This has an unfavourable effect on the
into the aerated suspension (Schubert, 1999; Schu- formation of nanobubbles, whereas the essential
18 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21
increase of the physical heterogeneity (irregular, On the condition that ē = 1.5 W/kg, as an example one
rough particle shapes!) as well as chemical heteroge- can assume that the energy dissipation rate e R in the
neity (inclusive of the surfactant association) should impeller stream at least amounts to 30ē c 45 W/kg.
further the nanobubble formation substantially. High stresses are the consequence in air dispersion,
According to the results of our own investigations, because for the bubble diameter d B in the inertial sub-
the microprocesses of air dispersion and particle–bub- range of microturbulence it is valid d B ~ 1 / e R0.4 as
ble attachment almost exclusively occur in the impeller well as high collision rates Z between bubbles and
streams of the flotation machines. These streams make particles for which one can correspondingly apply
up only a small percentage of the total volume of a Z ~ e R4/9(Schubert, 1996, 2003).
flotation cell (Schubert, 1999; Schubert and Bischof- It has been demonstrated by high-speed photo-
berger, 1998). This fact is in accordance with physical graphs in a specially designed flotation cell that the
considerations which suggest that the microprocesses kinetics of flotation processes are determined primar-
occur where the energy required for them dissipates. ily by the conditions in the impeller stream (see Figs.
Visually, one can get an idea of the position and 7 to 9 in Schubert and Bischofberger (1998)). Because
extension of the zone of high dissipation rate from of the highly turbulent flow conditions in the impeller
its small-bubbly (bmilkyQ) state as seen in Fig. 7, stream, it was impossible to identify attachment
where air bubbles were used as tracer (only a small events there. Notwithstanding the careful analysis of
air concentration was used in water without surfactant about 1400 m film, attachment events could also not
addition) (Schubert, 1999; Schubert and Bischofber- be detected outside of the impeller stream but only
ger, 1998). Furthermore, from stirring operations as already completed ones.
well as own studies it is known that the energy dis- The specific volume flow rate of air q L = V̇ L / V S
sipation rate e R in the impeller stream is a multiple of (V̇ Lvolume flow rate of air; V S suspension volume)
the mean dissipation rate ē = P / m ( P power input into amounts to about 0.5 to 1.5 m3/(m3 min) and the air
the mass m of the multi-phase system). Values of (e R / flow number c L = V̇ L / (nD 23) to about 0.07 to 0.3 (D 2
e )max c 5 to 200 are quoted for stirring equipment, and impeller diameter; n rotational speed of impeller)
¯ higher ones are valid for impeller–stator systems
the (Schubert, 1996). From these, the prerequisites for
(Schubert, 2003). In industrial flotation processes the supersaturation of the liquid phase with air can be
mean specific power input P / V S (V S aerated volume derived. Air dispersion proceeds in the regions at the
of the suspension) is mainly in the range 1 to 2 kW/m3. downstream side (wake) of the impeller elements
(blades, bars, fingers etc.) at peripheral speeds of the bles and coarser bubbles, i.e. so-called combined
impeller which are generally between 6 and 9 m/s. attachment events. The occurrence of such events
Under these conditions the liquid flow around an was already imagined by Taggart (1951) in the mid-
impeller element breaks away at the edges of the ele- 20th century and has been proved by Klassen (1960)
ment and a cavity forms, which is air-loaded, extended and Klassen and Mokrousov (1959) theoretically and,
in the flow direction and whose surface pulsates (Fig. later, experimentally. Eventually the pressure stresses
8). The latter is caused by the large eddies, which detach in the inertial sub-range according to Eq. (5) contri-
themselves on the flow around the element, periodically bute to overcome potential barriers in the water films
tear off parts from the cavity and transport them down- which have been found by Preuss and Butt in some of
stream, in the course of these events they are further their force–distance measurements.
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. 5. Conclusions
Furthermore, the turbulent pressure fluctuations in
the impeller stream have to be considered. Their All respective phenomena in flotation machines
RMS-value (root-mean-square value) in the inertial which concern the reagent regime and the hydrody-
sub-range can be written (Schubert, 2003): namics support the assumptions that nanobubbles can
qffiffiffiffiffiffiffiffiffiffiffiffi form on hydrophobic particle surfaces, exist there and
P P
DpV2 cð1 to 2Þq1 DuV2 c2q1 ðeR DrÞ2=3 ð5Þ even grow into microbubbles. Therefore, so-called
qP ffiffiffiffiffiffiffiffiffiffiffiffi combined attachment events should predominate in
DpV2 =RMS-value of turbulent velocity fluctua- the impeller stream.
tions which appear between two points at a dis- On account of the highly turbulent flow conditions
tance Dr in the microturbulence field (Dr = K); in the impeller stream and the consequent high fre-
K=macroscale of turbulence. quency velocity and pressure fluctuations, bubbles are
Although the frequencies of the pressure fluctua- subjected to continuous alterations of their size and
tions in the impeller streams are smaller than those in shape as well as oscillations. The consequence is that
the ultrasound range, it can be deduced from test adsorption equilibria in the interfaces liquid/gas can-
results obtained with the latter in air-saturated water not be supposed. This particularly affects the transfer-
that they further the heterogeneous nucleation as well ability of model calculations on the stability of
as the growth of already existing nanobubbles into wetting films during particle collisions. However,
microbubbles (Brennen, 1995). the pressure fluctuations in the impeller stream open
One can proceed from the fact that in the wakes the chance to overcome existing potential barriers.
downstream of the impeller elements both the air It would be welcome if future further research
dispersion and the events of particle–bubble attach- work on particle–bubble attachment would approach
ment occur and that they more or less run parallel. In the real situation in flotation processes more closely,
this case appears that the attachment events occur including, above all, consideration of the hydrody-
between particles coated with nano- and/or microbub- namic conditions.
Fig. 8. Air dispersion in the wake of an impeller element (Charčenko, 1986; Grainger-Allen, 1970; Schubert and Bischofberger, 1996).
20 H. Schubert / Int. J. Miner. Process. 78 (2005) 11–21
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