The Limits of Fine and CoarseParticleFlotation

Carlos de F. Gontijo, Daniel Fornasiero and John Ralston*

Ian Wark Research Institute, University of South Australia, Mawson Lakes Campus, Mawson Lakes, Adelaide,
SA5095,Australia

The flotation behaviour of quartz particles was studied over the particle size range from 0.5 m to 1000 m and for advancing water contact
angles between 0 and 83. Flotation was performed in a column and in a Rushton turbine cell. Particle contact angle threshold values, below
which the particles could not be floated, were identified for the particle size range 0.51000 m, under different hydrodynamic conditions. The
flotation response of the particles, either in a column or in a mechanically agitated cell with a similar bubble size, was comparable. Turbulence
plays a role, as does bubble-particle aggregate velocity and bubble size. The stability of the bubble-particle aggregate controls the maximum
floatable particle size of coarse particles. For fine particles, the flotation limit is dictated by the energy required to rupture the intervening liquid
film between the particle and bubble. Flotation of very fine and large particles is facilitated with small bubbles and high contact angles. These
results greatly extend our earlier observations and theoretical predictions.

On a tudi le comportement de flottation de particules de quartz pour des tailles de particules comprises entre 0,5 m et 1000 m et des
angles de contact de leau de 0 et 83. La flottation a t ralise dans une colonne et dans une cellule munie dune turbine Rushton. Les
valeurs de seuils des angles de contact, en dessous desquels les particules ne pouvaient pas flotter, ont t identifies pour une gamme de
particules de 0,5-1000 m, dans diffrentes conditions hydrodynamiques. La rponse de flottation, dans une colonne ou dans une cellule agite
mcaniquement avec une taille de bulles similaire, est comparable. La turbulence exerce une influence, tout comme la vitesse des agrgats de
bulles et de particules et la taille des bulles. La flottation des particules trs fines et des particules larges est facilite avec des bulles petites et
des angles de contact levs. Ces rsultats largissent de faon importante nos observations et prdictions thoriques antrieures.

Keywords: coarse particle flotation, detachment, stability, critical contact angle, kinetic theory of flotation

INTRODUCTION the aqueous phase and the air bubble (Gaudin, 1957). It is

F
accepted that the higher the contact angle of a mineral surface,
roth flotation is a process designed to separate hydropho-
the more readily it is wetted by air, and is thus more hydropho-
bic particles selectively in an aqueous medium, in which
bic (Lucassen-Reynders and Lucassen, 1984; Gaudin, 1957).
gas bubbles are dispersed. Hydrophobic particles selectively
Particle hydrophobicity or contact angle is dependent on the type
attach to the gas bubbles, forming aggregates. If the aggregate
and distribution of species present on the mineral surface
density is lower than the medium density the aggregates float to
(Crawford et al., 1987). Generally, the mineral particle surface
the top of the separation cell, where they overflow into a launder
may be covered with hydrophobic (e.g. collector, polysulphide)
(Schulze, 1993; Shergold, 1984). The flotation of mineral
and hydrophilic species (oxide, hydroxide, and sulphate) as well
sulphides and oxides, for example, operates most efficiently
as with different mineral phases, as found in composite particles
when the particle diameter is between 10 and 150 m (Shergold,
(Prestidge and Ralston, 1995). Recovery decreases with increas-
1984). Coarse and fine particles are often not recovered during
ing particle size because of detachment and decreases at small
the flotation process, or are recovered poorly.
particle sizes due to inefficient collision (Dai et al., 2000).
Flotation is achieved in part by increasing the hydrophobicity
of the particles (Lucassen-Reynders and Lucassen, 1984). The
degree of hydrophobicity can be expressed by the contact angle, * Author to whom correspondence may be addressed.
the angle at the three-phase line of contact between the mineral, E-mail address: john.ralston@unisa.edu.au

Volume 85, october 2007 The Canadian Journal of Chemical Engineering 739
 There is an upper size limit for floatable particles (Schulze,
1984; Glembotskii et al., 1963). The balance of forces acting on
the particle and bubble will determine the aggregate stability.
Coarse particles, whether they are of one type or composite, can
be detached from the bubble surface (Crawford and Ralston,
1988). After attachment, two conditions are necessary for
flotation: aggregate stability and buoyancy (Wark, 1933).
Consider a spherical particle at the liquid/gas interface as
shown in Figure 1. In the following analysis rb is the bubble
radius, rp is the particle radius, ro is the radius of the three-
phase contact line, a is the acceleration in the external field of
flow, b is the bubble velocity, p is the particle velocity, p is
the particle density, l the liquid density, LV is the liquid-vapour
surface tension, is the gravitational acceleration, and zo and
are defined in Figure 1. According to Huh and Scriven (1969)
and Schulze (1993, 1977) the forces acting on a spherical
particle at a static liquid/gas interface can be described by the
following equations:
the force of gravity;
4 3
Fg = p rp p g (1)
3 3 sin sin ( + q)
the static buoyancy force of the immersed part;
p 3 2 where dpmax,g is the maximum size of the particle that can stay
Fb = rp l g (1 cos ) ( 2 + cos ) (2)
3 attached to the liquid/gas interface, under static conditions.
the hydrostatic pressure of the liquid of height zo above the
contact area;
capillary pressure and the additional external acceleration act to
detach the particle. The sum of all the forces dictates whether
or not the particle detaches from the liquid/gas interface or
remains attached,
F = Fg + Fb + Fhyd + Fca + Fp + Fa (9)
The maximum floatable particle size can be calculated by
solving Equation (9) numerically. Schulze assumed that when
dp << db the effect of the capillary pressure of the gas bubble was
negligible (Schulze, 1984; Schulze, 1977). Neglecting the
hydrostatic term and considering that the static buoyancy of the
immersed part of the particle is approximately equal to the
buoyancy for the whole sphere (Equation (10)) Schulze derived
an approximate solution to calculate the upper floatable particle
size (Equation (9)),
4 3
Fb p rp l g (10)
3
Equating Equation (4) and Equation (10) with Equation (1) and
Equation (6), one obtains,
d p max, g = 2 (11)
2( g + p a )
Schulze (1977) showed that the energy necessary for detach-
ment, Ed is
hcrit

( )
Fhyd = p r02 l g z0 = p rp2 sin2 l g z0 (3) Ed = ( F ) dh (12)
heq
the capillary force on the three-phase line;
where heq is the equilibrium position of the particle at the
liquid/gas interface, hcrit is the maximum displacement of the
Fca = 2 p rp sin sin ( + q ) (4)
particle before detachment and F is the summation of all the
forces acting on the particle (Equation (9)). Schulze (1977)
the capillary pressure in the bubble acting on the contact area
found that in a freely moving system, as in flotation, particles
of the particle;
could only be loaded up to the maximum attachment force,
2 Fmax, which occurs when:
Fp = p r02 Pb p rp2 sin2 2 rb l g (5)
rb q
180 (13)
Additional detaching forces, for instance represented by the 2
acceleration provided by a mechanical impeller, can be accounted
for as the product of the particle mass and the acceleration in the
external flow field:
4
Fa = p rp3 p a (6)
3
Huh and Scriven (1969) developed a numerical solution that can
be used to calculate zo, whilst approximate solutions have also
been proposed (James, 1974):

Figure 1. Spherical particle located at the liquid/gas interface (Schulze,
4 1977, 1984, 1993; Huh and Scriven, 1969). rp is the particle radius, ro
zo = rp sin sin f ln 0.58 (7)
is the radius of the three-phase contact line, h is the immersion depth
l g rp2 sin2
(1 + cos f ) of the particle, H is the height of the spherical cap above the meniscus;
LV zo is the height of the meniscus above the three-phase line
(deformation of the liquid meniscus at the solid surface), is the
where f = w + q p (in degrees) (8) particle contact angle, is the polar angle, i.e., the angle between the
surface tension direction (the tangent of the meniscus at the three-
The capillary force, the buoyancy force of the immersed part phase line) and the horizontal, is the central angle at the particle,
and the hydrostatic pressure all contribute to the particle attach- ie., the angle between the surface tension direction and the vertical
ment at the gas/liquid interface, whilst the force of gravity, the downwards, LV is the liquid-gas surface tension.

740 The Canadian Journal of Chemical Engineering Volume 85, october 2007
 The additional acceleration, a, depends on the structure and
the intensity of the turbulent flow field, thus on the turbulent
energy dissipation, , in a given volume of the flotation cell
(Schulze, 1993). Schulze assumed that aggregates, the dimensions
of which correspond to those of the turbulent vortices, are
moved mainly by the centrifugal acceleration in the vortex. If rv
is the radius of the vortex in the turbulent eddies and V 2 is its
root mean square velocity, then
V2
a = 1.92 / 3 / rv1 / 3 (14)
rv
For aggregates, where the particle size is smaller than the
bubble size, the vortex radius should be set equal to the
aggregate radius. Hence,
a 1.9 2/3/(rb + rp)1/ 3 (15)
Hui (2001) derived an expression for the average acceleration of
the attached particle, as a function of the mean energy dissipa-
tion in the flotation cell, when the turbulent eddies and the
particle have similar size.
2 /3
a = 23.5
(rb )
1/3
+ rp
where e is the average energy dissipation in the flotation cell.
The existence of a critical contact angle, necessary for the
flotation of fine particles, was first proposed by Scheludko et al.
(1976). The kinetic energy of fine particles must be larger than
the energy needed to disrupt the intervening liquid film and
form a three-phase contact line, enabling bubble-particle attach-
ment to occur. When these energies are in balance, the minimum
particle diameter, dp(min), is given by
1/3
32
d p(min) = 2 2
(
b LV p - f
) (1 - cos qr )
where is the solid-liquid-vapour three-phase contact line
tension, and r is the receding particle contact angle. During
the process of bubble-particle attachment, the three-phase
contact line expands and the liquid front recedes, so that a
receding water contact angle is used in Equation (17). The
Scheludko et al. (1976) approach has not been validated to
date, due to the lack of experimental data for very fine particles
and the paucity of reliable line tension determinations
(Amirfazli and Neumann, 2004).
The purpose of this present study is to explore the limits of
flotation for extremely fine and coarse particles under very differ-
ent hydrodynamic conditions and particle hydrophobicities.
0.45 m A
90150 m B
150250 m C
501000 m D
A small quantity of very coarse particles, up to 3.5 mm in
diameter, was prepared for the bubble pick-up experiments.
The quartz particles were cleaned with hot aqua regia for 2 h
and then rinsed with high-purity water until the pH became
neutral. They were then exposed to a hot concentrated NaOH
solution to remove organic contamination and again rinsed
withhigh-purity water until the pH became neutral.
Trimethylchlorosilane (TMCS) solutions were used for particle
methylation (Crawford et al., 1987). Since TMCS reacts with
water, the methylation reaction was performed in a glove box
under a dry nitrogen atmosphere. Phosphorus pentoxide was used
as a drying agent. To prepare the required volume of solutions,
TMCS was delivered using a micro-syringe and diluted in
cyclohexane. The quartz samples were weighed into a reactor
flask and then heated in a clean oven at 110C overnight to remove
the physisorbed water. The TMCS solution was placed in the
reactor flask for the silylation process. Using different TMCS
concentrations and reaction times, different particle contact angles
were obtained. The quartz particles were then allowed to settle
(16)
and rinsed with cyclohexane. The cyclohexane was removed and
the flask containing the particles was transferred to a clean oven
to dry overnight at 110C. The measurements of contact angle on
the particles used in the flotation experiments were carried out
using the Washburn, sessile-drop, tape and film techniques (e.g.
Brckel and Lffler, 1991; Crawford et al., 1987). All glassware
was cleaned and methylated before use, using the same procedure
as for the particles.
(17)

EXPERIMENTAL SECTION
Flotation experiments were performed in a microflotation
column and in a Rushton turbine cell. Analytical grade reagents
were used throughout the experiments. High purity water, with
conductivity 0.8 S, pH 5.6, = 72.8 mNm1 at 20C was used
in the microflotation experiments. Flotation in the Rushton
turbine cell was performed using deionized water. Experiments
were performed at 25C. Figure 2. Apparatus for captive bubble pick-up experiments. A bubble,
The particles used in the experiments were pure, crystalline generated using a syringe, was held at the end of the needle. It was
quartz (Sigma and G. Bottley Pty Ltd., London). Particles were pressed against particles with known water advancing contact angle for
prepared by grinding, sieving and sedimentation, as necessary, 5 s and then raised by a motor at a constant velocity. The experiments
in the following size fractions: were recorded using a high-speed camera.

Volume 85, october 2007 The Canadian Journal of Chemical Engineering 741
 The experimental apparatus for the bubble pick-up experi-
ment consists of a syringe linked to a precision motor, enabling
the syringe to move vertically downwards or upwards at
constant velocity (Figure 2). Particles were placed into a vial
with a transparent wall, containing high-purity water. Using
the motor-driven syringe, a bubble was pressed against a
particle for attachment to the bubble. After this the syringe was
driven upwards at constant velocity. In these experiments a
slow (20 m/s) and a fast (200 m/s) velocity were used.
Experiments were repeated at least six times for each velocity.
It is important to note that there is an initial acceleration before
constant velocity is achieved. Using a microscope and a high-
speed camera, images of the experiment were recorded. Particle
and bubble sizes were measured using the images. Diagnostic
single bubble capture experiments were also performed for
sample A using procedures that we have described elsewhere
(Dai et al., 1998).
Column flotation was performed in a modified Hallimond
tube (Crawford and Ralston, 1988; Blake and Ralston, 1985). A
porous steel plate was used to generate a swarm of bubbles at
the bottom of the tube. A glass magnetic stirrer was used to
suspend the particles (Crawford and Ralston, 1988; Blake and
Ralston, 1985). For each flotation experiment, 1 g of quartz was
placed in the cell. The column was then assembled and filled
with high purity water (the total volume was 200 cm3). The
quartz particles were then conditioned for one minute. The
agitation was adjusted to a rotation speed that was just enough
to suspend the particles. At the beginning of flotation the solid
concentration of the suspension was approximately 27 wt.%.
Images of the bubbles were recorded and the bubble size was
analyzed using ImageJ software. Flotation under turbulent
conditions was performed using a 2.25 L Rushton turbine cell,
agitated by an overhead motor with variable speed capacity
(Duan et al., 2003). The impeller speed was adjusted and
confirmed independently using an optical tachometer. For each
experiment 100 gram of particles was placed in the cell and
conditioned for 1 min with 8 x 105 M polypropylene glycol
(MW 25). The solid concentration in the cell was approximately

Figure 3. Maximum size of quartz particle (dpmax,g) that could be

raised by a captive bubble in high purity water as a function of the
particle water advancing contact angle for various bubble sizes (db)
andrising velocities (b) of () db = 1.8 mm, b = 20 m/s; () db = 1
mm, b = 20 m/s; () db = 1 mm, b = 20 m/s). The lines were Figure 5. Quartz (sample C) recovery after 8 min of flotation obtained
calculated using Equation (11), with the external acceleration, a as a in a flotation column as a function of particle size and advancing water
fitting parameter. The external acceleration used are respectively,
contact angle of () 21, () 42, () 58; () 59; () 69; ( ) 74
(1)a= 0 ms2; (2) a = 0.5 ms2; (3) a = 7.2 ms2; (4) a = 14.6 ms2 (= 72.8 mNm-1; p = 2650 kg/m3; d50 = 262 10 m; db = 0.9 0.7
(particle density (p) = 2650 kg/m3; surface tension (LV) = 72.8 mNm1). mm; magnetic stirrer rotational speed = 560 10 rpm; Ref = 1582; gas
flow rate = 4.6 0.4 cm3/min)

Figure 4. Quartz (sample B) recovery after 8 min of flotation obtained Figure 6. Quartz recovery after 8 min of flotation obtained in a Rushton
in a flotation column as a function of particle size and advancing water turbine cell as a function of particle size and advancing water contact
contact angle of () 25; () 49; () 51, () 52; () 57; (): angle of () 40; () 57; () 75; () 83 (p = 2650 kg/m3; d50 = 353
62(= 72.8 mNm-1; p = 2650 kg/m3; d50 = 153 4 m; db = 8 m; [DF250] = 20 mg/l; db = 0.7 0.3 mm; rotational speed = 650
0.80.7 mm; magnetic stirrer rotational speed = 547 4 rpm; Ref = 4 rpm, turbulent energy dissipation = 6.46 m2/s3; Ref = 26063; gas
1573; gas flow rate = 4.3 0.4 cm3/min) flow rate = 4.5 l/min)

742 The Canadian Journal of Chemical Engineering Volume 85, october 2007
4.3 wt.%. The cell specifications are given in Table 1 (Pyke et
al., 2003).
RESULTS AND DISCUSSION
Coarse Particle Behaviour
Figure 3 shows the results of the maximum size of particles that
could be raised by a captive bubble as a function of particle
Table 1. Rushton turbine flotation cell specifications
Tank specifications Impeller specifications
Volume = 2.25 litre 6 blade Rushton turbine
Diameter = 144 mm Diameter = 48 mm
Height:diameter = 1:1 Width:height:diameter = 5:4:20
Baffle:diameter = 1:10
contact angle, in the absence of turbulence, when the hydrody-
namic and acceleration forces are minimized (dpmax,g). The
predominant forces are the gravitational and capillary forces.
The maximum particle size that can be raised is different from
the maximum floatable particle size, as we will see belowthe
former is obtained under static conditions whilst the latter of
course reflects a dynamic state. The results indicate that a higher
contact angle is required to raise particles with a larger particle
size. For example a 3.4 mm particle can only be raised by a 1.8
mm bubble, at a constant rising velocity of 20 m/s, if the
particle advancing water contact angle is at least 80. The size
of the particles that can be raised decreases with decreasing
bubble diameter. Rising velocity is also important and the size of
the particle that can be raised decreases when the rising velocity
increases. Equation (11) shows that dpmax,g depends on the
particle contact angle, the surface tension of the solution and on
the external acceleration. Three variables were explored in the
bubble pick-up experiments, the particle contact angle, the rising

Figure 7. Critical contact angle determination. Quartz recovery after Figure 8. Critical contact angle determination. Quartz recovery after 8
8min of flotation, obtained in a flotation column for sample B, at a min of flotation, obtained in a flotation column for sample C, at a fixed
fixed particle size ( = 72.8 mNm1; p = 2650 kg/m3, d50 = 153 particle size ( = 72.8 mNm1; p = 2650 kg/m3; d50 = 262 10 m;
4m, db= 0.8 0.7 mm; magnetic stirrer rotational speed = 547 db = 0.9 0.7 mm; magnetic stirrer rotational speed = 560 10 rpm;
4rpm; Ref = 1573; gas flow rate = 4.3 0.4 cm3/min). Ref = 1582; gas flow rate = 4.6 0.4 cm3/min).

Volume 85, october 2007 The Canadian Journal of Chemical Engineering 743
velocity (external acceleration), and the bubble volume. Using
Equation (11), an acceptable fit with the experimental data is
obtained in Figure 3 for a bubble diameter of 1.8 mm, with a
zero value of the acceleration. Acceleration occurs when the
bubble is raised from its stationary position to a finite velocity.
The lines in Figure 3 were calculated using Equation (11), with
the external acceleration, a, as a fitting parameter. Curve 4 has
the highest rising velocity and acceleration. 1 mm diameter
bubbles can raise quartz particles with an 80 contact angle up
to 2.4 mm in diameter, whereas 1.8 mm diameter bubbles can
raise 3.4 mm diameter particles, the theoretical maximum
particle size with a contact angle of 80 that remains attached to
a bubble (Schulze, 1984, 1977).
The results of flotation in the column for quartz samples B and
C are shown in Figures 4 and 5 and in the Rushton turbine cell in
Figure 6. Flotation recovery increases as the particle contact angle
increases and 100% recovery was obtained for the 83 particles in
the Rushton turbine cell and for particles with contact angles
Figure 9. Critical contact angle determination. Quartz recovery after
8min of flotation, obtained in a Rushton turbine cell at a fixed particle
size (p = 2650 kg/m3, d50 = 353 8 m, [DF250] = 20 mg/l,
db=0.7 0.3 mm, rotational speed = 650 4 rpm, turbulent energy
dissipation = 6.46 m2/s3, Ref = 26063, gas flow rate = 4.5 l/min).
744 The Canadian Journal of Chemical Engineering Volume 85, october 2007
above 59 in the column. In the flotation column the agitation
was set to the minimum value required to disperse and suspend
the particles. Particles larger than 550 m were not fully suspended
and their flotation behaviour could not be determined. In the
Rushton turbine cell, particles up to 1000 m were suspended at
rotational speeds equal or higher than 500 rpm. It is quite remark-
able that these very large particles could be floated readily in the
Rushton turbine cell in spite of the turbulent environment. For
83 particles, 90% recovery was obtained after 1.5 min of
flotation. When the recovery versus contact angle for each particle
size is considered (examples are given in Figures 7, 8 and 9) it is
observed that there is a critical contact angle, below which
flotation does not occur. This effect was first reported by Blake and
Ralston (1985) and confirmed by Crawford and Ralston (1988). In
this previous work, a rather monodisperse suspension was used,
whereas in the present study the suspension is quite polydisperse.
Figure 10. Critical contact angle/particle size at which flotation
commences, obtained for quartz, (p = 2650 kg/m3), under quiescent
and turbulent conditions for () sample B in a flotation column, d50 =
153 4 m, db = 0.8 0.7 mm, rotational speed = 547 4 rpm, Ref =
1573, gas flow rate = 4.3 0.4 cm3/min; () sample C in a flotation
column, d50 = 262 10 m, db = 0.9 0.7 mm, rotational speed =
560 10 rpm, Ref = 1582, gas flow rate = 4.6 0.4 cm3/min.; ()
sample D in a Rushton turbine cell, d50 = 353 8 m, [DF250] = 20
mg/l, db = 0.7 0.3 mm, rotational speed = 650 4 rpm, turbulent
energy dissipation = 6.5 m2/s3, Ref = 26063, gas flow rate = 4.5 l/min.;
sample A in a flotation column in a Rushton cell, in single bubble
capture experiments (db = 400 m, pH = 5.8, 0.1 M KNO3); () data
obtained by Crawford and Ralston (1988) in a flotation column;. ( ,
upper curve) gravitational limit, dpmax,g, calculated using Equation (11)
with no acceleration; ( ) experimental dpmax,g, db = 1.8 mm, b =
20m/s; (- -) kinetic limit for flotation, dpmax,K, as a function of contact
angle for various bubble velocities, b, given in the figure.
For this reason, the present recovery curves have a sigmoid shape, The critical contact angle/particle size relationship for
instead of showing a sharp cut-off value. flotation in the Rushton turbine cell falls between the results for
To determine the critical contact angle the recovery curves in samples B and C obtained in a flotation column using similar
Figures 7 to 9 were described by a sigmoid function of recovery bubble diameters. Large particles could be floated in the
at 8 min of flotation versus the water advancing contact angle. Rushton turbine cell, in spite of the much higher turbulence,
The point where the tangent at the inflexion point intercepts the since the maximum size of particle that could float is determined
horizontal axis determines the critical contact angle. The critical by the velocity of the bubble-particle aggregate as well as the
contact angle/particle size threshold values obtained for flotation corresponding detachment forces. We have demonstrated that
are shown in Figure 10. A flotation domain is evident in turbulence alone does not prevent coarse particle flotation.
Figure10, within which flotation occurs, outside of which there Bubble size and loading also have a strong influence on the
is no flotation. For comparison the results obtained by Crawford flotation of coarse particles.
and Ralston (1988) are also shown. The critical contact angle/
particle size threshold for flotation was affected by the particle Fine Particle Behaviour
size distribution of the quartz feed sample, as shown in The critical contact angle for quartz particles with a diameter
Figure10. The critical contact angle required for flotation is less than 5 m to float was determined using single bubble,
smaller for the sample with coarse particles, sample C. bubble swarm (flotation column) and Rushton turbine cell
The aggregate stability is controlled by the energy required to
detach the particle from the bubble and the kinetic energy of the
particle. The kinetic energy may come from the bubble velocity
and from turbulent stresses exerted on the bubble/particle
aggregate as the aggregate collides with other bubbles and
aggregates or when the aggregate is moved by turbulent vortices.
The kinetic energy of the particle can be represented by:
p 3
KE = d p p 2p (18)
12
Detachment will occur when the kinetic energy of the particle
(Equation (18)) equals the detachment energy (Equation (12)).
It is possible to calculate the maximum floatable particle size
by plotting the detachment energy as a function of the particle
size and overlaying the plot of the kinetic energy for a given
value of b. For a given contact angle, both curves intersect
each other, defining a critical particle size, dpmax,K. Figure 11
shows the detachment energy, solved numerically for 1 mm Figure 11. Energy of detachment calculated for a 1 mm diameter
bubbles and the kinetic energy for different bubble velocities. bubble as a function of particle size and contact angle, using Equation
The results are in agreement with the values calculated by (12) (full lines). Particle kinetic energy, calculated as a function of
Schulze (1984). Particles larger than the critical size detach, particle size and bubble velocity, using Equation (18) (dotted lines).
imposing a kinetic limit to flotation. The dependence of dpmax,K Critical contact angle/particle size is determined by the intersection
on is also shown in Figure10 for b = 1, 5, 10, 20, and ofboth curves.
30cm/s. In this calculation p = 2650 kg/m3 and = 72.0 x
103 N/m. Figure 10 shows that the experimental threshold
values or critical particle size as a function of contact angle are
much smaller than predicted under static conditions (dpmax,g).
The threshold values experimentally determined for sample B
in column flotation correspond to the dependence of dpmax,K for
b= 30 cm/s, for particles up to 150 m, as found originally
by Crawford and Ralston (1988).
We now focus on the different behaviour between quartz
samples B and C in column flotation. For particles larger than 150
m in sample B, the threshold values shift towards the theoretical
predictions of dpmax,K for smaller bubble velocities, reaching the
calculated curve for 10 cm/s. For sample C, the threshold values lie
between the theoretical predictions for
b = 5 cm/s and b = 10 cm/s. This seemingly odd behaviour
may be caused by bubble loading. King et al. (1974) and King
(2001) reported that the bubble load is proportional to the square
of the particle diameter and that the bubble velocity decreases with
increasing bubble load. This observation may explain why the
critical contact angle/particle size curve changes with the particle
size distribution of the sample, for the kinetic energy decreases for
a heavily loaded bubble. Since the kinetic energy of the bubble- Figure 12. Bubble-particle collection efficiency as a function of
particle aggregate also decreases for small bubbles, this suggests advancing water contact angle for 1 m diameter particles in single
that small bubbles can improve coarse particle flotation. bubble () and bubble swarm () experiments

Volume 85, october 2007 The Canadian Journal of Chemical Engineering 745

Figure 13. Recovery of methylated quartz particles (0.55 m) in a
Rushton flotation cell after 8 min of flotation as a function of particle
advancing water contact angle (800 rpm; 30 ppm MIBC; 4.5 dm3/min
gas flow rate; pH = 6.0)
flotation experiments. For 1 m diameter particles, the experi-
mental data for single bubble and bubble swarm experiments are
shown in Figure 12 as a function of advancing water contact
angle. Data for the Rushton turbine cell are shown in Figure 13.
Figure 12 and Figure 13 show a similar critical contact angle for
flotation of approximately 55 to 60, independent of the flotation
conditions. This self-consistency is quite remarkable.
Overall the results show that the advancing water contact
angle of fine quartz particles (0.5 to 5 m in diameter) has to be
55 to 60 or above for these particles to float. The increase in
recovery is very sharp for particles with contact angles between
50 and 60 but plateaus above 60.
During the process of bubble-particle attachment, the
three-phase contact line expands and the liquid front recedes,
so that a receding water contact angle is used in Equation
(17). To compare Scheludkos model with the experimental
data, receding water contact angles were obtained using the
equilibrium capillary pressure technique applied to particles
with heterogeneous surfaces (Stevens, 2006; Crawford et al.,
1987; Cassie, 1948). A receding contact angle of 50 was
obtained with this technique for particles with an advancing
contact angle of 60.
Figures 12 and 13 show that the critical advancing water
contact angle for the flotation of fine quartz particles (0.55 m)
is around 60. There is very little difference between the
critical contact angles required to float these very small
particles. The range is within experimental error, thus one
point is shown. This critical contact angle is compared in
Figure 10 with that calculated using the Scheludkos model
(Equation (17)) along with Crawford and Ralstons (Crawford
and Ralston, 1988) experimental data for critical contact angles
for flotation. A line tension of 3 x 1010 Nm for a bubble is
taken from the data of Yang et al. (2003) and bubble velocities
(1030 cm/s) are taken from experimental measurements in
the Hallimond tube and the Rushton turbine flotation cell
(Miettinen, 2007). dp(min) values between 0.9 to 1.4 m are
calculated using Equation (17). The agreement between the
Scheludko model and the experimental data for the 0.55 m
diameter particles is satisfactory.
746 The Canadian Journal of Chemical Engineering Volume 85, october 2007
CONCLUSION
The detachment process controls the maximum floatable
particle size for coarse particles. If the particle kinetic energy
exceeds the energy required to detach it from the gas-liquid
interface, the particle detaches, defining a kinetic limit for
flotation. For fine particles, the critical water receding contact
angle required for flotation is defined by the energy required to
rupture the intervening thin liquid film between particle and
bubble. The flotation response of coarse or fine particles was
similar either in a column or in a mechanically agitated cell,
for a similar bubble size. Flotation of very large and very fine
particles is possible, provided that they have high contact
angles with smaller bubbles enhancing the process. This
information may be incorporated into flotation models and has
major implications for flotation practice.
ACKNOWLEDGMENTS
Financial support from the Australian Research Council through
the Special Research Centre Linkage Scheme and from AMIRA
International is gratefully acknowledged. We thank Nicolas
Hugonnet from Lcole suprieure de chimie physique lectron-
ique de Lyon (CPE Lyon) for his valuable assistance in the
bubble attachment experiments.
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Manuscript received March 19, 2007; accepted for publication

May25,2007.

Volume 85, october 2007 The Canadian Journal of Chemical Engineering 747