Role of Frothers in Bubble Generation and

Coalescence in a Mechanical Flotation Cell

Rodrigo A. Grau1 and Janusz S. Laskowski2*
1. Helsinki University of Technology, Helsinki, Finland
2. The University of British Columbia, Vancouver, BC, Canada

Two frothers covering a very broad range from weak and selective (DF-200) to powerful (DF-1012) flotation performance were chosen to test
the effect of frothers on bubble generation and bubble coalescence in a laboratory scale flotation cell. In two-phase, gas-liquid systems, the
experiments showed that the frothers affect both the bubble breaking process and the coalescence of bubbles. While the DF-200 frother,
characterized by much larger critical coalescence concentration (CCC) values than DF-1012, has the ability to produce finer bubbles at concen-
trations exceeding the CCC value, the bubbles generated in the DF-1012 solutions at concentrations exceeding CCC are much larger.

On a retenu deux agents moussants couvrant une vaste gamme, allant d’une performance de flottation faible et sélective (DF-200) à puissante
(DF-1012), afin de tester l’effet des agents moussants sur la production et la coalescence des bulles dans une cellule de flottation à l’échelle de
laboratoire. Dans des systèmes gaz-liquide diphasiques, les expériences montrent que les agents moussants influent à la fois sur le processus de
rupture des bulles et la coalescence des bulles. Alors que l’agent moussant DF-200, qui se caractérise par des valeurs de concentration de
coalescence critique (CCC) beaucoup plus grandes que pour le DF-1012, a la capacité de produire des bulles fines à des concentrations excédant
la CCC, les bulles produites dans les solutions de DF-1012 à des concentrations excédant la CCC sont beaucoup plus larges.

Keywords: flotation, flotation frothers, bubble size, critical coalescence concentration, surface tension

F
rothers play a fundamental role in the flotation process.
According to the Schulman-Leja penetration theory (Leja
and Schulman, 1954; Leja, 1956/1957), frother molecules
are preferentially adsorbed at the water/air interface, and their
interaction with the collector molecules adsorbed on mineral
particles in the moment of the particle-to-bubble attachment is a
vital step in the attachment process. Because frothers adsorb at
the air/liquid interface they enhance gas dispersion into fine
bubbles and stabilize the froth. The role of the froth in a flotation
process is to act as a separating medium to segregate valuable
mineral particles from gangue (Booth and Freyberger, 1962).
Frother agents also enhance dramatically gas dispersion in
flotation machines and reduce the size of the bubbles. Ahmed
and Jameson (1985) found that bubble size has a strong
influence on the rate of removal of the particles (flotation rate
constant k). Yoon (2000) derived from first principles that the
first order kinetic constant varies as dv-3 (dv is the volume based
bubble size) at quiescent conditions. However, under turbulent
conditions, as in the case of mechanical cells, it is known that
the flotation rate constant is less influenced by the bubble size
(Heiskanen, 2000). Gorain et al. (1998) recently concluded that
the overall flotation rate constant k is strongly correlated with
6 Jg
the average bubble surface area flux in the cell Sb = d (where Jg
32
is the superficial gas velocity and d32 is the Sauter mean bubble
diameter), which in turn is inversely related to the bubble size.
Frother agents also affect the shape and the rising velocity of
bubbles. Bubbles become more spherical in the presence of
frother agents (Bogdanov, 1950; Fuerstenau and Wayman,
1958). The terminal velocity of a bubble in a liquid is dramati-
cally reduced by increasing the concentration of frother. Sam et
al. (1996) and Krasowska et al. (2004) demonstrated that this
improves the probability of bubble-particle attachment.
Laskowski and his co-workers (Cho and Laskowski, 2002a, b;
Laskowski et al. 2003; Laskowski, 2003) have shown that
frothers can be characterized using two parameters: the critical
coalescence concentration (CCC) and the Dynamic Foamabilty
Index (DFI), examples of which are shown in Table 1. They
showed that frothers reduce bubble size by preventing bubbles
* Author to whom correspondence may be addressed.
E-mail address: jsl@apsc.ubc.ca

170 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, APRIL 2006
 Table 1. Different operating conditions for all experiments
Common name Chemical formula
†(PO)1 CH3(OC3H6)1OH
(PO)2 CH3(OC3H6)2OH
‡DF-200 CH3(OC3H6)3OH
DF-250 CH3(OC3H6)4OH
DF-1012 CH3(OC3H6)6.3OH
MIBC CH3CHCH2CH(OH)CH3
* The CCC values have been published by Grau et al. (2005). The values shown here are the maximum CCC values measured. †PO is the acronym of polypropylene group,
-OC3H6. ‡The acronym DF stands for the trade name Dowfroth.
from coalescing. With increasing frother concentration, the
degree of bubble coalescence decreases and at a particular
frother concentration (CCC) the coalescence of bubbles is
entirely prevented. The CCC values for several frothing agents
have been determined using the University of Cape Town (UCT)
Bubble Size Analyzer.
Grau et al. (2005) measured bubble size with the use of the
Helsinki University of Technology (HUT) Bubble Size Analyzer
and recently verified the validity of the CCC values obtained
with the UCT technique. The experiments were carried out at
different frother concentrations using three commercial Dow
frothers: DF-200, DF-250 and DF-1012 (“polyglycol frothers”).
Although both methods provided rather similar CCC values for
the three tested frothers, they also revealed import differences.
The main conclusions can be summarized as follows:
1. The bubble size measurements carried out using the HUT
bubble size analyzer in a fifty dm3 Outokumpu lab flotation
cell and the UCT bubble size meter in a one dm3 Open-Top
Leeds flotation cell gave practically the same CCC values for
three Dow frothers (DF-200, DF-250 and DF-1012).
2. Almost identical CCC values obtained when using different
equipment, operating at different conditions, confirmed that
the CCC values can be treated as material constants for
frothers.
3. While the obtained experimental bubble size-frother
concentration curves showed the same trends irrespective of
the method used to size bubbles, the bubble sizes measured
at frother concentrations exceeding the CCC values were
much larger when the HUT method was utilized, especially
for DF-250 and DF-1012.
In this project, a set of experiments was designed to examine
the source of differences in the measured bubble sizes. The
commercial frothers DF-1012 and DF-200 were selected for the
experimental work. According to the DFI-CCC diagram published
by Laskowski et al. (2003), the DF-200 frother can be considered
to be weaker than DF-1012.
EXPERIMENTAL
Flotation Cell
An Outokumpu cylindrical flotation cell with a volume of
265 dm3 (65 cm in diameter and 80 cm high) was used through-
out. The cell is made of Plexiglas. Two types of commercial
rotor/stator mechanisms manufactured by Outokumpu, Multi-
Mix and Free-Flow (rotor diameter 15 cm) were used in the tests.
The rotational speed of the rotor is controlled by a variable speed
VOLUME 84, APRIL 2006
Molecular weight CCC* DFI
ppm (s⋅dm3/mol)
90.12 46.8 5,700
148.12 25.1 35,000
206.29 17.3 196,000
264.37 9.1 208,000
397.95 6.6 267,000
102.18 11.2 34,000
drive and is measured using a digital tachometer. In the
Outokumpu cell, air is introduced through a hollow shaft. The
air flow rate is continuously measured using a calibrated rotame-
ter. The cylindrical cell is enclosed in a Plexiglas open-top box
that is filled with water during the experiments to make visuali-
zation of the flow and gas dispersion conditions in the cell
possible. A special launder made also of Plexiglas is designed to
collect the foam overflowing the lip of the cell. This cell is
designed to carry out mainly gas-liquid (two-phase system)
experiments.
Only aqueous solutions of two commercial Dow frothers were
utilized: DF-200 and DF-1012 (Table 1). The solutions were
prepared using municipal tap water. All the experiments were
run at room temperature. The temperature in the cell was contin-
uously monitored.
Bubble Size Equipment
Bubble size was measured with the Helsinki University of
Technology’s (HUT) new Bubble Size Analyzer (BSA). This
technique (from now on referred to as HUT BSA) is based on
the apparatus developed by Jameson and Allum (1984) for
sizing bubbles in industrial scale flotation cells. The technique
was also adopted by Chen et al. (2001) and later improved by
Hernandez-Aguilar et al. (2003). Recently Ata and Jameson
(2005) used a similar apparatus to observe bubble-solid clusters
formed in a 12 dm3 mechanically agitated flotation cell. Earlier
designs of the HUT BSA and their operation have been
described in detail by Grau and Heiskanen (2002, 2003). The
apparatus comprises of a viewing chamber connected to a
sampler tube of adaptable length. The sampler tube has an
internal diameter of 2 cm and is made of a transparent Plexiglas
(Figure1). The lower end of the sampling tube is connected to
a pinch valve. The viewing chamber is made of two sloped
glass window sheets (20 x 15 cm and 20º angle) and PVC. The
apparatus is filled with an aqueous solution of a frother (see
Table 1) by using a peristaltic pump. The lower end of the
sampling probe is immersed in the flotation cell, below the
froth/liquid interface. As the pinch valve is opened, a swarm of
bubbles rises through the sampling tube and reaches the
viewing chamber. The bubbles rise up against the inner surface
of the glass window as a single layer. The bubbles are then
exposed to a video camera. As the bubbles reach the top of the
chamber and burst, the excess air is removed using a second
peristaltic pump, so that a controlled level of water is
maintained in the chamber. Since, the water level does not
change during bubble sampling, a down-flow of water in the
sampling tube and inlet is prevented.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 171

Figure 1. Schematic diagram of the HUT Bubble Size Analyzer
An inclined viewing chamber as suggested by Hernandez-
Aguilar et al. (2004) reduces the probability of bubbles overlap-
ping, so that the number of miscounted bubbles decreases. The
inclined viewing chamber allows better setting of the focus
plane. A JAI CV-M10 camera fitted with AF Micro Nikkor 60mm
f/2.8D macro lens is used to capture images of a swarm of
bubbles. The shutter speed of the camera was set at 1/2000 s. A
Light Emitting Diode (LED) Backlight, with a high light output
is used to expose the contour of the bubbles in the swarm. A
rather shallow depth of field is set for the measurements. Images
of the swarm of bubbles crossing the field of view (about 12 x
16 mm) are grabbed and then recorded on the hard disk of a
personal computer at a fixed sampling rate.
Image Analysis
The series of captured images is processed off-line using Matrox
Inspector (Matrox Electronic Systems) combined with in-house
software (a Visual Basic Application). The captured images are
digitized as greyscale images (8-bit = 256 intensity levels or
shades) with a resolution of 768 x 576 pixels (square pixels). In
order to size the bubbles, they are separated (segmented) from
the background by converting the images into binary images
(black and white). Each image is segmented by defining a
threshold intensity, which ranges from 180 to 190. The same
threshold intensity is set for the whole series of images by the
experimenter, based on the quality of the images. For each
bubble, its maximum and minimum diameter are computed by
evaluating the Feret diameter of the bubble at a specified number
of angles. Evaluation at 22 different angles was found to give
accurate results. The bubble volume equivalent diameter (dv) is
calculated using the maximum Feret diameter (Fmax) and the
minimum Feret diameter (Fmin) as indicated in Equation (1), by
assuming that the bubble is axisymmetric (Raymond and
Rosant, 2000):
2
dv = 3 Fmax Fmin (1)
The Feret diameter depends upon the selected threshold value.
In terms of the number of pixels, as the threshold intensity is
increased the Feret diameter increases (Leifer et al., 2003). The
172 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
dimension of a single pixel is calibrated by imaging an object of
a known size: in this study, a syringe needle with external
diameter of 0.710 mm. The calibration image is also converted
into a binary image using the same threshold intensity, so
accurate dimensions are assigned to each pixel in the image
(about 21 µm). Along with the Feret diameters, Matrox Inspector
computes the compactness of a bubble, which is given by:
p2
compactness = (2)
4πA
where p is the perimeter of the projected bubble, and A is the
projected area of the bubble. A circle has a minimum compact-
ness value of 1. The bubble compactness factor is used as a
criterion to identify clusters of bubbles or touching bubbles that
could not be separated into single bubbles despite the fact that a
separating algorithm (subroutine in Matrox Inspector) is applied
to each image to split touching bubbles or bubbles in clusters.
Often the algorithm failed to efficiently split each cluster. Thus,
the compactness was found to be useful for identifying clusters
and over-segmented objects or blobs in an image. A blob in an
image with a compactness exceeding 1.25 is identified as
possible cluster or over-segmented object and is therefore
excluded from the results.
The bubble volume equivalent diameters (dv) computed from
each image are stored automatically in an Excel workbook. It is
in the workbook where the Sauter mean bubble diameter (d32)
and the mean number diameter (d10, see Equation (3)) of the
sample are calculated, along with other parameters associated
with the bubble size distribution. The Sauter mean bubble
diameter is defined as the volume-to-surface mean, as described
by Equation (4). The diameters are reported under standard
temperature (298 K) and pressure (101 325 Pa) conditions.
N
∑ dvi
d10 = i =1
(3)
N
N
∑ dvi3
d32 = i =1
N (4)
∑ dvi2
i =1
Monodisperse distributions of glass microspheres (NIST tracea-
ble monodisperse standards), manufactured by Whitehouse
Scientific (England), are used to validate the image analysis
method. The glass spheres are dropped into an inverted viewing
chamber filled with water, mimicking a swarm of bubbles. The
microspheres slide down the inner surface of the glass window.
Although glass microspheres are rigid objects, which behave
differently than gas bubbles, they can be used to study the impact
of different parameters on image analysis and processing errors.
Preliminary results for different size classes are shown in
Table 2. The same methodology used for gas bubbles was
applied to the images of the glass microspheres. The relative
errors shown in Table 2 were computed using Equation (5),
where d10HUT is the number mean diameter calculated using the
HUT BSA and d10spheres is the certified mean size.
d10 HUT −d10 spheres
error = (5)
d10 spheres
VOLUME 84, APRIL 2006

Table 2. Validation of the HUT BSA using glass microspheres
d10spheres (µm) d10HUT(µm) Relative
monodisperse glass measured using errors
microspheres HUT BSA
405.9 +/-8.7 429 5.7%
589 +/-8 618 4.9%
774 +/-3 752 -2.80%
978 +/-7 988 0.99%
1917 +/-11 1955 1.94%
Sampling Location
Since a larger flotation cell is used in these tests, preliminary
experiments were conducted in order to determine an adequate
location for sampling bubbles. The lower end of the sampling
probe was placed at different axial locations in the cell, as shown
schematically in Figure 2. The impeller speed was set at 700
rpm, and the air flow rate was set at 99 dm3/min (Jg=0.5 cm/s)
and 197 dm3/min (Jg=1.0 cm/s). Non-coalescing conditions
were established in the cell by using frothers at concentrations
well above the CCC points see Table 1 or Laskowski et al. (2003).
The variation of bubble diameter (d32) with sampling location is
shown in Table 3. It was found that the HUT bubble size
analyzer detected larger bubbles as the lower end of the sampling
probe was placed at deeper locations in the cell, see Table 1. An
explanation for this finding might be that the sampling probe
only collects rising bubbles, and in the neighbourhood of the
rotor/stator mechanism fine bubbles are not necessarily rising;
they instead follow the flow lines. Therefore at locations 2 and
3, the bubble size measurements appear to be biased toward
larger bubbles. At location 1, which is often referred to as the
separation zone, the bubble population can be expected to travel
upward. It could be expected that bubble size measured at
locations near to the froth/liquid interface under non-coalescing
Figure 2. Measurement locations in the 265 dm3 OK cell
conditions, is identical to that measured in the rotor/stator zone.
In the preliminary experiments (with results shown in Table 3),
DF-200 was used with only the Free-Flow mechanism shown in
Figure 3 and DF-1012 was used with only the Multi-Mix
mechanism shown in the same Figure. Similar behaviour is
likely using other combinations of frothers and mechanisms.
The radial location of the lower end of the sampling probe was
not modified throughout the experimental work. In the tests
conducted in the 265 dm3 Outokumpu flotation cell, Rudolphy et
al. (2005) found that the Multi-Mix and Free-Flow rotor/slator
mechanisms shown in Figure 3 produce rather uniform air distri-
butions along the radial direction of the cell at impeller speeds
higher than 500 rpm and aeration rates below 197 dm3/min. The
tests were carried out at different frother concentrations. These
findings indicate that under non-coalescing conditions a represent-
ative sample of the bubble population in the cell can be collected
at any radial location near the froth/liquid- interface.
Methods
The experiments were carried out in a batch mode. The level of
liquid in the cell was set equal to the diameter of the cell (65
cm), so a total volume of 215 dm3 of tap water was added to the
cell. In the frother tests, the hydrodynamic conditions in the cell
were altered by modifying the aeration rate and impeller speed.
The impeller speed was set at 600 rpm (tip speed of 4.7 m/s) and
900 rpm (tip speed of 7.1 m/s) and the air flow rate was set at
99 dm3/min (Jg=0.5 cm/s) and 197 dm3/min (Jg =1.0 cm/s)
in the cell. The required volume of frother was added from a
stock solution (around 10 g/dm3). Owing to the large volume of
water used in the experiments, the cell was refilled with fresh
water only if the temperature of the water exceeded 25ºC. At
temperatures below 25ºC, only the volume of water required to
change the frother concentration was added. The bubble viewer
was filled with the same frother solution prepared in the cell.
Bubbles were sampled from the cell, once the foam reached a
stable level in the cell. However, in some of the experiments, the
foam flowed over the lip of the cell. As the foam overflowed the
lip of the cell, it was discharged into the launder, and collected
in a small vessel. The aqueous solution was recirculated back to
the cell with a peristaltic pump and is re-injected through a port
in the sidewall near the bottom of the cell. The location of the
inlet was chosen to avoid disturbances to the prevailing hydrody-
namic conditions in the cell. The recirculation flow rate was
chosen so that steady-state conditions were achieved in the cell.
The cell is operated with a maximum possible froth depth of
15 cm without considering air holdup. Foam overflow was
observed mostly at high concentrations of frother, high air flow
rates and high impeller speeds.
Bubbles were sampled exclusively from location 1 (see Figure
2) near the froth/liquid interface in the separation zone of the
cell. A sampler tube 70 cm in length was used. Images of the
swarm of bubbles were captured once steady state flow was
achieved. In general, bubbles were sampled for several minutes
before initiating the recording process. Two or more duplicate
measurements were made for each condition. On average, more
than 5000 bubbles were analyzed. In general, 500 images were
captured and analyzed in each run; however, at low frother
concentrations the number of images was increased so that a
relatively large number of bubbles were sized. The images were
captured at a fixed rate of either 1 s or 2 s intervals. Therefore,
the image acquisition process was at least 8.5 min in duration.
Surface tension was measured dynamically using a commer-
cial maximum bubble pressure tensiometer [KSV BPA-800P].

VOLUME 84, APRIL 2006 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 173
 Table 3. Effect of the sampling location on bubble size, impeller speed 700 rpm
Frother/mechanism DF-200 25 ppm/ DF-200 25 ppm/
Free-Flow Free-Flow
Gas velocity Jg=0.5 cm/s Jg=1.0 cm/s
Sampling location d32 (mm) d32 (mm)
Location 1 0.68 0.79
Location 2 0.72 0.85
Location 3 0.79 0.93
Figure 3. Rotor/stator mechanisms (from left to right): Free-Flow, Multi-Mix and Outokumpu rotor OK
RESULTS
The effect of two different frothers on bubble size under varying
aeration conditions is shown in Figures 4 through 7. These
experimental data can clearly be fitted as two linear regions with
the intersection between the two giving the critical coalescence
concentration (CCC). Figures 4 and 6 clearly show that in the
non-coalescing region, the bubble size depends on the aeration
rate when frother DF-1012 is used. Conversely, the effect of
aeration rate in this region is negligible when DF-200 is used, as
shown in Figures 5 and 7. This is again shown in Figure 8.
Figures 4 and 5 include experimental data measured in a 50 dm3
Outokumpu flotation cell (Grau et al., 2005). The narrow bands
in these figures illustrate the range over which the critical
coalescence concentration varies. Figures 6 and 7 include the
location for each of the CCC values, which are indicated using
arrows. The CCC values determined graphically are listed in
Tables 4 and 5 for different hydrodynamic conditions in the
flotation cell.
The rationale for determining the CCC in this way is described
below. A linear equation is fitted to the bubble size-frother
concentration curve at low concentrations using Microsoft
Excel. A second linear equation is then fitted to the horizontal
part of the curve that occurs at higher frother concentrations.
Each linear equation is fitted to a minimum of three points. It
was not always clear whether points close to the inflection of
the bubble size-concentration curves should be assigned to the
high- or low-slope lines. Therefore, the change in the slope of
the steeper line induced by adding a point near the intersection
was determined with a large change in slope indicating that the
point in question is part of the low-slope line. The curves for the
DF-200 frother are not linear over the entire low concentration
range, so only the linear portion that meets the horizontal
asymptote is used to determine the CCC point in each case (see
Grau et al., 2005).
174 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
DF-1012 15 ppm/ DF-1012 15 ppm/
Multi-Mix Multi-Mix
Jg=1.0 cm/s Jg=0.5 cm/s
d32 (mm) d32 (mm)
0.96 0.67
1.09 0.72
1.38 0.87
The Sauter mean bubble diameter, d32, and the mean bubble
diameter, d10, are not very sensitive to the hydrodynamic
conditions, particularly at low aeration rates. The maximum
stable diameter d90, which is defined as the bubble diameter
such that 90% of the total gas volume is in bubbles of smaller
diameter (see Figure 9), shows quite clearly the effect of the
impeller speed on the bubble size, especially for the DF-1012
frother (Figure 10). As Figure 11 demonstrates, DF-1012 frother
is much more surface active than DF-200. The dynamic surface
tension isotherms for three Dow frothers are shown in Figure 11.
Samples of the foam and solutions were taken as bubble size
was measured. The solution was sampled by pumping a small
amount of liquid from the zone close to the impeller. Results
obtained with the DF-250 frother are also included in Figure 11,
since this frother has been used in previous experimental tests
(Laskowski et al., 2003; Grau et al., 2005).
DISCUSSION
All the bubble size versus frother concentration curves show the
same patterns and agree very well with previous publications.
The curves can be fitted with two linear segments with the
intersection giving the CCC value. The curves in the region
where the frother concentration is less than the CCC show the
effect of frother on bubble coalescence. It is also evident that the
size of the bubbles in the region where the frother concentration
is greater than the CCC may be very different. This is the size of
the bubbles produced by the rotor/stator mechanism and as
Figure 8 demonstrates the size of these bubbles increases with
increasing aeration rate. Figure 10 indicates that the size of
largest bubbles in the non-coalescing frother concentration range
also depends on the type of frother. These bubbles are larger for
the DF-1012 frother than for the DF-200. As Figure 11 reveals,
DF-1012 is much more surface active than DF-200. The foam
generated in the aqueous solution of DF-200 is in equilibrium
VOLUME 84, APRIL 2006
 Table 4. CCC values for the DF-1012 frother

Frother: DF-1012 CCC, Jg=0.5 cm/s CCC, Jg=1.0 cm/s

Multi-Mix
Impeller speed (rpm) mmol/dm3 ppm mmol/dm3 ppm
600 rpm 0.017 6.8 0.019 7.6
900 rpm 0.018 7.2 0.018 7.2
Free-Flow
Impeller speed (rpm) mmol/dm3 ppm mmol/dm3 ppm
600 rpm 0.017 6.8 0.020 8.0
900 rpm 0.017 6.8 0.020 8.0
CCC average 0.017 6.8 0.019 7.6

Table 5. CCC values for the DF-200 frother

Figure 4. Effect of DF-1012 frother on bubble size at different aeration Frother: DF-200 CCC, Jg=0.5 cm/s CCC, Jg=1.0 cm/s
rates in the Outokumpu flotation cell fitted with a Multi-Mix Multi-Mix
mechanism. Note: TS is the abbreviation for impeller tip speed.
Impeller speed (rpm) mmol/dm3 ppm mmol/dm3 ppm
600 rpm 0.073 15.1 0.065 13.4
900 rpm 0.070 14.4 0.066 13.6
Free-Flow
Impeller speed (rpm) mmol/dm3 ppm mmol/dm3 ppm
600 rpm 0.067 13.8 0.071 14.6
900 rpm 0.073 15.1 0.071 14.6
CCC average 0.071 14.6 0.068 14.1

behaviour may be attributed to the frother depletion from the

Figure 5. Effect of DF-200 frother on bubble size at different aeration
rates in the Outokumpu flotation cell fitted with a Multi-Mix
mechanism
with the solution and the DF-200 concentrations are practically
identical in the solution and in the foam (Figure 11). This trend
is very different for DF-1012. Because of its surface activity, DF-
1012 accumulates in the foam and its concentration in the foam
quickly becomes much greater than in the solution.
Critical Coalescence Concentration
As Figures 4 through 7 shows, the CCC values for the frothers
tested here do not seem to be substantially influenced by the
hydrodynamic conditions prevailing in the flotation machine. As
shown in Figures 6 and 7, the CCC values for the DF-1012 frother
varied within a narrow range between 0.017 and 0.020 mmol/
dm3; for the DF-200 frother, the CCC values varied between 0.65
and 0.73 mmol/dm3 (See Tables 4, 5 and 6). It is noteworthy that
while the CCC values obtained for the DF-1012 frother seem to
increase slightly with increasing aeration rate in the flotation cell,
the CCC values obtained for the DF-200 were not affected by the
changes in aeration conditions in the cell (Tables 4 and 5). This
solution and its accumulation in the foam. As shown in Figure 11,
the dynamic surface tension-bubble life time isotherms exhibit
large differences for the two frothers tested here. For the less
surface active frother, the dynamic surface tension data obtained
from the collected samples of the foam and solution are almost
identical, indicating that the foam and solution (liquid phase)
were in equilibrium. For the more surface-active agents, large
deviations between the surface tension-bubble life time isotherms
are observed, which is an indicator that the frothing agents
accumulated in the foam. The rate of accumulation of the frother
in the foam and the amount accumulated may be correlated with
the gas dispersion conditions, and particularly with the bubble
surface area flux in the flotation cell, the surface activity of the
frothing agent and its rate of adsorption.
Bubble Coalescence
Sagert et al. (1976) studied coalescence of bubble pairs generated
on two adjacent capillary tubes in solutions of various alcohols.
They showed that the measured coalescence time versus concen-
tration curves obtained for various aliphatic alcohols correlate
well with the surface tension – concentration relationships for
these alcohols (Figure 12). Drogaris and Weiland (1983) further
confirmed the relationship between the measured coalescence
time and change in surface tension. These measurements were
carried out under static conditions, which are very different from
the dynamic conditions in the cell. However, if these coalescence
time measurements have the same meaning under dynamic
conditions then it is obvious that the coalescence under dynamic
conditions can take place only if the time of contact between two

VOLUME 84, APRIL 2006 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 175
Figure 6. Graphical determination of the CCC values for DF-1012 at different aeration rates in the 265 dm3 Outokumpu flotation cell; top figures:
Multi-Mix mechanism; bottom figures: Free-Flow mechanism
colliding bubbles is longer than the coalescence time. By extrap-
olating the relationship between the coalescence time and
concentration obtained for different alcohols by Sagert et al.
(1976) to polyglycols (Dowfrothers), it could be expected that for
a given concentration the coalescence time for DF-1012 would be
much greater than for DF-200 (Figure 12). With increasing
frother concentration the coalescence time increases; therefore,
the number of bubbles coalescing decreases. As a result, a
decrease in bubble size is observed (Figures 4 through 7). At
concentrations exceeding the CCC values of each frother, the
coalescence time might be longer than the time of contact, thus
preventing bubbles from coalescing.
Critical coalescence times were calculated from the coales-
cence time-concentration curves (Drogaris and Weiland, 1983)
by using the CCC values for n-butanol, n-pentanol, and n-
hexanol solutions given by Cho and Laskowski (2002a). It was
found that the critical coalescence times fall within a narrow
range between 0.05 and 0.1 s, indicating that the average contact
between two colliding bubbles in a flotation cell is shorter than
0.1 s. This provides a time scale for the dynamic events occurring
in a flotation cell.
It is usually assumed that bubble coalescene is a binary event,
and that the mechanism of coalescence is based on drainage,
176 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
thinning and rupture of the liquid film between two colliding or
adjacent bubbles (Marrucci, 1969). The thinning or deformation
of the film between two colliding bubbles can be regarded as a
highly dynamic process. When a thin film of a solution of a
surface-active agent is stretched or deformed, surface elasticity
forces arise because of variations in surface tension. As bubble
coalescence in the liquid phase is strongly retarded or prevented
in the presence of frothing agents, the bubbles reach the surface
of the liquid and form foam. Flotation foams are very unstable
systems: after gas bubbling is stopped they collapse quickly
(Malysa, 1992). Foam stability is generally explained by surface
elasticity forces. The surface tension of a foam film (bubble-
liquid surface) is higher than its static value during dilation and
lower during compression. This variation in surface tension
provides a restoring force that counteracts the disturbances
(Kitchener and Cooper, 1959; Harris, 1982). This is known as
the Marangoni effect:
dγ dγ
E= or E = AB (6)
d ln( AB ) dAB
Malysa et al. (1981), using a pulsating bubble technique,
determined the Marangoni dilational modulus of n-octanol
VOLUME 84, APRIL 2006
Figure 7. Graphical determination of the CCC values for DF-200 at different aeration rates in the 265 dm3 Outokumpu flotation cell; top figures:
Multi-Mix mechanism; bottom figures: Free-Flow mechanism
solutions (Figure.13). The Marangoni dilational modulus is
defined as the change in surface tension (dγ) with respect to the
relative change in surface area deformation. A general definition
of surface elasticity forces (modulus of elasticity) is given in
Equation (6). The Marangoni dilational modulus refers to the
so-called insoluble behaviour of the adsorption layer; that is to
say, its values of the surface elasticity forces are the greatest that
can be induced when frequencies of the interface disturbances
are much higher than kinetics of adsorption-desorption processes.
With increasing concentration of the surface-active agent, the
Marangoni dilational modulus was found to increase, reaching
values comparable to the equilibrium surface tension. This
finding indicates that low concentrations of a surface-active
agent might drastically modify the surface elasticity of a bubble.
The Marangoni elasticity is believed to be greater in presence of
more surface-active agents. Hence, it could be expected that this
elasticity would be much greater in the presence of the DF-1012
frother than in the presence of the DF-200 frother at any given
concentration. This seems to be the main reason why the molar
CCC value of the DF-200 frother is almost four times higher than
the CCC value of the DF-1012 frother (Table 6). It can also be
concluded that at any frother concentration exceeding its CCC
value, the film between colliding bubbles becomes elastic
enough to resist rupture.
VOLUME 84, APRIL 2006
Bubble Breakup
Bubble generation in a mechanically agitated cell has been
shown to occur in the zone close to the rotor/stator mechanism.
Grainger-Allen (1970) observed that air cavities formed at the
rear face of impeller blades in laboratory mechanical flotation
cells. At low aeration rates, aerated cavities behind the blades of
the Outokumpu rotor have been observed with the use of a high
speed camera. The aerated cavities showed a high rotational
speed, resembling the clinging cavities described by Bruijn et al.
(1974). The main mechanism of bubble generation seems to be
the shedding of bubbles from the tail of the rotating cavities
(Grainger-Allen 1970; Van’t Riet and Smith, 1973). The primary
bubbles generated by the action of the aerated cavities may be
further broken up in the region near the rotor/stator because of
the highly turbulent conditions in this zone. The bubble size
measured at concentrations exceeding the CCC values (non-
coalescing conditions) is that generated by the rotor/stator
mechanism at the hydrodynamic conditions prevailing in the
cell. It is clear from Figures 4 through 7 that the type of frother
has an effect on the size of the bubbles produced in the
neighbourhood of the rotor/stator. Under non-coalescing
conditions in the cell, the size of the bubbles produced by the
mechanisms increased sharply with increasing aeration rate in
the presence of the DF-1012 frother (Figure 8). In the presence
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 177
Figure 8. Effect of gas velocity on the bubble size under non-coalescing
conditions for frothers DF-200 (25 ppm) and DF-1012 (15 ppm) and at
constant impeller speed. The cell was fitted with the Multi-Mix
(OKMM) and Free-Flow (OKFF) mechanisms.
Figure 10. Effect of impeller tip speed on bubble size distribution in
the presence of the two tested frothers. Jg= 1.0 cm/s, DF-1012 frother
concentration is 15 ppm and DF-200 frother concentration is 25 ppm.
Tests carried out in the 265 dm3 Outokumpu cell fitted with the
Free-Flow mechanism.

Figure 9. Cumulative bubble volume distribution measured in the

presence of DF-1012 frother, in the 265 dm3 Outokumpu cell fitted Figure 11. Dynamic surface tension for DF-200, DF-250 and DF-1012
with the Free-Flow mechanism. The mean diameters d32, d10 and the Dow frothers measured in the solutions retrieved either from the cell,
maximum stable bubble diameter d90 are shown graphically. Note that or from the collapsing foam.
d10 is the linear (arithmetic) mean diameter (Equation (3)).
As shown in Figure 9, the value of d90 is calculated by fitting
the upper-limit distribution to the experimental data (ASTM
Table 6. CCC mean values
E799-92, 1996). The corresponding d10 (Equation 3) and d32
Frother CCC mean STDEV CCC mean STDEV (Equation 4) of the distribution are also included in the same
mmol/dm3 mmol/dm3 ppm ppm figure. The upper-limit distribution has been found to describe
DF-200 0.070 0.003 14.4 0.62 satisfactorily bubble size distributions in laboratory scale
flotation cells (Grau and Heiskanen, 2005). Other investigators
DF-1012 0.018 0.001 7.16 0.40
have taken different cut-off sizes in the cumulative bubble size
distribution as a measure of the maximum stable bubble size
of the DF-200 frother, only a moderate increase was observed. (dmax). Deglon et al. (1998) and Takahashi et al. (1992) adopted
This result suggests that frothers may affect bubble generation the (d95) criterion (95% bubble size based on the cumulative
differently. These differences become even more evident as the bubble size distribution) as the maximum stable bubble
maximum stable bubble diameter (d90) is plotted against diameter, while Hinzé (1955) chose the 95% drop size from the
impeller speed (Figure 10). It is usually assumed that there is a cumulative volume distribution, as the maximum stable drop for
maximum bubble diameter above which no stable bubble can a liquid-liquid dispersion. In this paper, the d90 value was
exist in a turbulent flow. It is also obvious from Figure 10 that selected as the adequate measure to represent the maximum
the Sauter mean bubble diameter (d32) and the number mean stable bubble diameter (dmax) in a flotation cell.
diameter (d10) did not reveal adequately the differences between Figure 10 reveals an interesting pattern: more surface active
the bubble size distributions produced in the presence of differ- agent produced larger stable maximum bubble diameters. This
ent frothers. finding seems to be contrary to the commonly accepted belief

178 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, APRIL 2006

Figure 12. Effect of surfactant concentration on the equilibrium surface
tension and coalescence time of adjacent bubbles. Equilibrium surface
tension-concentration isotherms for aqueous solutions of n-alcohol
from Addison (1945), coalescence time-concentration curves from
Sagert et al. (1976) and Drogaris and Weiland (1983).
that reducing the surface tension of the liquid decreases the
bubble size. The correlation for the maximum stable diameter
for drops in locally isotropic turbulent fluids derived by Hinze
(1955) has been adapted to model bubble breakup in stirred
tanks (Calderbank, 1958; Parthasarathy et al., 1991).
Parthasarathy and Ahmed (1994) obtained the following relation-
ship for estimating the maximum stable bubble diameter in
stirred vessels at low gas velocities and under non-coalescing
conditions (concentration of 50 ppm of MIBC, see Table 1):
γ3 / 5
dmax = C 2 /5
 P 
  ρ1 / 5
V 
where γ is the equilibrium surface tension, ρ is the density of the
continuous phase, P/V is the power input per unit of volume and
C is a constant. Although, this relationship, based on the theoret-
ical model for liquid-liquid dispersions, predicts a reduction in
the maximum stable diameter with decreasing surface tension,
the real effect of the surface tension on the bubble breakup was
not studied by the authors. Walter and Blanch (1986) studied the
effect of several surfactants on bubble breakup in a turbulent
pipe flow. They found that long hydrocarbon chain surfactants
VOLUME 84, APRIL 2006
Figure 13. Effect of a surface-active agent on the Marangoni dilational
modulus (EM) and equilibrium surface tension (Malysa et al., 1981).
Also plotted are the equilibrium surface tension isotherms for DF-200
and DF-1012 (Grau et al., 2005).
Figure 14. Comparison of the bubble size vs. concentration plots for
DF-frothers obtained at different aeration conditions in two different
Outokumpu (OK) cells.
produce larger stable bubbles than short chain surfactants in
solutions with similar surface tensions. In the presence of Dow
frothers the following trend has been observed: at concentrations
exceeding the CCC value, the maximum stable bubble diameter
increased with increasing chain length of the frother molecule.
The DF-1012 frother was found to produce larger stable bubbles
than DF-250 and DF-200 (Figure 14, Grau et al., 2005). This
trend seems to be more evident at higher aeration rates in the
cell (Figure 8). At low aeration rates in the non-coalescing
region, no large differences in the Sauter mean bubble diameters
(7) produced were observed. A similar pattern was observed
previously by Laskowski et al. (2003). These results might
suggest that in some cases the Sauter mean diameter is not a
suitable parameter to reveal differences in bubble size distribu-
tions, particularly at the coarse end of the distribution, as
depicted in Figure 10.
The reason why DF-1012 produced more stable bubbles than
the other Dow frothers can be also found in the surface elasticity
of adsorption layer of the bubbles. As bubbles are exposed to rapid
deformation of their interface during the breakage process, it is
likely that elasticity forces arise that withstand the disruptive
forces. Indeed, Walter and Blanch (1986) modified Equation (7)
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 179
by introducing the effect of surface elasticity on the breakage the bubbles measured in the non-coalescing region is the size
process as described by Equation (8): produced in the rotor/stator zone of the cell. In the presence
of DF-1012, the aeration conditions in the cell were found to
( γ + E )3 / 5 affect substantially the size of the bubbles produced over the
dmax = C 2 /5
P (8) non-coalescing range, while in the presence of DF-200, the
V  ρ1 / 5 effect of the hydrodynamic conditions in the cell was fairly
 
small.
where E is a dilational elasticity or dilational modulus (see 2. The tested frothers appear to affect both bubble coalescence
Figure 13). and bubble breakup processes. The CCC values obtained
Elasticity forces have also been found to play an important experimentally for the less surface active frother (DF-200)
role in drop breakup in liquid-liquid dispersions. Janssen et al. were higher than those obtained for the DF-1012 frother,
(1994a; b) concluded that the equilibrium surface tension could which is a more surface-active frother. The DF-200 frother
not explain the magnitude of the interfacial restoring forces was found to produce finer stable bubbles in the non-
arising during the deformation of an isolated single drop in the coalescing concentration range than the more surface–active
presence of surface-active agents in a Couette device. They frother (DF-1012).
defined an effective surface tension as described by Equation
(9), which accounts for the net effect of the presence of surface-
active agents:
NOMENCLATURE
A projected area of a bubble (mm2)
γ effective = γ + βE (9) AB surface area of a bubble (m2)
C dimensionless empirical constant
In Equation (9) E is the elasticity modulus, which represents CCC critical coalescence concentration (mol/dm3)
the dynamic component of the effective surface tension, γ is the DFI dynamic foamability index (s⋅dm3/mol)
equilibrium surface tension and β is a constant. dv bubble volume equivalent diameter (mm)
It seems that frothing agents endow bubbles with elastic d10 linear (arithmetic) mean bubble diameter (mm)
properties, which arise during rapid deformation of the bubble d10spheres mean size of glass spheres (mm)
interface. It is likely that in a turbulent flow, as in the zone close d10HUT mean size of glass spheres determined by the
to the rotor/stator in a flotation cell, the distribution of a HUT BSA (mm)
surfactant around the surface of a bubble is far from being d32 Sauter mean bubble diameter (mm)
uniform owing to the motion of the bubble. It is commonly d90 bubble diameter such that 90% of the total gas
accepted that the accumulation of surfactants at the gas/liquid volume is in bubbles of smaller diameter (mm)
interface of a rising bubble reduces the mobility of its interface, dmax maximum stable bubble diameter (mm)
which results in a reduction in the rising velocity (Levich, 1962). E modulus of elasticity (N/m)
According to Krzan and Malysa (2002) the concentration of Fmax maximum Feret diameter (mm)
surfactant at the interface of a rising bubble varies drastically. At Fmin minimum Feret diameter (mm)
the leading pole of the bubble (adsorption point) there is a low Jg superficial gas velocity (cm/s)
concentration of surfactant, while at the rear pole (desorption p perimeter of the projected bubble
point) there is a high concentration of surfactant. The rotor/ TS impeller tip speed (m/s)
stator neighbourhood is the zone where bubbles are broken up P/V power input per unit volume (W/m3)
and high rates of collision between bubbles can be expected. A
rapid deformation of a bubble will lead to even larger variation Greek Symbols
in frother concentration across the interface, resulting in local
β dimensionless constant
zones with high and low frother concentrations. The gradient in
γ surface tension (N/m)
surface density of the surfactant leads to variations in surface
γeffective effective surface tension (N/m)
tension, which might be an important factor stabilizing the
ρ density of the liquid phase (kg/m3)
bubble against coalescence and breakup. The distribution of the
surfactant at the gas/liquid interface of a bubble is influenced by
the surface activity of the surfactant, rate of transport to the ACKNOWLEDGEMENTS
surface, surface transport mechanisms, concentration of the
frothing agent in the solution, motion of the bubble and physical The authors are grateful to Outokumpu Technology for their
properties of the liquid. It can be expected that long hydrocarbon financial support to conduct this research. This paper was
chain frothers would show a lower rate of adsorption and lower mainly written during a visit to the Department of Chemical
ability to migrate along the surface of the bubble than shorter Engineering, University of Cape Town, which was made possible
chain frothers. thanks to the travel grant awarded to Rodrigo Grau by the
Outokumpu Oy Foundation. The assistance of Dee Bradshaw of
the University of Cape Town in organizing the visit is gratefully
CONCLUSIONS acknowledged.
The following conclusions can be drawn from this project:
1. The shape of the experimental bubble size-frother
concentration curves agree very well with early publications.
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Manuscript received June 21, 2005; revised manuscript received

September 15, 2005; accepted for publication February 2, 2006.

182 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 84, APRIL 2006