Int. J. Miner. Process. 64 Ž2002.

69–80
www.elsevier.comrlocaterijminpro

Effect of flotation frothers on bubble size

and foam stability
Y.S. Cho, J.S. Laskowski )
Department of Mining and Mineral Process Engineering, UniÕersity of British Columbia,
6350 Stores Road, VancouÕer, B.C., Canada V6T 1Z4
Received 1 March 2001; received in revised form 15 June 2001; accepted 2 July 2001

Abstract

In order to study the effect of frothers on the size of bubbles, experiments were carried out
using single- and multi-hole spargers and a flotation cell. It was found that the size of bubbles
strongly depends on frother concentration only when multi-hole spargers are utilized Žor when
measured in a flotation cell.. At low frother concentrations Ž C - CCC., the bubble size is much
larger, indicating coalescence as a main mechanism determining the size. Coalescence can be
prevented at frother concentrations exceeding the critical coalescence concentration ŽCCC..
The foamability tests indicate that stability of foams under dynamic conditions is determined
by bubble coalescence. q 2002 Elsevier Science B.V. All rights reserved.

Keywords: flotation; frothers; bubbles; spargers; critical coalescence concentration; dynamic foamability index

1. Introduction

Flotation kinetics involves a number of mass transfer processes with some taking
place in the pulp phase Žparticle–bubble collision and attachment, transport of particle–
bubble aggregate to the froth phase. and some in the froth phase Žrecovery of particle
from the froth phase to concentrate launder.. All of these subprocesses depend strongly
on bubble size and froth stability. In a flotation process, frothers are utilized to enhance
generation of fine bubbles and to stabilize the froth. According to Leja–Schulman’s
penetration theory, the interaction of frothers with a collector in the moment of the
particle-to-bubble attachment is a vital step in the particle–bubble attachment.

)
Corresponding author.
E-mail address: jsl@mining.ubc.ca ŽJ.S. Laskowski..

0301-7516r02r$ - see front matter q 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 1 - 7 5 1 6 Ž 0 1 . 0 0 0 6 4 - 3
70 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80

It is known that pure liquids do not foam, but the presence of surface active
molecules that preferentially adsorb at a liquidrgas interface changes this situation
radically. Recent measurements of bubble size, dynamic foamability index and surface
tension for a series of flotation frothers ŽFig. 1. showed a very good correlation between
bubble size and dynamic foamability ŽSweet et al., 1997.. While the bubble size and
dynamic foamability index were found to be sensitive to very low frother concentration
changes, the surface tension was observed to be affected by the frother only at
concentrations more than 10 times higher. Since the previously derived equations relate
the size of generated bubbles to surface tension, and the surface tension does not seem to
change much at very low frother concentrations, the question, therefore, arises why the
bubble size depends on frother concentration. In order to answer such questions, we
carried out a series of experiments in which specially designed spargers were used and
the size of the bubbles was measured over a broad concentration range for different
frothers. In concomitant experiments, the dynamic foamability index and the surface
tension were measured for the same frothers.

2. Experimental procedures
2.1. Materials
Experiments were performed using MIBC and four different hexanol isomersrderiva-
tives kindly provided by the Condea Vista.
MIBC Methyl isobutyl carbinol wŽCH 3 . 2 CHCH 2 CHŽOH.CH 3 x
Frother 1 1-hexanol wC 6 H 13 OHx
Frother 2 Di ethoxy-mono propoxy hexanol wC 6 H 13 OHŽEO. 2 ŽPO.x
Frother 3 Di ethoxy hexanol wC 6 H 13 OHŽEO. 2 x
Frother 4 Mono propoxy-di ethoxy hexanol wC 6 H 13 OHŽPO.ŽEO. 2 x

2.2. Methods
2.2.1. Bubble size measurements
The UCT bubble size meter was employed to measure the bubble size as described by
Tucker et al. Ž1994.. The bubbles were generated in a 3-l Plexiglas tank using distilled
water. All experiments were conducted at 21 8C. Approximately 3000 bubbles were
sampled during each run. Three runs were carried out for each concentration of tested
surfactant, the average of three runs was reported and the experimental details were
provided in another paper ŽCho and Laskowski, 2001..
Bubbles are commonly produced by sparging, that is pumping gas through a capillary
or frit into the bulk liquid. In mechanical flotation cells, they are produced by cavitation
at the trailing edge of the impeller blade, or if the air is supplied under pressure by
breaking it into fine bubbles by shearing forces. The size of a bubble forming at an
orifice under equilibrium conditions can be calculated using thermodynamic data which
show clearly dependence on the surface tension. However, in most practical cases in
which rapid bubble formation occurs, the equilibrium calculations are inadequate to
predict the detachment volume ŽLubetkin, 1993.. To create the conditions as close to
 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80 71

equilibrium as possible, the bubbles in our experiments were generated at very low air
flow rates of 2 cm3rmin and a Bel-Art Rite flowmeter was used. The sampler of the
UCT bubble size analyzer was placed 50 mm above the sparger.
A few different spargers were tested. A flexible latex sparger that contained two
punctures made using a hypodermic syringe in a stretched latex sheet, far away from
each other to eliminate coalescence, consistently produced bubbles of uniform size as
shown in Fig. 2 Žstandard deviations of 0.057 and 0.029 mm.. However, probably
because of the different hole dimensions, the size of the generated bubbles was observed
to be very different Ž1.45 vs. 2.15 mm.. Since in the latex type spargers used by Rice et
al. Ž1981., the punctured holes are not spherical, it is impossible to determine the exact
hole diameter. Therefore, we also employed rigid, bronze spargers. While the hole
diameter can easily be determined for such spargers, it turned out to be impossible to
obtain a steady stream of bubbles when using such spargers. Rice and Lakhani Ž1983.
noticed that at superficial gas velocities of less than 5 cmrs, a rubber sparger produced a
homogenous stream of bubbles as compared to the very unpredictable and irregular flow
of bubbles varying in size when rigid spargers were employed. Since the only difference
between the latex sparger and the rigid bronze plate sparger is the flexibility of the
former and its ability to oscillate and deform as gas passes through, it was decided to
vibrate the rigid sparger. The sparger tank was mounted on a Syntron Lapping–Polish-
ing Machine and vibration was applied. As the frequency of the vibration increased
stepwise, a small window of frequency was found in which the size of the generated
bubbles became very uniform and consistent Žwithin 5%. over five runs of the bubble
size measurements. This vibration frequency was, thus, set for the entire experiment.
In the bubble size measurements in an open top Leeds flotation cell, the impeller
speed was set at 1000 rpm and the air flow rate was 5 lrmin. The sampler of the bubble
size analyzer was positioned 50 mm above the stator.
2.2.2. Sparger hole size determination
Following published data ŽDobby and Finch, 1986; Diaz-Penafiel and Dobby, 1994.,
it was decided to work with bubbles of 1–2 mm in size, as they are most common for
flotation systems. Using Eq. Ž4. below, the required size of the sparger opening was
calculated to be within 0.1–0.15 mm, and drills of this size were used.
2.2.3. Dynamic foamability index
Since this methodology employs a two-phase system consisting of liquid and
dispersed air, we have decided to use the term foam instead of froth as used in the
original publications by Malysa et al. Ž1978, 1981.. The foamability measurement in
Malysa’s procedure defines the retention time, rt, as the slope of the linear part of the
dependence of the total gas volume contained in the system Žsolutionq foam. on the gas
flow rate. Values of the retention time are claimed to be independent of the gas flow rate
and geometry of the measuring column. Physically, rt is the average lifetime of a bubble
in the whole system, i.e. in both solution and foam. The dynamic foamability index
ŽDFI. is defined as the limiting slope of rt vs. concentration for c ™ 0.
Ert
DFI s ž /
Ec cs 0
Ž 1.
72 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80

Alternatively, it is possible to fit an equation to the rt values vs. c data in order to

alleviate the need to find the initial slope graphically. The equation takes the form of an
inverse exponential, which when expanded into a power series gives:
rt y 2.4 s DFI P c Ž 2.
where
DFI s rt` P k Ž 3.
The quantity 2.4 was given by Malysa as the value of rt for distilled water, rt` is the
limiting rt value for c ™ ` and k is a constant.
In our tests, the frother aqueous solutions were placed in the column Ž45-mm
diameter, 92-cm height.. Nitrogen was pumped through the sintered glass disk initially
at a flow rate of 100 cm3rmin, which was then increased stepwise up to 2000 cm3rmin.
After each change, the resulting steady state volume Žsolutionq foam. was recorded.
The total volume was plotted vs. flow rate to obtain the slope Žretention time. via linear
regression.

3. Results
Fig. 1 compares the effect of concentration of two hexanol isomers on bubble size,
retention time Žfoamability. and surface tension ŽSweet et al., 1997.. In order to facilitate
comparisons, the results were plotted in a normalized form. The term AnormalizationB is
used to describe the ratio of the parameter of interest to its value measured at zero
surfactant concentration.

Fig. 1. Normalized retention time, Sauter mean bubble diameter and surface tension of n-hexanol and MIBC
ŽSweet et al., 1997..
 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80 73

As shown, the surface tension seems to be least sensitive to the surfactant concentra-
tion; both bubble size and retention time are affected by the frother at the concentrations
at which the surface tension values are practically identical to that of distilled water.
This figure reveals that bubble size is much more sensitive to the surfactant concentra-
tion than surface tension and perhaps could be used for analytical purposes to test the
presence of surface active substances at very low concentrations. Similar plots for other
frothers show the same trend. Discussion of these results was hindered by the fact that
the bubble size and foamability in this project were measured in Cape Town tap water,
while the surface tension data obtained using distilled water were quoted after other
sources ŽSweet et al., 1997..

3.1. Single-hole spargers

Frothers did not show any effect on bubble size when bubbles were generated from a
single-hole latex sparger. Fig. 2 shows quite uniform bubble sizes regardless of frother
concentration. Eq. Ž4. quoted after Rubinstein Ž1995. shows that the bubble size depends
only on inner capillary Žor sparger size. and surface tension of the solution.
1r3
6 dc g
db s
ž g Ž r l y rg . / Ž 4.

where d b is the diameter of the bubble, g is the surface tension of the liquid, d c is the
size of the capillary, r l is the density of the liquid and rg is the density of gas.

Fig. 2. Effect of frother concentration on bubble size using a latex sparger.

74 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80

Table 1
Comparison of calculated vs. measured bubble diameter sizes
Capillary diameter Žmm. Calculated bubble Average measured bubble
diameter sizes Žmm. diameter sizes"S.D. Žmm.
0.10 1.65 1.65"0.029
0.15 1.88 1.89"0.017

Since the surface tension was practically constant throughout the tested frother
concentrations ŽCho and Laskowski, 2001., the size of bubbles was expected to be
uniform for the same spargers. As shown in Fig. 2, the results are consistent with
published Eq. Ž4..
The tests carried out using the bronze sparger gave similar results. Calculated Sauter
mean diameters of the bubbles generated from 0.1 and 0.15 mm spargers were 1.65 and
1.88 mm, respectively. The average bubble sizes actually produced from the bronze
spargers were in perfect agreement with the calculated sizes as shown in Table 1 and
Fig. 3. Indeed, the bubble size did not change with frother concentration.

3.2. Three-hole sparger (0.1 mm) and flotation cell tests

Since the frothers do not affect the size of bubbles generated using a single-hole
sparger, the only possible mechanism to change the bubble size when a multi-hole
sparger Žor a flotation cell. is utilized would be by coalescence andror breakage of the
bubbles. The measured bubble sizes were much smaller than the critical size subjected to
breakage ŽPrince and Blanch, 1990. and, therefore, bubble breakage should be ruled out

Fig. 3. Effect of frother concentration on bubble size using a bronze single-hole sparger.
 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80 75

Fig. 4. Effect of frother concentration on bubble size using 0.1-mm diameter three-hole bronze sparger.

as a possible mechanism for the bubble size changes. This leaves bubble coalescence as
the only possible mechanism responsible for bubble size changes in our multi-hole
sparger experiment.
Taking 1.65 mm Žfrom Table 1. as the average diameter of the bubble generated from
0.1-mm sparger, three 1.65-mm bubbles when coalescing should give a larger bubble of
2.38 mm in diameter. This is again in a perfect agreement with the measured bubble
diameters without frothers ŽFig. 4.. As the concentration of frothers increased in the
solution, the degree of coalescence decreased. More powerful frothers Žfrothers 2 and 4.
prevented the bubble coalescence at lower frother concentrations. As the measurements
of surface tension revealed ŽCho and Laskowski, 2001., frothers 2 and 4 turned out to be
more surface active than frother 3, hexanol and MIBC. The obvious difference between
these two groups is the presence of propylene oxide group in frothers 2 and 4.

4. Discussion

It is commonly believed that the bubble size decreases with an increase in the frother
concentration owing to a decrease in the surface tension induced by the addition of
surfactants. By the way, this was one of the conclusions drawn in a very recent paper
ŽAldrich and Feng, 2000.. As the results presented in our paper Žand in another paper by
Cho and Laskowski Ž2001. demonstrate, at frother concentrations typical for the froth
flotation systems, the bubble size is not affected at all by a frother if the bubbles cannot
collide with each other. The results obtained by Sweet et al. Ž1997. already hinted that
76 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80

Fig. 5. Effect of frother concentration on bubble size measured in an open-top Leeds flotation cell.

there is a poor correlation between bubble size and surface tension. Figs. 2–5 explain
why. As these figures reveal, in the experiments in which one-hole spargers were
utilized Žin other words, when the bubbles could not collide with each other., there was
no effect of frother concentration on the bubble size. If the experiments were carried out
using multi-hole spargers, or were carried out in a flotation cell, the size of bubbles was
substantially larger at low frother concentrations.

Fig. 6. Effect of frother concentration on bubble size Žschematic..

 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80 77

Table 2
Comparison of CCC values obtained using a three-hole sparger and an open-top Leeds flotation cell
Frothers Three-hole sparger Open-top flotation cell
CCC values Žmolrl. CCC values Žmolrl.
MIBC 0.000079 0.000083
Frother 1 0.000079 0.000083
Frother 2 0.000013 0.000015
Frother 3 0.000031 0.000037
Frother 4 0.000016 0.000015

It is obvious that with increasing frother concentration, the degree of bubble

coalescence decreases and at a particular concentration Žcritical coalescence concentra-
tion., the coalescence of the bubbles is completely prevented ŽFig. 6.. The stronger
frothers reach the CCC point at a lower concentration. The values of CCC seem to
characterize frothers very well. At concentrations higher than CCC, the coalescence does
not occur.
The three-hole sparger experiment, which was conducted in a controlled environment,
provided CCC values that were identical to those obtained in a flotation cell. This
implies that the CCC values obtained for a given frother in a small-scale laboratory
experiment Ži.e. three-hole sparger. do not depend on a type of flotation cell.
As seen from Table 2, the five tested frothers are characterized by unique CCC
values. As shown in another paper ŽCho and Laskowski, 2001., the CCC values could
also be obtained from Tucker et al.’s Ž1994. data who measured the size of bubbles in a
flotation cell using DIBK Ždi-isobutyl ketone., TEB Žtriethoxybutane. and MIBC
frothers.
Fig. 7 shows the interrelation between CCC and DFI and demonstrates that the
foamability of aqueous solutions measured under dynamic conditions is determined by

Fig. 7. Relationship between DFI and critical coalescence concentration for the tested frothers.
78 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80

Table 3
DFI values for various commercial frothers using Cape Town tap water ŽSweet et al., 1997.
Frothers rt` Žs. k Ždm3 rmol. DFI Žs dm3 rmol.
n-Butanol 20.5 65.3 1339
2-Butanol 12.7 65.0 826
t-Butanol 10.8 146.6 1588
n-Pentanol 22.6 243.7 5517
n-Hexanol 62.6 539.6 33,779
n-Heptanol 82.5 495.6 40,867
n-Octanol 87.3 908.5 79,338
n-Octanol 61.1 2313.3 141,226
2-Ethyl-hexanol 68.3 2066.8 141,147
MIBC 55.0 672.2 36,991
a-Terpineol 27.1 5093.9 138,171
Texanol 31.2 10,392.7 323,901
TEB 34.7 7279.4 252,589
DowFroth400 72.8 11,025.7 802,142
DIBK 21.5 3589.6 77,019
n-Butanola 20.8 61.0 1271
a
Test conducted in distilled water.

bubble coalescence. More surface active frothers are characterized by lower CCC and
higher DFI values. The DFI values determined for various frothers using Cape Town tap
water are shown in Table 3 ŽSweet et al., 1997.. It seems to be possible to predict the
CCC values for these frothers from this data.

Fig. 8. Effect of concentration of tested n-alcohols on the normalized Sauter mean bubble diameter ŽSweet et
al., 1997..
 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80 79

Fig. 9. Relationship between DFI and C0.6 ŽSweet et al., 1997., dashed line, and DFI and CCC Žfrom Fig. 7.,
continuous line.

In the paper by Sweet et al. Ž1997., an empirical coefficient that did not have any
physical meaning, the C0.6 concentration defined as the frother concentration at which
the Sauter mean bubble diameter is reduced to 0.6 of its original value in water Žat zero
surfactant concentration. was selected to discuss the obtained results. Fig. 8 shows how
the C0.6 values were obtained from the experiments. Because—as Fig. 8 indicates—it is
obvious that the C0.6 frother concentration is pretty close to the critical coalescence
concentration ŽCCC., Fig. 7 provides an entirely different physical meaning for the
correlations discussed by Sweet et al. Ž1997.. This is shown in Fig. 9. Only because the
experimental C0.6 values happen to be close to the CCC values, our DFI s f ŽCCC. plot
Žcontinuous bold line. that has a well defined physical meaning is not very different
from the empirical relation DFI s f Ž C0.6 . obtained by Sweet et al. Ž1997. for two series
of frothers.

5. Summary
The experiments described herein indicate that the frothers control the size of bubbles
in flotation systems by controlling bubble coalescence. At frother concentrations C
lower than CCC, the bubble size mainly results from coalescence. The ability of frothers
80 Y.S. Cho, J.S. Laskowskir Int. J. Miner. Process. 64 (2002) 69–80

to prevent bubble coalescence is well characterized by the critical coalescence concen-

tration ŽCCC.. At frother concentrations that exceed CCC, the bubble size is no longer
determined by coalescence and will then strongly depend on sparger’s geometry and
hydrodynamic conditions. Thus, efficiency of different spargers can be compared only
when the experiments are carried out at frother concentrations exceeding CCC.
Flotation experiments carried out using small-scale flotation devices Že.g. Hallimond
tube. equipped with either single capillary or a porous frit may be very difficult to
compare. They may give different flotation kinetics because of bubble coalescence in the
latter case at C - CCC, hence, resulting in much larger bubble sizes. Such results should
be more consistent at frother concentrations C ) CCC.
Foam stability measured under dynamic conditions is determined by bubble coales-
cence.

Acknowledgements

The authors would like to thank CONDEA Vista for supplying reagents for this
investigation.

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