Minerals Engineering 19 (2006) 766–773

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Fundamental properties of flotation frothers

and their effect on flotation
F. Melo, J.S. Laskowski *

Department of Mining Engineering, University of British Columbia, 6350 Stores Road, Vancouver, BC, Canada V6T 1Z4

Received 11 August 2005; accepted 9 September 2005

Available online 2 November 2005

Abstract

Froth flotation process requires the use of frothers. These important flotation agents are commonly characterized as either ‘‘selective’’
or ‘‘powerful’’ and are chosen following general guidelines and verification by laboratory and/or pilot plant tests.
Fundamental properties of the flotation frothers have been extensively studied over the last few years. These studies have led to the
development of standardised procedures to characterise frothers in terms of their ability to reduce bubble size and to increase foam
stability.
In this research project, the performance of five frothers in flotation of coal is evaluated and related to the fundamental properties of
these agents. Since the recovery of water in the concentrate is closely related to the non-selective transport of solid particles by entrain-
ment, the tested frothers are also assessed in terms of their ability to promote the transport of water towards the froth collection zone,
both in absence and in presence of solids.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Flotation frothers; Flotation froths; Flotation bubbles

1. Introduction entrainment is insignificant for particles coarser than

The research projects of the latest decade clearly demon-
strated that the first-order flotation rate constant is linearly
related to Sb, the bubble surface area flux, which in turn is
inversely related to the bubble size (Gorain et al., 1997).
The size of bubbles is mainly determined by frothers which
operate by preventing bubbles from coalescence. The fro-
thers which are more efficient in reducing bubble size were
also shown to produce more stable foams (Cho and Las-
kowski, 2002a,b).
Mineral particles report to the froth product either via
selective attachment of hydrophobic particles to bubbles
which carry them to the froth, or via the entrainment with
the pulp water which is carried out to the froth by a swarm
of bubbles, or via entrapment between particles in the froth
attached to air bubbles (Sawassai et al., 1998). Generally,
*
Corresponding author. Tel.: +1 604 822 4949; fax: +1 604 822 5599.
E-mail address: jsl@apsc.ubc.ca (J.S. Laskowski).
50 lm (Smith and Warren, 1989), but the actual size of
the entrained particles strongly depends on the froth prop-
erties. This is determined by frother concentration, but also
by wettability of solid particles and thus also by collector
concentration, particle size distribution and the content
of particles.
Foams are classified as unstable or metastable (Kitch-
ener and Cooper, 1959). The former are also referred to
as wet foams (Malysa, 1992). The wet foams are assemblies
of spherical bubbles separated by thick liquid walls and
they are well exemplified by dilute solutions of flotation
frothers. Such foams can exist only during bubbling and
collapse when the foam formation process is stopped. In
a metastable (‘‘dry’’) foam, bubbles acquire a polyhedral
shape and are separated by planar or only slightly curved
liquid films (Kitchener and Cooper, 1959).
Pure liquids do not foam. For a liquid to foam, it must
be able to form a shell around the gas bubble that opposes
the thinning of the lamellae. Foaming does not occur in

0892-6875/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.09.031
 F. Melo, J.S. Laskowski / Minerals Engineering 19 (2006) 766–773 767

phenomenon (Smith and Warren, 1989) additional amount

40 of water is carried to a foam/froth by a swarm of bubbles.
The three-phase flotation froth contains not only hydro-
phobic particles attached to bubbles, but also hydrophilic
Foam height [mm]

30 particles in the inter-bubble water. The entrainment was

identified to be linked to the amount of water carried in
the froth (Engelbrecht and Woodburn, 1975; Bishop and
20
White, 1976; Lynch et al., 1981; Smith and Warren, 1989;
Govindarajan et al., 1991; Maachar and Dobby, 1992;
10 Sawassai et al., 1998; Tao et al., 2000; Rahal et al.,
2001). A wetter froth should, therefore, produce higher
entrainment. But at the same time thicker inter-bubble
0 films (in wet foams) should allow for easier flow of water
(a) 0.00 0.50 1.00 1.50 2.00 2.50 through the foam and drainage of the entrained hydro-
philic particles. Malysa (1998) contended that what is
important here is the water distribution along the foam
12 KCl Concentration height. The wet foam, which allows for drainage of the
0
entrained (hydrophilic) particles at the bottom of the froth
Water in foam [cm3]

0.1 M
layer, would thus be advantageous, but the water content
8
2.0 M in the upper part of the froth should be as low as possible.
The froth, as opposed to a foam, is stabilized not only
by a frother but also by the presence of solid particles.
Therefore, while simple tests carried out with two-phase
4 systems have been recently developed to characterize flota-
tion frothers, it is still not clear how such indices developed
to characterize the frothers could be used to predict the
0
properties of a three-phase flotation froth. These issues
0.00 0.50 1.00 1.50 2.00 2.50 are further studied in this paper.
(b) Concentration of α-terpineol [g/dm3]
2. Experimental
Fig. 1. Effect of concentration of a-terpineol and KCl on foaming and
water content carried out by bubbles (from Iskra and Laskowski, 1969).
2.1. Materials

pure liquids because there exist no such mechanism (Kitch-
ener and Cooper, 1959). As Fig. 1(b) shows (Iskra and Las-
kowski, 1969), individual bubbles carry increasing amount
of water with increasing concentration of a-terpineol (up to
a given point) used in these experiments. This increasing
amount of water associated with a liquid/gas interface sta-
bilizes the foam which thus becomes more voluminous.
(Fig. 1(a)). The water content in a two-phase foam depends
critically on the frother concentration (Malysa, 1998).
It is worth pointing out that what Fig. 1(b) shows is the
amount of water carried out by individual bubbles as mea-
sured by a simple test developed by Klassen and Tikhonov
(1964). This amount of water increases with increasing con-
centration of a-terpineol; according to the bubble swarm
2.1.1. Reagents
Five different frothers were tested in this research (Table
1). The frothers were added as a 1 g/L solution prepared
with distilled water at room temperature.
The effect of frothers on bubble size has recently been
extensively studied (Cho and Laskowski, 2002a,b; Laskow-
ski et al., 2003). It was found that the effect of frothers on
bubble size results from their ability to prevent bubble coa-
lescence. As shown schematically in Fig. 2, with increasing
frother concentration, the degree of bubble coalescence
decreases and at a particular concentration (critical coales-
cence concentration, CCC), the coalescence of the bubbles
is completely prevented. As Fig. 2 explains, the CCC values
are obtained by finding the intersection of the horizontal

Table 1
List of tested frothers
Frother Chemical formula Molecular weight (g/mol) DFI (sd m3/mol) CCC (ppm)
MIBC (CH3)2CHCH2CH(OH)CH3 102 37 000 11.2
DF-200 CH3(PO)3OH 206 196 000 18.4
DF-1012 CH3(PO)6.3OH 400 267 000 6
a-Terpineol CH3–C6H8–C(CH3)2–OH 142 138 000 –
Diacetone alcohol (CH3)2(OH)CCH2C(O)(CH3) 116 12 000 –
Also includes the CCC (critical coalescence concentration) and DFI (dynamic foamability index) values.
768 F. Melo, J.S. Laskowski / Minerals Engineering 19 (2006) 766–773

Coalescence determines bubble silica (d50  200 lm). Unless otherwise mentioned this sam-
size ple was utilized in the flotation tests. Sample 2 was blended
The breakage process in the
with a very fine silica (d50  15 lm).
Bubble size

impeller neighbourhood controls

the size of the bubbles

2.2. Methods

2.2.1. Batch flotation tests

All the tests were carried out at a solids content of 10%
dbccc
by weight in a 3 L Open Top Leeds flotation cell. The froth
Zone I Zone II
height was set to 3 cm and was closely controlled during
CCC the tests. The pulp level was maintained constant by adding
Frother concentration water as required.
The concentrates were collected every 1 min in separate
Fig. 2. Schematic diagram of the effect of the frother concentration upon
bubble size in a flotation cell (Grau et al., 2005). trays (previously weighed) over a period of 5 min. The
froth was scrapped-off every 10 s. Five bottles filled with
water were weighed out before conducting each test. The
asymptote at higher concentrations to the bubble size–con- water in these bottles was used to wash-off the froth
centration curves with the sloped line approximating the attached to the scrapper when collecting the concentrates.
curve at lower concentrations. Further increase of the After each test, the water remaining in each bottle was
frother concentration above the CCC value does not affect weighed in order to determine the amount of ‘‘wash water’’
the bubble size. added to each tray. When analyzing the data, this amount
The DFI values for a-terpineol and diacetone alcohol was subtracted from the water recovered from the cell in
were determined using a well known procedure (Czarnecki each tray. The concentrates and tailings were dried in an
et al., 1982), the other CCC and DFI values were taken oven at 90 C for 24 h.
from earlier publications (Laskowski, 2003). The DFI All the tests were carried out at natural pH using fro-
stands for dynamic foamability index and is determined thers at four concentrations: 3.3 · 103, 5.5 · 103,
from the values of retention time, rt, which is the slope 7.7 · 103 and 1.1 · 102 g/L which corresponded to dos-
of the linear part of the dependence of the total gas volume ages of 30, 50, 70 and 100 g/t, respectively.
contained in the system (solution + foam), V, on the volu- Three hundred and ten gram batches of coal were mixed
metric gas flow rate, Q. This slope increases with increasing with 2 L of tap water in the flotation cell for 15 min (stir-
frother concentration and DFI is defined as the limiting ring at 1300 rpm) to ensure that all coal particles were com-
slope of the rt versus concentration for c ! 0, pletely wetted. Following conditioning, the cell was filled
  with water to a set level and impeller speed was adjusted
ort to 1000 rpm. The added frother was conditioned with the
DFI ¼ ð1Þ
oc c¼0 pulp for only 30 s to avoid its adsorption onto coal parti-
cles. The flotation tests were conducted at an air flow rate
2.1.2. Coal of 5 L/min.
Two samples of bituminous metallurgical coal were
obtained from the Fording mine in south-eastern BC. 2.2.2. Measurement of water recovery (water–frother
These samples were crushed and pulverized to produce a system)
feed of about 80–90% passing 150 lm. These tests were also conducted in a 3 L Open Top
The proximate analyses for these samples are set out in Leeds flotation cell. For each frother, a number of concen-
Table 2. According to the ASTM Coal Classification Sys- trations were tried. The procedure is described below:
tem, these samples can be classified as a medium-volatile
bituminous coal. • Weigh out 5 containers and number them from 1 to 5.
Since ash content of sample 1 was low, in order to • Fill flotation cell with tap water to approximately
increase it up to 30% this sample was blended with coarse 2900 cm3.
• Set the agitator to 1200 rpm.
• Add the required volume of frother from a stock solu-
tion (1 g/L) to the cell and complete the volume to 3 L
Table 2 with tap water.
Proximate analyses for samples 1 and 2 of bituminous coal • Condition for 5 min.
Coal Moisture Ash Volatile Volatile Fixed • Open the air valve and set the air flow rate to 4 L/min.
(%) (%) matter matter, carbon, • ‘‘Float’’ water for 5 min. Scrap the foam-off every 15 s
(%) d.m.m.f. (%) d.m.m.f. (%)
(4 times per minute) and collect the water in the trays
No. 1 0.68 11.18 23.54 26.7 73.3 previously weighed.
No. 2 0.48 12.1 22.24 25.4 75.6
• Weigh out each tray (tray + water recovered).
 F. Melo, J.S. Laskowski / Minerals Engineering 19 (2006) 766–773 769

All the tests were conducted adjusting the foam height Time [minutes]
to 1 cm, which allowed to recover water even when weak 0 1 2 3 4 5
frothers were utilized. 80
Surface tension measurements were conducted using a (a)
Du Nouy ring tension meter. All the solutions were pre-
pared at room temperature and stirred for 5 min before 60
the measurements.

Yield [%]
3. Results 40 Cumulative ash
after 5 minutes, [%]
3.3×10-3 g/L 5.0
As Fig. 3 shows, the tested frothers fall more or less dis-
5.5×10-3 g/L 6.0
tinctly into two groups, one includes quite surface active 20
compounds (DF-1012, a-terpineol), while the other (diace- 7.7×10-3 g/L 6.6
tone alcohol, MIBC) are not surface active at all, with the
1.1×10-2 g/L 8.1
DF-200 frother situated somewhere between these two
100
groups.
Fig. 4 displays the kinetic flotation curves; while
Fig. 4(a) shows cumulative yield of the froth product plot- (b)
ted versus flotation time, these results are replotted as

log (100 - Yield)

log (100  Y) = f(flotation time) in Fig. 4(b).
The semi-logarithmic plots were fitted to two straight
lines that represent flotation of the fast floating component
and flotation of the slowly floating component using the
following equation (Fig. 4) (Lynch et al., 1981):
C
¼ 100  RY ¼ C f þ C s
C0
¼ ð100  /Þ expðk f tÞ þ / expðk s tÞ ð2Þ
0 1 2 3 4 5
where Cf and Cs are the yields of the fast and slow floating
Time [minutes]
components remaining in the cell after time t, / is the yield
of the slow floating component in the flotation feed, and kf Fig. 4. Example of the graphical interpretation of the results obtained
and ks are the flotation rate constants for the fast and slow with MIBC.
floating components (see Fig. 5).

1E-005 0.0001 0.001 0.01 100

75 75

70 70

65 65 Slow floating component = 55.9 %

Surface tension [mN/m]

ksfc = 0.007 1/min

log (100-Yield)

log(100 - Yield) = 55.9 - 0.007 t

60 60
2.3

55 55 Fast floating component = 44.1

10
kffc = 1.26 1/min
50 DF-200 50 log(100-yield) = 44.1 - 1.26 t
2.3
α−Terpineol
45 45
DF- 1012
40 40
Diacetone Alcohol

35 MIBC 35

30 30 1
1E-005 0.0001 0.001 0.01 0 1 2 3 4 5
Concentration [mol/dm3] Time [minutes]

Fig. 3. Surface tension isotherms for five tested frothers: MIBC, diacetone Fig. 5. Determination of the rate constants for fast and slow floating
alcohol, DF-200, a-terpineol and DF-1012. components. MIBC at 3.3 · 103 g/L.
770 F. Melo, J.S. Laskowski / Minerals Engineering 19 (2006) 766–773

0.06 0.1 1 10 100 1000

100
concentrate 1
0.05 concentrate 2

Cumulative percent passing [%]

80 concentrate 3

0.04 concentrate 4
k [1/min]

concentrate 5
60
0.03 Tailings

MIBC
0.02 Alpha Terpineol 40

DF-200

0.01 DF-1012
20
Diacetone alcohol

0
0 100000 200000 300000 0

DFI [sdm3/mol] 0.1 1 10 100 1000

Size [microns]
Fig. 6. Correlation between the flotation rate constant for water (two-
phase system) and DFI for the tested frothers. Fig. 7. Particle size analysis for the flotation products obtained in the
experiment with 3.3 · 103 g/L of a-terpineol.

The same procedure was used to determine the flotation

rate constants for water in the flotation experiments with Table 3
aqueous solutions of the tested frothers. In this case it Ash content in the flotation products (a-terpineol 3.3. · 103 g/L)
was not necessary to split the curves into the fast and Sample 1 + silica Ash (%) Sample 2 Ash (%)
slowly floating components. Concentrate 1 4.4 Concentrate 1 5.4
As Fig. 6 demonstrates, quite a good correlation was Concentrate 2 4.8 Concentrate 2 6.1
obtained between the water flotation rate constants and Concentrate 3 5.5 Concentrate 3 7.2
the DFI values for the tested frothers. To avoid compari- Concentrate 4 5.9 Concentrate 4 8.2
Concentrate 5 6.2 Concentrate 5 7.5
son of frothers at arbitrarily chosen frother concentrations
the water flotation rate constants shown in Fig. 6 were Tailings 57.2 Tailings 22.9
measured at the frother concentrations slightly exceeding Sample 1 contained coal + coarse silica, sample 2 contained only coal
the CCC values for each frother (these concentrations were without silica.
as follows: 15 ppm for MIBC, 12 ppm for a-terpineol,
28 ppm for DF-200, 12 ppm for DF-1012 and 45 ppm for
diacetone alcohol).The CCC value for diacetone alcohol correlation between the flotation rate constants for the fast
was not available and was estimated based on the DFI– floating coal particles and the water flotation rate constants
CCC correlation (Laskowski, 2003). obtained from the water contents of the froth products.
The reasoning adopted in this paper rests principally on It is obvious that the correlation between the water rate
the assumption that since coarse silica was added as a gan- constants measured in a two-phase system and DFI is quite
gue to sample 1, fine coal particles will be reporting to the good (Fig. 6) and, in general, follows what could be
froth product during the first few minutes (fast floating inferred from Fig. 3. However, the correlation shown in
component) while only coarser coal particles will be float- Fig. 8 is quite different. The highest rates of water recovery
ing over the subsequent period of time, and that the behav- were observed for MIBC and diacetone alcohol, the fro-
iour of the fast floating component should strongly depend thers which in the two-phase experiments gave the lowest
on the recovery of water in the froth. Fig. 7 confirms rates of water recovery. The tests carried out with MIBC
entirely such assertion. and sample 2 blended with fine silica gave much higher
As this figure reveals, d50  20 lm for the 1st concen- water flotation rate constants.
trate, and d50  50 lm for the 5th concentrate. The tailings, The most surface active (DF-1012) and the least surface
d50 which contained mostly coarse silica (Table 3) was active (diacetone alcohol) frothers (see Fig. 3) gave the low-
about 100 lm. est yields of the froth product as shown in Fig. 9. The high-
All previous publications indicate that the flotation of est yields provided MIBC, a-terpineol and DF-200. The
fine particles should strongly depend on the content of rates of water recovery was also the highest for MIBC
water carried to the froth. Fig. 8 shows indeed a very good (Fig. 8). Much higher yields of the clean coal obtained
 F. Melo, J.S. Laskowski / Minerals Engineering 19 (2006) 766–773 771

4 16
MIBC
14
Alpha Terpineol
12
DF-200

3 DF-1012 10

Ash [%]
Diacetone Alcohol 8
k-coal [1/min]

MIBC (sample 2) 6

DF-1012 (sample 2) MIBC (sample 2)

2 4
MIBC (sample 2 + fine silica)
DF-1012 (sample 2 + fine silica)
2

0
30 40 50 60 70 80 90 100
1 Yield [%]

MIBC (sample 2 without silica) Fig. 10. Ash content versus yield of the froth product after 5 min flotation
of sample 2 using different frothers.
Alpha Terpineol (sample 2 without silica)

0
0 1 2 3 4

k-water (coal) [1/min]

3
Fig. 8. Correlation between the flotation rate constants for the coal fast
MIBC
floating component and flotation rate constant for water. Unless otherwise
mentioned sample 1 was used with added coarse silica; sample 2 was used Alpha Terpineol
either with added fine silica or without it.
DF-200
k-coal [1/min]

2 DF-1012

9.0
MIBC
8.5 Alpha Terpineol
DF-200
8.0
DF-1012
1
7.5 Diacetone alcohol
MIBC (sample 2, no silica
7.0
Ash [%]

6.5

6.0
0
5.5
0 2 4 6 8 10 12
5.0

4.5 DFIxC [s]

4.0 Fig. 11. Correlation of flotation rate constants for coal fast floating
30 40 50 60 70 80 90 100 component with DFI · C for MIBC, a-terpienol, DF-200 and DF-1012.
Sample 1 with coarse silica.
Yield [%]

Fig. 9. Ash content versus yield of the froth product after 5 min flotation
using different frothers. The tests included sample 1 with added coarse
silica, and sample 2 without added silica.
when floating sample 2 shows (Fig. 9) that this coal floats
better than sample 1.
Since sample 1 included only added coarse silica, in the
experiments involving sample 1 there was practically no
entrainment. Low ash contents in the froth product in
Fig. 9 corroborates such a conclusion. Fig. 9 also shows
that sample 2 (no silica added) with MIBC floated better
than sample 1. In the following tests with sample 2 fine sil-
ica was added and as Fig. 10 reveals the entrainment in
these cases is obvious. However, the entrainment depends
on water recovery and since low rates of water recovery
were observed with DF-1012 (in comparison with MIBC)
(Fig. 8) in this case even in the presence of fine silica the
entrainment was insignificant.
To compare the effect of the tested frothers on the flota-
tion rate of the fast floating component, the k-values were
plotted versus DFI · C for each frother and each concen-
tration (as suggested by Malysa et al., 1987). This plot
quite unexpectedly displays two curves with the points
for MIBC giving a different and very steep straight line
(Fig. 11). This implies that for MIBC the high flotation rate
constants for fast floating coal were obtained at much
lower equivalent MIBC concentrations. Similar results
were obtained for sample 2.
772 F. Melo, J.S. Laskowski / Minerals Engineering 19 (2006) 766–773
4. Discussion
As the experiments described in this paper indicate the
flotation rate constants obtained from the ‘‘flotation’’
experiments in which aqueous solutions were only utilized
correlate very well with the DFI values. Frothers charac-
terized by higher DFI values, that means the frothers that
give more stable two-phase foams, produce higher water
flotation rates. It is of interest to point out that in the
presence of hydrophobic particles of bituminous coal,
used here as a model of a hydrophobic solid, the water
flotation rates were different. This clearly indicates that
amount of water recovered with the froth product
depends not only on the properties of frother but also
on the solid particles. While the flotation rate constants
for water in a two-phase experiment gave the lowest val-
ues for diacetone alcohol and MIBC (in accordance with
their lowest surface activity) (Fig. 6), MIBC gave the
highest water rate constants in the flotation experiments
with coal (Fig. 8). When very fine silica was added to
the coal instead of the coarse silica, the flotation rate
for water increased further (Fig. 8). It is interesting to
observe, however, that the experiments with the frother
(DF-1012) which produced very low coal yields (Fig. 9)
and very low flotation rates (Fig. 8) did not bring forward
higher water recoveries when the coal used in these exper-
iments was blended with fine silica.
The effect of coal rank (wettability) on flotation was
extensively studied. Wheeler (1994) showed that while
MIBC is an excellent flotation agent for easy-to-float bitu-
minous coals, it looses quickly its effectiveness when used
to float lower rank coals. In this latter case 2-ethyl hexanol
was found to be much better. This was explained by collect-
ing abilities of the more efficient frothers. However, as
more recent results indicate, frothers affect froth structure
and water recovery and this brings into question whether
the more efficient frothers in coal flotation exhibit so-called
collecting ability, or whether they simply provide higher
water recoveries.
5. Conclusions
1. The flotation rate constants for water determined from
the flotation experiments with aqueous solutions of
frothers (a two-phase flotation experiment) correlate
very well with the CCC and DFI values for the
frothers.
2. The flotation rate constants determined for the coal fast
floating component correlate very well with the water
flotation rate constants obtained from the water recov-
ered with coal into the froth product.
3. Two frothers, diacetone alcohol and MIBC, which gave
the lowest water recoveries in the two-phase flotation
experiments, generated the highest water flotation rate
constants and the highest coal flotation rate constants
in the flotation experiments with coal. DF-1012, the
most surface active frother of the tested suite, which
gave the highest water recoveries in the two-phase flota-
tion experiments, provided very low flotation rates for
water in the flotation experiments with coal and turned
out to be the worst agent for the flotation of the tested
bituminous coal.
4. The presence of fine silica in the feed increased signifi-
cantly the flotation rate of water and the entrainment
of this silica in the froth product.
Acknowledgements
The authors wish to thank Miss Denise Nunes and
Dr. Feridun Boylu for assistance in some flotation tests.
The authors acknowledge the financial support of the
Natural Sciences and Engineering Research Council of
Canada under the NSERC Strategic Grant program.
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