ELSEVIER Int. J. Miner. Process.

55 (1999) 203–218

Characterization of materials by Hallimond tube flotation,

Part 3.
Maximum size of floating and interacting particles
Jan Drzymala *
Technical University of Wroclaw, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland
Received 25 March 1997; revised version received 17 August 1998; accepted 21 October 1998

Abstract

The tests carried out with solids of different hydrophobicities and densities, floated individu-
ally and as a collection of particles in the monobubble Hallimond tube, allowed to characterize
flotation in this small-scale laboratory flotation device and determine the maximum size of
entrained particles, maximum size of floating particles, particle hydrophobicity, increase of
the apparent density of the particle in contact with air bubble due to aggregation with other
particles, and flotometric equations interrelating these parameters. Hydrophilic particles do not
float in the Hallimond tube but there is some mechanical entrainment governed by the equa-
tions: amax .²p ²w /=²w D 0:023 š 0:002 valid for particles with density greater than 2 g=cm3
Ð0:75
and amax .²p ²w /=²w D 0:0225 š 0:0025 (cm) applicable for less dense particles, where
amax is the maximum size of entrained particles (in cm), ² p is the particle density, and ² w
denotes density of the aqueous phase (in g=cm3 ). Hydrophobic particles tend to form aggre-
gates and float as a cluster but no interaction was detected for contact angles ( s ) below 20º.
Thus, for  s < 20º the flotation of a collection of particles can be characterized by the same
equations as for flotation of individual particles including the simplified formula of Scheludko
2
Dmax .²p ²w / D 6¦ g 1 sin2 .s =2/ in which g is the acceleration due to gravity, ¦ stands for the
surface tension of water, and Dmax is the maximum size of floating particles. Hydrophobic inter-
actions between particles become significant for  s > 20º. When 20º >  s > 55º and the number
of particles in the cluster is greater than 1, the flotation of an ensemble of particles is given either
2
by: dmax n.²p ²w / D 6¦ g 1 sin2 .s =2/ or by: dmax .²p ²w / D k sin2 .s =2/ (g=cm2 ), where n is
defined as .Dmax =dmax /2 and the term n.²p ²w / represents a new apparent density of the particle
in contact with air due to aggregation with other particles which do not touch the bubble, dmax is
the maximum size of floating and interacting particles, and k is a constant equal to 2.08 g=cm3 .
It was established that the clustering does not occur sharply at s D 20º but it depends on the
density of particles and that for less dense particles occurs at higher hydrophobicity. For s > 55º

Ł Fax: C48 71 344 8123; E-mail: jd@ig.pwr.wroc.pl

0301-7516/99/$ – see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 1 - 7 5 1 6 ( 9 8 ) 0 0 0 3 3 - 7
204 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218

the flotation of a cluster of particles is not influenced by hydrophobicity and the equation:
dmax .²p ²w / D 0:40 š 0:05 (g=cm2 ) is valid.  1999 Elsevier Science B.V. All rights reserved.

Keywords: flotation; hydrophobicity; contact angle; flotometry; adhesion; particle entrainment

1. Introduction

Before any industrial flotation process is developed as a rule it is first tried on

a small laboratory scale to establish basic relationships between essential parameters
of the process. One of many laboratory flotation devices used for this purpose is
the monobubble Hallimond tube which requires very small, less than one gram,
mono-mineral samples and is very labor and time efficient. Our ten-year long research
concerning characterization of flotation and materials showed that this simple device
provides useful data for relating maximum size of floating particles, their density, and
hydrophobicity. The formulas that relate these parameters in the monobubble Hallimond
tube are termed flotometric equations while the method is referred to as flotometry
(Drzymala and Lekki, 1989b). Presently flotometry can be used for determination of
hydrophobicity of materials and comparison of different flotation systems.
In previous papers of this series the entrainment of particles (Drzymala, 1994a) and
flotation of individual particles (Drzymala, 1994b, 1995) were described in detail. This
paper deals with flotation of materials of different densities and hydrophobicities in a
monobubble Hallimond tube when a collection of particles is subjected to flotation.

2. Experimental

2.1. Materials

Solids of different hydrophobicities and densities were used in the flotation tests.
Their identity was checked by the X-ray method. Only very pure materials having more
than 95% of the basic component were used. Each material was ground manually in
an agate mortar and then screened to get the desired narrow size fractions. An average
size (diameter) of particles in each fraction was calculated as an arithmetical mean
of the size of the two screens used for the size fraction preparation. The screens had
square openings. The density of solids was measured in water with a pycnometer. If
pressed materials were used, their density was determined from the size and weight
of the pressed disc. In some tests, particles were coated with different substances. To
cover them with either paraffin, naphthalene, stearic or benzoic acids, the particles were
dipped for 10 s into a small amount of molten coating material. To remove excess of
the coating, the particles were transferred onto a watch glass, then onto another one and
finally kept for 10 min for solidification. In the case of coating materials which were
available as glues (universal, plexi-glass, polyvinyl) the procedure was similar to that
with paraffin but the solidification was accomplished by evaporation of the solvent, that
 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218 205

is, by drying in air for 18 h. The sources of chemical and their symbols used in the
text are as follows: paraffin (PA); naphthalene (NA); benzoic acid (BE) – POCH; stearic
acid (ST) – Baker; polyvinyl glue (PG) – Naftalex; universal glue (UN) – INCO. Other
chemicals were purchased from POCH. The liquid sample of the organic glass (plexi,
PL) was prepared by dissolution in ethyl acetate.

2.2. Equipment

All the tests were carried out in a cell referred to in literature as the monobubble
Hallimond tube. A scheme of the employed flotation cell along with its essential
parameters was given in a previous paper of this series (Drzymala, 1994a). The present
shape of the used monobubble Hallimond tube is due to Ewers (Sutherland and Wark,
1955) who redesigned the cell used by Hallimond (1944) and due to L. Lekki (unpubl.
data, 1973) who calibrated the receiver of the cell which allows continuous monitoring
of the recovery of particles during the course of the experiment. A similar improvement
was proposed by Dobias (1983).

2.3. Flotation of individual particles

Ten particles were selected from each needed for testing the size fraction. All ten
particles were equilibrated with doubly distilled water for 10 min and then one particle
and the solution were transferred to the Hallimond tube. If within 30 min of bubbling
the air through the tube at a rate of 0.625 cm3 =s the particle was found in the calibrated
receiver of the Hallimond tube, it was counted as floatable. Subsequently, the particle
was removed from the solution, and then a second particle was introduced for flotation.
In this way all ten particles were subjected individually to flotation. The flotation
recovery was calculated as the ratio of the number of floating particles to all ten tested
particles multiplied by 100%. The same procedure was repeated with another set of ten
particles or sometimes with a third set of ten particles. The final recovery was calculated
as an average recovery of all series. The pH of the aqueous solution was 6:5 š 0:4
or otherwise stated. The temperature of tests was 20 š 2ºC. The size of the bubbles
depended on the hydrophobicity of the solid. In flotation of hydrophilic or weakly
hydrophobic particles the diameter of the bubbles was 3.1 mm that is equal to the size
of bubbles formed in the Hallimond tube at the coalescent string of bubbles regime
(Drzymala, 1994a). When the bubbles were formed in the presence of hydrophobic
particles their size was increasing with the hydrophobicity due to adhesion of the bubble
to the particle allowing more time for the bubble to form. As a result bubbles up to a
size of 5 mm in diameter were formed (Drzymala, 1994b, 1995).

2.4. Flotation of a collection of particles

A sample of solids was introduced into 120 cm3 of water in a beaker and agitated for
10 min. Then, the mixture was transferred to the Hallimond tube and floated with air at
a flow rate of 0.625 cm3 =s. The volume occupied by the solids in the Hallimond tube
compartment before flotation was kept constant (0.2 cm3 ). Overall flotation time was 30
206 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218

min. The tests were carried out at 20 š 2ºC for different narrow size fractions of each
mineral at natural pH.

2.5. Contact angle measurement

Contact angle was measured with a simple laboratory goniometer of our own con-
struction on a piece of polished specimen which was coated with different hydrophobic
materials. The contact angles were measured at the solid surface–water droplet–air
interface and read through the liquid phase.

3. Results

Materials of different hydrophobicities and densities were subjected to flotation

individually and as a collection of particles. The results of the tests were plotted as the
recovery of particles vs. particle size shown in Fig. 1 for germanium as an example.
This type of plot, called the separation curve, allows to determine d50 which is the
most characteristic point of the separation curve. This point indicates the size of particle
which has equal probability to sink and float. d50 corresponds to the maximum size
of floating particles if the tests were carried out in an ideal flotation system. For
individually tested particles the maximum size of floating particles will be written as
Dmax while for particles subjected to flotation as a collection of particles the term dmax
will be used in this text. The values of the maximum size of floating particles for
individually floated particles (Dmax ) and floated as a collection of particles (dmax ) along

Fig. 1. Flotation results for germanium particles floated individually (ð) and as a collection of particles (ž)
in the form of a separation curve. Points d50 ¾D dmax and D50 ¾ D Dmax indicate the size of particle of equal
chance to float and sink or the maximum size of floating particle.
 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218 207

Table 1
Results of flotation of individual particles of different materials and their collection

Solid Remarks ²p A R Dmax  s dmax L n

(g=cm3 ) (º) (º) (mm) (º) (mm) (g=cm2 )
CaF2 monocrystal 3.18 30–70 n.d. 1.94 51.1 1.45 0.316 1.79
S spheres 2.10 n.d. n.d. 2.32 43 1.30 0.143 3.18
FeS2 pyrite 5.00 n.d. n.d. 1.20 42.4 0.70 0.280 2.94
Al2 O3 synthetic ruby 3.99 n.d. n.d. 1.32 40.2 0.75 0.224 3.09
Ge HF-cleaned 5.35 55 š 1 19 š 1 1.08 39.7 0.54 0.235 4.00
Si HF-cleaned 2.33 65 š 6 32 š 6 1.75 35.4 1.75 0.233 1.00
talc natural 2.75 55 š 3 0 1.31 30.2 0.66 0.116 3.94
SiC HF-cleaned 3.20 41 š 2 11 0.95 24.5 0.92 0.202 1.07
AgI HNO3 -cleaned 5.42 n.d. n.d. 0.60 21.9 0.54 0.239 1.23
FeTiO3 ilmenite, H2 SO4 -cleaned 4.70 35 š 5 0 0.42 14.0 0.42 0.155 1.00
PbS galena I 7.59 n.d. n.d. 0.248 11.0 0.24 0.158 1.05
As2 O3 pressed 3.60 n.d. n.d. 0.325 8.9 0.32 0.083 1.00
PbS galena II 7.59 n.d. n.d. 0.175 8.0 0.18 0.119 1.00
CuFeS2 chalcopyrite 4.04 n.d. n.d. 0.23 6.9 0.23 0.070 1.00
Cgraphite natural 2.20 68 š 8 44 š 2 0.32 6.1 0.32 0.0384 1.00
MoS2 pressed 4.53 a n.d. n.d. 0.175 5.8 0.18 0.0635 1.03
Cdiamond synthetic 3.51 n.d. n.d. 0.21 5.7 0.20 0.0527 1.10
CuS natural 4.40 n.d. n.d. 0.125 4.1 0.12 0.0442 1.30
Ferrosilicon synthetic 2.75 a n.d. n.d. 0.13 3.0 0.13 0.0227 1.00
Cu2 S chalcocite 5.06 a n.d n.d 0.064 2.2 b 0.064 0.0259 1.00
a Indicates density measured in this work, otherwise literature values were used for calculations (CRC

Handbook of Chemistry and Physics, 1986).

b Apparent hydrophobicity resulting from mechanical carryover of particles. L < 0:022 g=cm2 indicates

mechanical carryover of particles. If L > 0:022 g=cm2 and Dmax > dmax (that is n > 1), L can be used to
calculate hydrophobicity from Eq. 11. Abbreviation n.d. means not determined in this work.

with other essential data are given in Table 1. Table 2 gives similar data for fluorite
particles covered with different substances while Table 3 contains results of flotation
tests for different solids coated with paraffin.

Table 2
Flotation of fluorite particles coated with different substances

Substance Symbol  A (º)  R (º) Dmax (mm)  s (º) dmax (mm) L (g=cm2 ) n
Naphthalene NA 88 š 2 n.d 2.55 68.4 2.10 0.449 1.47
Stearic acid ST 80 š 2 n.d. 2.78 75.6 1.80 0.385 2.38
Plexi PL 66 š 2 50 š 3 2.10 55.2 2.04 0.437 1.06
Universal glue UN 68 š 2 34 š 1 1.96 51.2 1.80 0.385 1.19
Benzoic acid BE 67 š 2 45 š 1 1.60 41.3 1.60 0.342 1.00
Polyvinyl glue PG 38 š 2 0 0.56 14.2 0.56 0.120 1.00
10 3 m tannic acid CaF2 =TA 0 0 0.11 2.8 a 0.11 0.0235 1.00

n.d. means not determined. a Apparent hydrophobicity resulting from mechanical carryover of particles.
208 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218

Table 3
Flotation of paraffin-coated particles

Solid Symbol ² (g=cm3 ) Dmax (mm)  s (º) Dmax (mm) L (g=cm2 ) n

Galena PbS=PA 7.59 1.60 76.5 0.85 0.56 3.5
Pyrite FeS2 =PA 5.00 2.20 83.0 1.12 0.448 3.86
Fluorite CaF2 =PA 3.14 2.78 75.6 1.62 0.347 2.95
Quartz SiO2 =PA 2.65 3.35 80.8 2.45 0.404 1.87
Graphite C=PA 2.27 3.66 76.9 2.65 0.336 1.91
Sulfur S=PA 1.96 4.20 76.6 4.10 0.394 1.05

A D 110 š 1º, R 31 š 2º; Dmax is for flotation of individual particles and dmax for interacting particles; PA
stands for paraffin.

4. Discussion

4.1. Mechanical carryover of particles

The recovery of particles in a monobubble Hallimond tube results from true flotation
as well as from some mechanical carryover (Drzymala and Lekki, 1989a). The entrain-
ment of hydrophilic particles when a collection of them is subjected to flotation tests is
governed by the equation (Drzymala and Lekki, 1989b; Drzymala, 1994a):
²p ²w
amax D L H D 0:023 š 0:002 .cm/ (1)
²w
for particles with density greater than about 2.0 g=cm3 while for particles with density
smaller than 2.0 g=cm3 the following equation can be applied (Drzymala, 1996):
 
²p ²w 0:75
amax D L L D 0:0225 š 0:0025 .cm/ (2)
²w
In Eqs. 1 and 2 the term amax stands for the maximum size of entrained particles, ²p
for particle density, ²w denotes density of water, while L H and L L are constants. It was
shown in our previous papers (Drzymala, 1994b, 1995) that Eq. 1 results from Newton’s
(turbulent) mode of settling of particles behind a levitating bubble while Eq. 2 results
from Allen’s (intermediate between the laminar and turbulent) mode of settling.
The flotation tests carried out in this work for many solids confirmed that some of
them do not float but are entrained. Their entrainment follows Eq. 1 and is depicted in
Fig. 2 as a straight line with a slope equal to 0.023 cm. The results shown in Fig. 2
(lower line) indicate that Eq. 1 can be applied to delineate the entrainment of individual
particles as well as an ensemble of particles because the recovery in both cases is
identical.

4.2. Flotation of individual particles

A detailed analysis of the flotation process involving a spherical particle and a gas
bubble revealed that the flotation of individual particles in the monobubble Hallimond
 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218 209

Fig. 2. Results of flotation of solids with different hydrophobicities .s / and densities .²p / floated
individually (ð) and as a collection of particles (Ž). ²w stands for density of water.

tube is governed by the equation (Drzymala, 1994b, 1995):

²  ½¦
d 3 d
³rmax ¦ .1 cos d / 4
3
³r 3
²
max p g ³r 3
²
max w g 2
3
C cos 1
3
cos
2 2
¦ 
³rmax
2
.1 cos d / R²w g D 0 (3)
R
where rmax is the maximum size (radius) of floating particle, d is the detachment angle,
¦ is surface tension of water, ²p is density of particle, ²w is density of water, R is
radius of bubble, g is acceleration due to gravity, ³ is equal to 3.14. It should be noted
that formula 3 printed in the original paper contained an error which was corrected
in an erratum (Drzymala, 1994b, 1995). Formula 3 can be helpful in calculating the
equilibrium contact angle ./ because (Drzymala, 1994b, 1995):
 
rmax d d
 D arcsin sin C (4)
R 2 2
Eq. 3 is quite complex but it can be reduced to a much more simple form if only
the capillary and gravity forces, the main parameters operating in flotation systems, are
taken into account. The Scheludko equation (Scheludko et al., 1976) for the maximum
size of floating particle is:
s
2
Dmax ² 0 D 6¦ g 1 sin2 (5)
2
where s is the approximate detachment contact angle which will be also called the
Scheludko contact angle, and ² 0 stands for ²p ²w . Eq. 5 is quite accurate for the
determination of the detachment contact angles smaller than about 40º, while for larger
angles the difference is noticeable and increases with increasing hydrophobicity of
particles (Drzymala, 1994b, 1995). The contact angles calculated from the Scheludko
equation utilizing Dmax values are given in Tables 1–3.
210 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218

4.3. Flotation of a collection of particles

Interactions of particles present at the water–air interface are quite complex. Nutt
(1960) was perhaps first to notice that the detachment of an ensemble of particles from
the surface of a bubble was easier than for single particles. Somasundaran et al. (1992)
further tested the particle ensemble effect on flotation of particles at the water–air
interface and found that for a contact angle equal to 45º–47º this effect was observed for
particles smaller than 0.1 mm. Vinke et al. (1991) derived an equation to calculate the
maximum value of the ratio between the apparent weight of the cluster of particles and
that of a single particle before this particle, with attached to it other particles, is released
from the gas bubble. They also proposed equations for the case when a monolayer of
particles adheres to the surface of bubble. Their investigations confirm the existence of
the phenomenon of aggregation which coexists with the flotation process. It was shown
in other papers (Gifford and Scriven, 1971; Lucassen, 1992; Allain and Cloitre, 1993a,b;
Paunov et al., 1993) that the aggregation of particles at interfaces can also result from
lateral capillary forces arising from disturbance of the smoothness of the interface by
particles.
Differences between flotation of single particles and that of a collection of particles
can also be caused by factors essential in the probability model of flotation considered
by many investigators including Derjaguin and Duhkin (1961), Schulze (1984, 1993),
Nguyen et al. (1997) as well as Mao and Yoon (1997). In the case of the single particle
flotation, all three basic steps of flotation, that is, collision of particles and bubble (Pc ),
adhesion of particle to bubble (Pa ), and stability of the particle–bubble aggregate (Pstab ),
play a role in the flotation in the monobubble Hallimond tube. On the other hand, in
flotation of aggregates of coarse particles the probability of collision and adhesion most
likely approaches the value of 1 because the forming bubble is pressed against the bed
of particles and aggregates of particles. Therefore, the stability of the bubble–aggregate
of particles, due to their increased inertia, is most likely significantly reduced.
According to our results, when a collection of particles is subjected to flotation
the maximum diameter of floating particles, dmax , can be identical with the maximum
diameter of floating particle Dmax subjected to flotation individually or there could be a
great difference between these values (Tables 1–3). For weekly hydrophobic solids such
as PbS, CuFeS2 , and graphite (Fig. 2) with contact angles s between 7º and about 20º
there is no difference in the maximum size of floating particles for particles subjected
to flotation either individually or separately and the relationship between either Dmax or
dmax vs. ²w =.²p ²w / is parabolic as required by the Scheludko equation. Therefore, the
flotation of individual and a collection of particles, when they are weakly hydrophobic,
fulfils Eqs. 3–5 describing flotation of single particles. When the contact angle exceeds
40º there could be a difference between Dmax and dmax . For instance, for germanium
Dmax is equal to 1.08 mm while dmax is only 0.54 mm when the particles are floated
together as is shown in Figs. 1 and 2.
To get a more complete pictures regarding the influence of hydrophobicity on
flotation of an ensemble of particles a relationship between the size–density term Dmax ² 0
and the Scheludko contact angle s was plotted in Fig. 3 for solids floated individually
and as a collection of particles. The points lying on the upper line starting from the
 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218 211

Fig. 3. Relationship between maximum size of recovered particles Dmax or dmax and their density in water
² 0 D ²p ²w as a function of particle hydrophobicity (contact angle s ) for particles floated individually (Ž)
and floated as a collection of particles (ð).

origin represent the Scheludko equation that was used to calculate hydrophobicity s for
all tested materials. Open circles represent flotation of an ensemble of particles and are
located either on the same line as points for individual particle flotation or lie below the
line. There are two important features which can be seen from Fig. 3. First, for solids of
low hydrophobicity with a contact angle below 20º there is no difference in the results
for both modes of flotation. Above this value the maximum size of floating particles
can be identical (for instance Si) or very different (for instance talc and Ge) for the two
considered modes of flotation. Second, above s D 20º the difference between Dmax and
dmax is greater for denser solids. The difference between Dmax and dmax seems to be very
little affected by particles with densities below 2 g=cm3 . Fig. 3 clearly shows that for
greater hydrophobicity and density the Scheludko equation cannot be used to relate the
essential parameter of the flotation for a collection of particles.
To modify the Scheludko equation for the case of flotation of a cluster of particles
we have to consider the possible ways of interaction of a bubble with particles. The case
when a single bubble is attached to a single particle, as shown in Fig. 4a, was discussed
in detail elsewhere (Drzymala, 1994b, 1995), and Eqs. 3 and 4 as well as the simplified
version of these equations (the Scheludko equation) result from the model. A different
212 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218

Fig. 4. Models of bubble–particle aggregate for flotation tests to determine the maximum size of floating
particles. (a) Single bubble adhering to a single particle. (b) Cluster of particles attached to bubble through
one particle. (c) Cluster of particles is attached to the bubble with more than one contact (monolayer of
particles).

situation occurs when a collection of particles is subjected to flotation. The particles can
form either a cluster of particles that adheres to the surface of the bubble through one
contact particle (Fig. 4b) or all particles can be attached to the surface of the bubble
(Fig. 4c). For coarse particles with a diameter from 0.2 to more than 2 mm, the model
shown in Fig. 4b is from a geometrical point of view more realistic than other models
and it will be used for further considerations.
The force of detachment caused by the weight of additional particles influences the
maximum size (dmax ) of the floating particle in making it smaller. The perimeter of
wetting of the contact particle connected with the bubble is smaller. The additional force
of detachment can be taken into account in the Scheludko equation, for instance by
assuming that the contact particle is apparently n-fold heavier than the weight or density
of the particle before the cluster formation. This is equivalent to the assumption that the
contact particle is apparently n-fold denser than the particle without aggregation. Since
the hydrophobicity of the particle, s , does not change, one can write:
s
2
Dmax ² 0 D dmax
2
n² 0 D 6¦ g 1
sin2 (6)
2
It results from Eq. 6 that n is defined as:
2
Dmax
nD 2
(7)
dmax
and is a parameter that characterizes the number of particles in the aggregate and it can
be calculated from the experimental values of Dmax and dmax according to the formula
given in Eq. 7. The n values for the flotation systems investigated in this work are from
1 to 4 (Table 3).
To proceed further in the derivation of a modified Scheludko equation which would
be applicable to flotation of a collection of particles we have to utilize some experimental
facts observed previously when particles were tested individually and as a collection of
particles. It was found by Drzymala and Lekki (1989b) that the multi-particle flotation
 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218 213

Fig. 5. Relationship between maximum size of floating paraffin-coated particles (Dmax ) and their density in
water ² 0 D ²p ²w for particles floated individually (ð) and as collection of particles (Ž).

can be described by the empirical equation:

dmax ² 0 D L .g=cm2 / (8)
where L is a constant that increases with the hydrophobicity of flotation system.
The applicability of Eq. 8 was confirmed for highly hydrophobic particles including
sulfides in the presence of diethyldixanthogen (Lekki and Drzymala, 1991), oleate
flotation of selected minerals (Drzymala, 1993), and other flotation systems. Fig. 5
shows that the same relationship is valid for paraffin-coated particles with L equal to
0:40 š 0:05 g=cm2 . It should be added that Eq. 8 resembles Eq. 1 which describes the
mechanical carryover of particles having a density greater than 2.0 g=cm3 . The similarity
does not have any special meaning because the mechanisms of the two processes are
entirely different.
A comparison of the Scheludko equation (Eq. 5) with Eq. 8 indicates that there is a
relationship between Dmax and dmax in the form:
   
1 s Dmax 2
nD f D D (9)
dmax dmax dmax
where s is a proportionality factor. Its dimension is the length unit (cm).
To test the validity of Eq. 9 two plots of n vs. 1=dmax for two levels of hydrophobicity,
i.e. for particles with s near 45º and for paraffin-coated particles with s D 79 š 4º
taking into account only the solids with n above 1 were prepared. It is clear from Fig. 6
that there is a linear relationship between n and 1=dmax of particles. Therefore, the
equation for flotation of a cluster of particles can be rewritten to:
s
dmax ² 0 s D 6¦ g 1 sin2 (10)
2
Since the slope of the n D f .1=dmax / lines depends on the hydrophobicity of the
particles it is necessary to determine the relationship between L and hydrophobicity,
214 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218

Fig. 6. Relationship between terms n and dmax as well as hydrophobicity s .

s . Several functions were tried and the best results were obtained when L values were
related with sin2 .s =2/, the term which is already present in the Scheludko equation.
The relationship between L and sin2 .s =2/ is shown in Fig. 7. According to Fig. 7, there
is a linear relationship between parameter L and the hydrophobicity term up to about
sin2 .s =2/ D 0:2 that is up to s D 55º. The equation relating the maximum size of parti-
cles floating as a cluster, their density in water, and hydrophobicity can be expressed by:
s
L D dmax ² 0 D k sin2 .g=cm2 / (11)
2
where k D 2.08 g=cm2 .

Fig. 7. Relationship between term L and sin2 .s =2/. ð D paraffin-coated particles; N D fluorite particles
coated with different chemicals; ž D natural flotation of unmodified solids.
 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218 215

Fig. 7 also shows that for more hydrophobic solids .s > 55º/ flotation results are not
influenced by their hydrophobicity and for this case the following equation holds:

L D dmax ² 0 D 0:40 š 0:05 .g=cm2 / (12)

The results presented here indicate that depending on hydrophobicity there are
different modes of flotation of coarse particles in the monobubble Hallimond tube.
When particles are hydrophilic they either sink or can be entrained mechanically behind
a levitating bubble. Slightly hydrophobic solids with a contact angle up to 20º float
as individual particles according to the formula given by Eqs. 3 and 4 or by the
Scheludko equation (Eq. 5). This conclusion correlates well with the observation made
by Derjaguin and Churaev (1989) that up to 15º there is a significant hydrophilic
repulsion between particles and no aggregation of particles can occur. When the
contact angle is between 20º and about 40º the interactions between particles floated
in the monobubble Hallimond tube may appear and the flotation obeys Eq. 11 if the
aggregation takes place. When the hydrophobic interaction is significant, which takes
place when the advancing contact angle is greater than 65º (Derjaguin and Churaev,
1989) or according to our flotation tests for s > 55º, the flotation results for coarse
particles are not influenced by changes in hydrophobicity and Eq. 12 is applicable.
This also agrees with the theory of flotation which predicts that the maximum size of
floating particles increases with hydrophobicity up to equilibrium contact angles equal
to 90º. Above 90º there is a rupture of the bubble rather than detachment along the
bubble–particle line (Zimon, 1974; Drzymala, 1996). In practice, there is a negligible
increase in the maximum size of floating particles starting from about 70º (Fig. 8)
because the main adhesion force, the capillary force, depends on sine of  and the sine
values do not increase much between 70º and 90º.

Fig. 8. Influence of advancing contact angle A on maximum size of floating particles subjected to flotation
individually (ð) and as a collection of particles (Ž). Particles of fluorite were coated with different organic
substances.
216 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218

5. Conclusions

The flotation tests carried out with coarse individual particles as well as collections of
the particles in a monobubble Hallimond tube allow to establish relationships between
main parameters of flotation in this small-scale laboratory device. The results can be
summarized as follows.
(1) When particles undergo mechanical carryover the maximum size of entrained
particle amax is not influenced by the population of particles subjected to flotation and
the mechanical carryover is governed by the equations:
²p ²w
amax D L H D 0:023 š 0:002 .cm/ (a)
²w
for particles with densities ²p greater than 2.0 g=cm3 , and
 
²p ²w 0:75
amax D L L D 0:0225 š 0:0025 .cm/ (b)
²w
for particles with density smaller than 2.0 g=cm3 . In. Eqs. a and b the term ²w stands for
density of water.
(2) Hydrophobic interactions during flotation of a collection of particles are negligible
when the hydrophobicity of particles, expressed as contact angle s , is less than 15º.
Therefore, the flotation of a collection of particles (dmax ) can be characterized by the
same equations as for the flotation of individual particles (Dmax ) (Eqs. 3–5). The most
convenient equation is the simplified Scheludko formula (Eq. 5):
s
2
Dmax ² 0 D 6¦ g 1 sin2 (c)
2
(3) Hydrophobic interactions between particles are significant when the contact angle
is greater than 20º. For 20 > s > 55º the flotation of an ensemble of particles is
governed either by:
2 s
dmax n² 0 D 6¦ g 1 sin2 (d)
2
(where n is a factor indicating an n-fold apparent increase of the density of the particle
which is in contact with the bubble, due to the weight of the attached neighboring
particles that do not touch the bubbles) or by an empirical equation:
s
dmax ² 0 D k sin2 .g=cm2 / (e)
2
where k is a constant equal to 2.08 g=cm2 .
It should be noticed that the contact angle at which the interactions appear depends
on the density of the solids and less dense particles begin the interactions at higher
hydrophobicity s .
(4) Above about s D 55º the flotation of a cluster of particles is described by:
dmax ² 0 D 0:40 š 0:05 .g=cm2 / (f)
(5) The above relationships are valid for the monobubble Hallimond tube. Other cells
and flotation devices may require other flotometric formulas to relate their essential
parameters of flotation.
 J. Drzymala / Int. J. Miner. Process. 55 (1999) 203–218 217

(6) The meaning of equations relating the maximum size of particles subjected to
flotation individually and as a collection of particles is based on the assumption that
only one particle of the cluster is attached to the bubble making the contacting particle
heavier with a new n-fold greater apparent density than that of the individual particle.
Other possible factors that may influence the difference in flotation of individual and
clustered particles including the curvature of the interface and changes in the probability
of collision, adhesion, and stability of particle–bubble attachment were not taken into
account.

Acknowledgements

This work was financed by the Polish Committee for Scientific Research, Grant No. 3
01091 01. Careful execution of experiments by Eng. Alicja Szulmanowicz is gratefully
acknowledged.

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