Int. J. Miner. Process.

74 (2004) 85 – 90
www.elsevier.com/locate/ijminpro

Agglomerate flotation of fine oxide particles

Zygmunt Sadowski *, Izabela Polowczyk
Department of Chemical Engineering and Heating Equipment, Wroclaw University of Technology, Wybrzeze Wyspianskiego 27,
Wroclaw, 50-370, Poland
Received 20 July 2001; received in revised form 12 February 2003; accepted 11 September 2003

Abstract

This paper presents experimental data on using both flocculants and surfactants for aggregation and flotation of fines. The
work has been performed with water suspensions of two oxides, ZnO and MgO. Conventional flotation collectors (sodium
oleate (SOL), sodium dodecyl sulphate (SDS) and cetyltrimethylammonium bromide (CTAB)) were used. Commercial high
molecular weight polymers (MAGNAFLOC 1440, MAGNAFLOC E-10 and MAGNAFLOC 351) were the flocculants used.
Adsorption isotherms of surfactants adsorbing onto the two oxides were determined at natural pH. Adsorption density was the
greatest with sodium oleate. Zeta potential measurements indicated that addition of the cationic surfactant caused a positive
increase of the zeta potential. The positive zeta potential of MgO decreased with increased anionic surfactant concentration. A
decrease in stability indicated that the ZnO suspension pretreated with anionic surfactants caused the formation of larger flocs
when the cationic flocculant (MAGNAFLOC 1440) was added. Similar observations were obtained for a MgO suspension
pretreated with anionic surfactants and reacted with the nonionic flocculant, MAGNAFLOC 351. The negative charged
collector (SDS) appears to be good collector for ZnO floc flotation when hydrophobic flocs are created by the combination of
SDS and either cationic or nonionic flocculants.
D 2003 Elsevier B.V. All rights reserved.

Keywords: flotation; surfactant adsorption; flocculation; oxides

1. Introduction Aggregation of fine particles was developed as a

Small particle aggregation and flotation are of
importance in the minerals industry. During the last
few decades, various approaches to fine particle
aggregation have been reported (Laskowski and Ral-
ston, 1992; Elimelech et al., 1995; Subrahmanyam
and Forssberg, 1990; Rubio and Hoberg, 1993; Gard-
ner and Theis, 1996).
* Corresponding author.
E-mail address: sadowski@iic.pwr.wroc.pl (Z. Sadowski).
shear flocculation process, where the hydrophobic
particles were aggregated in a shear field (Warren,
1975). Spherical oil agglomeration was also achieved
at shear field conditions where the hydrophobic fines
were joined by oil bridges (Sadowski, 1994).
One possibility of obtaining effective agglomera-
tion can be through the interaction of classical ionic
surfactants (flotation collectors) pre-adsorbed on the
oxide fine particles with oppositely charged polymers
(flocculants). Such interaction may lead to an agglom-
eration mechanism that combines electrostatic and
hydrophobic interactions.

0301-7516/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2003.09.007
86 Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90
Hydrophobic flocculation arises as a result of
hydrophobic interaction between hydrophobic par-
ticles and an oppositely charged or nonionic floccu-
lant. The separation of the hydrophobic flocs can
then be achieved using froth flotation (Song and Lu,
2000).
The object of this present paper was to investigate
the interaction between surfactant and polymer and
the effect of these interactions on aggregation and
flotation of fine particles.
2. Experimental procedure
2.1. Materials and reagents
ZnO obtained from Huta Olawa (Poland) was
used in this study. This material has a medium
particle size of 0.115 Am and a BET surface area
of 5.75 m2/g. MgO was purchased from Ubichem
Limited, Hampshire, UK. The BET nitrogen specific
surface area of this sample was found to be 8.4 m2/
g. The mean particle size of MgO was found to be
0.88 Am.
Sodium dodecyl sulphate (SDS) used was
obtained from BDH. Sodium oleate (SOL) and
cetyltrimethylammonium bromide (CTAB) were also
used. Sodium oleate was supplied by Riedel-de Haën
(Germany).
The flocculants used in the study were polymer
reagents obtained from Allied Colloids, Bradford,
England (MAGNAFLOC 1440 cationic polymer,
MAFNAFLOC E-10 anionic polymer, MAGNA-
FLOC 351 nonionic polymer). All reagents were used
without any further purification.
2.2. Zeta potential measurements
Zeta potentials of oxide particles in the presence of
surfactants were determined from electrophoretic mo-
bility measurements. The NICOMP380 ZLS Zeta-
meter was used for the measurement of zeta
potential (calculated using the Smoluchowski equa-
tion). Measurements were made in triplicate and the
average zeta potential values were reported as results.
The ionic strength was maintained at 10
3 M using
KCl. All zeta potential measurements were carried out
at 20 jC. The pH of suspension was not adjusted. For
zeta potential measurements with surfactants, the
oxide suspensions were conditioned for 24 h to allow
the adsorption equilibrium.
2.3. Adsorption study
Adsorption isotherms were determined in the
following manner: A suspension containing 0.5 g
of solid in 50 ml of surfactant solution was taken at
natural pH and shaken for a definite time (8 h) to
attain equilibrium. Then the suspension was centri-
fuged and a supernatant was analyzed for remaining
surfactant. A colorimetric method (Fowler and
Steel, 1968) was used to determine the residual
surfactant concentration. The adsorption isotherms
were then obtained by plotting the amount of
adsorbed surfactant as a function of equilibrium
concentration.
2.4. Stability of suspensions
Stability or flocculation of oxide suspensions was
investigated by simple sedimentation measurement
using an Andreassen pipette. The concentration of
suspension in these experiments was 1.25 g/cm3. The
results of the sedimentation tests were reported in
terms of stability (S), which is defined as
W0
Wt
S¼
W0
where: W0 represents the weight of solids in a
sample at the initial time t = 0. Wt represents the
same after 3 min.
2.5. Flotation experiments
Column flotation experiments were carried out in a
glass column of 2.6 cm in diameter and 55 cm in
height, fed with fine particles at the bottom. A stirrer
bar magnet rotated on the bottom during flotation. A
suspension of hydrophobized fines was prepared in a
beaker and pumped to the column. The flocculant
solution was led in the column at the opposite side.
Compressed air was introduced into the column
through the glass porous membrane. The gas flow
rate during flotation was maintained at 64 cm3 min
1.
 Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90
3. Results and discussion
The zeta potentials of investigated powders in the
presence of the different concentrations of surfactants
are shown in Fig. 1A and B. All measurements were
performed in 10
3 M KCl electrolyte concentration.
The isoelectric points of ZnO and MgO, found from a
literature, were 8.95 and 12.4, respectively (Parks,
1965; Yoon et al., 1979).
The addition of sodium oleate causes an increase of
negative values of zeta potential for both oxides. In
Fig. 1. The effect of surfactants concentration on zeta potential of
oxide particles (A—ZnO, B—MgO).
87
the case of SDS addition, zeta potential of MgO was
positive at low surfactant concentrations and became
negative in the high concentration range (10
2 M).
On the other hand, the negative value of zeta potential
of ZnO decreases with an increase in surfactant (SDS)
concentration. With cationic surfactant addition
(CTAB), the positive values of zeta potential increase
for both oxides when the surfactant concentration
increased.
Surfactant adsorption isotherms for the investigat-
ed oxides at natural pH are shown in Fig. 2A – C. The
high adsorption density of SOL may be a result of
both zinc and magnesium oleate precipitation. There-
fore, the adsorption values of sodium oleate appear
higher than for other investigated surfactants. The
cationic surfactant (CTAB) exhibits higher adsorption
on ZnO due to electrostatic attraction between the
negative surface and positively charged surfactant.
Both anionic surfactant isotherms for magnesium
oxide exhibit a high affinity behavior. This can be
also explained by an electrostatic attraction between
the positively charged magnesium oxide surface and
anionic surfactant.
The effects of surfactant concentrations on the
stability of oxide suspension are presented in Fig.
3A and B. The relationship between sedimentation
rate (stability), the size of agglomerate and the ad-
sorption isotherms of surfactants were observed. In
the ZnO case, a small concentration (10
5 M) of
anionic surfactant causes a decrease of suspension
stability. At pH=11 CTAB adsorption onto the MgO
surface is low and is in agreement with the high
stability observed during the Andreasen pipette
experiments. The low adsorption of cationic surfactant
observed in this study may be due to the electrostatic
repulsion between the surfactant and the MgO surface.
The aggregation process depicted in this study can
be divided into two steps: (1) adsorption of surfactant
on the oxide particles and (2) addition of flocculants
for surfactant – polymer complex creation. The aggre-
gates size may be expected to vary with the conditions
of both surfactant and polymer addition.
The orientation of the polymer –surfactant complex
on the particle surface should be relevant in interpret-
ing both the stability and flotation. In order to inves-
tigate the influence of surfactant –polymer interaction
on the behavior of oxide suspensions, the stability of
suspension was measured. The results obtained from
88 Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90

these series of experiments are presented at Table 1.

The dosage of flocculant was 1 ppm, as suggested
from prior experimentation (Sadowski, 1994).
There is a substantial decrease in the stability of a
ZnO suspension when an anionic surfactant (SOL)
and a cationic polymer (Magnafloc 1440) are added.
The occurrence of such minimum stability is due to
electrostatic attraction between the ZnO, surfactant

Fig. 2. Adsorption isotherm of surfactants (A—sodium dodecyl

sulphate, B—sodium oleate and C—cetyltrimethylammonium Fig. 3. The influence of surfactant concentration on the stability of
bromide). oxide suspensions (A—ZnO, B—MgO).
 Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90 89

and polymer. A similar phenomenon was observed for

SDS and Magnafloc 1440. Pretreatment with cationic
surfactant (CTAB) of a ZnO suspension leads to the
increases of stability in the presence of the nonionic
polymer (Magnafloc 351). On the other hand, for the
MgO suspension the interaction of anionic surfactants
(SOL and SDS) with cationic polymer is associated
with poor flocculation (high stability). The optimum
conditions for flocculation of MgO suspension occur
when anionic surfactants (SLO and SDS) and a
nonionic polymer (Magnafloc 351) were used. The
significant increase in the size of flocs may be
interpreted from the small electrostatic interaction
between MgO particles covered by anionic surfactants
and nonionic flocculant.
Hydrophobic flocs flotation was examined by
flotation of the flocs created by surfactant – flocculant
interaction. The experimental conditions were identi-
Fig. 4. Flotation recovery versus time for the hydrophobic flocs of
cal to those used in the stability study (at the natural MgO and ZnO at 10
4 M SDS.
pH of both suspensions). The selected results for
sodium dodecyl sulphate (SDS) floc flotation are
shown in Fig. 4. results suggested that in these two cases the flocs have
A comparison of flocs flotation recoveries for both a hydrophilic surface.
MgO and ZnO shows that higher recovery was Besra et al. (2002) have suggested that pretreat-
obtained for ZnO. This result did not correspond well ment with all the three surfactants of kaolin results in
with the adsorption data (Fig. 2A). The pre-adsorption more compact and higher density flocs. It seems that
of sodium oleate led to a significant increase in the in the presence of both surfactant and flocculant, the
size of flocs, but the flotation recovery was about size of flocs does not play a significant role in
10%. Also, very low recovery was obtained as well flotation of the flocs. From the flotation results
with cationic surfactant (CTAB) pre-adsorption. These presented here the following explanation is proposed:
The low SDS adsorption density onto the ZnO
particles means that there is a high concentration
Table 1
Stability of oxide suspensions in the presence of both surfactant and
of SDS remaining in the solution. In the second
polymer stage, when the polymer is added to the suspension,
Reagents ZnO MgO
the strong polymer – surfactant interaction results in a
second adsorption of surfactant ions on the polymer
pH Stability pH Stability
[%] [%]
layer. As a result, the flocculant external layer
remained hydrophobic. In the case of strong surfac-
SOL (1  10
4 M), 7.4 2.08 11.1 42.51
Magnafloc 1440 (1 ppm)
tant adsorption (SOL), there are not free surfactant
SOL (1  10
4 M), 7.3 11.54 10.9 9.41 ions in the solution and the polymer layer remains
Magnafloc 351 (1 ppm) hydrophilic.
CTAB (1  10
4 M), 7.7 47.27 11.05 14.01
Magnafloc 351 (1 ppm)
CTAB (1  10
4 M), 7.4 25.93 11.0 15.33
Magnafloc E-10 (1 ppm)
4. Conclusions
SDS (1  10
4 M), 7.8 1.37 11.1 51.6
Magnafloc 1440 (1 ppm) Fine oxide particles are aggregated by the presence
SDS (1  10
4 M), 7.3 19.74 11.05 7.93 of surfactants as a result of a strong hydrophobic
Magnafloc 351 (1 ppm) interaction after adsorption. The addition of a floccu-
90 Z. Sadowski, I. Polowczyk / Int. J. Miner. Process. 74 (2004) 85–90
lant stabilizes and increases the size of the oxide
suspension. The strong flocculation was observed
when the anionic surfactants (SOL, SDS) and a
cationic flocculant (Magnafloc 1440) were adsorbed
onto the ZnO surface. In the case of MgO, the same
effects were observed when the nonionic flocculant
(Magnafloc 351) was used. Good flotation recovery
of the flocs was obtained with an anionic collector
(SDS) in the presence of both cationic and nonionic
flocculants.
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