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Minerals Engineering

journal homepage: www.elsevier.com/locate/mineng

size – Modelling the limits of ﬁne particle ﬂotation

Daniel Chipfunhu a, Massimiliano Zanin a,⇑, Stephen Grano b

a

Ian Wark Research Institute, University of South Australia, The ARC Special Research Centre for Particle and Material Interfaces, Mawson Lakes Campus,

Adelaide, South Australia 5095, Australia

b

Institute for Mineral and Energy Resources, The University of Adelaide, South Australia 5005, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The ﬂotation behaviour of ﬁne particles is studied in this work. Fine methylated quartz particles within

Received 13 July 2010 the size range from 0.2 to 50 lm, and with varying contact angles, were ﬂoated in a mechanical ﬂotation

Accepted 23 September 2010 cell. Results indicate that particles of a given size need to possess a minimum critical contact angle, which

increases in value as particle size decreases, for ﬂotation to be initiated. As a consequence, a non-ﬂoating

component exists within a given size fraction. This is interpreted as a fraction consisting of particles

Keywords: below the critical contact angle for ﬂotation for that size. The critical contact angle for ﬂotation is

Froth ﬂotation

explained in terms of the existence of an energy barrier for bubble–particle attachment. The ﬂotation

Flotation modelling

Contact angle

results are interpreted by means of Scheludko et al. (1976) and Drelich and Miller (1992) models for

Fine particles ﬂotation the ﬂoatability of ﬁne particles. The experimental data compared very well with calculations using the

Drelich and Miller equation, allowing extension to the prediction of the critical contact angle for ﬂotation

down to particle sizes well below the previous limits investigated, bridging the gap existing in the

literature.

Ó 2010 Elsevier Ltd. All rights reserved.

sion efﬁciency as particles are not able to deviate from ﬂuid stream-

In ﬂotation, ﬁne particles show lower ﬂotation rate, resulting in lines to collide with bubbles (Weber and Paddock, 1983; Yoon and

low ﬂotation recovery. The recovery of particles by air bubbles dur- Luttrell, 1989). The bubble–particle collision frequency is controlled

ing ﬂotation occurs after three consecutive sub-processes of by cell hydrodynamics and kinetics, making the problem of ﬁne par-

collision, attachment and stability have taken place to form a bub- ticle ﬂotation partly a kinetic one. This implies that particles should

ble–particle aggregate. The whole process, termed collection, may eventually ﬂoat if given sufﬁcient residence time in the ﬂotation

be expressed as (Dai et al., 1998): environment. However, ﬂotation of ﬁne particles may be hindered

by the existence of an energy barrier that prevents successful bub-

E ¼ Ec Ea Es ð1Þ

ble–particle attachment after collision, thus making the problem of

where Ec, Ea and Es are the collision, attachment and stability efﬁ- ﬁne particle ﬂoatability also a thermodynamic one. Put differently,

ciencies respectively. Collision is mainly controlled by hydrody- ﬁne particles may possess insufﬁcient kinetic energy to displace the

namics (e.g., bubble rise velocity, bubble size) in the ﬂotation cell, intervening liquid layer between the colliding particle and bubble

while attachment is dominated by interfacial behaviour (surface (Hewitt et al., 1995).

forces) between bubble and particle. For ﬁne particles, which pos- The energy barrier manifests as a critical contact angle, which

sess low inertia, the stability efﬁciency is essentially unity (Dai represents the amount of activation energy that must be overcome

et al., 1998). Particle recovery by ﬂotation is sensitive to both parti- before bubble–particle attachment can occur. Theoretical consider-

cle size and contact angle (Crawford and Ralston, 1988), with very ations and experimental data published to date support the exis-

ﬁne particles (<10 lm) and coarse particles (>100 lm) ﬂoating tence of a critical contact angle below which ﬂotation does not

poorly, but for different reasons. Coarse particles have low ﬂotation occur (Crawford, 1986; Gontijo et al., 2007; Miettinen, 2007), but

rate due to detachment problems associated with disruptive forces validation of the experimental data for ﬁne particles with theoret-

in the ﬂotation cell (Pyke et al., 2003), whereas ﬁne particles’ poor ical predictions has not yielded satisfactory agreement. This dis-

ﬂoatability emanates from low collision efﬁciency between bubbles parity is discussed further below.

In their theoretical analysis of the ﬂoatability of ﬁne particles,

⇑ Corresponding author. Tel.: +61 8 8302 3263; fax: +61 8 8302 3683. Scheludko et al. (1976) proposed that the kinetic energy of

E-mail address: massimiliano.zanin@unisa.edu.au (M. Zanin). particles must be larger than the energy needed to overcome the

0892-6875/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.

doi:10.1016/j.mineng.2010.09.020

D. Chipfunhu et al. / Minerals Engineering 24 (2011) 50–57 51

resistance to the formation and expansion of the three phase con- ting was determined in ﬁlm ﬂotation at 0% ﬂoating (Yarar and Kao-

tact line for successful particle–bubble attachment to occur. This ma, 1984), as opposed to 50% ﬂoating which is also suggested in

energy must be supplied by the kinetic energy of the particle. At the literature (Fuerstenau et al., 1991). This is because for very ﬁne

equilibrium, the kinetic energy balances the energy needed to form quartz particles the ﬁrst process to occur when particles are placed

and expand the three phase line of contact, from which a minimum on the liquid surface is capillary penetration, resulting in particles

particle diameter, Dmin,K, for ﬂotation maybe estimated (Scheludko sinking as aggregates. At 0% ﬂoating (or 100% sinking) it is ensured

et al., 1976): that both aggregates (which sink due to gravity at higher surface

" #13 tension values compared to individual particles) and individual

3c2slv particles sink, eliminating any ambiguity in the value of the surface

Dmin;K ¼ 2 ð2Þ

V 2t Dqclv ð1 cos hÞ tension of wetting. In essence, this approach gives the minimum

value of the surface tension of wetting from a range of possible val-

where h is the receding contact angle, cslv is the line tension (which ues. Film ﬂotation experiments were carried out on samples of feed

is the reversible work which must be done to isothermally expand and tailings, and differences in contact angle interpreted to be a re-

the unit length of the three phase contact line), clv is the liquid–va- sult of segregation in ﬂotation of particles having different size and

pour surface tension, Dq is the difference between the particle and contact angle values.

ﬂuid densities and Vt is the bubble–particle approach velocity. To Finally, the ﬂotation results are validated against the Scheludko

date, this theoretical model has not been satisfactorily validated model (Scheludko et al., 1976) and its variation (Drelich and Miller,

with experimental data due to the uncertainty in the value of the 1992), based on theoretical considerations in regards to the limits

line tension and the lack of data for very ﬁne particles. There is of ﬁne particle ﬂotation.

no consensus on the line tension value used in Eq. (2) (Mingins

and Scheludko, 1979; Drelich, 1996; Amirfazli and Neumann,

2. Materials and methods

2004; Lin et al., 1993; Li et al., 1992), since the experimental values

of line tension in the literature are quite varied, ranging from 1012

All glassware was cleaned by immersion in concentrated so-

to 105 N, while theoretically determined values range from 1012

dium hydroxide of pH above 13 and sonication for at least

to 1010 N (Drelich, 1996). A recent review of the theoretical and

30 min to remove any organic contamination. The glassware was

experimental data on line tension concluded that sometimes the

then thoroughly rinsed with de-ionised water to remove all the so-

values of line tension are inappropriately compared for dissimilar

dium hydroxide and ﬁnally dried overnight in a clean oven at

systems which may not be reasonably expected to have the same

110 °C. All chemicals used in this work were of analytical reagent

value even from a theoretical perspective (Amirfazli and Neumann,

quality and were used without further puriﬁcation.

2004). The values of line tension quoted by Scheludko et al. (1976)

were estimated for particles of a given size (about 2 lm) and con-

2.1. Materials preparation

tact angle (between 20° and 40°), and thus cannot be expected to

ﬁt experimental data for substantially larger particles (about

Microcrystalline quartz of particle size less that 10 lm was ob-

10 lm or larger).

tained from Sigma Aldrich. These particles are designated as Sigma

Drelich and Miller (1992) revised Scheludko et al. (1976) ap-

quartz. Other quartz size fractions were obtained by wet grinding

proach and proposed that a pseudo-line tension, which takes into

lumpy crystalline quartz in a laboratory stainless steel ball mill

account surface heterogeneities and roughness, will give a better

and wet sieving at 38 lm. The 38 lm size fraction was passed

correlation with experimental data compared to the line tension.

through a 1” cyclone (precyclone) with the overﬂow discarded

Using the same theoretical basis used to derive Eq. (2), Drelich

and the underﬂow classiﬁed in a Warman cyclosizer that split

and Miller (1992) recognised that:

the particles into six different size fractions (C1, C2, C3, C4, C5,

cslv ¼ clv ð1 cos hÞ rc ð3Þ and C6). Selected size fractions (C3, C5, C6 and Sigma) were subse-

quently cleaned separately to remove any organic and inorganic

where rc is the critical radius of wetting, i.e. the bubble drop radius

contaminants (such as iron from the grinding media) before subse-

below which there is no effective attachment between the solid and

quent manipulation to alter the contact angle values.

dispersed phases. Substituting Eq. (3) into Eq. (2), an alternative

expression for the minimum particle size, Dmin,K, was proposed:

2.2. Cleaning quartz particles

" #13

3r 2c clv ð1 cos hÞ

Dmin;K ¼ 2 ð4Þ Hot aqua regia and piranha solution were used to clean each of

V 2t Dq

the selected quartz size fractions of any surface impurities. The

Drelich and Miller (1992) determined experimental values for reaction time was varied from 6 to10 h depending on the particle

the critical radius of wetting, rc, as a function of contact angle, h. size and the reagent used. The acid was washed out by rinsing

The rc values were estimated by extrapolating a plot of h versus the particles with de-ionised water until the pH became neutral.

r to h = 0, for methylated quartz plates in distilled water at pH A centrifuge was used to accelerate particle settling for the ﬁnest

5.6. size fractions (Sigma and C6). The particles were dried overnight

In this paper, the ﬂotation behaviour of ﬁne methylated quartz in a clean oven at 110 °C in a covered clean beaker and subse-

of different particle size and contact angle was studied. The exis- quently stored in clean and sealable glass containers.

tence of a critical contact angle for ﬂotation, which is particle size

dependent, is shown. Further, to investigate contact angle hetero- 2.3. Methylation of silica particles

geneity within individual classes of particles, the contact angle of

feed and tails from selected tests was measured by means of ﬁlm The contact angle of clean silica particles was manipulated to

ﬂotation, which uses the critical surface tension of wetting different degrees of hydrophobicity by using trimethylchlorosilane

(Zisman, 1964). Other methods, such as Washburn technique (TMCS) (Blake and Ralston, 1985). Because TMCS reacts readily

(Washburn, 1921), were considered not reliable for ﬁne particles with water in the atmosphere, the methylation procedure was car-

(<10 lm), because ﬁne particles tend to form aggregates when ried out in a glove box under dry nitrogen. A known mass of

dry, biasing the measurement. The critical surface tension of wet- cleaned quartz for each size fraction was placed in a 1 l laboratory

52 D. Chipfunhu et al. / Minerals Engineering 24 (2011) 50–57

glass bottle and heated in an oven overnight at 110 °C to remove surface tension. The critical surface tension of wetting was deter-

any physisorbed water. While still hot, the quartz was transferred mined at 0% ﬂoating. Once the critical surface tension of wetting

to the glove box and allowed to cool, a measured amount of cyclo- was measured, the corresponding contact angle value was deter-

hexane added, and the glass bottle sealed. The sealed bottle was mined using a calibration curve developed by Miettinen (2007)

sonicated for 30 min in a bath in order to disperse the quartz par- (Fig. 3). The calibration curve was developed by methylating ﬁve

ticles before methylation. A known amount of TMCS was then sets of glass slides to different advancing water contact angles

added from a precision microsyringe under constant stirring with and then measuring the contact angle on the glass plates as a func-

a magnetic stirrer. To obtain different contact angles for the quartz, tion of surface tension of methanol–water mixtures (Miettinen,

different concentrations of TMCS and reaction times were used. A 2007). The contact angle value is the maximum contact angle value

small amount of particles was taken for contact angle measure- from a range of possible values as the surface tension of wetting is

ment using ﬁlm ﬂotation, while the remainder of the particles were the minimum value for the population of particles.

stored in a clean, sealable container and placed in a desiccator.

2.6. Flotation procedure

2.4. Bubble and particle size distribution measurement

Flotation of the different size fractions was carried out in a

Bubble size distribution in the ﬂotation experiments (Fig. 1a) 300 cm3 top driven mechanical ﬂotation cell, using demineralised

was measured using a bubble viewer connected to digital photo- water, at pH 6 and with potassium nitrate electrolyte concentra-

graphic equipment (Hernandez-Aguilar et al., 2004). The Sauter tion of 1 103 M. The pH was controlled with hydrochloric acid

mean bubble diameter for 50 ppm MIBC in the mechanical ﬂota- and potassium hydroxide. The air ﬂow rate was maintained at

tion cell was measured to be 0.42 mm. The particle size distribu- 150 cm3/min, corresponding to a superﬁcial gas velocity (Jg) of

tion for the clean quartz particles, ﬂotation feed (Fig. 1b), tailings

and concentrates was measured using a Mastersizer 2000 instru-

90

ment from Malvern Particle Sizing Systems. The system measures

particle size by applying a focussed laser beam through the parti-

80

cles, and Mie scattering model is then used to determine the parti-

cle size distribution as equivalent sphere diameters. Scanning 70

Electron Microscope (SEM) images for the particles used in this

study (Fig. 2) show that particles are angular and of irregular 60

shape, and not spherical.

50

2.5. Measurement of particle contact angle 40

20 25 30 35

A small quantity of particles (30–50 mg) was placed on the sur-

Critical surface tension, mN/m

face of methanol–water solutions of different concentration and

controlled surface tension, and the amount of particles that either Fig. 3. Calibration curve for advancing water contact angle of silica particles in

sink or remain on the surface determined as a function of the liquid water versus their critical surface tension used for ﬁlm ﬂotation, Miettinen (2007).

Number distribution (%)

4 20

(a) (b)

3 15

Frequency

2 10

1 5

0 0

0 0.2 0.4 0.6 0.8 1 0.1 1 10 100

Bubble Size, µm Particle diameter, µm

Fig. 1. (a) Bubble size (Sauter mean bubble diameter = 0.42 mm) in the mechanical ﬂotation cell and (b) particle size distribution for Sigma quartz (), d50 = 3 lm; C6 quartz

(d), d50 = 10 lm; C5 quartz (N), d50 = 16 lm and C3 quartz, (j), d50 = 33 lm.

Fig. 2. SEM images of particles used in this study: Sigma quartz (left) and C6 quartz (right). Other size fractions had similar particle shape to the C6 sample.

D. Chipfunhu et al. / Minerals Engineering 24 (2011) 50–57 53

approximately 0.5 cm/s. Methyl isobutyl carbinol (MIBC) was used experiments gave recoveries differing by more than 5%, a third

as a frother, at a concentration of 50 ppm. Methylated quartz experiment was carried out. For contact angle measurements, the

(about 1.0 g) of known size fraction and contact angle, was placed critical surface tension was determined using methanol-water

in a 250 cm3 beaker, and about 150 cm3 of electrolyte solution solutions with an approximate liquid/vapour surface tension dif-

added. The pulp was stirred for 5 min to properly disperse the par- ference of 2 mN/m, giving an error of approximately 1 mN/m sur-

ticles, and transferred to the ﬂotation cell. The pulp in the cell was face tension and an equivalent error of 4° in the contact angle

made up to about 300 ml, the pH was adjusted and frother added measurement.

(2 min conditioning time). Air was turned on and ﬂotation carried

out, at an impeller speed of 3000 rpm, for a total time of 8 min, 2.8. Subtraction of entrainment

with concentrate collected at 1, 3, 5 and 8 min intervals. For the

ﬁnest size fractions (Sigma and C6) the preparation of the ﬂotation The recovery of ﬁne particles is both a function of true recovery

feed also included sonication for 10 min, to avoid the formation of and mechanical carryover, or entrainment. In this work the ap-

aggregates. proach by Ross (1991) is used to estimate recovery by entrainment.

Since keeping methylated quartz in aqueous conditions for The rate of entrainment in the ith size fraction, Ei(t), at any given

more than approximately 25 min results in loss of hydrophobicity time is given by Ross (1991,1990):

and a decrease in ﬂotation recovery (Blake and Ralston, 1985), the

conditioning time was kept as short as possible. The concentrates W i ðtÞ C mi ðtÞ

Ei ðtÞ ¼ X i ðtÞ ð5Þ

and tailings were dried in an oven at 110 °C and weighed to deter- C W ðtÞ

mine the ﬂotation recovery. Selected samples of feed, concentrate

where Wi(t) is the rate of recovery of water (g/min), Cmi(t) and Cw(t)

and tailings, prior to oven drying, were also analysed to determine

are the concentrations of the particular mineral species and water

particle size distribution and contact angle.

(g/l of pulp) at time t, respectively. Xi(t) is a factor which character-

ises the degree of entrainment and is particle size dependent. In this

2.7. Analysis of error and reproducibility

work, the entrainment factor is the gradient of the curves (Fig. 4)

obtained by ﬂoating hydrophilic quartz particles and plotting parti-

The error on the ﬂotation recovery results was estimated by car-

cle recovery against water recovery.

rying out each ﬂotation test in duplicate. Where the two repeated

3. Results

45

Recovery, %

30

15 four different particle size fractions. For each size fraction the ﬂo-

tation recovery was also determined as a function of contact angle.

0 Flotation recovery was directly proportional to both nominal parti-

0 20 40 60 cle size and contact angle, across all size fractions (Fig. 5).

Water Recovery, % In Fig. 6 the fraction of particles remaining in the ﬂotation cell is

reported versus time (log scale) for all size fractions and for contact

Fig. 4. Solids recovery versus water recovery for hydrophilic Sigma (), C6 (d), C5

angles of 60° and 88°. Ideally, for equisized and surface homoge-

(N) and C3 (j) quartz (300 ml mechanical cell pH 6, Jg = 0.5 cm/s, 0.001 M KNO3,

8 min ﬂotation time, impeller speed 3000 rpm, MIBC frother concentration neous particles, the ﬂotation rate constant would be the same for

50 ppm). all particles, and a plot of log R (where R is recovery) against time

100

(a) (c)

80

60

40

Recovery, %

20

0

(b) (d)

80

60

40

20

0

0 2 4 6 8 0 2 4 6 8 10

Time, Minutes Time, Minutes

Fig. 5. Flotation recovery versus time for quartz (300 ml mechanical cell pH 6, Jg = 0.5 cm/s, 103 M KNO3 ﬂotation time 8 min, impeller speed 3000 rpm, MIBC frother

concentration 50 ppm) (a) Sigma quartz: CA 51° (N), CA 58° (D), CA 71° (d), CA 79° (), and CA 88° (x), (b) C6 Quartz: CA 35° (e), CA 42° (j), CA 48° (N), CA 60° (D), CA 73° (d)

and CA 88° (x). (c) C5 Quartz: CA 33° (e), CA 38° (s), CA 42° (j), CA 52° (N), CA 60° (D), CA 71° (d), CA 77° () and CA 88° (x). (d) C3 Quartz: CA 21° (+), CA 26° (h), CA 30° (;),

CA 42° (j), CA 60° (D), CA 71° (d) and CA 88° (x). The points are experimental values and the lines are the model ﬁt for R = Rmax(1 ekt).

54 D. Chipfunhu et al. / Minerals Engineering 24 (2011) 50–57

Time, min.

0 2 4 6 8 0 2 4 6 8 10

1

(a) CA = 88 o (b) CA = 60 o

Fraction Remaining

Sigma

Sigma

C6 C6

0.1

C5

C5 C3

C3

0.01

Fig. 6. Fraction remaining, log scale, versus time for Sigma (j), C6 (), C5 (N) and C3 (d) quartz for contact angle 88° (a) and contact angle 60° (b). The points are

experimental values and lines are model ﬁt for R = Rmax(1 ekt).

(t), should give a straight line (Imaizumi and Inoue, 1965) to low separately on feed and tailings of selected samples. Fig. 8 reports

fraction remaining values (<0.05). However, the curves obtained the cumulative percentage of ﬂoating quartz particles versus the

for the different classes of particles deviate signiﬁcantly from surface tension of wetting.

straight lines at high fraction remaining values, suggesting the sig- Consistently, for all samples the maximum contact angle of the

niﬁcant presence of at least two ﬂoating components. Therefore, a tailings was found to be lower than the maximum contact angle of

ﬂoating component (Rmax) and a non-ﬂoating component (100 the feed (Table 2), suggesting contact angle heterogeneity, as dis-

Rmax) have been assumed, and the experimental data ﬁtted to the cussed further below.

ﬁrst order rate equation:

The described procedure gave very close agreement between The particle size distributions of feed, concentrates and tailings

the experimental data points and the ﬁtted recovery value of some of the size fractions are shown in Fig. 9. A difference was

(Fig. 6). The ﬁtting parameters (Rmax, k) are reported in Table 1. It found in particle size distribution, with the concentrates having

is apparent that there is a larger proportion of unrecovered parti- on overall greater particle size than the tailings. For example, for

cles, non-ﬂoating component (100 Rmax), at contact angle 60° a sample of Sigma particles having contact angle 51°, the average

compared with contact angle 88° and that this non-ﬂoating com- particle size of the feed was 3 lm, while the average particle size

ponent increases with decreasing particle size and contact angle. of concentrates and tailings was about 5 lm and 1 lm, respec-

Even at very high contact angles (e.g., 88°), where recovery is ex- tively (Fig. 9). Similar trends were also observed for other size

pected to be virtually 100%, there are some particles that are not fractions.

recovered, meaning that either they required greater residence

time in the ﬂotation environment or they were below the critical

contact angle for ﬂotation. 4. Modelling the limits of ﬁne particles ﬂotation

Fig. 7 shows the maximum recovery, Rmax, as a function of par-

ticle contact angle and size. The results point to the existence of a The system studied by Drelich and Miller (1992) to determine

critical contact angle (hcrit) below which ﬂotation does not occur, in the values for rc is similar to the ﬂotation system in this study

agreement with previous studies (Crawford and Ralston, 1988). (i.e., quartz-TMCS), allowing direct comparisons and the use of rc

This critical contact angle is obtained by extrapolating the tangent

at the inﬂexion point to 0% recovery (Gontijo et al., 2007). The error

in determining hcrit is estimated to be equal to the error in deter-

100

mining the contact angle (±4°). The critical contact angle for the

range of particle sizes investigated increases with decreasing par-

ticle size (Table 1). 80

60

Rmax, %

investigated by means of ﬁlm ﬂotation, which was carried out

20

Table 1

Experimental critical contact angles derived from Fig. 7.

0

Designation Critical contact Particle size, CA = 88° CA = 60° 0 20 40 60 80 100

angle, hcrit (°) d50 (lm)

Rmax k Rmax k Contact Angle (o)

(%) (%)

Sigma 55 3 81 0.38 65 0.30 Fig. 7. Rmax versus contact angle for Sigma (), C6 (d), C5 (N) and C3 (j) quartz

C6 37 10 86 0.56 82 0.50 (300 ml mechanical cell pH 6, Jg = 0.5 cm/s, 1 mM KNO3 ﬂotation time 8 min,

C5 30 16 97 1.42 93 1.51 impeller speed 3000 rpm, MIBC frother concentration 50 ppm). The critical contact

C3 20 33 98 2.34 95 2.06 angle for ﬂotation, hcrit, is determined by extrapolation of the curves to 0% recovery

from the tangent at the inﬂexion point.

D. Chipfunhu et al. / Minerals Engineering 24 (2011) 50–57 55

100

(a) (b)

80

% Floating

60

40

20

0

20 40 60 0 20 40 60 80

Surface Tension, mN/m

Fig. 8. The cumulative % of ﬂoating quartz particles versus wetting surface tension as obtained from ﬁlm ﬂotation with aqueous methanol solutions (a) Sigma quartz CA 51°

() and CA 88° (j); (b) C5 quartz CA 58° () and CA 77° (j).

Table 2

Contact angles (CA) of feed and tails after ﬂotation of selected samples. Film ﬂotation Table 3

was used to ascertain the contact angle. Critical bubble drop radius, rc, versus contact angle (CA): A comparison between

model values (Eq. (7)) and measured values from Drelich and Miller (1992).

Designation Particle size, Critical CA, Max. CA Max. CA

d50 (lm) hcrit (°) feed (°) tailings (°) CA of quartz plates (°) Measured rc (lm) Model rc (lm)

C3 33 20 32 27 36 0.85 1.05

C5 16 30 58 36 46 0.30 0.32

C6 10 37 41 32 48 0.29 0.25

C6 10 37 88 48 60 0.09 0.06

Sigma 3 55 88 48 72 0.01 0.01

values from the former study. In the current study, an exponential Dmin,K, was determined by substituting the calculated rc values into

expression is used to determine the values of rc. An equation that Eq. (4). The other parameters used to calculate the minimum par-

best ﬁts the experimental relationship between rc and contact an- ticle size in Eq. (4) were the liquid vapour surface tension,

gle was determined by the least squares method (Eq. (7)). Experi- clv = 71.6 mN/ml, the liquid density, ql = 1000 kg/m3, quartz den-

mental rc values (Drelich and Miller, 1992) and those predicted by sity, qs = 2650 kg/m3, and the bubble–particle approach velocity,

Eq. (7) are shown in Table 3, giving a value of R2 = 0.96 for the Vt = 0.3 m/s. It is noted that the value of the line tension, or more

goodness of ﬁt. precisely the pseudo-line tension, in the approach by Drelich and

Miller (1992) is calculated as a function of particle contact angle

r c ¼ 79:68 e0:12h ð7Þ

(Eq. (3)), and shows a decreasing proﬁle as contact angle increases

Ultimately, Eq. (7) estimates and extrapolates the value of rc be- (Table 4).

low the contact angles for which it was determined by Drelich and The model ﬁt to the experimental data is also shown in Fig. 10,

Miller (1992). as well as the experimental data by Crawford (1986). On the plot,

Eq. (7) was used to calculate the values of rc for the critical con- the region of critical contact angle/particle size values calculated

tact angles in Table 1. The minimum particle size for ﬂotation, from Scheludko et al. (1976) is also reported.

100

Sigma C5 CA 58

o

C6 CA42

o

o

80 CA 51

60

40

20

Cumulative Volume %

0 o

Sigma CA 88 o o

C5 CA 88 C6 CA88

80

60

40

20

0

0 3 6 9 0 10 20 30 40 0 10 20 30

Particle size, µm

Fig. 9. Cumulative particle size distribution of feed (N), concentrates (j) and tailings (h) for Sigma, C6 and C5 quartz.

56 D. Chipfunhu et al. / Minerals Engineering 24 (2011) 50–57

Table 4

Theoretical and experimentally determined Dmin,K values for the ﬁne particles in this

study. The model to determine Dmin,K is based on the Drelich and Miller (1992) 100

Particle size, µm

approach.

Particles

hcrit Exp. Dmin,K Model rc Pseudo L.T., cslv Model Dmin,K float

10

(°) (lm) (lm) (N) (lm)

(b)

20 33 3.98 3.2E08 31

30 16 1.52 2.1E08 18 1

37 10 0.70 1.4E08 12 (a)

Particles

55 3 0.14 3.4E09 4

don’t float

0.1

0 15 30 45 60 75 90

5. Discussion

Contact Angle, (o )

5.1. Flotation recovery as a function of particle size and contact angle Fig. 10. Comparison of the model based on Drelich and Miller (1992) (solid line)

with the experimental values obtained in this study (N), Crawford (1986) (D) and

The experimental results show that the ﬂotation recovery of Miettinen (2007) (x). Upper and lower limits of the Scheludko et al. (1976) model

(dotted lines) are also reported where line (a) corresponds to cslv = 2.8 1010 N and

ﬁne particles is a function of both particle contact angle (hydro-

line (b) corresponds to cslv = 5.6 1010 N. For both lines, Vt = 0.3 ms1,

phobicity) and size. More precisely, the recovery increases with clv = 71.6 mN/m and Dq = 1650 kg/m3.

an increase in contact angle and decreases with a decrease in

particle size, in agreement with previous studies (Crawford and ﬁne Sigma particles, aggregation may also have contributed to the

Ralston, 1988). sinking of particles due to gravity, at higher surface tension values.

The increasing recovery with increasing contact angle, or parti- This may have magniﬁed the apparent contact angle heterogeneity.

cle hydrophobicity (Fig. 5), can be explained by the fact that the With respect to particle size heterogeneity, the greater average

attachment efﬁciency is increased. Kinetically, for successful bub- particle size of the concentrate with respect to the feed and tailings

ble–particle attachment to occur, the induction time (total time (Fig. 9) is because larger particles have a lower critical contact an-

needed for the thinning and rupturing of the thin liquid ﬁlm sepa- gle of ﬂotation (and possibly higher contact angle) than smaller

rating particle from bubble) must be shorter than the time it takes particles in the same feed sample.

a particle to slide on the bubble surface, also called the sliding The existence of a non-ﬂoating component, even in a narrow

time. Increasing surface hydrophobicity results in a more rapid size/contact angle class of particles, can be explained in terms of

rupture of the intervening liquid ﬁlm between bubble and particle heterogeneity of both contact angle and particle size as well as

(Hewitt et al., 1993), i.e. shorter induction time. From a thermody- the existence of a critical contact angle. A qualitative description

namic perspective, as particle hydrophobicity increases, the inter- of the phenomenon can be given assuming a statistical distribution

action potential energy between the particle and the bubble of contact angles in a class of particles around a nominal value. In

becomes more attractive thus enhancing the attachment efﬁciency this hypothesis (Fig. 11), the proportion of particles with contact

and ultimately ﬂotation recovery. angle above the critical value, hcrit, is equal to the maximum recov-

Further, ﬁne particles in this work ﬂoated at a lower rate than ery Rmax in the ﬂotation test (it is assumed that the total ﬂotation

coarser particles having similar contact angle values (Fig. 5 and time is long enough to ensure complete recovery of the ﬂoatable

Table 1), pointing towards the existence of a critical contact angle fraction). Inversely, 100 Rmax is the fraction remaining in the ﬂo-

(hcrit), which is particle size dependent (Fig. 7). This becomes espe- tation cell at long ﬂotation times. For the same particle size range,

cially important in sulphide mineral systems where ﬁne particles and therefore the same critical contact angle, hcrit, the proportion of

are believed not to ﬂoat well because they may have lower contact recovered particles (Rmax) increases with the increase in contact

angle due to surface oxidation compared to relatively coarser par- angle. This is described in Fig. 11, in which the different maximum

ticles, even though hydrophobised under the same conditions. recovery for the 77° and 58° contact angle samples is ascribed to

the different mass of particles below the critical contact angle for

ﬂotation in the two samples.

5.2. Heterogeneity of contact angle and particle size

cles, the maximum contact angle of the tailings was found to be

lower than the maximum contact angle of the feed (Table 2), sug-

gesting heterogeneity in the feed sample. Further, the contact angle

100 -Rmax

of tailings was very close to the previously determined critical va-

lue, giving some conﬁdence to the latter. The fact that the contact

angles of the tailings are slightly above the critical contact angle

suggest the presence of a small amount of weakly hydrophobic par- 58o

ticles in the tailings possibly for reasons related to rate processes.

100 -Rmax

Further indication of heterogeneity of contact angle was appar-

ent in the trends observed for the ﬁlm ﬂotation experiments, which

also suggest a spread of contact angle values within a sample

(Fig. 8). For very high contact angle particles there is a very narrow

surface tension range over which particles change from zero wet-

ting to complete wetting. As the hydrophobicity of the particles de-

creases, i.e. at low contact angle (e.g. Sigma quartz with contact Contact Angle, ( o )

angle of 51°), the transition gradient becomes shallower and the

Fig. 11. Relationship between critical contact angle for ﬂotation and Rmax for

majority of particles are wet even with water (surface tension particles of contact angle 58° and 77°, assuming statistical distribution of contact

72.8 mN/m). This indicates that the particles are not homogeneous angles in the sample. It is assumed that particles with contact angle below hcrit do

with respect to contact angle (Fuerstenau et al., 1991). For the very not ﬂoat.

D. Chipfunhu et al. / Minerals Engineering 24 (2011) 50–57 57

5.3. Limits for ﬁne particles ﬂotation previous limits in Crawford (1986), down to values below approx-

imately 2 lm, bridging the existing gap in the literature.

This study also provides insights on the limits for ﬁne particles

ﬂotation. The results presented support the hypothesis (Scheludko

Acknowledgements

et al., 1976) that ﬁne particle ﬂoatability is limited by the existence

of an energy barrier which is linked to the line tension. The mod-

The authors would like to acknowledge the sponsors of the

elling procedure presented in this work is based on the pseudo-line

AMIRA International P260E Project and the Australian Research

tension values proposed by Drelich and Miller (1992) and linking

Council (ARC) for the ﬁnancial support to this study. D.C. thanks

the line tension to particle contact angle and critical radius of

the Ian Wark Research Institute and AMIRA for his scholarship

wetting.

support.

There is good agreement (Fig. 10) between the experimental data

and predictions obtained using the model. On the contrary, calcula-

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