Mineral Processing and Extractive Metallurgy Review

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The depressing effect of clay minerals on the

floatability of chalcopyrite

Lina Uribe, Leopoldo Gutierrez & Oscar Jerez

To cite this article: Lina Uribe, Leopoldo Gutierrez & Oscar Jerez (2016): The depressing
effect of clay minerals on the floatability of chalcopyrite, Mineral Processing and Extractive
Metallurgy Review, DOI: 10.1080/08827508.2016.1168419

To link to this article: http://dx.doi.org/10.1080/08827508.2016.1168419

Accepted author version posted online: 23

Mar 2016.

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Download by: [Library Services City University London] Date: 23 March 2016, At: 16:58
 The depressing effect of clay minerals on the
floatability of chalcopyrite
Lina Uribe a, Leopoldo Gutierrez a,*, and Oscar Jerez b
a
Department of Metallurgical Engineering, Universidad de Concepcion, Edmundo Larenas 285,

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Concepcion, Chile
b
Institute for Applied Economic Geology (GEA), Universidad de Concepcion, Casilla 160-C,
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Concepción, Chile
*
Corresponding author: Tel. 56-41-2204956; fax: 56-41-2243418; lgutierrezb@udec.cl

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ABSTRACT

an
In this work, the depressing effect of clay minerals on the floatability of chalcopyrite using PAX

as collector was assessed through induction time and settling-turbidity measurements. The data
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obtained using these two techniques were correlated with the results of micro-flotation tests

carried out to study the effect of kaolinite and smectite particles on the floatability of
ed

chalcopyrite at pH 9, and 10. The results indicate that these techniques can be confidently used to

examine interactions between clay minerals and chalcopyrite, and their possible consequences on
pt

the flotation process. In particular, the use of settling-turbidity measurements to evaluate slime
ce

coating seems to be a useful technique that could be applied to study heterocoagulation in other

mineral systems. It was found that the depressing effect of clay minerals was stronger at pH 10
Ac

which was correlated to a possible effect of Ca2+ from lime on the process of coagulation

between clay minerals and chalcopyrite. Coating of bubbles with clays was detected in this work

by visual observations and it is proposed as a mechanism that might explain the depressing effect

1
 of clays on the floatability of chalcopyrite. Further research is needed to propose a mechanism

that explains this phenomenon.

Keywords: flotation, chalcopyrite, clay minerals, induction time, slime coating

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Introduction

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Processing of low grade ores rich in problematic species such as phyllosilicates has become more

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common in the copper mining industry, and represents one of the main challenges today in the

field of mineral processing. In particular, clay minerals are frequently found in copper ores in

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high concentrations (Kelm et al., 2013; Zhao and Peng, 2012). One of the most important

characteristic of clay mineral particles is their anisotropic surface properties. This results in the
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surface charge that is different on the faces and edges (Johnson et al., 1998). In addition to this,

expandable clay mineral platelets usually exhibit a significant cation exchange capacity (CEC)
ed

(Lagaly and Ziesmer, 2003). Due to their complex and heterogeneous nature, and the presence of

various types of active site on their surfaces, clay mineral particles can interact and attach to
pt

particles of valuable minerals. Kaolinite and smectite (montmorillonite) are two typical clay
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minerals found in copper porphyry deposits (Kelm et al., 2013; Zhao and Peng, 2012). Kaolinite

has two different surfaces generated during particle breakage, i.e., the basal silica-like and the
Ac

alumina-like faces (Hu et al., 2005, Johnson et al., 1998; Bickmore et al., 2002; Brady et al.,

1992). The silica-like faces carry a negative charge with an iep of around 2, while the alumina-

like displays a pH dependent surface charge resulting from protonation/deprotonation of exposed

hydroxyl groups with iep values around 7.0 (Johnson et al., 1998; Hu et al., 2005; Angove et al.,

2
 1997; Williams and Williams, 1978; Ran and Melton, 1977). Montmorillonite belongs to the 2:1

layer clay minerals with a pyrophyllite type alumino-silicate structure and is part of the clay sub-

group referred to as smectites (McFarlane et al., 2005). A single montmorillonite platelet is

composed of three layers where one octahedral aluminum–oxygen layer is sandwiched between

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two tetrahedral silicon–oxygen layers (Vanerek et al., 2006; Gungor, 2000). Montmorillonite
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particles can also be modeled as laminar particles with faces and edges with the basal silica-like

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layers carrying a permanent negative charge and the edges charge depending on pH (McFarlane

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et al., 2005). Distinctive properties of sodium montmorillonite dispersions are swelling, low

critical coagulation concentrations (c K ), adsorption of counterions on the clay surface, and

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dependence of c K with the solids content (Lagaly and Ziesmer, 2003).
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Some mechanisms have been suggested to explain the adverse effect of the presence of clay

minerals on the process of flotation of copper sulfide ores, i.e., slime coatings, coating of bubbles
ed

with clay particles, high reagent consumption (reagents uptake), and changes in froth stability

and pulp rheology. The phenomenon referred to as slime coating has been proposed to be one of
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the main mechanisms that negatively affect the efficiency of froth flotation (Fornasiero and

Ralston, 2005; Peng and Zhao, 2011; Zhao and Peng, 2012; Holuszko et al., 2008; Liu et al.,
ce

2002). Slime coating consists in the deposition of colloidal clay particles on the surfaces of larger

particles of valuable minerals. Then, the presence of the colloidal particles of clay minerals on
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the surfaces of the valuable particles induces hydrophilicity and the efficiency of the flotation

process is reduced. The magnitude of slime coating depends on the difference in the surface

charge of the clay and valuable particles (as indicated by the DLVO theory).

3
 Some methods to assess slime coating were previously proposed. For example, Liu et al. (2002)

developed a technique to investigate the bitumen-clay interactions through measurements of zeta

potential distributions. This technique was based on the fact that for a single component

suspension (e.g., clay or bitumen) the zeta potential distribution should display a single modal

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pattern, but when the two components are in suspension the distribution will show either one or
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two distribution peaks, depending whether the components interact with each other or not,

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respectively. This interesting method is carried out under mixing/hydrodynamic conditions that

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are more similar to those found in the real flotation process. However, some studies showed that

its application to the study of heterocoagulation between clay minerals and chalcopyrite is

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difficult as the zeta potential distributions of these individual minerals overlaps (Forbes, 2014).

Other researchers have used contact angle measurements to assess the effect of slime coating on
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coal wettability (Jowett et al., 1956) and AFM (Liu et al., 2003), but they need to be carried out

under very quiescent conditions which may not represent the real situation observed in the
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flotation process.
pt

In this work, the negative effect of clay minerals on the floatability of chalcopyrite using PAX as

collector is assessed by using induction time and settling-turbidity measurements to examine

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heterocoagulation between clay minerals and chalcopyrite. The results obtained using these two

techniques are correlated with micro-flotation data. In particular, the effect of kaolinite and
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smectite particles on the floatability of chalcopyrite at pH 9, and 10 are presented.

4
 Materials and methods

Samples and reagents

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Samples of kaolinite and smectite were provided by the Clay Minerals Society Source clays.

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These samples were analyzed by XRD using a Bruker D4-Endeavor operated with Ni-filtered Cu
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radiation (Chipera and Bish, 2001). Figure 1 and Table 1 show the XRD spectra and data of the

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quantitative analysis respectively. Table 1 also summarizes the results of cation exchange

capacity CEC and Brunauer–Emmett–Teller BET (Kelm and Helle, 2005) surface area for both

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types of clays. The cation exchange capacities (CEC) were determined using ammonium acetate

at pH 7 as described by Skinner et al. (2001). As it was expected the CEC value of the smectite
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sample was significantly higher than that of kaolinite. Besides, the smectite sample contained

around 75% of montmorillonite which was the main component of this clay sample.
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Figure 2 shows SEM (Jeol JSM-6380) pictures of the clay minerals samples used in this work.
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From the picture of kaolinite (Figure 2-A), it can be seen that the particle size of this sample was

finer than 4-5 microns with a rather random textural arrangement. It has to be noted that these 4-
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5 micron clay particles are stacks of sheets 7 angstrom thick (Mitchell, 1993, pp 27), so when

these particles enter into an aqueous medium, they can detach from another, and depending on
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solution and shearing, delamination of these particles into smaller stacks or even individual

sheets may occur. This textural pattern can be related to shearing on the weak bonds existing

between the interlayers 1:1 dominated by Van der Waals forces (Mitchell, 1993) which enhances

the delamination process (Nelson and Miller, 1992), and as a result a rather random micro-

5
 structure in aqueous media is generated. The electrical neutrality of the unit layers of the

particles of kaolinite also defines the low CEC of this type of clay mineral. The situation is

different in the case of the smectite sample (Figure 2-B). In this case the textural arrangement is

more consistent and homogeneous than in the case of the kaolinite sample. This behavior can be

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explained by the higher stability of the smectite lattice and the larger charge differences existing
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between the sheets. In aqueous media the type and concentration of cations, diffusion

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phenomena, and pH modify the balance of electrical charges existing between the sheets which

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results in expansion or swelling of the clay mineral particles (Mitchell, 1993).

The study was carried out using a highly pure sample of chalcopyrite which was prepared from
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mineralized rock specimens obtained from a mine located in northern Chile. The sample used in
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the experiments was prepared by hand-grinding pure crystals of this mineral in a mortar and

pestle ceramic grinder. Further purification was carried out using a magnetic separator to remove
ed

some magnetic impurities. Table 2 shows the chemical and XRD mineralogical composition of

the sample. It can be seen that the chalcopyrite content was 97.1 % with minor contents of pyrite,
pt

molybdenite and quartz. The chalcopyrite sample was then washed with acetone and distilled

water in order to remove some organic contaminants that could have potentially been
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incorporated to the sample during the process of handling and preparation. Additionally, in order

to keep oxidation at minimum, the samples were stored in a freezer in sealed plastic bags
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previously blown with nitrogen, at a temperature of about 1 °C (Ekmekci and Demirel, 1997;

Zhang et al., 1997; Ansari and Pawlik, 2007).

6
 It is important to point out that sample preparation of sulfide minerals strongly depend on the

grinding conditions, which is definitely important and to a large extent determine the flotation

properties of sulfides (Heyes and Trahar, 1979). These conditions also depend on the type of

grinding media and whether they are made of iron, steel, stainless steel or ceramic (Bruckard et

t
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al., 2011). It is because of this reason that the use of freshly ground ore samples of metal sulfides
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has been recommended when doing research on flotation of these types of minerals (Wark,

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1938). In this work the objective was to study the effect of clay minerals on the floatability of

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pure chalcopyrite, and it was important to use samples prepared under the same conditions. To

produce identical 1 gram samples of chalcopyrite for the micro-flotation is something very

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difficult by doing wet grinding, and that is why dry crushing/grinding, and the samples storage

under nitrogen was a reasonable choice. However, the authors recognize that the surface
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properties of chalcopyrite will change if grinding is carried out in air or water (Todd et al., 2003),

and the effect of surface oxidation on the interaction of chalcopyrite with clay minerals particles
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is something that deserves further investigation.

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Particle size analyses were done in a Sympatec's HELOS-Rodos laser diffraction system.

Figure 3 shows the particle size distributions of samples of kaolinite, smectite, and chalcopyrite.
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The measured mean particle sizes for ground kaolinite and smectite were 4.4 and 3.9 microns

respectively with top size values of 21 microns for kaolinite and 19 microns for the smectite
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sample. Chalcopyrite sample was in the size range 40 to 210 microns with a mean particle size of

113 microns.

7
 Potassium amyl xanthate (PAX), and methyl isobutyl carbinol (MIBC) were used as

collector and frother respectively. Distilled water of electrical conductivity of 21.5 µS/cm was

used in all the experiments. pH was adjusted using lime in all the tests.

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Procedures

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Micro-flotation

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The floatability of chalcopyrite was evaluated through micro-flotation tests that were carried out

in a 150 mL Patridge and Smith glass cell using nitrogen (N 2 ) at a flowrate of 20 mL/min. The

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flotation feed was prepared mixing 1 gram of chalcopyrite with different amounts of fine

particles of kaolinite/smectite, i.e., 0, 45, 60, 75, and 150 mg of clay. Considering that the
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volume of the micro-flotation cell was 150 mL, the masses of clay minerals used in these

experiments corresponded to concentrations of 0, 200, 400, 500, and 1,000 mg/L. The flotation
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feed was then mixed with 100 mL of a 0.01 M sodium chloride (NaCl) background solution, and

conditioned at the required pH for 3 minutes. These experiments were carried out at values of pH
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of 9 and 10 in order to match typical pH values found in the process of rougher flotation of
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copper ores. After 3 minutes of conditioning, PAX and MIBC were added at concentrations of

40 and 25 ppm respectively (based on the 150 mL of the micro-flotation cell), and conditioned
Ac

for 5 more minutes at the previously established value of pH. Additional solution was then added

to complete the 150 mL needed in the micro-flotation glass cell. Finally, the gas valve was

opened to start the process of flotation which was carried out for 2 minutes, scraping the froth off

every 10 seconds. The pulp level in the micro-flotation cell was kept constant by adding a

8
 background solution prepared at the same composition and pH of the original solution.

Concentrates and tailings were then sieved using a 400 mesh sieve to remove the particles of clay

minerals, and to measure the amount of sample chalcopyrite existing in each of the streams.

Finally, the samples were dried in an oven set at 105°C for 5 hours and the solids flotation yield

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was calculated dividing the mass of chalcopyrite in the concentrate by the mass of chalcopyrite
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in concentrate plus tailings. All the tests were conducted in triplicates thus the results presented

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in this paper are average values.

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Induction time measurements

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Induction time measurements were conducted using the procedure described by Castro et al.

(2014) and the induction time meter built by University of Alberta. According to this procedure a
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fresh bubble held on a capillary is pushed downward through a solution so that it is kept in

contact with a bed of particles for a measured and controlled contact time (Figure 4, stages 1 and
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2). Then, the bubble is lifted upwards to its initial position and observed through a microscope in

order to determine whether attachment occurred during the contact time or not (Figure 4, stage
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3). This process is repeated 10 times at different positions on the particles bed and the
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number/percentage of successful contacts is determined. Then, the contact time is changed to

different values and the procedure is repeated again in each case. The final result of the test is a
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plot of percentages of successful contacts (N sc ) versus the measured contact time (t c ). In this

work, the induction time was obtained by determining the contact time at which 50 % of the

contacts were successful. The experimental data were fitted using Equation 1.

9
 N sc = k1 (1 − Exp(− k 2tc K3 )) (1)

Where k 1 in %, k 2 and k 3 (both dimensionless) are fitting constants.

The beds of particles were prepared by mixing 3 grams of chalcopyrite with 30 mL of a 0.01 M

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NaCl background solution containing 40 ppm of PAX. Immediately after, fine particles of
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kaolinite/smectite were added at concentrations of 0, 300, 400, 500, and 1,000 mg of clay per

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liter of background solution. Then, the pH was adjusted to the required value (pH 9 and 10) and

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the slurry was conditioned for 12 minutes, after which it was transferred to a 15 mL cell in order

to start the induction time measurements. No frother was added in these experiments and air was

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used to generate the bubbles. All these experiments were conducted in duplicates thus the results

presented in this paper are average values.

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Settling-turbidity tests to measure heterocoagulation between clay minerals and
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chalcopyrite
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In this work, a method is proposed to assess the extent of the attachment between clay minerals

and particles of chalcopyrite. The method is described in Figure 5, and it is based on the
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assumption that if heterocoagulation between chalcopyrite and clay particles takes place during

the mixing period, and then the resulting suspension is left to settle in a cylinder for a given time,
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coarse particles of chalcopyrite (p80 around 100 microns) will settle and carry clay minerals

attached to them. As a result, it is expected that for a suspension of clay minerals and

chalcopyrite, turbidity of the upper part of the suspension, T 2 in Figure 5, will decrease in

comparison with the suspension that is prepared using only clay minerals particles, T 1 in Figure

10
 5. Then, the extent of slime coating can be quantified by measuring T 1 -T 2 . If this number is near

zero then it could be concluded that interactions between clay minerals and chalcopyrite are

negligible.

In this work the preparation of suspensions was carried out by mixing 0.8 grams of chalcopyrite

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and 120 mg of kaolinite/smectite, with 120 mL of a 0.01 M NaCl background solution
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containing 40 ppm of PAX and 25 ppm of MIBC. It has to be noted that in these tests the

concentration of clay mineral particles was 1000 mg of clay per liter of solution, which is the

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maximum clay concentration tested in the micro-flotation tests. After this, the suspensions were

conditioned for 3 minutes under controlled mixing conditions which was ensured by using the
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same magnetic stirrer and plate for all the tests. Then, suspensions were placed in a 100 mL
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graduated cylinder where they were left to settle for 5 minutes. After that, a 10 mL aliquot was

withdrawn using a syringe from a section positioned at 2/3 the height of the cylinder and tested
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for turbidity. Turbidity measurements were performed using a portable turbidimeter Orbeco

TB200 whose maximum reading was 999 NTU. In order to correlate this information with the
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floatability data, all these tests were performed at the same conditions used during the micro-

flotation experiments.
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11
 Results and discussion

Micro-flotation

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Figure 6 shows results of micro-flotation experiments performed with chalcopyrite in the

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presence of different concentrations of kaolinite and smectite, respectively. It can be seen that the
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presence of kaolinite and smectite negatively affects the recovery of chalcopyrite at both pH

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values. Clay minerals can depress chalcopyrite through slime coating phenomena which involves

coagulation of clay on chalcopyrite. All these mechanisms are affected by the surface properties

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of chalcopyrite, clays, and bubbles. All of them being negatively charged at pH levels above 9

(Leja, 1982; Healy, 1976; Johnson et al., 1998; McFarlane et al., 2005; Elmahdy et al., 2008;
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Laskowski et al., 1989). It is known that Ca2+ and Mg2+ ions coagulate clay suspensions

(O´Gorman and Kitchener, 1974; Wright and Kitchener, 1976; Sworska et al., 2000) and in the
ed

system containing chalcopyrite particles it may be responsible for the coagulation of the clay

particles onto chalcopyrite. Figure 6 shows that this mechanism is possible. This explanation is
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consistent with the fact that the observed depressing effect of clays on chalcopyrite was slightly
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stronger at pH 10 where the concentration of calcium ions is higher since lime was used to adjust

pH. It was shown that the presence of calcium enhanced the attachment of montmorillonite to
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bitumen leading to low bitumen recoveries (Liu et al., 2002; Liu et al., 2004). It was also

reported that the presence of Ca2+ ions in solution induces heterocoagulation between silica and

molybdenite (Tabares et al., 2006; Raghavan and Hsu, 1984). Figure 6 shows that recovery of

chalcopyrite in the absence of clays is slightly lower at pH 10, but the difference falls into the

12
 experimental error. It has to be noted that although Table 1 shows that kaolinite and smectite

samples display different CEC and BET values, the extent of the depressing effect of both clays

on the floatability of chalcopyrite is similar. The study of the correlation between the structural

properties of clays and flotation of sulfide minerals is something that deserves further studies.

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As was explained in the procedures, the chalcopyrite sample used in this work was prepared by
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manual crushing/grinding and protected from oxidation under nitrogen. It is well known that the

surface properties of sulfide minerals change whether grinding is carried out using wet or dry

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grinding. During wet grinding the response of sulfide minerals can be affected by the presence of

oxyhydroxide species dissolved from the mineral or grinding media, and the formation of
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sulphoxy species such as SO, SO 2 , SO 3 and SO 4 (Bruckard et al., 2011; Owusu et al., 2014).
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Todd et al. (2003) studied the type of species that are formed on the surface of chalcopyrite after

oxidation under atmospheric and aqueous conditions. They found that in aqueous solutions at
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high pH iron oxyhydroxide species similar to goethite are formed on the surface of chalcopyrite

and the soluble copper oxidation products are leached and dissolved in water. On the other hand
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when chalcopyrite is subjected to air oxidation, iron (III) oxyhydroxide species and copper

oxidation products such as sulfates are present in contrast to the situation observed in aqueous
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solutions. It is proposed by Todd et al. (2003) that a complex oxidized surface consisting of a

mixture of CuO, FeOOH, copper and/or ferric iron sulfates, and possibly Cu 2 O and/or Cu 2 S
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surface species may be formed. All the differences in the behavior of the surface properties of

chalcopyrite observed when it is ground using wet and dry procedures can affect the interactions

between clay mineral particles and chalcopyrite, and it is a subject that needs further

investigation. The effect of surface oxidation on the interactions between clay minerals and

13
 chalcopyrite is out of the scope of this paper and all the results presented in this work were

obtained using dry ground samples.

Induction time

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The results of the induction time measurements are shown in Figure 7. It can be seen that without
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clay minerals (Figure 7(a)), the induction time values increase from 45.4 to 68.3 ms as pH is

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increased from 9.0 to 10.0. Figure 7(b) also shows the effect of clay minerals on the induction

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time values as a function of the concentration of kaolinite, and smectite at pH 9, and 10. It has to

be noted that the error bars in this figure represent the standard deviation of two induction time
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measurements performed at the same conditions (duplicates). The figure indicates that at a given

pH the induction time values increase with the additions of higher amounts of kaolinite and
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smectite. The fact that the induction time values increase in the presence of clay mineral particles

may be associated with a phenomena of heterocoagulation which reduces the degree of

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hydrophobicity of chalcopyrite particles. As a result, higher induction time values should be

associated to lower recoveries in the micro-flotation tests, which is exactly what can be observed
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in Figure 6 that indicates a loss of chalcopyrite floatability as clay minerals particles are added to
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the suspension. It is also interesting to examine the relationship between pH and the effect of

clay minerals on the induction times presented in Figure 7(b). The increase of the induction time
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values as a result of clay additions is more pronounced at pH 10 which is in good agreement with

the micro-flotation results presented in Figures 6 that indicate that the depressing effect of fine

particles of clays was stronger at higher concentrations of Ca2+ ions.

14
 Some efforts were also made in this work to look for evidence of the occurrence of the coating of

air bubbles with fine clays. To achieve this objective, pictures of the bubbles obtained in the

presence of clays were taken after the induction time tests which were afterwards studied in

order to see if fine particles actually attached to the bubbles or not. Figure 8 shows two examples

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of these pictures. The images indicate that fine clay mineral particles coat the bubbles in both
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cases. This coating is expected to hinder the process of bubble-particle adhesion, leading to

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higher induction times and lower recoveries. This experimental observation indicates that the

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mechanism of coating of bubbles by fine clays has to be considered as a possible cause to

explain the depressing effect of fine clay particles on the floatability of copper sulfides. The

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interactions between clays and bubbles may be related to some degree of hydrophobicity of the

clay mineral particles which was previously reported (Sadda et al., 1995). However, a fully
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explanation of this phenomenon is still needed.
ed

Settling-turbidity tests to measure heterocoagulation between clay minerals and

chalcopyrite
pt

Heterocoagulation between clay minerals and chalcopyrite was assessed in this work through
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settling-turbidity tests. Figure 9 shows the results of the tests at different pH values. It can be

seen that turbidity values were lower in the presence of chalcopyrite which can be considered as
Ac

an evidence of the occurrence of a heterocoagulation between clays and chalcopyrite. It is also

interesting to note that the differences of turbidity between suspensions prepared with and

without chalcopyrite were larger at pH 10, which indicates that slime coating increased with

increasing Ca2+ concentration (pH). These results are in good correlation with the reduction of

15
 chalcopyrite floatability (Figure 6) and increase of induction time values (Figure 7) achieved in

the presence of clay minerals. The settling turbidity measurements indicate that the slime coating

phenomenon is a mechanism that could explain the depressing effect of clay minerals on the

floatability of chalcopyrite.

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Additional turbidity tests were carried out with coarse quartz particles (-210 + 20 microns) and
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kaolinite and the results are plotted in Figure 9. It can be seen that when quartz was used instead

of chalcopyrite, the turbidity of the suspensions of kaolinite with and without quartz was the

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same which indicates that no heterocoagulation took place. These results indicate that only fine

clay particles can attach to larger particles of chalcopyrite which reveals the distinctive
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characteristics of these anisotropic minerals.
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Conclusions
ed

Induction time and settling-turbidity measurements were used to assess the depressing effect of

clay minerals on the floatability of chalcopyrite. The analysis of the experimental results
pt

obtained using these techniques, and the observed relationships with the micro-flotation data
ce

indicate that both methods can be confidently used to study the interactions of clay minerals and

chalcopyrite and the possible consequences on the process of flotation. In particular the use of
Ac

settling-turbidity measurements to evaluate slime coating seems to be a useful technique that

could be tested to study heterocoagulation in other mineral systems. The analysis of the results

obtained in this work confirms that slime coating is an important mechanism of depression of

chalcopyrite. The experimental data show that the depressing effect of clay minerals increases as

16
 the pH changes from 9 to 10. It is proposed that Ca2+ (lime) is responsible for heterocoagulation,

and as a result the hydrophobicity of the chalcopyrite particles drops which results in lower

recoveries. This effect suggests that the presence of ions in solution is a variable that has to be

taken into account to explain the interactions between clay minerals and chalcopyrite. The

t
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phenomenon of coating of bubbles with clays was confirmed in this work by image analysis and
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it is proposed as a mechanism that might explain the depressing effect of clays on the floatability

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of chalcopyrite.

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Acknowledgements

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Support from the National Fund for Scientific and Technological Development

(FONDECYT) of Chile under the project initiation into research no. 11140184, Centro CRHIAM
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Proyecto Conicyt Fondap no.15130015, and Universidad de Concepcion under Project VRID no.

214.095.089-1.0 is gratefully acknowledged. Lina Uribe wants to acknowledge the support from
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Conicyt Scholarship for Doctoral Studies in Chile 2015 (Folio postulación 21150151). We want

to thank Dr. Janusz Laskowski for his valuable comments that allowed us to improve this
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manuscript. We also want to thank Mr. Cristian Melipichun and Mr. Roberto Vazquez for their
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valuable contributions during the experimental program.

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17
 References

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Figure 1. XRD diffractograms for samples of kaolinite (A) and smectite (B).

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Figure 2. SEM pictures of the clay samples used in the study, kaolinite (A), and smectite

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Figure 3. Particle size distributions of samples of kaolinite, smectite, and chalcopyrite.

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Figure 4. Schematic of method to determine induction time.

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Figure 5. Schematic of the method to assess slime coating.

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 Figure 6. Results of micro-flotation of chalcopyrite under the presence of different

additions of kaolinite and smectite. Error bars represent the standard deviation of the

measurements.

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 Figure 7. Effect of pH on induction time in the absence of clay minerals (A). Effect of clay

minerals on the induction time values as a function of concentration of kaolinite and

smectite at different pH values (B). Error bars represent the standard deviation of the

measurements.

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 Figure 8. Images of the air bubbles that were captured after the process of contact between

bubbles and chalcopyrite particles, and in the presence of clay minerals in suspension. (A)

t c = 500 ms, PAX 40 ppm, pH=10.0. (B) t c = 1000 ms, PAX 40 ppm, pH=10.0.

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 Figure 9. Turbidity measurements of clay minerals in the absence and presence of

chalcopyrite, and at different pH values.

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 Table 1. Mineralogical composition of clay samples.

Quantitative XRD mineralogy CEC, BET

Sample
cmol/kg , m2/g

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Kaolinite 96% kaolinite, 3% anatase, 1% other traces 0.7 180

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Smectite 75% montmorillonite, 16% feldspar, 8% quartz, 1% other traces 100 117

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 Table 2. Chemical and XRD mineralogical composition of chalcopyrite sample used in the

study.

Chalcopyrite sample

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XRD mineralogical composition
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CuFeS 2 % 97.1

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FeS 2
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MoS 2 % 0.00

Quartz % 1.1
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Chemical analysis
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Cu % 34.2
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Fe % 30.2

S % 35.5

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Mo

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%

35
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0.0

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