Proceedings of 2006 China-Mexico Workshop

on Minerals Particle Technology

San Luis Potos, Mexico

SURFACE PROPERTIES AND FLOATABILITY OF MOLYBDENITE

J. Ornelas Tabares1, I. Madrid Ortega2, J. L. Reyes Bahena2, A. A. Snchez Lpez2,
D. Valdez Prez3, A. Lpez Valdivieso2.
1

Depto. de Explotacin de Minas y Metalurgia, Facultad de Ingeniera, Universidad Nacional

Autnoma de Mxico (U.N.A.M.), Edif. Principal s/n, Deleg. Coyoacan, C.P. 04510, Mxico,
D.F.
2
Instituto de Metalurgia, Universidad Autnoma de San Luis Potos, Av. Sierra Leona 550, San
Luis Potos, C. P. 78210, Mxico
3
Depto. de Fsica. Universidad Autnoma Metropolitana (U.A.M.) Unidad Ixtapalapa, San
Rafael Atlixco, No. 186, Col. Vicentina C.P. 09340, Mxico, D.F.
Corresponding author: E-mail: alopez@uaslp.mx

Abstract
The properties of edges and faces of molybdenite particles in aqueous solutions have been studied
aiming at to determining their relationship to the floatability of molybdenite in the flotation circuit of
copper-molybdenum ores. Atomic force microscopy studies revealed that the faces of molybdenite
particles are heterogeneous in nature and formed by microcrystals of MoS2 having microedges and
microfaces. This heterogeneity of the faces leads to have both hydrophilic and hydrophobic areas on the
faces. The fraction of these two distinct areas on the face has been estimated using contact angle
measurements. The heterogeneity of the face is responsible for the pH effect on molybdenite flotation and
the low floatability of molybdenite fine particles. In addition, it causes adsorption of calcium ions on the
faces of molybdenite particles decreasing the floatability of molybdenite.

1. Introduction
Molybdenite (MoS2) particles consist of S-Mo-S crystal like sandwiches that are bonded to
each other by van de Waals forces. Within these crystals, S and Mo atoms are held together by
covalent bonds. The crystalline structure of MoS2, is presented in Fig. 1. Due to this structural
characteristic, the particles of MoS2 present two different types of surfaces, namely a surface that
is originated by rupture of van der Waals interactions, named as "face", and a surface that is
generated by rupture of covalent Mo-S bonds, named as "edge".
The rupture of molybdenite crystals along the faces generates non-polar surfaces, which
are characterized by a low energy. This allows molybdenite to exhibit an inherent
hydrophobicity, which is the basis of the separation by flotation of molybdenite from other ore
constituents in the mineral industry. The low surface energy of the face makes molybdenite to be
alike with liquids of low surface tension, such as hydrocarbons. These organic reagents are
commonly used to enhance the hydrophobicity of molybdenite in flotation. The wettability of the

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2006 China-Mexico Workshop on Minerals Particle Technology

faces has been studied by Kelebek (1988). He reported the critical surface tension of wetting of
the faces of molybdenite to be 29 mN/m.

Hydrophobic faces

Fig. 1.

Hydrophilic edges

Crystalline structure of molybdenite where hydrophobic faces and hydrophilic edges are shown.

The studies of Kelebek (1988), on the spreading of methanol solutions and syntex on the
face of molybdenite crystals, indicate a contact angle of the face of 80. This is equal to an energy
of adhesion of water of 84 ergs/cm2. This value is low in relation to the energy of cohesion of
water, which is about 146 ergs/cm2. Accordingly, the face presents hydrophobic characteristics.
Polar surfaces are produced when the molybdenite crystal is broken along the edges. These
polar surfaces are chemically active with water with the formation of thiomolybdates as proposed
by Fuerstenau and Chander, in 1972. These researchers propose that the species HMoO4- and
MoO42- determine the electric charge at the edges making them to have hydrophilic
characteristics.
The heterogeneous character of the molybdenite surface particles has a particular
importance in flotation. The face/edge relationship, which depends on the particle size,
determines the natural floatability of this mineral. For fine size particles this face/edge
relationship is low; as consequence, their floatability is low, in contrast to coarse particles. It has
been observed in a primary flotation bank that about 40 to 50% of the molybdenite in a coppermolybdenite porphyry type ore is lost. Hence, it is a great challenge to improve the recovery of
molybdenite.
In industrial operations, it is more common to establish both the grind size and a flotation
scheme for copper minerals rather than molybdenite minerals in porphyry ore type. Castro and
Mayta (1994) addressed that such operating conditions in industrial plants are not necessarily
adequate for optimum treatment of molybdenite which depends on several factors as the amount
of molybdenite oxide on the mineral surface, the association with siliceous gangue minerals,
particle size distribution, amount of lime used and other chemicals used to float copper minerals.
The effect of calcium ions on the molybdenite floatability has received a special interest due
to the presence of a high concentration of these ions in the flotation circuits of coppermolybdenite porphyry ore, where the molybdenite is recovered. In such flotation circuits, the pH
of the pulp is in the range of 10-11 which is adjusted with lime. The effects of the ions calcium

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117

are controversial; some authors indicate that the calcium ions promote the molybdenite
floatability while others report the opposite (Sutulov, 1979).
This work presents the results of an investigation that is carried out on the physicalchemical properties of the molybdenite/aqueous solution interface and its relationship with the
floatability of the molybdenite mineral, as well as the effect of the calcium ions on this interface
behavior and the floatability of molybdenite.
2. Experimental
The properties of the molybdenite/aqueous solution interface have been studied through
electrokinetic measurements and contact angle studies using natural crystals of molybdenite of
the La Caridad Mine, located in Sonora, Mxico. For the electrokinetic studies, the crystals have
been ground first to -625 mesh and then finer using an Agata planetary mill. The measurements
of contact angle have been carried out with molybdenite crystals. These crystals were placed on
an acrylic plaque, in such a way that measurements of contact angle were carried out on both the
edges and the faces of the crystal. These measurements were carried out in an apparatus of RamHart that has coupled a video camera that captured the image of the air bubble on the surface of
the crystal to a PC. The contact angle was calculated with the software Ram-Hart in which is
introduced the height and diameter of the bubble. It was studied the effect of the pH and the
concentration of calcium ions on the contact angle.
Also, studies of the morphology of the face of molybdenite crystals were carried out
through atomic force microscopy (AFM) in a Quesant Qscope 250. For these studies,
molybdenite crystals were used and placed on a mica plaque.
The floatability studies were carried out on different sizes of molybdenite particles such as 150+75, -75+45, -45+38 m. These molybdenite particles were obtained from a concentrate of
La Caridad concentrator plant. The mineral was previously washed with CS2 to remove any oil
excess and frother used during the flotation process. Thus, the washed concentrate was floated
and washed with CS2 again. It was possible to obtain a product with more than 95% MoS2. The
floatability studies were performed with 1 gram of molybdenite mineral in a Hallimond tube.
Prior to the microflotation test the mineral was conditioned to the desired pH for 30 min in the
absence and presence of calcium ions. The flotation in the Hallimond tube was carried out for 1
minute using nitrogen gas at a flow rate of 30 ml/min.
In this work, all aqueous solutions were prepared with deionized water. All inorganic salts
used were analytical grade reagents.
3. Results an Discussion
Contact angle studies performed on the molybdenite have reported that the face is totally
hydrophobic; as a result of the break of van der Waals bond among atoms of sulfur in the
structure S-Mo-S S-Mo-S. For these studies, natural crystals of molybdenite have been used,
obtaining a contact angle of 80 for the face (Fuerstenau and Chander, 1972; Kelebek, 1988). In
this work, the contact angle was determined in faces as well as in edges of molybdenite particles
in function of the pH. Fig. 2 presents the values of contact angle of the crystal face in presence of
0.001 and 0.015 moles/l of Ca2+, as calcium chloride.
The edge of the molybdenite particles doesn't present contact angle, indicating that it is
hydrophilic, just as it has been reported in previous studies. The angle of contact of the face is 61
to pH 5 which decreases slightly as the pH increases. It must be addressed that the measured
contact angle is smaller that the one determined by Fuerstenau and Chander (1972) and Kelebek

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2006 China-Mexico Workshop on Minerals Particle Technology

(1988). The different in values was further investigated using AFM on the faces of the
molybdenite particles. This work revealed that the face presents defects; it is very heterogeneous
and constituted by micro-crystal bands with micro-faces of an approximate size of 2 m (Fig. 3).
70

CONTACT ANGLE ( )

60
50
40
{ FACE Without CaCl2

30

FACE 0.001 M of CaCl2

20

U FACE 0.015 M of CaCl2

z EDGE Without CaCl2

10
0
0

10

12

14

pH
Fig. 2.

Contact angle of edges and faces of molybdenite particles as a function of the pH, in absence
and presence of several concentrations of calcium ions.

In these bands, the micro-crystals superimpose each others; in such a way that, the face of
the molybdenite particle is really formed by micro-faces and micro-edges. This knowledge of the
nature of the face is important since it is decisive for the explanation of studies of adsorption,
electrokinetics, floatability, etc., of molybdenite particles. It is probable that the faces of the
molybdenite crystals previously studied (Fuerstenau and Chander, 1972; Kelebek, 1988) had also
presented defects as shown in Fig. 3. Therefore, it is not possible to address that the molybdenite
face, in a copper-molybdenum mineral processing, is completely hydrophobic and only
constituted by atoms of sulfur. It has been determined, using the Cassie`s equation (Ulman,
1991), by pH 5, that the molybdenite particles studied presented faces with 62% hydrophobic and
38% hydrophilic characteristics, due to the edges of the micro-crystals. To pH 11, these values
are 52% and 48%, respectively.
A contact angle decrease of the molybdenite face as a pH function can promote a decrease
of the hydrophobicity of the crystal face due to a hydrate layer increase from the edges adjacent
to the face of the micro-crystals. This face/edge relationship originates an increase of the electric
charge in the edges. Fig. 4 showed that the zeta potential of molybdenite particles increases with
pH. In this figure, electrokinetic curves are shown as reported by several authors who differs each
others. The main reason of the different curves is due to the different face/edge relationships of
the molybdenite particles used. As observed in Fig. 4, as the face/edge relationship increases in
the particle, the magnitude of the zeta potential is smaller.

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A common characteristic in all electrokinetics curves in Figure 4 is that each value of zeta
potential as a function of pH is always negative. At low range of pH the zeta potential is low
meanwhile at alkaline pH, is very high.

Fig. 3.

AFM Images of faces of molybdenite particles used for contact angle measurements

Fuerstenau and Chander (1972) have explained that the zeta potential of molybdenite
particles is due to the generation of electric charges in the edges of the particles, since the faces
present only van der Waals forces and no electric charge at all. The molybdenite edges can
produce thiomolybdate ions as follows:
MoS x O y + H 2 O MoS x O y + n

MoS O

x y+n

+ 2H +

(1)

(2)

+ H + MoS x O y + n 2 H

n +1

These reactions explain the pH decrease of molybdenite powders dispersed in water. The
molybdate species are dissolved as HMoO4- and MoO42- as follows:
+

HMoO4 H + + MoO4
pK = 5.95
(3)
2The predominant species, under alkaline conditions, are MoO4 anions, which explains the high
negative values of zeta potential under these conditions. Thus, for the case of the particles used

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2006 China-Mexico Workshop on Minerals Particle Technology

in this study, this generation of electric charge is not only given in its edges, but also in the edges
of the micro-crystals that constitute the faces of the particles. Therefore, the contact angle is
affected as the pH increases. The contact angle decreases due to increasing of the electric charge
in the edges of MoO42- ions that originate an increase of their hydration layer.

Increase in face/edge relationship

ZETA POTENTIAL (mV)

-10
-20
-30
-40
-50
-60
-70

10

12

14

pH

Fig. 4.

Zeta potential of molybdenite particle as a function of the pH. Lpez Valdivieso (1980); z
Hoover and Malhotra (1976); { Raghavan and Hsu (1984); Chander and Fuerstenau (1974);
Madrid Ortega (2005).

Since the contact angle is affected by the electric charge in the edges of the molybdenite
particles and micro-crystals in the faces, it is expected that the floatability of the molybdenite
particle is affected in the same way. This is corroborated in Fig. 5 in which the molybdenite
floatability, with a size of -150+75 m, decreases as the pH increases. Smaller particles to this
size have a low floatability ranging pH between 2 and 12 due to a low face/edge relationship in
this particle.
As observed in Fig. 5, at high value of contact angle in alkaline pH values, the molybdenite
floatability is low as the particle size decreases. In order to explain this behavior, the interaction
energy among the nitrogen bubbles and the face and edge of the molybdenite particles is used.
The nitrogen bubble, under these pH conditions, presents a zeta potential of the order of -60 mV
(Gracia et al., 2002). According with Fig. 5, the zeta potential of the edge of the molybdenite
particle is about -60 mV. Therefore, the energy of repulsion between the nitrogen bubble and the
molybdenite, due to the electric charge in the edge and the bubble, is larger than the sum of the
energy of attraction of van der Waals and hydrophobic forces presented between the bubble and
the face of the molybdenite particle. When the particle size decreases, so does the energy
attraction for the smallest face/edge relationship; thus, the floatability of these particles is low.
In industrial flotation plants of copper-molybdenum, the pH is adjusted with lime. It has
been calculated that the dose of lime in these industrial circuits corresponds to a concentration of
about 0.015 mol/l of total calcium. Fig. 6 showed the effect of the calcium ions in the zeta
potential of molybdenite.

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FLOATABILITY (%)

80
SIZE FRACTIONS
-150+75 m
-75+45 m
-45+38 m

70
60
50
40
30
20
10
0
0

10

12

14

pH
Fig. 5.

Natural floatability of molybdenite particles by different size fractions as a function of the pH

with nitrogen bubbles.

ZETA POTENTIAL (mV)

0
-10
-20
-30
-40
-50

CaCl2 Addition
0.002 M
0.001 M
Without

-60
-70
-80
0

10

12

14

pH
Fig. 6. Molybdenite Zeta potential in absence and presence of several calcium ions concentrations

It is observed that calcium ions decrease the magnitude of the negative zeta potential of the
molybdenite. This phenomenon is associated to the formation of calcium molybdate in the edges
of the molybdenite particle (Fuerstenau and Chander, 1972; Raghavan and Hsu, 1984). The
maximum effect of the calcium ions on the zeta potential is within pH range of 11-12. It is due to
the specific adsorption of the hydroxo-complex ions of calcium, CaOH+, into the calcium
molybdate formed in the edges of the molybdenite particles. These hydroxo-complex ions of
calcium are in a high concentration within pH range of 11-12 (Fig. 7). Fuerstenau and Palmer

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2006 China-Mexico Workshop on Minerals Particle Technology

(1974) demonstrated that these hydroxo-complex calcium ions interacted specifically with the
surface of solids that contain hydroxides groups negatively charged, like in the case of the
calcium molybdate.

Fig. 7.

Distribution of species of calcium as a function of pH Diagram, showing a 10-3 mol/l total

calcium concentration.

FLOATABILITY (%)

60
MOLYBDENITE
-150+75 m
pH = 10.5

50
40
30
20
10
0
0

0.005

0.01

0.015

CaCl2 CONCENTRATION (mol/l)

Fig. 8.

The concentration effect of calcium ions on the natural molybdenite floatability.

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123

The calcium ions are adsorbed not only in the edges of the molybdenite particle, but also in
the edges of the micro-crystals that comprise the face of the particle. The adsorption of these
calcium ions decreases the contact angle in the face of the molybdenite particle as observed in
Fig. 2. When the initial concentration of calcium ions is 0.015 mol/l the contact angle decreases
close to a pH of 11 which can be a consequence of the Ca(OH)2(s) precipitation. This
precipitation occurs not only in the edges, but also in the faces of the molybdenite as
demonstrated happing in the precipitation of polyvalent cations in the surface of talc which
presents a surface constituted of edges and faces, as the molybdenite does (Fuerstenau et al.,
1988).
A decrease of the contact angle in the face of molybdenite particles due to presence of
calcium ions, indicates a decrease in the floatability of these particles as observed in Fig. 8.

4. Conclusions
The face of molybdenite particles is constituted by micro-crystals with microedges and
microfaces, which determine the hydrophobicity of this mineral and the adsorption of calcium
ions on the face. Increasing the pH, the zeta potential of the molybdenite increases due to the
formation of ionic species of molybdate on both, the edges and the microedges of the face of the
molybdenite particle. Due to this face/edge relationship, the hydrophobicity and floatability of
molydenite particles decreases. The calcium ions absorbed in the edges and in the microedges of
the particle have a significant effect on the floatability of molybdenite as a function of the pH.

Acknowledgements
Direccin General de Asuntos del Personal Academico (DGAPA) through the Programa de
Apoyo a Proyectos de investigacin e Innovacin Tecnologica (PAPITT) Proyecto No. IN
109606 for the financial support is gratefully acknowledged. Aldo Amir Snchez Lpez and Irma
Madrid Ortega thank to the Consejo Nacional de Ciencia y Tecnologa (CONACYT) for their
scholarship granted. The financial support from Fondo Mixto SLP-CONACyT and Southern
Copper, Mexicana de Cobre, Unidad La Caridad, Sonora, Mxico, are also gratefully
acknowledged.
References
Castro, S. H., Mayta, E., 1994. A kinetics approach to the effect of particle size on the flotation of
molibdenite. A. Sutulov Memorial Volume.Vol II. IV Meeting of the Southern of the Hemisphere
on Mineral Technology, and III Latin American Congress on Froth Flotation. Castro, S., Alvarez, J.
(Eds.). Concepcin, Chile, 331-344.
Chander, S., Fuerstenau, D.W., 1974. The Effect of potassium diethyldithiophoshate on the interfacial
properties of molybdenite. Trans. Inst. Min. Met. Vol 83, C180-C185
Fuerstenau, D.W., Chander, S., 1972. On the natural floatability of molybdenite. Transactions SME,
255(1), 62-69
Fuerstenau, M.C., Lpez Valdivieso, Fuerstenau D.W., 1988. Role of hydrolyzed cations in the natural
hydrophobicity of talc. Inter. J. Min. Proc. Vol 23, pp. 161-170
Fuerstenau M.C., Palmer, B.R., 1976. Anionic flotation of oxides and silicates. In: M.C. Fuersteanu
(Editor), Flotation, AIME, New York, N.Y. pp. 148-196
Gracia A., Creux P., Lachaise J., 2002. Electrokinetics of bubbles. Enciclopedia of Surface and Colloid
Science., pg. 1876-1886

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Hoover M.R., Malhotra D., 1976. Emulsion flotation of molibdenite. Flotation I. Gaudin memorial, Vol. I.
New York. pp. 485-505
Kelebek S., 1988. Critical surface tension of wetting and of flotability of molybdenite and sulfur. J.
Colloid Int. Science, Vol 124, No2, pp. 504-514
Lpez Valdivieso A., 1980. A study of the electrokinetics and flotation properties of talc and molybdenite.
Master of Science, South Dakota School of Mines and Technology, pg. 23
Raghavan S., Hsu L.L., 1984. Factors affecting the flotation recovery of molybdenite from porphyry
copper ores. Inter. J. Min. Proc., 12, pp. 145-162
Sutulov A., 1979. Flotation of Molibdenite. International Molybdenum Enciclopaedia. Intermet
Publications, Santiago, Chile, pag. 164-179
Ulman A., 1991. An introduction to ultrathin organic films from Langmuir-Blodgett to self-assembly.
Academic Press, New York, USA., pag. 48-57