PARTICLE SIZE EFFECT ON THE

HYDROFOBICITY AND THE NATURAL

FLOATABILITY OF MOLIBDENITE

AGUSTÍN FRANCISCO CORREA

Universidad de Concepción
1986
(2006 English Edition)
2

PARTICLE SIZE EFFECT ON THE HYDROFOBICITY AND THE NATURAL

FLOATABILITY OF MOLIBDENITE

A Thesis
Presented to the Faculty of
the Department of Chemical Engineering
Graduate School
Universidad de Concepción

In Partial Fulfilment of the Requirements for the Degree

Master of Science in Engineering and Metallurgy
By
Agustín Correa
Concepción, Chile, September 1986

Thesis directed by Professor Dr. Sergio Castro Flores

Head of the Program: Dr Igor Wilkomirsky

The original Spanish version of this thesis was revised by the Committee members:
Dr. Sergio Montes
Dr. Christian Hecker

2006 Revision and Translation by Agustín Correa and Alfredo Correa Tedesco
Table of Contents
Table of Contents..............................................................................................................3
Introduction.......................................................................................................................5
Motivation.......................................................................................................................5
Objectives of the work....................................................................................................5
Chapter 1
Bibliographic revision........................................................................................................6
1.1 Surface characterisation.............................................................................................6
1.1.1 Surface tension....................................................................................................6
1.1.2 Adsorption and Surface Free Energy..................................................................7
1.1.3 Energy and molecular interacting forces and their relationship with the surface
free energy...................................................................................................................8
1.2 Contact Angle...........................................................................................................10
1.2.1 Analysis of the terms that compose Young’s equation......................................12
1.3 Adhesion Work of a Liquid......................................................................................13
1.4 Adhesion Work.........................................................................................................14
1.5 Solid-liquid spreading coefficient............................................................................14
1.6 Characterisation of a liquid and its interrelation with a liquid through the contact
angle measurements.......................................................................................................14
1.7 Theoretical Studies of Models that link and with the surface energies
determination.................................................................................................................15
1.7.1 Zisman Model...................................................................................................15
1.7.2 Girifalco-Good’s Model....................................................................................17
1.7.3 Fowkes’ Model.................................................................................................20
1.7.4 Wu’s Model.......................................................................................................23
1.7.5 Dann’s model....................................................................................................24
1.7.6 Wetting diagrams..............................................................................................26
1.7.7 Relationship between the different models.......................................................28
1.8 Contact angle and adsorption...................................................................................29
1.9 Determination of by other methods........................................................................31
1.10 Floatability and natural hydrophobicity................................................................32
1.11 Hydrophobicity and Structure................................................................................32
1.12 Molybdenite: its structure and relationship with hydrophobicity.........................33
1.13 Hydrophobicity and Surface energy of Molybdenite ...........................................35
Chapter 2
Experimental Part............................................................................................................38
2.1 Materials..................................................................................................................38
2.2 Contact angle measurements on a cylindrical cake.................................................44
2.3 Contact angle measurements on a massive crystal..................................................44
2.4 Hornby-Leja’s method.............................................................................................45
2.5 Quantified wetting method......................................................................................45
2.6 Hallimond’s tube Flotation......................................................................................47
2.7 Conventional cell flotation of the sample in presence of quartz..............................48
2.8 Flotation of a collective of molybdenum samples...................................................49
4

Chapter 3
Results...............................................................................................................................50
3.1 Contact angle measurements....................................................................................50
3.1.1 Zisman’s model.................................................................................................50
3.1.2 Girifalco & Good’s Model................................................................................52
3.1.3 Wetting model (Lucassen-Rynders)..................................................................54
3.1.4 Fowkes’ model..................................................................................................56
3.1.5 Wu’s model.......................................................................................................57
3.1.6 Dann’s Model ...................................................................................................58
3.1.7 Neumann-Good’s model...................................................................................59
3.1.8 Comparison between the values predicted by different models.......................62
3.2 Techniques where water-methanol solutions were used..........................................64
3.2.1 Hornsby- Leja method......................................................................................64
3.2.2 Quantified sinking method................................................................................65
3.2.3 Hallimond tube flotation tests...........................................................................67
3.2.4 Common cells flotation tests.............................................................................69
Chapter 4
Discussion..........................................................................................................................71
4.1 Zisman’s model application.....................................................................................71
4.1.1 Thermodynamic Analysis of the Zisman’s slope..............................................71
4.1.2 Zisman’s slope analysis based on Girifalco-Good’s Model..............................77
4.1.3 Zisman’s slope analyses for measurements with alcohol-water solutions........79
4.2 Good’s Model Application.......................................................................................80
4.3 Wetting Diagram (Lucassen-Reynders) Applications .............................................80
4.4 Fowkes’ Model Application.....................................................................................80
4.5 Wu’s Model Application..........................................................................................80
4.6 Dann’s model Application........................................................................................82
4.7 Correspondent states equation.................................................................................83
4.8 Hornsby- Leja’s method...........................................................................................83
4.9 Quantified sinking method.......................................................................................83
4.10 Hallimond flotation tube........................................................................................84
4.11 Conventional flotation cell.....................................................................................87
Chapter 5
System integral analysis..................................................................................................89
Chapter 6
Conclusions.......................................................................................................................92
Appendix..........................................................................................................................94
Contact angle measurements.........................................................................................94
Addenda and Notes.........................................................................................................97
Bibliography..................................................................................................................100
Nomenclature................................................................................................................104
 Introduction
Motivation
The mineral molybdenite species has been studied by several authors because its
special properties [2][3][4]. This species and others such as graphite, talc, stibnite are
known as highly hydrophobic solids and they exhibit natural floatability [5].
In spite of their high hydrophobicity, a high rate of losses in the flotation processes has
been noticed especially in molybdenite at the finest particle sizes.
In order to explain these facts the following statements has been proposed:
1. Energy surface differences amongst the granulometric classes that cause the
hydrophobic properties of the finest particles to be partially lost.
2. The finest particles have adverse hydrodynamic conditions in conventional
flotation reactors.
Several authors have devoted their efforts to relate the floatability to the hydrophobic
properties of molybdenite [7][8][9][10]. Especial attention has been paid on
characterising these kinds of properties [11][12][13].
Statements based on the physical chemistry of surfaces were developed and applied for
low- surface- energy solids [14][15][16][17].
In spite of the success in the physical chemistry characterisation of the natural
hydrophobicity of MoS2, there are no clear evidences in the literature on the true
influence of the particle size on the aforementioned properties. On the contrary, an
increase in edges/faces ratio is presumed to happen because of the comminution
processes; besides, other factors related to the floatability of the finest, such as flotation
kinetics and the particle size/bubble, are known to be a stabilising factor in particle-
bubble adhesion process.
As previously said, it is necessary to complete the thermodynamics focusing and
evaluating quantitatively the particle size effect on the molybdenite surface free energy
and the components of its interaction forces with its surroundings. This approach will
allow us to reorient the problem and subsequently to evaluate the kinetic effects on a
stricter basis.

Objectives of the work

The purpose of the present work is to investigate the influence of the particle size on
the natural hydrophobicity of Molybdenite. We use the contact angle as a measurement
technique with liquids of well-known surface free energy and several models are applied
to get information about the surface free energy of the solid as a function of its particle
size. The critical tension of wetting in methanol-water solutions and the flotation
behaviour of fine particles are assessed, in the light of the knowledge of the variation of
the polar components of the surface free energy of MoS2; which is the responsible
property of the loss of hydrophobicity and floatability of fine particles.
Chapter 1
Bibliographic revision
1.1 Surface characterisation
1.1.1 Surface tension
One of the most suitable properties to characterise a surface is its surface energy or
surface tension. This is caused by the external layers in the boundary of the bulk known
as surface zone or interface. The molecules of this boundary layer, whose limits are not
well defined, are subject to attractive forces exerted by the adjacent similar molecules.
These forces have a resultant force addressed to the bulk of the phase in the normal
direction to the surface. These unbalanced forces cause the surface molecules get
additional energy by interacting with its surroundings.
The surface tension γ may considered either as a distributed force per length unit or as
energy per surface unit. It is better to give an energetic definition of this property by
associating it to the work W that it is done when the area A of the surface changes. For a
positive infinitesimal change it will be:
δW = −γdA (1-1)
If the first thermodynamic law is taken into account:
dE = δq + δW (1-2)
Where δq is the absorbed heat by the system, δW is the work done by the system and
E is the internal energy of the system.
δW is composed by:
δW = δWPV + δWno − PV = PdV + δWno − PV (1-3)

Where δW PV is the expansion work and δWno − PV are works not associated to the
pressure and volume changes (P = pressure; V = volume).
Applying the Second Law of thermodynamics:
δqrev = TdS (1-4)

Where δq rev is the reversible heat absorbed by the system, T is the absolute temperature
and S the entropy.
For a reversible process and according to (1-2), we obtain:
dErev = TdS − PdV − δWno − PV (1-5)
By introducing the free enthalpy definition,
G = E + PV − TS (1-6)
And its differential form:
 7

dG = dE + PdV + VdP − TdS − SdT (1-7)

Also, for a reversible evolution, introducing (1-5) in (1-7)
dGrev = TdS − PdV − δ Wno− PV + PdV + VdP − TdS − SdT (1-8)
For an evolution at T and P constant we have
dGrev = − δWno−PV = γdA (1-9)
Then we define:
 ∂G 
γ =  (1-10)
 ∂A  P ,T
This equation thermodynamically defines γ as a measure of the free energy per area
and it guides us to also define an internal energy per area E S , an entropy per area S S ,
and an enthalpy per area H S :
γ = H S − TS S (1-11)
and using another Gibbs’ equation
 ∂γ 
 =− S
S
 (1-12)
 ∂T  P
we get:
 ∂γ 
γ = HS +T   (1-13)
 ∂T  P
In these cases we may assume H S ≅ E S .
Equation (1-13) shows us that the variation of γ with temperature is a measure of the
entropy effects associated to the surface and must not be disregarded to infer E S ≅ γ [18].
Any possibility of a change in systems where surface energy are involved may be
evaluated by these equations either as a free energy variation or as a reversible work Wrev
done by the system at constant P and T conditions and in electric works absence; so we
have:
∆Gevolution = − Wrev evolution (1-14)

1.1.2 Adsorption and Surface Free Energy

In a biphasic system (α and β phases) at equilibrium, bounded by an αβ surface with
two components, in each phase we have:

∑ nα dµ α + ∑ n β dµ β + ∑ nα β dµ α β + Adγ = 0
i
i i
i
i i
i
i
/
i
/
(1-15)
8

α α
where ni is the number of moles of substance i in phase α and µ i is the chemical
potential of component i in phase α.
When we consider a liquid phase l in equilibrium with its vapour v; i.e. a solution with
components 1 and 2, we get

∑ n dµ + ∑ n
i
l
i
l
i
i
l /v
i dµil / v + Adγ = 0 (1-16)

the Gibbs-Duhem equation is complied in these phases, so

∑ n dµ
i
i i =0 (1-17)

Then we have in (1-16) that

n1l / v dµ1l / v + n2l / v dµ 2l / v + Aγ = 0 (1-18)
clearing up:
n1l / v n2l / v
dγ = − dµ1 −
l /v
dµ 2l / v (1-19)
A A
Where the differential coefficients or the chemical equilibrium are defined as the
component i superficial excess Γi :

niα / β
Γi ≡ (1-20)
A
Then we have
dγ = −Γil / v dµ1l / v − Γ2l / v dµ 21
l /v
(1-21)
Choosing the boundary between both phases so that one of the Γ be null (commonly
this presumption is applied to the solvent molecules) [19] we get that
dγ = −Γ2l / v dµ 21
l /v
(1-22)
This development gives us a very important relationship between the variation of the
surface tension of solutions formed by a solute and its adsorption on the solution/vapour
interface [19].

1.1.3 Energy and molecular interacting forces and their relationship

with the surface free energy
The origin of the surface tension or the surface free energy may be established on
studying the intermolecular forces.
These may be classified [20] in:
1. Attractive forces
a. Primary bonds (chemical)
i. Atomic (homopolars)
 9

ii. Ionic (heteropolars)

iii. Strongly polar (hydrogen bonds)
b. Metallic bonds
c. Secondary bonds
i. London’s dispersive forces (no-polar/no-polar)
ii. Debye’s forces (induced polar/polar)
iii. Keesom’s forces (polar/polar)
2. Born’s repulsion forces
The chemical and metallic bonds are very strong, with an important free energy of
formation and they are associated to the formation of a solid, and in especial cases either
in a liquid formation such as water (hydrogen bonds), or mercury (metallic bonds).
The secondary attraction forces between molecules or atoms are known as van der
Waals’ forces.
Calculating the surface free energy by associating it to particles bonds and multiplying
this by the bonds number per area has been successful only in few cases.
On the contrary, the Lennard-Jones’ electrical potential is more suitable. This potential
(E) has the following expression
B′ C
E= 12
+ (1-23)
(r1→2 ) (r1→2 ) 6
and its force field (F) in the radial direction:
B′ C
F = −12 13
+6 (1-24)
(r1→2 ) (r1→2 ) 7

Whence r1→2 is the distance between two molecules centres which interact, B′ is a
constant associated to Born’s repulsion forces and C is a constant related to the van der
Waals forces. These forces cause the surface tension of a system and each one may be
analysed in a different form as the usual classification says.
The Keesom’s forces are related to the interaction between the dipolar moments of the
molecules. These forces orient the molecules in preferential directions. Their energy is
described as:
2µ1′2 µ 2′2
EKessom =− (1-25)
2(r1→2 ) 6 kT

Where µ ′ are the dipolar moments, k is the Boltzmann’s constant and r1→2 is the
distance between the forces centres of two molecules of the same kind.

Debye’s forces appear when one or two molecules have a permanent dipole µ ′ that
produces an electric field in its environment that at its time induces other dipoles. Its
expression for two dissimilar molecules is
10

1
E Debye = − 6
(α1′µ 2′2 + α 2′ µ1′2 ) (1-26)
(r1→2 )
Where α ′ is the molecule polarisability.
The London “dispersion” forces are present in all type of substances; they are
additives. They are caused by the fluctuations of the electrons distribution into the atoms.
Besides, these fluctuant dipoles induce new dipoles in their adjoining atoms. So, the
energy of the “dispersion” forces caused by the interaction of two atoms is calculated this
way:
 3α ′α ′ h′ν 0ν 0 
ELondon =  − 1 02 10 2  (r1→ 2 )6 (1-27)
 2(ν 1 + v2 ) 
Where ν 0 are the main frequencies of the electronic fluctuations and h′ is the Planck
constant.
The relative importance of the London “dispersive” forces related to the Keesom’s and
Debye’s, specially in low energy materials, made Fowkes define the interaction term of
his interfacial energy model only as function of these “dispersive” forces, either for solid-
liquid or liquid-liquid systems.

1.2 Contact Angle

There are few possibilities when a liquid is brought in contact with a surface; either a
partial spreading or a complete wetting.
The partial wetting phenomena is characterised by the presence of a drop, a spherical
vault on top of the solid surface, in case the gravitational forces are not significant [20].
The best measurement of this situation is the contact angle. It is measured in a three-
phase boundary defined by the solid surface, and the liquid-vapour interface.
Young was the first to scientifically explain the contact angle phenomena by applying a
mechanical model without taking into account the gravitational forces (Figure 1-1).
Considering the tensions as forces per length unit, Young proposed a simple
equilibrium of forces by projecting them on the solid-liquid surface plane in the three-
phase contact boundary:

∑ forces || plane S =γ SL + γ LV cos θ − γ SV (1-28)

Equilibrium conditions requires the resultant of forces to be null in all the points of the
plane. So,
γ SV − γ SL
cos θ = (1-29)
γ LV
This equation is usually known as the first Young’s equation and may be applied only
when γ SV − γ SL ≤ γ LV .
 11

γ SL : interfacial tension solid/liquid

γ LV : interfacial tension liquid/vapour
γ SV : interfacial tension solid/vapour
θ : contact angle
Figure 1-1: Schematic representation of the contact angle

This approach has been the object of a lot of criticism for not considering the
equilibrium force on the perpendicular axis to the solid/liquid plane. This may be avoided
by ascertaining that (1.29) describes the phenomena when the component of γ LV on the
perpendicular axis is absorbed without deformation of the solid surface.
Modified equations of the Young’s relationship have been proposed by considering
another three-phase tension forces, but, they have not been well received by the surface
chemistry specialists [21].
Young’s equation is of paramount importance when surface tensions are defined as a
surface free energy.
A lot of efforts has been made in order to demonstrate Young’s equation by applying
thermo dynamical concepts instead of mechanical equilibrium.1
These requirements have been satisfied by Good’s (1952) and Goodrich’s (1969)
demonstrations by applying the principle of virtual-work.
The cos θ is a valid thermodynamical quantity if it is measured in equilibrium
conditions because it is associated to free energies and is usually written as cos θ e .
If we associate cos θ with equilibrium conditions, its measurements must be carried
out carefully, especially when hysteresis, rugosity and heterogeneity phenomena may
happen [22].
The differences in the values between the receding contact angle and the advance
contact angle measurements are caused by the hysteresis phenomena.
They are named this way because when a drop of a liquid is forced to move backward
or downward on a solid surface an advance or recede angles are formed. Generally the
advance angle is associated to the equilibrium conditions.
The simplest way to analyse the rugosity phenomenon is given by the Wenzel’s
equation [21][22]:
cos θ observed = r′ cos θYoung (1-30)
Where r ′ is a rugosity parameter defined as the ratio between the “actual” area
(considering the rugosity) and the apparent area (an ideal plain surface.)

1
These two statements do not contradict each other: macroscopic mechanical forces are ultimately
derivatives of a suitable free energy (Revisor Note)
12

On the heterogeneity issue, it is generally accepted that the experimental contact angle
is a weighted resultant of the cos θ of the different surface places considered, as Cassie
developed [22]:
cos θ = ∑ f j cos θ j (1-31)
j

where j represents each kind of superficial place and f j fraction of the surface of
type j.
These three aspects on matter: rugosity, heterogeneity and hysteresis shift the surface
from the ideal conditions. They have been studied in an independent way however they
are closely related [22].
An experimental method of contact angle measurement that incorporates mechanical
vibrations it is very interesting from the thermodynamic point of view, the contact angle
will take a unique equilibrium value because this is the minimum energy state [23].

1.2.1 Analysis of the terms that compose Young’s equation

As the angle θ is a resultant of the surface energy of the phases which are brought in
contact; it is necessary to analyse the origin of the terms in the Young’s equation and to
know what information we could extract from them.
γ LV : is the surface energy of the liquid phase in presence of its saturated vapour.
γ SV : is the surface energy of the solid phase in presence of the saturated vapour of the
liquid phase. It is the consequence of the adsorption of the vapour phase onto the solid
surface.
The relationship between this solid surface energy and γ S (vacuum condition) is:
γ SV = γ S − Π e (1-32)

where Π e is the equilibrium pressure that may be calculated by the equation of the
Gibbs’ isotherm adsorption [14]:
P
Π e = RT ∫ * Γd ln P (1-33)
P

where R is the universal constant of gases; T is the absolute temperature; Γ is the

Gibbs’ adsorption in excess; P is the vapour pressure and P* is a very low pressure
tending to zero.
Generally, low energy systems get very low Π e values.
γ SL : is the solid-liquid interfacial energy. Together with γ S and γ SV , it is difficult to
evaluate directly.
If we want to characterise the solid surface from an energetic point of view, we notice
that Young’s equation is limited in its application.
 13

Figure 1-2: Adhesion work; its schematic representation

We may express Young’s equation as:

γ SL cos θ = γ SV − γ SL (1-34)
and define:
Fadh ≡ γ SV − γ SL (1-35)

where Fadh is the adhesion force or adhesion tension. We notice that this adhesion force
may be calculated from (1-34) but the difficult is to clear up from it both γ SV and γ SL
and then infer γ S .
This task was faced up both by the theoretical models that we are going to show later
[24][25], and by the empiric models (such as Zisman’s); when calculating Fadh in
particular conditions.
We must clarify that sometimes, when certain surfaces are studied, the contact angle
measurement is carried out in a system made up of two non-miscible liquids and a solid;
i.e. mica, water and several organic liquids [26]. In this case the Young’s equation must
be written as:
γ SO − γ SW
cos θ = for θ ≥ 0 (1-36)
γ WO
where W and O subscripts indicate water and organic phases respectively.
Now we are going to introduce definitions based on surface free energy concepts
developed before

1.3 Adhesion Work of a Liquid

Adhesion work of a liquid WC is the free energy associated to the breakage of a liquid
column and the surfaces creation where new liquid and vapour faces are going to bring in
contact (Figure 1-2):
WC = G final − Ginitial = 2γ LV (1-37)
14

initial final
Figure 1-3: Adhesion work schematic representation

1.4 Adhesion Work

Adhesion work Wadh is the free energy associated to the interface A/B separation to
create A and B interfaces. We have for a solid A and liquid B system (Figure 1-3):
Wadh = G final − Ginitial = γ S + γ LV − γ SL (1-38)
On introducing the equilibrium pressure we have
Wadh = G final − Ginitial = γ SV + γ LV − γ SL − Π e (1-39)
When partial wetting occurs it is more useful to introduce the Young’s equation in (1-
39), so we have:
Wadh = γ LV (1 + cos θ ) + Π e (1-40)
which is the Young-Dupré equation.

1.5 Solid-liquid spreading coefficient

The solid-liquid spreading coefficient K is the difference between the adhesion work
and cohesion work of the liquid:
K = Wadh − WC (1-41)

If Wadh > WC , the solid liquid interaction will be strong enough to produce the total
wetting of the solid by the liquid. On the contrary, if WC > Wadh , the necessary work to
overcome the attraction of the molecules of the liquid is not balanced by the attraction
between solid and liquid molecules. Whatsoever, the total wetting occurs when K > 0 .
Replacing in (1.41) the Wadh and WC we have:
K = γ SV − γ SL − γ LV + Π e (1-42)

1.6 Characterisation of a liquid and its interrelation with a liquid

through the contact angle measurements
The Young’s equation, that Zisman [14] qualified as “deceptively simple”, has the
inconvenient that it does not distinguish the solid surface energies from the solid-liquid
 15

interfacial energies and it is even worse for the adsorptions conditions because these are
included in the aforementioned term defined as adhesion tension.
Different proposed statements about the adhesion tension are going to be observed
when we will analyse the models which have been applied in the study of the surface
through the contact angle measurements. The Zisman’s empirical model relates the
γ SV − γ SL (adhesion tension) to a particular condition, so well-based assumptions may be
made; i.e. γ SL is either in a minimum or is null; γ SV is almost equal to γ S , Π e is in a
minimum, et cetera.
The deductive model [24][25][27] approaches the problem by proposing a constituent
equation for γ SL as a function of γ S and γ L , so in this way we have a better
approximation to the true γ S value when we combine this equation with Young’s.

1.7 Theoretical Studies of Models that link cos θ and γ LV with

the surface energies determination
1.7.1 Zisman Model
This model is supported by a searching team. The works in the 1940-1950 decade were
carried out on a theoretical base which linked the contact angle to the solute activity in a
solution and to the adhesion tension; i.e. the butanol and butyl-amine activities in the
presence of graphite and stibnite related to angle contact measurements [28]. This kind of
work permitted to infer hypothesis about the adsorption in the system.
Paramount interest has been reported on determining the adhesion tension in especial
situations as those of critical wetting.
This is calculated as:
Fadh = γ LV cosθ (1-43)
On studying the low energy surfaces as polystyrene, Zisman related the measurements
of contact angles to the liquid superficial tension in contact with the solid surface through
a simple linear equation:
cos θ =1 + α ( γ LV − γ C ) (1-44)

where γ C is the value that γ L assumes when cos θ =1 and α is the slope of the
straight line it has got. As we see, this function is valid in the same range as the Young’s
equation is θ ≥ 0 .
This way, Zisman introduced a concentrated parameter γ C which allows us to establish
a relative scale of surface energies. This shows us that when the liquid tension is less than
γ C , the complete wetting of the solids happens.
The choice of this particular point is based on the usual concepts about the spreading
between two similar liquids.
16

Under these circumstances, we presume that the interfacial tension is null or reaches a
minimum and then Young’s equation may be written as:
γ C = γ SV (C ) − γ SL (C ) (1-45)

where supra-index (C) indicates critic conditions. At the extreme case, γ C ≅ γ S would
be true for a low energy surface solid ( Π e = 0 ) when γ SL ≅ 0 .
Some authors [29][30] support these last concepts. However, in other cases when the
surface energy of solids has been measured by fusion heat techniques serious
discrepancies have been found (Gardon 1963).
So, it remained the questions if γ C was a constant of the surface solid, and besides if it
was a measure of the solid surface energy independent of the sort of the liquids used in its
determination.
Experimentally, Zisman utilised a hydrogen-bond liquid series and he obtained a
γ C ≅ 33 mJ/m 2 for polystyrene. This had to be calculated by extrapolation because
surface dissolution caused problems. On the other hand, Zisman got γ C ≅ 43 mJ m for
2

the same solid utilising non-hydrogen bond liquids.

Later, Good [23] demonstrated that, using a more elaborated model, such discrepancy
was caused by Zisman’s model, which he qualified as limited.
A still in force question is the discussion about the critical wetting conditions obtained
using liquid mixtures or alcohol water solutions.
ASTM has edited standards in order to carry out this kind of measures utilising
formamide-2-ethoxi-ethanol mixtures and water-ethanol solutions [27]. This technique is
more flexible because this way it is possible to control the surface liquid tension by
changing the concentrations of either the mixtures or the alcohol-water solutions. It was
applied on the study of polyethylene, poly-tetrafluoride-ethylene [31], and sulphide [13]
[32] surfaces.
This method is criticised because it is not clear whether the preferential adsorption
phenomena modifies the surface conditions, so it becomes more or less energetic.
Zisman suggests that adsorption happens after the contact; furthermore, it is a
consequence and not the cause of wetting conditions [14].
Other authors [23] looked down on this method, basing their opinions on the isotherm
preferential adsorption described by the Gibbs’ equation. This phenomena would have a
marked influence on the γ SL value and on γ SV , either which would be different from γ S .
By the way, many researches have been carried out on systems composed by aqueous-
alcoholic solutions on low energy surface solids. They have confirmed the adsorption
onto polar sites; furthermore a partially covered surface by hydrocarbon chains is
obtained even in contact with aqueous-alcoholic solutions of alcohols of low number of
carbon such as methanol or ethanol [33][34].
 17

Figure 1-4: A typical Zisman’s plot

Lower values of γ C have been obtained when aqueous-alcoholic solutions were

utilised instead of pure liquids; i.e. graphite; with pure liquids a γ C ≅ 47 mJ/m has been
2

obtained [35], but with butanol and butyl-amine aqueous solutions values of
γ C ≅ 25 mJ/m 2 and γ C ≅ 34 mJ/m 2 have been respectively reported [28].
On the other side, the value of the dispersive component of the graphite surface energy
has been reported as 96 mJ/m 2 [36], furthermore, the γ C calculated either from solutions
or liquid mixtures is not suitable to be considered a direct measure of the solid surface
energy.
The α parameter was only considered as the slope of (1-44), but now it is known as
Zisman’s slope and it has got a paramount importance both from the theoretical point of
view [23] and in the characterisation of certain situations [11][35].

1.7.2 Girifalco-Good’s Model

This model [25] was the first based on aspects related to the molecular structure of the
surface which have been brought in contact.
We have explained how limited the Young’s equation is in order to determine the solid
surface energy and the γ SV (solid-vapour tension) too; and how this may be solved in
case γ SV were defined satisfactorily as a function of γ S and γ LV .
The construction of this model begins with describing a system where molecules of
kind ‘a’ and ‘b’ are present. The attraction constants between similar molecules are M aa
and M bb , and between different ones is M ab . According to Hildebrand [25], regular
solutions comply:
M ab
=1 (1-46)
M aa × M bb
By analogy, Girifalco and Good [25] applied the same relationship between both
adhesion and cohesion free energies between two phases; that is between strictly binary
systems. In this way:
18

∆Gab
− = φ ab (1-47)
∆Gac × ∆Gbc

where ∆Gab = γ ab − γ a − γ b is the adhesion free energy between phases ‘a’ and ‘b’;
∆Gac = − 2γ a y ∆Gbc = − 2γ b are the cohesion free energy of phases ‘a’ and ‘b’
respectively, and φ ab is a constant of the ‘ab’ system.
Clearing up we get:
γ ab = γ a + γ b − 2 φ ab γ a γ b (1-48)
Applying it to the liquid-solid interface:
γ SL = γ S + γ L − 2 φ SL γ S γ L (1-49)

If we combine it with the Young’s equation by admitting γ L ≅ γ LV

cos θ = − 1 + 2φ SL γ S γ L − Π e γ L (1-50)
so:

γS =
[ γ L (1 + cosθ ) + Π e ]
2

(1-51)
4φSL
2
γL

when Π e is negligible we have

cos θ = − 1 + 2φ SL γ S γ L (1-52)
and clearing up again

γS =
[γ L (1 + cos θ ) ] 2
(1-53)
4φ SL γ L
2

The importance of this model is that knowing the contact angle between a solid and a
liquid, the liquid surface tension and the φ SL parameter (that is a constant of the system),
it is possible to calculate the solid surface energy.
The main problem will be now how calculate φ SL . According of its authors φ SL may be
calculated using the equation:
4 (VS VL )
1/ 3
rS rL 4 rS rL
φSL = = ≅ (1-54)
rSL ( rS + rS )
2 2
(
VS1/ 3 + VL1 / 3 ) 2

where, rS and rL are the molecular radii corresponding to the distances between the
forces centres of the molecules; VS and VL are the molar volumes.
This deduction was elaborated for phases whose kinds of forces are alike, and then the
parameter φ SL is presumed to be one.
 19

When the kinds of forces are not similar, the follow equation must be applied [37]:
4 rS rL ΣC SL
φ SL = × (1-55)
( rS + rS ) 2
ΣC SS Σ C LL

where C are the constants coefficients of the r −6 of the Lennard-Jones potential,

defined in (1.24), and the summations are:
ΣC = C dispersion + Cinduction + C dipole−orientation (1-56)

The most general expression in order to calculate φ SL is:

4 (VS V L )
1/ 3

φ SL = ×
(V 1/ 3
S + V L1 / 3 ) 2

2 ( µ S′ µ L′ )
2
3 2I I
α S′ α L′ × I S S+ ILL + α S′ µ L′ 2 + (1-57)
× 4 3 kT
3 2 2µ S′   3 2
4
2µ L′ 4 
 α S′ I S + 2α S′ µ S′ +
2
 ×  α L′ I L + 2α L′ µ ′L + 2

4 3kT   4 3kT 
where α ′ are the polarisation constants, µ ′ the dipolar moments, I the ionisation
energy, k the Boltzmann’s constant and T the absolute temperature.
If one of the both phases is a non-polar type, i.e. the solid; then µ S′ = 0 and we get:
3 2I I
4 (VS V L )
1/ 3 α L′ × I S S+ ILL + µ L′ 2
φ SL = × 4
(V 1/ 3
+ V L1 / 3 ) 2
 3   3 ′ 2 2 µ ′L4 

(1-58)
 I S  ×  α L I L + 2α L′ µ ′L +
S 2

4  4 3kT 
According to this equation φ SL depends weakly on the non-polar solid properties.

If both µ S′ and µ ′L are null we obtain a system where only the London dispersion
forces are working; so:
4 (VS V L )
1/ 3
2 IS IL
φ SL = × (1-59)
(V 1/ 3
S +V 1/ 3 2
L ) IS + IL

Model application
It is evident this model has a lot of troubles when working on a non well-known
system. Nevertheless some correlations based on this model have been useful in order to
get consistent results.
At first, we remember the resolution of the ambiguous γ C that Zisman got when he
was studying a polymer using this correlation:
20

p
cos θ = Cte + (1-60)
γ SL

This was proposed by Good on replacing φ SL by a linear combination of this kind:

b
φ SL = a + (1-61)
γ LV
If we combine the last one with (1-52), it results in the semi empirical equation (1-60).
On the other side, under critical conditions, for a low energy surface solid; Π e ≅ 0 ; the
mentioned relationship may be used and we get:
2
γ S = γ C φ SL
(c )
(1-62)

In this way if we achieve to evaluate φSL under critical conditions, knowing the
supposed γ C , we are going to obtain γ S .

1.7.3 Fowkes’ Model

Fowkes developed a model based on the characteristics of the intermolecular forces
caused by the different sort of intermolecular bonds. Either the metallic or the hydrogen
bonds are both of specific nature. However, London’s dispersion forces are always
present amongst neighbouring molecules or atoms, even if these are not all of the same
substances or elements.
London forces are caused by the fluctuant electronic dipoles interaction with induced
dipoles of adjacent molecules. They depend upon the electric properties of volume
elements, they are always independent from the temperature and always attractive.
In this way, the surface tension of a condensed phase may be expressed as [24]:
γ =γ d +γ h +γ m +γ Π +γ i (1-63)
where the supra-indices indicate “d” as London dispersive forces; “h” hydrogen bond;
“m” metallic bond; H hydrogen bond; “ Π e ” ; electronic interaction; “i” ionic interaction.
In the mercury (Hg) case:
γ Hg = γ Hg
d
+ γ Hg
m
(1-64)
for the water (W):
γ W = γ Wd + γ Hg
h
(1-65)
and for normal aliphatic and saturated hydrocarbons (HC):
γ HC = γ HC
d
(1-66)
When two phases are brought in contact, the required work to carry a molecule to the
solid-liquid interface ( ESL ) , from the bulk of each phase, diminishes in a quantity ∆W
 21

related to the necessary energy to carry the same molecule either to the solid-vapour
(S/V) or to liquid vapour (L/V) interface.
Then for a molecule from the solid phase it is:
(S )
E SL = γ S − ∆W ( S ) (1-67)
for a molecule from the liquid phase it is:
( L)
E SL = γ L − ∆W ( L ) (1-68)

The addition of both works ESL and ESL gives the energy ( γ LS ) necessary in order to
(S ) ( L)

form the interface S/L:

γ SL = ESL
(S )
+ ESL
( L)
= γ S + γ S − ∆W ( S ) − ∆W ( L ) (1-69)
Fowkes assumes that both works are the same and that both are functions of the
dispersion components because he considers that they are the only capable of interacting
through the phases boundaries.
So:

∆W ( S ) = ∆W ( L ) = γ Sd γ Ld (1-70)

Then it remains

γ LS = γ S + γ L − 2 γ Sd γ Ld (1-71)

The utilisation of the geometric mean is justified by Fowkes in several articles basing
on London and Hildebrand concepts [24]. They claimed that the interaction of those
phases E12 is defined by the equation:
π N1 N 2 α1′α 2′
E12 = − × I1 I 2 (1-72)
8r11r22
where N is a constant of each phase; α ′ is the polarisation constant; I, the ionisation
constant and r, the intermolecular distance.
As Fowkes deduces that:

2
π N i α id I i
γ =−
i
d
(1-73)
8 rii2
and we get:

E12 = − γ id γ 2d (1-74)

In the same way Girifalco-Good’s model did; now we have an equation that allows us
to evaluate γ SL as a function of the liquid and solid phases properties.
22

Figure 1-5: Typical Fowkes’ diagram

If we replace γ SL by the Fowkes’ expression (1-71) in the equation that defines de

adhesion work, we get:

Wadh = 2 γ Sd γ Ld (1-75)

Besides, if we combine (1-71) with Young’s equation (1-29), we get:

γ Sd γ Ld Π e
cos θ = − 1 + 2 − (1-76)
γL γL
or in another way:
γ L2 [ (1 + cos θ ) + Π e γ L ]
2

γ = d×
d
S (1-77)
γL 4

If it is possible to neglect Π e , we get:

γ Sd γ Ld
cos θ = − 1 + 2 (1-78)
γL
and,
γ L2 (1 + cos θ ) 2
γ =
d
(1-79)
4γ Ld
S

This way, it is possible to evaluate γ S performing only one determination of the contact
d

angle using a liquid whose tensions components are well known.

On the other side, a correlation between cos θ vs. γ Ld γ L may be fitted according to
the contact angles measures performed with different well-known-property liquids and so
evaluate γ S as a parameter of the corresponding equation (1-78).
d

The complete wetting condition in Fowkes’ model, neglecting Π e , is given by:

γ Sd ≥ γ L (1-80)
 23

Then for the critical conditions (c) it gets:

γ ( c)
2

γ = Ld ( c )
d
(1-81)
γL
S

or
 γ 
γ Sd = γ c ×  d c( c )  (1-82)
γL 
where γ c is the wetting critical tension

So, only under very special conditions γ c may be assumed as the solid surface energy.
On the other side, we observe that, in order for a solid to be completely wetted by a
liquid, it is not enough to have a lower surface tension than the solid surface energy, but
instead the aforementioned conditions must be fulfilled.
If the liquid has only dispersive components and Π e may be neglected, we get
γ Sd = γ c (1-83)
and if the solid interacts only by dispersion forces:
γ S =γ c (1-84)
By extension, these concepts may be applied to the study of the wetting of solids,
which only interact by dispersion forces, utilising water-alcohol solutions mixtures. In
these cases we may assume, in a first approximation, that the dispersion forces are like to
the water ones; which says that γ L ≅ γ W ≅ 22 mNm . This way, for a solid with a
d d −1

γ Sd ≅ 50 mJm −2 according to (1-80), it gives:

γ c = 50 × 22 ≅ 33 mJm −2 (1-85)
This is only true if we assume that there is not preferential adsorption

1.7.4 Wu’s Model

This model tries to be more general than the Fowkes’. Beginning with the same
Fowkes’ criterion:
γ =γ d +γ p
(1-86)

where γ p is the summatory of the components which are not “dispersive”. Wu

included polar components of the surface tension and named them polar components of
the surface tension.
He considered both the polar and dispersive components related to the interaction of
the phases that have been brought into contact.
24

Doing the same analysis as Fowkes did:

γ LS = γ S + γ L − ∆WSL( S ) − ∆WSL( L ) (1-87)
(S) ( L)
Where ∆WSL = ∆WSL and they are defined as:

2γ Sd γ Ld 2γ Sp γ Lp
∆WSL( S ) = + (1-88)
γ Sd + γ Ld γ Sp + γ Lp
replacing in (1-87):
4γ Sd γ Ld 4γ Sp γ Lp
γ LS =γ S +γ L − d + (1-89)
γ S + γ Ld γ Sp + γ Lp
The geometric mean criterion (Fowkes) has been changed by the harmonic mean.
Combining this with the Young’s equation and neglecting Π e we have:

4γ Sd γ Ld 4γ Sp γ Lp
γ LV cos θ = − γ LV + + (1-90)
γ Sd + γ Ld γ Sp + γ Lp
If we place the critical wetting condition, it simplifies to:
 γ Sd γ Ld γ Sp γ Lp 
γC = 2  d + p  (1-91)
 γ S +γ L γ S +γ L
d p

It is interesting to observe that if γ S = γ L and γ S = γ L , it implies, whatsoever , that
d d p p

cos θ = 1 . So, one of the wetting conditions is reached when a solid is brought in contact
with a liquid with dispersive and polar components alike.
The validation of the model calls for knowing γ S and γ S , so it would be necessary to
d p

perform two cos θ measurements with different liquids; producing, in this way, two
equations that permit us to solve the problem.
An alternative mathematical method will be shown in the discussion of the present
work in order to manage this model.

1.7.5 Dann’s model

Both, Wu’s and Dann’s [27] models hypothesis are similar. We may consider Dann’s
model as an expanded expression of the Fowkes’ model; utilising besides, the interaction
of the polar components the same way Fowkes claimed for dispersive forces.
The expression that foretells γ SL is:

γ SL = γ S + γ L − 2 γ Sd γ Ld − 2 γ Sp γ Lp (1-92)

The author claims that the treatment based on the geometric means has had better
results than those which utilised harmonic means.
If the Young’s equation is introduced in (1-92) and neglecting Π e , it results that:
 25

γ Sd γ Ld γ Sp γ Lp
cosθ = − 1 + 2 +2 (1-93)
γL γL

The method consists in considering γ S and γ S as parameters to be optimised in a

d p

linear correlation and using the performed measurements in the presence of different
liquids as fitting points:

(1 + cos θ ) |i = xi γ Sd + y i γ Ld (1-94)

where i indexes each measured point ; xi = [γ d

L ]
γ l i ; yi = [γ p
L ]
γl i.
This method has been also used in order to study high energy solids surfaces.
It is well known that it is very difficult to find liquids which do not wet completely
these sort of surfaces (mica, oxides, et cetera).
Contact angle measurements on this sort of surfaces are performed in front of a water-
saturated n-hydrocarbon system.
The Young’s expression for this new system is:
γ WH cos θ = γ SH − γ SW (1-95)

Where γ SH is the solid-saturated hydrocarbon interfacial tension; γ SW is the water-

saturated n-hydrocarbon interfacial tension.
It is correct to assume that this kind of hydrocarbons interacts only by London’s
dispersion forces; so applying Fowkes’ equation:

γ SH = γ S + γ H − 2 γ Sd γ H (1-96)

and

γ WH = γ W + γ H − 2 γ Wd γ H (1-97)

For γ SW Dann’s equation is applied:

γ SW = γ S + γ W − 2 γ Sd γ Wd − 2 γ Sp γ Wp (1-98)

When these expressions are introduced into the modified Young’s equation (1.95), it
gets:

γ H − 2 γ Sd γ H = γ W − 2 γ Sd γ Wd − 2 γ Sp γ Wp + γ HW cos θ (1-99)

In this equation γ H , γ W , γ HW and θ are measured and γ W has been obtained from
d

Fowkes’ model. However, the γ S and γ S terms remain independent from the
d p

hydrocarbon utilised.
26

Then, measurements may be performed with two different saturated hydrocarbons

getting two independent equations with two unknown factors; so, the system of equations
is solved and γ S and γ S are calculated
d p

Dann took the credit for claiming for a geometric mean expression of the polar
interaction. The solid water interaction term has been expressed as I SW by other authors,
so, they are not compromised with an expression as function of the polar components of
both solid and water.
This happens because the London’s dispersive components are rather known [16], on
the other hand, this does not happen with the so named “polar” components that embrace
metallic bonds, hydrogen bonds and neither with Keesom’s and Debye’s bonds too.

1.7.6 Wetting diagrams

The wetting diagram [38] is a different way of display the cos θ measurement data. In
this diagram we represent the adhesion tensions as ordinates axis vs. the surface tension
of the liquid utilised in the cos θ measure as abscissa axis.
The adhesion tension Fadh was defined as:
Fadh ≡ γ SV − γ SL
and it is calculated as
Fadh = γ LV cos θ

The region between the straight lines Fadh = γ LV and Fadh = − γ LV has got a physical
meaning. The first straight line is the geometrical place when cos θ = − 1 and the latter;
cos θ =1 is the geometrical place when the wetting critical conditions happens.
The data processing in this diagram, is carried out performing a linear correlation
between γ LV cos θ vs. γ LV :
Fadh = mγ LV + Cte (1-100)
where m is the slope of this straight line and Cte is the intersection point of this straight
line with y-axis.
This methodology has been followed by several researchers [21], [32] on studying the
minerals wettability with water-alcohol solutions or tensoactive agents.
Otherwise, other authors have utilised second order correlations between Fadh and γ LV
[39].
Generally, a wetting diagram will offer us the following information:
1. Critical wetting conditions by the intersection of the modelled straight line (or
another function) with the identity function.
2. The differential wetting between two solid species. Generally, the slope of the
straight line m is very well defined. The crossed zone in Figure 1-6 will show us
 27

Figure 1-6: Wetting diagram

the complete wetting of solid #1 under the same conditions at which solid #2 is
partially wetted (Hornsby-Leja, 1980).
3. To establish a relative quantification of the superficial excess Γ of the tensoactive
agents between liquid-vapour, solid-vapour and solid- liquid interfaces.
If we analyse the derivate of the studied function, either in a point or as a whole in case
a linear model has been performed [21] we have:
dFadh d ( γ SV − γ LV )
m= = (1-101)
dγ LV dγ LV
According to the Gibbs’ isotherm (1-22), if we replace the differentiation in both
interfaces and if we consider that there exists an equilibrium state either, we obtain that:
ΓSV − ΓSL
m= (1-102)
ΓLV
or, in another way:
ΓSV = m ΓLV + ΓSL (1-103)

If the slope m is negative, as it happens usually, then ΓSL > ΓSV , in a quantity that
depends upon of m. If the absolute value of m is large, it may be considered ΓSV ≅ 0 , and
we could claim for a null adsorption in the solid-vapour interface.
Finch and Smith have reported positive slopes for high surface energy solids, so
ΓSV > ΓSL , this means that its tensoactive adsorption tension is predominant in the solid-
vapour interface over the solid-liquid adsorption.
This situation was reported on a γ C determination on a molybdenite species using
methanol-water solutions [32].
28

1.7.7 Relationship between the different models

The models that we have presented must have point of coincidences between them,
because they have been generally applied successfully to the study of low energy solids
surface, and even in high energy solids surface as micas and metallic surfaces.
The Zisman’s model treatment offers its versatility as advantage; its method is plain.
It must be noticed that when the aforementioned methods have been applied the γ C
calculated coincided with the liquids surface tensions of low interfacial energy.
Among these resemblances, we will mention the one between Zisman’s and Good’s
models. The latter based his demonstration on Taylor series expansion of his expression
model. He made this development in γ L = γ C and establishing Φ SL as independent of γ L
and he got:
2 3
γ L − Φ 2SL γ S 3  γ − Φ 2SL γ L  5  γ − Φ 2SL γ L 
cos θ = 1 − +   −   + ... (1-104)
Φ 2SL γ S 4  Φ 2SL γ  8  Φ 2SL γ 

which will be convergent when γ L < 2 Φ SL γ S .

2

Having into account γ C = Φ SL γ S , we get:

2

2 3
γ −γ 3 γ −γ C  5 γ L −γ C 
cos θ = 1 − L C +  L  −   + ... (1-105)
γC 4  γC  8  γC 
If the expansion is truncated at the second term and we compare it with Zisman’s
equation (1-29) we have that:
1
α ≅− (1-106)
γC
Both models, Fowkes’ and Good’s are very alike because they have a very similar
starting point. If we compare their equations, (1-52) and (1-78), and we equalise them, we
get:

γ Sd γ Ld
Φ SL = (1-107)
γ SγL

and if we are in the presence of a solid and a liquid which only interact by dispersive
forces then Φ SL ≅ 1 [37].
The Fowkes’ model has been the most frequently used because it obtains a paramount
piece of information, which is the dispersion component of the solid surface energy. On
the contrary, to obtain Girifalco-Good’s Φ SL parameter, a tedious calculation is required
in its model original model version.
However on account of the Fowkes’ model has got only one parameter, this model is
not flexible in order to interpret situations as Parekh and Applan describe in the study on
coals wetting [11]. This case, the coal species were differentiated between them by the
 29

different contact angle they form with the very same liquids but they converged to a same
critical wetting condition.
When the high energy solids problem is raised, it is necessary to consider the polar
components in the interfacial interaction. Wettability of quartz in water is a typical case.
If we apply Fowkes’ criterion γ Sd γ Ld > γ L , quartz will not be completely wetted by
water. If we replace the energy surfaces by their experimental values; γ S ≅ 78 mJm and
d −2

γ Wd ≅ 22 mJm −2 , its geometric mean gives 42 mJm-2, less than the experimental value
γ W ≅ 72 mJm −2 (according to literature data reported for silica and water [24]).
On account of this, some authors [17] define the work adhesion not only with
dispersion components (d), as Fowkes did, but they also include ionic (i) and metallic (m)
components that in a first approximation may be considered as independent:
(d ) (i) ( m)
Wadh = Wadh + Wadh + Wadh (1-108)

So, we observe that the condition for complete wetting, Wadh > WC , will be fulfilled on
increasing appreciably the adhesion work by means of its polar component rise.
These anomalies happen when Fowkes’ model is applied, and they were the base for
constructing new models [27], where the dispersive forces are present and the remainder
are embraced into the polar term (1-90)(1-93).
It must be noticed that the treatment of the surface energy based on the determination
of dispersion and polar components are not accepted by all the authors, i.e. Good [23]. He
precisely argues, amongst other things, that the signs of dispersion and induction energy
in a solid will not be independent of the solid-liquid system. Besides, he claims to pay
attention to an orientation term whose characteristics would be closely related to the
surface entropy of the system interface.

1.8 Contact angle and adsorption.

The deductive models of contact angle have restrictions in theirs use when we are in
presence of adsorption phenomena even in solid-pure liquid systems
In these situations, the proposal of a state equation that links the adsorption with the
surface free energies ( γ SV , γ LV , γ SL ) is of paramount significance [39].

Authors have calculated γ SV in low energy surface solids using these concepts [39].
The construction and justification of this state equation is as follows: First, the Gibbs’
equation is set up for each of the interfaces which form the contact angle,
γ i = Ei − TS i − Γi µi (1-109)
where i subscript refers to each interface, E is the internal energy per surface unit, Γ is
the vapour adsorption at each interface and µ is the adsorbent chemical potential in each
face.
Differentiating and introducing the first principle of thermodynamics:
30

dγ i = − Si dT − Γi dµi (1-110)
and, expanding it for each interface, we get:
dγ SV = − S SV dT − ΓSV dµ ⇒ γ SV = γ SV ( T , µ ) (1-111)
dγ SL = − S SL dT − ΓSL dµ ⇒ γ SL = γ SL ( T , µ ) (1-112)
dγ LV = − S LV dT − ΓLV dµ ⇒ γ LV = γ LV ( T , µ ) (1-113)

This differential equation system permits one solution γ SL as function of γ SV and γ LV :

S LV ΓSL − S SL ΓLV S Γ − S SV ΓSL
dγ SL = dγ SV + SL SV dγ LV (1-114)
S LV ΓSV − S SV ΓLV S LV ΓSV − S SV ΓSL
and its solution may be written down as:
γ SL = f (γ SV , γ LV ) (1-115)
These expressions are considered by Good as an equation of corresponding states.
By replacing these equations in (1.34), we get:
γ SV − f ( γ SV , γ LV ) = γ LV cos θ (1-116)
This equation permits us to conclude that, in a wetting diagram, the adhesion tension
(that is calculated as Fadh = γ LV cos θ ) will have a good correlation as function of γ LV ,
only when γ SV is constant.
This will happen in solid-liquid systems when the adsorption is null or constant.
On the contrary, if the correlation is not good we may presume that adsorption is
happening and it is different for each liquid in contact with the solid.
This thermodynamic point of view allows us to set up constitutive equations which
express γ SV as function of γ SL and γ LV , even in an empiric form.

According to this theory, in order to calculate γ SV , a methodology has been developed

applying the Girifalco - Good’s model that we are going to explain now.
Once the aforementioned correlation was satisfied, γ SV is calculated:

1. Guessing an arbitrary γ SV , may be close to γ C .

*

(i)
2. Using this value, we calculate, in each measure (i), γ SL as function of γ LV and
i

cos θ ( i ) :
(i) (i) (i)
γ SL = γ SV − γ LV cos θ ( i ) (1-117)
(i)
3. With this value; γ SL ; the Good’s parameter Φ SL is calculated for each
measurement:
 31

(i) (i)
γ SV
*
+ γ LV − γ SL
Φ SL = (1-118)
(i)
2 γ SV
*
γ LV
(i) (i)
4. Φ SL vs. γ SL are correlated through a straight line function:

Φ (SLi ) = − ω γ SL
(i)
+ β 0 with ω > 0 (1-119)

Steps are repeated from step 1, for different γ SV until

*

0.999 < β 0 < 1.000 (1-120)

is achieved; since Φ SL = 1 when γ SL = 0 .

This methodology is not only suitable to estimate γ SV but also to estimate γ SL and
Φ SL in each contact angle measurement; both of them will give us an idea of the degree
of interaction between different liquids with the surface solid we are studying.

1.9 Determination of γ C by other methods

Other methods; that have been applied to fine-size-hydrophobic solids, have been
developed in order to determine critical wetting conditions related to the solid surface
free energy.
1. Hornsby-Leja’s method [12]
It consists in bringing up in contact the solid species on study with methanol-water
solutions of different surface tension. Furthermore; we could define wetting and no-
wetting zones up to when we establish a wetting γ C with the precision permitted by the
error of the technique.
We must clarify that this method was suggested as a possible technique in order to
separate hydrophobic materials i.e. PTFE and coals.
2. Sinking time method [10]
This method measures the time a particle lasts in sinking in different surface tension.
So, the ultimate surface tension indicates that the sinking time is infinite and it is
calculated by extrapolation. This value may be linked to the immersion free energy
variation (air-solid-liquid system):
∆Ginmersion = γ SL − γ S −air (1-121)
and applying Young’s equation:
∆Gimmersion = γ SL − γ S −air = − γ LV cos θ (1-122)

The immersion condition is given by ∆Ginmersion < 0 . If we accept the approximation

γ SV ≅ γ S − air the critical wetting tension is going to be associated at cos θ = 1 . This should
be modified if gravitational forces and particle shapes must be taken into account in the
immersion process [10].
32

3. Gamma flotation [13]

This method may be carried out using a tube-Hallimond flotation with different water-
alcohol solutions whose composition determines the superficial tension of the liquid. The
data are represented as a recovery vs. solution surface tension function.
It is observed than the recovery keeps on nearly constant as the surface tension solution
decreases with respect to water’s. However, at a given point, the recovery drops
dramatically, almost linearly. Their authors associate γ C with the value at which the
extrapolated aforementioned fall intersects the abscissa axis.

1.10 Floatability and natural hydrophobicity

The minerals flotation is based on reducing the surface free energy of the species to be
floated, using certain kind of chemical reagents. Furthermore, the hydrophobicity of the
species rises and it acquires the property of adhering spontaneously to air bubbles. Hence,
the interest to study the minerals species that are naturally hydrophobic comes up .
Natural flotability and hydrophobicity has been considered as synonyms and both had
been related to solids with low surface free energy.
The “hydrophobic-solid” term indicates that such a solid does not have affinity with
water.
This terminology has been ambiguous to describe the liophobic behaviour of a surface.
The aforementioned solid introduced in a water-gas system adheres to the gaseous
phase, forming a partial-solid/gas interface as a result of the interfacial tensions balance.
The particle-bubble adhesion may be quantified through the contact angle measure and its
value will depend upon the hydrophobic grade of the particle we are studying on.

1.11Hydrophobicity and Structure

Relating natural hydrophobic solids to their crystallographic structure has been a
constant source of concern to scientific searchers and therefore to outline generalisations
on the subject [5].
The basic hypothesis is that the behaviour of these species is linked to the available free
forces they have in order to interplay with its environment and these for their part with
interatomic forces of the crystalline lattice.
It has been found that a crystal or mineral particle shows hydrophobicity when it
cleavage breaks preferably residual bonds (van der Waals). This way, the particle will
interact with its environment mainly through London’s dispersion forces [5].
However, on especial occasions a violent breakage as it happens in minerals
comminution, may break another sort of stronger bonds, such as the covalent ones,
generating more energetic sites. These sites are capable to interact with its environment in
a more energetic way i.e. oxidation surface reactions, adsorption et cetera. This
mechanism increases the solid surface energy and whatsoever spoils its hydrophobic
properties.
The energetic character of a bond is associated to the equilibrium distance between the
atomic centres of interaction.
 33

Furthermore, the analysis of the crystalline structure of these solids results a suitable
method to foretell their hydrophobic properties.
The laminated crystalline structure is a common property of the inorganic hydrophobic
solids (graphite, talc, mercury oxide, boric acid, molybdenite, et cetera).
The graphite crystalline lattice is a typical case, having a laminar structure in hexagonal
arrangement, a 1.42 Å interatomic distance and its links between layers with 3.4 Å
bonds.
Boric acid is a special case, despite having an ionic behaviour, it is naturally
hydrophobic because it forms perfect hexagonal layers through hydrogen bonds;
however; such sheets interplay through van der Waals bonds.
The exception is given by micas and chlorites, despite having a layered structure, they
present substitutions in the SiO -4 by aluminium, which cause unbalanced charges
building up a poly-functional structure. So, polar groups appear on the crystal surface that
render it hydrophilic.

1.12 Molybdenite: its structure and relationship with

hydrophobicity
Molybdenum sulphide crystallises in two different habits. The hexagonal habit is the
most common with a = 3.16 Å and c = 12.29 Å axes; the other is the rhombohedric
habit with a = 3.17 Å and c = 18.38 Å . These frameworks were discovered and
described, in natural crystals by Dickinson and Pauling [2].
The hexagonal habit is characterised by two-layer MoS2, whose molybdenum atoms
have prismatic coordination, trigonal with 6 atoms of sulphur. Each cell is composed by
two molecules of MoS2.
The shortest distance between Mo and S atoms is 2.41±0.6 Å. The faces of a imaginary
prism of Mo-S6 are 3.15 ± 0.02 Å wide. Whereas, the distance between adjacent layers is
3.49 Å long.
The rhombohedric structure happens in some deposits [41], it has a similar
arrangement of Molybdenum atom layers and the very same type of trigonal
coordination.
Other possible frameworks has been claimed for the molybdenite; they are:
a) rhombohedric, with 3 molecules per cell unity (3R), b) two hexagonal with two
molecules per unity cell (2H); and c) trigonal with two molecules per cell unity. However,
2H1 and 3R (Figure 1-9) are the only ones type of structures which have been detected.
34

Figure 1-7: MoS2 crystalline structure.

These details of structure cause the anisotropic phenomena to be present in

Molybdenite, which is a typical property of hydrophobic species. For example; the
microhardness of the (001) plane is 320 MPa and the (100) plane’s is 9000 MPa.
Furstenau has called faces to the planes determined by sheets (001) and edges the
plane (100) perpendicular to the aforementioned.
According to Gaudin’s theories, in a molybdenite crystal, we may foretell that the
breakages of van der Waals’ bonds produce cleavages in the face plane; besides; this sort
of bonds has got its centres on the S-atoms of different layers. This plane (001) may be
characterised as hydrophobic.
On the other side, breakages of the molybdenum-sulphur chemical bonds will cause
cleavages through the edge planes; so these planes are the most energetic.
This reasoning was useful in order to explain not only the molybdenite anisotropic
behaviour of its electric and thermal conductivities [42], but also its hydrophobic
behaviour as a function of particle size [6].
According to Chander and Fuerstenau, generally, and particularly for molybdenite, the
smaller its particle size is, the larger its possibility of producing cleavages through edge
planes are; furthermore a loss of flotability and natural hydrophobicity is produced.
 35

Figure 1-8: Fragment of a MoS2 layer. S atoms are represented by hollow circles. Doble circles
lay on the (110) plane.

This happens when the surfaces become richer in strong bonds of marked polarity,
furthermore, they become richer also from the energetic point of view.
This is of paramount importance for its concentration-flotation process, because these
phenomena explain in a simply way the low recoveries observed in molybdenite-fine
particles during the aforementioned process.
However, Trahar and Warren [9] do not agree with these statements. They claim that
largest particles may become richer energetically on being subjected to tensions during
the comminution processes without dissipating energies through breakages.

1.13 Hydrophobicity and Surface energy of Molybdenite

Contact angle measures, ‘pzc’ determinations on different cleavages planes and
Hallimond’s tube flotation tests (all considered to be pH functions) have been carried out
in order to confirm the aforementioned hypothesis [6].
This approach has allowed some authors to obtain interesting conclusions related to
chemical superficial reactions that have an influence on molybdenite hydrophobic/
hydrophilic behaviour [8][6][43].
However, there is a lack in scientific literature related to the straight links between the
surface free energy and the particle size. This may be achieved through a suitable
interpretation of the contact angle measurements, because this is an energetic sign of its
composing faces.
A suitable implementation of wetting thermodynamic models may reach an adequate
estimation of the surface free energy and its dispersion and polar components. It is very
convenient in this sort of treatments to carry out direct or indirect measures of the contact
angle of the solids in contact with different pure liquids.
The parameters that the evaluation of this models yield; particularly; surface energy of
different granulometric classes, will be an evidence for the edges-faces sites theory and
its links with the particle size.
36

(a) (b)

(a) (b)
Figure 1-9: Views of different MoS2 crystals: (a) Simple polytype in ‘ab’ plane. (b) Simple
polytypes along the ‘c’ axis. Figures (a) and (b) can be considered as top views and side views of
variuos simple polytypes of MoS2, if the plaquettes were in their base planes on an horizontal
plane. Black circles represent Molibdenum atoms and open circles represent Sulfur atoms. In
(a) the solid circle inside the open circle represents Mo atoms and S located on top of others.
(c) (d) (e)
Figure 1-10: Mo1−xS2 crystalization model. Triangles indicate fragments of Mo1−xS2 layers.
(a) Random arrangement of MoS2 layers (b) Piling order of layers with random orientation
with respect to ‘c’ axis and 001-plane. (c) Hexagonal MoS2 with imperfect piling ordering
(d) hexagonal MoS2 in antiparallel orientation (e) Rombohedric MoS, all layers are in parallel
orientations.

Solids of low surface energy, hydrophobicity and natural flotability are terms that have
been utilised as synonyms with a few exceptions as Warren and Trahar [9].
Either the surface energy ( γ s ) and its components (γ S , γ S ) or the parameters of the
d P

different angle contact models, α (Zisman); Φ SL (Girifalco-Good), will allow us to set

up and inherent hydrophobicity ranking in a more precise way.
The natural flotability will be a consequence of hydrophobicity, however we do not
have to forget that the hydrodynamic aspects that are present in the flotation process.
Flotation process can be defined as a probabilistic event
PF = PC × Pad × Pes (1-123)

where PF is the flotation probability, PC is the particle-bubble collision probability,

Pad is the adhesion probability and Pes is the probability of setting up a bubble-solid
system.
We observe that the flotation probability is determined by two terms, PC and Pad
(defined chiefly by the hydrodynamics of the system) and a third one Pes (related to an
equilibrium system and associated to thermodynamic properties such as solid surface
energy or the contact angle of the system.)
In this way, we aim to evaluate the different meaning between floatability and
hydrophobicity such as Trahar [9] did on treating the flotation behaviour of fine particles.
Though, it is not right to link straight and strongly the contact angle with the flotation
behaviour (natural or induced), however; it is impossible not to take into account the
 37

extreme conditions that the equilibrium thermodynamic defines, such as the complete
wetting conditions that prevent genuine flotation of a mineral species.
Chapter 2
Experimental Part
2.1 Materials

Molybdenite mineral:
A sample from a molybdenite concentrate of Chuquicamata Division was used. This
was sized in six granulometric classes using a Cyclosizer equipment.
Only one of them was larger than 44 µm. Every sample was washed and purified.
They were cleaned thoroughly with diethyl ether to eliminate the flotation agents
remaining, and then lixiviated in 1:1 H2SO4 solution. After this, they were thoroughly
washed with distilled water until the complete removing of sulphate into de wasted water.
At once, the samples were treated overnight with a 40 g/L-CNNa solution in order to
eliminate the surface impurities such as Cu, Fe and Re. These might be present either as
substitutions in the crystal lattice of molybdenite or as sulphide remains disseminated into
the Molybdenite. The excess of cyanide was removed through a profuse washing with
distilled water, subsequently, particles were dried up at room temperature.
The chemical analyses are shown in Table 2.1.
Table 2-1: Chemical Analyses. Content of Mo and Cu, Fe and Re impurities in the molybdenite
samples after being purified.
Cyclosizer Size Re Fe Cu Mo
class [µm] [%] [%] [%] [%]
+C1 >44 .004 .622 . 49.7
7 594
C1/C2 44- .018 .487 . 50.5
33 343 7
C2/C3 33- .019 .507 . 52.9
23 281 6
C3/C4 23- .017 .046 . 54.9
16 8 299 5
C4/C5 16- - - - -
12
−C5 <12 .29 .543 . 54.9
293 6

Liquids:
Glycerine, formamide, di-I-methane, tetra- Br- ethane and methanol (p.a.) were used
(Table 2.2). The water was bi-distilled in a quartz-equipment.
MIBC (methyl-iso butyl carbinol), technical grade commonly used in flotation.
 39

Table 2-2: Properties of the used liquids (20o C, after Fowkes).

Liquid δ γL γ LD γ Ld γ ×102 γ LP
−3 −1
[kgm ] [mNm ] [mNm−1] [mNm−1]
[mN-½m½]
Water 998 72.1 21.8 ±.7 6.5 ± .2 50.2
Glycerine 1261 63.4 37 ±4 9.6 ± .5 26.4
Formamide 1133 58.4 39.5 ±7 10.8 ± .95 18.9
Di I methane 3325 50.8 48.5 ±9 13.7 ± 1.4 2.3
Tetra Br ethane 2960 49.7 49.7 14.2 -
 : Density
γ L : Liquid surface tension.
γ LD : Dispersive component of the surface tension
γ LD γ : Fowkes’ ordinate
γ LP : polar component of the surface tension

Equipment:
• Cyclosizer classifier
• Paul Weber–Marsch U Apparetebau Stuggart hydraulic press
• Cathetometer
• Tripod with an adjustable platform and indicator of horizontally
• Transparent Chamber
• Dosage injection
• Spray
• Microscope with goniometer
• Hallimond flotation tube with a 40 cm- height and 3 cm diameter column.
• Magnetic stirrer
• Cylindrical containers with pressurised nitrogen.
• Agitair L-500 flotation cell.
• 20 mL test tubes
• Modified test tubes with an underflow discharge
• 25 mL tubes

Synthetic molybdenite:
• MoS2 Merck (p.a.)

Molybdenite massive crystal:

A high purity crystal was cut in a prismatic shape so the polished “face” plane was a
1.5 cm side square and the polished “edge” plane was a 1.5 cm x 0.8 cm rectangle. The
polishing was carried out utilizing baize and an alumina power; this polishing was
repeated after each one of the contact angle measurements, previously washed by
methanol.
40

Methyled Silica:
• Aerosil reagent (p.a.) purity

High purity quartz:

A sample of quartz was ground at <74 µm, treated with HCl to eliminate Fe, and then
profusely washed with distilled water until the complete chloride removal.
 41

Table 2-3: Performed measurements carried out by the Kossen and Heerjes’ method.
(a) Sample +C1 (> 44 µ m)
42

Liquid (1−Ev) h ×103 cosθ Fadh W

adh
Water .824 4.24 −. − 62.8
127 9.17
Glycerine .799 2.4 .430 27.2 90.6
Formamide .818 2.08 .541 31.6 90.0
Di I methane .831 0.12 .959 48.7 99.5
 43

Tetra Br ethane .800 nil 1.0 49.7 99.4

(b) Sample C2/C1 (44-33 µ m)
Liquid (1−Ev) h ×103 cosθ Fadh W
adh
Water .821 4.40 −. − 58.6
160 13.4
Glycerine .821 2.96 .222 14.1 77.5
Formamide .821 1.84 .605 35.3 93.7
Di I methane .813 0.04 .986 50.1 101
Tetra Br ethane .820 nil 1.0 49.7 99.4
(c) Sample C3/C2 (33-23 µ m)
Liquid (1−Ev) h ×103 cosθ Fadh W
adh
Water .805 4.20 −.114 − 63.8
8.17
Glycerine .848 2.76 .319 20.2 83.6
Formamide .842 1.40 .711 41.7 99.9
Di I methane .847 0.24 .914 46.4 97.2
Tetra Br ethane .807 nil 1.0 49.7 99.4
(d) Sample C4/C3 (23-16 µ m)
Liquid (1−Ev) h ×103 cosθ Fadh W
adh
Water .881 4.20 −. − 67.4
064 4.63
Glycerine .861 2.40 .450 28.5 91.9
Formamide .799 1.92 .578 33.6 91.8
Di I methane .844 nil 1.0 50.8 102
Tetra Br ethane .817 nil 1.0 49.7 99.4
(e) Sample C5/C4 (16-12 µ m)
Liquid (1−Ev) h ×103 cos Fadh Wadh
θ
Water .849 3.45 .270 1 91.4
9.4
Glyceriene .851 2.40 .506 3 95.6
2.2
Formamide .859 1.95 .586 3 92.6
4.2
Di I methane .858 0.10 .982 4 100.
9.9 7
Tetra Br ethane .860 nil 1.0 4 99.4
9.7
(f) Sample −C5 (< 12 µ m)
Liquid (1−Ev) h ×103 cos Fadh W
θ adh

Water .815 3.35 .290 20. 92.9

9
Glycerine .812 2.30 .466 29.5 92.9
Formamide .809 2.00 .560 32.7 91.1
Di I methane .799 0.20 .927 47.1 97.9
Tetra Br ethane .805 nil 1.0 49.7 99.4
(g) Sample p.a.
Liquid (1−Ev) h ×103 cosθ Fadh W
adh
Water .851 4.25 −.116 − 63.7
8.35
Glycerine .781 2.55 .370 23.5 86.9
Formamide .820 1.90 .589 34.4 92.8
Di I methane .782 nil 1.0 50.8 102
Tetra Br ethane .812 nil 1.0 49.7 99.4
44

2.2 Contact angle measurements on a cylindrical cake

The Kossen and Heertjes’s method [1] was applied. It consists in performing the
measure of the equilibrium height of a lying drop on a compressed cake (Table 2-3.)
The molybdenite cylindrical cakes have approximately a 1.5 cm diameter and a
variable height. They were obtained by applying a 7-ton force.
The measure equipment was a small closed transparent chamber that contained the
tablet inside with a device that assures it to be laid down horizontally. The measurement
was carried out with a cathetometer. A drop of liquid was deposited over the surface of
the cake using a syringe, and then the interior atmosphere is saturated with a vaporiser.
These steps are repeated until the drop reached to a constant height. The authors of this
method suggest doing the final measurement within an hour, in our case we decided for a
3-hour operation to assure the equilibrium conditions. Especial care was taken with the
illumination in order to minimise the problems of reflection and background which
difficult the observation during the test.
The formula (A-184) from the appendix was applied in the calculations

B h2
cos θ = 1 − (2-124)
3 (1 − EV ) (1 − B h2 2 )
Defining
ρg
B= (2-125)
2 γ LV
where ρ is the liquid density, h is the equilibrium height of the drop, g the acceleration
of natural gravity, EV is the factor of packaging of the cylinder cake. In these tablets the
packaging factor is simply calculated by:
M
( 1 − EV ) = (2-126)
ρ S VP

where M is the pellet mass and ρ S is the mineral density and V P is the cake volume.

M was obtained by weighing, ρ S of molybdenite was considered as 4801 kg m-3. The

geometric measures of the cake were carried out with high precision instruments in the
Metrology Division Department of the Metallurgical School of Engineering (Universidad
de Concepción.)

2.3 Contact angle measurements on a massive crystal

The direct method of the laying drop was applied utilising a microscope with a
goniometer. A series of measures were performed in different zones of the crystal before
reaching to an ultimate value. The measurements were performed in the aforementioned
closed chamber.
 45

Table 2-4: Contact angles measurements on a molybdenite crystal

(a) Edge plane
Liquid θ cosθ Fadh Wadh
Water 66± .407±. 2 101
2 03 9.3
Glicerine 50± .643±. 4 104
3 04 0.8
Formamide 42± .743±. 4 102
2 02 3.4
Di I methane 24± .914±. 4 97.2
2 03 6.4
Tetra Br ethane 15± .966±. 4 97.7
2 01 8.0
(b) Faces plane
Liquid θ cosθ Fadh Wadh
Water 84± .105±.1 7 79.6
6 .56
Glicerine 63± .454±. 2 92.2
3 05 8.8
Formamide 55± .574±. 4 91.9
5 06 4.5
Di I methane 17± .956±. 4 99.4
1 04 8.6
Tetra Br ethane 0 1.0 4 99.4
9.7
θ : contact angle in sxagesimal degrees
Fadh y Wadh: Idem before

2.4 Hornby-Leja’s method

Several methanol-bi-distilled solutions were prepared. 10 mL of each solutions were
poured in a 25 mL test tube. A little sample of mineral was brought in contact with a
water-methanol solution into the test tube. These tubes were tapped with Parafilm and
shaken during 30 seconds. After a few hours we observed if the complete wetting of the
sample was carried out.
This way the intervals of wetting of the surface tension variable (methanol
concentration) were determined.
This interval of wetting was diminished with a series of runs until getting the finest
possible determination.
The p.a. Molybdenite and Methylated silica were tested besides the granulometric class
samples.

2.5 Quantified wetting method

This is a new method proposed by the authors of this work. The procedure to be
followed is similar to the Hornsby-Leja’s method. The test tubes utilised in our method
46

were modified with an underflow discharge in order to remove the sunken material and
so quantify the process.
The sunk fraction is denominates sink and the floated float.
The concentration of methanol (%) in the solution vs. float (%); and the surface tension
the solutions vs. float (%) were plotted for every tested sample.
Table 2-5: Measurments by quantified sink method
(a) Fraction +C1 ( > 44 µm)
Float CMet γLV [mNm−1]
6.4 5 63.9
13.0 10 58.0
11.6 14 54.5
1.9 20 50.0
2.0 25 46.9
1.2 30 44.0
(b) Fraction C2/C1 (44−33 µm)
Float CMet γLV [mNm−1]
6.4 5 63.9
13.0 10 58.0
11.6 14 54.5
1.9 20 50.0
2.0 25 46.9
1.2 30 44.0
(c) Fraction C3/C2 (33−23 µm)
Float CMet γLV [mNm−1]
13.9 5 63.9
19.9 10 58.0
10.0 14 54.5
2.6 20 50.0
1.9 25 46.9
0.7 30 44.0
(d) Fraction C4/C3 (23−16 µm)
Float CMet γLV [mNm−1]
13.8 5 63.9
10.7 10 58.0
10.8 14 54.5
9.31 20 50.0
3.1 25 46.9
1.4 30 44.0
(d) Fraction C4/C3 (23−16 µm)
Float CMet γLV [mNm−1]
13.8 5 63.9
10.7 10 58.0
10.8 14 54.5
9.31 20 50.0
3.1 25 46.9
1.4 30 44.0
(e) Fraction −C5 ( < 12 µm)
Float CMet γLV [mNm−1]
18.7 0 72.0
25.7 2 68.0
24.5 5 63.9
8.0 10 58.0
10.7 14 54.5
5.7 20 50
(f) MoS2 (p.a)
Float CMet γLV [mNm−1]
16.1 5 63.9
11.3 10 58.0
2.0 14 54.5
1.2 20 50.0
0.2 25 46.9
0.0 30 44.0
CMet: percentage volume in aqueous solution
γLV: surface tension of the solution
 47

A. Collector tube
B. Rubber plug
C. Frosted union
D. Magnetic bar
E. Porous glass stabe
F. Magnetic stirrer
G. Water level
H. Water tramp
I. Rotameter
J. Valve

Figure 2-11: Hallimond’s tube, modified for fine particles.

2.6 Hallimond’s tube Flotation

Flotation tests were performed in Hallimond’s tube adapted for fine particles (Figure 2-
11). See Table 2-6.
The tests were carried out with the molybdenite granulometric fractions and p.a.
Molybdenite.
All the different samples were treated in independent tests and using different water-
methanol solutions.
The gas was nitrogen; it was supplied from a pressurised balloon; it entered to a
general line that worked as a reservoir. Its flow was controlled and measured with a flow-
meter. The gases were washed before entering the Hallimond’s tube with KOH, pyrogalol
and water. The tests were performed with an additional open column with water in order
to avoid a gas overpressure at the very beginning of all the tests. This column presented a
resistance to the flow-gas equal to the resistance produced by the Hallimond’s tube.
48

The experiment was a semi batch process; the operation time was fixed in three
minutes. The amount of solid sample was of 2 grams and the gas flow was also fixed
constant to 60 cm3/minute. During the operation time the pulp was homogenised by a
magnetic stirrer bar.
Table 2-6: Flotation test in Hallimond tube. Recovery percentage obtained for each especies vs.
Methanol concentration CMet and it surface tension γ L
% Recovery
CMet γL Test 1 Test 2 Test 3 Test 4 Test 5 Test 6
−1
% (v/v) [mNm ] >44µm 44–33µm 33–23µm 23–16µm <12µm MoS2 (p.a.)
0 72 62 55 60 56 44 85
2 68 - - - - - 70.7
5 63.9 - - - - - 29.3
8 60 42.1 54 62 56 24 22
10 58 58 66 56 - - -
12 56.2 47 47 55 55 7.8 23
14 54.5 47 - 55 42 60.2 -
16 53 32 52 30 40 32 21
18 51.5 36 57 - 52 26 -
21 49.4 13.4 35 35 41 13 20
25 46.9 31 21 39 25 10 -
40 39 32 38 29 31 28 26
100 23 - 13 13 5 19 -

2.7 Conventional cell flotation of the sample in presence of

quartz
Semi–batch tests were performed on a composite sample containing 11 g of each
granulometric fraction and 554 g of quartz in order to simulate the presence of a quartz
gangue. The solids concentration in the pulp was 16 %.
The only reagent utilised was MIBC (methyl-isobutil-carbinol), as a frother: three
droplets. The cell was a conventional Agitair L-500 one.
The samples of the concentrate were removed from the cell at scheduled times
(flotation kinetics). The recoveries are calculated through molybdenum analyses.
The flotation nitrogen flow was kept constant.
 49

Table 2-7: Flotation test in conventional cell for each fraction in the presence of quartz
% Recovery
Time Test 1 Test 2 Test 3 Test 4 Test 5 Test 6
minutes >44 µm 44−33 µm 33−23 µm 22−16 µm < 12 µm MoS2 (p.a)
1 - 31.5 57.7 51.0 23.7 18
2 79.1 60.8 67.9 58.6 57.1 53.9
3 83.1 - - - - -
4 - 77.6 81.9 65.3 71.5 62.4
5 84.4 - - - - -
6 - 90.8 84.9 67.2 74.1 63.3
7 85.3 - - - - -
8 - 91.1 84.9 69.3 75.3 67.2

2.8 Flotation of a collective of molybdenum samples

The same method as described before was followed.
The sample of the concentrates was separated by Cyclosizer in granulometric classes of
the same size as those which composed the feed. This allowed us to calculate the
recoveries of each fraction through a granulometric analysis.
Table 2-8: Flotation test in a conventional cell of a collective of granulometric samples.
% No flotado
Time Total Test 1 Test 2 Test 3 Test 4 Test 5 Test 6
minutes > 44 µm 44−33 µm 33−23 µm 23−16 µm < 12 µm MoS2 (p.a.)
1 87.2 86.7 87.2 87.6 86.9 87.2 87.3
2 76.3 75.0 77.2 76.9 75.9 75.6 76.6
4 51.3 53.9 55.1 53.2 50.1 50.4 45.1
8 27.1 31.6 29.6 28.3 25.6 26.6 23.2
16 9.3 11.2 8.92 9.25 9.37 10.3 8.0
Chapter 3
Results
3.1 Contact angle measurements
The results are shown in Table 2-3; they were processed according to the previously
described models.

3.1.1 Zisman’s model

The parameters of this model were obtained using the minimum least square technique
and are shown in Table 3-9. This model fits well according to the correlation coefficients
an its plotting (Figure 3-12).
The obtained critical wetting tensions γ c range around a mean value of 49.5 mJ/m2.
There is no significant variation between the γ c ’s obtained considering the analytical
precision of the experimental data.
The largest absolute values of the Zisman’s slope α belong to largest size fractions
(<16 µm) and p.a. Molybdenite.

Figure 3-12: Wettability of different types of molybdenite, according to Zisman’s model

(A: water, G: glycerine, F: formamide, I: di-I-methane y B: tetra-Br-ethane).
 51

There is a marked difference between α slopes values of edge and face surfaces; face
surface slope is larger.

Figure 3-13: Wettability of different types of molibdenites, accordind to Good’s model

(A: water, G: glycerine, F: formamide, I: di-I-methane y B: tetra-Br-etane).
52

Table 3-9: Results after modelling cosθ vs. γLV for each species acording to Zisman’s model
[cosθ = 1 + α(γ − γc)]
Species γc −α ×102 Regression
[mNm−1]
coefficient
> 44µm 49.9 ± 4.92 ± .3 .99
3.6
44−33µm 50.2 ± 5.40 ± .3 .995
2.6
33−23µm 50.0 ± 4.94 ± .4 .98
4.5
23−16µm 50.3 ± 4.76 ± .3 .99
3.2
16−12µm 49.0 ± 3.36 ± .4 .97
5.5
< 12µm 47.9 ± 3.20 ± .4 .95
6.7
MoS2 (p.a.) 50.8 ± 5.22 ± .15 .99
1.5
Edge 47.9 ± 2.42 ± . .99
1.8 087
Face 49.3 ± 4.00 ± .22 .99
2.8

3.1.2 Girifalco & Good’s Model

This model fits well too, according to the correlation coefficients and its plots (Figure
3-13). In this case, γ c ranges narrowly around a mean value of 50.0 mJ/m2.
The p parameter is larger for the largest sizes (>16 µm) and for MoS2 p.a.
There is also a marked difference between p parameter values of edge and face
surfaces; face surface slope is larger.
Table 3-10: Results after modeling cosθ vs. γLV relationship for each species according to Girifalco-
Good semiempiric model [ cos   p   Cte ].
Species γc p Regression
−1
[mNm ]
coefficient
> 44µm 50.2 4 .98
4.9
44−33µm 50.5 4 .99
9.4
33−23µm 50.3 4 .97
4.8
23−16µm 50.5 4 .98
 53

3.4
16−12µm 49.7 3 .99
1.1
< 12µm 48.9 2 .98
9.9
MoS2 (p.a.) 51.3 4 .99
9.0
Edge 48.7 2 .993
2.1
Face 49.8 3 .997
6.8
54

Figure 3-14: Wettability of different types of molibdenites, accordind to Lucassen-Rynders’

model (A: water, G: glicerine, F: formamide, I: di-I-metane y B: tetra-Br-etane).

3.1.3 Wetting model (Lucassen-Rynders)

The correlation coefficient is acceptable for every fitting but little less than the value
we got in previous models (Figure 3-14).
The obtained γ c are very similar for each of the species on study and ranges around
50 mJ/m2 as a mean value. The m slope is quite different for MoS2 p.a. and the largest
sizes from the finest diameters. This difference appears too between the m slope of the
edge and face planes. Face’s are larger (Table 3-11)
Table 3-11: Results after modelling cosθ vs. γLV relationship for each species according to the
Lucassen-Reynders semiempirical model [Fadh = mγLV + Cte].
 55

Species γc −m Regression
−1
[mNm ]
coefficient
> 44µm 50.5 2.5 .96
44−33µm 50.6 2.8 .98
33−23µm 50.7 2.5 .95
23−16µm 50.8 2.6 .97
16−12µm 49.7 1.4 .98
< 12µm 48.9 1.3 .97
MoS2 (p.a.) 50.8 2.6 .97
Edge 49.1 .77 .96
Face 50.0 1 .993
.85
56

Figure 3-15: Wettability of different types of molybdenite, according to Fowkes’ model

(A: water, G: glicerine, F: formamide, I: di-I-metane y B: tetra-Br-etane).

3.1.4 Fowkes’ model

This model is suitable for obtaining γ S . The parameters (Table 3-12) are calculated on
d

the basis of the least square technique, they show uncertainty; such as the obtained as an
average in each one of the measures.
The value of γ S is larger for the finest sizes (< 16 µm) compared with the largest sizes
d

and MoS2 p.a. The “edge” surface gets a γ S larger than the “face” surface. On watching
d

Figure 3.4 it could be appreciated that the correlation in “edge” surfaces is not good,
 57

although the experimental points are on a straight line this function does not match the
point (0,-1) as the Fowkes’ model demands.
Table 3-12: Results after modelling wetting conditions for each species according to Fowkes’ model [
cos θ = −1 + 2 γ sd γ L ].
Species γsd* γsd**
[mNm−1] [mNm−1]
> 44µm 50.8 ± 49.8 ±
1.6 4.2
44–33µm 48.9 ± 47.9 ±
3.6 6.5
33–23µm 51.1 ± 51.0 ±
3.7 6.7
23–16µm 52.6 ± 53.0 ±
1.2 2.7
16–12µm 55.5 ± 62.6 ±
5.7 1.9
< 12µm 54 ±7 61.6 ±
2.1
MoS2 (p.a.) 51.5 ± 50.3 ±
1.4 3.1
Edge 63.7 ± 30 63 ± 30
Face 54.9 ± 58.6 ± 10
3.4
*
Calculated as aparameter of equation: cos θ = −1 + 2 γ sd γ Ld γ L .
(1+cosθ ) 2 γ L2
Calculated as an average of each determination γ s =
d
**
4 γ Ld .

3.1.5 Wu’s model

The γ S and γ S foretold by this model are shown in Table 3.5. The method used to
d p

calculate these parameters will be described in Chapter 4.

It may be observed that γ S is very similar for the different models we are applying.
However, the smaller the particle is, the larger its polar component is. It could be
observed also a larger polar component for the “edge” surface than the polar component
of the “face” surface.
All the values this model obtains have a high range of uncertainty.
Table 3-13: Resultados del tratamiento de mojabilidad de acuerdo a la ecuación de Wu.
Species γsp γsd γs (γsp/γs) × 102
[mNm ] [mNm−1]
−1
[mNm−1]
> 44µm .75 ± .3 48.4 ± 49.4 ± .4 1.5
1.2
58

44−33µm 1.8 48.2 50.0 3.6

33−23µm 2.4 ± 3.1 45.8 ± 48 ± .2 5.0
2.2
23−16µm 1.8 ± .6 48.5 ± 50.3 ± 3.6
2.3 2.0
16−12µm 5 ± 4.3 46.6 ± 51.6 ± 9.7
1.8 2.6
< 12µm 5.3 ± 4.8 44.0 ± 48.7 ± 11.0
1.5 2.3
MoS2 (p.a.) .9 ± .3 49.0 ± 49.9 ± 1.8
2.8 2.5
Edge 9.7 ± 3.8 41.7 ± .7 51.4 ± 3 18.8
Face 3.4 ± 2.2 45.8 ± 49.2 ± . 6.9
1.3 95

3.1.6 Dann’s Model

Dann and Wu’s model are aimed at calculate the polar and dispersion components of
the solid surface energy γ S . The resolutions method was analysed and explained in
Equation (1-94).
By observing the results (Table 3-14), it can be noticed that the largest particles and
MoS2 p.a. have got a larger dispersion component than the finest sizes. On the contrary,
the 12-16 µm and <12 µm fractions have got the largest polar components. The
comparison between both “edge” and “face” shows a similar situation to the mineral
species ones; having the “edge” surfaces a larger polar component.
Table 3-14: Results for treatment of wettability according to Dann’s equation
Species γsp γsd γs (γsp/γs)×102
[mNm−1] [mNm−1] [mNm−1]
> 44µm - 51.4 51.4 -
44–33µm - 51.2 52.7 -
33–23µm 3.4 × 10−5 51.2 51.2 0
23–16µm .025 51.8 51.8 .05
16–12µm 2.37 46.4 48.8 4.9
< 12µm 2.58 44.6 47.2 5.5
MoS2 (p.a.) - 52.8 52.8 -
Edge 6.21 43.8 50.0 12.4
Face 0.76 48.1 48.8 1.6
 59

MoS2 (p.a.)

FACES

EDGES

Figure 3-16: γ SW (interfacial tension solid/water) as a function of the particle size. According
to Neumann-Good’s model.

3.1.7 Neumann-Good’s model

A procedure based on the state equation described in Section 1.8 was applied.
The calculated values of γ SL and Φ SL for each of liquid-molybdenite species pair were
written down in Table 3-15.
As it might be expected, the larger the liquid surface tension is, the larger the liquid-
solid tension becomes; and Φ SL increases as we get closer to critical-wetting conditions.
The calculated values of γ SV (solid-vapour tension), γ SW (interfacial solid-water tension)
and the solid-water interaction parameter Φ SW are shown in Table 3-16.

The calculated γ SV for each MoS2 species are similar.

On the contrary, the calculated γ SW for the largest particles are almost nearly twice of
the < 16 µm values’. The same happens when we compare “edge” and “face” surfaces
γ SW values. The “face” values double the “edge’s” values.

Inversely; the interaction parameter Φ SW of the finest particles is larger than those of
the largest’s. The “edge’s” surface has got also a larger interaction parameter than the
“face’s”.
The opposite trends of Φ SW and γ SW is obvious if we keep in mind the constitutive
Equation (1-119).
60

EDGES

FACES

MoS2 (p.a.)

Figure 3-17: φSW (solid/water interaction parameter) as a function of particle size according to
Neumann-Good model.

Both parameters γ SW and φSW are plotted against the size particle (Figure 3-16 and
Figure 3-17).
 61

Table 3-15: Results after applying the equation of state (Neumann-Good)

(a) Species > 44 µm
Liquid γSL φSL calculated
[mNm−1]
Water 60.4 .501
Glicerine 24.0 .808
Formamide 19.6 .843
Di I methane 2.5 .980
Tetra Br ethane* 1.5* .988
(b) Species 44−33 µm
Liquid γSL φSL calculated
Water 65.5 .476
Glicerine 38.0 .696
Formamide 16.8 .865
Di I methane 2.0 .984
* *
Tetra Br ethane 2.4 .981
(c) Species 33−23 µm
Liquid γSL φSL calculated
Water 59.4 .524
Glicerine 31.0 .751
Formamide 9.5 .924
Di I methane 4.8 .961
* *
Tetra Br ethane 1.5 .988
(d) Species 23−16 µm
Liquid γSL φSL calculated
Water 55.9 .555
Glicerine 22.5 .821
Formamide 17.4 .861
Di I methane* 0.2* .998
Tetra Br ethane* 1.3* .99
(e) Species 16−12 µm
Liquid γSL φSL calculated
Water 31.1 .756
Glicerine 18.3 .856
Formamide 16.3 .872
Di I methane .6 .995
* *
Tetra Br ethane .8 .994
(f) Species < 12 µm
Liquid γSL φSL calculated
Water 29.6 .763
Glicerine 21.0 .832
Formamide 17.8 .857
Di I methane 3.4 .972
* *
Tetra Br ethane .8 .993
(g) Species MoS2 p.a.
Liquid γSL φSL calculated
Water 60.4 .520
Glicerine 28.5 .773
Formamide 17.6 .860
* *
Di I methane 1.2 .990
* *
Tetra Br ethane 2.3 .982
(h) Species borde
Liquid γSL φSL calculated
Water 20.3 .837
Glicerine 8.8 .930
Formamide 6.2 .950
Di I methane 3.2 .974
Tetra Br ethane 1.6 .987
(i) Species cara
Liquid γSL φSL calculado
Water 43 .657
Glicerine 21.8 .826
Formamide 17.1 .864
Di I methane 2.0 .984
* *
Tetra Br ethane .9 .993
*
wetting complete conditions
62

Table 3-16: γSV, γSW, φSW determined by the equation of state (Neumann-Good) for each fraction
Species γSV γSW φSW ω × 103
[mNm ] [mNm−1]
−1
[mNm−1]
> 44µm 51.2 60.4 .516 8.000
44−33µm 52.1 65.5 .476 8.000
33−23µm 51.2 59.4 .524 8.000
23−16µm 51.5 55.5 .555 7.960
16−12µm 50.5 31.1 .756 7.839
< 12µm 50.5 29.6 .763 7.970
MoS2 (p.a.) 52.0 60.4 .520 7.937
Edge 49.6 20.3 .837 8.000
Face 50.6 43.0 .657 7.970
γSV: interfacial tension solid-vapor
γSW: interfacial tension solid-water
φSW: Good’s parameter of solid-water interaction
ω: relation parameters φSL = −ωγSL + 1

3.1.8 Comparison between the values predicted by different models

It is illustrative to compare the experimental cos θ vs. the predicted values by each
model for different kinds of MoS2; these are shown in Table 3.9. The parameters obtained
by different models are introduced in their equations and so getting the cos θ fitting
value that we must compare with the experimental value. It is difficult to define which
model is the best; but; it is possible to asses that the Fowkes’ model does not fit well
neither the finest particles behaviour (<16 µm) nor the measures done on the MoS2
massive crystal; especially the “edge” surface.
 63

Table 3-17: Comparison of obtained data vs. Predicted for each species and different models
(a) Fraction > 44 µm
Liquid cosθ cosθ calculated
Experimental Zisman Good DM Fowkes Dann Wu
Water −.127 −.087 −.046 −.045 −0.73 −.070 −.124
Glicerine .430 .337 .301 .288 .368 .376 .369
Formamide .541 .582 .538 .527 .540 .543 .539
Di I methane .959 .956 .962 .979 .953 .966 .952
Tetra Br ethane 1.000 1.000* 1.000* 1.06 1.024* *
.973
(b) Fraction 44−33 µm
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water −.160 −.177 −.130 −.129 −0.91 −.058 −.070
Glicerine .222 .287 .253 .233 .343 .393 .427
Formamide .605 .557 .512 .492 .510 .563 .600
Di I methane .986 .968 .979 .985 .916 .990 .983
* *
Tetra Br ethane 1.000 1.000 1.000 1.000* .986 *
.969
(c) Fraction 33−23 µm
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water −.114 −.087 −.037 −.035 −0.071 −.070 −.052
Glicerine .319 .338 .310 .299 .372 .374 .430
Formamide .711 .585 .545 .539 .544 .541 .599
Di I methane .914 .960 .969 .993 .959 .963 .947
* * *
Tetra Br ethane 1.000 1.000 1.04 1.070* 1.030* *
.918
(d) Fraction 23−16 µm
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water −.064 −.033 +.008 −.060 −0.057 −.035 −.068
Glicerine .450 .376 .343 .285 .392 .407 .430
Formamide .578 .614 .572 .532 .567 .573 .604
Di I methane 1.000 .976 .982 1.0* .987 .983 .989
Tetra Br ethane 1.000 1.000* 1.05* 1.08* 1.06* *
.976
(e) Fraction 16−12 µm
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water .270 −.227 .254 .257 −.032 .186 −.078
Glicerine .506 .516 .494 .481 .430 .556 .566
Formamide .586 .684 .658 .642 .609 .695 .735
Di I methane .982 .940 .952 .948 1.04* .960 .995
*
Tetra Br ethane 1.000 .976 1.000 1.000* 1.11* .932 .936
(f) Fraction < 12 µm
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water .290 +.229 .248 .262 −.044 −.182 −.076
Glicerine .466 .504 .479 .474 .411 .541 .547
Formamide .560 .664 .637 .626 .587 .677 .709
Di I methane .927 .907 .919 .914 1.013* .927 .943
Tetra Br ethane 1.000 .942 .965 .963 1.09* .895 .878
(g) Sample p.a.
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water −.116 −.107 −.067 −.06 −.067 −.058 −.113
Glicerine .370 .342 .313 .285 .378 .394 .385
Formamide .589 .603 .571 .532 .550 .563 .557
* *
Di I methane 1.000 1.0 1.03 1.00 .966* .992 .970
*
Tetra Br ethane 1.000 1.06 1.1 1.08* 1.03* *
.986
(h) Edges
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water .407 .417 .438 .437 .038 .407 .247
Glicerine .643 .625 .609 .600 .532 .761 .684
Formamide .743 .746 .725 .718 .723 .893 .828
Di I methane .914 .930 .934 .941 1.187* *
.912
Tetra Br ethane .966 .956 .970 .979 1.27* *
.825
(i) Faces
Liquid Experimental Zisman Good DM Fowkes Dann Wu
Water .105 .092 .122 .129 −.037 .071 −.003
Glicerine .454 .436 .407 .398 .423 .472 .481
Formamide .574 .636 .601 .590 .600 .623 .650
Di I methane .956 .940 .948 .955 1.03* .954 .963
*
Tetra Br ethane 1.000 .984 1.005 1.02* 1.1* .968 .918
*
wetting critical condition or total predicted by the models
DM: Wetting model (Lucassen-Reynders).
64

3.2 Techniques where water-methanol solutions were used

3.2.1 Hornsby- Leja method
The γ c obtained by applying this method are shown in Table 3.10. They are all similar
for the different sorts of Molybdenite (γ c = 55 mNm ) except for the largest particle
−1

fraction (> 44 µm), with a γ c = 49 mNm and the finest particle fraction (<12 µm) with a
−1

γ c = 59.5 mNm −1 .
Additionally, the Methylated silica is shown in order to observe the behaviour of an
almost ideal hydrophobic species.
Table 3-18: Critical methanol in water solution concentrations of wetting determined by the
Hornsby-Leja’s for different species
Species Cmet γc
[%] [mNm−1]
> 44µm 21− 49
22
44−33µm 13− 55
14
33−23µm 13− 55
14
23−16µm 11−12 56.5
< 12µm 8−9 59.5
MoS2 (p.a.) 13− 55
14
Methilade Silica 48− 36
49
Cmet: percentage volume of methanol in water solution
γc: solution surface tension (critical)
 65

(a) (b)

(c) (d)

(e) (f)
γ
Figure 3-18: % Float vs. LV , quantified sink model for the different fractions.

3.2.2 Quantified sinking method

The values obtained for each species are shown in Table 3-19. Their plot may be
appreciated in Figure 3-18 (% Float vs. solution interfacial tension) and in Figure 3-19
(% Float vs. methanol (v/v) )
From a concentration methanol value, the float percentage begins to fall in a more or
less dramatic way. This point is named γ max or Cmax (Table 3-19 and Table 3-20) and it
has got a value between 55 and 59 mNm-1 (14 and 9 % of methanol solution) for >16 µm
size fractions, and it ranges between 63 and 66 mNm-1 (5 and 3 % methanol solution) for
<12 µm and MoS2 p.a.
66

(a) (b)

(c) (d)

(e) (f)
Figure 3-19: % Float vs. % methanol, quantified sink model for the different fractions.

The curve falls down to a point where the percent float becomes a constant. This point
is named γ break or Cbreak . It ranges in the 48.5 mMm-1 to 50 mMm-1 range (25 and 20 %
methanol), for almost all of the granulometric fractions, but it is slightly different for
MoS2 p.a.: 55 mNm-1 (14 % methanol solution.)
 67

Table 3-19: Surface tension associated to characteristic points in the curve of float % vs. γ LV of the
methanol-water solution, according the quantified sink model
Species γbreak γmax J
−1 −1
[mNm ] [mNm ]
> 44µm 50 57 1
4.5
44−33µm 50 57 1
3.7
33−23µm 50 59 11.5
23−16µm 48.5 55 1
3.2
< 12µm 50 66 5.9
MoS2 (p.a.) 55 63 1
5.9
J: homogeneity index

Table 3-20: Methanol concentration in aqueous solution associated to characteristic points in the
float % vs. methanol concentration according the quantified sink model
Species Cbreak Cmax
[% methanol v/v] [% methanol v/v]
> 44µm 20 11
44−33µm 20 10
33−23µm 20 9
23−16µm 25 14
< 12µm 10 3.5
MoS2 (p.a.) 14 5

3.2.3 Hallimond tube flotation tests

The results we have obtained by this technique are shown in Table 2-6 and they are
plotted for each fraction and MoS2 p.a. in Figure 3-20(f) (Recovery vs. methanol %). It
may be observed two characteristic point: γ b or Cb (break point) and γ f or Cf, which are
defined in Table 3-21.
The point where recovery falls dramatically is similar in the largest size fractions and it
ranges between 53 and 58 mNm-1 (10 and 16 % methanol).
Both the finest fraction, < 12 µm, and MoS2 p.a. show a marked sensitivity to the
addition of methanol, that results in a dramatic fall of the recovery.
On the contrary, a point defined as “break up” ranges over a 50 mNm-1 value in the
largest sizes but the 22-33 µm fraction this point is not well defined.
The < 12 µm fraction yields erratic answers in its low flotability zone, probably due to
the mechanical drag phenomena.
On the other hand, MoS2 p.a. shows a higher flotability than the other species in
distilled water.
68

(a) (b)

(c) (d)

(e) (f)
γ
Figure 3-20: % recuperation vs. LV , Hallimond flotation for the different fractions.

Table 3-21: Hallimond flotation. Values obtained from recovery vs. surface tension (methanol
concentration) of the aqueous solution curves
 69

Species γbreak up Cbreak up γf Cf

[mNm−1] [% methane v/v] [mNm−1] [% methane v/v]
> 44µm 50 20 58 10
44−33µm 47 25 5313.7 16
33−23µm - - 55 12
23−16µm 45 30 57 11
< 12µm 55 12 72 0
MoS2 (p.a.) 60 8 72 0
γbreak up, Cbreak up: Surface tension and methanol concentration at which the flotation undergoes a sudden increase
γf, Cf : Surface tension and methanol concentration at which the flotation undergoes a sudden increase

3.2.4 Common cells flotation tests

The performed tests for each granulometric fraction in the presence of quartz are shown
in Table 2-7.
Values of R∞ and K were obtained (Table 3.14) when these test were fitted according
to a first order kinetic model.
The R∞ values of the largest-size fractions were the highest. Nevertheless the K values
do not show a noticeable trend.
There were not noticeable differences among the different size fractions when a
flotation test using only a frother (MIBC) as flotation reagent was performed on a sample
composed with a mixture of all the fraction sizes on study (Table 2-8). The tested sample
was composed by a mixture of all the size fractions on study.
Table 3-22: Flotation in conventional cell in the presence of quartz. Kinetic parameters for each
species for the expression R = R∞(1−e−Kt).
Fraction R∞ K
[m−1]
> 44µm .8 1.15
5
44−33µm .9 .50
4
33−23µm .8 .68
5
23−16µm .7 .88
0
16−12µm .7 .53
8
< 12µm .6 .54
9
70

(a) (b)

(c) (d)

(e) (f)
Figure 3-21: % Float vs. % methanol v/v, Hallimod flotation for the different fractions.
Chapter 4
Discussion
The relationship between contact angle and surface free energy in the molybdenite case
is of basic-science and technological interest. If a suitable link between particle size and
polar and dispersion components of its surface free energy is established, it is possible to
obtain a significant advance in order to correlate hydrophobicity with natural flotability;
so answering to the hypothesis that postulates the most hydrophilic behaviour to the
finest size particles.
The approach of this discussion will include the analyses of the obtained values of the
superficial tension and the parameters of the different wetting thermodynamic models
applied on studying molybdenite surfaces.
The correlation of these backgrounds; with Hallimond’s flotation-tube tests and
regulating solution surface tension; will allow us a better comprehension of the concepts
that have caused the present study: the relationship between hydrophobicity and
flotability.

4.1 Zisman’s model application

The results presented in the section before permit us to learn that γ c is a low sensitivity
parameter in order to express the hydrophobicity differences between all the kind of
MoS2 studied. In effect, the γ c values are around 49.5 mJm-2 without exhibiting an
especial trend. However, it was noticed that the Zisman’s slope showed a marked trend
with the particle size. Similar results in carbons were reported by Parekh and Applan
[11]. So, it may be concluded that analysing this slope is more useful than doing it with
the γ c ; in order to characterise the relative hydrophobicity of a set of samples.

4.1.1 Thermodynamic Analysis of the Zisman’s slope

Firstly, the Young’s equation will be written in using energetic terms:
Wa
cos θ = 2 −1 (4-127)
Wc

where Wa is the adhesion work and Wc is the cohesion work of the liquid.
There is an advantage in writing down this equation this way because it is suitable to be
analysed on the basis of the contribution of the different kind of forces that took part in
the adhesion work.
If we define α as:
d cos θ
α= (4-128)
dγ LV
on introducing (4.1) it gets:
72

d  
2Wa
Wc 
α =  (4-129)
dγ LV
Now, if the Laskowski and Kitchener concepts [17] are accepted as we did in (1.108) it
is possible to write in a general form:

Wa = Wad + Wap (4-130)

where Wad is the dispersive component of the adhesion work, Wap is the polar
component.
Working on (4.4) it gets:
 2W d   2W p 
d a  d a
 Wc   Wc  (4-131)
α = +
dγ LV dγ LV
Now, the slope is defined as a function of the polar and dispersive forces. Then:
α = α d +α p (4-132)
where α d is the London forces contribution and α p the contribution of the polar one
to the Zisman’s slope α .
Now we get:
 2W d 
d a
 Wc  (4-133)
α =
d

dγ LV

 2W p 
d a
Wc 
αp = 
(4-134)
dγ LV
Some conditions have to be satisfied in order to develop a consistent explanation about
the causes of hydrophobic behaviours.
When the solid has got a low energetic surface α = α d and negative. By the way, when
polar interactions are coming up at the liquid–solid system the absolute value of α drops;
obviously; only a α p > 0 describes the situation.

When Wa > 0 is satisfied under any condition, α slope will be modified at least in
p

qualitative terms. This approach is suitable in order to analyse the effect of the
hydrophobicity on the α slope. The soundness of these suppositions will demand to
d p
introduce Wa and Wa mathematical expressions.
It is advisable to use handy expressions as function of the solid free energy because the
relationship between α and the hydrophobicity grade are of paramount importance.
 73

Figure 4-22: Dispersion component γLd and polar γLp of the liquids vs. surface tension of the
liquid L (A: water, G: glycerine, F: formamide, I: di I methane
and B: tetra Br ethane)

Dann’s model gives us two suitable expressions:

Wad = 2 γ Sd γ Ld (4-135)

Wap = 2 γ Sp γ Lp (4-136)

On appearing polar interactions in the system, the wetting behaviour will not depend
only upon the solid but on the global liquid-solid system.
It is necessary to introduce correlations that links independently γ Ld and γ Lp with γ LV .
The following empiric relationships have been found out over 50 mNm-1 for the
particular liquids set used in this work (Figure 4.1):
γ Ld = η ( C1 − γ L ) (4-137)
γ Lp = β ( γ L − C2 ) (4-138)
where η and β are positive values from the absolute values of the slopes shown in
4.1 Figure. C1 and C2 are intersection points on extrapolating the straight lines fitted
with X-axis ( γ L ). The particular values are η = 1.2, C1 = 91.7, β = 2.2 and C2 = 49.96.
By deriving the (4-133) expression and applying the (4-137) correlation it gets:
74

d  2Wad  Wad  Wad  Wc 

 d
2  d   (4-139)
d L Wc  Wa Wc 
Where
dWc
Wc  2 (4-140)
d L
and taking into account (1-37):

Wad ′ =
dWa
=
d
dγ L dγ L
( W d γ d′
2 γ S γ L = a dL
2γ L
) (4-141)

′
according to (4-137); γ Ld = − η :

d′Wad 1
W =− × (4-142)
2 C1 − γ L
a

on replacing into (4-139)

Wad  1 1 
αd =2  − −  (4-143)
Wc  2( C1 − γ L ) γ L 
Wad (2C1 − γ L )
αd =2 (4-144)
Wc γ L (C1 − γ L )
and finally
γ sd η 2C − γ
αd = − × 12 L (4-145)
C1 − γ L γ

The same procedure may be applied on α p ; joining (4-134) with (4-136) it gets:

Wap  Wap ′ Wc' 

α p =2  −  (4-146)
Wc  Wap Wc 
Where

p′ dWap Wap γ Lp ′
W = = (4-147)
dγ L 2 γ Lp
a

according to (4-138), γ Lp ′ = β
Wap
Wap ′ = (4-148)
2 ( γ L − C2 )
it comes out
 75

Wap  2C2 − γ L 
α p =2   (4-149)
Wc  2 γ L ( γ L − C2 ) 

Finally, taking (4-136) and (4-138) into account

γ Sp β 2C − γ
αp = × 22 L (4-150)
γ L − C2 γL

Looking through the α d and α p (4.19) and (4.24); valid for γ L > 50 mNm −1 ; it is
noticed that they are proportional to γ s and γ s respectively. If we also give the
d p

constants its numerical value α d is negative while α p is positive.

Now, some especial cases will be analysed:
1. A solid –liquid system where both faces interact only by London’s forces.
It will be applied to low energy surface solid and liquid γ L < 50 mNm −1 . So,
γ S = γ Sd and γ L = γ Ld ; therefore Wa =Wad and α = α d .
For this especial case (4-139) is:
Wad
Wad ′ = (4-151)
2γ L
Then
Wad
α =− (4-152)
Wc γ L
that may be written down as:

γ Sd
α =− 3/ 2 (4-153)
γ cd
It may be noticed that α varies with the liquid superficial tension, so the slope
will not be constant and a straight line is not possible.
However; if we applied (4-152) to the wetting critical condition, where both the
adhesion work (Wa) and the cohesion work (Wc) are equals, we arrive at the Good’s
relationship α ≅ − 1 γ c which was demonstrated in the field of low energy solids and
liquids.
2. The solid interacts only by London’s forces while the liquid interacts by both
dispersion and polar forces.
This may be applied on low energy solids when they are brought in contact with
γ L > 50 mNm −1 liquids.
The follow conditions are fulfilled: γ S = γ S and γ L = γ Ld + γ Lp .
d
76

Figure 4-23: Effect of the surface tension of the liquid γLV on the polar component of the α slope,
α(αsp)

The expression obtained was (4-144). If we take into account that de adhesion
( )
work will have only a dispersion component Wa = Wa and that for critical
d

wetting conditions the adhesion work equals the liquid cohesion work, we get:
2C1 − γ c
α ( ref ) = − (4-154)
γ c (C − γ c )
The slope defined this way is practically a reference state in order to study the loss
of hydrophobicity when “ionic” sites appear onto the surfaces.
3. The most complete case; γ S = γ S + γ S and γ L = γ Ld + γ Lp .
d p

This was developed from (4-139) to (4-150).

The expressions for α d and α p will be (4-145) and (4-150). The quotients
α sp γ Sp and α sd γ Sd are plotted in Figure 4-23 and Figure 4-24 against the
tension of the liquid in order to obtain a relationship independently of the γ S and
p

γ Sd of the solids on study.

On introducing (4-135) and (4-143) we are giving a thermodynamic meaning to
the Zisman’s slope. It quits as a function of γ S and γ S , however; the function
p d

drifts away from the linearity Zisman claimed for.

This inconvenient does not allow us to make a strict interpretation of the Zisman’s
slope. However, it is quite clear that the occurrence of little polar components on
 77

Figure 4-24: Effect of the surface tensions of the liquid γLV on the dispersion component of the
slope α(αsd)

the surface of a hydrophobic material, such as molybdenite is, will modify the
slope of a cos θ vs. γ L plot.
It will be interesting in the preset work to evaluate (4-154). We call it reference
slope value of a hydrophobic solid which only interacts through dispersion forces,
in a liquids set with dispersive and polar components.
When the numerical values are introduced in this equation; for the present case
γ c ≅ 50 mNm −1 it gets:
2 × 91.7 − 50
α reference = − = − 6.4 ×10 −2 mNm −1 (4-155)
50 × ( 91.7 − 50 )
This values is the greatest of all values obtained in this work for the slopes of
different species of molybdenite, whose slope maximum absolute value was
5 × 10 −2 mNm −1 .

4.1.2 Zisman’s slope analysis based on Girifalco-Good’s Model

It was demonstrated that α = −1 γ c in a previous section. This was done based on the
Good’s model when its mathematical expressions are developed in Taylor series around
the critical wetting conditions.
( c)
The independence of Φ SL from γ L was assumed.
Now, if the same development is carried out until the first order term it gets:
78

 γ SV 1 γ  dΦ SL  
cos θ = 1 +  − Φ (SLc ) + 2 S    ( γ − γ c ) (4-156)
 γc γc γ c  dγ LV  c 
where sub indices or supra indices ‘c’ refer to critical conditions.
On equalising with Zisman’s expression (1.29) and knowing that for critical wetting
conditions relationship Φ SL γ SV = γ c it gets:
2

1 2  dφ SL 
α = −1 + ( c)   (4-157)
γ c Φ SL  dγ LV c
We observe that if Φ SL does not vary with γ L we get α ≅ −1 / γ c .
Now,
 dΦ SL   dΦ SL   dγ SL 
  =     (4-158)
 dγ LV  c  dγ SL  c  dγ LV c

When the state equation was applied in the γ SV calculation the equation (1.119) was
obtained; Φ SL as linear function of γ SL . This allows us to write:

 d  SL   d  SL 
       (4-159)
 d  SL  c  d  LV  c
where both factors of the right member are positives.
 d SL 
As the solid has less affinity with liquids, it says, it is more hydrophobic,   will
 d LV 
increase.
It gets:
1   d SL 
   2 c   (4-160)
c  SL  d LV  c

When we are working on solids that do not have the characteristics of the low energy
surfaces, the Zisman’s slope will be modified as the hydrophobicity increases.
This relationship is useful in the case we are studying; molybdenite with a
γ c ≅ 50 mMm −1 . The aforementioned expression α = − 1 γ c yields α ≅ − 2 ×10 −2 .

The same way while α ref (4-154) belongs to a solid that interacts only trough
dispersion forces with a liquid that has got polar component; − 1 γ c corresponds to the
Zisman’s slope of a solid in its minimum of hydrophobicity state among different kinds
of surfaces of specie with the very same γ c .
A similar situation to the molybdenite was described in a paper about coal wetting [35].
 79

Here it is observed too that the slopes are lesser in absolute value than that we named
reference slope α ref ; it says the maximum hydrophobicity state; and slope values close
to α ≅ − 1.97 ×10 −2 for a sub-bituminous specie and −1.67 ×10 −2 for a lignite that are
the lest rank species (56.1% and 46.2%, respectively).

4.1.3 Zisman’s slope analyses for measurements with alcohol-water

solutions
The interpretation of the Zisman’s slope obtained from measures performed using
water-alcohol solutions has not been established yet. Nevertheless, several authors give
an interpretation based on the absorption phenomena that reports the m slope of the
wetting model; as we marked in (1-102).
If we express the equation model as:
Cte
cosθ = m + (4-161)
γ LV

and we develop in Taylor’s series from γ = γ c , it gets:

Cte
cosθ =1− ( γ LV − γ c ) + 2 Cte ( γ LV − γ c ) 2 +  (4-162)
γc2
γc3

As
Cte = γ c (1 − m) (4-163)
it results:

cosθ =1−
(1 − m ) ( γ −γ c ) +
2 (1 − m )
( γ LV − γ c ) 2 + (4-164)
γc γc
LV 2

On truncating the develop in the first order term and equalising it with Zisman’s
expression; it gets:
m =1 + α γ c (4-165)
There is preferential adsorption in the solid-vapour interface if m > 0, [21]. Then if
1
α >− (4-166)
γc

Then, if α < 1 γ c in a Zisman’s diagram for water- alcohol solutions, it is a possible

indication of adsorption.
When m ≅ 0 implies α ≅ −1 γ c , that is the Good’s relationship he claims to be valid in
the proximity of γ = γ c for low energy solids in front of pure liquids.
80

4.2 Good’s Model Application

This model that correlates linearly cos θ vs. γ LV gives in similar results of critical
wetting tension to the other models (Figure 3-13).
The p slope of this model may be associated to more or less grade of hydrophobicity
(Figure 6.1b) as the Zisman’s slope does.

4.3 Wetting Diagram (Lucassen-Reynders) Applications

When experimental data were treated using this model, it might be possible to establish
a suitable correlation between Fadh vs. γ LV (Figure 3-14), this means a low equilibrium
pressure Π e ; therefore this pressure might be considered roughly as a constant in the
measure range [39][44].
Again, there is a likeness between the γ c values obtained of different granulometric
fractions, MoS2 p.a. and crystal surfaces, besides; there is also a likeness with the values
obtained using other models (Table 3-11). Nevertheless, the difference is given by the
slope m (Figure 6-28), this is obvious if the relationship between Zisman’s slope and m is
taking into account according to (4-165).
A linear model has been chosen but we could have adopted a second order one. This
will take the advantage of showing whether or not our system gets closer to the low
energy solids behaviour, where for γ = γ c the adhesion tension has got an analytical
maximum. Unfortunately, the liquid pure set is not enough in the γ c ≅ 50 mm zone; so
−1

the parabolic model would not have whatsoever, the necessary freedom degrees to
describe this situation.

4.4 Fowkes’ Model Application

If the results obtained with this model are compared it is noticed that the less the
particle size is the more the dispersion component γ S is (Table 3-12). This not only
d

quantifies γ S but is showing the poor versatility this model has. It may be noticed that
d

only one parameter is not enough to describe those conditions whose wetting critical
conditions are alike but the water-solid contact angle are different.
Fowkes attributes these deviations to the existence of large values of equilibrium Π e
and to all little dirty, rough and heterogeneous composition surfaces.
All seems to show that it is not satisfactory to express the adhesion work only as a
function of London’s dispersion components. Laskowski et al. have claimed for
incorporating polar components to the adhesion work; see (1-108). Thus, the idea of
considering Wu and Dann’s Model has come up.

4.5 Wu’s Model Application

The results show a similar γ S for the different size classes, MoS2 p.a. and crystal
surfaces (Table 3-13).
 81

(a) (b)

(c) (d)

(e) (f)

(g) (h)

(i)
Figure 4-25: γsp and γsd obtained by means of a graphical/numerical, Wu’s model, for the each
fraction

The proportion of tension components signals the difference. So, the quotient γ S γ S is
p

chosen as polarity index; see (A-185).

82

The highest polarity indices are observed in both “16-12 µm” and “<12 µm” and a very
low one in the “MoS2 p.a.”.
When we compare the results between the two different of molybdenite crystal surfaces
we realise that the edge surface has a higher polarity than the face surface.
The results of working with Wu’s equation are shown in Figure 4-25; they were
calculated using a graphical-numerical method.
Each contact angle measure generates a hyperbole in the γ S − γ S plane as we have
d p

written down here:

γ =
d (Wadh 4) γ Ld γ Lp − γ Ld (γ Lp −Wadh )
4 γ Sp
S
(γ d
L + γ −Wadh 4 γ + γ
p
L ) p
S
p
L ( γ Ld −Wadh 4 ) (4-167)

where Wadh = γ LV (1+ cosθ ) .

In order to carry out the calculations only is useful the hyperbola branch between the
asymptotes:
γ Lp (Wadh 4 − γ Ld )
γ p
= p (4-168)
γ L + γ Ld − Wadh 4
S

and
γ Ld (Wadh 4 − γ Lp )
γ Sd = (4-169)
γ Lp + γ Ld −Wadh 4

in the region of the plane where both, γ S and γ S are positives.

p d

Thus, the solution will be given in the intersection values of the hyperbolas that each
measure generates.
It may be observed that the obtained solutions are different for each pair of liquids; this
signals that a marked dispersion in the found values is going to be produced. It is
preferable to obtain solutions using the intersections of the hyperbola generated by
Methylen Iodide because this is the best defined curve and the closest one to the critical
wetting conditions.

4.6 Dann’s model Application

The same conclusions we obtained in the Wu’s model Application may be expounded.
The obtained values are shown in Table 3-14 and a noticeable polarity difference may
be observed according to the particle size of the granulometric classes and the MoS2 p.a.
that trends to behave as the largest size granulometric surfaces. Besides, a different
polarity is observed between the edge and face crystal surfaces
When we try to calculate the dispersive γ S and polar components γ S applying these
d p

both models: Wu’s and Dann’s we come up against the lack of precision that the
dispersion and polar components of the utilised liquids have (Table 2-2).
 83

Both, the γ S and γ S values obtained used to have high uncertainties, specially γ S .
d p p

These uncertainties could be higher than the resolution uncertainty.

4.7 Correspondent states equation

This kind or treatment was proposed by Wade and Neumann [39]; it authorises to set
out thermodynamically relationships between γ SV , γ LV and γ SL further away beyond the
Young’s equation. This may be applied to the study of minerals surfaces as molybdenite.
Previously it might take into account that there is a good correlation between
Fadh vs. γ LV (wetting diagram) for each variety. This condition is necessary in order to
assure that Π e is constant, it says, independent of the liquid that forms a contact angle
with the solid.
When γ SV was calculated for each granulometric fraction, MoS2 p.a., and massive
crystal, their values were almost equal (Table 3-16).
So, the hydrophobicity may be estimated calculating γ SL and Φ SL for the water-surface
solid system. Amongst the granulated classes the highest values of γ SW indicate less
affinity between solid and water (Figure 3-16). On the contrary, the least hydrophobic
fractions have the highest Φ SW (water-solid) parameter, showing this way more affinity
for water (Figure 3-17).

4.8 Hornsby- Leja’s method

A certain correlation is observed between γ c and the particle size. The value of the
middle-of-the-range fractions are alike to those reported by Garshva [10] for the
immersion critical condition ( γ i ≈ 58 mNm ). Coincidence was almost complete for the
−1

methylated Silica case ( γ i ≈ 36 mNm ).

−1

The determination was very precise because its surface is very homogenous, it does not
happen the same with Molybdenite species.
The behaviour of the MoS2 natural species is owing perhaps to a definite heterogeneity
of its superficial properties; even between the same granulometric classes particles.
The Hornsby-Leja’s method actually gives a modified critical wetting condition owing
to the air bubble formed during the previous agitation, producing this way a certain foam
or froth. This may explain the similarity between our wetting results and those reported
by Garshva.

4.9 Quantified sinking method

This method is similar to the Hornsby Leja’s; but this case both, floated (F) and sunk
masses are quantified.
Owing to the heterogeneity of the minerals species on study this new method was
designed. It may be established as a critical wetting condition γ c , the situation when the
floating masses percent is almost null.
84

This way, the quantification allows perhaps a better definition of the wetting γ c and
also determining the dispersion conditions. The Hornsby Leja’s method produces an
uncertainty in the γ c value owing to the heterogeneity of natural materials. This has just
happened in Molybdenite case. When the wetted and sunk masses are quantified it is
possible to define any sort of criterion in order to precise much better the γ c value.
Besides, the wetting distribution may help us to understand both the surface sites of
dispersion and polar of the same specie.
A break-up point (Fb, γ b ) more or less well defined gives similar values to those
obtained by contact angle method, but the synthetic specie. The γ max ; where both the
float fraction (Fmax) and the dispersion conditions attain its maximum (Figure 3-18 and
Figure 3-19).
The kindness of the curves allows us to introduce a parameter of sensitivity J between
the surface tensions and their respective float percentage.
ln ( Fmax Fb )
J= (4-170)
ln ( γ max γ b )
This index might show the grade of homogeneity J of each species related to the
wetting properties; and going the higher index to the more homogenous surfaces (Table
3-19).
On applying this index; MoS2 p.a. surface was the most homogeneous and on the other
side “<12 µm” fraction surface was the most heterogeneous. This conclusion is in
agreement with what we were just expecting because the finest fraction “<12 µm” has
been subjected to different comminution mechanisms.

4.10Hallimond flotation tube

The flotation of molybdenite using water alcohol solutions was carried out in order to
find a link between flotation, wetting conditions and the hydrophobicity established by
the contact angle models.
It was observed that flotation with distilled water produces a high recovery on MoS2
p.a. and medium particles fractions but a low recovery for the “<12 µm” fraction.
When the surface tension decreases the recovery of the largest fractions keep on
constant, while both “<12 µm” fraction and MoS2 p.a. low their recovery dramatically
(Figure 4-25c and Figure 4-25d.) We have defined previously the flotation as a
probabilistic phenomenon (1-123) including probabilities of hydrodynamic and
thermodynamic origin.
The relative weighting of these factors seems to depend upon the characteristics of the
liquid medium; if the flotation is carried out in water the recovery obeys to the
hydrophobicity scale observed in the contact angles measures and the process happens
mainly under thermodynamic control.
 85

Figure 4-26: Hallimond flotation. Recovery % vs. surface tension of the solution γLV curves

However, when the surface tension diminishes, flotation remains subjected to the
dynamic conditions of the system because the suitable thermodynamic conditions of
flotation have been spoiled.
Therefore, the drop in the recovery of both MoS2 p.a. and “<12 µm” fraction may be
explained because they are the less advantaged form the hydrodynamic point of view
(Figure 4-26 and Figure 4-27.)
A γ b has been also defined; it is the point when the specie floats by dragging ( γ break )
and a γ f is the point where flotation drops dramatically. These points indicate a largest
sizes trend to float and dragging when γ LV is in a range between 45 to 50 mNm-1. Both,
86

“<12 µm” and MoS2 species do not produce these parameters well defined because their
ill-dynamic-condition to float (Figure 3-21e and Figure 3-21f) . It may be noticed that the
point where the dramatic fall in recovery begins ( γ f ) is near to γ i reported by
Garshva [10].
Whereas, the point where the recovery begins to be performed by dragging γ LV is
similar to γ c wetting. Qualitative explanations have been given on these three latest
methods behaviour and mainly in Hallimond’s flotation. Being the flotation away from
the equilibrium conditions, it is not convenient to get from its information concentrate
thermodynamic parameters related to free energies changes ( γ c , wetting, γ i immersion et
cetera.)
 87

Figure 4-27: Hallimond flotation. Recovery % vs. methanol v/v % of the aqueous solution

It is convenient to determine these parameters by other methods (contact angle, et

cetera) and then to explain their influence on such phenomena, if this is possible and
reasonable from the thermodynamic point of view.

4.11Conventional flotation cell

Plain tests were performed in order to establish links with the classical flotation; the
only reagent utilised was an alcoholic frother. When the different fractions were floated
independently and removed form a quartz gangue, the ultimate recovery parameter (R∞)
seems to be higher in the larger sizes fractions.
88

Where as, on floating a collective of these samples all the R∞ parameters obtained are
very similar.
Furthermore, the nearer to the real conditions the systems are, the more difficult is to
extract conclusions about the relationship between particle size and both, hydrophobicity
and flotability.
Chapter 5
System integral analysis
It was demonstrated that it is possible to detect the particle size effect associated to the
hydrophobicity by using a measure method of contact angle on pressurised pellets. This is
the main achievement of the present work, so the Kossen and Hertjes’ method is
authorised as a tool to be applied on natural hydrophobicity systems.
Both, mineral molybdenite and synthetic MoS2 exhibit a marked natural
hydrophobicity in agreement to literature reports. This is clearly shown in the measures in
all, cosθ measurements, Hornsby Leja’s wetting technique and flotation test using
methanol-water solutions.
The crystallographic character of molybdenite determines the presence of both polar
and no polar superficial sites, being the non polar which interact only by London’s
dispersion forces. This determines a inherently anisotropic surface from the point of view
of its hydrophobicity.
Thermodynamically, the surface free energy of molybdenite will be given by the
addition of both polar and dispersion contributions.
The surface free energy value for molybdenite is associated to γ c  50 mJm with the
2

definite predominance of dispersion forces over polar ones.

On the contrary, the little fraction of polar components determines a change in
hydrophobicity that is associated to the particle size or to the cleavage plane in the crystal
case.
So, the analysis of contact angle measures, processed through the different models
treatment, indicates a wetting condition similar for all the species on study. Whereas, it is
shown a higher polarity in the less size particle fractions and also in the “edge” sites
compared to the “face” sites of the massive crystal.
These conclusions strongly bear out Fuerstenau’s hypothesis which claims that the fine
particle size fractions hydrophobicity has been spoiled by the occurrence of polar sites.
The origin of them would be associated to the way the fine particles have been
generated. So, the produced particles by comminution would have more probability of
being broken in their covalent bonds Mo-S then, there must be an increase in polar sites
occurrence on their surfaces. Another superficial phenomenon may explain these facts
such as the crystalline deformation by collision without being associated necessarily to
bonds breakage [9].
On the other hand, MoS2 p.a., a species prepared by chemical synthesis, shows a high
hydrophobicity behaviour, similar to crystal low energy planes; this suggests an absence
of polar sites.
We learned that the relative hydrophobicity of the different studied samples is better
correlated by both the Zismam’s slope and the wetting diagram than the  c obtained.
90

Despite the validity of applying some models used in this work may be debatable, it
must be stressed that generally the gathered information for molybdenite is coherent and
permitted a better characterisation of the samples. Some of the more conflictive
suppositions on applying these models are: adsorption absence (e =0), clean,
homogenous and smooth surfaces, and finally the forces components of the superficial
sites are independent and there is not any interaction amongst them.
The  c value obtained for molybdenite in this work ( 50 mJm-2) is strongly in
disagreement with the dates reported elsewhere in literature. . Some authors have
reported a γ c ≅ 26 mJm for molybdenite and γ c ≅ 24 mJm for synthetic molybdenite.
−2 −2

Both were obtained using water-methanol solutions and applying the gamma flotation
method [45]. Other authors have reported similar values using the same technique [32].
Hornsby and Leja pointed, when they exposed their work [12] on selective separation
of hydrophobic solids: “The measure of the wetting critical tension may depend
significantly upon the kind of surfactant used to prepare the aqueous solutions series”.
It is not evident either, that the water-methanol solutions do not adsorb onto the solid
surface, not modifying this way the estimation of γ c , whatsoever. On the contrary,
methanol adsorption on low energy surfaces has been detected [33] [34].
We have mentioned previously that different graphite γ c value have been got
depending whether both alcohol and amine-water solutions [28] or pure liquids are
utilised [11].
Measures performed on a molybdenite disk [32], and a molybdenite specie both using
methanol-water solutions are precedents that point out the methanol adsorption on
molybdenite surface. The first case has a positive slope in the Lucassen-Reynders’ model
so indicating a preferential adsorption in the solid-vapour interface in agreement with (1-
103). This adsorption will be higher than the solid liquid adsorption one and at least
comparable with that of the liquid-vapour [46][47]
There are not precedents that report studies of wetting in molybdenite surfaces using
pure liquids but water [6][7].
The present work is a contribution on the subject because the pure liquids in the contact
angles measures were taken into account. This has a clear advantage over the use of
mixtures because in the later case the interpretations will not be valid whatsoever “until a
correct theory of the thermodynamic of wetting for mixtures had not been elaborated” (R.
Good, 1977) [23].
Another contribution has been developed by the quantitative sinking method. This
method allows assessing that the behaviour of the sinking and wetting is heterogeneous
even inside a granulometric fraction.
The relative hydrophobicity scale of the different fractions serves to explain the
behaviour of these very fractions, this added to the assessment of the deterioration of the
thermodynamic probabilities of adhesion for fine particles, fulfils the probabilistic scope
of flotation that this work is claiming for.
 91

Table 5-23: Bibliographic records of wetting determinations carried out on different molybdenite
species.
Obtained
Value Technique Variety Ref.
parameters
Contact angle in 80.5°
Laying drop Molybdenite crystal [6]
water 60.5°
26 MoS2 (synthetic)
Flotation and contact angle in
29 MoS2 [13]
water-alcohol solutions
γc of wetting 31 Mo1−xS2
[mNm−1] 29.2 Molybdenite in
Contact angle in water-methanol
cleavage plane [32]
41.7 solution
γc of sinking 55 Sinking time in aqueous
MoS2 p.a. [10]
[mNm−1] 60 solutions
Chapter 6
Conclusions
1. Different granulometric fractions of mineral molybdenite, synthetic
molybdenite sulphide both p.a. and both “face” and “edge” crystals, and edge
showed the same value of γ c ≅ 50 mJm obtained by measurements of contact
−2

angles using pure liquids of lesser surface tension than water.

2. The idea of correlating hidrophobicity with particle size by means of a γ C
revealed this parameter is not sensitive enough to this purpose.
3. A more elaborated treatment of data, applying well known models, allowed us
to determine the components of free energy surface components of
Molybdenite. Thus γ d varies in range from 41.7 to 48.5 mJm-2 (Wu’s model);
S

43.8 to 52.8 mJ/m-2 (Dann’s model) and from 48.9 to 63.7 mJm-2 (Fowkes’
model). On the other hand, γ S varies between 0.75 and 9.7 mJm-2 (Wu’s
p

model) and between 0 and 6.21 mJm-2 (Dann’s model).

4. A complementary analysis of theses models allowed us to conclude that the
slope of some of them is a parameter which suitably correlates to the relative
hydrophobicity of the samples. A thermodynamic interpretation of Zisman’s
model was elaborated, giving so a well defined theoretical sense to the
observations and fulfils the use of this slope as a relative hydrophobicity criteria
of a set of samples.
5. Most of the experimental techniques to measure γ S (except for the contact
angle methods, such as Hornsby-Leja’s method and both microflotation and
immersion in methanol-water solutions) failed to precise a well defined value
due to the existence of and heterogeneous surface behaviour.
6. A new technique of quantified sinking are put forward in the present work. This
allows us to define an anisotropy index of wetting which must be of paramount
importance in mineral science.
7. It is a well known fact that fine particles are quite hydrophilic but from the
previous arguments in molybdenite case; they keep on being hydrophobic
enough to perform natural flotability behaviour. So, we suggest that the loss of
thermodynamic probability of flotation would be smaller than the loss of
hydrodynamic probability; due to the difficulties of adhesion between fine
particles and large bubbles.
 93

(a) (b)

(c) (d)

(e)
Figure 6-28: Slopes of the different models as a function of particle size. (a) Ziman’s slope vs.
particle size (b) Good’s model slope vs. particle size (c) Slope of wetting diagram vs. particle
size (d) cosθ in water vs. particle size (e)  S  S Good’s model vs. particle size.
p
Appendix
Contact angle measurements
There are several methods in order to measure contact angles, such as: the vertical
cylinder, capillary methods, the slanting plate and the lying or hanging drop or bubble.
Generally, these methods are of direct measure of the angle or through trigonometric
relationships measures of the shapes the bubbles have got [20].
In our case, when the contact angle measures must be performed on fines particles
lesser than 50 µm size, the choice of the methods are restricted precisely by this
characteristic.
The contact angles measures should be indirect in these conditions; they must be
associated to a capillary rise time [48] or geometrical dimensions. This later method must
be utilised in our study not only for the material porosity but having into account that a
drop in equilibrium on a porous solid rises to such a dimension that the gravitational
forces should not be excluded whatsoever when a mechanic or energetic balance is
performed.
The chosen method (Kossen-Heeertjes, 1965) [1] has got a theoretical based on all
three, the Young, Laplace and Padday’s equations.
In order to obtain a final equation of the aforementioned method some aspects must be
analysed:
1. The relationship between cos  and the shape of a drop that has been brought in
contact with a smooth surface.
This case, the different energies of the system included the potential one should define
cos  .
The drop shape on study will be a kind of cylinder with it lateral surfaces much lesser
than the basis’ [49].
Applying an energy balance of virtual displacements when an infinitesimal amount of
liquid is added we have:

d (Potential Energy)  d (Internal Forces Energy) (A-

171)
The potential energy EP is:
1 (A-
EP  Vg
2 172)
Where V is the drop volume, h is the drop height,  is the liquid density and g is the
gravity acceleration.
The height h keeps on constant in the process, so:
 95

1 (A-
 ghdV   LV dALV   SL dASL   SV dASL
2 173)
Being dV = hdA. In this conditions dA = dALV = dASL ; where the subscripts define both
interfaces; liquid-solid (SL) and liquid-vapour (LV).
Then it gets:
1 (A-
 gh 2   LV   SL   SV
2 174)
If Young’s equation is guessed:
(A-
cos  1  B h 2
175)
g
Where B 
2 LV
The (A.5) formula is utilised to measure contact angles on smooth surfaces when the
mass drop acquires paramount importance and cos  is difficult to be measured directly
[49].
2. The same situation as 1; but in the presence of rough surface.
This case, the energy balance must consider the surface porosity since the measure will
be performed on a pressed pellet.
The liquid that is brought in contact with this kind of surfaces will not form a steady
drop but the pellet will suck it up. When the liquid saturates the surface a well-defined
shaped drop is formed; so; its height can be measured.
The Young’s equation has the same form when is applied to a porous solid but the
  SV  porous and   SL  porous will be:
  SV  porous  ES  LV   1  ES   SV (A-
176)

  SL  porous   1  ES   SL (A-
177)
Where ES is the superficial porosity defined as the wetted surface fraction.
The Young’s equation quiets:
 SV   SL (A-
 1  ES    ES  cos  
 LV 178)
Where   is the apparent contact angle of liquid onto a porous surface.
On replacing the first factor of (A.8)

cos   1  ES    ES  cos   (A-

179)
By analogy with (A.5)
96

(A-
cos    1  B h 2
180)
And replacing in (A.9)
B (A-
cos   1  h2
 1  ES  181)
According to Kossen and Heertjes [1] Es and EV (volumetric porosity) are linked by:
1  cos 
1  ES  (A-
1  EV  1  cos  
2

 182)
3 2
Replacing (1 – Es) in (A.11) gives a quadratic equation:

cos   1 

Bh2 1 3  1  EV   1 2  1  cos  
2
 (A-
1  cos  183)

And resolving yields:

B h2 (A-
cos   1 
3  1  EV   1  B h 2 2  184)

If B h2 < 0.1; (A14) may be simplified as:

Bh 2 (A-
cos   1 
3  1  EV  185)

It must be noticed the characteristic of the drop height (h); it is the ultimate height the
drop reaches after the surface solid is saturated and one of the curvature radii becomes
infinite.
Both, this method and the capillary rise are the most applied in liquid-powder cos 
calculations.
Addenda and Notes
These are responses to questions raised by the Committee at the time of the oral
presentation of the work:
• Section 1.7, page 21
The γs is a constant. On the contrary γc is not a constant; generally it varies according to
the different series of aqua alcoholic solutions, glycerine mixtures et cetera that are used
in its determination.
• Section 2.5
The question of whether the comminution enhances or not the loss of hydrophobicity
is precisely the subject of the present work.
Generally, the behaviour of fines particles are based on the Fuerstenau’s postulates
summarised by him in a modified figure of the Klassen’s original work.
This has been completed with the “edges & faces” theory that has been built by
Gaudin, Miaw and Spedden. This theory was useful in order to give an staight and plain
explanation of the loss of fine particles in a flotacion process; they claim a greater
hydrophilicity and superficial energy for these sort of particles. This properties have not
been confirmed until nowadays or tested experimentally. Then, it was necessary to use
laborious methods as Kossen and Heertjes’ in order to be applied without changing the
samples sizes.
It must be stressed that Trahar and Warren do not accept the Fuerstenau’s postulates
whatsoever; they employed arguments based on theoretical developments of the given
explanations and certain observations made on experiments. They impugned the “Kelvin
effect” as an explanation of the loss of hydrophobicity because it is only valid for
particles sizes under 0.1 mm.
Similar concerns were reported about the comminution processes: The largest particles;
do they have more high energies sites than small ones because they have been subject to
impacts which did not result in breakage?
Until now Flotability and hydrophobicty have been taken as synonyms especially when
these properties are inherent, and the surface has a low eneregy. On the contrary, Trahar
and Warren claim for separating both properties. This concept influenced on the
execution and conclusions of the present work.
We introduce here a paragraph of these authors about this subject: “However , it may
be argued just as convincingly that large particles have more high energy sites than small
ones because they have been subject to impacts which did not result in breakage” (W.J
Trahar and L.J. Warren, 1976. The flotability of very fine particlesa review. Int.
Journal of Min. Processing, 3:103–131, 1976.)
• Section Conclusions, page 102
This technique aims to be justified in the Discussion chapter. It has been described only
the operative part during the development of the method. Besides, we considered so
98

boastfully to develop it in the same item where we explain methods claimed by first line
authors.
This method ought to have a stricter justification. It must be noticed that we have
avoided to put the γb on an equal footing with the thermodynamic concept of γc (wetting
critical point) and γmax with γi (immersion critical tension).
• γ Sd values

In the finest fractions, the higher the values of γ S were in the finest fractions the
d

greater their statistical dispersion values were.

This behaviour may be caused by the rift between the conditions the model states. This
case, the model establishes that a straight line passes by the (0, -1) coordinates point.
In some ways it is true that we cannot propose differences into γ S from a statistical
d

point of view; but the observed dispersion and the forced change in the slopes could
indicate nonetheless that we should turn to ; either another kind of interaction or
another models.
• γ S values
p

The obtained values come from the average of the different determinations. We may
presume a difference, from a statistical point of view, in the polarity between the edge
surfaces and the face ones in a massive crystal (9.7 ± 3.8 mJ/m2 vs. 3.4 ± 2.2 mJ/m2). We
may assume there are not any significant differences between the values of the different
granulometric fractions from a strict statistical point of view.
This observed statistical dispersion reminds us the Girifaco and Good’s advices when
they criticise the models which use the forces decomposition; these forces should not be
independent of the system they interact with.
 99

Figure Addenda-29: Critical surface tension conversion curves: A, pure hydrocarbon liquid
series; B, mixed glycol, polyglycol, and ASTM liquid series; C, ethanol/water series. [Extracted
from Journal of Colloid and Interface Science, Vol. 22, No. 2, February 1970]

• Variations between the γ c obtained in this work and the previous ones.
This was analysed in 5 “System integral analysis”, basing on concepts of Good,
Fowkes and the determinations reported by Ottewill and Murphy. Besides we show a
graph elaborated by Dann who worked in this subject and calculated the dispersive
components of binary systems as alcohol-water solutions series et cetera.
For example; if we have a solid whose wetting critical tension ( γ c ) is 50 mJ/m2
determined with normal-hydrocarbon-liquid series it will get a 36 mJ/m2 value for γc with
the ASTM mixtures and 28 mJ/m2 value for γc with ethanol-water solutions series (see
Figure Addenda-29.)
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Nomenclature
Variable Description
A Area
B ρg / 2µL
B′ Associated parameter to the Born’s repulsion forces (Lennard-Jones equation)
C Associted parameter to van der Waal’s forces (Lennard-Jones equation)
Cte Constant
C1, C2 Constants in (4-137) and (4-138)
E Internal energy
1 − Ev Packaging factor
Es Surface porosity of the wetted area
F Forces of a Lennard-Jones potential
Fi percent of mass floated in a liquid of superficial tension “i”
Fadh Adhesion force or tension
G Free energy
H Enthalpy
I Ionisation energy
J Homogeneity index in (4-170)
K Spreading coefficient
Mab Attraction constant between ‘a’ and ‘b’ phases
N Constant in (1-72)
P Pressure
Padh particle-bubble attaching probability
PCH Collision probability
Pes Stabilisation probability
PF Flotation probability
R Ideal Gases Universal constant
R∞ Ultimate recovery
S Entropy
T Temperature
V Molar Volume
W Work
Wadh Adhesion work
Wc Cohesion work
g Gravitational acceleration
fi Surface fraction
h Height of the drop
h′ Planck constant
k Specific rate constant
k′ Boltzmann’s constant
m Lucassen-Rynders’ slope
n Number of moles
p Girifalco- Good’s model slope
q Heat adsorbed by the system
 105

r Interaction distance
r′ Rugosity factor
α Zisman’s slope
α′ Polarisation constant
β Parameter in (4-138)
β0 Relationship parameter between φSL y γSL in (1-119)
γ Surface tension
γd Dispersive (London) Components
γp Polar components
γSV Solid vapour interfacial tension
γSL Solid-liquid interfacial tension
γLV Liquid vapour interfacial tension
γc Critical tension of complete wetting
γi Critical tension of immersion
Γi Surface excess of adsorption
ΓSV Solid-vapour interface adsorption
ΓLV Liquid vapour interface adsorption
ΓSL Solid liquid interface adsorption
∆W Difference between two values of variable W
θ Contact angle
θ′ Apparent contact angle
µ Chemical potential
µ′ Dipolar moment
η Parameter in (4-137)
ν0 Fundamental frequency of electronic vibration
Πe Adsorption equilibrium pressure in the solid
ρ Density
φ Interaction parameter (Girifalco-Good’s model)
ω Relationship parameter between φSL andγ SL in (1-119)