CHAPTER 1

INTRODUCTION

1.1 GENERAL
Surface free energies and its components between two interacting surfaces are
critically important in a number of industrial applications including adhesion, coating
operations, printing, deinking, lubrication; and has an influence in daily life, biology,
chemistry and biochemistry (1-5). Many of the mineral processing techniques, e.g.
flotation, selective flocculation, filtration, thickening also depend on the interfacial
interactions between solid and liquid, essentially water. These interactions are mainly
controlled by the interfacial tension between two phases, which dictates the strength of
interaction. The characterization of the surface properties and especially the surface free
energy components of the solids are, therefore, recognized as the key to understanding
the mechanism of surface-based phenomena. This information provides essential insight
into the mechanism of such interactions as the stability of colloidal suspensions,
molecular self-assembly, wetting, spreading, bubble-particle, particle-particle interaction
in the industrial applications.
Contact angle measurements, first described by Thomas Young in 1805, remains
at present the simplest and most accurate method for characterizing the surface properties
of solids and determining the interaction energy between a liquid (L) and a solid (S), at
the minimum equilibrium distance (6-11). The value of contact angle θ is a measure of
the competing tendencies between the energy of cohesion of the liquid molecules and the
energy of adhesion between liquid and solid. When the work of cohesion between liquid
molecules exceeds the work of adhesion between solid and liquid, a drop of liquid placed
onto the solid surface forms a finite contact angle. On the contrary, if the work of
adhesion is higher than the work of cohesion spreading occurs. The water contact angle
is more often used as a measure of surface hydrophobicity (12-16), i.e., the higher the
contact angle is, the more hydrophobic the solid surface becomes. It can also be used to
calculate the surface free energy of a solid surface. In principle, solids having lower
surface free energies (γS) exhibit higher values of water contact angles (17-20).
 The contact angle measurements are easy to perform on a smooth and flat surface,
and there are several well-known techniques for measuring the contact angles of liquids
on flat surfaces. By placing a drop of water on the surface of a solid of interest, the
contact angle can easily be measured through the aqueous phase at the three-phase
contact, i.e., solid-liquid-air. To prepare a smooth flat surface, a mineral specimen is cut
by a diamond saw and polished with an abrasive powder such as alumina. It is well
known, however, that mineral surfaces, particularly those of sulfide minerals, undergo
significant chemical changes and atomic rearrangements during polishing. Therefore, it
would be more desirable to measure contact angles directly on powdered samples. It is
also unreliable and impractical to use the conventional contact angle measurement
techniques for the characterization of fine powders such as fillers, pigments and fibers.
Some times the solids of interest exist only in powdered form, in which case the
sessile drop technique cannot be used for contact angle measurements. It becomes
somehow difficult to obtain the value of contact angle, when the solid is in powdered
form. Despite the difficulties associated with the contact angle measurements, some
methods are available for determining the contact angles of powders (11, 21). The
capillary rise (22-24) and thin layer wicking (25-26) methods are most commonly used
for powdered solids.
Another method of determining the contact angles of powders is to measure the
heat of immersional wetting in various testing liquids, e.g. water, formamide, etc. In this
technique, a powdered sample is degassed to remove the pre-adsorbed water and then
immersed in liquid (23, 27-31). In general, the more hydrophobic a solid is, the lower the
heat of immersion in water becomes. Thus, one should be able to obtain the values of
contact angles from the heats of immersion and converting it into the contact angle value
using thermodynamic relations. Different investigators use different methods of
calculating contact angles from the heat of immersion (29-31).
Besides obtaining the contact angle values of various liquids on powdered solid
surfaces, microcalorimeter may be used to determine percentages of hydrophobic and
hydrophilic surface, and acidic and basic surfaces of powdered solids (32-37). The
interactions between various reagents and solid surfaces in aqueous or non-aqueous
media can be studied by using a microcalorimeter as well (38-42). Microcalorimetric

2
studies should also be particularly useful in explaining the physico-chemical aspects of
mineral separation techniques such as flotation, selective flocculation and coagulation.
It is the objective of the present work, in general, to characterize the solid surfaces
in the powdered form in terms of their surface free energy components (the total, γS; the
Lifshitz-van der Waals, γSLW; the Lewis acid-base, γSAB; the Lewis electron donor, γS- and
the Lewis electron acceptor, γS+) and compare to those of flat surfaces. To meet this
objective, a flow microcalorimeter was used to determine the heat of immersion and heat
of adsorption enthalpies of various liquids on a number of powdered talc surfaces. Also,
direct contact angle measurements were conducted using various liquids to determine the
surface free energy parameters of talc samples. Another objective of the present work
was to study the role of surface free energies and their components in mineral separation,
e.g. in flotation and selective flocculation. To this end, a crude clay from east Gergia
(d90=2.0 µm) sample was chosen as a model ore and subjected to flotation and selective
flocculation experiments to remove anatase (TiO2), which is the main discoloring
impurity found in kaolin clay. Microcalorimetric and direct contact angle measurements
were conducted using anatase (TiO2) particles with varying hydrophobicities to explore
the effect of surface hydrophobicity and surface free energies of solids on the separation
efficiency of flotation and selective flocculation processes.
In what follows is a review of literature presented with an aim to provide a
relevant background to the research presented in this work.

1.2 LITERATURE REVIEW

1.2.1 Surface Free Energy and Acid-Base Interactions

1.2.1.1 Lifshitz-Van der Waals Interactions

The existence of a general attractive interaction between a pair of neutral atoms
was first postulated by van der Waals (43-44) to explain the observed deviation of a real
gas behavior from the ideal gas law (Eq. [1.1]). In spite of the qualitative character of the
argument used by van der Waals in his derivation, the great success of his equation of
state in explaining experimental data on the properties of gases spurred thinking on the

3
origin of the interatomic or intermolecular forces. Van der Waals (43-44) showed that
the ideal gas law,

PV = RT [1.1]

does not apply to the real gases or liquids due to the interatomic or intermolecular forces.
In Eq. [1.1], P is the pressure, V the molar volume, R the gas constant and T the absolute
temperature. These non-covalent and non-electrostatic molecular forces are referred to as
van der Waals forces. Van der Waals forces play a central role in all phenomena
involving intermolecular forces, for while they are not as strong as Coulombic or H-
bonding interactions, they are always present.
Collectively called as the van der Waals forces, these intermolecular forces
originates from: a) randomly orienting dipole-dipole (or orientation) interactions,
described by Keesom (45); b) randomly orienting dipole-induced dipole (or induction)
interactions, described by Debye (46); c) fluctuating dipole-induced dipole (or
dispersion) interactions, described by London (47-48).

a) Keesom’s dipole-dipole interactions in vacuo:

Keesom (45) suggested that two molecules with permanent dipole moments orient
themselves in such a way as to attract each other. The interaction energy due to this
orientation effect is given by:

µ12 µ 22
V= [1.2]
3(4πε 0 )2 kTr 6

where V is the potential energy (J), µ1 and µ2 dipole moments (Cm), ε0 dielectric
permittivity in vacuo (8.854 x 10-12 C2J-1m-1), k Boltzman constant (1.381 x 10–23 JK-1), T
absolute temperature (K) and r distance between interacting atoms or molecules (m). As
shown, the Keesom’s interaction energy is inversely proportional to the sixth power of
the interatomic distance. Note that Keesom’s interactions are identical with Coulombic

4
interactions between two charged bodies separated by a distance r, in vacuo which is
given by:

q1q2
F= [1.3]
4πε 0 r 2

where F is the Coulomb force, q1 and q2 the electrical charge (C) of two interacting
bodies.

b) Debye’s dipole-induced dipole interactions in vacuo:

Debye (46) proposed that the polarizability of molecules is the cause of
intermolecular forces. He showed that a molecule with a permanent dipole moment
polarizes a neighboring neutral molecule. The interaction between the electric field of
these two different dipoles gives rise to an interaction force. The interaction energy can
be calculated using

αµ 2
V= [1.4]
(4πε 0 )2 r 6

where α is polarizability (C2m2J-1). Eq. [1.4] suggests that similar to the Keesom’s
interaction, Debye’s interaction energy is inversely proportional to the sixth power of the
interatomic distance.

c) London’s fluctuating dipole-induced dipole interactions in vacuo:

The existence of attraction between pair of neutral molecules has led to the
definition of the dispersion forces by London in 1930. London (47-48) showed that the
energy of dispersion interaction between two atoms or molecules is obtained using

3α 2 hv
V =− [1.5]
4( 4πε 0 ) 2 r 6

5
in which h Plank’s constant (6.626 x 10-34 Js) and v frequency of fluctuation (s-1). As
shown, the London’s interaction energy is also inversely proportional to the sixth power
of the interatomic distance.
The dispersion forces have been considered as a result of the charge fluctuations
associated with the motion of electrons in their “orbitals”. These charge fluctuations
result in a time-dependent dipole moment. The phase difference in fluctuating dipoles
leads to a mutual interaction, while the time-dependent dipole generates an instantaneous
electric field which polarizes any neighboring neutral atom or molecule, inducing a
dipole moment in it. As a result, a mutual instantaneous interaction is also generated.
The interactions between the atoms or molecules obtained such a way causes an increase
in the magnitude of the interaction force.
Of the there interactions given, Keesom and Debye interactions are only found
among molecules which have permanent dipole moments. The Keesom theory and
Debye theory in combination, therefore, have been used successfully to explain the
interactions between polar molecules in a phenomenological way. On the other hand, for
neutral gas molecules such as H2, N2 and CH4 which posses no permanent dipole
moments, the intermolecular forces deduced from Van der Waals thermal equation (Eq.
[1.1]) are far greater than the force accounted for by the orientation and induction effect.
The London dispersion interaction, however, is universal and is present in atom-
atom interactions as well. All three interaction energies between atoms or molecules
decay very steeply with distance (r), as r-6. Of the three components of intermolecular
forces, only van der Waals-London (dispersion) interactions have significant importance
between macroscopic bodies, in the condensed systems (49-50). The already small
Keesom interaction is virtually completely screened out, especially in aqueous media
which contain electrolytes (51). The dispersion forces play also a significant role in a
number of industrially important processes such as flocculation, coagulation, adhesion,
polymer conformation and physical adsorption.

6
 I) Dispersion Forces Between Two Macroscopic Materials - Hamaker’s Approach
Hamaker (52) conducted pair-wise summation of the dispersion (van der Waals-
London) energies theoretically, based on microscopic interactions, for macroscopic
bodies (of flat surfaces) interacting with each other.
The Hamaker constant, Aii, is commonly used to estimate the dispersion
interaction at short distances between two microscopic bodies of material i as given by:

Aii = π 2 qi2 β ii [1.6]

where qi is the number of atoms per unit volume and βii the London constant for the

interaction between two atoms i, i.e., β ii = 3α 2 hv / 4( 4πε 0 ) 2 (see Eq. [1.5]).

The total attractive dispersion energy, VLondon, for two flat parallel surfaces,
separated by a distance r, is given by:

Aii
VLondon = − [1.7]
12πr 2

which allows one to determine the dispersion interaction energy between two atoms or
molecules of material i using Hamaker’s constant.
Knowing that β ii = 3α 2 hv / 4( 4πε 0 ) 2 , the Eq. [1.5] can be rewritten as:

β ii
V =− [1.8]
r6

which is useful for calculating dispersion interaction energy from the known value of
London constant.
According to the Berthelot’s principle (53), the interaction constant between two
particles of different materials equals to the geometric mean of the interaction constants
of individual materials. Thus, the London constant, βii, between two different types of
atoms or molecules can be written as:

7
 β ij = β ii β jj [1.9]

It follows that

Aij = Aii A jj [1.10]

which is known as geometric mean combining rule (Berthelot), and is widely used for
calculating dispersion energies of interaction between dissimilar materials.
By assuming additivity and using Hamaker’s pair-wise summation it can be
shown that for two identical spheres of radius R, the (free) energy of interaction becomes,

AR
V = ∆G = − [1.11]
12r

and the force between the same two spheres becomes,

AR
F= [1.12]
12r 2

Note that the force is obtained by differentiating the energy with respect to
r
distance, i.e., V = ∫0 Fdr .

For two interacting flat parallel surfaces, the attractive (dispersion) energy may be
written as:

A
V = ∆G = − [1.13]
12πr 2
and:
A
F= [1.14]
6πr 3

8
 For the other geometries, the reader is referred to the references 51 (Israelachvili)
and 54 (Nir).
Hamaker’s pair-wise summation procedure can also be used to calculate the
combined Hamaker constant of two macroscopic identical and different particles
interacting in a third medium. For two identical materials (e.g. material 1) in a medium
3, the Hamaker combining rule can be described by:

A131 = A11 + A 33 − 2A13

[1.15]
= ( A11 − A 33 ) 2

in which A11 and A33 refer to the Hamaker constants of the solid and the medium,
respectively, in vacuo.
For materials 1 and 2 in a medium 3, the Hamaker combining rule can be given
by:

A132 = A12 + A33 − A13 − A23

[1.16]
= ( A11 − A33 )( A22 − A33 )

Eq. [1.15] suggests that the value of A131 is always positive (A131>0). Therefore,
two identical molecules or particles in medium 3 (i.e., liquid) always attract each other,
although it can become zero, when A11=A33. However, A132 can have negative values
(A132<0), i.e., when:
A11>A33>A22, and
A11<A33<A22
under which conditions the dispersion interaction energy becomes repulsive, i.e.,
VDispersion>0 (55-57).
Fowkes (6) proposed a more practical approach for determining the Hamaker
constant of material i, from the known values of γid:

9
 Aii = 6πrii2γ id [1.17]

in which rii is the distance between interacting atoms or molecules and γid is the
dispersion component of the surface free energy of the substance in question. Fowkes (6)
found that the value of 6πrii2 be 1.44 x 10-14 cm2 for most materials. Thus, Eq. [1.17]
allows one to calculate the value of Hamaker constant of a material from the
experimentally determined value of γid or vice versa. Since the use of Eq. [1.17] only
requires the value of dispersion component of surface free energy of materials that can be
readily obtained from simple contact angle measurements, it is convenient to use this
method for practical purposes. Due to its simplicity, this method has been widely used in
practice (58-62).
It can be seen from the foregoing descriptions that the Hamaker approach to
dispersion interaction between two microscopic bodies has the virtue of ease of
comprehension. As an approximation, it is customary to use Equation [1.10] for the
calculation of Aij and Equations [1.15] and [1.16] for the calculation of A131 and A132 from
the known values of Aii that can be obtained from Equation [1.6]. Padday and Uffindell
(63) demonstrated the applicability of Hamaker approach to the n-alkanes by calculating
the theoretical values of surface tensions of various n-alkanes using the following
equation:

Aii
Wii = 2γ ii = [1.18]
12πrii2

where rii is the separation distance between two atoms in the bulk. The calculated results
have shown a good agreement with experimentally measured values of surface tension,
which suggest that the intermolecular forces of n-alkane are mainly of dispersion type. It
is clear that the calculated value of surface tension depends critically on the assumed
value of rii.
Table 1.1 gives the values of Hamaker constants for two identical materials
interacting across vacuum (or air), along with some other properties taken from the

10
literature (51). As shown, the Hamaker constants for n-alkanes are substantially smaller
compared to those obtained for the various minerals and metals.
Table 1.2 shows the values of Hamaker constants for two different materials in
another medium other than air or vacuum (51). As shown, the Hamaker constants for n-
alkanes are substantially smaller compared to those obtained for the various minerals and
metals. For example, the values of Hamaker constants for n-alkanes are in the range
from 3.8-5.1 x 10-20 J, whereas it is 43 x 10-20 J for rutile (TiO2). According to the
Hamaker’s theoretical approach, TiO2 should collide much faster than hydrocarbon oil in
water (see Equation [1.15]). Contrary to the suggestions made by Hamaker’s theoretical
approach, collision tendency of hydrocarbon oil droplets in water is much higher and
their collision kinetics is much faster than the particles of TiO2 and other oxide minerals
and metals. Hamaker approach, like the classical DLVO theory, ignores the existence of
hydrophobic interaction between the two particles of hydrophobic materials.

II) Dispersion Forces Between Two Macroscopic Materials - Lifshitz Approach

In contrast to Hamaker’s approach, which started with single interatomic
interactions, to arrive at the total interaction energy for macroscopic bodies by a process
of summation, Lifshitz (64) has constructed a more accurate approach through a purely
macroscopic framework. The problems associated with the use of summation process
have been completely eliminated in this macroscopic treatment of dispersion forces.
Lifshitz treated the interacting bodies as continuous media. The dispersion forces in this
approach have been derived in terms of the macroscopic properties of interacting bodies,
such as their dielectric constants or refractive indexes.
Lifshitz (64) calculated interaction energy using quantum mechanical and
electromagnetic approach. As mentioned, this theory is for macroscopic bodies and
considers the effect of the medium and the retardation effect, which caused by a finite
velocity of propagation of electromagnetic fields. The basic idea lies in the fact that
oscillation of electrons around a nucleus creates an oscillation of the electromagnetic
field around an atom. It has been noted that this field is always present within any
medium due to thermodynamic fluctuations, and it also extends to outside of the medium.

11
 Lifshitz’s theory of condensed media interactions has its origins in Maxwell’s
equations, where the electric and magnetic fields are subjected to fast temporal
fluctuations. In order to accommodate the temporal fluctuations of the fields, Lifshitz has
adopted the fluctuation theory developed by Rystov (65). The derivation of Lifshitz
model is beyond the scope of this work. Therefore, only the results and its utility are
presented here.
A general expression for the free energy of interaction between two flat surfaces
is given by

A
∆G = − [1.19]
12πr 2

which is of the same form of as Eq. [1.13]. The Hamaker constant, A, may be designated
as A132 and A131 for the interactions between materials 1 and 2 in a medium 3 and
materials 1 and 1 in a medium 3, respectively. The Lifshitz theory gives (51):

3  ε 1 − ε 3  ε 2 − ε 3 
A132 = kT   
4  ε 1 + ε 3  ε 2 + ε 3 
[1.20]
3hv e (n 2
− n32 ) (n − n )
1/ 2 2 2 1/ 2

) {(n + n ) + (n }
+ 1 2 3

(
8 2 n12 + n32 ) (n
1/ 2 2
2 + n32
1/ 2 2
1
2 1/ 2
3
2
2 + n32 )
1/ 2

and

3 ε −ε 
A131 = kT  1 3  +
2
3hve n12 + n32 ( ) 2

[1.21]
4  ε 1 + ε 3  16 2 n12 − n32 3 / 2 ( )

where ε1 , ε2 and ε3 are the dielectric constants of the three media and n1 , n2 and n3 are
the refractive indexes of the same. In each of Eqs. [1.20] and [1.21], the first term on the
right hand side gives the zero-frequency energy of the van der Waals energy (which
includes the Keesom and Debye interaction energies), while the latter term represents the

12
dispersion energy which includes London energy contribution. ve is the absorption
frequency in the UV region (≈3x1015 s-1) (51).
Israelachvili (66) calculated the Hamaker constants of different liquids from the
data of their refractive indexes using the Lifshitz macroscopic approach. The author then
calculated the surface tensions of these liquids from the already estimated values of the
Hamaker constants using the following equation:

Aii
∆Gii = − [1.22]
24πr02

where ∆Gii stands for the free energy of cohesion of species i in vacuo. Since
1
γ i = − ∆Gii ,
2

Aii
γi = [1.23]
12πr02

where γi is the (apolar component) of the surface tension of material i and r0 is the
separation distance between two flat parallel surfaces when they are in van der Waals
contact. Note that this is the same form of Eq. [1.18] from which Padday and Uffindell
(63) calculated the theoretical values of surface tensions of various n-alkanes using
Hamaker approach. The value of r0 was defined to be 0.157±0.009 nm (51).

III) Interfacial Lifshitz-Van der Waals Interactions

Good and Grifalco (67) and Fowkes (68) showed that if only dispersion
interaction forces are available between two condensed phases, e.g., a solid and a liquid,
the interfacial tension (γ12LW) is given by the following equation:

γ 12LW = (γ 1
LW
− γ 2LW )
2

[1.24]
=γ 1
LW
+γ LW
2 −2 γ 1
LW
γ LW
2

13
which is referred to as Good-Grifalco-Fowkes combining rule.
The Lifshitz-van der Waals interaction energy between materials 1 and 2 in vacuo
is given by Dupre equation (21):

LW LW
∆G12 = γ 12 − γ 1LW − γ 2LW [1.25]

Substituting Eq. [1.24] into Eq. [1.25] one obtains,

LW
∆G12 = −2 γ 1LW γ 2LW [1.26]

which is a very important relation. This equation states that the atoms at an interface are
pulled by those in the neighboring phase. Since the Lifshitz-van der Waals forces are
universal and always available at the surface, Eq. [1.26] also suggests that the energy of
interaction is negative, i.e, the interaction energy between two condensed phases is
always attractive.
Similarly, the interaction energy between molecules or particles of material 1,
immersed in a liquid 2 is:

LW LW
∆G121 = −2γ 12 [1.27]

and the energy of cohesion of material 1 is:

LW
∆G11 = −2γ 1LW [1.28]

Also, the energy of interaction between materials 1 and 2, in a medium 3, is given

by:

LW LW LW LW
∆G132 = γ 12 − γ 13 − γ 23 [1.29]

14
 LW LW LW LW
Thus, defined values of interaction energies, i.e., ΔG11 , ΔG12 , ΔG121 , ∆G132 , can
be linked to the respective Hamaker constants as:

A
∆G LW = − [1.30]
12πr 2

which provides one to determine the Hamaker’s constant and to check the correctness of
Hamaker’s combining rule via a surface thermodynamic approach.

1.2.1.2 Polar or Acid-Base Interactions

It has been known for many years that acid-base interactions are important in
adhesion of organic substances to inorganic substrates (69-73), but the adhesion between
two nonpolar substances has been described by the term “polar” for a long period of time.
The reason is that intermolecular forces were studied first in dense gases, where
dispersion forces (London) dipole-dipole interactions (Keesom), and dipole-induced
dipole interactions (Debye) explain most of the intermolecular interactions between pairs
of atoms or molecules (43-48). For many years, these intermolecular forces were used to
explain the intermolecular forces between solids and liquids, even after the discovery of
the hydrogen bonding and acid-base interactions.
In the last twenty years significant advances have been made in the
thermodynamic treatment and interpretation of interfacial tension between two
interacting surfaces, i.e., solid and liquid. It is now clear that especially in aqueous media
the polar interactions are mainly governed by the interactions between hydrogen-donors
and hydrogen-acceptors (or between Bronsted acids and Bronsted bases) (21, 50, 74). It
is, however, preferable to extend the concept of polar interactions more widely, including
hydrogen bonds, and to define them to comprise all electron-acceptor-electron-donor, or
Lewis acid-base interactions, designated by superscript AB (50, 76-79).
Fowkes (28, 68, 79) proposed that the surface tension of a material i can be
broken down into separate components originating from different kinds of intermolecular
forces:

15
 γ i = ∑ γ ij [1.31]
j

where j stands for different types of surface tension component, e.g., dispersion, dipolar,
induction, hydrogen bonding and metallic interactions.
One may group the different types of surface tension components into apolar
(nonpolar) and polar interactions. The former can be represented by the Lifshitz-van der
Waals (or LW) interactions and the latter includes all others. The polar interactions are
generally considered to be interactions between Lewis acids and bases on the surface.
Thus, Eq. [1.31] can be rewritten:

γ i = γ iLW + γ iAB [1.32]

where γ iLW and γ iAB refer to the apolar (Lifshitz-van der Waals) and polar (acid-base)
components of surface tension, respectively.
Since ∆Gii ≡ −2γ i by definition, Eq. [1.32] can be written:

∆G = ∆G LW + ∆G AB [1.33]

where ∆GLW is the free energy change due to Lifshitz-van der Waals interaction, and
∆GAB is the same due to acid-base interactions.
The work conducted by Fowkes (50) is probably the best example for
demonstrating the presence and importance of acid-base interactions between two
interacting surfaces. This author determined the values of acid-base (WSLAB) and
Lifshitz-van der Waals (WSLLW) components of work of adhesion for various acidic and
basic liquids on polymer surfaces as a function of acidity or basicity of polymer. He
showed that the contribution of acid-base (or polar) component to the work of adhesion
(WSL) is strictly dependent on the acidity or basicity of the solid (polymer) of interest.
For example, when studying with polyethylene (a basic polymer) which is co-
polymerized with various contents of acrylic acid (an acidic monomer), he found that the
acid-base contribution to the work of adhesion increased with increasing acid content of

16
the polymer in the case of using basic liquids such as dimethylsulfoxide,
dimetylformamide and 0.1 M aqueous solution of sodium hydroxide, in the adhesion
(contact angle) measurements. However, a strongly acidic liquid (35% phenol in
tricresylphosphate) had nothing but dispersion force interactions with the acidic polymer;
no dipole contribution to adhesion was observed.
The author obtained similar results with acidic liquids on copolymers of ethylene
with varying contents of vinyl acetate, which is a basic monomer. In this case, he
showed that WSLAB for acidic liquids (35, 48 and 72% phenol in tricresylphosphate,
respectively) increased with increasing vinyl acetate content of the polymer, and, WSLAB
for pyridine, a basic liquid, was zero; again no dipole contribution was observed.
Recently, there have been numerous publications in the field of acid-base interactions
either to prove (80-83) or disprove (84-86) the existence of these types of interactions
between two interacting surfaces.
Van Oss et al (87) showed, based on Fowkes’s acid-base interaction approach
(50), that electron-acceptor (Lewis acid) and electron-donor (Lewis base) interactions are
essentially asymmetrical in the sense that of a given polar substance i the electron-
acceptor and the electron-donor parameters are usually quite different. For acid-base
interactions between materials i and j,

∆GijAB = −2 γ i+γ −j − 2 γ i−γ +j [1.34]

and

∆GiiAB = −4 γ i+γ i− [1.35]

where γ+ is the acidic component and γ- is the basic component of the surface tension.
Since ∆Gii ≡ −2γ i , Eq. [1.35] becomes:

γ iAB = 2 γ i+γ i− [1.36]

17
 From Dupre equation, which is applicable for any type of interaction, one may
define:

∆G12AB = γ 12AB − γ 1AB − γ 2AB [1.37]

The above relation is valid irrespective of polarity or apolarity. One can rearrange
Eq. [1.37] to express the interfacial tension γ 12AB between materials 1 and 2 as:

γ 12AB = ∆G12AB + γ 1AB + γ 2AB [1.38]

Substituting this into Eq. [1.34] and [1.36] one obtains:

(
γ 12AB = 2 γ 1+ γ 1− + γ 2+ γ 2− − γ 1+ γ 2− − γ 1− γ 2+ ) [1.39]
= 2( γ 1
+
− γ 2+ )( γ 1
−
− γ 2− )
which is equivalent to Eq. [1.24] for Lifshitz-van der Waals (LW) interactions.
Fowkes’s surface tension components approach can be applied to interfacial
tensions as follows:

LW
γ 12 = γ 12 + γ 12AB [1.40]

Substituting Eqs. [1.24] and [1.39] into Eq. [1.40], one obtains the total interfacial
surface free energy between phases 1 and 2:

(
γ 12 = γ 1LW + γ 2LW − 2 γ 1LW γ 2LW + 2 γ 1+γ 1− + γ 2+γ 2− − γ 1+γ 2− − γ 1−γ 2+ ) [1.41]
= (γ 1
LW
− γ 2LW ) + 2( γ
2
1
+
− γ 2+ )( γ 1
−
− γ 2− )

18
 It should be stressed here that the apolar interactions are additive, while the acid-
base interactions are not due essentially to the asymmetric properties mentioned earlier.
If one of the phases does not posses the component γ+ or γ- the proper term concerning
them disappears in Eq. [1.41]. If phase 1 (i.e., liquid) or phase 2 (i.e., solid) does not
have both electron donor (γ-) and electron acceptor (γ+) interactions it is termed apolar
surface. If the surface possesses both components γ+ and γ-, it is called bipolar. Lastly, if
the surface has only electron donor or electron acceptor interactions, it is named
monopolar surface, but neither γ+ nor γ- component participates in the surface tension of a
liquid or a surface free energy of a solid. However, they do participate in interfacial
interactions if the contacted phase exposes the complementary component γ+ or γ-,
respectively (21). Eq. [1.41] shows that apolar (or dispersion) component is always
positive, while polar (or acid-base) component can be positive or negative.
The Dupre equation can also be used in the form of:

∆G12 = γ 12 − γ 1 − γ 2 [1.42]

to describe the interaction between materials 1 and 2, suspended in liquid 3 and by taking
both the LW and AB into account and substituting Eqs. [1.24] and [1.39] into Eq. [1.42]
one obtains,

 γ 1LW γ 3LW + γ 2LW γ 3LW − γ 1LW γ 2LW − γ 3LW + 

 
∆G132

( ) (
= 2 γ 3+ γ 1− + γ 2− − γ 3− + γ 3− γ 1+ + γ 2+ − γ 3+ )


[1.43]
 − γ + γ − − γ −γ + 
 1 2 1 2


Eq. [1.43] suggests that the interaction energy between two different materials can
be either negative (attractive) or positive (repulsive) depending on the surface free energy
parameters of material 1 and 2 in medium 3, e.g. water.
Similarly, for describing the interaction between molecules or particles of
material 1, suspended in liquid 3:

19
 (
∆G131 = −2γ 13 = −2 γ 1LW − γ 3LW )
2

[1.44]
− 4( γ γ
+ −
1 1
+ − +
+ γ γ − γ γ − γ γ
3 3 1
−
3
− +
1 3 )
The hydrophobic interaction is more closely related to Eq. [1.44]. When low
energy (or hydrophobic) materials interact with each other in aqueous systems (water is
the medium 3), γ13 becomes positive and ∆G131 negative, giving rise to an attraction. If
the polar surface free energy component of hydrophobic material is negligibly small, in

this case the most important parameter in Eq. [1.44] is − 4 γ 3+γ 3− which represents the

polar contribution to the cohesive energy of water. The value of − 4 γ 3+γ 3− is 102 mJ/m2

and is present in all type of interactions. In fact, this term is the main contributor to the
interfacial attractions between low-energy materials immersed in water (21, 88).

1.2.1.3 Van Oss-Chaudhury-Good Equation

According to Fowkes (28, 79, 89), the work of adhesion (Wa) between a liquid on
a solid surface proposed to be given by:

Wa = Wadd + Wadnd [1.45]

where Wad represents the contributions from dispersion (nonpolar) interactions, and Wand
represents the same from non dispersion (polar or ionic) interactions. Laskowski and
Kitchener (90) suggested that all solids would be hydrophobic if Wadnd=0, i.e., if the
surface is free of polar groups on which water molecules can be bonded.
Fowkes (50, 75) and van Oss et al (76-78) showed that surface free energy
components of a material i can be given by:

γ i = γ iLW + γ iAB [1.32]

where γ iLW and γ iAB refer to the apolar (Lifshitz-van der Waals) and polar (acid-base)
components of surface tension.

20
 For the interactions between a solid S and a liquid L, Eq. [1.33] may be written
as:

LW AB
∆GSL = ∆GSL + ∆GSL [1.46]

where ∆GSLLW is the free energy change due to Lifshitz-van der Waals interaction, and
∆GSLAB is the same due to acid-base interactions.

Fowkes (68) showed that

LW
∆GSL = −2 γ SLW γ LLW [1.47]

while Van Oss et al (76-78) showed that

AB
∆GSL = −2 γ S+γ L− − 2 γ S−γ L+ [1.48]

Substituting these into Eq. [1.46],

∆GSL = −2 γ SLW γ LLW − 2 γ S+γ L− − 2 γ S−γ L+ [1.49]

Let us consider a process in which an air bubble is brought to the surface of a

solid immersed in water. If the solid surface is sufficiently hydrophobic, the air bubble
will stick to the surface forming an angle. The angle measured between the solid surface
and the surface of the air bubbles through the aqueous phase is referred to as “contact
angle”. Young (91) showed that

γ L cosθ = γ S − γ SL [1.50]

21
where γL is the surface tension of water and γSL is the interfacial tension between the solid
and liquid. The changes in free energy associated with the bubble-particle adhesion is
given by the following relation (92):

∆G SL = γ SL − γ S − γ L [1.51]

Combining Eqs. [1.50] and [1.51],

− ∆G SL = γ L (1 + cos θ ) [1.52]

which is known as the Young-Dupre equation.

Substituting Eq. [1.52] into Eq. [1.49], one obtains:

(1 + cos θ )γ L = 2( γ SLW γ LLW + γ S+ γ L− + γ S− γ L+ ) [1.53]

which is known as the Van Oss-Chaudhury-Good (OCG) thermodynamic approach to

determine the values of surface free energy components of solids. This is very useful
information for characterizing a solid surface in terms of its surface free energy
components, i.e., γSLW, γS+, and γS-. To determine these values, it is necessary to
determine contact angles of three different liquids of known properties (in terms of γL+,
γL-, γLLW) on the surface of the solid of interest. One can then set up three equations with
three unknowns, which can be solved to obtain the values of γSLW, γS+, and γS-.
If an apolar liquid is placed on the surface of a talc sample and its contact angle is
measured, Eq. [1.53] can be reduced to:

(1 + cos θ )γ L = 2 γ SLW γ LLW [1.54]

because γL+ and γL- are zero. Thus, Eq. [1.54] can be used to determine γSLW from a
single contact angle value, provided that the contact angle measurement is conducted

22
with an apolar liquid of known γL and γLLW. (In fact, γL=γLLW, γL+ and γL- are zero.) In
this case, Eq. [1.53] can be solved to determine the values of γS+ and γS- by solving two
rather than three simultaneous equations.
Once the three surface tensions, i.e., γSLW, γS+, and γS-, are known, one can
determine the surface tension of the solid, γS, as follows:

γ S = γ SLW + 2 γ S+ γ S− [1.55]

Table 1.3 shows the surface tension parameters and components of a number of
liquids taken from literature that can be used in the contact angle measurements using
various techniques (21). The surface free energy components of various polar and apolar
solid surfaces obtained from OCG thermodynamic approach are given in Table 1.4 (21,
26, 94-95, 97).

1.2.2 Contact Angle Measurements

As discussed in the foregoing section, it is essential to be able to measure the
contact angle (θ), if one wishes to characterize the surface of a solid in terms of its
surface free energy components. There are several different methods of measuring it.
The measurement method chosen depends on which form the solid of interest is
available. Sessile drop and captive bubble techniques are widely used for the flat
surfaces. The Wilhelmy plate technique developed by Neumann is also widely used to
determine the advancing and receding contact angles on the flat (or plate) surfaces (98).

1.2.2.1 Sessile Drop and Captive Bubble Techniques

The easiest methods of measuring contact angles on solid surfaces are the sessile
drop and the captive bubble techniques, both of which require that the surface of the solid
be flat. In the sessile drop technique, a liquid droplet is placed on the surface of a solid of
interest and the angle is measured through the liquid phase, as illustrated in Figure 1.1.
In this technique, the estimate of the contact angle, θ, is made from the tangential line
formed between the solid surface and the sessile drop profile where the drop intersects
the surface by means of a comparator microscope fitted with a goniometer scale.

23
Recently, the sessile drop resting on a horizontal solid surface have been analyzed using
the photographic or digital images to get information about the drop shape and dynamic
contact angle value (99-102).
Figure 1.1 shows that a finite contact angle is formed when a drop of liquid is
brought into contact with a flat solid surface, the final shape of the drop depending on the
relative magnitudes of the molecular forces that exist within the liquid (cohesive) and
between liquid and solid (adhesive). Thus, the contact angle is a measure of the
competing tendencies of the liquid drop and solid determining whether it spreads over the
solid surface or rounds up to minimize its own area. For example, when a low surface
energy liquid wets a solid surface (i.e, γL<γS), giving a zero contact angle, the molecular
adhesion between solid and liquid is greater than the cohesion between the molecules of
the liquid. On the contrary, liquids with high surface tension (i.e, γL>γS) tend to give a
finite (non-zero) contact angle, indicating that the cohesive force is greater than the
energy of adhesion between liquid and solid [21]. The figure also illustrates the
importance of acid-base interactions on the value of contact angle, hence on the
magnitude of adhesion. The concept of the equilibrium of the surface forces is expressed
mathematically by Young’s equation (Eq. [1.50]).
In the captive bubble technique, the solid is immersed on the surface of a liquid
and an air bubble (or drop of another liquid) is brought to the solid/liquid interface. If the
surface is hydrophobic, the bubble will stick to the surface. The angle between the
surface of the solid and the air bubble is then measured through the liquid phase from
either photographs of the bubble profile, or directly, by means of a goniometer
telemicroscope (98). The main advantage of this technique is that there is no question
that the solid-vapor interface is in equilibrium with the saturated vapor pressure of the
liquid.

1.2.2.2 Wilhelmy Plate Technique

A third method, which is developed by Neumann (98), consists of dipping a solid
into a liquid and measure the height (h) of a liquid rising along the surface. If the surface
tension (γL) and the density (ρ) of the liquid are known, one can use the following
equation (103) to calculate the contact angle θ:

24
 h 2 ρg
1 − sin θ = , [1.56]
2γ L

where g is the gravitational acceleration. This method, which is known as Wilhelmy plate
method, also requires that a flat surface is available. It has been reported that this method
is capable of measuring contact angles to 0.1o precision (98). The Wilhelmy plate
technique is suitable for measuring contact angles as a function of temperature (103).
With this technique, both advancing and receding contact angles could be measured by
moving the plate up or down positions, leaving the position of the line of contact
essentially unchanged.

1.2.2.3 Capillary Rise and Thin Layer Wicking Techniques

If a solid in question exists only in powdered form, none of the above can be used
to measure its contact angle. In one method, a powdered solid is packed into a capillary
tubing, one end of which is subsequently immersed into a liquid of known surface
tension. The liquid will rise through the capillaries formed in between the particles
within the tubing. The distance l traveled by the liquid as a function of time t is
measured. If one knows the mean radius r* of the capillaries present in the tubing, he can
calculate the contact angle using the Washburn equation (22, 98, 104):

γ LV r *t cosθ
l2 = , [1.57]
2η

where η is the liquid viscosity. The derivation of Washburn equation (Eq. [1.57]) is
made as follows:
The rate of penetration of a liquid (v) into a capillary under laminar flow
conditions can be given by (30)

dl r ∆P
v= = [1.58]
dt 8ηl

25
where r is the radius of the circular capillary and ∆P the pressure gradient across the
curved interface. The pressure gradient, ∆P, term can be expressed as

2γ L cos θ
∆P = + ∆p [1.59]
r

if the liquid penetrates exclusively under the influence of the surface tension of the liquid
and an external pressure difference ∆p over the capillary. Eq. [1.59] is known as the
Laplace equation, i.e, when ∆p=0.
Substituting Eq. [1.59] into Eq. [1.58] and integrating with the boundary
conditions l=0 and r=0 gives

r 2  2γ L cos θ 
l2 =  + ∆p t [1.60]
4η  r 

Since a powder bed in a tubing may be considered to consist of a bundle of

capillaries with varying radii, an effective radius r* is substituted for r. For a given
particle bed the value of r* will be constant. The r*, here, takes into account all the
randomly oriented capillaries and other errors introduced by the simplification of the
assumption. In such a case, Eq [1.60] is given in the form of

r *,2  2γ L cos θ 
l2 =  *
+ ∆p t [1.61]
4η  r 

In the capillary rise method l2 is measured as a function of time t as a given value

of ∆p. In most cases, experiments are conducted with ∆p=0 and, therefore Eq. [1.61] will
take the form of Eq. [1.57] which is known as the Washburn equation for determining the
values of contact angles on powdered solid surfaces.

26
 The value of r* can be obtained by using a liquid which is known completely wet
the powder, i.e., θ=0. The completely wetting liquid may be chosen from low energy
liquids such as alkanes (hexane, heptane, octane etc.).
The capillary rise technique has frequently been used on mineral powders (22-24,
104). Bruil and van Aartsen [22] studied the surfaces of polyethylene terephthalate
(PETP), polyamide (nylon 11), aluminum and graphite powders treated with varying
amounts of sodium dodecyl sulfate and measured the contact angles. Crawford et al. [24]
determined the contact angles on partially methylated quartz plates and particles with
varying surface coverage. The advancing contact angles measured on methylated quartz
plates and particles were in good agreement.
One problem with this technique might be the uncertainty associated with
determining r*. There is no guarantee that the value of r* determined with a completely
wetting liquid is indeed zero. Reproducibility and repeatability of test results also depend
on the shape and size of the particles. It has been stated that monosized and spherical
particles give more reproducible results [25, 104]. However, particle bed disturbances
and skewing may be observed when the particles are extremely fine and platy in shape
leading to unrealistic values of contact angles. It should be mentioned here that the
method of using the Washburn equation gives only advancing contact angles rather than
equilibrium or receding contact angles.
Van Oss et al (25) developed an extremely useful alternate technique where only
polydispersed suspensions of irregularly shaped particles are available for determining
contact angles. It is named as the “thin layer wicking” technique. Similar to the capillary
rise technique, the thin layer wicking technique uses the Washburn equation for obtaining
the values of contact angles on powdered solid surfaces. In this technique, a powdered
sample is deposited on a microscopic glass slide in the form of aqueous slurry. After
drying the sample, one end of the glass slide is immersed vertically in a liquid. The
liquid starts to creep up the slide through the capillaries formed between the particles
deposited on the glass surface. The velocity at which a liquid creeps up the slide is
measured, and then converted to a contact angle using the Washburn equation (Eq.
[1.57]).

27
 The value of r* in the Washburn equation can be obtained by using completely
spreading liquids (apolar) such as hexane, heptane, octane, decane and dodecane. In this
case, it is considered that cosθ=1. For each powdered solid surface, the 2ηl2/t vs. γL for
alkanes should yield a straight line whose slope is the mean pore radius (r*) (25-26).
Once the value of r* is known, it is then possible to calculate the value of the contact
angle for a given liquid on the powdered talc surface using the Washburn equation (Eq.
[1.57]). The contact angle liquids can be chosen from high-energy polar (e.g., water,
formamide, ethylene glycol) and nonpolar liquids (e.g. methylene iodide and 1-
bromonaphthalene) for the wicking measurements.

1.2.2.4 Contact Angle Determination From Heat of Immersion

Another technique of measuring contact angles for powders is to measure the heat
generated when a powder is immersed in a liquid. A microcalorimeter may be used to
measure the heat effect (hi) created by wetting powdered talc samples with various
liquids such as water and n-heptane. By dividing hi with the total surface area of the
sample used in the experiment, one obtains the heat of immersional wetting (-∆Hi) given
in units of mJ/m2.
Consider a solid is suspended over a liquid in a closed container. In this case, the
solid surface will be in equilibrium with the liquid vapor. Imagine now that the solid is
immersed into the liquid. The free energy change (∆Gi) associated with this process may
be given by the following relationship:

∆Gi = γ SL − γ SV , [1.62]

in which γ SL is the solid/liquid interfacial tension and γ SV is the solid/vapor interfacial

tension.
When a solid is immersed into a liquid from its own vapor phase (i.e., the solid is
not exposed to the vapor phase of the liquid by which it is wetted, or the solid is in
vacuum), the free energy ∆Gi of immersional wetting is given by the following
relationship:

28
 ∆Gi = γ SL − γ S [1.63]

where γ S is the surface free energy of the solid, which is in equilibrium with its own
vapor.
Of the two different free energies represented by Eqs. [1.62] and [1.63], the latter
is more useful in that it can be related to the heat (-∆Hi) of immersion that can be readily
measured in experiment. The heat of immersion is routinely measured by immersing a
powdered solid in vacuum into a liquid.
The enthalpy of immersion (∆Hi) determined using the heat of immersion
measurement can be related to ∆Gi as follows:

 d∆Gi 
∆H i = ∆Gi − T  
 [1.64]
 dT p

where T is the absolute temperature. Substituting Eq. [1.63] into Eq. [1.64], one obtains:

 d (γ SL − γ S )
∆H i = (γ SL − γ S ) − T   [1.65]
 dT p

Substituting Eq. [1.50] into [1.65],

 ∂ (γ L cos θ ) 
∆H i = −γ L cos θ + T  
 ∂T p

  ∂γ   ∂ cos θ  
= −γ L cos θ + T cos θ  L  + γ LV    [1.66]
  ∂T  p  ∂T  p 
  ∂γ    ∂ cos θ 
= − cos θ γ L − T  L   + γ LT  
  ∂T  p   ∂T  p

Since the enthalpy of the liquid ( H L ) is given by

29
  ∂γ 
HL = γ L − T L  , [1.67]
 ∂T  p

Eq. [1.66] is reduced to:

 ∂ cos θ 
∆H i = − H L cos θ + γ LT   [1.68]
 ∂T  p

Solving Eq. [1.68] for cosθ, one obtains the following relationship:

1   ∂ cos θ  
cos θ = γ LT   − ∆H i  , [1.69]
H L   ∂T  p 

which is a first-order differential equation with respect to cosθ. Eq. [1.69] have been
derived by Adamson (98) and used by Malandrini et al (29) for determining contact
angles on various talc samples from Europe by ignoring the ∂ cosθ / ∂T term. However,
the methodology used by Malandrini et al (29) is erroneous because of the assumptions
made in converting the heat of immersion to free energy of immersion.
There are no analytical solutions for Eq. [1.69]. Numerical solutions are possible,
provided that a value of contact angle is known at one particular temperature.
Nevertheless, Eq. [1.69] can be useful for determining θ from the value of ∆Hi
determined using a calorimeter. For this to be possible, it is necessary to have the values
of HL, γLV and ∂cosθ/∂T for a given liquid at a given temperature. The first two are
usually available in the literature.
There are several ways of determining temperature coefficient of cosθ. First, one
measures θ on polished solid surfaces as a function of temperature and determine
∂cosθ/∂T experimentally. An assumption made here is that although contact angle may
change when the solid is pulverized, its temperature coefficient may remain the same.
Second, the contact angle of a powdered sample is measured by pressing it into a pellet.
Again, the pressed solid sample may have a different contact angle from that of lose
powders. However, its temperature coefficient may be assumed to remains the same.

30
Third, the contact angles of powdered samples are measured using the capillary rise
technique. This technique gives advancing rather than equilibrium contact angles. If one
uses this technique to determine ∂cosθ/∂T, an implicit assumption is that the temperature
coefficients of the equilibrium and the advancing angles are the same.
Adamson (2, 98) related the heat of immersion enthalpy which can be readily
measured by a microcalorimeter (Eq. [1.65]) to the contact angle, θ, through the
application of Young’s equation (Eq. [1.50]) as follows:

 ∂γ ∂γ 
H i = −γ L cos θ − (γ S − γ SV ) − T  SL − S  [1.70]
 ∂T ∂T 

Since in practice, γS-γSV and ∂γS/∂T are negligibly small for systems having large
contact angles and also the value of ∂γSL/∂T assumed to be relatively constant for low
energy surfaces, i.e, ∂γSL/∂T=0.07±0.02 mJ m-2 K-1, a simple relationship between contact
angle and heat of immersion enthalpy can be established as:

− 0.07T − H i
cos θ = [1.71]
γL

Eq [1.71] has been shown to work well for low energy (nonpolar) solids such as
graphon (27), teflon (105), fluorinated hydrocarbons (30) and methylated silica surfaces
(31).

1.2.3 Limitations of Contact Angle Measurements

1.2.3.1 Spreading Pressure

One of the major problems in the use of Young’s equation is that its assumption
of γS ≈ γSV. This may or may not be the case, depending on the experimental conditions.
In particular, the surface free energy of solid can significantly be reduced as a result of
the adsorption of the vapors of the wetting liquid (at saturation) onto the solid surface.
When the solid surface is in equilibrium with the liquid vapor, the reduction of the

31
surface free energy of the solid due to the vapor adsorption is termed the equilibrium
spreading pressure, πe, and hence its addition into Eq. [1.50] leads to the modified Young
equation:

γ L cosθ = γ S − γ SL + π e [1.72]

where πe=γS - γSV. Thus, the reduction in the value of the ideal surface free energy of a
solid (γS) due to the adsorption of liquid vapor onto the solid surface can be measured as
a function of πe [21, 83]. The distinction between γS and γSV seems first to have been
made by Bangham and Razouk (106). Later, the difference between the two (or the value
of πe) has been determined on various high- and low-energy solids by other investigators
(25-26, 107- 110).
The equilibrium spreading pressure may be measured experimentally from the
adsorption isotherms for the vapors of the liquid on the solid surface, Γ = Γ(p), where p
is the partial pressure of the vapors of the liquid, using the Gibbs adsorption equation
[98]:

P
π e = γ S − γ SV = RT ∫ Γd ln P [1.73]
0

where P is the saturation vapor pressure of the liquid. However, the measurement of πe is
cumbersome and is not, in general, a simple task on a macroscopic solid surface and its
theoretical estimation is difficult.
It is, therefore, common among the investigators to assume that πe should be
negligible for all cases in which the contact angle is finite, i.e., for so-called smooth,
homogenous, hydrophobic low energy surfaces [25, 108]. Fowkes et al [108] studied the
possibility of spreading pressures arising with high-energy liquids (e.g. water vapor)
deposited on low-energy solids, and found that this did not occur. On the other hand,
when the vapor of a low-energy liquid (e.g. cyclohexane or heptane) could interact with a
somehow higher-energy solid surface, the effect of resulting positive spreading pressure
caused an increase in the contact angle of water on that solid surface, which allowed the

32
determination of πe [108]. Van Oss et al. [25] also showed by conducting thin layer
wicking measurements, with non-spreading liquids (i.e. γL > γS and cosθ < 1) neither
spreading nor pre-wetting takes place on low-energy solid surfaces. Thus, it appears not
to be justified to take the equilibrium spreading pressures into account, under non-
spreading conditions.
It has been shown, however, that substantially positive πe values could exist with
non-spreading liquids [111, 112]. Busscher et al [111] studied the adsorption of water
and propanol on various solid surfaces using ellipsometry technique. The authors
showed that even when γL > γS, spreading pressures can have a considerable effect on the
contact angle value. They correlated the adsorption of water and propanol on solid
surfaces with equilibrium spreading pressures. They found that the equilibrium spreading
pressures are in the same order of magnitude for water and for propanol on both high-
and low-energy surfaces. However, it is well known that the spreading behavior of low-
energy liquids (e.g, propanol, γpropanol = 23.7 mJ/m2) differs fundamentally from the high-
energy liquids (e.g., water, γwater = 72.8 mJ/m2), especially on solids with γS ≈ 35 ± 10
mJ/m2 (Fowkes et al., [108]). Fowkes et al (108) showed that the vapor of water does not
spread over low energy polymers, whereas cyclohexane vapor spreads over the polymer
surface. Thus, the correlation between the ellipsometric results and the equilibrium
spreading pressures, particularly when using alcohol-water mixtures, must be regarded as
questionable. It appears that πe can be neglected in cases where γL > γS, and where
vapors of low-energy substances are absent.

1.2.3.2 Surface Heterogeneity – Contact Angle Hysteresis

It has been shown that the wetting process can be assumed as an adsorption-
desorption process (2, 21, 113). A drop of liquid, which is placed on a solid surface,
spreads until equilibrium is attained. If additional liquid is added to the drop, the contact
line advances and eventually stops. Each time the motion of drop ceases (i.e. within a
few seconds), the drop exhibits an advancing contact angle θa. Alternatively, if liquid is
withdrawn from the drop using a syringe the contact angle decreases without movement
of the contact line. If a large amount of liquid withdrawn, the contact angle would start
retreating. When the motion ceases, the drop exhibits a receding contact angle θr. This is

33
illustrated schematically in Figure 1.2. Obviously, the drop size has an effect on the
measured contact angle value.
The difference between θa and θr is called the contact angle hysteresis and is
defined empirically as an arithmetic difference between the two (102, 113),

∆θ = θ a − θ r [1.74]

The contact angle hysteresis is usually attributed to chemical and morphological

heterogeneity of surface, roughness, swelling, rearrangement, inter-diffusion and/or
surface deformation (21, 98, 114-118). For ideally smooth and homogenous solid
surfaces, the values of θa and θr should be very close. However, the difference between
θa and θr can be quite large, as much as 50o for water on mineral surfaces, suggesting
surface heterogeneity (2). The contact angle hysteresis can be quite important in various
industrial applications, e.g., coating etc.
It has been suggested that both advancing and retreating contact angles should be
measured wherever possible. Because, there is likely to be chemical information residing
in retreating contact angle data that is different from the information in advancing contact
angles for the same solid surface. In general, if the solid surface is smooth, θa is used as a
measure of apolar aspect of surface (low surface energy sites), while θr of its polar
aspects (high surface energy sites), as θa is always larger than θr (2, 29, 83, 93).
However, it is generally assumed that the Young’s equation is valid for contact angles
measured as the advancing angles (11, 21, 83, 102, 119). In some publications
equilibrium contact angles (θe) are measured (120-121), but they are not necessarily equal
to the contact angle which is used in Young’s equation (102).
For solid surfaces with heterogeneities due to impurities or polycrystallinity,
Cassie equation can be used to model the surface over small length scales (2, 24),

cos θ A = f1 cos θ1 + f 2 cosθ 2 [1.75]

34
where θA is the average contact angle measured on the heterogeneous surface, and
f1+f2=1, while θ1 and θ2 are the contact angles one would measure on a solid surface
solely consisting of material, 1, and of material, 2, respectively. In general,

n
cos θ A = ∑ f i cos θ i [1.76]
i =1

for an n region surface (24, 122). Another averaging expression has been proposed (21)

[1 + cosθ A ] = f1 (1 + cosθ1 )γ L + f 2 (1 + cosθ 2 )γ L [1.77]

which is equivalent to Cassie’s equation (Eq. [1.75]).

Recently, some investigators have proposed modifications of Cassie’s equation
(123-124). However, it has been reported that Cassie’s equation, in the form of Eq.
[1.75], correlates well with a variety of experimental situations (2, 21, 125-129) and it
seems reasonable to use it without modification.

1.2.4 Contact Angle, Surface Hydrophobicity and Surface Free Energies

Direct surface force measurements conducted on various solid surfaces have
shown that the macroscopic hydrophobicity of a surface (as measured by contact angle θ
value) and the magnitude of the hydrophobic force are uniquely related (130-134). It has
also been shown that as the water contact angle value increases, the value of γS decreases
(17-19, 21, 26, 95-96). However, the relationship between the contact angle and, the
surface hydrophobicity and surface free energy components, γSLW, γSAB, γS-, γS+ was not
fully established with the exception of one study. The work has been done, recently, at
Virginia Tech by Pazhianur (135) should be addressed in this regard. Pazhianur
conducted direct force measurements between methylated silica plates with varying
hydrophobicities and a hydrophobic glass sphere (θa=109o) that has been used to simulate
the air bubble, and contact angle measurements on methylated silica surfaces with
varying hydrophobicities. Figure 1.3 shows a plot taken from the work of Pazhianur
where the K (hydrophobicity constant) values obtained from force measurements and

35
surface free energy components of methylated silica surfaces obtained from Van Oss-
Chaudhury-Good (OCG) thermodynamic approach, plotted as a function of the
advancing water contact angle (θa). According to Figure 1.3: i) the value of K increases
as θa increases, ii) the increase in the value of θa is essentially due to a decrease in the
values of both Lifshitz-van der Waals (γSLW) and Lewis acid-base (γSAB) surface free
energy components. Essentially, Pazhianur argued that the magnitude of hydrophobicity
constant (K) and the γSLW and γSAB surface free energy components were strictly
dependent on the θa exhibited by a solid surface.

1.3 REPORT ORGANIZATION

The results obtained in the present work have been reported in Chapters 2 to 5.
Each chapter comprises of an introduction, experimental, results and discussion, and
conclusion sections, and may be considered as an article for publication. In Chapter 2 the
results of direct contact angle measurements conducted on various flat and powdered talc
surfaces and surface free energy components obtained using Van Oss-Chaudhury-Good
(OCG) thermodynamic approach on these surfaces are reported. It was found that the
surface hydrophobicity of talc increases with decreasing particle size. On the other hand,
both the Lifshitz-van der Waals (γSLW) and the Lewis acid-base (γSAB) surface free energy
components and, hence, total surface free energy (γS) on talc surface decrease as the
particle size decrease associated with increase in the values of contact angles. The
increase in the surface hydrophobicity of talc and decrease in the values of total surface
free energy (γS) and its components (γSLW and γSAB) is attributed to the exposure of more
basal plane surfaces upon pulverization. It was also found that the Lewis electron-donor
(γS-) component on talc surface is much higher than the Lewis electron-acceptor (γS+)
component, suggesting surface basicity of talc.
In Chapter 3 heat of immersion measurements were conducted by a flow
microcalorimeter on a number of powdered talc surfaces using various liquids. The heats
of immersion values were then converted to the contact angles using a rigorous
thermodynamic relation. The measured heat of immersion values in water and contact
angles showed that the surface hydrophobicity of talc samples increase with decreasing
particle size, which confirms the findings of Chapter 2. A relationship between

36
advancing water contact angle θa, and surface free energies and heat of immersion (-∆Hi)
was established. It was found that i) the value of -∆Hi decrease as θa increases, ii) the
increase in the value of θa is essentially due to a decrease in the values of both Lifshitz-
van der Waals (γSLW) and Lewis acid-base (γSAB) surface free energy components. The
most interesting finding was that the basic surface component (γS-) on talc surface
increased with increasing θa, while the acid component (γS+) slightly decreased.
In Chapter 4 the heats of adsorption of butanol on various talc samples from n-
heptane were determined using a flow microcalorimeter. The heats of adsorption values
were used to estimate % hydrophilicity and hydrophobicity and the areal ratio (the ratio
between basal and edge surface area) values of various talc samples. In addition, contact
angle measurements and heat of butanol adsorption measurements were conducted on a
run-of-mine talc sample that is ground to two different particle size fractions, i.e,
d50=12.5 µm and d50=3.0 µm, respectively. The results were used to estimate the surface
free energy components at the basal and edge surfaces of talc. It was found that the total
surface free energy (γS) at the basal plane surface of talc is much lower than the total
surface free energy at the edge surface. The results of the work suggest also that the
basal surface of talc is monopolar basic, while the edge surface is monopolar acidic. The
results explain why the basicity of talc surface increases with decreasing particle size as
defined in Chapter 3, simply due to the increased basal plane surfaces that are basic in
character. It has to be noted that this information becomes available for the first time in
the present work.
Chapter 5 is a summary of test work done on the east Georgia kaolin clay in order
to investigate the possibility of removing discoloring impurities such as anatase (TiO2)
and iron oxides and producing high-brightness clay with GE brightness higher than 90%
using flotation and selective flocculation techniques. The results of the work show that a
clay product with +90% brightness can readily be obtained with recoveries (or yields)
higher than 80% using selective flocculation technique. It was found that the proper
control of surface hydrophobicity of anatase, which is a main discoloring impurity found
in east Georgia kaolin, is crucially important for a successful flotation and selective
flocculation process. Heat of immersion and contact angle measurements conducted on
anatase surface showed: i) the magnitude of the contact angle value, and hence surface

37
free energy and its components on anatase surface is critically dependent on the amount
of surfactant (e.g. hydroxamate) used for the surface treatment, ii) as the concentration of
hydroxamate increases from 2 lb/t to 4 lb/t the surface becomes more hydrophobic and
the γS decreases. Due to a decrease in the value of γS with increasing surface
hydrophobicity, the Gibbs free energy of interaction (-∆G131) between two anatase
particles in water increases, and so does the efficiency of the separation process.
Finally, Summary and Conclusions and Future Work are given in Chapters 6 and
7, respectively.

1.4 REFERENCES

1. Good, R. J., and van Oss, C. J., in Modern Approaches to Wettability: Theory and
Applications, Eds: M. E. Schrader, and G. Loeb, Plenum Press, New York, pp. 1-
27, 1992.
2. Adamson, A. W. and Gast, A.P., Physical Chemistry of Surfaces, 6th ed., John
Wiley and Sons, 1997.
3. Janczuk, B, Wojcik, W., Zdziennicka, A., J. of Colloid and Interface Science, 157,
384-393, 1993.
4. Padday, J. F., (Ed), Wetting, Spreading, and Adhesion, Academic Press, New York,
1978.
5. Zisman, W. A., in: Handbook of Adhesives, Skeist, I., Ed: van Nostrand, NewYork,
Chapter 3, 1977.
6. Fowkes, F.M., Industrial and Engineering Chemistry, 56/12, 40, 1964.
7. Fowkes, F.M., J. of Adhesion, 4, 153, 1972.
8. Van Oss, C. J., Chaudhury, M. K., and Good, R. J., J. Separation Sci. and
Technology, 22, 1, 1987.
9. Van Oss, C. J., Good, R. J., and Chaudhury, M. K., Langmuir, 4, pp. 884-891,
1988.
10. Van Oss, C. J., Chaudhury, M. K., and Good, R. J., J. Colloid Interface Science,
128, 313, 1989.

38
11. Neumann, A. W. and Good, R.J., Techniques of Measuring Contact Angles, Surface
and Colloid Science, Volume II, Experimental Methods, Eds: R.J. Good and R. R.
Stromberg, Plenum Pres, New York, 1979.
12. Fuerstenau, D. W., Mining Engineering, Transactions AIME, December, pp. 1367-
1367, 1957.
13. Leja, J., Surface Chemistry of Froth Flotation, Plenum Press, New York, 1982.
14. Yoon, R.-H., Aufbereitungs-Technik, 32, 474, 1991.
15. Yoon, R.-H., and Ravishankar, S. A., J. Colloid Interface Science, 179, 391, 1996.
16. Yoon, R.-H., and Pazhianur, R., Colloid Surfaces, 1999.
17. Van Oss, C. J., Giese, R. F., and Good, R. J., Langmuir, 6, pp. 1711-1713, 1990.
18. Spelt, J. K., Li, D., and Neumann, A. W., in Modern Approaches to Wettability:
Theory and Applications, Eds: M. E. Schrader, and G. Loeb, Plenum Press, New
York, pp. 101-142, 1992.
19. Bilinski, B., and Chibowski, E., Powder Technol., 31, 39, 1983.
20. Yoon, R.- H. and Yordan, J. L., J. of Colloid and Interface Science, Vol. 146, No.
2, pp. 101-108, 1991.
21. Van Oss, C. J., Interfacial Forces in Aqueous Media, Marcel Decker Inc., New
York, 1994.
22. Bruil, H. G., and van Aartsen, J. J., Colloid & Polymer Science, 252, pp. 32-38,
1974.
23. Hansford, D. T., Grant, D. J. W., and Newton, J. M., J. C. S. Faraday I, 76, 2417-
2431, 1980.
24. Crawford, R., Koopal, L. K. and Ralston, J., Colloids and Surfaces, 27, 57-64,
1987.
25. Van Oss C.J., Griese, R.F. Jr., Li, Z., Murphy, K., Norris, J., Chaudhury, M. K., and
and Good, R. J., J. Adhesion Sci. and Technology, Vol. 6, No.4, 413-428, 1992.
26. Wu, W., Griese, R.F. Jr., and van Oss C.J., Powder Technology, 89, 129-132, 1996.
27. Young, G. J., Chessick, J. J., Healey, F. H., and Zettlemoyer, A. C., J. Phys. Chem.,
58, 313, 1954.
28. Fowkes, F.M., Ind. and Eng. Chem., 56/12, 40, 1967.

39
29. Malandrini, H., Clauss, F., Partyka, S., and Douillard, J. M., J. Colloid and
Interface Sci., 194, 183-193, 1997.
30. Spagnolo, D. A., Maham, Y., Chuang, K. T., J of Physical Chemistry, 100, 6626,
1995.
31. Yan, N., Maham, Y., Masliyah, J. H., Gray, M., and Mather , A. E., J of Colloid
and Interface Sci., 228, pp.1-6, 2000.
32. Groszek, A. J., Carbon, Vol. 25, No.6, pp. 717-722, 1987.
33. Groszek, A. J., and Templer, C. E., Fuel, Vol. 67, pp. 1658-1662, 1988
34. Groszek, A. J., and Partyka, S., Langmuir, 9, pp. 2721-2725, 1993.
35. Basilio, C., Ph.D. Thesis, Virginia Tech, 1989.
36. Fowkes, F. M., and Joslin, S. T., see Ref. 75, 1983.
37. Malhammar, G., Colloids and Surfaces, 44, pp. 61-69, 1990.
38. Zettlemoyer, A. C., in Surfaces and Coatings Related to Paper and Wood, Eds: R.
H. Marchessault and C. Skaar, Syracuse University Press, 1967.
39. Botero, J. Y., Bruant, M., and Cases, J. M., J of Colloid and Interface Sci., 124,
515, 1988.
40. Celik, M. S. and Yoon, R.-H., Langmuir, Vol. 7, No. 8, pp. 1770-1774, 1990.
41. Sanders, N. D., J. of Pulp and Paper Sci., Vol. 18, No. 5, pp. 168-175, 1992.
42. Moudgil, B. M., Behl, S., and Kulkarni, S., J of Colloid and Interface Sci., 148, pp.
337-341, 1992.
43. Van der Waals, J. D., 1873, in Ref. 21.
44. Van der Waals, 1899, in Ref. 21.
45. Keesom, W. H., Phys. Z., 22, 643, 1921.
46. Debye, P., Phys. Z., 21, 178, 1920.
47. London, F., Z. Phys. Chem., 11, 222, 1930.
48. London, F., Trans. Faraday Soc., 33, 8, 1937.
49. Overbeek, J. Th. G., in Colloid Science, Ed: H. R. Kruyt, Elsevier, Amsterdam, 1,
245, 1952
50. Fowkes, F.M., in: Physicochemical Aspects of Polymer Surfaces, Ed: K.L. Mittal,
vol. 2, p. 583, Plenum Press, New York, 1983.

40
51. Israelachvili, J. N., Intermolecular and Surface Forces, Second Edition, Academic
Press, London, 1991.
52. Hamaker, H. C., Physica, 4, 1058, 1937.
53. Berthelot, D., Comp. Rend. Acad. Sci., 126, 1703, 1898.
54. Nir, S., Progr. Surface Sci., 8, 1, 1976.
55. Visser, J. Adv. Colloid Interface Sci., 3, 331, 1972.
56. Neumann, A. W., Omenyi, S. N., and Van Oss, C. J., Colloid Polymer Sci., 257,
413, 1979.
57. Van Oss, C. J., Omenyi, S. N., and Neumann, A. W., Colloid Polymer Sci., 257,
737, 1979.
58. Israelachvili, J. N., Intermolecular and Surface Forces: With Applications to
Colloidal and Biological Systems, Academic Press, London, 1985
59. Fowkes, F. M., and Pugh, R. J., in Polymer Adsorption and Dispersion Stability,
Eds: E. D. Goddard and B. Vincent, American Chemical Society, 1984.
60. Hough, D. B., and White, L. R., Adv. Colloid Interface Sci., 14, 3, 1980.
61. Van Oss, C. J., and Good, R. J., Colloids and Surfaces, 8, 373, 1984.
62. Van Oss, C. J., Chaudhury, M. K., and Good, R. J., Chem. Revs., 88, 927, 1988.
63. Padday, J. F., and Uffindell, N. D., J. Phys. Chem., 72, 1407, 1968.
64. Lifshitz, E. M., J. Exp. Theor. Phys., 29, 94, 1955.
65. Rytov, S. M., Theory of Electric Fluctuations and Thermal Radiations, Moscow
Academy of Science Press, Moscow, 1953.
66. Israelachvili, J. N., Q. Rev. Biophys., 6, 341-387, 1974.
67. Grifalco, L. A., and Good, R. J., J. Phys. Chem., 61, 904, 1957.
68. Fowkes, F. M., J. Phys. Chem., 67, pp. 2538-2541, 1963.
69. Fowkes, F. M., Ronay, G. S., and Schick, M. J., J. Phys. Chem., 63, 1684, 1959.
70. Fowkes, F. M., J. Phys. Chem., 64, 726, 1960.
71. Bolger, J. C., and Michaels, A. S., Interface Conversion for Polymer Coatings, Ed:
P. Weiss, pp. 3-60, Elsevier, New York, 1968
72. Lipatov, Y. S., and Sergeeva, L. M., Adsorption of Polymers, Halsted, New York,
1974.
73. Sorensen, P., J. Paint Technol., 47, 31, 1975.

41
74. Fowkes, F. M., and Mostafa, M. A., Ind. Eng. Chem. Prod. Res. Dev., 71, pp. 3-7,
1978.
75. Fowkes, F. M., J. Adhes. Sci., 1, pp. 7-27, 1987.
76. Van Oss, C. J., Good, R. J., and Chaudhury, M. K., J. of Colloid and Interface
Science, 111, pp. 378, 1986.
77. Van Oss, C. J., Chaudhury, M. K., and Good, R. J., Adv. Coll. Interface Sci., 28, pp.
35-64, 1987.
78. Van Oss, C. J., Chaudhury, M. K., and Good, R. J., J. of Colloid and Interface
Science, 128, 313, 1988.
79. Fowkes, F. M., J. Phys. Chem., 66, 382, 1962.
80. Johnson, R. E., Jr., and Dettre, R. H., Langmuir, 5, 293, 1989.
81. Janzcuk, B., Kerkeb, M. L., Bialopiotrowicz, T., and Gonzalez-Caballero, F., J.
Colloids Interface Sci., 151, pp. 333-342, 1991.
82. Janczuk, B., Wojcik, W., and Zdziennicka, A., J. Colloids Interface Sci., 157, pp.
384-393, 1992.
83. Berg, J. C., Nordic Pulp and Paper Research Journal, 1, 75-85, 1993.
84. Holländer, A. J., J. Colloids Interface Sci., 169, 493, 1995
85. Morra, M. J., J. Colloids Interface Sci., 182, 312, 1996.
86. Kwok, D. Y., Lee, Y. and Neumann, A. W., Langmuir, 14, pp. 2548-2553, 1998.
87. Van Oss, C. J., Chaudhury, M. K., and Good, R. J., Adv. Colloid Interface Sci., 28,
35, 1987.
88. Van Oss, C. J. and Good, R. J., J. Dispersion Sci. Tech., 1988.
89. Fowkes, F. M., in Surfaces and Interfaces, Eds: J. J. Burke, Syracuse University
Press, 1967.
90. Laskowski, J. S., and Kitchener, J. A., J. of Colloid and Interface Science, 29, 670,
1969.
91. Young, T., 1805. in Ref. 21.
92. Dupré, A., 1869. in Ref. 21.
93. Good, R. J., Srivasta, N. R., Islam, M., Huang, H. T. L., and Van Oss, C. J., J.
Adhesion Sci. Technol., Vol. 4, No. 8, pp. 607-617, 1990.
94. Holysz, L., and Chibowski, E., Langmuir, 8, pp. 303-308, 1992.

42
95. Holysz, L., and Chibowski, E., Langmuir, 8, pp. 717-721, 1992.
96. Li, Z., Giese, R. F., Van Oss, C. J., Yvon, J., and Cases, J., J. Colloids and Interface
Sci., 156, pp. 279-284, 1993.
97. Holysz, L., and Chibowski, E., J. Colloids and Interface Sci., 164, pp. 245-251,
1994.
98. Adamson, A. W., Physical Chemistry of Surfaces, 5th ed., John Wiley and Sons,
1990.
99. Amirfazli, A., Chatain, D., and Neumann, A. W., Colloids and Surfaces, 142, pp.
183-188, 1998.
100. Del Rio, O. I., Kwok, D. Y., Wu, R., Alvarez, J. M., and Neumann, A. W., Colloids
and Surfaces, 143, pp. 197-210, 1998.
101. De Ruijter, M., Kölcsh, O., Voué, M., De Coninck, J., and Rabe, J. P., Colloids and
Surfaces, 144, pp. 235-243, 1998.
102. Kwok, D. Y., Leung, A., Lam., C. N. C., Li, A., Wu, R., and Neumann, A. W., J.
Colloids and Interface Sci., 206, pp. 44-51, 1998.
103. Neumann, A. W., and Tanner, W., J. Colloids and Interface Sci., 34, pp. 1-8, 1970.
104. Ku, C. A., Henry, J. D., Siriwardane, R., and Roberts, L., J. Colloids and Interface
Sci., 106, pp. 377-385, 1985.
105. Chessick, J. J., Healy, F. H., and Zettlemoyer, A. C., J. Phys. Chem., 60, 1345,
1956.
106. Bangham, D. H., and Razouk, R. I., Trans. Fraday Soc., 33, 1459, 1937.
107. Harkins, W. D., and Livingston, H. K., J. Chem. Phys., 10, 342, 1942.
108. Fowkes, F. M., McCarthy, D. C., and Mostafa, M. A., J. of Colloid and Interface
Science, 78, 200, 1980.
109. Chibowski, E. and Holysz, L., J. of Colloid and Interface Science, 112, pp. 15-23,
1986.
110. Chibowski, E. and Holysz, L., J. of Colloid and Interface Science, 127, pp. 377-
387, 1989.
111. Busscher, H. J., Kim, K. G. A., Van Silfout, G. A. M., and Arends, J., J. of Colloid
and Interface Science, 114, 307, 1986.

43
112. Bellon-Fontaine, M.-N. and Cerf, O., J. Adhesion Sci. and Technology, 4, 475,
1990.
113. Extrand, C. W., J. Colloid and Interface Sci., 207, pp. 11-19, 1998.
114. Johnson, R. E. Jr., and Dettre, R. H., J Phys. Chem., 68, 1744, 1964.
115. Dettre, R. H., and Johnson, R. E. Jr., J Phys. Chem., 69, 1507, 1965.
116. Andrade, J. D., Smith, L. M., and Gregonis, D. E., in Surface and Interfacial
Aspects of Biomedical Polymers, Ed: J. D. Andrade, Vol. 1, Plenum Press, New
York, 1985.
117. De Gennes, P. G., Rev. Mod. Phys., 57, 828, 1985.
118. Garbassi, F., Morra, M., and Occhiello, E., Polymer Surfaces, From Physics to
Technology, Wiley, New York, 1994.
119. Good, R. J., Surface Colloid Sci., 11, 1, 1979.
120. Neumann, A. W., Adv. Colloids Interface Sci., 4, 105, 1974.
121. Marmur, A., Colloids Surf., 116, 25, 1996.
122. Swain, P. S., and Lipowsky, R., Langmuir, 14, pp. 6772-6780, 1998.
123. Israelachvili, J. N., and McGee, M. L., Langmuir, 5, 288, 1989.
124. Drelich, J., and Miller, J. D., Langmuir, 9, 619, 1993.
125. Cassie, A. B. D., and Baxter, S., Trans. Faraday Soc., 40, 456, 1944.
126. Wenzel, R. N., J. Phys. Chem., 53, 1466, 1949.
127. Oliver, J. F., Huh, C. and Mason, S. G., J. Adhes., 8, 273, 1977.
128. Lamb, R. M., and Furlong, D. N., J. Chem. Soc. Faraday Trans. I, 8, 61, 1977.
129. Blake, P., and Ralston, J., Colloids Surfaces, 15, 11, 1985.
130. Fielden, M. L., Hayes, R. A., and Ralston, J., Langmuir, 12, 3721, 1996.
131. Israelachvili, J. N., and Pashley, R. M., Nature, 300, 341, 1982.
132. Rabinovich, Ya. I., and Yoon, R.- H., Langmuir, 93, 263, 1994.
133. Yoon, R.- H.and Ravishankar, S. A., J. Colloid and Interface Sci., 166, 215, 1994.
134. Yoon, R.- H.and Ravishankar, S. A., J. Colloid and Interface Sci., 179, 401, 1996.
135. Pazhianur, R., Ph.D. Thesis, Virginia Tech, 1999.

44
Table 1.1 Hamaker constants for two identical media interacting across vacuum (51)
Absorption Hamaker constant, A (10-20 J)
Dielectric Refractive
Medium Frequency
Constant Index Eq. [1.21] Exact Experi-
ve
n 15 -1 ε3=1 Solution mental
(10 s )
Water 80 1.333 3.0 3.7 3.7, 4.0
n-Pentane 1.84 1.349 3.0 3.8 3.75
n-Octane 1.95 1.387 3.0 4.5 4.5
n-Dodecane 2.01 1.411 3.0 5.0 5.0
n-Tetradecane 2.03 1.418 2.9 5.0 5.1, 5.4
n-Hexadecane 2.05 1.423 2.9 5.1 5.2
Hydrocarbon
2.25 1.50 3.0 7.1 10
(crystal)
Cyclohexane 2.03 1.426 2.9 5.2
Benzene 2.28 1.501 2.1 5.0
CCl4 2.24 1.460 2.7 5.5
Acetone 21 1.359 2.9 4.1
Ethanol 26 1.361 3.0 4.2
Polystyrene 2.55 1.557 2.3 6.5 6.6, 7.9
PVC 3.2 1.527 2.9 7.5 7.8
PTFE 2.1 1.359 2.9 3.8 3.8
Fused quartz 3.8 1.448 3.2 6.3 6.5 5-6
Mica 7.0 1.60 3.0 10 10 13.5
CaF2 7.4 1.427 3.8 7.2 7.2
Liquid He 1.057 1.028 5.9
Alumina (Al2O3) 11.6 1.75 3.0
Iron Oxide (Fe3O4) -- 1.97 3.0
Zirconia (n-ZrO2) 20-40 2.15 3.0
Rutile (TiO2) -- 2.61 3.0
Silicon carbide 10.2 2.65 3.0
Metals (Au, Ag, Cu) ∞ -- 3-5 30-50

45
Table 1.2. Hamaker constants for two media interacting across another medium (51)
Hamaker constant, A (10-20 J)
Interacting Media
Exact
Eq. [1.20] Experiment
1 3 2 solutions
Air Water Air 3.70 3.70
Pentane Water Pentane 0.28 0.34
Octane Water Octane 0.36 0.41
Dodecane Water Dodecane 0.44 0.50 0.5
Hexadecane Water Hexadecane 0.49 0.50 0.3-0.6
Water Hydrocarbon Water 0.3-0.5 0.34-0.54 0.3-0.9
Polystyrene Water Polystyrene 1.4 0.95-1.3
Fused quartz Water Fused quartz 0.63 0.83
Fused quartz Octane Fused quartz 0.13
PTFE Water PTFE 0.29 0.33
Mica Water Mica 2.0 2.0
Alumina (Al2O3) Water Alumina 4.2 5.3 6.7
Zirconia (n-ZrO2) Water Zirconia 13
Rutile (TiO2) Water Rutile 26
Au, Ag, Cu Water Au, Ag, Cu -- 30-40 40 (gold)
Water Pentane Air 0.08 0.11
Water Octane Air 0.51 0.53
Octane Water Air -0.24 -0.20
Fused quartz Water Air -0.87 -1.0
Fused quartz Octane Air -0.7
Fused quartz Tetradecane Air -0.4 -0.5
CaF2, SrF2 Liquid He Vapour -0.59 -0.59 -0.58

46
Table 1.3. Values of the surface tension components (in mJ /m2) and of the viscosities
(in poise) of various liquids used in direct contact angle determination, or in
the capillary rise and thin layer wicking experiments (21)
Liquid γL γLLW γLAB γL+ γL- η
Hexane 18.4 18.4 0 0 0 0.00326
Heptane 20.3 20.3 0 0 0 0.00409
Octane 21.6 21.6 0 0 0 0.00542
Decane 23.8 23.8 0 0 0 0.00907
Dodecane 25.35 25.35 0 0 0 0.01493
Tetradecane 26.6 26.6 0 0 0 0.0218
Cyclohexane 25.5 25.5 0 0 0 0.00912
Carbon tetrachloride 27.0 27.0 0 0 0 0.00908
Benzene 28.9 27.1 0 0 2.8 0.00604
Toluene 28.5 28.5 0 0 2.3 0.00604
Methanol 22.5 18.2 4.3 ≈0.06 ≈77 0.00544
Ethanol 22.4 18.8 2.6 ≈0.019 ≈68 0.01074
Chloroform 27.15 27.15 0 3.8 0 0.00473
cis-Decalin 32.2 32.2 0 0 0 0.0338
1-Bromonaphthalene 44.4 44.4 0 0 0 0.0489
Methylene iodide 50.8 50.8 0 0 0 0.028
Ethylene glycol 48.0 29.0 19.0 1.92 47.0 0.199
Formamide 58.0 39.0 19.0 2.28 39.6 0.0455
Glycerol 64.0 34.0 30.0 3.92 57.4 14.90
Water 72.8 21.8 51.0 25.5 25.5 0.010

47
Table 1.4. Surface tension components and parameters of various solid surfaces at 20
o
C in mJ/m2 (21, 26, 94-95, 97, 109)
Solid γS γSLW γSAB γS+ γS-
Teflon FEP 18.5 18.5 0 0 0
Polyisobutylene 25.0 25.0 0 0 0
Polypropylene 25.7 25.7 0 0 0
Corona-treated
33.0 33.0 0 0 0
polypropylene
Polyethylene 33.0 33.0 0 0 0
Nylon 6,6 37.7 37.7 0 0 0
Polymethylmetacrylate
40.6 40.6 0 0 12.0
(PMMA)
Polystyrene 42.0 42.0 0 0 1.1
Polyvinylalcohol 42.0 42.0 0 0 17-57
Polyvinylchloride 43.8 43.0 0.75 0.04 3.5
PEO - M.W. 6,000 43.0 43.0 0 0 64
Polyoxytetramethyleneglycol
44.0 41.4 2.6 0.06 27.6
- M.W. 2,000
Co-poly(ethylene glycol,
propylene glycol)- 43.0 43.0 0 0 64
M.W. 2,000
Coal 39.8 39.8 0 0 2.5
Talc 41.6 37.4 4.2 2.0 2.2
Calcium Carbonate 48.0 48.0 0 0 79.0
Quartz (untreated) 191.0 76.0 115.0 -- --
Quartz (treated-DAHCl) 35.3 28.2 7.1 -- --
Silica Gel 48.8 42.0 6.8 58.4 0.2
Bentonite clay 55.5 41.2 14.3 1.5 33.3
α-Alumina 44.8 43.7 1.1 0.004 80.5
Barite 52.9 26.2 26.7 1.5 118.9

48
 γL

γS θ γSL L

TOT LW
(1 + cos θ ) γ L = − ∆ G SL = − ∆ G SL − ∆ G SLAB

(1 + cos θ ) γ L = 2 (γ LW
S γ LW
L + γ S+ γ −
L + γ S− γ +
L )
Figure 1.1. Schematic representation of the contact angle formed between a liquid droplet
and a solid surface. cosθ is a measure of the equilibrium between the
molecules of liquid L (horizontal arrows) and adhesion between liquid L and
solid S (vertical arrows). Apolar energies are indicated by solid horizontal or
vertical lines and arrows; polar (Lewis-acid base) energies are shown by
dashed horizontal or vertical lines and arrows (21).

a b

θa θr

Figure 1.2. Schematic representation of (a) advancing and (b) retreating contact angles
formed on a solid surface. When liquid is injected into the sessile drop the
contact line advances, and when liquid is withdrawn from the drop the contact
line recedes.

49
Figure 1.3. The values of hydrophobicity constant (K) and surface free energy parameters
of methylated silica surfaces vs. advancing contact angle (θa) plot taken from
the work of Pazhianur (135).

50