Thermodynamics of

Surfaces and Interfaces

What is thermodynamics dealing

with?
Thermodynamics is the branch of science that id
concerned with the principles of energy
transformation in macroscopic system.
Macroscopic properties of matter arise from the
behavior of a very large number of molecules.
Thermodynamics is based upon experiments and
observation , summarized and generalized in the
laws of thermodynamics.
These laws are not derivable from any other
principles: they are in fact improvable and
therefore can be regarded as assumptions only.

Some Definitions

Intensive variables
Extensive variables
System, isolated, open, closed
Surroundings
Boundary
Equilibrium
Process
Thermodynamic state

Equilibrium between phases in

heterogeneous closed system
What does equilibrium mean?
A system is in eq if no further spontaneous changes
takes place and if the same state can be reached by
other directions.

A phase?
A phase equilibrium is defined when the same
species are present in different phases.
A heterogeneous closed systems is composed
of two or more phases, with each phase is
considered as an open system within an overall
closed system.

Equilibrium between phases in

heterogeneous closed system
If the system initially, is not in an
internal eq, then any process should
occur in irreversible direction.
So, according to first law:

And, combining with Clausius

inequality: (for both reversible and irreversible
processes)

Equilibrium between phases in

heterogeneous closed system
Or finally:

Equilibrium between phases in

heterogeneous closed system

Equilibrium between phases in

heterogeneous closed system

Equilibrium between phases in

heterogeneous closed system

Equilibrium between phases in

heterogeneous closed system

Equilibrium between phases in

heterogeneous closed system

Equilibrium between phases in

heterogeneous closed system

Wettability and Contact

Angle
Reference:

Wettability and contact

angle

 In the case of a liquid that forms a uniform

film (i.e., where = 0), the solid is said to
be completely wetted by the liquid, or that
the liquid wets the solid.
Where a nonzero angle is formed, there
exists some controversy as to how to
describe the system. If a finite contact
angle is formed (> 0), some
investigators describe the system as
being partially wetted.

 Others prefer to make a distinction based on

the size of the contact angle. For example, a
given worker may define as wetting any
liquid that produces a contact angle of 30 or
less on a solid. Between 30 and 89 the
system would be partially wetting, and 90
and above nonwetting.
Alternatively, any system with 0<< 180
would be partially wetting, and only for 180
would the nonwetting term be applied.

 While the contact angle of a liquid on a solid may be

considered a characteristic of the system, that will be
true only if the angle is measured under specified
conditions of equilibrium, time, temperature,
component purity, and other parameters.
The great utility of contact angle measurements
stems from their interpretation based on equilibrium
thermodynamic considerations. As a result, most
studies are conducted on essentially static systems in
which the liquid drop has (presumably) been allowed
to come to its final equilibrium value under controlled
conditions.

 As an application, contact angles, for example, can

be extremely useful as aspot test of the cleanliness
of sensitive surfaces such as glass or silicon wafers
for microelectronics fabrications.
Both surfa es are high energy and are completely
wetted by pure water.
If the surface is contaminated by something such
as an oil that interferes with the processing of the
material (e.g., the coating of a photoresist
polymer), a drop of water will have a nonzero
contact angle, and the contamination will be
immediately apparent.

Contact angle hysteresis

For systems that have true nonzero
contact angles, the situation may be
further complicated by the existence of
contact angle hysteresis.
Thus, the contact angle one observes may
vary depending on whether the liquid is
advancing across fresh surface (the
advancing contact angle, A) or receding
from an already wetted surface (the
receding contact angle, R) (Fig. 17.3).

 As an operational convenience, many, if not

most, static contact angles measured and
reported are in fact advancing angles. For a
given system, it will be found that A R.
In practice, very few systems exhibit a complete
lack of hysteresis, so that the problem can be
operational as well as philosophical.
One should keep in mind that when discussing
contact angle data, one must always be aware of
how the angle has been measured in order to
interpret its significance properly.

Why hysteresis
In dynamic contact angle studies, additional
complications arise because the movement of the
wetting line is not always a steady, continuous process.
It is often observed that the movement is jerky, with
the drop or liquid front holding a position for a time and
then jumping to a new configuration.
This phenomenon is often referred to as a stickslip
process and is not fully understood as yet. It has also
been observed that in dynamic systems, the values of
A and R will vary as a function of the velocity of
wetting line movement, with A increasing with
velocity and R decreasing.

Why hysteresis
When used with Youngs equation and other such
relationships, the contact angle provides a relatively
simple yet sensitive insight into the general chemical
nature of a surface through such thermodynamic
quantities as the work of adhesion. Unfortunately, as
already mentioned, contact angles often exhibit
hysteresis and cannot be defined unambiguously by
experiment.
It is always important to know as much as possible
about the cleanliness, topography, homogeneity, and
other characteristics of a solid surface, as well as the
purity and composition of the liquid employed, when
attempting to interpret contact angle data.

Why hysteresis
Although the existence of contact angle
hysteresis has been recognized for at
least 100 years, the root of the evil has
not always been understood. In addition
to the physicochemical adsorption
process already mentioned, which leads
to differences in advancing and receding
contact angles, it is recognized that
several physical and kinetic factors also
contribute to the overall problem.

Contact Angle Measurement

Techniques
There are a variety of simple and inexpensive
techniques.
The most common direct methods (Fig. 17.4) include
the sessile drop (a), the captive bubble (b), the sessile
bubble (c), and the tilting plate (d). Indirect methods
include tensiometry and geometric analysis of the
shape of a meniscus.
For solids for which the above methods are not
applicable, such as powders and porous materials,
methods based on capillary pressures, sedimentation
rates, wetting times, imbibition rates, and other
properties, have been developed.

The Effects of Surface Roughness

on Contact Angles and Wetting

FIGURE 17.5. The apparent contact angle of a liquid on a

surface may differ from
that expected, the true contact angle (a), due to irregularities
either physical or
chemicalincluding surface roughness (b) or chemical
heterogeneity (c).

The Effects of Surface Roughness

on Contact Angles and Wetting
The theoretical discussion of contact angle and wetting to this
point has assumed implicitly that the solid surface in question
is a smooth, ideal plane.
In fact, of course, very few solid surfaces even begin to
approach such a state.
The finest polished glass surface, for example, will usually
have asperities of 5 nm or more.
Commonly encountered polished surfaces, will be much
rougher
by factors of 101000.
The earliest, and still most useful, quantitative attempt to
correlate the observed contact angle of a liquid on a solid with
the surface roughness is the Wenzel relationship which
proposes a thermodynamic relationship such that

 Wenzel relationship:

where Rw is defined as the surface

roughness factor, the ratio of the true
and apparent surface areas of the
solid (Fig. 17.5b). Defining the
apparent contact angle as yields:

Recall Young equation

(with new notations)

FIGURE 17.7.
Youngs
equation for
determining
the contact
angle was
originally
based on an
analysis of the
force balance
among the
three surface
tensions

The last equation may be taken as a fundamental definition of

the effect of
surface roughness on wetting and spreading phenomena.

 As a final note on the effects of surface roughness,

examination of the Equation, leads to a useful rule
of thumb for some important applications of
wetting and spreading phenomena; that is:
If the true contact angle of a liquid (an adhesive,
say) is less than 90 on the smooth surface, the
angle will be even smaller on a rough surface.
For a true contact angle 90, roughness will
increase the apparent angle. Mathematically the
situation can be described as:

Heterogeneous Surfaces
Roughness represents just one aspect of the
effects of the nature of the solid surface on
contact angles and wetting phenomena.
A second potentially important factor is that of
the chemical heterogeneity of the surface (Fig.
17.5c).
It is possible to develope the following
relationship relating apparent contact angle to
the chemical composition of a surface:

Heterogeneous Surfaces
where f1 and f2 are the fractions of the surface
having inherent contact angles 1 and 2.
Since f2= 1-f1, the equation can be written in
terms of one component.
Theoretically, if the inherent contact angles of a
test liquid on the homogeneous surfaces are
known, then the composition of a composite
surface can be determined from a simple contact
angle measurement.

Heterogeneous Surfaces
Experiments employing specially
prepared composite surfaces have
shown that contact angle data can
give results that agree reasonably
well ( 15%) with more sophisticated
surface composition data obtained
using, for example, X-ray
photoelectron spectroscopy (XPS).