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Surface wetting and contact angle: basics and characterisation

Article in Himia Fizika ta Tehnologia Poverhni · March 2022

DOI: 10.15407/hftp13.01.003

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PACS: 68.03.Cd; 68.08; 68.08.Bc doi: 10.15407/hftp13.01.003

G.V. Beketov, O.V. Shynkarenko

SURFACE WETTING AND CONTACT ANGLE:

BASICS AND CHARACTERISATION
V.E. Lashkaryov Institute of Semiconductor Physics of National Academy of Sciences of Ukraine
41 Nauki Ave., Kyiv, 03028, Ukraine, E-mail: [email protected]

Wettability is of pivotal importance in many areas of science and technology, ranging from the extractive
industry to development of advanced functional materials and biomedicine problems. An increasing interest to
wetting-related phenomena stimulates impetuous growth of research activity in this field. The presented review is
aimed at the cumulative coverage of issues related to wettability and its investigation. It outlines basic concepts of
wetting as a physical phenomenon, methods for its characterisation (with the emphasis on sessile drop techniques),
and performances of contemporary instrumentation for wettability measurements.
In the first section, physics of wettability is considered. The intermolecular interactions related to wetting are
classified as dependent on their nature. Thus, discussion of interactions involving polar molecules covers permanent
dipole - permanent dipole interactions and freely rotating permanent dipoles. Consideration of interactions resulting
from the polarization of molecules includes interactions between ions and uncharged molecules, Debye interactions,
and London dispersion interactions. Hydrogen bonds are discussed separately.
The second section deals with the issues related to surface tension and its effect on shaping the surface of a
liquid brought in contact with a solid body. The relationship between the surface tension and the contact angle as
well as equations that quantify this relationship are discussed. The Young–Laplace equation governing the shape of
the drop resting on the surface is analysed.
The third section is devoted to the experimental characterization of surface wettability and the underlying
theoretical analysis. Particular attention is paid to the method known as the Axisymmetric Drop Shape Analysis
(ADSA). Principles of automated determination of relevant physical values from experimental data are briefly
discussed. Basics of numerical techniques intended for analysing the digitized image of the drop and extracting
information on surface tension and contact angle are outlined.
In the fourth section, an overview of commercially available instrumentation for studying wettability and the
contact angle measurements is presented. The prototype contact angle analyser designed and manufactured at the
ISP NASU is introduced.
Keywords: wettability, intermolecular interactions, surface tension, contact angle, sessile drop, Young–Laplace
equation, axisymmetric drop shape analysis, contact angle goniometry, digital image contour extraction, methods of
optimization

INTRODUCTION composition, morphology, reactivity, and many

other characteristics of surfaces. Phenomenon of
Over almost three past decades, the topic of
surface wettability also received a new impetus
wetting has generated an unprecedented growth
for further investigation, which stimulated both
of interest from both fundamental and applied
the improvement of theoretical models and the
points of view. The annual number of
experimental techniques related to this area.
publications on wettability issues has increased
Research efforts in this direction cover a huge
by orders of magnitude during this period [1].
variety of different fields ranging from the
Current progress in development of advanced
extractive industry (increasing the efficiency of
materials and technologies is largely based on
the oil fields exploitation, ore mining and
achievements in chemistry, physics and
processing industry etc. [3–6]) to development of
technology of surface, which, in their turn, were
biocompatible materials [7–12] and studying the
attained due to advent of the contemporary
intricate interfacial biomolecular interactions
methods of surface analysis [2]. The techniques
realizing signalling pathways in the living
of X-ray surface spectroscopy (XPS), secondary
organisms [13].
ion mass-spectrometry (SIMS), atomic force
Wetting is a physical interaction of a liquid
microscopy (AFM) etc. made available
with the surface of a solid or with other liquid.
comprehensive information on chemical

© G.V. Beketov, O.V. Shynkarenko, 2022 3

 G.V. Beketov, O.V. Shynkarenko
______________________________________________________________________________________________

As an analysis of publications shows, there are at determined is the angle between the surfaces of
least two major reasons for the increasing the liquid drop and the solid phase at the point
interest to this phenomenon. One of them is that where they meet. This angle, termed as the
wetting plays important role in a vast array of contact (or wetting), angle, is considered as the
modern technologies involving formation of measure of surface wettability. The contact angle
coatings, use of adhesives, painting applications, measurements have gained wide popularity due
soldering, brazing, etc. For example, wetting in to their simplicity and robustness. Though the
combination with the surface tension enables contact angle can also be measured in geometries
formation of tiny solder bumps interconnecting that differ from the sessile drop geometry, the
the hybrid multielement focal matrices for last one possesses important advantages in
infrared and ultraviolet vision [14–16]. practical applications. In particular, only a small
Consequently, the degree of surface wettability, portion of the surface to be examined is enough
that is the ability or inability to wet, needs to be to carry out the experiments. This enables
explained and quantified. The second reason wettability measurements for various finished
arises from the need in a fast and inexpensive products, such as dental implants, ophthalmic
technique for monitoring the efficiency of contact lenses, etc. [9–12]. In contrast, the vast
various surface treatments. Modification of majority of other methods, for example, the
physical and chemical structure of the surface is Wilhelmy plate method [18], require the use of
widely used as the means to impart it certain specimens of a certain shape and size.
functional properties. Any modification is highly This review covers the basic issues related to
likely to affect the surface wettability. Thus, it is research and practical applications of the
possible to use the monitoring of wettability as a wettability phenomenon. These issues include
tool for experimental evaluation of modification the nature and classification of intermolecular
efficiency. In this case, measurements of forces involved into wetting process, the effect
wettability become a helpful supplement to other of surface tension, the mathematical analysis of
techniques of surface analysis. droplet shapes resulting from this effect, the
Wettability depends on interrelation between techniques designed for characterization of
the adhesion and cohesion forces in the liquid- surface vettability, and the modern
solid system. The cohesion forces are the forces instrumentation for the sessile drop
of mutual cohesion of the molecules constituting measurements.
the liquid, while the adhesion forces act between
PHYSICS OF WETTABILITY
the molecules of the liquid phase and the wetted
surface. The ratio of adhesion to cohesion forces Wetting is generally understood to mean the
results in effects that can be used to characterize spontaneous spreading of a liquid over solid
wettability. If the cohesion forces significantly surfaces or other liquids, the impregnation of
exceed the adhesion forces, the liquid drop on porous materials and powders, and the curving of
the solid surface tends to get a spherical shape, the liquid surface upon contact with a solid. The
so minimizing the contact area. This situation susceptibility to wetting is called wettability. The
corresponds to low wettability and occurs, for degree of wettability depends on the balance of
example, with a water drop deposited onto the cohesive and adhesive forces, respectively,
surface of polysiloxane (silicone rubber). The between the molecules in the liquid phase and at
opposite situation corresponds to predominance the liquid-surface interface, which arise due to
of adhesion forces over cohesion forces (high intermolecular interactions [19, 20]. In principle,
wettability). In this case, the fluid tends to spread wetting may involve chemical reactions between
out over the surface, and the contact area the liquid and the solid surface, interdiffusion
increases (at that, in both cases the acquired drop and formation of surface layers, that is called a
shape minimizes the free energy of the fluid- reactive wetting [21]. The reactive wetting is of
solid system). huge importance for the soldering and brazing
The most popular approach to evaluation of technologies [22, 23] and deserves separate
surface wettability consists in analysing the consideration. The scope of this review is
shape of the drop that rests on the surface to be restricted to phenomena related to the non-
characterized. This approach is referred to as the reactive type of wetting that occur as a result of
sessile drop method [17], where a quantity to be intermolecular interactions of purely physical

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nature. The non-reactive wetting does not lead to misunderstanding, we will refer the reader to the
the change in the chemical state of interacting corresponding sources, where appropriate.
molecules and is usually reversible. The Interactions involving polar molecules.
reversibility of the non-reactive wetting is Permanent dipole – ion interactions. The
extensively used in experimental techniques interaction energy between the molecules
intended for determination of wettability possessing a permanent dipole moment and the
characteristics. Typically, water and organic ions is determined by the Coulomb’s potential
solvents behave as the non-reactive wetting and is given by the following expression:
fluids. Wettability of solids by liquids is
commonly quantified by a contact angle (wetting w  r, u   
 ze  ur  . (1)
angle). The contact angle measures the tilt of the 4  0  r 3
tangent to the liquid surface at the point where
the liquid – gas/vapour interface meets the solid Here u = ql is a vector representing the
surface. The concept of cohesive and adhesive dipole moment of the molecule (l is the distance
forces interpreted at a phenomenological level between electric charges q), e is the electron
was employed by Young to deduce the value of charge, z is the multiplicity of the ion charge,
contact angle for a given pair of liquid and a and the magnitude of the vector r is the distance
solid [24]. The modern understanding of between the ion and the centre of the dipole. For
intermolecular interactions has undergone radical example, for two electronic charges q = ±e
transformation and refinement since publication separated by l = 0.1 nm, the dipole moment is
of this pioneering work. The interactions that u = (1.602·10–19)(10–10) = 1.6·10–29 C·m, or 4.8 D.
control wettability have been found to involve The unit of dipole moment is the Debye, where
various mechanisms, which can differ as 1 Debye (D) is 3.336–10 C∙m, which corresponds
dependent on the nature of the wetting fluid and to two unit charges separated by about
the wetted surface. However, it should be ~ 0.02 nm. Small polar molecules have dipole
realized that the classification of intermolecular moments of the order of 1 D. Under normal
forces into a number of seemingly different conditions, the ion-dipole interaction is much
categories is actually just a convenient scheme, stronger than kT at typical interatomic
while fundamentally they are of the same origin separations (0.2–0.4 nm). Thus, it is strong
and stem from interactions between electrically enough to bind polar molecules to ions and
charged particles constituting atoms and mutually align them when the ionic species are
molecules. Thus, the common terms such as van dissolved in polar solvents.
der Waals forces, ionic bonds, hydrophobic Permanent dipole – permanent dipole
interactions, hydrogen bonds, solvation forces interactions. When the two polar molecules with
etc. are the result of this classification rather than no net charge but possessing a permanent dipole
separate entities. Moreover, there is some moment are considered fixed, the energy of their
ambiguity in the literature regarding the interaction can be deduced based on (1), where
distinction between certain intermolecular the single ion is to be replaced by the two
interactions sharing similar features. Therefore, separated charges of the opposite sign:
in order to maintain the consistency within the
w r, u1 , u2   
 u1 u2  r 2  3 u1 r  u2 r 
below consideration, we will follow the . (2)
approach adopted in the classic textbook by 4  0  r5
J.N. Israelachvili [25]. This approach consists in Here u1, u2 are the dipole moments of
dividing the interactions into groups according to interacting molecules, and the magnitude of the
characteristics of participating molecules, which vector r is the distance between the dipoles. The
includes the interactions involving polar energy of the dipole-dipole interaction for a
molecules, the interactions involving the system of dipoles is the sum of the energies of all
polarization of molecules, and the van der Waals pairwise dipole interactions. Most dipolar
forces acting between molecules. There exist, molecules are also anisotropic in shape, making
however, approaches that proceed from other the point-like approximation for molecular
principles when considering the intermolecular dipoles inaccurate. For instance, the centres of
forces (see, for instance, [26]). In order to avoid two cigar-shaped molecules can come

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significantly closer together when they align in orientations, can be calculated using the
parallel, thereby making this interaction more Boltzmann distribution:
favourable. Strong orientational interactions  w r , , 12  k T
between the molecules are accounted for within
e  w r  k T 
e sin  d d12
(4)
the theory of associated fluids [27].
The electric dipole-dipole interaction is not
 sin  d d12
as strong as the ion-dipole interactions. For where θ and φ12 vary between 0 and π and 0 and
dipole moments of order approximately 1 D, it is 2π, respectively, T is the absolute temperature
weaker than kT at distances of about 0.35 nm in and k is the Boltzmann constant. For w(r, θ, φ12)
vacuum, while in a solvent medium this distance less than T, Eq. 4 can be expanded in terms of
will be even smaller. This means that the dipole- 1/T according to
dipole interaction, unlike the ion-dipole
interaction, is usually not strong enough to result w r 
e  w r   1   .. . . (5)
in any distinct mutual alignment of polar kT
molecules in the liquid state. In this case the
resulting interaction energy is to be calculated by Upon averaging over θ1, θ2, and φ12, it can be
appropriate averaging over all admissible shown that w(r) is given by
configurations. However, there are some u12 u22 u1u2
exceptions, which pertain to the molecules such w r  for kT  . (6)
3 40  kTr6 40 r3
2
as water, its small size and large dipole moment
does lead to short-range association in the This expression relates the interaction energy
liquid. between freely (or almost freely) rotating
Freely rotating permanent dipoles. Highly permanent electric dipoles and their separation
polar molecules with no net charge, such as distances due to the Keesom effect.
water, HCl, HF, and NH3 can interact Qualitatively, the resulting attraction can be
dynamically if they are free to rotate. This explained by the Boltzmann weighting factor
interaction, known as the Keesom effect, comes that gives more weight to those orientations that
about from the fact that on the average, two have a lower (more negative) energy.
freely rotating dipoles will align themselves so Interactions involving polarization of
as to result in an attractive force [28]. In order to molecules. Molecular polarization is the
calculate the net dipole-dipole interaction, it is emergence of a dipole moment induced by an
necessary to examine all the possible orientations external electric field. The polarization of
of the dipoles with respect to one another and molecules may occur through different
consider what happens if the dipoles can reorient mechanisms. For a nonpolar molecule, the
in each other's fields. To do so, it is convenient polarizability arises from the displacement of its
to rewrite expression (2) so as to represent the negatively charged electron cloud relative to the
dependence of the interaction energy on the positively charged nucleus, known as the
mutual orientation of dipoles evidently: electronic polarizability. For polar molecules,
there is another contribution to the polarizability.
u1 u2  2cos1 cos2  sin1 sin2 cos12  While for a freely rotating dipolar molecule the
w r,1,2 ,12  
4  0 r3 time averaged dipole moment is zero, the
(3) presence of an electric field will orient the
dipoles, inducing in sum the non-zero
The two dipoles are oriented with respect to polarization. The total polarizability of a polar
the axis separating them along the angles θ1, θ2 molecule is given by the Debye-Langevin
and φ12 represents the angular orientation of one equation:
dipole with respect to the other about this axis.   0  u2 3k T . (7)
At large separations or high dielectric constant
medium, the thermal energy would be greater In a condensed liquid or solid medium
than the interaction energy. At that, the consisting of many polarizable molecules, when
interaction energy, averaged over all the reaction fields of all the induced dipoles are
added up, the resulting field is known as the

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 Surface wetting and contact angle: basics and characterization
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“polarization” field, Ep, which always opposes More generally, for two molecules
the inducing field E. possessing both the permanent dipole moments
Interactions between ions and uncharged u1 and u2 and polarizabilities α01 and α02, their
molecules. When a molecule of polarizability α net dipole-induced dipole energy is
is at a distance r from an ion of charge, ze, the
u12  02  u22  01
electric field of the ion E = ze/4πεε0r2 will induce wr    . (12)
 4   0 
2
in the molecule a dipole moment of r6
uind   E   ze 4   0 r 2 . (8) This is often referred to as the Debye
interaction, or the induction interaction. It
For small molecules like CH4, the induced
constitutes the second of three inverse sixth
dipole moments can be of order of 1 Debye.
power contributions to the total van der Waals
Mutual orientation of the induced moment and
interaction energy between molecules, the first
the ion corresponds to arising an attractive force
one being the Keesom force given by Eq. (6).
between them:
Instantaneous dipole – induced dipole
2 interaction (London dispersion interactions).
F  r    ze Er   2  ze  4 0 
2
r5 , (9)
The types of physical forces described so far are
that results in formation of a physical bond with fairly easy to understand, since they arise from
the energy w(r) = (αE2)/2. This energy is half straightforward electrostatic interactions
that expected for the interaction of an ion with a involving charged or dipolar molecules. But
similarly aligned permanent dipole, because there is another type of force that acts between
some energy is taken up in polarizing the all atoms and molecules, even totally neutral
molecule. For the ion in a solvent susceptible to ones such as helium, carbon dioxide, and
polarisation, the ion – induced dipole interaction hydrocarbons. These forces have been variously
results in decreasing the Gibbs free energy, known as dispersion forces, London forces,
which can be estimated in terms of the Born charge-fluctuation forces, electrodynamic forces,
energy [25]. and induced dipole – induced dipole forces. They
Permanent dipole-induced dipole are referred below as the London forces.
interactions (Debye interactions). The The London forces constitute the third and
interaction between a polar molecule (a perhaps most important contribution to the total
permanent dipole) and a nonpolar molecule van der Waals forces between atoms and
susceptible to polarization (an induced dipole) molecules, because they are always present. Their
can be described in analogy to the ion-induced main features may be summarized as follows:
dipole interaction just discussed by replacing a 1. They are long-range forces and,
single ion with the two that form a permanent depending on the situation, can be effective from
dipole. For a fixed dipole u oriented at an angle large distances (> 10 nm) down to interatomic
θ to the line joining it to a polarizable molecule, spacing (~ 0.2 nm).
the interaction energy is 2. These forces may be repulsive or
attractive, act both between the molecules and
1
w r,   0 E2  u2 0 1  3cos2   2 4 0  r 6 . between larger particles, and in general do not
2

2 follow a simple power law.

(10) 3. The London forces not only bring
molecules together but also tend to mutually
For typical values of u and α0, the strength of
align or orient them, though this orienting effect
this interaction is not sufficient to mutually
is usually weaker than that with dipolar molecules.
orient the molecules, as occurs in ion-dipole or
4. The London forces are not additive. The
strong dipole-dipole interactions. The effective
force between two bodies is affected by the
interaction is therefore the angle-averaged
presence of other bodies nearby.
energy. Since the angle average of cos2θ is 1/3,
The London forces participate in a variety of
Eq. (10) becomes
fundamentally and practically significant
phenomena including adhesion, surface tension,
w r    u20  4   0 
2
r6 . (11) physical adsorption, wetting, the properties of
gases, liquids, and thin films, and shaping the

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structures of macromolecules such as proteins Except for a numerical factor, Eq. (15) is the
and polymers. The London forces are quantum same as that derived by London in 1930 using
mechanical in origin and are explained most quantum mechanical perturbation theory. More
rigorously within the frame of quantum information on London dispersive forces can be
electrodynamics. However, their origin may also found in [29–32].
be understood intuitively. The London forces can Hydrogen bonds. Comparing to many other
be thought to arise from the motion of electrons. fluids, water possesses unusual and unique
The electrons in the molecules are in constant properties including abnormally high boiling
movement around the nuclei, which can point, freezing point, surface tension, heat of
spontaneously result in temporary uneven vaporization etc. Similar abnormalities are
distribution of electric charges. This uneven characteristic also to fluids that consist of
distribution can create a temporary dipole, even molecules with the functional groups containing
on a non-polar molecule. The instantaneous hydrogen atoms: O––H+, N––H+, and F––H+. This
dipole generates an electric field that polarizes indicates that the presence of hydrogen atom
any nearby neutral atom, inducing a dipole may lead to some unusually strong and
moment in it. The resulting interaction between orientation-dependent bonds involved in the
the two dipoles gives rise to an instantaneous intermolecular interactions. To clarify this issue,
attractive force with the time average of this L. Pauling implicated the concept of hydrogen
force being finite. A semiquantitative bonds, which at first sight appeared to possess
representation of mechanism giving rise to this some covalent character [33]. This idea was
force and the role played by the quantum further developed in a number of fundamental
mechanics can be deduced by considering a works [34–37]. According to modern concepts,
simple model based on the interaction between the hydrogen bond (or H-bond) arises from the
two Bohr atoms. In the Bohr atom the electron is electrostatic attraction between the hydrogen (H)
pictured as orbiting around a proton. The atom that is covalently bound to a more
smallest distance between the electron and electronegative atom or group, and another
proton is known as the first Bohr radius, a0 at electronegative atom possessing a lone pair of
which the Coulomb energy, e2/4πε0a0 is equal to electrons. The H-bond is usually denoted
2hν: Dn–H···Ac, where the solid line indicates a polar
covalent bond, and the dotted (dashed) line
a0  e 2 8  0 h  0.053 nm, (13) designates the hydrogen bond (Dn and Ac are the
where h is the Planck constant, and ν is the donor and acceptor atoms of the H-bond,
orbiting frequency of the electron. For the Bohr respectively). Depending on the nature of the
atom,   3.3 1015 cm–1, so that h  2.2 1018 J. donor and acceptor atoms, geometry of the
interacting system, and the environment, the
An instantaneous dipole of moment, u = a0e, energy of a hydrogen bond can vary between
will polarize a nearby neutral atom, giving rise to approximately 4 and 160 kJ/mol [38–40]. This
an attraction that is analogous to the permanent makes them somewhat stronger than a van der
dipole – induced dipole (Debye) interaction Waals interaction, and weaker than fully
discussed above. The energy of this interaction covalent or ionic bonds. This type of bond can
in a vacuum will therefore be expressed, in occur in both inorganic and organic molecules.
analogy with the Eq. (11), as The H-bonds are responsible for supporting the
w r   u2 0  40  r6    a0 e 0  40  r6 ,
2 2 2 double spiral structure of the DNA molecule.
The interplay between empirical and theoretical
(14) approaches to the problem of an elusive notion
where α0 is the electronic polarizability of the of H-bonds is discussed in a historical outline
second Bohr atom, which is approximately [41].
4  0 a03 (see [25] for more details). With the As it has been already mentioned, the
expressions for a0 and α0, the interaction energy classification of intermolecular forces adopted in
can be written approximately as many literary sources may differ from that
presented above. In particular, the Keesom
w  r     02 h  4  0 
2
r6 . (15) interactions, the Debye interactions, and the
London dispersion interactions are frequently

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 Surface wetting and contact angle: basics and characterization
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considered as the partial contributions to the total the sapphire surface after a contact with the setae
van der Waals forces arising from their sum using interface-sensitive spectroscopy provided a
[25, 28, 42]. Moreover, recent scientific advance direct evidence for involvement of interactions
essentially extends the existing classification of between polar lipid headgroups exposed on the
intermolecular interactions. Thus, in addition to setal surface and the hydroxyl groups present at
well-known van der Waals forces, the hydrogen the surface of sapphire.
bonds, and the others discussed above, some Another example is the adhesion force
more non-covalent interactions were revealed to between the conductive monomolecular sheets
be involved in bonding mechanisms inside and constituting the layered structure of graphene.
between molecules. They include the halogen Graphene is a two-dimensional carbon allotrope.
bonds, the metal–ligand coordination, pi–pi It is composed of carbon atoms arranged in a
interactions, cation/anion–pi interactions, honeycomb-like hexagonal structure that form a
classical Derjaguin–Landau–Verwey–Overbeek single graphene sheet. As it has been predicted
(DLVO) interactions and others [43, 44]. theoretically by H. Casimir (1909–2000) in
It is also worth noting that the descriptive 1948, the two parallel and perfectly conducting
models of intermolecular interactions discussed plates placed in vacuum should experience
above are rather pictorial but somewhat attraction due to what is now referred to as the
simplified. They can be partially or completely Casimir force [50]. The Casimir force is a
abandoned by applying a more fundamental fundamental quantum-mechanical relativistic
theoretical treatment [26, 45, 46]. Therefore, the phenomenon, which originates from the vacuum
reader of this review should not feel stunned if fluctuations of the electromagnetic field. It
very different terms were encountered in some couples electrically neutral objects with or
publications instead of the interaction models without permanent electric and/or magnetic
discussed here. moments. It has been now realized that the
To date, the progress in the experimental Casimir force is involved into mutual adhesion
techniques based on the scanning probe of graphene sheets [51–53].
microscopy (SPM) made it possible to The special attention in this review to the
investigate the mechanisms of intermolecular distinctive features of various intermolecular forces
interactions by the direct force measurements at stems from the importance of understanding their
the nanoscale. With the development of colloidal nature for the experimental study of the wetting
and bubble probes, SPM can serve as one of the mechanisms discussed below.
most powerful techniques for nanomechanical
SURFACE TENSION AND CONTACT ANGLE.
quantification of interaction forces between the
LAPLACE EQUATION
solid surfaces and the liquid media. The
bubble/drop probe SPM technique allows for the This section discusses the role of
direct measurement of the force exerted from the intermolecular forces in shaping the surface
surface onto the cantilever-attached bubble or geometry of a finite portion of liquid,
drop [44, 47]. particularly in the close vicinity of a contacting
Fundamental notion of intermolecular solid body. The following consideration is
interactions is still under development. Some essentially based on the concept of surface
seemingly well-established ideas about the tension. It is evident that the energy state of the
nature of intermolecular interactions observed in molecules in the surface layer and in the bulk of
several specific cases have recently been refuted. a fluidic body is not equivalent. At the interface,
For instance, it was long time believed that the molecules are exposed to the action of
gecko’s1 famous ability of climbing up upon the attractive forces only from the neighbouring
mirror-like wall depends only on the van der molecules located beneath the surface (Fig. 1 a).
Waals forces. However, it has been revealed This action tends to minimize surface area that
recently that it involves also the acid-base can be effectively accounted for as a tension
interactions between the gecko’s setal surface within the surface layer, termed the surface
and the wall material [48, 49]. Investigation of tension. The effect of surface tension resembles
the action of a stretched elastic membrane
1
A small lizard belonging to the family Gekkonidae, covering the surface of a liquid body.
found in warm climates throughout the world.

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Surface tension can be defined in terms of surface tension in solids manifests itself only by
both force and energy [54]. The first definition the energetic effect of the interaction with the
relates the surface tension γ to the force F contacting media. Therefore, when referring to
exerted by the surface upon its side boundary l of solids, it is common to use a more general term
unit length: surface energy, defined according to (17). More
rigorously, the surface energy (surface free
F
 . (16) energy, interfacial free energy) is the energy
l required to expand the surface area of a body
The unit of surface tension defined in terms under constant temperature and pressure by a
of force is a Newton per meter (N/m). The unit area. This “excess energy” is a result of the
second one defines the surface tension as the incomplete, unrealized bonding at the interface.
energy required to extend the surface of liquid by The surface energy quantifies the disruption of
a unit area: intermolecular bonds that occurs when the
surface is expanded. For the solids to be stable,
F x W the surfaces must be intrinsically less
  , (17)
l x  A energetically favorable than the bulk of a solid
(the molecules on the surface have more energy
where W is the work of the surface tension force, compared to the molecules in the bulk),
and ∆A is the increment of surface area. In this otherwise there would be a driving force for the
case, the surface tension is expressed in Joules surfaces to be created on account of disappearing
per square meter (J/m2). However, the numerical the bulk. The surface energy may therefore be
values of surface tension in both cases remain defined as the excess energy at the surface of a
the same. material compared to the bulk, or as the work
Similar forces act also on the surface of required to build an area of a particular surface.
solids. However, while the surface tension in
liquid can affect the shape of a liquid body, the

Fig. 1. Intermolecular forces between the molecules acting in the surface layer and in the bulk of a fluidic body (a).
The shape of a sessile drop at the solid surface under equilibrium conditions. Here γs1, γsg denote the surface
tensions at the solid-liquid and at the solid-gas (vapour) interfaces, respectively, and γ1g is the surface
tension of the solid-gas (vapour) interface. The contact angle measures the tilt of the tangent to the liquid
surface at the point where a liquid – gas/vapour interface meets a solid surface (b)

The concept of surface tension is a simplest way to access its value is direct
convenient model for analyzing the shape of a measurement of the tangent angle at three-phase
finite portion of a liquid resulting from the action equilibrium interfacial point. This measurement
of intermolecular forces. As it has been already can be performed using several different
mentioned, a characteristic parameter of this geometries of the liquid-vapour-surface system.
shape is the contact angle. The contact angle Most common of them include the sessile drop
measures the tilt of the tangent to the liquid technique, the captive bubble method, the
surface at the point where a liquid – gas/vapour Wilhelmy plate method, and the capillary rise at
interface meets a solid surface (Fig. 1 b). The a vertical plate [54]. Among these methods, the

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 Surface wetting and contact angle: basics and characterization
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sessile drop technique currently has become one Unlike Young’s equation, the Dupré –
of the most extensively employed in wettability Young equation allows us to calculate the work
studies due to its convenience and versatility. of adhesion of a liquid to a solid, since the
Further improvement of this technique continues, quantities (θ, γ1g) included into this equation can
and its several drawbacks noted in [54] have easily be measured. This approach simplifies the
already been successfully overcome. system by reducing surface energy to a single
Consider the action of surface tension on the number γ1g, and excluding the other components,
shape and the contact angle of a sessile drop, i.e. γs1, γsg from consideration.
a liquid drop resting on a solid surface. It worth be noted that, despite the more than
Physically, the contact angle is determined by two centenary history of Young's equation, the
equilibrium between the surface tension and the problem of adequate theoretical description of
adhesion forces between the liquid and the solid surface tension still continues to be debated and
phase. Under the action of the first one, the refined till now. In particular, a careful
sessile drop tends to take the shape of a truncated examination of equation (19) shows that the
sphere, while the second one promotes spreading component of surface tension γ1g is not balanced
of the liquid over the surface. The relationship (Fig. 1 b). This issue was discussed in [62–69].
between the tension forces and the contact angle Bikerman [64, 65] contended that if there is no
for the equilibrium drop shape is expressed by opposite balancing force, the Young’s equation
Young's equation [24, 55], derived in 1804: is not valid (see also [66]). However, Bikerman
 sg   sl did not take into account the strain field in the
cos   , (18)
 lg solid beneath the surface, which provided the
needed balancing [67, 68]. Recently, more
where cos θ is the contact angle, and γ1g, γs1, γsg
findings supporting the role of strain at the
denote surface tensions of liquid-gas, solid-
liquid-solid contact line and its effect on the
liquid, and solid gas, respectively. Note that the
wetting characteristics were presented [69, 70].
last two quantities were introduced rather
In these publications the strain of the elastic
formally, since they cannot be measured directly.
substrate or the rod under the influence of
This flaw was improved in the Dupré equation
wetting force was directly observed and the role
(see [56]) based on the balance of surface
of this effect in behaviour of the contact line was
energies under the equilibrium conditions under
discussed. Nevertheless, further debates still
constant temperature and pressure:
continue. A comprehensive review related to this
Wa   lg   sg   sl . (19) topic is presented in [71].
There are also other reasons that require the
Here Wa is the reverse work of adhesion, that equation representing the surface tension to be
is, the reverse thermodynamic work of forces refined. The Young equation does not account
aimed at separating two dissimilar (hetero- for a layer of adsorbed molecules which
geneous) phases brought into contact, γs1, γsg, and inevitably present at the surface under regular
γ1g are, respectively, works of adhesion between conditions. Bangham and Razouk [61]
the solid phase and the liquid, the solid phase highlighted the difference in the values of
and the gas (external environment), and between solid/vapour and solid/vacuum surface tensions
the liquid and the gas. The work of adhesion is as early as in 1937. More recently, the
related to the Gibbs free energy as: importance of adsorbed and wetting films
covering solid surfaces has been generally
Wa    G 0 . (20) recognized and widely discussed [72–83]. It was
In the equilibrium state, the Gibbs energy found that there is a transition region between
has a minimum, so its derivative of the the liquid phase and the substrate surface, which
coordinate that describes the shape of the drop is makes an additional contribution to the measured
equal to zero. This allows us to get rid of the value of the contact angle. One of possible
inaccessible γs1, γsg and arrive at the Dupré – geometries of this region is shown in Fig. 2
Young equation [54, 57–61]: (adopted from [79]). The effect of the transition
region, which is now termed the contact line, can
Wa   lg (1  cos  ) . (21)

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be accounted for by introducing additional term angle can readily be obtained starting from the
in the Young equation [80–82]: “energetic” interpretation of the Young’s
equation. Combining (19) and (20), for the case
L
cos   cos    1 r  , (22) of the non-uniform surface we arrive at:
 lg
G0    lg  1 1sl  1sg   2  2sl   2sg  , (23)
where r is the radius of the liquid-solid contact
area, θ∞ is the contact angle at the infinite radius, where σ1, σ2 are the fractional areas of the two
and γL is the line tension. surface states that differ in wettabilities, and γ1sl,
γ1sg, γ2sl, γ2sg are corresponding interfacial
tensions of the solid-gas and the solid-liquid
interfaces. This equation is analogous to (19)
and, similarly to (18), results in:
cos  c   1 cos1   2 cos 2 , (24)
known as the Cassie’s law for heterogeneous
surfaces [90].
The Wenzel contact angle is an “apparent”
contact angle that characterises the rough
surface. In the original article [91], it was deuced
Fig. 2. Profile of film/meniscus transition zone: 1 – on the basis of “roughness factor” defined as
uniform film region; 2 – transition region; 3 –
flat film; 3 – concave film; 4 – convex film; actual surface
r  roughness factor  (25)
5 – concave film; 6 – meniscus geometric surface .
The contribution from the line tension is
especially important in case of nanodroplets, This definition assumes that the actual
since the ratio between the contact line area and surface of any real solid will be greater than the
the drop surface increases along with decreasing geometric surface because of surface roughness.
the droplet volume. As the nanoscience has Surface tensions, like specific energy values, are
become one of hottest fields of research, the related to one unit of actual surface. But when
problems related to the role of the contact line in liquid spreads over the surface of a real solid, the
nanodroplet properties is currently attracting forces that oppose each other along a given
much attention [83–85]. length of the advancing periphery of the wetted
Other modifications of Young equation area are proportional in magnitude to their total
outlined here were aimed at accounting for the energies per unit of geometric surface. This must
micro- or nanoroughness of the solid surface, be true if surface tensions themselves are
chemical inhomogeneity of the substrate and characteristic properties, unaltered by surface
some other deviations from ideal surface roughness. Thus, the Wenzel contact angle
conditions. A recent review [86] summarizes should be related to the Young contact angle as
most significant issues related to wettability of cosW  r cosY . (26)
imperfect surfaces. While Young’s equation
provides fundamental insights on wetting of flat The thermodynamic status of the Wenzel
surfaces, it has also been the basis of advanced equation was discussed in [92]. It was explained
wetting models on uneven surfaces: the Cassie- and demonstrated by an example that the Wenzel
Baxter contact angle and the Wenzel contact equation may be incorrect. However, it was
angle [87–91]. mathematically proven that the Wenzel equation
The Cassie-Baxter contact angle relates to correctly quantifies the apparent contact angle
the chemically heterogeneous surface, where when the drop size becomes infinitely larger than
small (compared to the drop size) areas are the scale of roughness.
characterized by different wettabilities. In We broached just a few approaches of many
particular, it can be applied to the porous surface others proposed for quantifying various
when the pores are not wetted and remain filled phenomena associated with wetting and
with air. The Cassie-Baxter equation for contact wettability. We have touched on them here as

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they are relatively well established and geometry of a capillary rise at the contact with
ubiquitous. More recent trends in wettability solid surfaces and provides a basis for
research are characterized by increasing attention interpretation of wettability-related experiments.
to wetting of “imperfect” surfaces, which A nonlinear partial differential equation that
demonstrate various peculiar effects. Thus, describes the capillary pressure difference
among the hottest topics today are the problems sustained across the water-air interface (or
of superhydrophobic, superoleophobic and between two static fluids), due to the
superhydrophilic surfaces, which have phenomenon of surface tension (or thin wall
significant potential for practical use. The tension), is known as the the Young–Laplace
extraordinary properties of these surfaces are equation:
achieved by formation of micro- and nanoscale
 1 1 
surface relief. An exhaustive survey of  p     (27)
investigations in this direction is given in a R
 1 R 2 .

recent review article [93]. In this work, the major

challenges related to the use of the sessile droplet This equation relates the pressure difference
contact angle for characterizing surface wetting to the shape of the surface or wall in terms of
behaviour are reviewed. Different kinds of surface tension γ and the principal radii of
surface nonuniformity result also in the contact curvature, R1 and R2, which is fundamentally
angle hysteresis (CAH) [94–96] (the hysteresis important for the study of static droplet and
of the contact angle is the difference between the capillary surfaces. It represents a statement of
advancing and receding angles that typically normal stress balance for static fluids meeting at
depends on the surface geometries and degrees an interface, where the interface is treated as a
of wetting). surface (zero thickness). The equation is named
Many interesting examples of wetting and after Thomas Young, who developed the
wettability in nature and technology are qualitative theory of surface tension in 1805, and
described in a recent textbook by Pierre-Simon Laplace who completed the
E.Yu. Bormashenko [97]. This textbook mathematical description in the following year.
introduces into the physics of surface wetting The Young–Laplace equation is often
and its engagement for explaining phenomena of encountered in the literature covering the
floating objects, condensation and evaporation of concepts of capillary pressure and wettability
droplets, capillary waves, bouncing droplets, since it is quite general.
walking of water striders, and many other This equation may be derived either by
curious effects. In particular, Marangoni flows, requiring a force balance at the interface, or by
surface tension inspired instabilities, liquid considering the energy increment resulting from
marbles, superhydrophobicity and super- variation of interface geometry. A simplified
oleophobicity (lotus effect) are considered. Many derivation of the Laplace equation can be found,
other aspects of wetting phenomena remain for instance, in [98]. However, a mathematically
untouched here; however, the scope of this rigorous treatment requires familiarity with the
review does not leave more space for their properties of surfaces established in differential
consideration. geometry. We outline here the approach to
Young–Laplace equation. As follows from derivation of the Young-Laplace equation just
the above, the intermolecular interactions conceptually, referring the interested readers to a
involved in wetting phenomena can be more comprehensive elucidation (see [99]). For
experimentally assessed by analysing the surface simplicity, we restrict ourselves to the quasi-one-
geometry of a finite portion of liquid contacting dimensional case of the infinitely long elastic
the solid body. The most characteristic feature of pipe. To determine the pressure jump between
this geometry is the contact angle. Further the inner volume of this pipe and the
discussion on surface geometry and contact environment, consider first the force balance at
angle requires consideration of pressure jump its cross-section. Let the inner radius of the pipe
across curved liquid surface exerted by the be R (Fig. 3), the tension on the pipe wall be γ,
surface tension. This jump, or the capillary and the length of pipe segment under
pressure, determines the shape of droplet consideration, dl be equal to unit. When the
surfaces, liquid meniscus in a capillary tube, the surface tension is defined as a mechanical force

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per unit length, then the resultant of tension two different radii of curvature, R1 and R2 are
forces acting on the section of the pipe confined required to describe liquid surfaces. At any given
within the angle dφ is γdφ. At equilibrium, it point on the surface, they are defined by
should be equal to the force of pressure, ∆p Rdφ. intersecting the liquid surface with two
This results in an equation perpendicular planes, both containing the local
surface normal. The resulting values of R1 and R2
 p   1 R  . (28) will in general depend on the azimuthal
orientation of the two surfaces. Rotating the two
surfaces around the surface normal, a unique
orientation can be reached, for which R1 and R2
attain a maximum and a minimum value,
respectively. These maximum and minimum
values are known as principal radii of curvature.
The mean curvature, the specific combination
1 1 1 
   , (30)
2  R1 R 2 

is a well-defined quantity, which determines the

pressure jump across the liquid surface. With
these definitions, the two-dimensional version of
the Young–Laplace law reads as (27). This
Fig. 3. To derivation of the Young-Laplace equation equation underlies the methods for calculating
from consideration of the energy increment the surface geometry of a liquid body resulting
(the one-dimensional case) from the combined action of surface tension and
adhesion.
Another approach consists in determination
of the energy increment when inflating the pipe. EXPERIMENTAL CHARACTERISATION OF
Thermodynamically, the macroscopic surface SURFACE WETTABILITY. THE SESSILE
energy is defined as the amount of mechanical DROP TECHNIQUE
work δW required to deform a surface in such a Before discussing in detail the
way that the total surface area changes by dA: characterization of surface wettability by analysis
W dA. (29) of a sessile drop shape, we briefly outline and
compare some most common techniques
Let the inner radius be increased by dR. employed in this area of research. A general
Then, according to (29), the mechanical work review of these techniques can be found in [100].
will amount at  d A    2 d R   p 2 R d R , It is convenient to roughly classified them as
resulting again in (28). Thus, both definitions are “immediate”, based on a direct measurement of
equivalent and can be used interchangeably the force of surface tension, and “implicit”, where
depending on convenience. the wettability is quantified by analysis of
For the above example, the longitudinal experimental data involving the wettability
section of the pipe is a straight line with zero characteristics indirectly.
curvature. When the curvature is non-zero in two The first group is represented mainly by the
orthogonal directions, it can be expected that the Wilhelmy method (Wilhelmy plate method) in
pressure jump is a sum of contributions from various versions. This method was proposed by
both curvatures, thus yielding (27). This situation F.L. Wilhelmy in 1863 and consists in a direct
has been analysed in [98] in a similar way as the measuring the downward pull exerted by a liquid
above by the example of an elastic spherical upon a thin plate of solid material which is
balloon. However, for a sphere, both radii of partially immersed [101] (Fig. 4). The plate is
curvature are obviously equal and independent suspended from a balance arm. Its apparent
on the position by symmetry, thus limiting the weight will be the sum of the actual weight
generality of the results. In a general case of (in air) and the downward force exerted by the
three-dimensional surfaces of arbitrary shape, surface tension of the liquid with the deduction

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of the buoyant effect of the displaced liquid. a video camera with the contour analysis
Obviously, the vertical pull depends upon the software.
degree to which it is wet and hence upon the
contact angle. A wide range of the research-
grade instrumentation realizing this method is
now commercially available (Fig. 5). Currently,
Wilhelmy method is considered as one of the
most reliable techniques for measuring contact
angles on fibers of known dimension [102, 103].

Fig. 6. Diagram of an arrangement for measuring the

contact angle: 1 – light source; 2 – diffuser;
3 – sample chamber; 4 – syringe; 5 – telescope;
6 – video camera; 7 – monitor

Fig. 4. The schematics of the Wilhelmy plate

method (after [101])

Fig. 7. Optical contact angle measuring and contour

analysis systems OCA-50EC (Dataphysics
Instruments, GmbH, Germany)
Fig. 5. Dynamic Contact Angle measuring device
and Tensiometer DCAT-9 (DataPhysics Other techniques that rely on measuring the
Instruments GmbH, Germany) curvature of a liquid surface in contact with a
solid are capillary rise at a vertical plate [107]
Among the other group the first place is
and a capillary bridge method. The first one
occupied by methods based on measuring the
exploits the capillary rise of a liquid brought in
shape of the sessile drop [100, 104–106]. The
contact with a vertical and infinitely wide plate.
basic scheme and a contemporary instrument
The height of capillary rise, h, contact angle θ,
designed for these measurements are shown in
and the surface tension γ are related by the
Figs. 6 and 7, respectively. The today’s instru-
equation
mentation for contact angle (CA) measurements
combines high-resolution optics, exact liquid 2  lg
dosing, precise sample positioning, and h 1  sin   , (31)
 g
computer-aided image processing into powerful
and reliable measuring systems. The contact where ∆ρ is the difference in density between
angle is derived from the drop image recorded by liquid and gaseous environment, g is the

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gravitational acceleration, and γ1g is the surface The simpliest technique that can be related to
tension of liquid-gas interface. The Wilhelmy this group is the tilting plate method (not to be
balance method can be modified to measure the confused with the tilted plate technique). The
capillary rise h at a vertical plate in order to tilting plate method developed by Adam and
determine the contact angle θ [105, 106]. Jessop [114] was once favored due to its
Dynamic contact angles are achieved by moving simplicity. In this method, a solid plate with one
the plate up or down. This method has been end gripped above the liquid is rotated toward
widely used, and has proved to be particularly the liquid surface until the end of the plate is
suitable for measuring the temperature immersed in the liquid, forming a meniscus on
dependence of contact angles [107–109]. Later, both sides of the plate. The plate is then tilted
the Wilhelmy method has been automated by slowly until the meniscus becomes horizontal on
Budziak and Neumann [110]. For a specially one side of the plate. The angle between the plate
prepared surface that forms a straight meniscus and the horizontal is then the contact angle of
line, an accuracy of ±0.1° can be obtained. This interest. Some less common techniques were not
technique also inherited most of the advantages mentioned here since they are more specific, or
and disadvantages of Wilhelmy balance method. of lesser importance for the topic under
The capillary bridge method is a high- consideration. More information on this topic
precision contact angle measuring technique, can be found in [100, 104–106].
developed by Restagno et al. [111–113]. In their
experiment, a spherical solid surface (usually a
watch glass) is put in contact with a large liquid
bath. Due to the capillary effect, a meniscus or
“capillary bridge” forms around the contact line,
which defines the wetted area on the solid
surface (Fig. 8). The shape of this “capillary
bridge” between the solid surface and the liquid
changes as the solid is slowly moved up or down
to give a systematically varying wetted area. By
monitoring the changes of the wetted area and
the distance that solid surface moves, the
dynamic contact angles can be quantitatively Fig. 8. Diagram of the contact angle measurements
determined through numerical resolution of the according to the capillary bridge method
Young-Laplace equation or by a simplified (after [100])
approximated relation: No single method can accommodate any
kind of sample geometries, dimensions, or

A  2  R k 1 2 1 cos   h  (32) experimental conditions, but the most appro-
priate one can be selected in every situation.
where A represents the wetted area, h is the Among different methods, the advantage of the
distance of solid surface from liquid bath sessile drop technique is that it is the least
surface, R is the radius of the sphere surface, and dependent on the sample configuration and
k–1 is the capillary length, which is known for a measurement conditions. Moreover, it has been
given liquid. The contact angle θ can be deduced demonstrated that it can be applied for contact
from the experimentally determined A(h) curve. angle measurements not only on a flat, but also
The capillary bridge method offers several on a curved surface [115]. This makes it the most
advantages. Both advancing and receding contact popular approach to studying surface wettability.
angles can be found by slowly pulling the Sessile drop technique: measuring contact
surface away from the liquid or pushing back angle. Direct measurement by telescope-
toward the liquid; thus, the dynamic contact goniometer. A technique for characterising the
angles can be studied. Due to its high sensitivity, surface wettability by the contact angle
the technique can be used to characterize measurement on a sessile drop profile was first
surfaces with low contact angle hysteresis (of the introduced by Bigelow, Pickett and Zisman in
order of 1°). 1946 [116]. Originally, it was intended for a

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direct measurement of the tangent angle at the accurately measured due to the uncertainty of
three-phase contact point of various liquids on assigning a tangent line when the droplet profile
polished surfaces. For this purpose, they is almost flat. It is generally recognized that the
suggested a simple and convenient instrument, direct measurement of sessile drop contact
which they referred to as a “telescope- angles with a telescope-goniometer can yield
goniometer”. Later, the first commercial contact accuracy not more than ± 2° [117, 118]. To
angle goniometer, designed by W.A. Zisman, overcome these and other issues, various
was manufactured by ramé-hart instrument approaches to computer-aided image analysis
company in the early 1960s (Fig. 9). The were developed to date.
instrument consisted of an adjustable optical Indirect contact angle measurements. The
stage for mounting a sample, a micrometer exact shape of the sessile drop as a whole is
pipette to form a liquid drop, a light source, and defined by the Laplace equation (27). Though
a telescope equipped with a protractor eyepiece. there is no closed-form solutions of this
These parts were assembled on an optical bench. nonlinear equations, it nevertheless imposes
The measurements were carried out by interrelations between certain generalized
measuring the angle between the tangent to the parameters characterizing geometry of the drop.
drop profile and the surface of substrate at the Due to this, the contact angle can be derived
contact point through the eyepiece by the indirectly from measured values of these
protractor. The principle of the “telescope- parameters taken in appropriate combination.
goniometer” had proven to be very convenient Potentially, this approach may result in a more
due to its simplicity and versatility, and grown accurate determination of the contact angle
over the years into a powerful technique with compared to direct measurements, provided the
greatly improved accuracy and precision. required parameters can be measured with
Contemporary instruments integrate video sufficient precision.
cameras, high quality objective lenses with This idea that lies behind the method for
adjustable magnification, computer-controlled measuring the contact angle was proposed by
motor-driven dosing syringes, enclosed G.H. Quincke (1834-1924) in 1870. The
temperature and atmosphere controlled sample Quincke method was based on the observation
compartment, powerful software for image that the height of a sessile drop resting on a
analysis, and many other advanced features. horizontal substrate approaches a limit value as
its volume is increased. In 1870, Quincke
derived an approximate equation, now known as
the Quincke relation, which relates the contact
angle, c with the height h of a large enough
drop [119, 120]:
  g h2 
 c  cos 1 1  . (33)
 2 

In this equation, g stands for the acceleration

of gravity, ρ is the density, and γ is the surface
tension. The method is particularly accurate
Fig. 9. Zisman’s goniometer for measuring the when measuring the height of an extended liquid
contact angle manufactured by ramé-hart front because in this case the surface curvature
instrument company in the early 1960s resides entirely in the vertical plane and Eq. (33)
is satisfied exactly. However, with the advent of
The direct goniometer method suffers from
more powerful techniques, the Quincke relation
serious limitations. The accuracy and
was gradually abandoned in the latter half of the
reproducibility of the measurement relies on the
1920s and emerged anew only in a text of 2004
consistency of the operator in the assignment of
[121]. Moreover, this method was essentially
the tangent line, which can lead to significant
improved by F. Behroozi [122] who employed
error and inconsistency between different users.
laser-assisted technique to detect a state of
Small contact angles (below 20°) cannot be

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complete flatness attained by the top surface of droplet volume with the use of an “analog
the drop while enlarging its size. device”, namely using a high-precision dosing
Another simple method for indirect pipette. With a known volume of the droplet, the
determination of contact angle, known as half- determination of the contact angle was reduced
angle method, was described in [123]. The idea to measuring the droplet height and the footprint
of this method is underpinned by the assumption radius, which could be done with sufficiently
that the sessile drop is a spherical cap in shape (a high accuracy.
spherical segment of one base, i.e., bounded by a
single plane). The cross section passing through
its axis of symmetry is shown in Fig. 10. It can
be proven within the frame of the plane
trigonometry that the angle between the base of
the cap and the segment connecting the triphase
point with its top is half of the contact angle (the
triphase point is the point where the arc of the
cap section joins the base). Thus, having
measured the height and the base length of the
cap, the contact angle could be obtained from the
expression:
 2h  Fig. 11. The profile of a sessile drop resting on a flat
 c  2  arctan  . (34) surface. The surface band of infinitesimal
 l  width encircling the drop is shown between
However, as it has been noted above, this the dashed lines (after [126])
expression is valid only for exactly spherical To derive governing equations for the drop
cup, that is when the droplet is small enough for shape, they considered equilibrium conditions
not to be distorted by gravity. However, with for an infinitesimal surface belt encircling the
decreasing the drop size the contribution from drop (Fig. 11). The pressure at the base level of
the line tension discussed in section 2 (see the shaded section of the drop is
Fig. 2) increases, influencing the obtained value
of the contact angle. p  2 / r0   g y . (35)
The first term is the pressure jump due to
surface tension (note that the two principal radii
of curvature at the apex are degenerate and equal
to r0), and the second term accounts for gravity
(g is the acceleration of gravity, and ρ is the
density of liquid). The balance of forces acting
on the surface band in the vertical direction is
given by the following equality:
 2 
   g y   2 x d x  2 x sin 
 r0  (36)

Fig. 10. The cross section of a sessile drop illustrating  2   x  d x  sin   d   .

a half-angle method for determination of
contact angle In the limit of dθ → 0, they obtained after
transformation the set of two parametric
In 2019, F. Behroozi and P.S. Behroozi equations describing the droplet contour:
proposed a more elaborated approach to
determination of contact angle from the dx  sin
experimental contour of the sessile drop [124].  (37)
d  2   
Instead of solving the Laplace equation, they    g y   sin
resorted to an ingenious solution, setting the  r0  x

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 Surface wetting and contact angle: basics and characterization
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and several other similar methods that have not been

discussed here can be found in the cited
dy  sin
 (38) literature. With the widespread use of
d  2    automation tools for experiments, the
   g y   sin
 r0  x simplification of measurements has lost its
relevance, and the main criterion for the
(the second of these equations follows from the effectiveness of the method has become an
equality dy/dx = tanθ that is fulfilled along the increase in accuracy. A priori, the best accuracy
contour of the drop). An auxiliary equation gives will be achieved if the calculations will fully take
the drop volume: into account the entire array of obtained
h experimental data. Thus, we proceed to
V    x2 d y . (39) consideration of the currently most relevant
0 approach to determining the contact angle,
known as the Axisymmetric Drop Shape
The system of differential equations (37),
Analysis (ADSA), which was developed by
(38) can be integrated numerically, starting from
Y. Rotenberg, L. Boruvka, and A.W. Neumann
the drop apex (θ = 0), to obtain x(θ), y(θ), and
in early 1980 [126]. In view of its importance,
the profile curve y(x) when the parameters r0, γ,
special attention will be paid to the mathematical
and R are known. In order to obtain θc, the
foundations of this method.
integration is to be terminated at the end point of
Axisymmetric Drop Shape Analysis
the profile curve where the drop volume given
(ADSA).
by (38) reaches the experimentally preset value
Whereas the experimental methods outlined
V0. As it is difficult to measure the parameter r0
above were aimed at determining the contact
precisely, the authors resorted to an iterative
angle as a purely geometrical quantity, ADSA
process, setting the starting value r0 to h and
exposes also a related physical meaning.
comparing the resulting parameter V with the
Development of ADSA was aimed at creating a
preset value V0. With proper adjustment of r0
technique capable of the overall drop shape
from iteration to iteration, the condition of
analysis. This approach promised to improve
V = V0 is finally fulfilled with the required
radically the accuracy of contact angle
accuracy. At this point, the iterations are
determination compared to the methods, which
terminated with the parameters θc and,
rely on the measurements of only a few
additionally, r0 being determined. The iterative
preselected characteristic points. A distinctive
procedure employed in this research actually
feature of the ADSA technique is that it accounts
belongs to a spacious domain of numerical
for the distortion of a drop by gravity. Actually,
techniques known as methods of optimization.
the gravity serves there as a built-in standard
An introductory course into these methods was
enabling quantification of the surface tension on
written by Brian D. Bunday [125]. In this book,
the basis of the experimentally observed drop
the most popular optimisation methods (The
distortion. This feature is especially helpful
Hooke-Jeeves algorithm, also known as “pattern
when using different liquids with different
search”, the Davidon-Fletcher-Powell penalty
surface tension for studying the dependence of
function method, the Fletcher-Reeves conjugate
wettability on the chemical structure of the
method, and some others) are described and
surface. Otherwise, it would be impossible to
supplemented with the source program codes.
bring into correlation the contact angle
We have considered several well-known
difference for fluids differing by molecular
methods for determining the contact angle from
mechanisms of liquid-surface interactions (the
the experimentally obtained image of the droplet
last is of special importance when studying the
contour. The authors of these methods sought
chemical modification of solid surfaces).
reducing the number of parameters to be
The ADSA analysis is based on the solution
measured in order to simplify the experiment.
of the Laplace equation, modified to take into
However, the price for this simplification was
account the forces of gravity. As it was discussed
the requirement for high measurement accuracy,
above, the Laplace equation (27) relates the
since errors are not compensated in any way and
pressure jump across a liquid-air (or liquid-
significantly affect the result. Information on
vapour) interface with the curvature of the liquid

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surface. To account for the contribution from the Here the quantities k1 and k2 denote the
gravity force to this pressure difference, an principal curvatures. The theorem is named for
additional term dependent on the elevation was Leonhard Euler who proved it in 1760. The
added: proof of this theorem at a level not burdened
with modern mathematical terminology and
 P   P0   g z . (40)
notation is given in the textbook [129] available
Here ∆P0 is the pressure difference at a at a public domain through the Internet. The
selected reference plane, ρ is the density of the equality (42) results in a remarkable conclusion:
liquid phase, g is the gravitational acceleration, curvatures of any mutually perpendicular normal
and z is the vertical height measured from the sections x1, x2 give in sum the mean curvature of
reference plane. With the addition of the gravity the surface at the point of their intersection.
term, the Laplace equation takes the following Taking into account that in this case the angles θ1
form [126, 127]: and θ2 between these sections and the principal
direction ξ1 differ by π/2, we obtain for the
 1 1  corresponding curvatures:
      P0   g z . (41)
 R1 R2  x1  k1 cos2 1  k2 sin2 1,
A manageable solution of this equation can
be obtained (using numerical techniques) for the x2  k1 sin2 1  k2 cos2 1 . (43)
case of the axisymmetric problem. This case
Thus, it is evident that κx1 + κx2 = k1 + k2.
applies to the liquid drop lying on a flat uniform
This result makes it possible to calculate the
horizontal surface, where it acquires the axially
mean curvature of the surface using any arbitrary
symmetric shape under the pressure of the
normal sections provided they are mutually
surface tension. The axial symmetry imposes
perpendicular.
interrelation between the radii of curvature, R1
The most natural coordinates on the surface
and R2, making them mutually dependent. This
of the axisymmetric drop are the meridians and
dependence fundamentally facilitates the
the local arcs normal to the meridians at the
solution of the Laplace equation for calculating
surface point under consideration, as shown in
the droplet shape. However, the rigorous
Fig. 12. It is convenient to place the origin of the
consideration of the drop geometry is essentially
r-z coordinate system at the apex of the drop and
based on the results of differential geometry,
to direct the z coordinate axis down along its axis
which are usually omitted in publications
of symmetry. In this case, the r-axis appears to
devoted to physics of wetting phenomena. In
be tangent to the curved interface at the drop
order to give the reader a more profound
apex, R1 turns along the meridian, and R2 lies in
understanding of underlying mathematics, we
the plane normal to the meridian. In this
will try to fill this gap here rather in an intuitive
geometry, it becomes possible to reduce the
way.
Laplace equation (that actually is a partial
First, we should refine the definition of the
differential equation for the surface) to the
surface curvature. The intersection of the surface
ordinary differential equation (ODE) for the
with a plane that contains a normal of this
droplet generatrix with a single independent
surface is called the normal section curve. The
variable z and one unknown r(z). For this, it is
Euler's theorem [128] establishes the existence
necessary to find a relationship between the radii
of principal curvatures and associated principal
directions on the surface in which the curvature R1 and R2, imposed by the axial symmetry of the
of normal section attains its the most and the drop.
least values. The Euler’s theorem asserts that the Construct a circular conical surface tangent
vectors ξ1 and ξ2 lying in the principal directions to the droplet surface, as shown in the
are mutually perpendicular and that, moreover, if Fig. 13 a, b. Let the plane S intersect the cone at
X is any vector making an angle θ with ξ1, then some point of contact with the droplet surface
the curvature κx along this x direction is given by perpendicular to the cone generatrix. Then the
secant plane S forms the normal section
 x  k1 cos 2   k2 sin 2  . (42) perpendicular to the meridional one. Thus, as
follows from (43), the curvatures of this section

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 Surface wetting and contact angle: basics and characterization
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and the meridional section of the drop enable

calculation of the mean curvature. To perform
this calculation, we resort to analytical geometry
that establishes multifarious interrelations
between the geometric properties of conics. In
fact, we will need only two of them, the property
referred to as an eccentricity, and the parameter
a introduced later.
The conical section (a conic) may form three
types of curves, dependent on the slant angle of
the cone. The quotient e = cosψ/cosθ gives the
eccentricity of the conic. Here ψ is the angle
between the secant plane and the cone axis. Fig. 12. Definition of the coordinate system of
When the secant plane is normal to the axisymmetric drop. Radius R1 (segment
generatrix, then ψ = π/2–θ, and the elliptical, O1M) rotates in the meridional plane
parabolic, and hyperbolic conics correspond to (lightened), radius R2 (segment O2M) rotates
the angles θ < π/4, θ = π/4, and θ > π/4, in the plane of normal section (shadowed)
respectively. Note that in the literature the This results from an alternative choice of the
formula for eccentricity of conics often is given angles characterizing the eccentricity (Fig. 13 a),
in a different form: for which α = π/2–ψ and β = π/2–θ (see
[129–131] for details).
e  sin  sin  . (44)

Fig. 13. To derivation of expression for radius R2. The meridional section of a drop with the normal section S is shown
in panel (a), and the correspondent 3D view is displayed in (b)

It is convenient to proceed further with the x2 y 2

rectangular equations of conics in the Cartesian   1 for ellipse, (46)
a 2 b2
coordinates, taking the y-axis coincident with the
directrix and passing the x-axis through the focus x2 y 2
  1 for hyperbola, (47)
(see [131]). Then the equation a 2 b2

(1  e2 ) x 2  y 2  2 k x  k 2  0 (45) y 2  2 p x  0 for parabola. (48)

For ellipse, a and b are half-lengths of its
represents any conic (here k is the distance width and the height (a semi-major and semi-
between the focus and the directrix). This minor axes). For hyperbola, a is half-distance
equation can be further reduced to a canonical between its apical points, and b defines the
form. The canonical equations of different conics incline of the asymptotes:
are:

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b 2 a b2 2 tg 
y
a
x. (49) 
l a 1  tg 
2 2  tg 2   1
,
For parabola, p is the distance of the focus
or, after reducing,
from the directrix.
The eccentricities of conics in terms of a and b2 l  sin  r
b are given by the following expressions:  l  tg    . (56)
a cos cos 
If the conic is a parabola,
e = 1; (50) Substitution of expression for R2 (53) into
(56) yields:
if the conic is an ellipse,
b2 r
e  1 ; (51) R2  . (57)
a2 cos 

and if the conic is a hyperbola, Taking into account (57), the equation (27)
can then be rewritten as:
b2
e  1 . (52)  1 cos   2 
a2      gz. (58)
 R1 r  R0
The eccentricity e of the ellipse has a visual
meaning, characterizing the degree of its We arrived at the equation for the meridional
elongation in comparison with a circle. The contour of sessile drop given in [126] (except for
detailed explanation of the above formulas can the definition of the angle θ). Here ∆P0 is
be found in references [130–134]. expressed by the Laplace equation through R0,
Below we consider as an example a the radius of curvature at the apex of the drop (at
relationship between the radii R1 and R2, for the the apex, both radii of curvature, R1, R2 become
elliptical conical section. Other types of conics equal due to the symmetry of this configuration).
can be treated in a similar way. The radius R2 is Before switching to solution of this equation, the
the radius of curvature at the end of the major choice of the appropriate drop size for ADSA
axis of the ellipse [134]: experiments is to be discussed.
As explained above, the efficiency of the
R2  b 2 a . (53) ADSA approach depends on a balance between
the surface tension and the gravity that
From this, the radius R2 can be expressed
determines the deviation of the drop shape from
through the cone angle θ (Fig. 13 a). Let us
the sphere. The importance of gravitational
denote the distance from the top of the cone to
forces can be assessed by the magnitude of the
the line of contact with the surface of the drop as
dimensionless parameter called the Eötvös
l. Then the length of the semi-major axis a can
number (Eo), also known as the Bond number
be expressed through l and the angle θ:
(Bo) [135, 136]. These two names commemorate
2a 2 tg  the Hungarian physicist Loránd Eötvös
 tg (2 )  . (54)
l 1  tg 2  (1848–1919) and the English physicist Wilfrid
Noel Bond (1897–1937), respectively. This
If the generatrix of the cone is normal to the number is defined as:
secant plane, then the angle ψ is π/2–θ, and
cos  sin  . Then the equality (44) turns to  g L2
Eo  Bo  , (59)
e = tanθ. Substitution of this equation to (51) 
gives: where ρ is the density of the liquid in the drop, L
b 2 is the characteristic length of the drop (that can
 1  tg 2  . (55) be estimated from the drop volume V), and γ is
a2
the surface tension of the interface between the
Multiplying the left and right sides of drop and the ambient phase. Another frequently
equation (54), respectively, by the left and right used formula for the Bond number is:
sides of equation (55), we obtain:

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 L
2 wettability). Thus, consider the approaches to
Bo    , (60) numerical solving the equation (61).
 c  A representation of the sessile drop contour
that is more suitable for calculations can be
where c    g is the capillary length. In the obtained by converting the equation (61) into a
limit of small Bond number, the shape deviation parametric form, according to [126]. Assuming
due to gravity is negligible, and the interface x = x(s) and y = y(s) with s being the arc length
shape can be approximated as a spherical cap. measured from the top of the drop (Fig. 13 a),
This approximation permits analytical solutions we get:
for the drop configuration. When Bo ~ 1, the
forces of surface tension and gravity become dx
 cos , (62)
comparable, resulting in a distortion of the drop. ds
This arises at a length scale commensurable with
the capillary length. For an air-water surface, for and
example, γ ≈ 70 dynes/cm, ρ = 1 g/cm3 and dz
g = 980 cm/s2, so that lc ≈ 2 mm. Within this  sin , (63)
ds
domain the ADSA approach is most effective.
Since the equation (58) can be solved only where variables have the same meaning as in
by numerical techniques, the most common way Fig. 12. By definition,
to extract physical parameters from the
experimental results using ADSA method 1 d
 . (64)
involves fitting procedures. The general scheme R1 d s
of the fitting method consists in finding a
numerical solution to the equation, which Combining (58) with (64) yields
depends on some fitting parameters, determining d 2 g sin
the discrepancy between the found solution and   z , (65)
d s R0  x
the experimental result, and achieving their
coincidence by varying the fitting parameters. where cos θs replaced with sin ψ. Equations (62),
Calculation of the drop contour r(z) requires (63), and (65) with the boundary conditions
that the equation (58) be reduced to the ODE
form. In general, this can be done in different x 0   z  0     0   0 (66)
ways depending on the selected solving method
form a set of first-order differential equations for
and the appropriate coordinate system. Thus, an
x, z, and ψ, as functions of the argument s. For
analogous equation that describes the meniscus
given R0 and given ρg/γ the complete shape of
shape r(z) reduced to the Cartesian coordinates
the curve may be obtained by integrating
r, z for the capillary rise of liquid was given in
simultaneously these three equations. In [126],
[54, 137.]
the solution of this set of equations was obtained
  using a numerical procedure by minimising the
 zr zr . (61) objective (or target) function defined as:
 gz    3
 1 
 1   zr 2  2 r 1   zr 2  2  N
   FN     un , vn  
2
  (67)
n 1
Here the first term in the brackets is a
standard expression for the curvature of a plane (see Fig. 14). This definition represents the
curve defined by the function z(r) [138], that objective function in the form that completely
replaces the curvature given above in term of conforms to the generally accepted approach.
1/R1. The expression for the second term follows However, its calculation is rather complicated
from the trigonometric formula cos 1 1 tan2  , and computationally burdened as it requires
determination of normal vectors to the drop
taking into account that tan   1 zr . However, contour in many points and calculating distances
the direct use of the equation (61) for ADSA is along these vectors to the experimental points.
aggravated by the ambiguity of solution when Additional inconvenience may arise from the
the contact angle exceeds π/2 (the case of poor representation form of experimental data points:

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for the computational procedure to be reliable, should result in identification of these pixels.
the normal vectors to the calculated drop contour Most of algorithms implementing this operation
always must target the corresponding point in the can roughly be divided into two categories. One
experimental one. of them relies upon calculating the derivative of
the luminance function, while another one traces
the boundary by “crawling” along the
consecution of boundary pixels between two
image regions which have distinctions in
luminance. The first category is commonly
referred to as “edge detectors”, or “boundary
detectors”, while another one is termed
“boundary tracing”, or “contour tracing”. The
essential difference between the two is that the
edge detectors highlight any luminance
discontinuity regardless of the general topology
of the image, while the boundary tracer is
designed to delineate closed regions possessing
Fig. 14. Calculation of the objective function which some distinguishing features. Both methods can
quantifies the discrepancy between the be implemented for assessment of the contact
calculated Laplacian contour of the drop (1) angle, however, in our opinion, the later one has
and the experimental points (2)
the advantage of an implicit parameterization of
Over these and other problems, the ADSA the revealed contour pixels by their ordering.
method has undergone various improvements Several edge detectors have been proposed
since it had been presented in its initial version. in literature for enhancing and detecting edges in
In [139], a streamlined version of the images. The simplest technique for determining
development of ADSA over the past several the contours is the spatial differentiation of the
decades is presented to illustrate its validity and luminance function. Among the most used
range of utility. Numerous related approaches contour detection algorithms using spatial
have been proposed, similar in tasks to the differentiation are the Sobel operator [155], the
ADSA method [140–148]. Factors influencing Roberts cross operator [156], the Laplacian edge
precision of sessile drop method when used for detector [157], and the Prewitt edge detection
determination of surface tension and contact technique [158]. For instance, the Sobel edge
angle are analysed in [149, 150]. detector was used for the axisymmetric drop
Basics of image processing techniques for shape analysis (ADSA) in [155, 160].
determination of drop contours. The algorithms mentioned above have many
As follows from the above, the methods similarities. To outline briefly the idea behind
intended for determination of surface tension, these algorithms, consider the Laplacian edge
contact angle, surface energy of solid, and other detector, which has an advantage of
values accessible through the analysis of the independency on the boundary direction. The
sessile drop shape require the drop contour to be Laplace function can be presented in the
singled out in the image. Contours characterise following form:
the physical extent of objects, and their accurate
detection plays a key role in problems related to d2 f d2 f
image analysis. These problems arise in L  x, y    . (68)
d x2 d y2
computer vision and its applications related to
pattern recognition in various fields ranging from
For discrete functions of two variables,
cartography and processing of aerial and space
which represent images, the second derivatives
surveying data [151] to tomography-based
can be approximated by finite differences with
techniques for medical diagnostics [152–154].
the coefficients written as a matrix function.
The contour of the digital image is composed
For instance, the Sobel differentiating operator
by its pixels, which are located in the area of a
can be represented in matrix form by two
sharp change in the luminance function. The
matrix transformations:
operation performing selection of contours

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1 2 1 1 0 1 edge. Owing to its optimality to meet with these

criteria and the simplicity of process for
P 0 0 0 ; Q  2 0 2 . (69)
implementation, the Canny algorithm became
1 2 1 1 0 1 one of the most popular edge detectors. It
organizes the points at which image brightness
Then the value of the gradient can be changes sharply into a set of curved line
calculated according to the expression: segments. In particular, this method was
employed for extracting the edge of the sessile
G p2  q2 , (70) drop, which was then used in comparative
evaluation of four different techniques designed
to measure apparent contact angles of non-
where p, q are results of operations (67) on the axisymmetric drops [162]. However, various
image. factors like reflection of light, shadows, or
Among the edge detection methods illumination heterogeneity result in
developed so far, one of the most strictly defined discontinuities of the detected contours, which
methods is the Canny edge detection algorithm put obstacles when using these contours in fitting
that provides good and reliable detection [161]. procedures. An example of edges detected using
As a purpose, Canny have formulated three Canny algorithm is illustrated in Figs. 15 a, b.
criteria to be met by an optimal operator for step Current state and prospects of further
edge detection: good detection, good improvement of edges detection algorithms are
localization, and only one response to a single discussed in [163].

Fig. 15. An example of edges detected using Canny algorithm. The raw half tone image (a) and the extracted
contours (b). Note that many contours are open-ended

Consider now algorithms that realise contour pixel again. The image pixels it walked over will
tracing. One of the earliest approaches to be the contour of the pattern.
extracting contours in the image was the square
tracing algorithm (STA). It was quite simple and
capable of extracting contours only when the
image does not contain half tones and can be
represented by a binary pattern. Its idea is
traditionally explained by example of the
ladybird’s2 trajectory when it moves along the
edge of continuous area (Fig. 16). The algorithm
begins from locating the image pixel that
belongs to the boundary (the start pixel). The
ladybird standing on the start pixel turns left, and
every time it finds herself standing on a white
pixel, turns right, until it encounters the start
Fig. 16. Extraction of contour in binary image using
2
Ladybird (Coccinellidae) is a widespread family of small the square tracing algorithm
beetles ranging in size from 0.8 to 18 mm.

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INSTRUMENTATION FOR CONTACT

ANGLE MEASUREMENTS USING THE
SESSILE DROP METHOD
As noted above, at present the research and
technological areas where the measurement of
surface wettability and contact angle is highly
important are rapidly expanding. In response to
this tendency, manufacturers offer nowadays a
broad line of instruments, which meet a wide
variety of technical requirements: from the
simplest models of primary and educational level
to perfect highly automated systems suitable for
Fig. 17. Contour tracing using Moore algorithm. The scientific research of the highest complexity
traced contour pixels are shown shadowed (Table). Technical characteristics of several
Another approach to tracing the contours is contact angle analyzers produced by the well-
known as the Moore neighbour tracing algorithm known manufacturers are considered below in
[164]. To explain this method, we define first an more detail.
important concept of the Moore neighbourhood Among the manufacturers indicated in the
of a pixel. The Moore neighbourhood, M(p) (also above Table, the ramé-hart instrument co.
known as the 8-neighbors or indirect neighbours) deserves special attention. It was this US-basing
is the set of eight pixels around the central pixel company, which developed the world’s first
p. After having located the start pixel, s at the mass produced contact angle goniometer ramé-
boundary of the image, the algorithm proceeds hart Model A100 (see Fig. 9). This instrument
with testing in series the pixels that belong to its and its successor, Model 100-00, enjoyed a
Moore neighbourhood, as shown in Fig. 17. The useful lifespan of nearly fifty years with
general idea consists in the following: every time thousands units produced during this time. Many
the pixel under test appeared to be the image hundreds of them are still in use today
pixel (grayed), the “ladybird” backtracks (i.e. throughout the world.
goes back to the white pixel previously visited), Currently, ramé-hart produces about a dozen
then goes around the new central pixel in a of different models and their modifications.
clockwise direction, visiting each pixel in its Among the entry-level instruments, the device
Moore neighbourhood until hits another grayed that attracts attention is the goniometer
pixel. The algorithm terminates when the start Model 90 CA Edition [168], which is optimized
pixel is visited for a second time. for contact angle measurement. The 90 CA Edition
Actually, both the above algorithms are includes a DROPimage CA as well as a
impractical for extracting contours of real images German-made SuperSpeed U3 series digital
obtained with the video camera, as their camera with a resolution of 1920×1080 pixels,
boundaries inevitably contain half tones. These LED illumination (fiber optic upgrade available),
algorithms were described here just to give sample alignment stage and high modulus optical
understanding of general principles of contour bench.
detection. Realistic procedures should involve The professional instrument, Model 790
preliminary enhancement of image contrast, (Fig. 18) [169] is a research-grade device, which
smoothing noise, and detection (or tracing) the is one of the most powerful and feature-rich in
contours with more elaborated algorithms this class equipment. This model includes
capable of managing the half-tone pixels. An automated tilting, automated dispensing,
example of practical approach to measuring the oscillation, high-speed camera (210 fps),
contact angles from digital images of liquid environmental control from –50 °C to 300 °C,
drops is described, for instance, by M. Mirzaei and optical overhead imaging. Powered by
[165]. For a comprehensive learning the subject DROPimage Advanced software, Model 790 can
of contour extraction techniques, readers are measure static contact angle, dynamic contact
advised to refer to dedicated monographs angle, surface energy, work of adhesion, surface
[166, 167]. tension, interfacial tension, surface dilatational

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 Surface wetting and contact angle: basics and characterization
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viscosity and elasticity. The system is a complete on the optical bench. An evident advantage of
turn-key setup and ships ready to plug-and-play. this design is its easiness in adaptation to
Conceptually, the contemporary ramé–hart different measurement conditions and research
instruments inherit the classic design of the tasks, which can be accomplished simply by
Model A100, where different units were installed replacing correspondent units.

Table. Commercially available instrumentation for contact angle measurements

Manufacturer’s name / brand, location, web site Instrument models

ramé-hart instrument co. Models 90, 210, 250, 260, 290, 400, 500,
19 Route 10 East, Suite 11,Succasunna, NJ 07876 USA 590, 790.
http://www.ramehart.com
KRÜSS Scientific. DSA 25, DSA 100
Hamburg, Germany (different modifications).
https://www.kruss-scientific.com/en/
Biolin Scientific/Attention®. Optical tensiometers:
Headquarter in Gothenburg, Sweden Theta Flow, Theta Flex
https://www.biolinscientific.com/attension (different modifications)
Kyowa Interface Science Co. Ltd. Contact angle meters. DropMaster series:
5-4-41 Nobitome, Niiza-City, Saitama 352-0011, Japan DMe -211, DMs -401, DMo (series)
Tel: +81-48-483-2629, Fax: +81-48-483-2702 DMo –WA (series)
Email: [email protected] Devices:
https://www.face-kyowa.co.jp/english/ PCA-4, MCA-4; FAMAS Software
Holmarc Opto-Mechatronics Pvt. Ltd. Models:
B.7, HMT Rd, Industrial Estate, P.O, Kalamassery, Kochi, HO-IAD-CAM-01, HO-IAD-CAM-01A,
Kerala 683503, India HO-IAD-CAM-01B, HO-IAD-CAM-01BC,
https://holmarc.com/contact_angle_meter.php HO-IAD-CAM-LLE
DataPhysics Instruments. OCA series– Optical contact angle
DataPhysics Instruments GmbH, Raiffeisenstraße 34, 70794 measuring and contour analysis systems:
Filderstadt, Germany OCA 15EC, OCA 15LJ, OCA 25
https://www.dataphysics-instruments.com/
Ossila. Product Code L2004A1
Solpro Business Park, Windsor Street, Sheffield, S4 7WB Price £1,500.00 (57000 UAN)
+44 (0)114 2999 180. Email: [email protected]
(Founded in 2009 by organic electronics research scientists)
https://www.ossila.com/pages/about
Open Science LLC NPK. Goniometer LK-1
143444, Moscow region, Krasnogorsk, Russia.

Another world leader in development of possibilities. Due to this high level of

instrumentation intended for surface studies, automation, the DSA 100 is an optimal choice as
KRÜSS Scientific, places particular emphasis on the instrument for quality control, for instance, in
the greatest possible user comfort for their the analysis of cleaned, pre-treated or coated
customers. One of their most elaborated devices, solid materials. A simpler device from the same
Drop Shape Analyser Model DSA 100, manufacturer is the Drop Shape Analyzer
combines high scientific demands with ever- DSA30 model. In its basic version, the DSA30 is
simpler operating concepts achieved due to intended for the accurate determination of
intense use of computer control and dedicated wettability using the static contact angle
software for data analysis [170]. This instrument, measurements. Fast and simple exchange of
equipped with the ADVANCE software, solid samples and dosing liquids makes this
perfectly exemplifies this approach: the system instrument especially convenient for evaluating
measures the contact angle and surface free the effectiveness of cleaning procedures or the
energy (SFE) using easy to create measuring quality of coating and wetting processes.
procedures with the highest degree of automation Optionally, this instrument can be equipped with

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 G.V. Beketov, O.V. Shynkarenko
______________________________________________________________________________________________

accessories for wetting measurements at higher involved, in particular, into formation of

temperatures. The range of its applications can interconnecting solder bumps for assembling the
be enlarged with various available upgrade multielement hybride focal planes, which are
options. More details on its performances are employed as sensor devices for infrared vision.
outlined in [171]. The non-reactive wetting characteristics are of
Performances of other instruments listed in crucial importance in developing the diagnostic
Table are generally intermediate between the kits for biomedical applications, which are based
simplest and most advanced instruments on the enzyme-linked immunosorbent assay
discussed here. We refer the readers to the (ELISA) principles.
provided links for more details.
CONCLUDING REMARKS
In this review, we presented a cumulative
coverage of different issues related to wettability
and its investigation. The discussed topics
include the basic concepts of wetting as a
physical phenomenon, the most common
methods for its characterisation (with an
emphasis on the sessile drop technique), and the
general overview of contemporary instruments
for wettability measurements. A distinctive
feature of these measurements as a tool for
surface research is that they provide a direct
quantitative assessment of the interactions
Fig. 18. The ramé-hart Model 790 contact angle
goniometer between the surface under study and the wetting
liquid, expressed either through surface forces or
through surface energy. The wettability
measurements can be performed in real time and
under different experimental conditions,
allowing the study of various transient
phenomena often encountered during wetting.
They can also contribute to investigation of
interfacial chemistry of solids by the use of
wetting fluids of different physical properties
and/or incorporating different functional groups.
Typical applications of wettability measure-
ments, usually in combination with the surface-
sensitive analytical techniques are aimed at
assessing surface properties relevant to a specific
Fig. 19. The prototype contact angle analyser research purpose or application. The efficiency
designedt at V.Ye. Lashkariov Institute of of this method is evidenced by continuously
semiconductor physics (NASU) growing area of its applications over the past
decades.
A prototype contact angle analyser intended
The topics outlined in this review were
for testing technical solutions and software is
restricted mainly to theoretical and experimental
currently under development at V.Ye. Lashkariov
approaches concerning stationary measurements
Institute of Semiconductor Physics (NASU)
on a homogeneous surface. Many other
(Fig. 19). Similarly to the ramé-hart instruments,
significant issues that go beyond the basic
it implements a modular design including the
concepts were left outside the consideration. To
optical bench and replaceable modules for
guide the reader interested in deeper
installing the samples under study. It is assumed
understanding of the subject, we refer him to
to be used, depending on the task at hand, to
some of these issues that complement the scope
study the processes of both non-reactive and
of this review.
reactive wetting. The reactive wetting is

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 Surface wetting and contact angle: basics and characterization
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– The surface of a solid, like a liquid, is stationary conditions can be influenced by

characterized by increased potential energy surface roughness, inhomogeneous wetting
compared to the volume and presence of characteristics, or other factors, which can lead
corresponding surface tension. However, in to ambiguous results. This problem can be
contrast to a liquid, the bulk stiffness of a solid mitigated by resorting to a technique that uses
prevents it from changing its geometry under the dynamic contact angle measurements. In this
surface tension forces. Therefore, in general, the approach, the volume of the drop is first
surface tension of solids cannot be measured gradually increased by the supply of liquid, and
directly (with the exception of specially prepared then decreased, with the corresponding sequence
specimens). The problem can be resolved by the of drop images being recorded. The following
measurements of wettability, which, in addition analysis takes into account both the advancing
to the interaction forces between a liquid and the and receding contact angles, as well as the
surface of a solid (or other liquid), also make it observed hysteresis between them [87, 176–179].
possible to estimate the surface energy of solids There are many other important issues
[172, 173]. related to wetting. They include the effect of
– Besides the ADSA method for analysing surface diffusion and the effect of surfactants,
the results of wettability measurements, another reactive wetting, interfacial chemical reactions,
related technique was proposed for extraction of interdiffusion and other irreversible processes
contact angle based on the sessile drop between a wetting liquid (including melts) and a
experiments. This technique, termed Theoretical solid surface. Most of them, as being
Image Fitting Analysis (TIFA), relies on complicated by involvement of additional
processing the image directly at a pixel level, concomitant effects apart from wetting, were not
which eliminates the need for an independent touched upon in this review. On these and other
edge detection procedure and simplifies the issues, we refer the reader to more specialized
algorithm as a whole [174, 175]. literature.
– As has long been known, the
measurements of the contact angle under

Змочуваність поверхні та кут змочування: фізичні основи та методи дослідження

Г.В. Бекетов, О.В. Шинкаренко

Інститут фізики напівпровідників ім. В.Є. Лашкарьова Національної aкадемії наук України
пр. Науки, 41, Київ, 03028, Україна, [email protected]

Характеристика змочуваності поверхні має вирішальне значення у багатьох галузях науки і технології,
від видобувної промисловості до створення сучасних функціональних матеріалів і виробів біомедичного
призначення. Зростаючий інтерес до явищ, пов’язаних зі змочуваністю, стимулює стрімке зростання
дослідницької діяльності в цьому напрямку. Метою представленого огляду є послідовне висвітлення низки
питань, пов’язаних з природою змочуваності та методами її дослідження. В ньому розглядаються базові
концепції змочуваності як фізичного явища, методи для кількісного визначення її характеристик та
сучасний рівень приладів для визначення характеристик змочуваності.
У першому розділі розглядаються фізичні основи змочуваності. Міжмолекулярні взаємодії, якими
обумовлюється змочуваність, класифікуються залежно від їхньої природи. Так, обговорення
міжмолекулірних взаємодій, у яких беруть участь полярні молекули, охоплює взаємодії між молекулами, які
мають постійний дипольний момент, включаючи особливий механізм взаємодії між молекулами, який
виникає, коли молекули можуть вільно обертатися. Розгляд взаємодій, що відбуваються в результаті
поляризації молекул, включає взаємодії між іонами та незарядженими молекулами, взаємодії Дебая та
дисперсійні сили Лондона. Водневі зв’язки розглядаються як окремий тип взаємодій.
У другому розділі розглядаються питання, які стосуються поверхневого натягу та його впливу на
форму поверхні рідини, яка знаходиться у контакті з твердим тілом. Обговорюється взаємозв’язок між

ISSN 2079-1704. Him. Fiz. Tehnol. Poverhni. 2022. V. 13. N 1 29

 G.V. Beketov, O.V. Shynkarenko
______________________________________________________________________________________________

величиною поверхневого натягу та значенням контактного кута змочування. Розглядається рівняння Юнга-
Лапласа, яке визначає форму краплі рідини, яка лежить на твердій поверхні.
Третій розділ присвячений експериментальному визначенню характеристик змочуваності поверхні та
теоретичним засадам відповідних методів вимірювання. Особлива увага приділяється методу, відомому в
англомовній літературі як метод ADSA, який засновується на аналізі форми краплі, що лежить на поверхні.
Коротко розглядаються чисельні методи виявлення геометричних структур на оцифрованих зображеннях,
які призначені для отримання кількісних даних про силу поверхневого натягу та значення крайового кута
змочування.
У четвертому розділі наводиться огляд приладів для дослідження змочуваності та вимірювання
крайового кута, які серійно випускаються приладобудівельними підприємствами у різних країнах світу.
Представлений також прототип приладу аналогічного призначення, створений у ІФН НАНУ.
Ключові слова: змочуваність, міжмолекулярні взаємодії, поверхневий натяг, крайовий кут змочування,
крапля, що лежить, рівняння Юнга-Лапласа, аналіз форми вісесиметричної краплі, гоніометрія крайового
кута змочування, виділення контурів на цифрових зображеннях, методи оптимізації

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