AUTHOR:

White Paper SUSANNA LAURÉN, PHD

BIOLIN SCIENTIFIC

Contact angle – What is it

and how do you measure it?
Contact angle – What is it and how do you measure it? 2

Contact angle – What is it

and how do you measure it?
Contact angle, θ (theta), is a quantitative measure of wetting of a solid by a liquid.
The behavior of single drop on a surface tells you a lot about the properties of your solid.

The most obvious example is the application of different types of coatings and surface
treatments. For example, if contact angle between the paint and the surface to be painted
is high, that will lead to poor spreading and non-uniform coating. Contact angles can
also be used to check if a surface treatment has been successful. Plasma treatment is
often utilized to improve the adhesion between the substrate and the coating to be
applied. The low contact angle between water and treated substrate indicate the success
of the surface treatment.

In practice, a drop of liquid is placed on a surface and the contact Contact angle basics
angle is measured as shown in Fig.1. Low contact angle values, i.e. The contact angle is geometrically defined as the angle formed
below 90°, are related to good wetting whereas high contact angle by a liquid at the three-phase boundary where a liquid, gas, and
values, above 90 °, indicate poor wetting. When the contact angle solid intersect. There are three different forces acting on this
is 0°, the surface is said to wet completely. If the liquid applied three-phase contact point between solid, fluid and fluid as shown
on the surface is water, terms hydrophilic and hydrophobic are in Fig. 2.
used, respectively.

θ < 90 θ > 90

gas gas
liquid
liquid θ θ

solid solid

Figure 1 Figure 2
A drop of water on hydrophilic and hydrophobic surfaces Three-phase contact point where solid, fluid and fluid meet

The γlv is the surface tension of a liquid, γsl is the interfacial tension
This white paper gives a very practical tutorial for contact angle between the solid and liquid and γsv is the surface tension of the
theory and measurement techniques. Concepts like static, dynamic, solid i.e. surface free energy.
and roughness corrected contact angle are explained and linked
to the real-life application. Different measurement methods are The well-known Young´s equation describes the balance at the
reviewed and compared to help you to choose the best method three-phase contact.
for your surface. At the end of the white paper, contact angle
measurements on more advanced substrates, like fibers and γsv = γsl+ γlvcosθY (1)
powders are discussed.
The interfacial tensions, γsv, γsl, and γlv, form the equilibrium
contact angle of wetting, many times referred to Young´s contact
angle θY.
Contact angle – What is it and how do you measure it? 3

Young’s equation assumes that the surface is ideal. This means role, as the droplet should easily roll-off the surface. Hysteresis
that it is flat, rigid, perfectly smooth, and chemically homogenous. is however also important in other situations such as intrusion of
Furthermore, it assumes that the system is stable i.e. there is no water into porous media, coating, and adsorption at liquid/solid
interaction between the liquid and the substrate. As neither of the interface.
above-mentioned criteria is fulfilled in real life, advancing and
receding (i.e. dynamic) contact angle measurements are often Roughness corrected contact angles to separate
performed. Surface roughness can also be corrected by measuring the effect of roughness from surface chemistry
roughness corrected contact angle. Contact angles are thus divided Contact angles are affected by roughness. Surfaces with the same
into three categories; static, dynamic and roughness corrected. chemical composition but different roughness will have different
contact angles. Two wetting states can be distinguished; Wenzel
Static contact angles – quick and easy and Cassie-Baxter. Cassie-Baxter refers to a situation where
Static contact angles are measured when the droplet is sitting droplet sits on a rough surface so that air pockets are formed in
on the surface and the three-phase boundary is not moving. between the drop and the substrate (see Fig. 3 a). When, the
Static contact angles are by far the most measured wettability whole surface area is wetted, and no air pockets are formed
values. It is most suitable for relatively smooth and homogenous (see Fig. 3 b), surface roughness can be related to the contact
surfaces. Static contact angles are also used to define the surface angle by Wenzel equation [5].
free energy (i.e. surface tension of solid) of the substrate. Static
contact angle offers a quick, easy and quantitative measurement cos θm=r cos θY (2)
of wettability. They are thus utilized in quality control and in
various research and product development, ranging from printing , where θm is the measured contact angle, r is the roughness ratio
to oil recovery and coatings to implants. Static contact angle and θY is the Young contact angle.
measurement is based on Young’s equation which assumes that
The roughness ratio is defined as the ratio between the actual and
interfacial forces are in thermodynamically stable. In practice,
projected solid surface area (r = 1 for a smooth surface and > 1 for
however, there exist many metastable states of a droplet on a
a rough surface). It is important to note that the Wenzel equation
solid, and the observed contact angles are not equal to Young
is based on the assumption that the liquid completely penetrates
contact angle. Because phenomenon of wetting is not just a static
into the roughness grooves (as in Fig. 3b). If you are more
state, other contact angles i.e. dynamic and roughness corrected
interested in the theories behind the roughness measurements and
are measured.
contact angle correction, please download the white paper “The
Attension Theta optical tensiometer with 3D topography module
Dynamic contact angles and contact angle
for roughness corrected contact angles”.Roughness corrected contact
hysteresis for more information angles are especially useful when different types of surface
When the three-phase boundary is moving, dynamic contact angles
can be measured, and are referred to as advancing and receding
angles. As the terms imply, advancing contact angle is measured
when the droplet front is advancing and receding when the droplet
Liquid
front is receding. On an ideal surface, these two values are close Liquid
to each other. However, most often, the measured contact angle
depends on the direction on which the contact line is moving.
Contact angle hysteresis is the difference between the advancing Figure 3
and receding contact angles. Contact angle hysteresis arises Droplet on (a) Cassie-Baxter (b) Wenzel state

mostly from the chemical and topographical heterogeneity of the

surface, solution impurities absorbing on the surface, or swelling,
rearrangement or alteration of the surface by the solvent [1, 2].
treatments are done. Surface treatments such as plasma treatment
Advancing and receding contact angles give the maximum and
affect both the chemistry and the roughness of the surface. By
minimum values the static contact angle can have locally on the
correcting the contact angles measured, it is possible to separate
surface. The difference between advancing and receding angles
the effect of roughness on the contact angle. Roughness corrected
can be as high as 50°.
contact angles can also be utilized to measure roughness corrected
Dynamic contact angles and contact angle hysteresis are utilized surface free energies. Surface free energy is the chemical property
to study the heterogeneity of the surface. It has become a popular of the solid. As static contact angles do not take the roughness
topic because of the recent interest in superhydrophobic and into account, the surface free energies calculated are affected
self-cleaning surfaces [3, 4]. Criteria for the surface to be super­ by the surface roughness. Thus, chemically the same material
hydrophobic is that the static contact angle is above 150° and with different roughness levels will lead to different surface free
that the contact angle hysteresis is less than 10 degrees. energies if contact angles are not corrected for roughness. This can
In the applications where superhydrophobicity is utilized, such lead to misinterpretation of the results.
as self-cleaning, the contact angle hysteresis plays an important
Contact angle – What is it and how do you measure it? 4

Measurement methods This makes the placement of the droplet less critical as the optical
Contact angles are typically measured by using either optical or path is not changing. The method is described in a standard [7].
force tensiometers. With the optical method static, dynamic and
roughness corrected contact angles can be obtained whereas force
Recending
tensiometry can only be used for the dynamic measurements. contact angle, θR
Optical methods include the sessile drop (static), needle method,
tilting (dynamic) and meniscus methods. The force-based
measurement is called Wilhelmy method. In this section, a short Advancing
contact angle, θA
description of each method is given.
Tilting angle
Sessile drop
A sessile drop is the most used contact angle measurement Figure 5
Measuring advancing and receding angles with the tilting method
method. In practice, a droplet is placed on the solid surface and
an image of the drop is recorded. The static contact angle is then
defined by fitting Young-Laplace equation around the droplet,
although other fitting methods such as circle and polynomial
can also be used. Sessile drop method is also used to calculate Meniscus method
roughness corrected contact angles. It is also possible to measure contact angles by a meniscus method.
This method is especially useful when measuring thin objects
Needle method like rods and fibers down to 7 um. In this method, the sample is
In the needle method, a small droplet is first formed and placed immersed into liquid as shown in Fig 6. When the sample is pulled
on the surface. The needle is then brought close to the surface from the liquid a meniscus is formed and the contact angle is
and the volume of the droplet is gradually increased while optically measured. The contact angles measured with the meniscus
recording the contact angle at the same time. This will give the method cannnot be directly compared to static nor dynamic ones
advancing contact angle. The receding angle is measured the as the wetting conditions are different. Also, angles above 90°
same way but this time, the volume of the droplet is gradually can not be measured.
decreased. The principle is shown in Fig. 4. The method is also
described in a standard [6].

Advancing CA Recending CA
Figure 4 Figure 6
Advancing and receding angles by needle method Meniscus measurement principle (redraw with contact angle fitting
and proper container)

Tilting method Wilhelmy method

In Fig. 5, the principle of the tilting method is shown. The droplet is Dynamic contact angles can be measured by using force tensiometry
placed on the substrate which is then gradually tilted. The advancing and the Wilhelmy method. Force tensiometer measures the mass
angle is measured at the front of the droplet just as the droplet affecting to the balance when a solid sample is brought in contact
starts to move. The receding contact angle is measured at the back with a test liquid. The contact angle can then be calculated by using
of the droplet, at the same time point. With this method, the the equation (3) when the surface tension of the liquid (γl) and the
roll-off or sliding angle can also be determined. The roll-off angle perimeter of the sample (P) are known.
refers to a tilting angle at which the droplet starts to move. A low
roll of angle is related to low contact angle hysteresis. Wetting force = γl Pcosθ (3)

The tilting can be done either by tilting the sample stage or by In Fig. 7, a complete contact angle measurement cycle is presented.
tilting the whole instrument. When the whole instrument is tilted, As can be seen, with the force tensiometry the measured contact
the camera is tilted along with the sample, so the software sees angle is always dynamic since the sample is moving against the
the substrate being horizontal throughout the experiment. liquid.
Contact angle – What is it and how do you measure it? 5

When the sample is immersed in the liquid the advancing contact Powders
angle is recorded and when the sample is emerging the receding Contact angles on powders can be measured by using sessile drop
contact angle is measured. measurement on the compressed powder tablet or by using the
force tensiometer with the Washburn method. When compressed
σ tablets are measured, it can behave like the absorbing substrate
F/Lr Advancing if the powder is hydrophilic or the droplet can stay on the surface
4 Receding
if the powder is hydrophobic. The main issue with the tablet
F/La compression is that the surface properties of the tablets can vary a
Force/wetted lenght

3 lot, which can lead to misinterpretation of the results. Roughness

1 2 3 4 on the tablet surface could be taken into account by measuring
1 2
the roughness corrected contact angle.
0 Depth
To study loose powders, the Washburn method must be utilized.
Figure 7
Wilhelmy method In this method, the powder is packed in a cylinder with holes at
the bottom (Fig. 8). The holder is slightly immersed into measure-
ment liquid and the liquid uptake as a function of time is recorded.
The time it takes for the liquid to penetrate is related to contact
angle through Washburn equation. As the method is based on the
Comparison of the contact angle measurement
capillary action, it is limited to below 90° contact angles.
techniques
The optical tensiometer is the main measurement method for
contact angle since measurement of both static and dynamic sleeve
contact angles are possible. It is also possible to study the homoge- (powder holder)
neity of the sample by measuring contact angle on several different
powder Absorption
places on the same sample. This is not possible with the Wilhelmy of liquid
method since the calculated contact angle is the average over the
whole immersed area. For the same reason, in Wilhelmy method,
the sample must be homogenous on both sides. [8] Liquid

Contact angle measurements of special samples Figure 8

Washburn method
Although contact angle measurement is many times quite
straightforward, there are some special cases that require more
careful planning for the measurement set-up. These include fibers
and powders.

Fibers
Fibers and other thin objects can be measured by using optical
tensiometry equipped with picoliter dispenser, with meniscus Conclusions
method or with force tensiometry using Wilhelmy method. Contact angle measurements offer a quick and versatile method
With the optical tensiometer, the picoliter dispenser can produce to study wettability of the surface. As wettability of the surface
droplets with the diameter of about 30 µm in air. With special can be related to phenomena such as adhesion and spreading,
optics and a high-speed camera, it is possible to take an image it offers a very useful tool to the variety of industries. Although
of this small droplet and the contact angle can be determined in static contact angle measurements are by far the most used,
a similar fashion than by using microliter size droplets. Meniscus measuring advancing, receding and roughness corrected contact
measurement can also be used for fibers. If the fiber is thin angles are also widely utilized. These methods can offer additional
(below 200 µm) a special optics is required. information on the properties of the solid surface. With several
different measurement methods available, the method has to be
Force tensiometer, on the other hand, can be used by utilizing a chosen based on the sample and application at hand.
special holder for the fiber. Down to 7 µm, fibers can be measured.
It should be noted that the measurement with picoliter droplets
leads to static contact angles whereas Wilhelmy method is a
dynamic method, giving both advancing and receding angle. The
contact angle measured with the meniscus method is somewhere
in between and cannot be directly compared with contact angles
measured with other two methods.
Contact angle – What is it and how do you measure it? 6

References

1. A. Marmur, “Thermodynamic aspects of contact angle hysteresis”, Advances in Colloid

and Interface Science 50 (1994), 121-141.

2. l. Gao and T. J. McCarthy, “Contact angle hysteresis explained”, Langmuir 22 (2006),

6234-6237.

3. L. Feng, S. Li, Y. Li, H. Li, L. Zhang, J. Zhai, Y. Song, B. Liu, L. Jiang and D. Zhu, “Super-
hydrophobic surfaces: From natural to artificial”, Advanced Materials 14 (2002), 1857-1860.

4. R. Blossey, “Self-cleaning surfaces – virtual realities”, Nature Materials 2 (2003), 301-306.

5. R.W.Wenzel, “Resistance of solid surfaces to wetting by water”, Industrial and engineering

chemistry 28 (1936) 988.

6. International standard. (2017). Paints and varnishes – wettability – Part 6: Measurement of

dynamic contact angle (ISO 19403 – 6:2017(E)). Switzerland. ISO.

7. International standard. (2017). Paints and varnishes – wettability – Part 7: Measurement of

contact angle on a tilt stage (roll-off angle) (ISO 19403 – 7:2017(E)). Switzerland. ISO.

8. L.M. Lander, L.M. Siewierski, W.J. Brittain, and E.A. Vogler, “A systematic comparison of
contact angle methods”, Langmuir 9 (1993), 2237-2239.

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