Advances in Colloid and Interface Science 210 (2014) 2–12

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Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Electrowetting — From statics to dynamics

Longquan Chen, Elmar Bonaccurso ⁎
Experimental Interface Physics, Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt, Germany

a r t i c l e i n f o a b s t r a c t

Available online 10 October 2013 More than one century ago, Lippmann found that capillary forces can be effectively controlled by external
electrostatic forces. As a simple example, by applying a voltage between a conducting liquid droplet and the
Keywords: surface it is sitting on we are able to adjust the wetting angle of the drop. Since Lippmann's findings,
Wetting electrocapillary phenomena – or electrowetting – have developed into a series of tools for manipulating
Electrowetting microdroplets on solid surfaces, or small amounts of liquids in capillaries for microfluidic applications. In this
Static & dynamic capillary phenomena
article, we briefly review some recent progress of fundamental understanding of electrowetting and address
Electrocapillarity
some still unsolved issues. Specifically, we focus on static and dynamic electrowetting. In static electrowetting,
we discuss some basic phenomena found in DC and AC electrowetting, and some theories about the origin of
contact angle saturation. In dynamic electrowetting, we introduce some studies about this rather recent area.
At last, we address some other capillary phenomena governed by electrostatics and we give an outlook that
might stimulate further investigations on electrowetting.
© 2013 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Wetting fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Contact angle and contact angle hysteresis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Contact angle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Contact angle hysteresis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Wetting dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.1. Fast wetting stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.2. Slow wetting stage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3. Static electrowetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. The Young–Lippmann equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. DC electrowetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.1. Contact angle hysteresis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.2.2. Polarity effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. AC electrowetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.1. Why AC? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.2. Frequency dependence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.3.3. Hydrodynamic flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.4. Contact angle saturation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Abbreviations: AC, alternating current; DC, direct current; EWOD, electrowetting on dielectric; HD, hydrodynamic (model); MK, molecular kinetic (theory); A, area (m2); C, capacitance
per unit area (F/m2); E, electric field strength (V/m); F, force (N); H, drop height (m); H⁎, characteristic drop height (m); L, characteristic length (m); LC, capillary length (m); R, drop
wetting radius (m); R⁎, characteristic drop radius (m); R0, initial drop radius; T, absolute temperature (K); U, contact line velocity (m/s); U⁎, characteristic contact line velocity (m/s);
V, voltage, applied potential (V); VS, saturation voltage (V); Vth, threshold voltage (V); Veff, effective voltage (V); c, coefficient; d, thickness (m); f, frequency (Hz); f0, molecular jump
frequency (Hz); fC, critical frequency (Hz); g, gravitational acceleration (m/s2); kB, Boltzmann constant; l, slip length (m); t, time (s); α, wetting exponent; γ, surface tension (N/m);
γLS, liquid–solid interfacial tension (N/m); γSV, solid–vapor interfacial tension (N/m); ε, relative permittivity; ε0, free space permittivity; λ, molecular displacement (m); μ, viscosity
(Pa s); θeq, equilibrium contact angle; θ, contact angle; θA, advancing contact angle; θR, receding contact angle; Δθ, contact angle hysteresis; ρ, density (kg/m3); σ, conductivity (S).
⁎ Corresponding author at: Experimental Interface Physics, Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt, Germany. Tel.: +49
615116 2282; fax: +49 615116 2048.
E-mail address: bonaccurso@csi.tu-darmstadt.de (E. Bonaccurso).

0001-8686/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cis.2013.09.007
 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12 3

4. Dynamic electrowetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1. “Fast” dynamics of electrowetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2. “Slow” dynamics of electrowetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5. Other capillary phenomena governed by electrostatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5.1. Electro-coalescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5.2. Electrically assisted capillary wrapping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5.3. Electrostatic control of interfacial flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.4. Electric enhancement of heat and mass transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6. Conclusion and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction 2. Wetting fundamentals

Wettability is a key parameter to describe the chemical–physical
properties of a surface and is usually characterized by a very simple
method: measuring the angle of contact – or wetting angle – of a
droplet of a test liquid with the surface. Triggered by many industrial
applications, such as coating, printing, cleaning, or friction and wear
control, many chemical or physical methods have been developed to
control the wettability of surfaces [1–3]. Eventually, lyophilic,
superlyophilic, lyophobic and superlyophobic surfaces can be
fabricated in laboratory by modifying the surface chemistry and
introducing multiscale physical roughness [1–3]. Such surfaces
maintain their wetting properties over some time, but do not allow
for an active control of their wettability after being manufactured.
In practical applications, however, active control of the wettability
is more attractive. Indeed, smart approaches such as thermal tuning
[4,5], optical switching [6], as well as electrostatic controlling of
contact angles [7,8] have been developed. Among them, the
electrostatic method is the most popular one due to its real-time
actuation, fast response, long term reliability, and good stability of
the actuation.
During his works, Lippmann found that applying a voltage
between mercury and aqueous electrolytes allowed for controlling
the position of the mercury meniscus in a capillary. In 1875, he was
probably the first to report this electrocapillary phenomenon, which
is at the foundations of electrowetting [9]. He further proposed a
physical model and developed a number of applications. Later,
Möller [10], Frumkin et al. [11], Gorodetskaya and Kabanov [12],
Smolders [13], and Nakamura et al. [14] conducted contact angle
measurements at the mercury/metal-electrolyte interfaces. They
found that the contact angle decreased with applied potential, and
argued that the decrease of contact angle was due to the change of
interfacial energy [10–15]. However, Lippmann's discovery and the
other works did not attract much attention until the 1980s, when
the term electrowetting was coined and proposed for designing
display devices [16,17]. Since then, electrowetting started to develop
rapidly and nowadays it has been successfully applied in areas like
lab-on-chip systems [18–20], adaptive optical lenses [21], electronic
display technology [17,22], or mixing in microfluidic channels
[23,24]. In principle, electrowetting can be applied to drops sitting
on a bare electrode, or on thin dielectric layer on top of an electrode.
However, most of the recent electrowetting studies and applications
are carried out on dielectric, giving rise to the definition of
electrowetting-on-dielectric (EWOD).
In this review, we focus on the latest progress on some
fundamental aspects of electrowetting. In Section 2, we give a short
description of the basics of static and dynamic wetting. Section 3 is
devoted to static electrowetting. We will discuss the basic
phenomena in DC and AC electrowetting, as well as the contact
angle saturation (CAS) phenomenon. In Section 4, recent results
about fast and low speed electrowetting will be presented. Finally,
we briefly address some other interesting capillary phenomena
governed by electrostatics.
2.1. Contact angle and contact angle hysteresis
2.1.1. Contact angle
When a liquid drop is brought into contact with a solid surface, the
drop spreads on the surface to minimize the free energy of the system.
Eventually, the drop comes to rest on the surface in a minimum energy
state.q the drop size, R0, is smaller than the capillary length, LC, e.g. R0 ≪
If ffiffiffiffi
γ
LC ¼ ρg , with γ and ρ respectively the surface tension and the density
of the liquid and g the acceleration due to gravity, the gravity does not
distort the spherical drop shape and can thus be neglected [25]. This
condition is usually satisfied in all published electrowetting studies.
For chemically and physically homogenous surfaces, the drop in
equilibrium adopts a spherical cap shape, as shown in Fig. 1. The
equilibrium contact angle, θeq, near the contact line is determined by
the interfacial tensions, γLV, γLS, and γSV at the liquid–solid–vapor
interfaces.
γ SV −γLS
cosθeq ¼ ð1Þ
γ
Usually, γLV is denoted as γ for brevity. The above equation is
called Young's equation, in honor of Thomas Young who expressed
it with words in his work published in 1805 [26]. Young's equation
can be derived either from a mechanical perspective [1,3] or from
a thermodynamic perspective [27]. θeq is a useful parameter to
characterize the wettability of surfaces, as one can easily relate the
contact radius R to θeq with
2 31=3
6 4 7
R ¼ R0 sinθeq 4 2  5 : ð2Þ
1− cosθeq 2 þ cosθeq
Taking the limit as θeq → 0°, we find R → ∞ which means the liquid
tends to wet the surface completely. While if θeq → 180°, we obtain
R → 0, which reflects that the surface repels the liquid extremely.
2.1.2. Contact angle hysteresis
Natural surfaces are decorated with physical roughness or chemical
moieties. The physical or chemical heterogeneity of surfaces leads to
deviations of the contact angle from the one predicted by Young's
equation. Pinning of the contact line of a wetting/dewetting drop due
Fig. 1. Sketch of a drop sitting on a solid substrate in equilibrium.
4 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
to surface heterogeneity causes an advancing contact angle θA/a
receding angle θR. The difference between θA and θR is defined as the
contact angle hysteresis Δθ [1,3,28,29]
Δθ ¼ θA −θR :
The contact angle hysteresis characterizes the homogeneity of
surfaces. Larger values of Δθ correspond to more pronounced surface
heterogeneities.
2.2. Wetting dynamics
When a drop touches a surface, the initial contact angle θ is largest
and close to 180°. Contact leads to a net horizontal capillary force of
γ(cos θeq − cos θ). This force drives drop wetting until equilibrium is
attained. Three sources resist drop wetting: (i) the kinetic energy of
the spreading drop, (ii) viscous dissipation within the liquid, and
(iii) contact line dissipation at the drop rim. In recent years, benefiting
from the development of high speed imaging techniques, dynamic
wetting has received considerable attention. Many studies showed
that the wetting proceeds in two stages, a “fast” early stage followed
by a “slow” later stage.
2.2.1. Fast wetting stage
For low viscosity liquids, the spreading velocity is very high just
after a drop touches a solid surface. The Reynolds number in
 
characteristic (*) experiments, Re ¼ 2 ρUμ R , compares the balance
of inertial and viscous forces and is larger than unity.  is the ratio
of the characteristic drop height H⁎ and the characteristic drop
radius R⁎, and is approximately unity. U⁎ is the characteristic velocity
of the moving contact line and is of order 1m/s [30–34]. μ is the liquid
viscosity. Thus, capillarity drives and inertia resists the fast wetting
stage. The change (release) of surface energy is transformed into
kinetic energy of the moving drop. Based on this energy balance,
Bird et al. found that the spreading radius R grows with time t
according to a power law [31,35].
α
R ¼ ct
c is a coefficient, while the exponent α is only related to the
wettability of the surface. It was experimentally found that α takes
values between 0.5 and 0.25 when θeq changes from ~0° to ~110°
[31–33,35,36]. Biance et al. carried out a scaling analysis based on
drop coalescence theory. They obtained a power law dynamics with
α = 0.5 for complete wetting [30], which was also observed by Winkels
et al. in molecular dynamics (MD) simulations [34]. Shanahan et al.
alternatively derived an inertial drop spreading model and found that
α takes values between 0.5 and 0.2 [33] depending on θeq. However,
all these models are at most semi-quantitative and do not capture all
details of the wetting dynamics.
2.2.2. Slow wetting stage
The inertial wetting stage lasts several milliseconds only, depending
on drop size. After this fast stage wetting crosses into a slow stage in
which drop spreading is resisted by viscous friction within the liquid
and by molecular friction near the contact line. Two types of models
were proposed, accounting for different mechanisms. The hydrodynamic
(HD) model considers viscous dissipation as the main resisting force.
Based on the introduction of a cutoff or slip length near the contact
line by Huh and Scriven [37] to get rid of the shear stress singularity,
Voinov derived a relationship between the dynamic contact angle θ
and the spreading velocity U [38].
 
3 3 μ L
θ ¼ θeq þ 9 U ln
γ l
L is a macroscopic characteristic length and is typically of the order of
the drop size. l denotes a microscopic slip length of the order of a
molecular size. If the surface is very lyophilic, e.g. θeq ≪ 1, one obtains
the growth of the spreading radius as a function of time [28,29,39].
ð3Þ
1=10
Ret ð6Þ
The above equation is sometimes referred to as Tanner's law [40].
The spreading could also be dominated by microscopic friction near
the contact line. In the molecular kinetic (MK) theory, the drop rim
moves via individual molecular jumps activated by thermal energy,
with an equilibrium frequency f0 and a displacement distance λ. The
relation between the spreading velocity and the dynamic contact angle
is given by [27,41]
2 2 3
γλ cosθeq − cosθ
U ¼ 2 f 0 λ sinh 4 5: ð7Þ
2kB T
kB is the Boltzmann constant and T is the absolute temperature. If the
term of sinh in Eq. (7) is small and the surface is very lyophilic, the
spreading radius can be simplified to [42]
1=7
Ret : ð8Þ
Blake et al. also combined both the effects of hydrodynamic stress
and molecular friction in the modified molecular kinetic theory [43].
Details about these wetting models can be found in a recent review by
Ralston et al. [44].
3. Static electrowetting
3.1. The Young–Lippmann equation
Fig. 2a shows the sketch of a typical electrowetting setup in which a
thin dielectric layer with thickness d is deposited between a conductive
drop and a flat electrode. The insulating layer is few micrometers thick
ð4Þ and is mainly used to prevent electrolytic processes at the interface
between drop and electrode. When a direct current (DC) voltage is
applied between the drop and the electrode, the contact angle θ decreases
with voltage V according to the so-called Young–Lippmann equation
C 2
cosθ ¼ cosθeq þ V ð9Þ
2γ
θeq is the equilibrium contact angle with zero applied voltage and is
determined by Young's equation. C is the capacitance per unit area. If
we treat the capacitor between the drop and the electrode as a plate
capacitor, C = ε0εd/d. εd and ε0 are the permittivities of the dielectric
layer and of vacuum, respectively. For alternating current (AC) voltage,
the root mean square (rms) value of the voltage – or effective voltage –
V2eff, is used instead of V2. The Young–Lippmann equation can be derived
by several approaches, as summarized, e.g., by Mugele and Baret [7]. A
rigorous thermodynamic derivation of Eq. (9) was also presented by
Bormashenko recently [45]. These theories can be understood from two
perspectives:
ð5Þ
Fig. 2. (a) Standard electrowetting setup. (b) Schematic plot of electrowetting curve.
 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
• Thermodynamic or electrochemical perspective. The classic model for
electrowetting was proposed by Lippmann [9]. In his experiments, a
voltage was directly applied between the electrode (mercury) and the
aqueous electrolyte. An electric double layer builds up spontaneously
at the liquid–solid interface, with charges of opposite polarity being
repelled from the interface. Thus, the liquid–solid interfacial energy,
γLS, decreases along with the new equilibrium contact angle, i.e. the
surface becomes more hydrophilic [46]. In EWOD, the thickness of the
dielectric layer is significantly larger than that of the electric double
layer [16,47], and hence electrostatic energy stored in it is the main
source to decrease γLS.
• Electromechanical perspective. Electrowetting could also be understood
considering the forces exerted on the liquid near the contact line, as
proposed by Jones et al. [48,49]. When a voltage is applied, the electric
field near the contact line attracts the free charges as well as the
polarized dipoles, which gives rise to a Maxwell stress on the liquid–
air interface. In order to balance this stress, the liquid–air interface
must decrease its curvature to reduce the Laplace pressure. Eventually,
a smaller apparent contact angle depending on the magnitude of the
applied voltage is attained.
A large amount of experimental studies showed that the Young–
Lippmann equation can well predict the contact angle when the voltage
is smaller than a critical value VS [7,8,23,47]. When V ≥ VS, the
electrowetting contact angle does not increase with applied voltage
(Fig. 2b), which is the effect known as contact angle saturation (CAS).
The physics underlying CAS is not fully clear yet. A detailed description
of the recent progress on theories about CAS is presented in Section 3.4.
3.2. DC electrowetting
3.2.1. Contact angle hysteresis
The phenomenon of contact angle hysteresis also plays a role in
electrowetting [50–52]. Typically, the contact angle hysteresis has two
main effects: first, electrowetting can start only when the applied
voltage is larger than a threshold value Vth [53–56]; second, the contact
angle hysteresis leads to different contact angles with the same applied
voltage, depending if the voltage is increasing or decreasing. This is
referred as irreversibility or hysteresis of electrowetting [50,57].
The existence of the threshold voltage Vth can be explained by
accounting for contact line pinning. Due to the natural heterogeneities
of real surfaces, the equilibrium contact angle has a value between
the receding and the advancing contact angle, e.g. θR b θeq b θA.
When electrowetting is initiated, the electrostatic force wants to
reduce the contact angle. However, the contact line will move only
if the electrostatic force exceeds the pinning force [50,51,58–60].
Balancing these two forces, Fréchette et al. predicted the threshold
voltage by [50]
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2γ   electrowetting curve since they interact more strongly with the Teflon
V th ¼ cosθeq − cosθA :
C
Thus, the threshold voltage can be decreased by using, e.g., low
contact angle hysteresis surfaces. Until then, the lowest threshold
voltages in electrowetting were reported in the range of 15–20 V [19].
In their paper, Fréchette et al. showed that nearly no threshold voltage
existed on an oil-impregnated polydimethylsiloxane (PDMS) surface
with only 1° contact angle hysteresis [50]. Eq. (10) also indicates that
Vth can be reduced by decreasing the interfacial tension γ. This was
achieved by changing the fluid around the drop from air to a liquid, as
liquid–liquid interfacial tensions are usually smaller than liquid–air
interfacial tensions [55,57,61]. Moreover, the contact angle hysteresis
in liquid/liquid/solid systems is also smaller than in liquid/solid/air
systems, as liquid–liquid friction is much smaller than liquid–solid
friction [61].
5
Similarly, the advancing/receding contact angle as the drop
spreads/recedes with increasing/decreasing applied voltage can be
modified by considering the effects of the contact line pinning force
[50,58]
2
V¼0 CV
cosθA or R ¼ cosθA or R þ ð11Þ
2γ
where θVA = 0
or R is the advancing/receding contact angle measured with
zero voltage applied. As the contact angle hysteresis is independent of
the applied voltage [50–52], reversible electrowetting could be achieved
with low contact angle hysteresis systems such as in the liquid/liquid/
solid system [57,61] or on superhydrophobic/superlyophobic surfaces
[62].
3.2.2. Polarity effects
According to the Young–Lippmann equation in Section 3.1, the
contact angle decreases with the applied voltage following the same
parabolic curve regardless of the polarity of the voltage. However,
early studies showed different polarity effects of electrowetting on
different materials. On one side, when Parylene was used as an
insulating layer, the change of contact angle was independent of
polarity [63–65]. On the other side, when Teflon was used several
groups reported a strong deviation from the theory with a positive
applied voltage [66–68]. Since the liquids (water or aqueous electrolyte
solutions) used in experiments were similar, authors attributed the
polarity effects to material properties [66–68]. Werner and co-workers
investigated the interfacial charge on Teflon in aqueous electrolyte
solutions [69]. They found that hydroxyl ions (OH−) have stronger
interaction to the Teflon surface than the hydronium ions (H3O+) due
to the presence of oxygen atoms in Teflon [66,70]. As a result, the
capacitance of the liquid–solid interface is better described by both a
dielectric layer and an electric double layer, rather than by only a
dielectric layer, as done in the Young–Lippmann model [68,71], and it
can explain the polarity effects of electrowetting on Teflon surfaces.
In standard electrowetting experiments or applications, water and
aqueous electrolyte solutions were normally used [18,19,50–68,70,71].
Although water has useful solvent properties, its poor thermal stability,
it tendency to evaporate, and its corrosion ability lead to significant
limitations in microfluidic applications. Ionic liquids, as first pointed
out by Ralston et al., are more promising for robust applications due to
their unique properties: high thermal stability, non-flammability, and
no significant vapor pressure [72]. In the same paper, Ralston et al.
showed polarity effects and related them to the different properties/
sizes of cations and anions [72]. A systematic study was carried out
later by Armstrong and coworkers. They found that anions or cations
with smaller size have stronger influence on the asymmetry of the
ð10Þ surface than larger anions or cations do [73].
As discussed above, polarity effects in electrowetting are recognized
to be most probably due to molecular processes near the liquid–solid
interface, which cannot be captured by simple optical instruments.
Thus, MD simulations could help in understanding the physical
mechanisms. Luzar and co-workers studied the electrowetting of
water nanodrops on apolar hydrophobic surfaces, such as graphene
or paraffin [74–77]. They observed that the electrowetting contact
angle is sensitive to the polarity of an electric field directed
perpendicular to the surface. The explanation was that water is
easier to be polarized along the outgoing, rather than along the
incoming, electric field to the surface [74–76]. However, in the
presence of any salt ions, the strong affinities of them towards the
surface increase the screening of the electric field, and eventually
suppress the polarity effects caused by different electric responses
of hydrogen bonding [78].
6 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
3.3. AC electrowetting
3.3.1. Why AC?
In most microfluidic electrowetting systems [19], alternating current
(AC) voltage is applied because of following benefits:
• Reduction of contact angle hysteresis. As discussed above, the contact
angle hysteresis exists in DC electrowetting due to pinning effects
[50–52]. In contrast, using AC voltage electrowetting continuously
perturbs the force balance at the contact line and essentially leads to
the depinning of the contact line from the surface [51,58]. Eventually,
the contact angle hysteresis is smaller in AC than in DC electrowetting
[51,58,79].
• Delay of contact angle saturation. Many experimental results showed
that the contact angle saturation occurs at a smaller contact angle
and at a higher effective voltage for AC rather than DC electrowetting,
in both liquid/solid/air [80,81] and liquid/liquid/solid systems [82–84].
Hong et al. provided the explanation that the effective electric field
strength is reduced by increasing the frequency, and that this can
lead to a delay of the dielectric breakdown [85]. The underlying
physics of delayed saturation in AC electrowetting is still not fully
understood.
• Reduction of ion adsorption. Another possible reason leading to
irreversibility or a large contact angle hysteresis in DC electrowetting
is ion adsorption at the liquid–solid interface. It was reported that the
ion adsorption at the liquid–solid interface was reduced by applying
AC instead of DC voltage [86,87].
3.3.2. Frequency dependence
The Young–Lippmann equation is only valid for AC electrowetting
when the liquid can be treated as a perfect conductor. This holds if the
AC frequency is larger than the resonance frequency of sessile drops
(typically of few hundreds hertz) and is far smaller than a critical
frequency fC (typically of 10–100 kHz) [7]. The electrowetting efficiency
diminishes with frequency increasing beyond the upper limit, while it is
dependent on the frequency between the two limits [48,49,58,85]. The
general AC electrowetting behavior can be captured by the analogy
with an equivalent electric circuit, as shown by Mugele and Baret [7]
(Fig. 3). The drop is represented as a resistor and a capacitor, and the
dielectric layer is treated as another capacitor. The electric double layers
formed at the liquid-dielectric layer or at the liquid-counter electrode
interfaces are not considered. At low frequency (≪fC), the drop behaves
more like a conductor rather than an insulator, which satisfies the
assumption for Young–Lippmann's equation. However, at very high
frequency (≫fC), the drop behaves more like an insulator, which
leads to the breakdown of electrowetting. The critical frequency is
related to the physical properties of the drop as well as to its geometry
[7].
σ d þ σ lk
fCe
ε0 ðεd þ εl kÞ
Fig. 3. The equivalent circuit for AC electrowetting.
σd, σl and εl are the conductivities of the dielectric layer and liquid
and the permittivity of the liquid, respectively. k ~ d/R is the size ratio
of the dielectric layer and the drop. For deionized water, fC is typically
few kHz, which matches with experimental observations [48,49,58].
The above discussion qualitatively introduces the frequency
dependence of AC electrowetting, while a quantitative understanding is
still missing. Hong et al. carried out a numerical investigation of AC
electrowetting [85]. They found that the electric field strength was
remarkably reduced in the dielectric layer near the contact line, which
may lead to a decrease of the electrostatic contribution to the wetting
tension. Their numerical results were consistent with experiments. Most
recently, Klarman et al. proposed a model based on a similar configuration
as shown in Fig. 3 [88]. They also accounted for the effects of the electric
double layer at the immersed counter-electrode and discussed this effect
on AC and DC electrowetting. Among others, they concluded that the
effect of the polarization of the counter-electrode could be neglected in
most practical cases, since the area of the counter-electrode is usually
much smaller than the contact area between the drop and the solid.
3.3.3. Hydrodynamic flow
In recent years, researchers have reported hydrodynamic flows
inside drops in AC electrowetting [24,89–93]. The flow patterns are
dependent on the frequency of the applied voltage as well as on the
conductivity of the liquid (Fig. 4a). In the low frequency range (typically
up to 1 kHz), the flow forms two axisymmetric toroidal vortexes whose
center is not visible [90,93] (Fig. 4b). The low frequency flow is rather
unstable and is very sensitive to the counter-electrode position. In
contrast, in the high frequency range (larger than few tens of kHz),
the flow is highly stable and the vortex center is always located around
the counter-electrode [90]. Also, the vortex direction of the low
frequency and high frequency flows are different (Fig. 4b & d), which
indicates that the flow generation mechanisms are different. For
intermediate frequencies, no flow is observed in the drop (Fig. 4c).
The low frequency flow is mainly driven by the oscillations of the
drop [90]. The oscillation of the contact line caused by AC potential can
result in a hydrodynamic viscous streaming inside the drop. However,
the low frequency flow observed is not as steady as the viscous flow.
Moreover, the direction of the low frequency flow in air [90] is opposite
to the one observed in mixing experiments of water/glycerol drops in
silicone oil ambient [24,93]. Both phenomena point out that some
additional mechanisms may influence the hydrodynamics. Based on
these experiments in oil, Mugele et al. suggested that the capillary
Stokes drift induced by the capillary wave drives the internal flow in
the drop [93,94]. These studies pointed to more open questions, like
how do the viscosity or the density of the atmosphere surrounding the
drop influence flow pattern and flow stability inside the drop.
The high frequency flow is induced by the so-called electrothermal
effects [89,91]. With high frequency AC voltage applied, the liquid
behaves like an insulator as there is not sufficient time to completely
charge the capacitor of the dielectric layer [7,88]. As a result, the electric
ð12Þ
field inside the drop leads to Joule heating of the liquid, giving rise to
a gradient in conductivity and permittivity [89,91]. Eventually, the
voltage applied on the electrically inhomogeneous drop generates an
electric body force resulting in an internal flow.
3.4. Contact angle saturation
In the past years, many models or hypotheses have been proposed to
explain the contact angle saturation, as reviewed by Mugele [7,23], and
recently by Chevalliot et al. [80], Koopal [95] and Sedev [96]. Here, we
briefly recap the latest progress:
(1) Zero interfacial tension. According to the classical thermodynamic
model of electrowetting, the change of the contact angle is
entirely ascribed to the reduction of the liquid–solid interfacial
tension (γLS). Ralston and coworkers suggested that γLS should
 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
Fig. 4. (a) The influence of electrolyte concentration on the frequency range of hydrodynamic flows with V = 80 V and the three typical flow patterns with frequency of 1 kHz (b), 18 kHz
(c) and 128 kHz (d). The electrolyte concentration in (b)–(d) is 10−3 M.
Reproduced with permission from Ref. [90].
not be less than zero to keep thermodynamic stability [47,97].
Thus, the thermodynamic limit with γLS = 0 causes the contact
angle saturation. They showed a consistence between their
model and experimental results [47,97]. Berry and coworkers
confirmed this model by low voltage electrowetting in both
liquid/liquid/solid systems and liquid/solid/air systems [98,99].
One big challenge to verify this model is that it is hardly possible
to directly measure liquid–solid interfacial tensions. However,
recent measurements of thin films [100] and adhesion force
[101] showed no major change of the liquid–solid interfacial
tension upon applying an external potential. Other groups also
noticed that the zero interfacial tension theory does not predict
reliably the saturation contact angle, e.g. with cos θS = γSV/γ
[80,82,83]. Moreover, Mugele and co-workers numerically
found that the electrostatic force does not affect the interfacial
tensions force balance at the contact line [102], and they further
experimentally observed that the microscopic contact angle
always equals Young's angle [103]. This was later confirmed
by MD simulation by Liu et al. [104]. Till now, no studies
considered the possibility of a significant change of the
liquid–vapor or solid–vapor interfacial tensions upon
applying an electric potential. Recent work, however, showed
that the surface tension of water decreased remarkably by
approx. 50% upon electrically charging the water surface
[105] – even if the external potential was in the kV range; or
that the solid–vapor and solid–liquid interfacial energy can
be reduced upon weak electron irradiation [106] – causing a
reversed electrowetting effect, i.e. increasing the contact
angle upon irradiation. These results suggest that electric
charges can affect either of the interfacial tensions playing a
role in electrowetting or in contact angle saturation.
(2) Dielectric breakdown. Near the contact line, the electric field
diverges as the interface curvature is extremely small. The electric
field may locally become so strong that it exceeds the dielectric
breakdown strength of the insulating layer [64]. As a result, the
dielectric layer locally breaks down [107,108]. The charges
transferred to the dielectric layer lead to screen the electric field,
which eventually reduces the electrostatic contribution and
causes electrowetting saturation. This hypothesis was proposed
by Drygiannakis et al. who showed a good match between their
experimental results and theory [107]. Similar conclusions were
also drawn by Berry et al. based on their experiments on thin
amorphous fluoropolymer films [98,109]. However, Chevalliot
et al. recently reported experimental results on DC electrowetting
showing that the saturation contact angle is invariant with
respect to a number experimental parameters, among which are
7
the electric field strength, the interfacial curvature near the
contact line, or the type of dielectric used [80].
(3) Contact line instability. In early AC electrowetting studies, Vallet
et al. observed an instability of the contact line close to the
critical (saturation) voltage for low conductivity liquids such as
water [110]. They found that microdrops spontaneously ejected
from the contact line as the voltage was larger than a critical
value. This phenomenon was reproduced later by Mugele and
Herminghaus with various liquids [111] and was attributed to
the diverging of charge density around the contact line. While
the applied voltage is larger than a critical value, the Maxwell
force exceeds the capillary force near the contact line, which
leads to emission of (charged) satellite droplets. This instability
at the contact line was identified as a possible cause for contact
angle saturation [110,111]. Park et al. also suggested that the
instability with droplet ejection is preceded by a contact angle
reduction and the extrusion of a thin layer from the edge of the
droplet [112,113]. However, these models cannot explain the
suppression of the instability by increasing the conductivity of
the liquids, e.g. with salts [110,111]. As contact line instability
does not arise in DC electrowetting, it hence may not capture
the actual physics of contact angle saturation.
(4) Gas ionization or insulating fluid charging. Vallet et al. also reported
air ionization around the contact line for voltages larger than the
saturation voltage and suggested that it could be responsible for
contact angle saturation [110]. Indeed, it was experimentally
found that the contact angle of a drop can be controlled by
charging its surface via a corona discharge [114,115] or by
electrons [106]. As corona discharge or air ionization is dependent
on relative humidity [115], one possible way to validate this
hypothesis would be to check whether the relative humidity of
the surrounding air influences contact angle saturation. On the
other hand, corona discharge is not applicable to liquid–liquid–
solid electrowetting systems. In such systems, Chevalliot et al.
suggested that it could be possible that the insulating fluid is
charged due to ejection of charges or satellite drops from the
conducting drop [80]. However, this hypothesis calls for further
experimental evidence.
(5) Minimization of the electrostatic energy. Lin et al. proposed a
theoretical model based on an energy balance [116] instead of a
force balance, as is used in the derivation of the Young–Lippmann
equation. In AC electrowetting, especially at higher voltages and in
a well-defined frequency range, a strong hydrodynamic flow
develops inside the drop [24,89–93]. The flow causes additional
energy dissipation and the dissipated energy increases with the
applied potential. Eventually, this leads to a minimum electrostatic
8 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
contribution to the total energy of the system when V ≥ VS [116].
However, this model fails to explain the contact angle saturation
of DC electrowetting, as no internal flow develops there, and
does not reproduce the correct dependence cos θ ∝ V2 for V b VS.
Klarman and Andelman also developed a model based on energy
dissipation [88], and accounted for the electrostatic energy of the
electric double layer around the counter-electrode. This is a
reasonable approach, as the electric field is always stronger near
the electrode than that in the bulk drop [89,91]. They found a
minimum of the electrostatic energy contribution to the saturation
voltage for both DC and AC electrowetting systems. This was based
on the assumption that the capacitance C is not constant but
function of θ and has a minimum at VS. However, this assumption
is not based on first principles and would require a rigorous proof.
(6) Tailor cone. Most recently, Chevalliot et al. carried out a systematic
study of all physical and chemical parameters which may lead to
contact angle saturation according to the above models [80].
Based on their experimental results, they state that there are
parallels between the phenomena of Tailor cone formation and
contact angle saturation. This, if confirmed, could provide a new
direction for a universal theory of the saturation problem in
electrowetting.
4. Dynamic electrowetting
In many applications, such as lab-on-chip, electrowetting dynamics is
of great interest as it controls the response time of the devices [19]. During
the wetting process, the dynamics is determined by the energy balance
between the driving and the resisting forces [28,29,39]. The driving
force of the spreading drop is always the change of surface energy,
which is related to the difference between the initial and equilibrium
contact angle. The resisting force could be the kinetic energy of the
moving drop [30–33], the viscous dissipation in the vicinity of the moving
contact line [28], or the microscopic dissipation of the molecular jumps
[67]. In electrowetting systems it is thus expected that the addition of
electrostatic energy to the energy balance will modify the dynamics of
spreading. In literature, many experimental configurations have been
applied to study the dynamics of electrowetting, as shown in Figs. 2a & 5.
Fig. 5. Typical experimental configurations for dynamic electrowetting setups. (a) Dynamic wetting experiments with a spreading sessile drop. (b) Wilhelmy plate method and (c)
capillary rise experiments.
4.1. “Fast” dynamics of electrowetting
The early wetting stage after a drop touches a surface runs very fast,
as discussed in Section 2.2. This type of electrowetting is ubiquitous as
most surfaces are naturally charged, which is the reason – except for
well controlled conditions – that there is always difference of potential
between drops and surfaces before they wet each other. These naturally
arising excess surface charges need to be redistributed between drop
and surface upon meeting, and thus play a role in most spontaneous
wetting processes like rain drops hitting the soil or ink drops wetting
paper. Stone and co-workers were the first to investigate the fast
dynamic wetting of sessile drops just after contact with a surface
under an applied electric potential [35]. They found that the drop
spreading radius grows with a power law with a larger exponent,
α′ ≈ 2/3. Without applied potential α = 1/2 on completely wetting
surfaces. The effect of the applied potential was to deform the spherical
drop into a conical shape close to the point of contact. The authors set up
an energy balance accounting for this new contact geometry and
derived a power law with an exponent of 2/3. Exponents larger than
1/2 were also observed by Chen et al. [117] in experiments. However,
exponents were not constant, but a function of the applied potential,
of surface wettability, and of electrolyte concentration. Similar to static
electrowetting, where the contact angle saturates when the applied
voltage is larger than VS, they found a saturation of the wetting
exponent α′ for aqueous electrolyte drops with low salt concentration.
For high electrolyte concentrations, no saturation was observed at the
voltages applied (up to V ≈ 1000 V). Chen et al. modified Stone's early
model for partial wetting [31] by adding the contribution of the
electrostatic energy stored in the electrostatic double layer near the
liquid–solid interface as a driving force. The proposed model can explain
the experimental observations. MD simulations confirmed that the
electric double layer is formed in a time scale of few hundred picoseconds
[117], which satisfies the assumption that the electrostatic double layer
exists during the fast wetting process (typically, ~10 ms). However, the
saturation of the wetting exponent in dependence of salt concentration
and applied potential is still an open question.
The inertial wetting stage was also observed in the MD simulations
of the early wetting of nanodrops [117]. However, the electrostatic
energy did not enhance the wetting exponent here. One plausible
 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
explanation is that the electrostatic double layer is not yet fully formed
in this short period. In fact, the ion migration time needed to form the
electrostatic double layer near the liquid–solid interface by applying a
potential was ~500 ps, which is two times longer than the inertial
wetting time [117]. Thus electrostatics does not influence the early
spreading of nanodrops, but it does for their later (viscous) wetting
and for their equilibrium contact angle.
4.2. “Slow” dynamics of electrowetting
The electrostatic effects on the viscous stage of dynamic wetting are
difficult to investigate experimentally with a configuration as in Fig. 5a,
since the drop detaches from the needle during this stage. Losing contact
with the needle (which also acts as counter-electrode) leads to an open
circuit configuration. Alternatively, MD simulations can be applied to
investigate the slow electrowetting. It was found that wetting follows a
power law R ~ t0.1 without applied electric field [117] — which is
consistent with the HD model [28,29,39]. With an applied electric field
of 0.1 V/nm the wetting exponent was larger and the wetting law was
R ~ t0.15 [117]. Similar wetting exponents from MD simulations were
also obtained by Yuan and Zhao [118]. Despite these preliminary findings,
there is still a lack of knowledge on the effect of an applied electric
potential on slow electrowetting dynamics. Another unsolved issue is
the influence of the electrolyte concentration on slow electrowetting
dynamics.
Most studies of dynamic electrowetting in literature were carried out
with the standard configuration shown in Fig. 2a, with the needle
(counter-electrode) permanently inserted in the drop for applying the
electric potential. The driving force due to the electrostatic contribution is
 
E
F ¼ γ cosθeq − cosθeq : ð14Þ
θEeq is the new equilibrium electrowetting contact angle that is a
function of the applied voltage. This force is compensated by viscous
dissipation or contact line friction during the spreading. Decamps and
De Coninck modified the MK theory with this electrocapillary force and
applied it to spontaneous spreading experiments of glycerol drops on
Teflon [119]. They found that the contact line friction was constant over
a large range of applied potentials. Ralston and co-workers studied the
dynamic electrowetting of various ionic liquids in liquid/liquid/solid
systems [82,83] and liquid/solid/air systems [120]. They used both HD
model and MK theory to interpret their data. They found that viscous
dissipation dominates the dynamics when the contact angle and contact
line velocity are small, while the MK theory was more suitable to explain
the dynamics at high contact angles and with high contact line velocity
[83,120]. They also showed that the equilibrium frequency of molecular
jumps decreased with liquid viscosity, which indicates that it is more
difficult for liquid molecules with higher viscosities to move from one
adsorption site to another since the cohesion force between the molecules
is much stronger. Very recently, Hong et al. reported that liquid viscosity
has a weak effect on electrowetting velocity over a broad range of
viscosities (from approx. 1 to 200 mPa s) [121]. McHale and co-workers
investigated the dynamic dielectrowetting of dielectric liquids
[122,123]. In their paper, they modified the HD model and found that
when the applied voltage was larger than a threshold value the wetting
exponent increased with the voltage [123]. Yuan and Zhao studied the
dynamic electrowetting of cylindrical water nanodrops with MD
simulations [118]. They observed a power-law growth of the
spreading radius with time and an increase of the wetting exponent
with the electric field. When a critical value of the field strength was
reached, the exponent saturated similarly to the saturation found in
static electrowetting [7,23].
Dynamic electrowetting studies were also carried out with the
Wilhelmy plate configuration (Fig. 5b). Schneemilch et al. studied the
electrowetting of a Teflon-covered rod and applied the MK theory to
9
fit their data. They showed that the applied potential controlled the
wettability of the surface and that average molecular displacement, λ,
decreased with the applied potential [124]. Puah et al. applied a similar
method to investigate the influence of the electric surface charge on
wetting dynamics [125]. Also there, MK theory was applied. This time
it was found that the equilibrium displacement frequency, k0, depended
on the applied potential and was determined by the charges at the
liquid–solid interface, while λ did not show a significant relation to
surface charge density. The values of λ were determined mainly by the
spacing of the adsorption sites on the solid surface. This was consistent
with previous work of the group using a standard electrowetting
configuration [82,83,120]. Blake et al. modified the MK theory by
introducing the actual capillary force in Eq. (14) [126]. However, they
found that both k0 and λ were independent of the applied voltage.
This brief presentation of experimental results is just to show that also
experiments performed with different configurations and materials
are not always in agreement, and that the cause of disagreement is not
yet clear. On the other hand, it becomes increasingly clear that MD
simulations are now at a level that they can well capture the processes
at the scale of the contact line [127]. They represent thus a promising
tool for exploring the influence of external potentials on molecular
displacements of the contact line in particular and of the electrowetting
process in general.
In recent years, electrostatic assisted flow in capillaries or
microchannels attracted quite some attention because of envisioned
applications in microfluidics and lab-on-chip applications (Fig. 5c).
Wang and Jones proposed a hydrodynamic model to describe the
electrowetting-induced capillary rise in a millimeter-sized plane-
parallel channel [128]. According to this model, there is a critical
potential below which contact line friction dominates over viscous
dissipation, and above which these effects are reversed. However,
when the channel size shrinks to several tens of micrometers,
Herminghaus and co-workers showed that viscous dissipation always
dominates the electrowetting dynamics [129–131].
5. Other capillary phenomena governed by electrostatics
5.1. Electro-coalescence
When two drops of the same liquid come into contact, they merge
with each other to minimize the surface energy. Drop surface charges
or externally applied potentials can favor – or in some cases delay –
coalescence [132,133]. If the drops are oppositely charged, non-
coalescence was observed when the electric field was larger than a
critical value EC (Fig. 6). The failing of coalescence can be explained by
considering the local pressure at the drop apex during coalescence
[132,134]. Exposed to an electric field, the drop deformed into a conical
shape upon approaching the oppositely charged interface. The aperture
angle of the cone depends on the field strength. If the cone angle is
larger than 31°, the local curvature in the liquid thread results in such
a high pressure that prevents coalescence. A similar phenomenon was
also observed in the coalescence of a drop with a flat solid surface
[117]. When the electric field was below the critical value EC, the
impinging drop partially coalesced with the interface [135–138]. The
coalescence was only partial, since a daughter drop was ejected and
moved away from the interface, as it acquired an opposite charge during
contact. The size of the daughter drop is determined by electrostatic and
capillary forces [136].
5.2. Electrically assisted capillary wrapping
It was recently demonstrated by several authors that capillary forces
can be used to fold thin films and to wrap them around droplets
[139–141]. In order to achieve a reversible wrapping, an additional force
is needed to oppose the capillary folding force. One way is using the
electrostatic force. Pineirua et al. controlled the folding and unfolding of
10 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
Fig. 6. Influence of an electric field on drop coalescence: below a critical field strength EC the drop coalesces with the interface, and above EC the impinging drop rebounds from the
interface. The scale bar is 0.5 mm.
Reproduced with permission from Ref. [132].
capillary origami by varying the unfolding torques with an external DC
voltage [142]. The authors showed that this technique can be used to
assemble small scale three dimensional soft structures. Zhao and co-
workers reported a similar effect using low frequency AC voltages [143].
5.3. Electrostatic control of interfacial flow
The electrostatic force can also be used to control interfacial flows, as
it deforms the shape of a drop or a rivulet. Lee et al. transferred the
electrostatic energy into the surface energy by applying a voltage to
spherical drops sitting on superhydrophobic surfaces [144]. If the
increased surface energy overcomes a critical barrier, the drop can be
induced to jump off the surface. The voltage for making a 5 μl water
drop jump off is approx. 100V. The authors also showed that it is possible
to transfer drops between two parallel plates, which is envisioned to find
applications in three-dimensional digital microfluidics. Bormashenko
et al. investigated the deformation of liquid marbles under electric field
and found that liquid properties influence the deformation [145].
When a composite liquid marble was exposed to a sufficiently high
electric field, the highly polarizable drop climbed on top of the low
polarizable drop to minimize the total energy of the system. Noblin
and Celestini proposed a new method for controlling water jet dynamics.
Applying an AC voltage between the metallic nozzle generating the jet
and a metallic electrode below a dielectric polymer layer, they showed
that they could control the reflection angle of the jet, or even to
completely prevent bouncing. For water, the authors determined a
maximum threshold frequency of approx. 1.5 kHz above which the
effects disappear, since the liquid starts behaving like a dielectric [146].
Very recently, Yun et al. presented an experimental and numerical
study about the prevention of drop rebound from solid surfaces by
electrostatic charging of the drops. Electric charges were transferred to
water droplets while they fell through variously shaped ring electrodes.
Such an electrostatic charging affected drop oscillations and thus
induced a kinetic energy dissipation, which in turn reduced – or even
suppressed – drop rebounding [147]. Most recently, the electrostatic
forces were also applied to suppress the Leidenfrost effect [148]. By
applying an electric field between a Leidenfrost droplet and the heated
substrate on which it was levitating, the vapor layer thickness decreased.
Eventually, a millimeter-sized drop contacted the heated substrate with
an applied voltage of approx. 40 V.
5.4. Electric enhancement of heat and mass transfer
Many authors also reported that the heat and mass transfer can be
controlled by applying an external electric field. Takano et al.
experimentally studied the evaporation of various drops of liquids at
temperatures exceeding the Leidenfrost temperature [149–151]. They
found that the evaporation was enhanced under an applied field, as the
field induced interfacial instability leading to direct contact between the
levitating drop and the heated substrate [150]. They concluded that the
enhancement was more remarkable for polar liquids than for non-polar
liquids, as charge relaxation time on them was much shorter [150,152].
Recently, Butt and co-workers calculated that the presence of an electric
field can reduce the saturation vapor pressure and lead to a field-
induced condensation of, e.g., water [153]. This explains the anodic
oxidation at the nanoscale in dependence of relative humidity [154,155].
6. Conclusion and outlook
In the last 10years the topic of electrowetting spawned an increasing
number of theoretical, numerical, and experimental works. A good deal
of fundamental and especially technological issues has been addressed
and solved. The Young–Lippmann equation, despite its simplicity, is
able to quantitatively describe the physical processes and to predict
the wetting behavior of most systems most of the time. The unbound
creativity of researchers, however, continuously finds new ways of
combining capillary and electric forces with new material properties
and system geometries. The Young–Lippmann equation can thus not
account for all new observed phenomena. Some issues remain to be
solved, most important being the understanding of the saturation
potentials in static and in dynamic electrowetting, of the molecular
transport processes in the bulk and at the interfaces associated with
applying electric potentials to various liquids, and of the ionic and
electrochemical processes taking place at the surface of the electrodes.
The natural contact angle hysteresis inherent to real surfaces leads
to poor controllability and sometimes to the irreversibility of the
electrowetting process. Controllability could be improved either using
liquid/liquid/solid systems, by applying AC instead of DC potentials, or
by using superhydrophobic/superlyophobic surfaces. Polarity effects in
DC electrowetting, generating a non-symmetric wetting behavior for
positive and negative voltages, have been found to be most probably
caused by molecular processes in the liquids. So the use of special ad-
hoc liquids is recommended in certain applications. AC voltage is applied
more and more in electrowetting, as it can overcome many disadvantages
of DC electrowetting. However, additional phenomena arise and set
limitations for the applicability, such as the frequency dependence of
the conductivity of the liquid, or the generation of hydrodynamic flows
inside the liquid. Such side effects need also to be considered in designing
lab-on-chip devices. Saturation, referring to the existence of a critical
threshold voltage above which the electrowetting effectiveness does not
further increase, remains a challenge for all electrowetting theories.
Since saturation is most probably dominated by microscopic interfacial
 L. Chen, E. Bonaccurso / Advances in Colloid and Interface Science 210 (2014) 2–12
processes, molecular dynamics simulations could represent a useful tool
for triggering novel investigations. First papers in this areas appeared,
but more are required.
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