Drops on Homogeneous and Non-homogeneous

Surfaces

1
 The Shape of Micro-drops

Comparison of the shape between micro-drops and macro-drops

The two pressures are of the same order when

“l” is called the capillary length. A drop of dimension smaller than the
capillary length has a shape resembling that of a spherical cap. A drop larger
than the capillary length is flattened by gravity.
2
 Bond Number

R is of the order of the drop radius. If Bo < 1, the drop is spherical (microscopic
drops), or else the gravitational force flattens the drop on the solid surface (large
drops).

The capillary length is of the order of 2 mm for most liquids, even for mercury.

These equations are valid for a perfectly flat surface.

3
 Wetting: Partial or Total Wetting

A liquid spreads on a substrate in a film if the energy of the system is lowered by the presence
of the liquid film .

The surface energy per unit surface of the dry solid surface is γSG; the surface energy of the
wetted solid is γSL+γLG.

The spreading parameter S determines the type of spreading (total or partial)

S = γSG − (γSL + γLG)

If S > 0, the liquid spreads on the solid surface; if S < 0 the liquid forms a droplet.
4
 Contact Angle—Young’s Law

At equilibrium, the resultant of the forces must be zero.

γLG cos θ = γSG − γSL

Schematic of forces at the contact line

Nano-bubbles and droplets

θ* is the real contact

angle, r is the contact
radius

Recent measurements have shown that nano-bubbles have very flat profiles—the base radius is 5–20
times larger than the height —because the contact angle of the bubble is much smaller than the
macroscopic contact angle of the bubble on the same substrate
5
 γLG cos θ = γSG − γSL
Modified Young’s Law at Nanoscale

The molecules close to the

triple line experience a
different set of interactions
than at the interface. To
take into account this effect,
a line tension term has been
introduced in Young’s law

Where r is the contact radius, γSLG the line tension (unit N), and θ∗ the real contact angle.

For droplet contact radius larger than 10 μm, the effect of the line tension is negligible; the value of the
second term is of the order of 10−4 . But it is not the case for nano-drops and nano-bubbles.

6
 γLG cos θ = γSG − γSL

Young’s law can be more rigorously derived from free energy minimization.

Consider a sessile droplet large enough for the effect of the triple line to be neglected. The
change of free energy due to a change in droplet size can be written as

dF = γSLdASL - γSG dASG + γLG dALG

= (γSL − γSG + γLG cos θ) dASL

where θ is the contact angle.

At mechanical equilibrium dF = 0 and

γSL − γSG + γLG cos θ = 0.

7
 Work of Adhesion

Imagine a body contacting another

body on a surface S. The surface
energy of S when there is contact is

E12 = γ12 S

The work of adhesion is the work required to separate the two bodies. After separation, the
surface energies are

E = E1 + E2 = (γ1 + γ2) S

The work of adhesion (per unit area) is then

Wa = γ1 + γ2 − γ12
8
 Work of Cohesion

The work of cohesion is obtained similarly, but this time the body being split is
homogeneous. The same reasoning yields

Wc = 2γ1

In other words, the surface energy is half the work of cohesion

9
 Work of Adhesion - Young–Dupr´e Equation

Work of adhesion for a liquid and a solid

Using the work of adhesion Wa = γ1 + γ2 − γ12

with the surface tensions γ1 = γLG = γ, γ2 = γSG, and γ12 = γSL, we obtain

Wa = γ + γSG − γSL

10
 Wa = γ + γSG − γSL γLG cos θ = γSG − γSL
Work of Adhesion - Young–Dupr´e Equation

Upon substitution of Young’s law [γLG cos θ = γSG − γSL], one can obtain the Young–Dupr´e
equation for the work of adhesion as

Wa = γ (1 + cos θ)

For a super-hydrophobic contact, θ = π; Wa = 0: no work is required to separate a super-

hydrophobic liquid from a solid.

Thus, a droplet of water rolls freely over a super-hydrophobic surface.

The more hydrophobic is the contact between a liquid and a solid, the smaller is the work
of adhesion.
11
 Drops on Inhomogeneous Surfaces

Young’s law should be corrected to take into account the imperfections of the surface.

Roughness amplifies the hydrophilic or hydrophobic character of the contact.

θ∗ is the angle with the surface with roughness and θ the angle with the smooth surface.

The size of the roughness is very small, so that

the molecules of the liquid are macroscopically
interacting with a plane surface but
microscopically with a rough surface.

12
[γLG cos θ = γSG − γSL] Wa = γ + γSG − γSL S = γSG − (γSL + γLG)

For a very small displacement of the contact line, the work of the different
forces acting on the contact line is given by

where r is the roughness (rdx is the real distance on the solid surface when
the contact line is displaced by dx). Therefore, by definition, r > 1.

Thus the change in energy is

13
The drop finds its equilibrium state after the small perturbation dx, it finally stops at a
position where its energy is minimum, so

Therefore,

14
Young’s law for a smooth surface

Substitution gives Wenzel’s Law

As r > 1, this relation implies that

15
If θ is larger than 90◦ (hydrophobic contact), then θ∗ > θ and the contact is
still more hydrophobic due to the roughness.

If θ is smaller than 90◦ (hydrophilic contact), then θ∗ < θ and the contact is
still more hydrophilic.

Surface roughness increases the wetting character.

16
 Cassie–Baxter Law
Chemically inhomogeneous
solid surfaces.

Small size heterogeneities

compared to interaction size
between the liquid and the
solid wall.

A solid wall constituted by microscopic inclusions of two different materials.

θ1 and θ2 are the contact angles for each material at a macroscopic size, and f1 and
f2 are the surface fractions of the two materials.
17
 γLG cos θ = γSG − γSL
The energy to move the interface by dx is

Minimizing dE

Using Young’s Law

Casey-Baxter Relaion

18
The Cassie–Baxter law explains some unexpected experimental results.

Sometimes during micro-fabrication—a microfabricated surface may present

chemical inhomogeneity and the wetting properties are not those that were
intended.

For example, if a uniform layer of Teflon is deposited on a rough substrate,

the surface should become hydrophobic.

However, if the layer is too thin, the Teflon layer may be porous and the
coating inhomogeneous; the wetting properties are then modified according
to the Cassie–Baxter law and the gain in hydrophobicity may not be as large
as expected.

The scale of change of the different chemical materials of the solid surface is
very small compared to that of the drop 19
 Topographically patterned surfaces

Droplets wetting rough surfaces

(a)Wenzel state with enhanced solid–liquid interfacial area

(b) Cassie–Baxter state with entrapped air underneath the droplet.

In Fig. (a), roughness increases the actual solid–liquid interfacial area Asl with
respect to the apparent, projected one Asl,p.

Lessons from nature

20
 Microfabricated Substrate - Case of Hydrophobic Contact

Contact angle of a sessile drop sitting on microfabricated pillars

If the drop penetrates between the pillars, one can write the Wenzel angle as

cos θW = r cos θ

If the drop stays on top of the pillars, one can write the Cassie law

cos θC = f cos θ + (1 − f) cos θ0

θC is the “Cassie” contact angle, θ0 the contact angle with the layer of air, and f
the ratio of the contact surface (top of the pillars) to the total horizontal surface.
21
Wenzel’s law

cos θ = r · cos θY with r = Asl /Asl, p.

Quantitatively, the validity of the picture turns out to be limited to a range

of θC < θY < 90◦, with θC depending on the surface roughness .

As a result, the contact angle on a rough surface will be increased or

(decreased) as compared to the contact angle on a smooth surface of the
same material, depending on whether θY > 90◦ or (θY < 90◦), respectively.
For θY > 90◦, a completely different liquid morphology is possible (Fig. b).

Asl is dramatically reduced and much of the apparent solid–liquid interface is in

fact a liquid–vapor interface.

This reduction in Asl gives rise to a very high mobility with extremely small
contact angle hysteresis.

In this state, the contact angle is given by the Cassie–Baxter equation,

cos θ = −1 + f · (1 + cos θY ), where f is the fractional surface area of the
pillar tops and θ2 (on air) = 180o

The range of stability for both morphologies depends on the aspect ratio, the
spacing between the pillars, and the contact angle
23
cos θW = r cos θ cos θC = f cos θ + (1 − f) cos θ0

Sketch of a Cassie drop (fakir effect). The interface between the pillars
is roughly horizontal.

If the pillars are not too far from each other, the value of θ0 is roughly θ0 = π

cos θC = −1 + f (1 + cos θ)

24
 Plot the Wenzel and
Cassie Laws

cos θW = r cos θ

cos θC = −1 + f (1 + cos θ)

Plot of the Wenzel and Cassie laws for a

sessile droplet sitting on a surface textured
with micro-pillars.

The two lines intersect at a Young contact

angle θi defined by θC = θW , so that
25
 cos θW = r cos θ
In the diagram, for a given Young angle,
there are two contact angles

From energy considerations—for

example using Laplace’s law—it can be
deduced that the real contact angle is the
smaller one.

cos θC = −1 + f (1 + cos θ)

So when the Young contact angle is not very hydrophobic (θ < θi ), the contact
corresponds to a Wenzel regime and the drop wets the whole surface.

When the Young contact angle is more hydrophobic (θ > θi), the drop is in a Cassie
regime and sits on top of the pillars.

General rule, exceptions are common, droplets are sometimes at metastable regimes.

26
Microfabricated pillars of silicon.

27
 Transition from a Cassie droplet to a Wenzel droplet by electrowetting actuation.

(a)When no electric actuation, the drop sits on top of the pillars, b)electrode actuated
with 22V electric potential: the droplet wets the flat part of the substrate. The wire at the
top is the zero potential electrode.
28
 Example of a Square Lattice

Square pillars along a square grid

Square pillars of size a×a, height H and spacing b

29
The roughness “r” is determined by

Where,

The Cassie coefficient is given by -

30
Substitution of these into the Wenzel and Cassie formulas leads to the following relations
for square pillars
cos θW = r cos θ

cos θC = −1 + f (1 + cos θ)

Using these relations the shift from Wenzel to Cassie state occurs when

31
 Super-Hydrophobicity
A surface is said to be super-hydrophobic when the contact angle of aqueous liquid is close to 180◦.
In nature, some tree leaves in wet regions of the globe have super-hydrophobic surfaces in order to
force water droplets to roll off the leaves, preventing rotting of the leaves.

Super-hydrophobicity requires either a super-hydrophobic Young contact angle or a Cassie

regime. Super-hydrophobicity corresponds to θreal = π and cosθreal = −1.

32
 Super-Hydrophobicity

It can only be approached in a Cassie

regime when the value of “f” is very small

“f” is small when b/a >> 1. In such a case, the

pillars are very thin and the contact area of the
droplet with the solid substrate is very small.

The best situation for super-hydrophobicity for

a geometrically textured surface is “f” as small
as possible and “r” as large as possible.

If H is sufficiently high, “r” will be large

33
Fabricated Surfaces: The Transition Between the Wenzel and Cassie Laws
PDMS, Teflon, SU8, glass, silicon, gold. Plastics are generally
hydrophobic whereas glass and metals are hydrophilic and silicon neutral.

Chemical deposition of a hydrophobic/hydrophilic coating on top of the substrate.

A flat gold plate with CF4–H2–He plasma deposition becomes very hydrophobic.

(a) A water droplet bounces back from the surface treated with CF4–H2–He
plasma deposition, (b) whereas it spreads on the original gold surface
34
Partial Rebound of Droplets on Unidirectionally Structured Hydrophobic Surfaces

35
Partial rebound over flat as well as wrinkled PDMS surfaces with varying topography.
Partial rebound is observed for DI water even for moderately wrinkled surfaces (S1),
whereas for CTAB it is experienced for narrow wrinkles (S4) only. No partial rebound is
seen for Glycerol for even highly wrinkled surfaces. 36
37
Water repellent treatment to make the viewing surface hydrophobic

38
 Drops Moving by Capillarity
At the microscopic scale there are other forces to move fluids that are not
efficient at the macroscopic scale. These forces are electro-osmosis and
capillarity. In particular capillarity is widely used for actuating droplets.

1. Drop Moving Over a Transition of Wettability

Resulting force
directed towards the Droplet at equilibrium
hydrophilic region

If L1 and L2 are the contact lines in the

hydrophilic and hydrophobic planes,
and θ1 and θ2 the contact angles, the
force acting on the drop is 39
 2. Drop Moving Uphill

Capillary forces may be sufficient to make micro-drops move upwards on

an inclined plane.
M.K. Chaudhury and G.M. Whitesides, “How to make
water run uphill,” Science, Vol. 256, pp. 1539–1541, 1992.

The required gradient in surface

free energy was generated on a
polished silicon wafer by
exposing it to the diffusing
front of a vapor of
decyltrichlorosilane,

The average velocity is

approximately 1 to 2 mm/s
A drop moves uphill towards the more hydrophilic region.

40
 3. Drop Moving up a Step

A micro-drop of water is initially located on a step at the boundary of a

hydrophilic region (on top of the step) and a hydrophobic region (at the
base of the step). The drop progressively moves towards the hydrophilic
region, even if this region is located at a higher level (simulation result)

Motion of a drop up a step towards the hydrophilic plane

(simulation)

41
4. Drop Moving Over a Gradient of Surface Concentration of Surfactant

Chemical reactions between the liquid of the droplet and the substrate can create
droplet motion. A droplet of n-alkanes containing silane molecules is placed on a
hydrophilic surface. Silane molecules form dense grafted monolayers on silicon
or glass, rendering the surface hydrophobic.

If such a droplet is deposited on a glass surface and pushed with a pipette, then
the droplet continues to move on the substrate. It moves in nearly linear segments
and changes its direction each time it encounters a hydrophobic barrier. The
droplet cannot cross its own tracks.

The advancing contact line has a hydrophilic

Young contact angle. Molecules of silane
concentrate at the vicinity of the receding contact
line and form a hydrophobic layer. 42