HW4- Wetting

Exercise 1.

a) Spreading parameter, S distinguishes the two different regimes of wetting. It measures the
difference between the surface energy (per unit area) of the substrate when dry and wet:

S   solid  ( liquid   solid liquid )

S > 0: Total wetting

If the parameter S is positive, the liquid spreads completely in order to lower its surface energy.
Condition favorable for this condition is a high value of γsolid (high energy surfaces like glass, clean
silicon) and a lower value of γliquid (ethanol, toluene). [See above figure]

S < 0: Partial wetting

The drop does not spread but, instead, forms at equilibrium a spherical cap resting on the substrate
with a contact angle θ. A liquid is said to be "mostly wetting" when θ < 90°, and "mostly non-
wetting" when θ > 90°.

b) The capillary length or capillary constant, is a length scaling factor that relates gravity and
surface tension. It is a fundamental physical property that governs the behavior of menisci, and is
found when body forces (gravity) and surface forces (Laplace pressure) are in equilibrium.


c 
 g

The pressure of a static fluid does not depend on the shape, total mass or surface area of the fluid.
It is directly proportional to the fluid's specific weight – the force exerted by gravity over a specific
volume, and its vertical height. However, a fluid also experiences pressure that is induced by
surface tension, commonly referred to as the Young-Laplace pressure. Surface tension originates
from cohesive forces between molecules, and in the bulk of the fluid, molecules experience
attractive forces from all directions. The surface of a fluid is curved because exposed molecules
on the surface have fewer neighboring interactions, resulting in a net force that contracts the
surface. There exists a pressure difference either side of this curvature, and when this balances out
the pressure due to gravity, one can rearrange to find the capillary length.

c) Lagrangian multiplier in variational method determines the condition of minimized the surface
area so that the relationship in Laplace equation can be derived.

d) Considering it is a closed system, work done by external force. The internal energy will be
changed because the work done making the bigger surface area meanings an equivalent amount of
molecules must be brought up to the surface, which definitely change the internal energy of the
system.

e) The Helmholtz energy is defined F  U  TS

Where

F is the Helmholtz free energy

U is the internal energy of the system

T is the absolute temperature (kelvins) of the surroundings

S is the entropy of the system

n thermodynamics, the Helmholtz free energy is a thermodynamic potential that measures the
useful work obtainable from a closed thermodynamic system at a constant temperature and volume
(isothermal, isochoric). The negative of the change in the Helmholtz energy during a process is
equal to the maximum amount of work that the system can perform in a thermodynamic process
in which volume is held constant. If the volume were not held constant, part of this work would
be performed as boundary work. This makes the Helmholtz energy useful for systems held at
constant volume. Furthermore, at constant temperature, the Helmholtz free energy is minimized at
equilibrium.

Exercise 2.

Sketch the normal component of kinetic (pkn) and cohesive pressure (Psn) and its sum
(Pn)

Sketch the tangential component of kinetic (Pkt) and cohesive pressure (Pst) and its sum (Pt).
mechanical definition of surface tension


  

0  t ( z )  dz

Exercise 3
Derived the governing equation for the shape of a drop on a fiber (Young-Laplace Equation), rotating
with an angular velocity of w, with respect to x-axis, by using the variational method. Consider the effect
of gravity.
Solution

The Young Laplace equation is derived base on the force balance. The key element in the derivation was
the point that the pressure drop p is constant and equal to the pressure drop 𝛥𝑃𝐿 = 𝛾𝜅 across the surface.
There is the presence of gravity and rotating force. Therefore, the Young-Laplace equation is modified to
be

2𝛾𝜅 = 𝑃0 − 𝜌𝑔𝑧 + 𝜌𝑤 2 (𝑅 − 𝑧)2

𝐺 = 𝛾𝐴 − 𝜆𝑉 + 𝜌𝑔𝑧𝑉 + 𝜌𝑤 2 (𝑅 − 𝑧)2 𝑉
= ∫ 𝛾 ⅆ𝐴𝑙𝑣 + ∫ (𝛾𝑠𝑙 − 𝛾𝑠𝑣 ) ⅆ𝐴𝑠𝑒 + ∫ (𝜌𝑔𝑧 − 𝛥𝑝 + 𝜌𝑤 2 (𝑅 − 𝑧)2 ) ⅆ𝑉
Define 𝑧(𝑥), 𝑧 ′ (𝑥) = ⅆ𝑧 ∕ ⅆ𝑥

Where: 𝜆 is Lagrange multiplier or 𝛥𝑝

surface area can be approximate as 𝐴 = ∫ 2𝜋𝑧 ⅆ𝑠 = 2𝜋∫ 𝑧√1 + 𝑧 ′ 2

𝑎𝑛ⅆ 𝑉 = ∫ 𝜋(𝑧 2 − 𝑏 2 ) ⅆ𝑥
Thus,
𝐺 = 2𝜋𝛾∫ 𝑧√1 + 𝑧 ′ 2 ⅆ𝑥 − 𝜆𝜋∫ (𝑧 2 − 𝑏 2 ) ⅆ𝑥 − 𝜌𝑔𝜋∫ 𝑧(𝑧 2 − 𝑏 2 ) ⅆ𝑥 − 𝜌𝜔2 𝜋∫ (𝑅 − 𝑧)2 (𝑧 2 − 𝑏 2 ) ⅆ𝑥
Euler Largrange equation

Define 𝑓(𝑧, 𝑧 ′ ) = 2𝜋𝛾𝑧√1 + 𝑧 ′ 2 − 𝜆𝜋(𝑧 2 − 𝑏 2 ) − 𝜌𝑔𝜋𝑧(𝑧 2 − 𝑏 2 ) − 𝜌𝜔2 𝜋(𝑅 − 𝑧)2 (𝑧 2 − 𝑏 2 )

𝑓 𝜆 𝜌𝑔 𝜌𝜔2
𝑔̃ = = 𝑧√1 + 𝑧 ′ 2 − (𝑧 2 − 𝑏 2 ) − 𝑧(𝑧 2 − 𝑏 2 ) − (𝑅 − 𝑧)2 (𝑧 2 − 𝑏 2 )
2𝜋𝛾 2𝛾 2𝛾 2𝛾

⇒ 𝐺 = ∫ 𝑓(𝑧, 𝑧 ′ ) ⅆ𝑥, the extremum of G satisfies the condition of drop shape equation:
𝜕𝑔 ⅆ 𝜕𝑔
− ( )=0 (∗)
𝜕𝑧 ⅆ𝑥 𝜕𝑧 ′
After calculating each term in (*), we can obtain en equation of z(x), and finally we got
𝛾𝜅(𝑥) = 𝛥𝑝 − 𝜌𝑔ℎ(𝑥) + 𝜌𝑤 2 (𝑅 − 𝑧(𝑥))2
Where
−ℎ′′
𝜅= 3∕2
(1 + ℎ′ 2 )

The above equation is the Young-Laplace equation including the gravitational term and rotation.

Exercise 4
The bubble will move to the right. As the bubble always tends to minimize its surface emery
according to minimum energy principle, when the bubble moving to the right its shape
approaches a sphere which shows the state of minimum energy principle.

Exercise 5

a)

C ( S ) 2
F  ( SL   SA ) S   S1  Evol 
2

where  SL and  SA are the interfacial tensions at the solid-liquid and solid-air interfaces
respectively,  is the surface tension of a liquid, C is the capacitance of the double layer, S is
the wetted solid area before applying voltage  , and S1 is the surface of a liquid cap. Evol is the
energy of the drop volume in an external electric field.

C ( S ) 2  C ( S ) 2 
dF  ( SL   SA )dS   dS1  dS    SL    SA  dS   dS1
2dS  2dS 

b)
 C ( S ) 2
c) Let the effective surface tension :  *SL   SL 
2dS

Then, dF    *SL   SA  dS   dS1

Taking into account a simple geometrical relation: dS1  dS cos  * (θ* is the equilibrium apparent
contact angle of electrowetting after applying voltage)

C ( S ) 2
 SA    SA   SL 
2dS  cos    dC ( S )
* 2
Then cos  *  SL

  Y
2 dS

 2 dC
For the asymmetrical droplet: cos  *  cos Y 
4 a dr r a