Fundamentals of Capillarity and

Wetting (CLL763)

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Why particle diameter not the radius?

σ/2 σ/2

‘r’ is center to center distance. Minimum center to center distance

could be (σ/2 + σ/2) = σ ; (hard sphere concept)

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Surface Energy: mechanical definition

2σ l 2σ 2σ

x dx
For new surface, additional surface area=dA
Mechanical work required =dW ; i.e. proportional to the number of
molecules that would be brought up to the surface.
dW= 2σ.dA
𝐝𝐖 = 𝑭𝒅𝒙 = 𝟐𝝈𝒍𝒅𝒙 2
𝐝𝐖 [𝝈]≡ mN/m or mJ/m
𝝈= =𝒇
𝟐𝒍𝒅𝒙 3
Surface Energy on wetting
air
water

substrate

𝛉≈𝝅 𝟎<𝛉<𝝅 𝛉≈𝟎

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Fun fact: Drop bounces and then spreads

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Consequence of Surface tension: Laplace pressure
Laplace (1805): Surface tension is at the origin of the overpressure
existing in the interior of drops and bubbles.
Change in free energy or the work done by the
dR pressure and capillary force:
𝛅𝐖 = −𝒑𝒊 𝒅𝑽𝒊 − 𝒑𝒐 𝒅𝑽𝒐 + 𝝈𝒅𝑨 ;
𝒘𝒉𝒆𝒓𝒆, 𝒅𝑽 = 𝟒𝝅𝑹 𝟐 𝒅𝑹 = −𝒅𝑽
R Po 𝒊 𝒐
pi 𝒂𝒏𝒅 𝒅𝑨 = 𝟖𝝅𝑹𝒅𝑹
Vi
for mechanical equilibrium: 𝛅𝐖 = 𝟎
𝒑𝒊 − 𝒑𝒐 𝒅𝑽𝒊 = 𝝈𝒅𝑨
𝒅𝑨 𝟐𝝈 ∆𝒑 = 𝟐𝝈𝜿
∆𝒑 = 𝒑𝒊 − 𝒑𝒐 = 𝝈 =
𝒅𝑽𝒊 𝑹 Young-Laplace law
𝟏 𝟏 𝟏
𝜿 → 𝒎𝒆𝒂𝒏 𝒄𝒖𝒓𝒗𝒂𝒕𝒖𝒓𝒆 = +
𝟐 𝑹𝟏 𝑹𝟐 6
Consequence of Surface tension: Laplace pressure

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Capillary bridge and adhesion

θ ′
h/2 𝑹
R θ

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Capillary bridge and adhesion
Capillary pressure within the bridge:
𝟏 𝟏
𝜟𝒑 = 𝝈 ( + )
𝑹𝟏 𝑹𝟐
R1 = R and R2 = R’
𝒉ൗ
𝑹’ = 𝟐
𝒄𝒐𝒔𝜽
𝟏 𝒄𝒐𝒔𝜽
𝜟𝒑 = 𝝈 ( − )
𝑹 𝒉ൗ
𝟐 9
Capillary bridge and adhesion
Force due to capillary pressure:
FC = 𝜟𝒑 𝑨
A= π R2

𝟏 𝒄𝒐𝒔𝜽
FC = π R2 𝝈( − 𝒉ൗ )
𝑹 𝟐

𝟐𝝈𝒄𝒐𝒔𝜽
If R >> h ; ‫ ׀‬FC ‫ ~ ׀‬π R2 ( )
𝒉

1
0
Capillary bridge and adhesion

concave cylinder convex sphere

FC = 0
Attractive capillary force
1
1
Wetting: Young equation

𝛉≈𝝅 𝟎<𝛉<𝝅
𝛉≈𝟎

𝝈 𝛉 𝛉𝑬
𝝈𝑺𝑽 𝑬𝝈
𝑺𝑳
𝝅 𝝅
𝛉 < ; 𝒉𝒚𝒅𝒓𝒐𝒑𝒉𝒊𝒍𝒊𝒄 𝛉 > ; 𝒉𝒚𝒅𝒓𝒐𝒑𝒉𝒐𝒃𝒊𝒄
𝟐 𝟐

𝝈𝑺𝑽−𝝈𝑺𝑳
𝐜𝐨𝐬 𝜽𝑬 = Young equation
𝝈
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Normal force component in Young equation
Force balance:
𝝈𝑺𝑳 + 𝝈𝐜𝐨𝐬𝜽𝑬 − 𝝈𝑺𝑽 = 𝟎
𝝈 𝝈𝑺𝑽−𝝈𝑺𝑳
𝛉𝑬
𝐜𝐨𝐬 𝜽𝑬 =
𝝈𝑺𝑽 𝝈
𝝈𝑺𝑳
Energy minimization:
𝛅𝐖 = 𝝈𝑺𝑳 𝒅𝒙 + 𝝈𝒅𝒙′ − 𝝈𝑺𝑽 𝒅𝒙 = 𝟎
𝝈 dx’ 𝒅𝒙′ = 𝒅𝒙𝐜𝐨𝐬𝜽𝑬
dx’
𝝈𝑺𝑽 𝝈𝑺𝑳
𝜽𝑬
dx
dx
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Normal force component in Young equation
Young equation
𝝈𝑺𝑽−𝝈𝑺𝑳
𝐜𝐨𝐬 𝜽𝑬 =
𝝈

❖ In mechanical equilibrium, all forces must balance each other;

otherwise contact line will start to move along the surface.
❖ Gradual increase in σSV will gradually decrease 𝜽𝑬 and at some
point, it will reach to zero. This is called wetting transition.
❖ What happens with normal force component of σ?
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