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1
σ1
¥ Work of adhesion in a 3rd medium:
σ1 W123 = σ 1 3 + σ 2 3 − σ 1 2
1
= [σ 1 + σ 3 − W13 ] + [σ 2 + σ 3 − W23 ] − [σ 1 + σ 2 − W12 ] θ L
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Modelling of adhesion, cohesion
Gravitational effects:
and wetting. ¥ bulk modes
¥ Let both materials be represented by a ε i (ω ) = 0 ; ω ibulk = ω 02i + 2 a
dielectric function of the form:
2a ω ¥ surface modes
ε i (ω ) = 1 − 2 i i 2 ; i = 1, 2 ε i (ω ) + 1
ω − ωi = 0 ; ω i = ω 02i + a
2
¥ density of carriers in the two substances the ¥ interface modes
same 2a
ε i (ω ) = 1 − 2 ; i = 1, 2 ε1 (ω ) + ε 2 (ω ) (ω 012 + ω 022 ) + a ± ω 01
2
− ω 02
2
2
ω − ω 02i 2
= 0 ; ω± =
2
2
+a
2
10 11 12
( )
s2
σ
2 = ω 2 − ω 02 2− 1 ω bulk − ω
2 02 = ω 2
02 + 1 − ω 02 − 12 ω 02
2
+ 2 − ω 02 0.1
s1/2
( ) ( )
w01
σ 1 / 2 = ω + + ω − − ω 01 − ω 02 − 12 ω1 − ω 01 − 12 ω 2 − ω 02
3 w02 bulk bulk
w1
w2
( ) ( )
0
wp 1 + ω 02
2 2
1 + ω 02
2 2
2 wm
1 − ω 02
2 1 − ω 02
2 0 1 2 3
ω
= +1+ +1 + +1− +1 ω 02
2 2 2 2
1
( )
− 12 3 + 1 − 12 ω 02
2
+ 2 + ω 02 ¥ four characteristic regions: I : σ 2 > σ 1 2 > σ 1
II : σ 2 > σ 1 > σ 1 2
0
0 1 2 3 ¥ Assumed that there are N modes (q-values) III : σ 1 > σ 2 > σ 1 2
ω 02 and all modes give the same contribution. IV : σ 1 > σ 1 2 > σ 2
13 14 15
¥ Also always smaller than the largest of the 0.2 fully wetting
spreading
partly wetting not wetting
Surfactants have this property.
σ s2
two surface energies for the free surfaces.
1: Liquid
s1/2 2: Solid
s1+s1/2
2.5 0.15 s2
0.15 s1 s1/2
s1/2+s1
s2 s1/2-s1
0.1
2
σ s12 σ zero level
0.1
1.5 0.05
ω
0.05
1 0
w1
0.5 w2 0 -0.05
wp 0 0.5 1 1.5 2 2.5 3 0 0.5 1 1.5 2 2.5 3
wm
0 b b
0 0.5 1 1.5 2 2.5 3
b 19 20 21
and 2.
E=
(ω 012 + ω 022 ) + a + ω 01
2
− ω 02
2
2
(ω 012 + ω 022 ) + ω 01
2
− ω 02
2
2 0.15
+a −
2
Energy
2 2 2 2
They have both the same number of atoms. 0.1
+
(ω 012 + ω 022 ) + a − ω 01
2
− ω 02
2
2
(ω 012 + ω 022 ) − ω 01
2
− ω 02
2
2
+a −
2
¥ What happens with the energy when we 2
2 2
2
0.05
22 23 24
¥ If the three media are diluted or if we use ¥ Let us now study the free energy of a unit ¥ If the Hamaker constant is positive there is an attractive
area of the film. It is force between the free surface of the film and the solid-
summation over pair interactions to liquid interface;
calculate the Hamaker constant for the W (d ) = −
A
+ ρdgh Ð this tends to thin the film and in this case one needs to
system this constant may be written as 12πd 2 include other energy terms as well to get a non-zero
thickness.
¥ The minimum defines the equilibrium
¥ The dielectric constant of liquid He is very close to one.
A = A11 + A 23 - A12 - A13 thickness:
¥ This means that its dielectric constant lies between most
¥ With the London approximation these ∂ A −A
13 solids and air with the effect that the Hamaker constant for
W (d ) = + ρgh ⇒ d0 =
constants are ∂d 6πd 3 6πρgh
if A negative a film on a solid is negative.
3π n α i (0)α j (0)hω 0,i hω 0, j
2 2 ¥ This has the effect that the film thickens and explains why
Aij =
(
2 hω 0,i + hω 0, j ) the liquid climbs the walls of a beaker.
40 41 42