FUNDAMENTALS OF

WORK OF ADHESION Measuring surface tension

SURFACE MODES:
¥ WORK OF ADHESION AND COHESION
1
1
σ1
Ð We will define work of adhesion and cohesion σ1/2 l
F = 2 γ. l
2 σ2
Ð wetting
2
Ð model studies
Ð precipitation F ⋅ ∆x 2 ⋅ γ ⋅ l ⋅ ∆x
σ= = =γ
Ð capillary rise Wa = σ 1 0 + σ 2 0 − σ 1 2 ∆A 2 ⋅ ∆x ⋅ l
Ð Liquid helium climbing up the walls of a beaker
¥ 0 indicates vacuum. We may skip this ¥ Water: 73 erg/cm2
index! ¥ Mercury (Hg) 490 erg/cm2
1 2 ¥ (UNDER CONDITION THAT THE FILM IS THICK ENOUGH) 3

WORK OF COHESION ¥ Work of adhesion in vacuum: WETTING

1
W12 = σ 1 + σ 2 − σ 1 2 θ θ

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

Wc = 2σ 1 0 = 2σ 1 = σ 3 − W13 + σ 3 − W23 + W12 = W12 − W13 − W23 + Wc3 S

¥ Work of cohesion in a 3rd medium: σ S = σ S / L + σ L ⋅ cos(θ )

W113 = W11 + Wc3 − 2W13 = W11 + W33 − 2W13 = Wc1 + Wc3 − 2W13
¥ The liquid is said to wet the solid if the
contact angle, θ, is sharp, i.e. < 90°.
4 5 6

¥ In vacuum we have: ¥ Interesting to notice that if σL1/L2< σL2

σS/ L < σS +σ L ⇒ σS/ L −σ L < σS
Liquid drop on a liquid surface: energetically favorable if droplet entirely
submerged as compared to fully above
¥ i.e. work of adhesion always positive. L2 surface, but even more favorable if droplet
not wetting partly wetting
64447448 64447448 64447444
fully wetting
L1 penetrates surface;
σS/L- σL σS/L σS/L+σL σS Complete wetting.A layer of ¥ not until σL1/L2< σL2 - σL1 will droplet let go
144424431444444424444444
σ L1 > σ L 2 + σ L1 L 2 ; 
L2 covers thesurface of L1. of surface and enter interior;
σ L 2 > σ L1 + σ L1 L 2 ; {L2 will be engulfed by L1.
Lyophobic solid Lyophilic solid

¥ if σL2< σL1 this will never happen.

σ L1 L 2 > σ L1 + σ L 2 ; Will never happen.
¥ If σS/L< σL the left limit is 0.

7 8 9
 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

¥ Let both a and ω01 be equal to unity.

Surface energies 0.3
I II III IV


( ) ( )
0.2
 σ = ω − ω − 1 ω bulk − ω = 2 − 1 − 1 3 − 1
 1 1 01 2 1 01 2 σ s1


( )
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

Criterion for wetting

¥ Surface energy of the interface smallest ¥ By reducing the surface energy of the liquid
when the two media have the same 0.3 we may extend the region of spreading.
I II III
dielectric properties; in that case it is zero.
IV

¥ 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

¥ The solid is metal like towards the left and

0.1 s1/2-s1
They also reduce the tension at the interface
insulator like towards the right. and extend the partly wetting region.
0
0 1 2 3
ω 02 Surfactants have a tendency to accumulate
¥ Rough indication that metals have a at the interface.
tendency to be wet while wetting is less
16 likely for insulators like, teflon. 17 18
 Variation the numerator
Quantities important for the
¥ We have now varied the frequency. Let us just Surface energies:
very briefly vary the numerator instead. We let a wetting properties:
in the numerator for material 2 now be b.
0.2 0.2

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

Birds of a feather flock together. ¥ With a and ω01 both unity :

(Lika barn leka bŠst)
¥ We have two equal volumes of materials 1 ¥ The energy change is proportional to 0.2

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

combine them into one material with the −

1
[ ω 01
2
+ 2 a − ω 01 + ω 02
2
+ 2 a − ω 02 ]
same density as before?
2 0
0 1 2 3 4 5
ω0 2/ω0 1

22 23 24

Precipitation and the need for Original system

¥ Energy should be lowered when the two
nucleation centers phases separate, i.e., when precipitation
¥ The eq ε (ω ) = 1 −
a
−
b
=0
¥ System consisting of a host material with a occurs . ω 2 − ω12 ω 2 − ω 22
fraction of impurity atoms. has two solutions:
¥ Two types of atom have the same size; this ω ± ( a, b,ω1,ω 2 ) = 1
(
a + b + ω12 + ω 22 ± (a + b) + ω12 − ω 22
2
)
2
(
+ 2(a − b) ω12 − ω 22 )
we do to avoid complications from strain
2

¥ In this case we also create an interface

fields building up in the system. ¥ Energy per atom proportional to:
between the two materials and that, we
know, costs energy. E1 = ω + (1 − x, x,ω1,ω 2 ) − ω + (0, 0,ω1,ω 2 )
+ω − (1 − x, x,ω1,ω 2 ) − ω − (0, 0,ω1,ω 2 )
25 26 27
 ¥ The energy change per impurity atom at ¥ For close packing we have:
¥ Energy per atom in the pure host system precipitation is: η π
 area = ≈ 0.91
proportional to: ∆E E2 (1 − x ) surface atoms E1
 2 3
= + E3 + E2,3 − ηvol ≈ 0.74
E2 = ω + (1, 0,ω1,ω 2 ) − ω + (0, 0,ω1,ω 2 ) Ni x volume atoms x
¥ Typical result for the change in energy per
+ω − (1, 0,ω1,ω 2 ) − ω − (0, 0,ω1,ω 2 ) E2 (1 − x ) ηarea E
= + E3 + E2,3 2 1
− 1
(ηvol ) 3 Ni 3 x impurity atom when the impurities precipitate:
¥ and in the pure impurity system:
x

E3 = ω + (0,1,ω1,ω 2 ) − ω + (0, 0,ω1,ω 2 ) and

0

+ω − (0,1,ω1,ω 2 ) − ω − (0, 0,ω1,ω 2 )

Energy change per atom

-0.004
1

¥ Energy per surface atom in the precipitated 4πR3 4πr 3 R  N 3

ηvol = Ni → = i  -0.008
r  ηvol 
system is proportional to: 3 3
E2,3 = ω + ( 12 , 12 , ω1, ω 2 ) − 12 [ω + (1, 0, ω1, ω 2 ) + ω + (0,1, ω1, ω 2 )] -0.012
¥ where R is the radius of the precipitate, r the
+ω − ( 12 , 12 , ω1, ω 2 ) − 12 [ω − (1, 0, ω1, ω 2 ) + ω − (0,1, ω1, ω 2 )]
radius of the atom and η the packing -0.016
0 200 400 600 800 1000
¥ All proportionality constants are the same. 28
fraction. 29 Number of atoms 30

Capillary rise ¥ These examples are the results from

Learn two things: ¥ Upper surface of a liquid in a beaker minimization of the surface energies and
potential energies in the gravitational field
¥ No gain until the number of atoms exceeds a ¥ This means that the results are quite
critical value, around 50 in our example. different in micro gravity.
Need for nucleation centers or seeds
¥ I will here not go into these effects.
¥ Energy gain per atom increases with the size of
¥ I have in the book made a more extensive
the precipitate. This means that large
precipitates grow at the cost of smaller ones. derivation of the capillary rise in thin tubes.
This is a typical behavior. It is called particle
coarsening, or sometimes Oswald ripening or ¥ The rise of the liquid in a capillary tube
Ostwald ripening.
31 32 33

¥ Let us now determine the thickness, and its

¥ In most cases the energies are just the areas
variation with height, of a thin liquid film adhered
times the surface energies for flat surfaces. to a vertical solid surface.
¥ Only for very small objects or if for other ¥ We are interested in corrections to the results ¥ Let us study a system where we have two
reasons interfaces are very close apart there neglecting interference.
half spaces of two different media 2 and 3
will be effects from the interference ¥ In the case of a capillary tube we limit ourselves to separated by a thin film of medium 1.
between modes on different interfaces or on the region where the film is very thin, at large
parts of the same interface. heights. ¥ In our case medium 1 is the liquid, medium
Ð In this situation we may treat the film as having 2 the solid, and medium 3 air.
¥ An example where this interference occurs
is thin films. A spectacular result of such an constant thickness at each height and we may ¥ Since we are only considering thin films we
disregard the change in surface energy with any can neglect retardation effects.
interference is, as I have demonstrated in deformation of the film. We make use of the
the book, that liquid Helium climbs the theory developed in Sec 6.5 and the result in the
walls of a beaker. 34 35 36
exercise E 4.15.
 ¥ Then the interaction energy between the air and the solid is ¥ We should also notice that if the middle medium ¥ The Hamaker constant for the system
h
∞∞
  ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   has dielectric properties in between the other two
∆E( d ) = 2 2 ∫ ∫ dωdxx ln 1 − e −2 x  2
4π d 0 0  
 ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )  
considered is
 the interaction is repulsive. n
3h ∞ ∞
1  ε 2 ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )  
dω ∑
π ∫0 n=1 4n3  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )  
∞∞ n
A=
h 1  ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   ¥ The force per unit area, or pressure, is  
= − 2 2 ∫ ∫ dωdxx ∑ e −2 xn  2  
4π d 0 0 n n  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )  
3h ∞  ε 2 ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )  
4π ∫0  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )  
∞ ∞ n ∂ ≈ dω  
h 1  ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   P( d ) = − ∆E( d )
= − 2 2 ∫ dω ∑ 3  2  ∂d
4π d 0 n =1 4n  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )   n
h ∞ ∞
1  ε 2 ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )  
dω ∑
2π 2 d 3 ∫0 n=1 4n3  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )  
∞ =−  
 ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )  
≈−
h
∫ dω  2 
16π 2 d 2 0  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )  
¥ and ∆E( d ) = −
A
12πd 2
;
∞
h  ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )  
8π 2 d 3 ∫0  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )  
≈− dω  2  A
P( d ) = −
6πd 3
¥ where in the last line we have assumed that the dielectric
properties of the three media are not very different from
each other; if this is the case it is enough to keep just the
first term of the expansion. 37 38 39

¥ 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