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adhesion

adhesion

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1

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

·
⋅ ⋅ ⋅
⋅ ⋅
·
F x
A
l x
x l




2
2
4
WORK OF COHESION
1
σ
1
1
σ 1
1
W
c
· · 2 2
1 0 1
σ σ
5
¥ Work of adhesion in vacuum:
¥ Work of adhesion in a 3rd medium:
¥ Work of cohesion in a 3rd medium:
W
12 1 2 1 2
· + − σ σ σ
W
W W W
W W W W W W W
c
12
3
1 3 2 3 1 2
1 3 13 2 3 23 1 2 12
3 13 3 23 12 12 13 23
3
· + −
· + − [ ] + + − [ ] − + − [ ]
· − + − + · − − +
σ σ σ
σ σ σ σ σ σ
σ σ
W W W W W W W W W W
c c c 11
3
11
3
13 11 33 13
1 3
13
2 2 2 · + − · + − · + −
6
WETTING
¥ The liquid is said to wet the solid if the
contact angle, θ, is sharp, i.e. < 90°.
θ
θ
σ σ σ θ
S S L L
· + ⋅ ( )
/
cos
θ
S
L
7
¥ In vacuum we have:
¥ i.e. work of adhesion always positive.
¥ If σ
S/L
< σ
L
the left limit is 0.
σ σ σ σ σ σ
S L S L S L L S / /
< + ⇒ − <
σ
S σ
S/L
σ
S/L
σ
L
+ σ
S/L
σ
L
-
64447448 64447444 64447448
partly wetting fully wetting not wetting
144424431444444424444444
Lyophobic solid Lyophilic solid
8
Liquid drop on a liquid surface:
L2
L1
σ σ σ
σ σ σ
σ σ σ
L L L L
L L L L
L L L L
1 2 1 2
2 1 1 2
1 2 1 2
> +
¹
'
¹
> + {
> +
;
;
;
Completewetting. Alayer of
L2coversthesurfaceof L1.
L2will beengulfedbyL1.
Will never happen.
9
¥ Interesting to notice that if σ
L1/L2
< σ
L2
energetically favorable if droplet entirely
submerged as compared to fully above
surface, but even more favorable if droplet
penetrates surface;
¥ not until σ
L1/L2
< σ
L2
- σ
L1
will droplet let go
of surface and enter interior;
¥ if σ
L2
< σ
L1
this will never happen.
10
Gravitational effects:
11
Modelling of adhesion, cohesion
and wetting.
¥ Let both materials be represented by a
dielectric function of the form:
¥ density of carriers in the two substances the
same
ε ω
ω
ω ω
i
i i
i
a
i ( ) · −

· 1
2
1 2
2 2
; ,
ε ω
ω ω
i
i
a
i ( ) · −

· 1
2
1 2
2
0
2
; ,
12
¥ bulk modes
¥ surface modes
¥ interface modes
ε ω ω ω
i i
bulk
i
a ( ) · · + 0 2
0
2
;
ε ω
ω ω
i
i i
a
( ) +
· · +
1
2
0
0
2
;
ε ω ε ω
ω
ω ω
ω ω
1 2
01
2
02
2
01
2
02
2
2
2
2
0
2 2
( ) + ( )
· ·
+
( )
+ t
− |
.

`
,

+
t
; a a
13
¥ Let both a and ω
01
be equal to unity.
0
1
2
3
0 1 2 3
w01
w02
w 1
w 2
w p
w m
ω
ω
02
14
Surface energies
¥ Assumed that there are N modes (q-values)
and all modes give the same contribution.
σ ω ω ω ω
σ ω ω ω ω ω ω ω ω
σ ω ω ω ω ω ω ω ω
ω
1 1 01
1
2 1 01
1
2
2 2 02
1
2 2 02 02
2
02
1
2 02
2
02
1 2 01 02
1
2 1 01
1
2 2 02
2 1 3 1
1 2
1
· − − − · − − −
· − − − · + − − + −
· + − − − − − −
·
+
( ) ( )
( )
|
.
`
,
( ) ( ) + −
bulk
bulk
bulk bulk
/
02 02
2
02
2
2
02
2
02
2
2
1
2
1
2 02
2
02
2
1
1
2
1
1
2
1
1
2
1
3 1 2
( ) |
.

`
,

( ) |
.

`
,

( )
|
.
`
,
¹
'
¹
¹
¹
¹
¹
¹
¹
¹
¹
¹
¹
¹
¹
¹
¹
+ +

+ +
+
+ −

+
− + − + +
ω
ω
ω
ω ω
15
¥ four characteristic regions:
0
0.1
0.2
0.3
0 1 2 3
s 1
s 2
s1/2
σ
ω
02
I II III
IV
I
II
III
IV
:
:
:
:
σ σ σ
σ σ σ
σ σ σ
σ σ σ
2 1 2 1
2 1 1 2
1 2 1 2
1 1 2 2
> >
> >
> >
> >
16
¥ Surface energy of the interface smallest
when the two media have the same
dielectric properties; in that case it is zero.
¥ Also always smaller than the largest of the
two surface energies for the free surfaces.
¥ The solid is metal like towards the left and
insulator like towards the right.
17
Criterion for wetting
¥ Rough indication that metals have a
tendency to be wet while wetting is less
likely for insulators like, teflon.
0
0.1
0.2
0.3
0 1 2 3
s 2
s1/2
s1+s1/2
s1/2-s1
σ
ω
02
I II III
IV
fully wetting
spreading
partly wetting not wetting
1: Liquid
2: Solid
18
¥ By reducing the surface energy of the liquid
we may extend the region of spreading.
Surfactants have this property.
They also reduce the tension at the interface
and extend the partly wetting region.
Surfactants have a tendency to accumulate
at the interface.
19
Variation the numerator
¥ We have now varied the frequency. Let us just
very briefly vary the numerator instead. We let a
in the numerator for material 2 now be b.
0
0.5
1
1.5
2
2.5
0 0.5 1 1.5 2 2.5 3
w 1
w 2
w p
w m
ω
b
20
Surface energies:
0
0.05
0.1
0.15
0.2
0 0.5 1 1.5 2 2.5 3
s 1
s 2
s12
σ
b
21
Quantities important for the
wetting properties:
-0.05
0
0.05
0.1
0.15
0.2
0 0.5 1 1.5 2 2.5 3
s 2
s1/2
s1/2+s1
s1/2-s1
zero level
σ
b
22
Birds of a feather flock together.
(Lika barn leka bŠst)
¥ We have two equal volumes of materials 1
and 2.
They have both the same number of atoms.
¥ What happens with the energy when we
combine them into one material with the
same density as before?
23
¥ The energy change is proportional to
E a a
a a
·
+ ( )
+ +
− |
.

`
,

+ −
+ ( )
+
− |
.

`
,

+
+ ( )
+ −
− |
.

`
,

+ −
+ ( )

− |
.

`
ω ω
ω ω
ω ω
ω ω
ω ω
ω ω
ω ω
ω ω
01
2
02
2
01
2
02
2
2
2 01
2
02
2
01
2
02
2
2
01
2
02
2
01
2
02
2
2
2 01
2
02
2
01
2
02
2
2 2 2 2
2 2 2 2 ,,

− + − + + −
[ ]
2
01
2
01 02
2
02
1
2
2 2 ω ω ω ω a a
24
¥ With a and ω
01
both unity :
0
0.05
0.1
0.15
0.2
0 1 2 3 4 5
E
n
e
r
g
y
ω
0 2

0 1
25
Precipitation and the need for
nucleation centers
¥ System consisting of a host material with a
fraction of impurity atoms.
¥ Two types of atom have the same size; this
we do to avoid complications from strain
fields building up in the system.
26
¥ Energy should be lowered when the two
phases separate, i.e., when precipitation
occurs .
¥ In this case we also create an interface
between the two materials and that, we
know, costs energy.
27
Original system
¥ The eq
has two solutions:
¥ Energy per atom proportional to:
ε ω
ω ω ω ω
( ) · −



· 1 0
2
1
2 2
2
2
a b
ω ω ω ω ω ω ω ω ω
t
· + + + t + + − + − − ( ) ( ) ( )( )
( , , , ) a b a b a b a b
1 2
1
2 1
2
2
2 2
1
2
2
2
2
1
2
2
2
2
E x x
x x
1 1 2 1 2
1 2 1 2
1 0 0
1 0 0
· − −
+ − −
+ +
− −
ω ω ω ω ω ω
ω ω ω ω ω ω
( , , , ) ( , , , )
( , , , ) ( , , , )
28
¥ Energy per atom in the pure host system
proportional to:
¥ and in the pure impurity system:
¥ Energy per surface atom in the precipitated
system is proportional to:
¥ All proportionality constants are the same.
E
2 1 2 1 2
1 2 1 2
1 0 0 0
1 0 0 0
· −
+ −
+ +
− −
ω ω ω ω ω ω
ω ω ω ω ω ω
( , , , ) ( , , , )
( , , , ) ( , , , )
E
3 1 2 1 2
1 2 1 2
0 1 0 0
0 1 0 0
· −
+ −
+ +
− −
ω ω ω ω ω ω
ω ω ω ω ω ω
( , , , ) ( , , , )
( , , , ) ( , , , )
E
2 3
1
2
1
2 1 2
1
2 1 2 1 2
1
2
1
2 1 2
1
2 1 2 1 2
1 0 0 1
1 0 0 1
,
( , , , ) ( , , , ) ( , , , )
( , , , ) ( , , , ) ( , , , )
· − + [ ]
+ − + [ ]
+ + +
− − −
ω ω ω ω ω ω ω ω ω
ω ω ω ω ω ω ω ω ω
29
¥ The energy change per impurity atom at
precipitation is:
and
¥ where R is the radius of the precipitate, r the
radius of the atom and η the packing
fraction.
∆E
N
E x
x
E E
E
x
E x
x
E E
N
E
x
i
i
·
− ( )
+ + −
·
− ( )
+ +
( )

2
3 2 3
1
2
3 2 3
1
1
1
2
3
1
3
,
,
surfaceatoms
volumeatoms
area
vol
η
η
4
3
4
3
3 3
1
3
π
η
π
η
R
N
r R
r
N
vol i
i
vol
· → ·
|
.

`
,

30
¥ For close packing we have:
¥ Typical result for the change in energy per
impurity atom when the impurities precipitate:
η
π
η
area
· ≈

¹
'
¹
¹
¹
2 3
0 91
0 74
.
.
vol
-0.016
-0.012
-0.008
-0.004
0
0 200 400 600 800 1000
E
n
e
r
g
y

c
h
a
n
g
e

p
e
r

a
t
o
m
Number of atoms
31
Learn two things:
¥ No gain until the number of atoms exceeds a
critical value, around 50 in our example.
Need for nucleation centers or seeds
¥ Energy gain per atom increases with the size of
the precipitate. This means that large
precipitates grow at the cost of smaller ones.
This is a typical behavior. It is called particle
coarsening, or sometimes Oswald ripening or
Ostwald ripening.
32
Capillary rise
¥ Upper surface of a liquid in a beaker
¥ The rise of the liquid in a capillary tube
33
¥ These examples are the results from
minimization of the surface energies and
potential energies in the gravitational field
¥ This means that the results are quite
different in micro gravity.
¥ I will here not go into these effects.
¥ I have in the book made a more extensive
derivation of the capillary rise in thin tubes.
34
¥ In most cases the energies are just the areas
times the surface energies for flat surfaces.
¥ Only for very small objects or if for other
reasons interfaces are very close apart there
will be effects from the interference
between modes on different interfaces or on
parts of the same interface.
¥ An example where this interference occurs
is thin films. A spectacular result of such an
interference is, as I have demonstrated in
the book, that liquid Helium climbs the
walls of a beaker.
35
¥ Let us now determine the thickness, and its
variation with height, of a thin liquid film adhered
to a vertical solid surface.
¥ We are interested in corrections to the results
neglecting interference.
¥ In the case of a capillary tube we limit ourselves to
the region where the film is very thin, at large
heights.
Ð In this situation we may treat the film as having
constant thickness at each height and we may
disregard the change in surface energy with any
deformation of the film. We make use of the
theory developed in Sec 6.5 and the result in the
exercise E 4.15.
36
¥ Let us study a system where we have two
half spaces of two different media 2 and 3
separated by a thin film of medium 1.
¥ In our case medium 1 is the liquid, medium
2 the solid, and medium 3 air.
¥ Since we are only considering thin films we
can neglect retardation effects.
37
¥ Then the interaction energy between the air and the solid is
¥ 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.

∆E d
d
d dxx e
d
d dxx
n
e
x
n
xn
( ) · −
( ) − ( )
( ) + ( )

]
]
]
( ) − ( )
( ) + ( )

]
]
]
¹
'
¹
¹
'
¹
· −

∞ ∞

∫ ∫

h
h
4
1
4
1
2 2
2 2 1
2 1
3 1
3 1
0 0
2 2
2
π
ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
π
ω
ln
' '
' '
' '
' '
εε ω ε ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
π
ω
ε ω ε ω
ε ω
2 1
2 1
3 1
3 1
0 0
2 2 3
1
2 1
2
4
1
4
' '
' '
' '
' '
' '
'
( ) − ( )
( ) + ( )

]
]
]
( ) − ( )
( ) + ( )

]
]
]
¹
'
¹
¹
'
¹
· −
( ) − ( )
( ) +
∞ ∞
·

∫ ∫

n
n
d
d
n
h
εε ω
ε ω ε ω
ε ω ε ω
π
ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
ε ω
1
3 1
3 1
0
2 2
2 1
2 1
3 1
3
16
'
' '
' '
' '
' '
' '
'
( )

]
]
]
( ) − ( )
( ) + ( )

]
]
]
¹
'
¹
¹
'
¹
≈ −
( ) − ( )
( ) + ( )

]
]
]
( ) − ( )
( ) +


n
d
d
h
εε ω
1
0
' ( )

]
]
]
¹
'
¹
¹
'
¹


38
¥ We should also notice that if the middle medium
has dielectric properties in between the other two
the interaction is repulsive.
¥ The force per unit area, or pressure, is

P d
d
E d
d
d
n
d
d
n
n
( ) · − ( )
· −
( ) − ( )
( ) + ( )

]
]
]
( ) − ( )
( ) + ( )

]
]
]
¹
'
¹
¹
'
¹
≈ −
·
∞ ∞
∑ ∫


π
ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
π
ω

h
h
2
1
4
8
2 3 3
1
2 1
2 1
3 1
3 1 0
2 3
' '
' '
' '
' '
εε ω ε ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
2 1
2 1
3 1
3 1 0
' '
' '
' '
' '
( ) − ( )
( ) + ( )

]
]
]
( ) − ( )
( ) + ( )

]
]
]
¹
'
¹
¹
'
¹


39
¥ The Hamaker constant for the system
considered is
¥ and ;

A d
n
d
n
n
·
( ) − ( )
( ) + ( )

]
]
]
( ) − ( )
( ) + ( )

]
]
]
¹
'
¹
¹
'
¹

( ) − ( )
( ) +
·
∞ ∞
∑ ∫
3 1
4
3
4
3
1
2 1
2 1
3 1
3 1 0
2 1
2
h
h
π
ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
ε ω ε ω
π
ω
ε ω ε ω
ε ω
' '
' '
' '
' '
' '
' εε ω
ε ω ε ω
ε ω ε ω
1
3 1
3 1 0
'
' '
' ' ( )

]
]
]
( ) − ( )
( ) + ( )

]
]
]
¹
'
¹
¹
'
¹


∆E d
A
d
( ) · −
12
2
π
P d
A
d
( ) · −
6
3
π
40
¥ If the three media are diluted or if we use
summation over pair interactions to
calculate the Hamaker constant for the
system this constant may be written as
¥ With the London approximation these
constants are
A = A + A - A - A
11 23 12 13

A
n
ij
i j i j
i j
·
( ) ( )
+ ( )
3 0 0
2
2 2
0 0
0 0
π α α ω ω
ω ω
h h
h h
, ,
, ,
41
¥ Let us now study the free energy of a unit
area of the film. It is
¥ The minimum defines the equilibrium
thickness:
W d
A
d
dgh ( ) · − +
12
2
π
ρ

∂ π
ρ
πρ d
W d
A
d
gh d
A
gh
A ( ) · + ⇒ ·
− |
.

`
,

6 6
3 0
1 3
if negative
42
¥ If the Hamaker constant is positive there is an attractive
force between the free surface of the film and the solid-
liquid interface;
Ð this tends to thin the film and in this case one needs to
include other energy terms as well to get a non-zero
thickness.
¥ The dielectric constant of liquid He is very close to one.
¥ This means that its dielectric constant lies between most
solids and air with the effect that the Hamaker constant for
a film on a solid is negative.
¥ This has the effect that the film thickens and explains why
the liquid climbs the walls of a beaker.

teflon. ω± = 2 2 2 (ω 01 + ω 02 ) + a ± 2 2 2  ω 01 − ω 02  2   +a 2   2 12 ¥ Let both a and ω01 be equal to unity.Gravitational effects: Modelling of adhesion. Criterion for wetting 0. 3 ω 2 w01 w02 w1 w2 wp wm 1    σ = ω − ω − 1 ω bulk − ω = 2 − 1 − 1 3 − 1 1 1 01 2 1 01 2   2 2 bulk σ 2 = ω 2 − ω 02 − 1 ω 2 − ω 02 = ω 02 + 1 − ω 02 − 1  ω 02 + 2 − ω 02   2 2    1 ω bulk − ω 1 ω bulk − ω σ 1 / 2 = ω + + ω − − ω 01 − ω 02 − 2 1 01 − 2 2 02  2 2  2 2 2 2 1 + ω 02 1 + ω 02  1 − ω 02   1 − ω 02   = +1+  +1−   +1 +  +1  2 2  2   2     ω2 + 2 +ω  − 1 3 + 1 − 1  02  02  2 2  Surface energies ( ( ) ) ( ( 0. cohesion and wetting.1 II fully wetting spreading III partly wetting IV not wetting ¥ By reducing the surface energy of the liquid we may extend the region of spreading.3 I 0. ¥ Also always smaller than the largest of the two surface energies for the free surfaces. 2 ω − ωi ¥ density of carriers in the two substances the same 2a ε i (ω ) = 1 − 2 2 . 3 s2 s1/2 s1+s1/2 s1/2-s1 1: Liquid 2: Solid 0 0 1 ω 02 2 16 ¥ Rough indication that metals have a tendency to be wet while wetting is less likely for insulators like. 17 18 . ω i = ω 0i + a 2 ¥ interface modes ε1 (ω ) + ε 2 (ω ) = 0 . Surfactants have this property. i = 1. ω ibulk = ω 0 i + 2 a ¥ surface modes ε i (ω ) + 1 2 = 0 . ¥ The solid is metal like towards the left and insulator like towards the right. in that case it is zero. 2 ω − ω 0i 10 11 ¥ bulk modes 2 ε i (ω ) = 0 .2 σ 0. Surfactants have a tendency to accumulate at the interface. 14 15 ¥ Surface energy of the interface smallest when the two media have the same dielectric properties. They also reduce the tension at the interface and extend the partly wetting region.3 I 0. i = 1.1 II III IV ) s1 s2 s1/2 ( ) ( ) ( ) ) 0 0 1 ω 02 2 3 ( ) ¥ four characteristic regions: I : σ 2 > σ 1 2 > σ 1 II : σ 2 > σ 1 > σ 1 2 III : σ 1 > σ 2 > σ 1 2 IV : σ 1 > σ 1 2 > σ 2 0 0 1 ω 02 2 3 13 ¥ Assumed that there are N modes (q-values) and all modes give the same contribution.2 σ 0. ¥ Let both materials be represented by a dielectric function of the form: 2a ω ε i (ω ) = 1 − 2 i i 2 .

0. when precipitation occurs .ω1.2 2 Energy E= 2 2 (ω 01 + ω 02 ) + a + 2 2 (ω 01 + ω 02 ) + a − 2 2  ω 01 − ω 02  2   +a − 2   2 2  ω 01 − ω 02  2   +a − 2   2 ω 02 2 2 2 2 (ω 01 + ω 02 ) + 2 2 (ω 01 + ω 02 ) − 2 2  ω 01 − ω 02    2   2 2  ω 01 − ω 02    2   0.ω 2 ) = 1 2 2 2 2 2 a + b + ω1 + ω 2 ± ( a + b ) + ω1 − ω 2 2 ( ) 2 2 2 + 2(a − b) ω1 − ω 2 ( ) ¥ In this case we also create an interface between the two materials and that. They have both the same number of atoms.e. 0.ω 2 ) +ω − (1 − x. ¥ What happens with the energy when we combine them into one material with the same density as before? 22 ¥ With a and ω01 both unity : ¥ The energy change is proportional to 2 2 0.15 0.ω1.1 0.5 3 0 -0. x.ω 2 ) 27 .5 3 0. ¥ Energy should be lowered when the two phases separate. i.5 1 1.ω1.ω1. we know.05 0 0.5 1 0.5 1 1. Let us just very briefly vary the numerator instead. (Lika barn leka bŠst) ¥ We have two equal volumes of materials 1 and 2.2 0. Original system ¥ The eq ε (ω ) = 1 − a b 2 − 2 =0 ω 2 − ω1 ω 2 − ω 2 has two solutions: ω ± ( a.Variation the numerator ¥ We have now varied the frequency.5 b 2 2. this we do to avoid complications from strain fields building up in the system. 25 26 ¥ Energy per atom proportional to: E1 = ω + (1 − x. x. b. ¥ Two types of atom have the same size.ω 2 ) − ω − (0.15 s2 s1/2 s1/2+s1 s1/2-s1 zero level s1 s2 s12 σ 0.2 2.5 0 0 0.15 Surface energies: Quantities important for the wetting properties: 0.1 σ 0.05 ω 1.ω 2 ) − ω + (0. costs energy.05 0 0 1 2 3 4 5 [ 2 ω 01 + 2 a − ω 01 + + 2 a − ω 02 ] 23 ω0 2/ω0 1 24 Precipitation and the need for nucleation centers ¥ System consisting of a host material with a fraction of impurity atoms.ω1. 0.1 2 + 1 − 2 2 2 0.5 3 2 19 20 21 Birds of a feather flock together.5 b 2 2.5 1 1.05 0 0 2. We let a in the numerator for material 2 now be b..5 2 0.5 b w1 w2 wp wm 0.

34 ¥ Let us now determine the thickness.3 − 1 2 1 x (ηvol ) 3 Ni 3 x Energy change per atom and 4πR3 4πr 3 R  N 3 → = i  ηvol = Ni 3 3 r  ηvol  1 -0. medium 2 the solid.1. 1 .ω 2 ) − ω + (0. It is called particle coarsening. of a thin liquid film adhered to a vertical solid surface. ω1. ¥ We are interested in corrections to the results neglecting interference. A spectacular result of such an interference is.91  area = 2 3  ηvol ≈ 0.ω1. 28 ¥ The energy change per impurity atom at precipitation is: ∆E E2 (1 − x ) surface atoms E1 = + E3 + E2.ω 2 ) − ω − (0. 0. 36 . ω1. Ð In this situation we may treat the film as having constant thickness at each height and we may disregard the change in surface energy with any deformation of the film. ω 2 )] 2 2 2 +ω − ( 1 . Need for nucleation centers or seeds ¥ Energy gain per atom increases with the size of the precipitate. ω1.ω 2 ) − ω − (0.1. 0. ω 2 ) + ω + (0.ω1. This is a typical behavior.1.012 -0. r the radius of the atom and η the packing fraction.ω1.ω 2 ) − ω + (0. ω 2 ) + ω − (0. We make use of the theory developed in Sec 6.004 -0. at large heights.¥ Energy per atom in the pure host system proportional to: E2 = ω + (1.ω 2 ) ¥ and in the pure impurity system: E3 = ω + (0. and medium 3 air. 0. as I have demonstrated in the book.ω1.74  ηarea E2 (1 − x ) E + E3 + E2. ω 2 )] 2 2 2 ¥ All proportionality constants are the same. ¥ An example where this interference occurs is thin films.ω1. 1 . ω 2 ) − 1 [ω − (1.15.ω1. This means that large precipitates grow at the cost of smaller ones. ¥ I will here not go into these effects. ¥ Let us study a system where we have two half spaces of two different media 2 and 3 separated by a thin film of medium 1.ω1.ω 2 ) +ω − (1. ¥ Only for very small objects or if for other reasons interfaces are very close apart there will be effects from the interference between modes on different interfaces or on parts of the same interface.3 − Ni x volume atoms x = ¥ For close packing we have: ¥ Typical result for the change in energy per impurity atom when the impurities precipitate: 0 π η ≈ 0.1. 0. 0. ¥ The rise of the liquid in a capillary tube 32 33 ¥ In most cases the energies are just the areas times the surface energies for flat surfaces. ¥ I have in the book made a more extensive derivation of the capillary rise in thin tubes. around 50 in our example. or sometimes Oswald ripening or Ostwald ripening.ω 2 ) +ω − (0. ¥ In the case of a capillary tube we limit ourselves to the region where the film is very thin. ω1.ω 2 ) ¥ Energy per surface atom in the precipitated system is proportional to: E2. ¥ In our case medium 1 is the liquid. ω1.008 ¥ where R is the radius of the precipitate.016 29 0 200 400 600 Number of atoms 800 1000 30 Learn two things: ¥ No gain until the number of atoms exceeds a critical value. 0. that liquid Helium climbs the walls of a beaker. -0. 31 Capillary rise ¥ Upper surface of a liquid in a beaker ¥ These examples are the results from minimization of the surface energies and potential energies in the gravitational field ¥ This means that the results are quite different in micro gravity. 0.5 and the result in the 35 exercise E 4.3 = ω + ( 1 . 0. and its variation with height. ¥ Since we are only considering thin films we can neglect retardation effects. ω1. ω 2 ) − 1 [ω + (1.ω1.

A 6πd 3 37 38 39 ¥ If the three media are diluted or if we use summation over pair interactions to calculate the Hamaker constant for the system this constant may be written as A = A11 + A 23 . ¥ where in the last line we have assumed that the dielectric properties of the three media are not very different from each other. It is W (d ) = − A + ρdgh 12πd 2 ¥ The minimum defines the equilibrium thickness: ∂ A  −A  + ρgh ⇒ d0 =  W (d ) =   6πρgh  ∂d 6πd 3 13 ¥ With the London approximation these constants are Aij = 3π n α i (0)α j (0)hω 0. ¥ The force per unit area. ¥ This has the effect that the film thickens and explains why the liquid climbs the walls of a beaker.¥ Then the interaction energy between the air and the solid is   ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   ∆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 )    h  ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   1 = − 2 2 ∫ ∫ dωdxx ∑ e −2 xn  2   4π d 0 0  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )   n n h 1  ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   = − 2 2 ∫ dω ∑ 3  2  4π d 0 n =1 4n  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )     h ∞  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 )      ∞ ∞ n ∞∞ n ∞∞ ¥ We should also notice that if the middle medium has dielectric properties in between the other two the interaction is repulsive. ¥ The dielectric constant of liquid He is very close to one. Ð this tends to thin the film and in this case one needs to include other energy terms as well to get a non-zero thickness.i + hω 0. or pressure.i hω 0. j 2 2 if A negative 2 hω 0. if this is the case it is enough to keep just the first term of the expansion.A12 . 40 41 42 .A13 ¥ Let us now study the free energy of a unit area of the film. j ( ) ¥ If the Hamaker constant is positive there is an attractive force between the free surface of the film and the solidliquid interface. ¥ This means that its dielectric constant lies between most solids and air with the effect that the Hamaker constant for a film on a solid is negative. is P( d ) = − =− ≈− ¥ The Hamaker constant for the system considered is A= ≈ ∞ 3h ∞ 1  ε 2 ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   dω ∑   π ∫ n=1 4n3  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )      0 n ∂ ∆E( d ) ∂d ∞ h ∞ 1  ε 2 ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   dω ∑   2π 2 d 3 ∫ n=1 4n3  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )      0 n 3h ∞  ε 2 ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   dω   4π ∫  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )      0 A 12πd 2  ε ' (ω ) − ε1' (ω )   ε 3' (ω ) − ε1' (ω )   dω  2  8π 2 d 3 ∫  ε 2 ' (ω ) + ε1' (ω )   ε 3' (ω ) + ε1' (ω )      0 h ∞ ¥ and ∆E( d ) = − P( d ) = − .

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