Colloid Stability ?

A state of subdivision in
which the particles,
droplets, or bubbles
dispersed in another
phase have at least one
dimension between 1 and
1000 nm

all combinations are
possible between :
gas, liquid, and solid
W. Ostwald
Colloidal systems
Surface area of colloidal systems
Cube (1cm; 1cm; 1cm)
after size reduction to an edge length of 500 nm:
surface area of 60 m
2

Spinning dope (1 cm
3
)
after spinning to a fibre with diameter of 1000 nm:
fiber length of 1273 km

1 liter of a 0.1 M surfactant solution:
interfacial area of 40000 m
2


Surface atoms [in %]
in dependence on the particle size [in nm]


0
10
20
30
40
50
60
70
80
90
100
20 10 5 2 1
part of surface
atoms in %
%
nm
Colloidal systems
have large surface areas

surface atoms become dominant
Colloid stability
Colloidal gold: stabilized against coagulation !

Creme: stabilized against coagulation !

Milk: stabilized against coagulation !
Particle Particle interactions

Interaction Energy ( V
tot
) Distance of
Separation (d) Relationship


d
V
tot
(d)

= V
attr
(d)

+ V
rep
(d)

- Van der Waals attraction - Electrostatic repulsion
- Steric repulsion
DLVO - Theory
1940 Derjaguin; Landau; Verwey; Overbeek

Long range attractive van der Waals forces
Long range repulsive electrostatic forces

DLVO Theory
Van der Waals attractive energy


a) between two plates:
b) between two spheres:
2
.
12 d
A
V
attr
Waals der Van
t
=
d
a A
V
attr
Waals der Van
12
.
=
Double layer models
Helmholtz

Gouy Chapman

Stern
Gouy Chapman model

planar double layer

Ions as point charges



Electrolyte theory
( )
( )
( )
kT
x e z
i i
i
i
e n e z
x d
x d

c c
t

E

=
0
2
2
4
I distribution of ions in the diffuse double layer
(Boltzmann equation)
II equation for the room charge density
III Poisson relation
Aus I, II und III folgt:

Poisson Boltzmann - relation
( ) ( )
( )
kT
x e z
e n x n
i
i i

=
( ) ( ) x n e z x
i i
i
E =
( ) ( )
c c
t
0
2
2
4 x
x d
x d
=
Solution of the P-B equation
( )
( )
( )
x
e k x
x
x d
x d
k

k


=
=
0
2
2
2
For small potentials (< 25 mV) :
Integrable form
( )
( )
( )
kT
x e z
i
i i
i
e n e z
dx
x d

c c
t

=

0
2
2
4
DLVO Theory
Electrostatic repulsive energy
Resulting repulsive overlap energy

a) Between two plates:

c volume concentration of the
z valent electrolyte
b) Between two spheres
d rep
elektrost
e
kT c
V
k
k

=
64
.
2
2
2
2 2
0
2 2
.
1
1 8
(
(
(

=

kT
ze
kT
ze
d rep
elektrost
e
e
e
z e
T k
V

k
o c c
V
tot
(d)

= V
attr
(d)

+ V
rep
(d)

V
van der Waals
= - A a / 12 d V
electrost.
= k e
-kd

A Hamaker constant
a particle radius
d distance between the particles
1/k - thickness of the double-layer

Electrostatic stabilization

stabilized against coagulation
Kinetically stable state
energetic metastable state in the
secondary minimum
with an energy barrier
Critical coagulation concentration (CCC)

The energy barrier disappears by adding a
critical amount of low molecular salts
DLVO Theory
(CCC)
V
tot
/ dd = 0 V
tot
= 0
for two spheres:
( )
2
2 6 6
3
0
3 5 5 3
2
2
2
2
1
2 2
0
2 2
1
1
4
10 39 , 3
12
1
1 8
(
(
(

+

=
=
(
(
(

kT
ze
kT
ze
kT
ze
kT
ze
e
e
A z e
T k
ccc
d
a A
e
e
e
z e
T k

t
c c
o cc
DLVO Theory
(CCC)

For two spheres the ccc should be related to
the valency (1 : 2 : 3) of the counterions as:

1000 : 16 : 1,3
CCC of a colloidal dispersion as a function of
the salt concentration
AlCl
3
CaCl
2

MgCl
2

KCl
NaCl
electrolyte
1,7 9,3 10
-5

13 6,5 10
-4

13 7,2 10
-4

1000

5,0 10
-2

1000 5,1 10
-2
Schulze-Hardy-ratio CCC of a
Arsensulfid -Dispersion
Steric stabilization
What will be happen when we add polymers
to a colloidal dispersion ?
Particle Particle interactions


Polymer adsorption layer
Particle Particle interactions


Overlap of the
polymer adsorption layer
Overlap of the adsorption layer

Osmotic repulsion
Entropic repulsion
Enthalpic repulsion
Sterically stabilized systems can
be controlled by
The thickness of the adsorption layer
The density of the adsorption layer
The temperature
Stabilization and destabilization in
dependence on the molecular
weight of the added polymer
Stabilization and destabilization in
dependence on the
polymer-concentration