Colloids and Rheology

Lecture 4

Interparticle forces
van der Waals forces between particles
 VDW in teraction energy between two spheres of radii R1 and R2 :
A12
W H   
R1 R2
6 H R1  R2  H
R1 R2
where,
A  the Hamaker const ant J 
H is the separation dista nce m
H ~ 0.2 nm for particles in contact equilibriu m separation dista nce 

 Theory assumes additivity and ignores retardation.

Retardation is when the time taken for the electric field of an atom to affect another
atom is comparable with the period of the fluctuating dipole.
1
For H  100 nm, dispersion energy approaches a - 7 dependence.
H

 VDW in teraction energy is derived by summing in teraction energies of all

atoms in one body with all atoms in the other body.
van der Waals forces between particles
 The Hamaker constant, A12   2 C 1  2
where,
 is the number of atoms per unit volume
C is the coefficient in the atom  atom pair potential
 C
 w r   
r 6 
Typical value of A across a vacuum between surfaces is 10 19 J, whether solid or liquid.

 VDW attractive force for like spheres :

dW A11 R
F   .
dH 12 H 2
This is the force of adhesion between two rigid spheres .

 For two identical particles 1 in liquid 3 :

A131  A11  A33  2 A13
from summing particle  particle and liquid  liquid in teractions , minus cross  terms.
Then, assume the geometric mean :
A jk  A jj A kk .
e. g. A13  A11 A33
Thus : A 131  A111/ 2  A133/ 2 
2
DLVO theory
 The stability of many suspension s depends on the balance between the attractive
VDW forces and repulsive electrical double layer in teractions.

 The DLVO theory ( due to Derjaguin , Landau, Verwey and Overbeek )

is based on assumi ng a linear combination of the two potentials.
For particles of radius R :
 64  k T R n i 0  2    AR 
Interaction energy  W H    
 exp   H  
 2   12 H 
where,
n i 0  bulk number density of ions Separation, H (nm)

 1  Debye length
 z e 0 
  tanh 2  
 4kT 
where,
z  ionic valency
e  electronic charge  1.602  10 19 C
0  electrostatic surface potential V

 For highly cha rged surfaces, which exhibit a long Debye length,
i.e. exp   H   1,
there is a strong long  range repulsion with a peak at ~ 1  4 nm .
This energy barrier leads to very stable colloids .
DLVO theory
 For more concentrated electrolyt es , there is a significan t
se condary minimum, usually beyond 3 nm before the energy barrier .

The potential energy minimum at contact is known as

the primary minimum.

If the energy barrier is sufficiently la rge , the colloid particles

may be in the weaker se condary minimum and thus
be kinetically stable.
Separation, H (nm)

 For particles of low surface cha rge and / or high electrolyt e

concentration , the energy barrier will be ineffective W  0.

W  0 correspond s to a critical coagulation concentration ,

when a colloid will be unstable.

 If surface cha rge  0, in teraction curve  VDW curve.

Polymers at surfaces - steric stabilisation
 If the in teractions between segments of a polymer in solution are weak ( a theta solvent ) ,
it forms a random coil of radius of gyration given by :
l n l M / M0
Rg  
6 6
where,
l  effective segment length
n  number of segments
M  total molecular weight
M 0  molecular weight of a monomer unit

 More formally, a theta solvent is defined as a solvent in which no change in free energy occurs
when polymer chains interpenetrate.
Such a solvent is a function of temperature, pressure and solvent composition.

 In a non  theta solvent , the coil size ( defined by the Flory radius , R f )
may be greater or smaller than Rg :
R f   Rg

In a theta solvent   1
In a good solvent ,   1 and R f  l n 3 / 5

 When two surfaces with adsorbed polymer approach each other , a repulsive potential
is developed that arises from an unfavourable entropic change due to
compressi ng / confining the polymer chains. This repulsive force acts to stabilise
colloid particles and is termed steric stabilisat ion.
Polymer adsorption

• Steric stabilisers are usually block

copolymers containing two distinct regions:
(i) a lyophobic region (an ‘anchor’ group)
Train
which attaches to the surface of a particle;
Loop
(ii) a lyophilic region (often a chain) which
trails freely in the dispersion medium.
2RF
• If the dispersion medium is a good solvent
Tail
for the lyophilic region, interpenetration of
Random coil Adsorbed chains is not favoured and interparticle
repulsion results.

• If the dispersion medium is a poor solvent

for the lyophilic region, interpenetration of
chains is favoured and interparticle attraction
results.

• A low surface coverage resembles the

adsorption of random coil in solution.
RF L 0 > RF
Low surface coverage High surface coverage • A high surface coverage resembles a brush-
- adsorption - brush layer
like layer with the chains extended away from
the surface.
Polymer beads or blobs

• When the spacing of the tethered

chains is relatively large, the chains
resemble ‘mushrooms’ and the radius
of gyration of the chains is comparable
to that of the random coil in solution.
s
• When the spacing of the tethered
s chains is relatively small, the chains
resemble ‘brushes’ as the radius of
gyration of each chain is restricted,
forcing the chains further away from
the surface into the dispersion medium.

• The entropic penalty associated with

L0
stretching the chains out from their
RF
random coil configurations is offset by
s >> RF s < RF the free energy gain of reduced
excluded volume interactions..
Mushroom regime Brush regime
Static brush-brush interactions

L0

H d H

L0

• When two surfaces displaying polymer brushes interact, the distance between them with
respect to the distance the brushes extend into the dispersion medium is all-important.

• Repulsive forces will often be experienced once the separation distance is below a few RF.

• These repulsive forces are often referred to as steric repulsion or overlap repulsion and play
an important role in many industrial processes, with colloidal particles which usually
coagulate under certain solution conditions being stabilised by the addition of polymer
brushes to their surfaces.
Dynamic normal brush-brush interactions

LH

H d H

LH

For the sphere-flat configuration:


H  2 LH : FH  6  R 2 H LH  L0 
H  2 LH 
* 
H  2 LH : F  6  R
*
H
2
H
H
 *
 

LH
H : Force dominated by the osmotic pressure
2
Learning outcomes – Lecture 4

1. van der Waals forces between particles

2. DLVO theory
3. Polymers at surfaces - steric stabilisation