STABILIZATION MECHANISMS

(Prevention of agglomeration)

Two major stabilization mechanisms:

1) Electrostatic stabilization
2) Steric stabilization

Electrostatic stabilization is kinetically stable,

Steric stabilization is thermodynamically stable

Colloidal stability
Continuous phase (dispersion medium)
Particles Material (dispersed phase)

The stability of colloids is determined by the

interaction between the particles during collision.

There are two basic interactions:

Attractive and Repulsive

Attraction dominates, particles adhere, finally coalesce

Repulsion dominates; system stable & dispersed state
Primary attraction source ‘Van der Waals forces’
Short range interactions
Long range attractions

Surface charged density

(electrode potential)

(1) Adsorption of ions

(2) Dissociation of surface charged species
(3) Substitution of ions
(4) Accumulation or depletion of electrons at the surface
(5) Physical adsorption of charged species onto the surface.

Electrical double layer structure & electric potential near the solid
surface
ELECTROSTATIC STABILIZATION
Counterbalance of VDWL Coulombic repulsion
In liquid dispersion media, ionic groups can adsorb to
the surface of a colloidal particle forming charged
layer

To maintain electroneutrality, an equal number of

Counter-ions with the opposite charge will surround
the colloidal particles and give rise to overall charge-
neutral double layers.

In charge stabilization, it is the mutual repulsion of

these double layers surrounding particles that
provides stability.
Conditions for occurrence of electrostatic repulsion between two
particles
Electrostatic Repulsion
Electrostatic forces are only present where charged
particles are interacting through a polar medium
(e.g. water, ethanol)

Electrostatic (or Coulomb‘s) forces are in general

stronger and longer range than all other surface
forces

Decays exponentially with particle separation

Affected by the ionic strength of the suspension
Limitations of Electrostatic stabilization

(1) Electrostatic stabilization is a kinetic stabilization

method.

(2) It is only applicable to dilute systems.

(3) It is not applicable to electrolyte sensitive

systems.

(4) It is almost not possible to redisperse the

agglomerated particles.

(5) It is difficult to apply to multiple phase systems,

since in a given condition, different solids
develop different surface charge and electric
potential.
DLVO Theory
(Derjaguin, Landau, Venvey and Overbeek)

The total interaction between two particles, which are

electrostatic stabilized, is the combination of van der
Waals attraction and electrostatic repulsion:

DLVO potential: VA = attractive van der Waals potential,

VR = repulsive electrostatic potential.
Assumptions of DVLO Theory:

1. Infinite flat solid surface,

2. Uniform surface charge density,

3. No redistribution of surface charge, i.e. the

surface electric potential remains constant,

4. No change of concentration of both counter ions

and surface charge determining ions, i.e. the
electric potential remains unchanged

5. Solvent exerts influences via dielectric constant

only, i.e. no chemical reactions between the
particles and solvent
Steric Stabilization (Polymeric stabilization)
It is achieved by attaching (grafting or chemisorption)
macromolecules to the surfaces of the particles. The
stabilization due to the adsorbed layers on the dispersed
particle is generally called steric stabilization.

Schematics of steric stabilization

Solvent & Polymer

Aqueous solvents & Non-aqueous solvents or organic

solvents

Protic and aprotic Solvents

Protic solvent
Which can exchange proton like methanol and ethanol

Aprotic solvent
Which cannot exchange protons like acetone and benzene
Solvent & Polymer
Depending on the interaction between polymer and
solid surface, a polymer can be grouped into:

(1) Anchored polymer, which irreversibly binds to

solid surface by one end only, and typically are
diblock polymer

(2) Adsorbing polymer, which adsorbs weakly at

random points along the polymer backbone

(3) Non-adsorbing polymer, which does not attach to

solid surface and thus does not contribute to polymer
stabilization.

(a) (b)
Interaction between polymers and solid surface:
(a) anchored polymer and (b) absorbing polymer.

Adsorption Chemical or physical

Interactions between polymer layers

(a) (b)
(a) Schematic of two approaching polymer layers,
(b) Gibbs free energy as a function of the distance between two particles.

Conditions
Interactions of two layers, separation distance, H, less than
twice thickness, L, of polymer layers

However, distance reduces to 2L > L interaction occurs

No direct interaction of polymer layer of one particle and

solid surface of other particle

Less coverage of solid surface, insufficient polymer

concentration therefore interpenetration of polymer layers
of approaching particles, increase in Gibbs free energy

High coverage of solid surface, no interpenetration, coil up

of layers, increase in Gibbs energy and repel of particles
Interactions between polymer layers

(a) (b)
(a) Two approaching polymer layers and
(b) Gibbs free energy as a function of the distance between two particles.

Poor solvent, low coverage, L< H < 2L, polymer adsorb on

one particle tend to penetrate to layer of approaching
particle, coil up of polymer & increase in Gibbs free energy

High coverage, similar to good solvent, increase in overall

energy and reductions in distances and repulsive force
produces
STERIC STABILIZATION
(ADVANTAGES)

(1) It is a thermodynamic stabilization method, so that

the particles are always redispersible.

(2) A very high concentration can be accommodated,

and the dispersion medium can be completely
depleted.

(3) It is not electrolyte sensitive.

(4) It is suitable to multiple phase systems.

 STABILIZATION MECHANISMS

Electrostatic stabilization is kinetically stable,

Steric stabilization is thermodynamically stable

ELECTROSTATIC STABILIZATION

Counterbalance of VDWL Coulombic repulsion

In liquid dispersion media, ionic groups can adsorb to
the surface of a colloidal particle forming charged
layer
To maintain electroneutrality, an equal number of
Counter-ions with the opposite charge will surround
the colloidal particles and give rise to overall charge-
neutral double layers.
Application Involved Principles
• Pharmaceutics, cosmetics, • Formation and
inks, paints, foods, foams, stabilization of end-use
chemicals products
• Photographic products, • Formation of colloids for
ceramics, paper coatings, use in subsequent
catalysts, magnetic media manufacturing processes
• Pumping of slurries, coating • Handling properties of
technology, filtration colloids, rheology,
sintering
• Water purification, fining of • Destruction of unwanted
wines and beer colloidal systems
Metal Oxides Stabilization
The surface charge in oxides is mainly derived from
preferential dissolution or deposition of ions.

In the oxide systems, typical charge determining ions

are protons & hydroxyl groups & their concentrations
are described by pH (PH = -log [H+]).

As the concentration of charge determining ions

varies, the surface charge density changes from
positive to negative or vice versa.

The concentration of charge determining ions

corresponding to a neutral or zero-charged
surface is defined as a point of zero charge (P.z.c.)
or zero-point charge (z.P.c.).

At pH > P.z.c., the oxide surface is negatively

charged, since the surface is covered with hydroxyl
groups, OH-, which is the electrical determining ion.

At pH < P.z.c., H+ is the charge determining ions and

the surface is positively charged.
DLVO Theory
(Derjaguin, Landau, Venvey and Overbeek)

DVLO theory suggests that the stability of a particle

in solution is dependent upon its total potential
energy function VT.

This theory recognizes that VT is the balance of

several competing contributions:

VT = VA + VR + VS

VS is the potential energy due to the solvent.

DVLO theory suggests that the stability of a colloidal

system is determined by the sum of these van der
Waals attractive (VA) and electrical double layer
repulsive (VR) forces that exist between particles as
they approach each other due to Brownian motion.

Finally, if the particles have a sufficiently high

repulsion, the dispersion will resist flocculation and
the colloidal system will be stable. However if a
repulsion mechanism does not exist then flocculation
or coagulation will eventually take place.
DLVO applying conditions

(1) Dispersion is very dilute, so that the charge

density and distribution on each particle surface and
the electric potential in the proximity next to each
particle surface are not interfered by other particles.

(2) No other force is present besides van der Waals

force and electrostatic potential, i.e. the gravity is
negligible or the particle is significantly small, and
there exist no other forces, such as magnetic field.

(3) Geometry of particles is relatively simple, so that

the surface properties are the same over the entire
particle surface, and, thus surface charge density and
distribution as well as the electric potential in the
surrounding medium are the same.

(4) The double layer is purely diffusive, so that the

distributions of counter ions and charge determining
ions are determined by all three forces: electrostatic
force, entropic dispersion and Brownian motion.
Total interaction energy Φ between two spherical particles, as a
function of the closest separation distance So between their
surfaces, for different double layer thickness K-I obtained with
different monovalent electrolyte concentrations. The electrolyte
concentration is C (mo1.L-I) = 10-15K2 (cm-I)
Electric potential is dependent on the concentration
and valence state of counter ions.
Van der Waals attraction potential is almost
independent of the concentration and valence state of
counter ions.
The overall potential is strongly influenced by the
concentration and valence state of counter ions.

An increase in concentration and valence state of

counter ions results in a faster decay of the electric
potential

As a result, the repulsive barrier is reduced and its

position is pushed towards the particle surface

Two ways of understanding repulsion forces

Interaction between the double layers

The repulsion derives from the overlap of electric

potentials of two particles. Repulsion is not directly
due to the surface charge on solid particles; instead it
is the interaction between two double layers.
Osmostic flow
Two particles approach one another, the
concentrations of ions between two particles where
two double layers overlap, increase significantly,
since each double layer would retain its original
concentration profile.
As a result, the original equilibrium concentration
profiles of counter ions and surface charge
determining ions are destroyed. To restore the
original equilibrium concentration profiles, more
solvent needs to flow into the region where the two
double layers overlap.

Such an osmotic flow of solvent effectively repels

two particles apart, and the osmotic force disappears
only when the distance between the two particles
equals to or becomes larger than the sum of the
thickness of the two double layers.
Mixed Steric and electric interactions
Electrosteric Stabilization: When polymer attached to
charged particle, polymer layer forms and in addition an
electric potential to the solid surface would retain.
Therefore both electrostatic repulsion and steric restriction
prevents agglomeration.

(a)

(b)

Schematic representation of electrosteric stabilization:

(a) Charged particles with nonionic polymers and
(b) Polyelectrolytes attached to uncharged particles