Colloids

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Hofmeister Series
H+>Al3+>Ba2+>Sr2+>Ca2+>Mg2+>NH4+>K+>Na+>Li+

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Ex:

• In general Na+ would be readily replaced by H+ or Ca2+

H+>Al3+>Ba2+>Sr2+>Ca2+>Mg2+>NH4+>K+>Na+>Li+

• If we wish to replace adsorbed Ca2+ on clay with Na+ by using NaCl,

a high concentration of NaCl solution should be used

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Hofmeister Series
Clays prefer to adsorbed small cations like H+ or ions
Or
Ions of high valancy like Ca2+

H+>Al3+>Ba2+>Sr2+>Ca2+>Mg2+>NH4+>K+>Na+>Li+

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Stability of Colloids
• In practice the zeta potential is the main factor in governing
the stability of colloids.

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Nernst Potential
The difference in the potential between actual surface and the
electroneutral region of the solution.
(Potential at the solid particle surface)

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Stern layer
The layer of ions that surround a charged colloid particle in a
liquid medium. (strongly adsorbed monolayer of counter ions)
This layer consists of ions that are attracted to the charged
particle and are held tightly in a layer adjacent to the particle
surface.

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Stern layer

The thickness of the Stern layer depends on the concentration

of ions in the solution and the charge of the colloid particle.

Stern potential
Potential at the outer boundary of stern layer.

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Slipping plane
When the particle migrates, the water layer together with the
ions in the stern layer moves with it.

Stern layer + Diffused layer = Electrical double layer

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slipping plane
• Slipping plane is the interface which separates mobile fluid
from fluid that remains attached to the surface.

This is the layer of liquid that moves or slips past the surface
of the particle when a force is applied to the liquid.

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Slipping plane
The slipping plane distance depends on the,
nature of the liquid,
charge of the colloid particle,
concentration of ions in the solution.

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Zeta potential , ζ
• Zeta potential is the electrical potential at the slipping plane.

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Zeta potential , ζ
Definition
• The difference in the potential between shear plane (slipping plane)
and electro neutral region of the solution.

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Zeta potential , ζ
• The magnitude of the ζ potential indicates the degree of electrostatic
repulsion between adjacent, similarly charged particles in dispersion.

High Zeta Potential – Stable colloidal system

Low Zeta Potential – Less stable colloidal system

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Factors that affect on the ζ
• pH of the medium
• ionic strength,
• The concentration of any additives,
• and temperature

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Factors that affect on the ζ
• Alkali ions and ammonium produce high zeta potential.
The order of magnitude;
Li+ > Na+ > K+ > NH+4

• Divalent and polyvalent ions produce low zeta-potentials.

• High concentrations of any ion cause the Stern layer to become

‘crowded’ and so reduce the Stern and zeta-potentials.

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Determination of ζ
• Consider a charged particle separated from an equal and opposite
charged layer by a distance d, forming an electrical capacitor.

C D
d

A B

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Determination of ζ
If the charge density on each layer is σ and the dielectric constant of
the medium is ε,
Capacity of parallel plate condenser= (∈∈ )/
A= area of the plate
But, ζ = total charge/capacity
ζ=(σ )/{(∈∈ )/ }

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Determination of ζ
• Zeta potential is measured by causing a colloidal particle to move
under the influence of an electric field and measuring the rate of
migration.

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Zeta potential of different cationic forms of a fire
clay
Nature of clay Zeta Potential (mV)
Ca-clay -10
H-clay -20
Mg-clay -40
Na-clay -80
Natural –clay -30
Treated with calgon -135

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ζ

There is a minimum value of Zeta potential for a colloidal

suspension to be stable.

Particles with zeta potentials more positive than +30 mV or

more negative than -30 mV are normally considered stable.

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Flocculation and deflocculation
• Ceramic slips are suspensions of ceramic particles in a liquid medium,
typically water.
• The goal of slip preparation is to create a uniform and stable
suspension of ceramic particles in the liquid medium.

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Flocculation
• The process of agglomerating ceramic particles together to form
larger clusters or flocs.
• This process can be induced by adding flocculating agents.
• Flocculated suspensions have a high viscosity and low fluidity, and the
particles tend to settle more quickly.

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Flocculation
• If the particles carry an overall low zeta potential , they can then
approach closely enough for the short-range van der Waals’ forces to
operate and cause the particles to gather into flocks or aggregates.

• Then the suspension becomes unstable and it is said to be

flocculated.

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Deflocculation
• is the process of dispersing ceramic particles evenly in the liquid
medium, making them more stable and less likely to settle.
•.

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Deflocculation
• Deflocculated suspensions have a low viscosity and high fluidity, and
the particles tend to stay in suspension for a longer period of time.

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Deflocculation
• If the particles carry an overall high zeta potential , they repel one
another and tend to remain separate.it is said to be defloculated.

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Defloculant
• One method of defloculation is to replace law zeta potential ions by
high zeta potential ions,
Ex: Na+

Also , Sodium silicate, sodium phosphates (Calgon) and sodium

polyacrylate (dispex) act as defloculant by anion exchanging.

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Flocculation and deflocculation
Practical Aspects

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Suspension Viscosity
When suspension is on flocculated state

Particles are grouped together in loose aggregate

Those aggregate occupy much greater volume (than particles)

Therefore apparent viscosity at low shear rates is high

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 Suspension Viscosity
If the suspension is difloculated

Aggregates are broken up

Dispersed in to individual particles

Remain disperse because of repulsion

Individual particles occupy a much smaller effective volume

Viscosity low
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Settling from suspension

• Flocculated aggregates behave like large particles and they

settle more easily than small individual particles.

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Casting rate
Casting rate is high in deflocculated slips since cast layer is
closely packed more permeable to water.

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Unfired Modulus of Rupture
• Higher for deflocculated materials due to close packing of
particles. Product will be hard

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Wet to dry shrinkage
• Higher for flocculated materials since they are loosely
packed.

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Sediment volume
• Flocculated have grater sediment volume.
• After setting, it is difficult to re-disperse a deflocculated
suspension.

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Water tolerance
• For flocculated water tolerance is high.
• When particles loosely packed water can be trapped between
them.

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Adsorption of Organics by clay
• Surface have a greater activity than interior and frequently subjected
to attack by other molecules or ions.
• The phenomenon is known as adsorption.
• It is to reduce free energy of surface.

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Adsorption of organic dyes
Based on
⁻ Cation exchange(CE)
First layer of dye is adsorbed by CE
Surface completely covered by monolayer of dye
Adsorbed layer is irreversible

⁻ Physical adsorption (by van der Waals’ forces)

Layers are not subjected to a strong attraction forces
Reversible
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Adsorption of organic dyes
Up to point B
• Irreversible adsorption
• Colorless supernant
• Monolayer formation
• Strongly held layer

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Adsorption of organic dyes
Beyond point B
• Reversible adsorption
• Colored supernant
• Monolayer formation
• Strongly held layer

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