PROPERTIES AND APPLICATIONS RELATED

TO SURFACTANTS

September 2019
 Reduction of
Solubility
surface tension

Dispersion and
Wettability
Aggregation

Foaming and
Emulsions
Defoaming

Synthesis and
Detergency
Nanotechnology
Where can you find Emulsions ?

Pesticide Asphalt Skin cream

Metal cutting oils Margarine Ice cream

Stability of emulsions may be engineered to vary from seconds to years depending on application
Emulsion
Suspension of liquid droplets (dispersed phase) of certain size within a second immiscible
liquid (continuous phase).

Emulsion composition

Interfacial layer (emulsifying agent): Essential to stabilizing the emulsion

Internal phase (Dispersed medium): The phase that is added tends to

become the internal phase

External phase (Continuous medium): The predominant solubility of the

emulsifier tends to determine the external phase (Bancroft’s rule)

Generally, the phase of the greatest volume tends to become the external phase
 Emulsion
Emulsion classification
- Based on dispersed phase
+ Oil in Water (O/W): Oil droplets dispersed in water
+ Water in Oil (W/O): Water droplets dispersed in oil
Emulsion
Emulsion classification
O/W vs W/O
Emulsion

- Based on size of liquid droplets

(1) macroemulsions, the most well-known type, opaque

emulsions with particles >400 nm (0.4 μm), easily
visible under a microscope
(2) microemulsions, transparent dispersions with
particles <100 nm (0.1 μm) in size
(3) Nanoemulsions (miniemulsions), a type that is blue-
white, with particle sizes between those of the first
two types (100–400 nm [0.1–0.4 μm]).
Emulsion

Differences of emulsion types

 Emulsions are non-stable?

• Emulsions are thermodynamically unstable

• This means that their natural tendency is to
revert to a state of least energy i.e.
separated into two layers

• The process of emulsification is to

produce droplets but also to maintain
them in this state over a reasonable
shelf life
 Emulsion breaking phenomena
Emulsions are non-stable?

Factors that contribute to emulsion

instability

 Forces of attraction between

droplets

 Gravity

 Random movement of droplets

 Creaming / Sedimentation

• No change in droplet size

• Reversible
• Driven by density difference
• Usually results from gravitational forces

Creaming Sedimentation
 Flocculation
Flocculation refers to the process by which fine particulates are caused to clump together into a floc

• No change in droplet size

• Reversible
• Improve in the presence of flocculants
 Coalescence and Ostwald Ripening

Coalescence A process in which 2 drops of discontinuous phase combine together to form a bigger one

• Fat or ice crystals present

• Viscosity of continuous phase is
decreased
• Emulsion is agitated
• Interfacial viscosity is decreased

• In the presence of promoters

- Non-polar oils
- Lower polar co-solvent

Ostwald Ripening The process by which components of the discontinuous phase diffuse from smaller to larger droplets
through the continuous phase.
 Forces between colloidal particles

• Interaction (attractive/repulsive) forces

• Two main interacting forces in affecting colloid systems:
(1) van der Waals attractive forces
(2) electrostatic repulsive forces.

• Attractive forces tend to destabilize colloids whereas repulsive forces generally impart stability.

Van der Waals forces

• Originates from the dipole-dipole interactions.

• The force between two droplets arising from van der Waals interactions
is always attractive for like droplets.
_ + _ +
• The attractive force increases more and more rapidly as the droplets
approach F

Electrostatic repulsive forces

The force between two droplets arising from intrinsic bearing charges from surfactants

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 Electrical Double Layer & Zeta Potential

Oppositely charged ions (counterions) are

Slipping plane
preferentially attracted towards the surface, and ions
of the same charge (coions) tend to be repelled away. Stern layer

The combination of the charged surface & the Diffuse layer

unequal distribution of coions & counterions
near the surface is called the electrical double
layer.
The formation of a double layer is very important
for the stability of the colloid.

The double layer is sensitive to electrolytes and also Particle with negative Surface potential
temperature. Stern potential
surface charge
Zeta potential
This means that the stability of the colloid may be mV
manipulated by adding electrolytes or changing the
temperature.

0
Distance from particle surface
Electrical Double Layer & Zeta Potential

DLVO theory — named after four scientists:

Derjaguin, Landau, Verwey and Overbeek +
Repulsion potential
When two charged surfaces approach so that their
electrical double-layers begin to overlap, a
Secondary minimum
repulsive force is induced which tends to oppose Primary minimum
further approach. Total potential

Energy
DLVO theory suggests that electrical double-layer
repulsion will stabilize emulsion, when the
electrolyte concentration phase is less than a Attraction potential
certain value. (van der Waals)
DLVO theory relates the stability of emulsified
droplets to two independent potentials that come
_ Increasing interdroplet distance
into action when two droplets approach each other.
Electrical Double Layer & Zeta Potential

Zeta potential is the electrical potential at the 60

hydrodynamic plane of shear Stable

Zeta potential (mV)

40
Particles interact according to the magnitude of
the zeta potential, not their surface charge 20
Zeta potential tells us the effectiveness of the Isoelectric point
surface charge 0 Unstable
For electrostatically stabilized dispersions, the
-20
higher the value of zeta potential, the more
stable the dispersion is likely to be
-40
Stability dividing line is generally considered Stable
-60
to be ±30mV 2 4 6 8 10 12
Particles with zeta potential more positive than +30 pH
mV or more negative than -30 mV are formed a stable
dispersion.
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 Improving emulsion stability

Emulsion stability – ability to resist changes in its physicochemical properties with time

• Charge stabilisation • Steric stabilisation

• Interfacial film strengthening • Continuous phase viscosity
• with powders • Droplet size
• Co-emulsifiers / polar waxes
• with polymers
• Liquid crystals
• with non-ionic emulsifiers
 Ionic (Electrostatic) Stabilization

+
The introduction of charged groups on the surface of
the emulsion droplets increases the repulsive forces. Addition of salt changes
salt added the distance distribution
Ionic emulsifiers will form an electrically charge
double layer in the aqueous solution surrounding No salt present of the repulsive potential
each oil droplet.

Energy
The thickness of the electrical double layer is
affected by ionic strength. As long as ionic strength is
low, electrical repulsion is > van de Waals attraction Attraction potential is not
 the droplets remain suspended.
affected
With ionic emulsifiers, low [salt] enhances
stability, while high [salt] concentration
increase flocculation and/or coalescence.
Increasing interdroplet distance
_

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9
Emulsion Stabilization
Steric Stabilization

 Hydrocolloids such as xanthan gum, arabic gum, CMC, guar gum, etc., significantly
increase emulsion stability (function as stabilizers).

 The macromolecules act by either increasing the viscosity or partitioning into the o/w
interface as a physical barrier to coalescence

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9
 Emulsion Stabilization
Steric Stabilization
• Interfacial film strengthening
• Reduces the probability of coalescence when
droplets collide

Interfacial film strengthening

• with powders • with polymers • with non-ionic emulsifiers

Tighter
packing at
interface

Pickering emulsion with powders PVAc stabilized emulsions

Powder particle size must be very small Interface strengthening is depended
Polymer sits at emulsion interface
Powder must have an affinity for both the on the number of molecules that are
Polar groups orient into the water phase
oil and water phase packed into the interface
 Improving emulsion stability

• Continuous phase viscosity • Co-emulsifiers / polar waxes

• Thickening the water phase restricts • e.g. Cetyl alcohol
movement of oil droplets + Co-emulsifiers have weaker surface activity than
• Thickeners with yield points are most primary emulsifiers
effective + Adds body and helps prevent coalescence

• Droplet size distribution

Increasing uniformity

Increasing stability

• Temperature
• Increase of temperature promote movement of
droplets and normally enhances flocculation and
coalescence