Microemulsion Method

For The Preparation Of Nanometerials

Microemulsion method is one of the recent and ideal
technique for the preparation of nanoparticles.
Bottom up technique
Liquid phase synthesis
Emulsions
 An emulsion is a mixture of two or more liquids that are usually immiscible
but, under specific transforming processes, will adopt a macroscopic
homogeneous aspect and a microscopic heterogeneous one. In an emulsion,
one liquid (dispersed phase)is dispersed in the other liquid(continuous
phase) stabilized by the presence of some stabilizing agents(surfactants).
 Kinetically stable but thermodynamically unstable.

 There are several types of emulsions:

1. Oil in water emulsions
2. Water in oil emulsions
3. Multiple emulsions like
4. O/W/O or W/O/W
4. Microemulsions
MICROEMULSIONS
 Microemulsions are isotropic,
thermodynamically stable,
transparent systems of oil,
water and surfactants,
frequently in the combination
of cosurfactants, with a
droplet size usually in the
range of 20-200nm.
 Their higher shelf life differs
them from kinetically stable
emulsions, which will separate
into oil and water over time.
Comparison of emulsions and
Microemulsions
Emulsions Microemulsions
Kinetically stable Thermodynamically stable
Droplet size 1-10 micro meter 10-100 nanometer

Opaque Transparent

Biphasic Monophasic

Anisotropic Isotropic

Require a large amount of energy More amount of surfactant is used for stabilization

High viscosity Low viscosity

High inter facial tension Ultra low interfacial tension

Types of Microemulsions

Based on the phase equilibrium, they

are classified into four types

Winsor I-oil in water; oil droplets

surrounded by surfactants dispersed in
water
Winsor II – water in oil; water droplets
surrounded by surfactants dispersed in
oil media, also called reverse micelles.
Winsor III-bicontinuous phase is in
equilibrium with excess oil phase at the
top and excess water phase at the
bottom- three phases are in equlibrium
Winsor IV-macroemionuls may exict in
the form of one of the three possible
micro structures o/w, w/o and
bicontinuous
Types of microemulsions
Microemulsion Formulation
 A microemulsion generally consists of four different components,
1. a lipophiic phase,
2. a hydrophilic phase,
3. Surfactant
4. and co-surfactant.

Accurate formulation is necessary, for the microemulsions to attain low

interfacial tension and good solubilisation ability.
 Formulation variables :The nature of the components like the oil,
surfactant, co-surfactant and water, as well as temperature and pressure
which affect the microemulsion systems.
 Composition variables :The quantities of different substances present, are
also likely to change the properties, and are referred to as which can be
expressed as weight, percentage or proportion.
Factors one should consider while
formulating
Following factor must be considered while formulating a microemulsion
 Oil/surfactant and surfactant/co-surfactant ratio
 pH
 Nature and concentration of the oil, surfactant, co-surfactant and
aqueous phase
 Temperature
 Hydrophilicity/lipophilicity of polarity
Ternary phase diagram
 To study the phase behavior of
simple microemulsion systems
comprising of surfactant, oil
and water at fixed pressure
and temperature ternary
phase diagrams are used. Each
corner of the ternary phase
diagram represents 100%
concentrations of a particular
component.
 A typical ternary phase
diagram surfactant/co-
surfactant, is shown in Figure
Components of Microemulsion
Water phase: May be in the form of water pool or
dispersion medium.
Oil Phase: The oil phase must be chosen
appropriately, since it governs the selection of the
other ingredients for the microemulsion and there are
two main factors: Firstly, the solubilizing potential of
the oil for the selected substance must be seen and
secondly, the chosen must be such that the
microemulsion forming region is enhanced.
Oils with shorter hydrocarbon chains are easier to
micro-emulsify as compared to oils with long
hydrocarbon chains.
Surfactants in Microemulsions
 Surfactants are molecules that typically contain
a polar head group and a non polar tail.
 They are surface-active and microstructure-
forming molecules with a strong chemical
dipole.
 They can be ionic (cationic or anionic),
nonionic, or zwitterionic.
 Surfactant molecules self-associate due to
various inter- and intra-molecular forces as well
as entropy considerations.
 The surfactant molecules can arrange
themselves in a variety of shapes. They can form
spherical micelles, rod-shaped micelles, a
hexagonal phase(consisting of rod-shaped
micelles), lamellar (sheet) phases, reverse
micelles, or hexagonal reverse micelles.
Reverse Micelle
There are some factors that affect the stability
of an emulsion and further affect the
morphology and size distribution of
produced particles.
These factors include
 type and amount of surfactant and co-
surfactant,
 the concentration of precursor solution,
 the kind of oil phase.
Micro-emulsion is generated by gradual
addition of several drops of an agent as a
non-continuous phase and the other material
as a continuous phase and rapid mixing of
these two phases. Oil drops in the water is a
good example of micro-emulsions.
Reverse Micelle
 Reverse micelles are most widely used as reaction media or
templates for the synthesis of various inorganic nano-particles.
 The biomineralization process in nature uses organized
aggregates of bio macromolecules to synthesize nanoparticles
with dimensional. morphological and architectural specificity
 It has full control over nucleation. growth and the patterns
formed.
 Water can be solubilized in the core forming water-in-oil
droplets (5 nm) which eventually become the w/o micro-
emulsion as the water content increases (5 to 100 nm).
Characterstic of Reverse Micelles
Reverse micelles are generally characterized by the molar
ratio of water to surfactant, a of (H:0)/(surfactant)].This ratio
has a decisive influence on the diameter of the reverse
micelles.

 The shape can be spherical, rod-like or lamellar and depends

on the concentration of surfactant, electrolyte, other
additives, etc. The droplets undergo continuous collisions
and exchange their contents.
Formation of Nano-particles in W/O
Microemulsion System
Nano-particles (NPs),are
synthesized by single phase
w/o micro-emulsion with
reverse micelles.
 Good dispersion of
generated drops in the
micro-emulsion is suitable
for synthesis of nano-
particles.
It has good enough
potential to control the
chemical reaction.
Mechanism of the Formation of Nano-particle
 The mechanism has not yet been understood well. However, it can be
explained by the results achieved. Researchers suggests following steps:
I. When the microemulsions material including reactants are mixed together
reactants exchange takes place during the colliding of water droplets
microemulsion.
II. The reactant exchange is too fast and precipitation reaction occurs in the
nano droplets,
III. Nucleation
IV. Growth,
V. Coagulation of primary particles,
VI. Resulting in the formation of the final nanoparticles surrounded by water
and/or stabilized by surfactants.
 It is generally accepted that the wàter contents of microemulsion droplets are
exchanged rapidly through droplet collision and fusion, with the fusion step as
the rate determining step.
How Reaction Takes place?
 Reaction may take place in two different ways
First route(A): On the other hand reactant ions exchange may be occurred
because of coalescence of two droplets with each other (In this case, the contact of
reactants and subsequent reaction can be regarded as a number of sequential steps:
 Diffusion and convection to bring the emulsion droplets together.
 Surfactant layer opening and coalescence.
 Diffusion of the solubilizate molecules in the temporary dimeric aggregate.
 Reaction between solubilizate molecules.
 Nucleation and crystal growth of precursor particles, and
 Decoalescence to return as smaller droplets.
Second route(B),: reactant diffusion is taken place through oily phase into
aqueous droplets including the second reactant. While the particles achieve their
final size, molecules of surfactant stick to particles surface,and cause their
durability, stability and maintenance in a certain level and prevent more growing
of particles.
Two routes of Reaction
Factors Affecting the Size of Nano-particles
In the Microemulsion, the surface activated and stable
micró-cavities produce cage-like effect and cause to
limit growth nucleation and particles agglomeration.
The size of micro-emulsion drops has a clear effect on
the particles size.
 On the other hand, the size of microemulsion drops
in turn depends on these collisions and created
interactions. And these interactions are dependent on
the viscosity of mixture.
Advantages of Microemulsion Method
These characteristics facilitate their use in the preparation of nanometerials

Ease of preparation: Microemulaions form spontaneously at room

temperature, and are easy to manufacture, w hen compared to liposomes and
macroemulsions which require high pressure homogenization during
preparation.
 Thermodynamic stability: The stability and shelf life of the formulation
improved due to the thermodynamic stability of the microemulsions
 Ability to incorporate both hydrophilie and lipophilic
therapeutic agents: solubilize both hydrophilic and hydrophobic drugs,
either alone or in combination.
 As a template for the synthesis of nano-particles: Microemulsion
are thermodynamically stable, and consists of small droplets which possess large
interfacial area.
Disadvantages of
Microemulsion Method
Formation of Microemulsions generally requires large
amounts of surfactants and/or co-surfactants. All of
these at high concentrations are generally irritating.
Limited solublizing capacity for highly melting
substances.
Many external factors, such temperature and pH,
influence the stability of microemulsions as well.