Microemulsions

Definition and properties

Microemulsions are especially well suited for active ingredients used at low application rates, low active content formulations, wood treatment or when a clear solution is required at the application rate.

A microemulsion is a clear, thermodynamically stable mixture of at least three components:

• a hydrophobic component (non water-soluble oil) which could be a liquid, a low melting solid (less than +50 °C), or a solid dissolved in an organic solvent.
• a surfactant system
• water

A cosurfactant (cosolvent) is often added to the mixture to increase the solubilising power of the surfactant system. Different substances can be used as cosurfactants, mainly alcohols, amines or ether-alcohols. Differently to an emulsion, the characteristic size of the hydrophobic or the hydrophilic domains is typically 10 nm. In fact, microemulsions are a particular type of colloidal system. The typical dimension of the local structure explains why microemulsions are transparent.

Phase diagrams are very useful to describe such systems. This simplified ternary representation describes the different phases obtained when oil, surfactants and water are blended.

As the water content increases, the shape and the volume of the hydrophilic core of inverse micelles expands. At a given water content, there exists a continuous water path; the water phase becomes continuous. The water and the oil phases make an interpenetrated bi-continuous network. Near the water corner, the oil content is low and then the microemulsion looks like a direct micellar solution. The structure of these different systems can be studied or characterized by low angle X rays of neutron scattering, rheological or conductivity measurements.

General method of preparation

Defining a suitable active ingredient

Microemulsions are suitable for liquid active ingredients. A low melting point or solid active ingredient must first be solubilised in an appropriate solvent. Active ingredients have to be chemically stable in water. 

The criteria for the choice of a solvent are the following:

• high flash point and not toxic

• high solubilising properties for the active ingredient to avoid crystallizations during storage

Effects of surfactants

The process to obtain microemulsions (ME) is simpler than those used to prepare emulsions (EW). Since a microemulsion is a thermodynamically stable phase, the result is absolutely independent from the way of preparation. Microemulsification is spontaneous. Water in oil (w/o) microemulsions (near the oil-surfactant border of the phase diagram) are easier to formulate than oil in water (o/w) microemulsions. This difference arises from the energy difference between solubilising water in oil and solubilising oil in water. The water in oil process is thermodynamically more favourable.

Surfactants are basic components in microemulsions. Nevertheless, it is somehow difficult to find the appropriate surfactants and cosurfactants (surfactant system) to obtain stable formulations for a large temperature range (-10 °C to +54 °C). Microemulsions require quite high concentrations of surfactants (typically 2% to 30%). This high amount is due to the small size of the oil and water domains and thus to the large area of the interface. Nevertheless, this amount can be reduced by optimizing the choice of the surfactant and co-surfactant. There are no real definitive guide rules that one may use, but we recommend using a blend of nonionic and anionic surfactants to guarantee the physical stability vs temperature.

Selection of a cosurfactant

A cosurfactant is often added to the mixture to increase the solubilizing power of the surfactant system. The best cosurfactants are, generally speaking, small molecules which have a great affinity for the oil/water interface. They have to be chosen according to the nature of surfactants and to the nature of the oil to be microemulsioned. They can also prevent the formation of a viscous phase (lamellar phase etc.). The ratio R = cosurfactant/surfactants normally varies from 0.3 to 0.8. This ratio and the nature of the cosurfactant have to be optimized in order to lower the surfactants content, to obtain the best thermal stability and to avoid forming viscous phases.

Laboratory formulation and industrial production

Microemulsions are thermodynamically stable formulations, and the result is independent from the way of preparation. This makes microemulsions very attractive from a manufacturing point of view. However, we recommend blending the organic phase (active ingredient with solvent if necessary) with surfactants and cosurfactant and then adding water while mixing slowly.

Control methods

Storage stability

The commercial formulations should be stable for at least 2 years. Microemulsions are thermodynamically stable - meaning that in a determinate range of temperature their physical stability is not affected by time if no chemical degradation occurs. Some accelerated aging tests give an indication of the long term stability:

• tropical test: 2 weeks at +54 °C  (CIPAC 1 -MT 46.1.3)

• cold stability test: 1 week at 0 °C  (CIPAC 1 -MT 39)

• stability at high temperature for two months at +45 °C

• stability at thermal shocks: samples in sealed opaque glass bottles are submitted to temperature cycles
  (24 hours at -5 °C and 24 hours at +45 °C) for a one or two month period.

Microemulsions should remain clear. Chemical degradation of the active ingredient should be evaluated especially for low active content formulations.