Microemulsion

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Microemulsions are clear, thermodynamically stable, isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons. In contrast to ordinary emulsions, microemulsions form upon simple mixing of the components and do not require the high shear conditions generally used in the formation of ordinary emulsions. The three basic types of microemulsions are direct (oil dispersed in water, o/w), reversed (water dispersed in oil, w/o) and bicontinuous.

Contents

In ternary systems such as microemulsions, where two immiscible phases (water and ‘oil’) are present with a surfactant, the surfactant molecules may form a monolayer at the interface between the oil and water, with the hydrophobic tails of the surfactant molecules dissolved in the oil phase and the hydrophilic head groups in the aqueous phase.

IUPAC definition

Micro-emulsion: Dispersion made of water, oil, and surfactant(s) that is an isotropic and thermodynamically stable system with dispersed domain diameter varying approximately from 1 to 100 nm, usually 10 to 50 nm.

Note 1: In a micro-emulsion the domains of the dispersed phase are either globular or interconnected (to give a bicontinuous micro-emulsion).

Note 2: The average diameter of droplets in macro-emulsion (usually referred to as an“emulsion”) is close to one millimeter (i.e., 10−3 m). Therefore, since micro- means 10−6and emulsion implies that droplets of the dispersed phase have diameters close to 10−3 m, the micro-emulsion denotes a system with the size range of the dispersed phase in the 10−6 × 10−3 m = 10−9 m range.

Note 3: The term “micro-emulsion” has come to take on special meaning. Entities of the dispersed phase are usually stabilized by surfactant and/or surfactant-cosurfactant (e.g., aliphatic alcohol) systems.

Note 4: The term “oil” refers to any water-insoluble liquid. [1]

Micro-emulsion polymerization: Emulsion polymerization in which the starting system is a micro-emulsion and the final latex comprises colloidal particles of polymer dispersed in an aqueous medium.

Note: Diameters of polymer particles formed in the micro-emulsion polymerization usually are between 10 and 50 nm. [2]

Uses

Microemulsions have many commercially important uses:

Much of the work done on these systems have been motivated by their possible use to mobilize petroleum trapped in porous sandstone for enhanced oil recovery. A fundamental reason for the uses of these systems is that a microemulsion phase sometimes has an ultralow interfacial tension with a separate oil or aqueous phase, which may release or mobilize them from solid phases even in conditions of slow flow or low pressure gradients.

Microemulsions also have industrial applications, one of them being the synthesis of polymers. Microemulsion polymerization is a complex heterogeneous process where transport of monomers, free radicals and other species (such as chain transfer agent, co-surfactant and inhibitors) between the aqueous and organic phases, takes place. [4] Compared with other heterogeneous polymerization processes (suspension or emulsion) microemulsion polymerization is a more complicated system. Polymerization rate is controlled by monomer partitioning between the phases, particle nucleation, and adsorption and desorption of radicals. Particle stability is affected by the amount and type of surfactant and pH of dispersing medium. [5] It is also used in the process of creating nanoparticles.

The kinetics of microemulsion polymerization has much in common with emulsion polymerization kinetics, the most characteristic feature of which is the compartmentalization, where the radicals growing inside the particles are separated from each other, thus suppressing termination to a high extent and, as a consequence, providing high rates of polymerization.

Theory

Various theories concerning microemulsion formation, stability and phase behavior have been proposed over the years. For example, one explanation for their thermodynamic stability is that the oil/water dispersion is stabilized by the surfactant present and their formation involves the elastic properties of the surfactant film at the oil/water interface, which involves as parameters, the curvature and the rigidity of the film. These parameters may have an assumed or measured pressure and/or temperature dependence (and/or the salinity of the aqueous phase), which may be used to infer the region of stability of the microemulsion, or to delineate the region where three coexisting phases occur, for example. Calculations of the interfacial tension of the microemulsion with a coexisting oil or aqueous phase are also often of special focus and may sometimes be used to guide their formulation.

History and terminology

The term microemulsion was first used by T. P. Hoar and J. H. Shulman, professors of chemistry at Cambridge University, in 1943. Alternative names for these systems are often used, such as transparent emulsion, swollen micelle, micellar solution, and solubilized oil. More confusingly still, the term microemulsion can refer to the single isotropic phase that is a mixture of oil, water and surfactant, or to one that is in equilibrium with coexisting predominantly oil and/or aqueous phases, or even to other non-isotropic phases. As in the binary systems (water/surfactant or oil/surfactant), self-assembled structures of different types can be formed, ranging, for example, from (inverted) spherical and cylindrical micelles to lamellar phases and bicontinuous microemulsions, which may coexist with predominantly oil or aqueous phases. [6]

Phase diagrams

Microemulsion domains are usually characterized by constructing ternary-phase diagrams. Three components are the basic requirement to form a microemulsion: two immiscible liquids and a surfactant. The majority of microemulsions use oil and water as immiscible liquid pairs. If a cosurfactant is used, it may sometimes be represented at a fixed ratio to surfactant as a single component, and treated as a single "pseudo-component". The relative amounts of these three components can be represented in a ternary phase diagram. Gibbs phase diagrams can be used to show the influence of changes in the volume fractions of the different phases on the phase behavior of the system.

The three components composing the system are each found at an apex of the triangle, where their corresponding volume fraction is 100%. Moving away from that corner reduces the volume fraction of that specific component and increases the volume fraction of one or both of the two other components. Each point within the triangle represents a possible composition of a mixture of the three components or pseudo-components, which may consist (ideally, according to the Gibbs' phase rule) of one, two or three phases. These points combine to form regions with boundaries between them, which represent the "phase behavior" of the system at constant temperature and pressure.

The Gibbs phase diagram, however, is an empirical visual observation of the state of the system and may, or may not express the true number of phases within a given composition. Apparently clear single phase formulations can still consist of multiple iso-tropic phases (e.g. the apparently clear heptane/AOT/water microemulsions consist multiple phases). Since these systems can be in equilibrium with other phases, many systems, especially those with high volume fractions of both the two imiscible phases, can be easily destabilised by anything that changes this equilibrium e.g. high or low temperature or addition of surface tension modifying agents.

However, examples of relatively stable microemulsions can be found. It is believed that the mechanism for removing acid build up in car engine oils involves low water phase volume, water-in-oil (w/o) microemulsions. Theoretically, transport of the aqueous acid droplets through the engine oil to microdispersed calcium carbonate particles in the oil should be most efficient when the aqueous droplets are small enough to transport a single hydrogen ion (the smaller the droplets, the greater the number of acid water droplets, the faster the neutralisation). Such microemulsions are probably very stable across a reasonably wide range of elevated temperatures.

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<span class="mw-page-title-main">Colloid</span> Mixture of an insoluble substance microscopically dispersed throughout another substance

A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others extend the definition to include substances like aerosols and gels. The term colloidal suspension refers unambiguously to the overall mixture. A colloid has a dispersed phase and a continuous phase. The dispersed phase particles have a diameter of approximately 1 nanometre to 1 micrometre.

An emulsion is a mixture of two or more liquids that are normally immiscible owing to liquid-liquid phase separation. Emulsions are part of a more general class of two-phase systems of matter called colloids. Although the terms colloid and emulsion are sometimes used interchangeably, emulsion should be used when both phases, dispersed and continuous, are liquids. In an emulsion, one liquid is dispersed in the other. Examples of emulsions include vinaigrettes, homogenized milk, liquid biomolecular condensates, and some cutting fluids for metal working.

In polymer chemistry, emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomers, and surfactants. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer are emulsified in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.

<span class="mw-page-title-main">Micelle</span> Group of fatty molecules suspended in liquid by soaps and/or detergents

A micelle or micella is an aggregate of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension. A typical micelle in water forms an aggregate with the hydrophilic "head" regions in contact with surrounding solvent, sequestering the hydrophobic single-tail regions in the micelle centre.

<span class="mw-page-title-main">Suspension (chemistry)</span> Heterogeneous mixture of solid particles dispersed in a medium

In chemistry, a suspension is a heterogeneous mixture of a fluid that contains solid particles sufficiently large for sedimentation. The particles may be visible to the naked eye, usually must be larger than one micrometer, and will eventually settle, although the mixture is only classified as a suspension when and while the particles have not settled out.

Lipophilicity is the ability of a chemical compound to dissolve in fats, oils, lipids, and non-polar solvents such as hexane or toluene. Such compounds are called lipophilic. Such non-polar solvents are themselves lipophilic, and the adage "like dissolves like" generally holds true. Thus lipophilic substances tend to dissolve in other lipophilic substances, whereas hydrophilic ("water-loving") substances tend to dissolve in water and other hydrophilic substances.

<span class="mw-page-title-main">Flocculation</span> Process by which colloidal particles come out of suspension to precipitate as floc or flake

In colloidal chemistry, flocculation is a process by which colloidal particles come out of suspension to sediment in the form of floc or flake, either spontaneously or due to the addition of a clarifying agent. The action differs from precipitation in that, prior to flocculation, colloids are merely suspended, under the form of a stable dispersion and are not truly dissolved in solution.

A dispersion is a system in which distributed particles of one material are dispersed in a continuous phase of another material. The two phases may be in the same or different states of matter.

<span class="mw-page-title-main">Miniemulsion</span> Particular type of emulsion

A miniemulsion is a particular type of emulsion. A miniemulsion is obtained by ultrasonicating a mixture comprising two immiscible liquid phases, one or more surfactants and, possibly, one or more co-surfactants. They usually have nanodroplets with uniform size distribution (20–500 nm) and are also known as sub-micron, mini-, and ultra-fine grain emulsions.

<span class="mw-page-title-main">Suspension polymerization</span> Polymerization reaction among monomers suspended in a liquid

In polymer chemistry, suspension polymerization is a heterogeneous radical polymerization process that uses mechanical agitation to mix a monomer or mixture of monomers in a liquid phase, such as water, while the monomers polymerize, forming spheres of polymer. The monomer droplets are suspended in the liquid phase. The individual monomer droplets can be considered as undergoing bulk polymerization. The liquid phase outside these droplets help in better conduction of heat and thus tempering the increase in temperature.

<span class="mw-page-title-main">Water-in-water emulsion</span>

Water-in-water (W/W) emulsion is a system that consists of droplets of water-solvated molecules in another continuous aqueous solution; both the droplet and continuous phases contain different molecules that are entirely water-soluble. As such, when two entirely aqueous solutions containing different water-soluble molecules are mixed, water droplets containing predominantly one component are dispersed in water solution containing another component. Recently, such a water-in-water emulsion was demonstrated to exist and be stable from coalescence by the separation of different types of non-amphiphilic, but water-soluble molecular interactions. These molecular interactions include hydrogen bonding, pi stacking, and salt bridging. This w/w emulsion was generated when the different water-solvated molecular functional groups get segregated in an aqueous mixture consisting of polymer and liquid crystal molecules.

<span class="mw-page-title-main">Lyotropic liquid crystal</span> Solution of amphiphilic molecules which has both fluid and crystalline properties

Lyotropic liquid crystals result when amphiphiles, which are both hydrophobic and hydrophilic, dissolve into a solution that behaves both like a liquid and a solid crystal. This liquid crystalline mesophase includes everyday mixtures like soap and water.

A dispersant or a dispersing agent is a substance, typically a surfactant, that is added to a suspension of solid or liquid particles in a liquid to improve the separation of the particles and to prevent their settling or clumping.

<span class="mw-page-title-main">Ouzo effect</span> Phenomenon observed in drink mixing

The ouzo effect, also known as the louche effect and spontaneous emulsification, is the phenomenon of formation of a milky oil-in-water emulsion when water is added to ouzo and other anise-flavored liqueurs and spirits, such as pastis, rakı, arak, sambuca and absinthe. Such emulsions occur with only minimal mixing and are highly stable.

A Ramsden emulsion, sometimes named Pickering emulsion, is an emulsion that is stabilized by solid particles which adsorb onto the interface between the water and oil phases. Typically, the emulsions are either water-in-oil or oil-in-water emulsions, but other more complex systems such as water-in-water, oil-in-oil, water-in-oil-in-water, and oil-in-water-in-oil also do exist. Pickering emulsions were named after S.U. Pickering, who described the phenomenon in 1907, although the effect was first recognized by Walter Ramsden in 1903.

<span class="mw-page-title-main">Emulsion dispersion</span> Thermoplastics or elastomers suspended in a liquid state by means of emulsifiers

An emulsion dispersion is thermoplastics or elastomers suspended in a liquid state by means of emulsifiers.

<span class="mw-page-title-main">Membrane emulsification</span>

Membrane emulsification (ME) is a relatively novel technique for producing all types of single and multiple emulsions for DDS, solid micro carriers for encapsulation of drug or nutrient, solder particles for surface-mount technology, mono dispersed polymer microspheres. Membrane emulsification was introduced by Nakashima and Shimizu in the late 1980s in Japan.

Paint has four major components: pigments, binders, solvents, and additives. Pigments serve to give paint its color, texture, toughness, as well as determining if a paint is opaque or not. Common white pigments include titanium dioxide and zinc oxide. Binders are the film forming component of a paint as it dries and affects the durability, gloss, and flexibility of the coating. Polyurethanes, polyesters, and acrylics are all examples of common binders. The solvent is the medium in which all other components of the paint are dissolved and evaporates away as the paint dries and cures. The solvent also modifies the curing rate and viscosity of the paint in its liquid state. There are two types of paint: solvent-borne and water-borne paints. Solvent-borne paints use organic solvents as the primary vehicle carrying the solid components in a paint formulation, whereas water-borne paints use water as the continuous medium. The additives that are incorporated into paints are a wide range of things which impart important effects on the properties of the paint and the final coating. Common paint additives are catalysts, thickeners, stabilizers, emulsifiers, texturizers, biocides to fight bacterial growth, etc.

Emulsified Fuels are emulsions composed of water and a combustible liquid, either oil or a fuel. Emulsions are a particular example of a dispersion comprising a continuous and a dispersed phase. The most commonly used emulsion fuel is water-in-diesel emulsion. In the case of emulsions, both phases are the immiscible liquids, oil and water. Emulsion fuels can be either a microemulsion or an ordinary emulsion. The essential differences between the two are stability and particle size distribution. Microemulsions are isotropic whereas macroemulsions are prone to settling and changes in particle size over time. Both use surfactants and can be either water-in-oil, or oil-in-water or bicontinuous.

Macroemulsions are dispersed liquid-liquid, thermodynamically unstable systems with particle sizes ranging from 1 to 100 μm, which, most often, do not form spontaneously. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light. They are part of a larger family of emulsions along with miniemulsions. As with all emulsions, one phase serves as the dispersing agent. It is often called the continuous or outer phase. The remaining phase(s) are disperse or inner phase(s), because the liquid droplets are finely distributed amongst the larger continuous phase droplets. This type of emulsion is thermodynamically unstable, but can be stabilized for a period of time with applications of kinetic energy. Surfactants are used to reduce the interfacial tension between the two phases, and induce macroemulsion stability for a useful amount of time. Emulsions can be stabilized otherwise with polymers, solid particles or proteins.

References

  1. ↑ Slomkowski, Stanislaw (2011). "Terminology of polymers and polymerization processes in dispersed systems (IUPAC Recommendations 2011)" (PDF). Pure and Applied Chemistry . 83 (12): 2229–2259. doi:10.1351/PAC-REC-10-06-03.
  2. ↑ Slomkowski, Stanislaw (2011). "Terminology of polymers and polymerization processes in dispersed systems (IUPAC Recommendations 2011)" (PDF). Pure and Applied Chemistry . 83 (12): 2229–2259. doi:10.1351/PAC-REC-10-06-03.
  3. ↑ Gibaud, Stéphane (2012). "Microemulsions for oral administration and their therapeutic applications" (PDF). Expert Opinion on Drug Delivery. 9: 937–951. doi:10.1517/17425247.2012.694865. PMID   22663249.
  4. ↑ "A Microemulsion Process for Producing Acrylamide-Alkyl Acrylamide Copolymers", S. R. Turner, D. B. Siano and J. Bock, U. S. Patent No. 4,521,580, June 1985.
  5. ↑ Ovando-Medina, Víctor M.; Mendizábal, Eduardo; Peralta, René D. (May 2005). "Kinetics modeling of microemulsion copolymerization". Polymer Bulletin. 54 (1–2): 129–140. doi:10.1007/s00289-005-0369-2.
  6. ↑ Hoar, T. P.; Schulman, J. H. (July 1943). "Transparent Water-in-Oil Dispersions: the Oleopathic Hydro-Micelle". Nature. 152 (3847): 102–103. doi:10.1038/152102a0.

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