The Bancroft rule in colloidal chemistry states: "The phase in which an emulsifier is more soluble constitutes the continuous phase." [1] This means that water-soluble surfactants tend to give oil-in-water emulsions and oil-soluble surfactants give water-in-oil emulsions. It is a general rule of thumb, still used, but regarded as inferior to HLD theory (Hydrophilic Lipophilic Difference), which takes many more factors into consideration. [2]
It was named after Wilder Dwight Bancroft, an American physical chemist, who proposed the rule in the 1910s. [3] [4]
In all of the typical emulsions, there are tiny particles (discrete phase) suspended in a liquid (continuous phase). In an oil-in-water emulsion, oil is the discrete phase, while water is the continuous phase.
What the Bancroft rule states is that contrary to common sense, what makes an emulsion oil-in-water or water-in-oil is not the relative percentages of oil or water, but which phase the emulsifier is more soluble in. So even though there may be a formula that's 60% oil and 40% water, if the emulsifier chosen is more soluble in water, it will create an oil-in-water system.
There are some exceptions to Bancroft's rule, [5] but it's a very useful rule of thumb for most systems.
The hydrophilic-lipophilic balance (HLB) of a surfactant can be used in order to determine whether it's a good choice for the desired emulsion or not.
Bancroft's rule suggests that the type of emulsion is dictated by the emulsifier and that the emulsifier should be soluble in the continuous phase. This empirical observation can be rationalized by considering the interfacial tension at the oil-surfactant and water-surfactant interfaces.
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.

Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. Surfactants may function as emulsifiers, wetting agents, detergents, foaming agents, or dispersants. The word "surfactant" is a blend of surface-active agent, coined c. 1950.
Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. 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.
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.
Lipophilicity, refers to the ability of a chemical compound to dissolve in fats, oils, lipids, and non-polar solvents such as hexane or toluene. Such non-polar solvents are themselves lipophilic, and the axiom that "like dissolves like" generally holds true. Thus lipophilic substances tend to dissolve in other lipophilic substances, but hydrophilic ("water-loving") substances tend to dissolve in water and other hydrophilic substances.
In the physical sciences, a partition coefficient (P) or distribution coefficient (D) is the ratio of concentrations of a compound in a mixture of two immiscible solvents at equilibrium. This ratio is therefore a comparison of the solubilities of the solute in these two liquids. The partition coefficient generally refers to the concentration ratio of un-ionized species of compound, whereas the distribution coefficient refers to the concentration ratio of all species of the compound.

Wilder Dwight Bancroft was an American physical chemist.
A cream is a preparation usually for application to the skin. Creams for application to mucous membranes such as those of the rectum or vagina are also used. Creams may be considered pharmaceutical products as even cosmetic creams are based on techniques developed by pharmacy and unmedicated creams are highly used in a variety of skin conditions (dermatoses). The use of the finger tip unit concept may be helpful in guiding how much topical cream is required to cover different areas.
An amphiphile, or amphipath, is a chemical compound possessing both hydrophilic and lipophilic (fat-loving) properties. Such a compound is called amphiphilic or amphipathic. Common amphiphilic compound is surfactant, which is a main ingredient of soaps, detergents, and lipoproteins. The phospholipid amphiphiles are the major structural component of cell membranes.
The hydrophilic–lipophilic balance (HLB) of a surfactant is a measure of its degree of hydrophilicity or lipophilicity, determined by calculating percentages of molecular weights for the hydrophilic and lipohilic portions of the surfactant molecule, as described by Griffin in 1949 and 1954. Other methods have been suggested, notably in 1957 by Davies.
A miniemulsion is a particular type of emulsion. A miniemulsion is obtained by shearing a mixture comprising two immiscible liquid phases, one or more surfactants and, possibly, one or more co-surfactants.
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.
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.
An oil dispersant is a mixture of emulsifiers and solvents that helps break oil into small droplets following an oil spill. Small droplets are easier to disperse throughout a water volume, and small droplets may be more readily biodegraded by microbes in the water. Dispersant use involves a trade-off between exposing coastal life to surface oil and exposing aquatic life to dispersed oil. While submerging the oil with dispersant may lessen exposure to marine life on the surface, it increases exposure for animals dwelling underwater, who may be harmed by toxicity of both dispersed oil and dispersant. Although dispersant reduces the amount of oil that lands ashore, it may allow faster, deeper penetration of oil into coastal terrain, where it is not easily biodegraded.
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.
Polyelectrolytes are charged polymers capable of stabilizing colloidal emulsions through electrostatic interactions. Their effectiveness can be dependent on molecular weight, pH, solvent polarity, ionic strength, and the hydrophilic-lipophilic balance (HLB). Stabilized emulsions are useful in many industrial processes, including deflocculation, drug delivery, petroleum waste treatment, and food technology.
Sucrose esters or sucrose fatty acid esters are a group of non-naturally occurring surfactants chemically synthesized from the esterification of sucrose and fatty acids. This group of substances is remarkable for the wide range of hydrophilic-lipophilic balance (HLB) that it covers. The polar sucrose moiety serves as a hydrophilic end of the molecule, while the long fatty acid chain serves as a lipophilic end of the molecule. Due to this amphipathic property, sucrose esters act as emulsifiers; i.e., they have the ability to bind both water and oil simultaneously. Depending on the HLB value, some can be used as water-in-oil emulsifiers, and some as oil-in-water emulsifiers. Sucrose esters are used in cosmetics, food preservatives, food additives, and other products. A class of sucrose esters with highly substituted hydroxyl groups, olestra, is also used as a fat replacer in food.
The n-octanol-water partition coefficient,Kow is a partition coefficient for the two-phase system consisting of n-octanol and water. Kow is also frequently referred to by the symbol P, especially in the English literature. It is also called n-octanol-water partition ratio.
Emmie Helena Lucassen-Reynders was a Dutch scientist specialising in colloid chemistry and theoretical physics. She worked in both academia and in industry.