Pickering emulsion

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A Ramsden emulsion, sometimes named Pickering emulsion, is an emulsion that is stabilized by solid particles (for example colloidal silica) 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. [1] [2]

If oil and water are mixed and small oil droplets are formed and dispersed throughout the water (oil-in-water emulsion), eventually the droplets will coalesce to decrease the amount of energy in the system. However, if solid particles are added to the mixture, they will bind to the surface of the interface and prevent the droplets from coalescing, making the emulsion more stable.

Particle properties such as hydrophobicity, shape, and size, as well as the electrolyte concentration of the continuous phase and the volume ratio of the two phases can have an effect on the stability of the emulsion. The particle’s contact angle to the surface of the droplet is a characteristic of the hydrophobicity of the particle. If the contact angle of the particle to the interface is low, the particle will be mostly wetted by the droplet and therefore will not be likely to prevent coalescence of the droplets. Particles that are partially hydrophobic are better stabilizers because they are partially wettable by both liquids and therefore bind better to the surface of the droplets. The optimal contact angle for a stable emulsion is achieved when the particle is equally wetted by the two phases (i.e. 90° contact angle). The stabilization energy is given by

where r is the particle radius, is the interfacial tension, and is the contact angle of the particle with the interface.

When the contact angle is approximately 90°, the energy required to stabilize the system is at its minimum. [3] Generally, the phase that preferentially wets the particle will be the continuous phase in the emulsion system. The most common type of Ramsden emulsions are oil-in-water emulsions due to the hydrophilicity of most organic particles.

One example of a Ramsden-stabilized emulsion is homogenized milk. The milk protein (casein) units are adsorbed at the surface of the milk fat globules and act as surfactants. The casein replaces the milkfat globule membrane, which is damaged during homogenization. Other examples of emulsions where Ramsden particles may be the stabilizing species are for example detergents, low-fat chocolates, mayonnaises and margarines.

Ramsden emulsions have gained increased attention and research interest during the last 20 years when the use of traditional surfactants was questioned due to environmental, health and cost issues. Synthetic nanoparticles as Ramsden emulsion stabilizers with well-defined sizes and compositions have been the primarily particles of interest until recently when also natural organic particles have gained increased attention. They are believed to have advantages such as cost-efficiency and degradability, and are issued from renewable resources. [4] Pickering emulsions find applications for enhanced oil recovery [5] or water remediation. [6] Certain Pickering emulsions remain stable even under gastric conditions and show an extraordinary resistance against gastric lipolysis, [7] facilitating their use for controlled lipid digestion and satiation [8] or oral delivery systems. [9]

Additionally, it has been demonstrated that the stability of the Ramsden emulsions can be improved by the use of amphiphilic "Janus particles", namely particles that have one hydrophobic and one hydrophilic side, due to the higher adsorption energy of the particles at the liquid-liquid interface. [10] This is evident when observing emulsion stabilization using polyelectrolytes.

It is also possible to use latex particles for Ramsden stabilization and then fuse these particles to form a permeable shell or capsule, called a colloidosome. [11] Moreover, Ramsden emulsion droplets are also suitable templates for micro-encapsulation and the formation of closed, non-permeable capsules. [12] This form of encapsulation can also be applied to water-in-water emulsions (dispersions of phase-separated aqueous polymer solutions), and can also be reversible. [13] Pickering-stabilized microbubbles may have applications as ultrasound contrast agents. [14] [15]

See also

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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.

<span class="mw-page-title-main">Emulsion</span> Mixture of two or more immiscible liquids

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.

<span class="mw-page-title-main">Hydrophobe</span> Molecule or surface that has no attraction to water

In chemistry, hydrophobicity is the physical property of a molecule that is seemingly repelled from a mass of water. In contrast, hydrophiles are attracted to water.

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">Antibubble</span> Droplet of liquid surrounded by a thin film of gas

An antibubble is a droplet of liquid surrounded by a thin film of gas, as opposed to a gas bubble, which is a sphere of gas surrounded by a liquid. Antibubbles are formed when liquid drops or flows turbulently into the same or another liquid. They can either skim across the surface of a liquid such as water, in which case they are also called water globules, or they can be completely submerged into the liquid to which they are directed.

<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.

Microencapsulation is a process in which tiny particles or droplets are surrounded by a coating to give small capsules, with useful properties. In general, it is used to incorporate food ingredients, enzymes, cells or other materials on a micro metric scale. Microencapsulation can also be used to enclose solids, liquids, or gases inside a micrometric wall made of hard or soft soluble film, in order to reduce dosing frequency and prevent the degradation of pharmaceuticals.

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, reversed and bicontinuous.

<span class="mw-page-title-main">Ultrahydrophobicity</span> Material property of extreme resistance to wetting

In chemistry and materials science, ultrahydrophobic surfaces are highly hydrophobic, i.e., extremely difficult to wet. The contact angles of a water droplet on an ultrahydrophobic material exceed 150°. This is also referred to as the lotus effect, after the superhydrophobic leaves of the lotus plant. A droplet striking these kinds of surfaces can fully rebound like an elastic ball. Interactions of bouncing drops can be further reduced using special superhydrophobic surfaces that promote symmetry breaking, pancake bouncing or waterbowl bouncing.

<span class="mw-page-title-main">Coffee ring effect</span> Capillary flow effect

In physics, a "coffee ring" is a pattern left by a puddle of particle-laden liquid after it evaporates. The phenomenon is named for the characteristic ring-like deposit along the perimeter of a spill of coffee. It is also commonly seen after spilling red wine. The mechanism behind the formation of these and similar rings is known as the coffee ring effect or in some instances, the coffee stain effect, or simply ring stain.

<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 shearing 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">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">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.

<span class="mw-page-title-main">Janus particles</span> Type of nanoparticle or microparticle

Janus particles are special types of nanoparticles or microparticles whose surfaces have two or more distinct physical properties. This unique surface of Janus particles allows two different types of chemistry to occur on the same particle. The simplest case of a Janus particle is achieved by dividing the particle into two distinct parts, each of them either made of a different material, or bearing different functional groups. For example, a Janus particle may have one half of its surface composed of hydrophilic groups and the other half hydrophobic groups, the particles might have two surfaces of different color, fluorescence, or magnetic properties. This gives these particles unique properties related to their asymmetric structure and/or functionalization.

<span class="mw-page-title-main">Nanocellulose</span> Material composed of nanosized cellulose fibrils

Nanocellulose is a term referring to nano-structured cellulose. This may be either cellulose nanocrystal, cellulose nanofibers (CNF) also called nanofibrillated cellulose (NFC), or bacterial nanocellulose, which refers to nano-structured cellulose produced by bacteria.

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<span class="mw-page-title-main">Emmie Lucassen-Reynders</span> Dutch chemist (1935–2023)

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References

  1. Pickering, Spencer Umfreville (1907). "Emulsions". Journal of the Chemical Society, Transactions. 91: 2001–2021. doi:10.1039/CT9079102001.
  2. Ramsden, W (1903). "Separation of Solids in the Surface-layers of Solutions and 'Suspensions'". Proceedings of the Royal Society of London. 72 (477–486): 156–164. doi: 10.1098/rspl.1903.0034 .
  3. Velikov, Krassimir P.; Velev, Orlin D. (2014). Colloid Stability. pp. 277–306. doi:10.1002/9783527631193.ch35. ISBN   9783527631193.
  4. Dupont, Hanaé; Maingret, Valentin; Schmitt, Véronique; Héroguez, Valérie (2021-06-08). "New Insights into the Formulation and Polymerization of Pickering Emulsions Stabilized by Natural Organic Particles". Macromolecules. 54 (11): 4945–4970. Bibcode:2021MaMol..54.4945D. doi:10.1021/acs.macromol.1c00225. ISSN   0024-9297. S2CID   233595006.
  5. Sharma, T.; Velmurugan, N.; Patel, P.; Chon, B. H.; Sangwai, J. S. (17 September 2015). "Use of Oil-in-water Pickering Emulsion Stabilized by Nanoparticles in Combination With Polymer Flood for Enhanced Oil Recovery". Petroleum Science and Technology. 33 (17–18): 1595–1604. doi:10.1080/10916466.2015.1079534. S2CID   99044892.
  6. Heise, Katja; Jonkergouw, Christopher; Anaya‐Plaza, Eduardo; Guccini, Valentina; Pääkkönen, Timo; Linder, Markus B.; Kontturi, Eero; Kostiainen, Mauri A. (September 2022). "Electrolyte‐Controlled Permeability in Nanocellulose‐Stabilized Emulsions". Advanced Materials Interfaces. 9 (26): 2200943. doi: 10.1002/admi.202200943 .
  7. Scheuble, Nathalie; Schaffner, Joschka; Schumacher, Manuel; Windhab, Erich J.; Liu, Dian; Parker, Helen; Steingoetter, Andreas; Fischer, Peter (30 May 2018). "Tailoring Emulsions for Controlled Lipid Release: Establishing in vitro–in Vivo Correlation for Digestion of Lipids". ACS Applied Materials & Interfaces. 10 (21): 17571–17581. doi:10.1021/acsami.8b02637. PMID   29708724.
  8. Bertsch, Pascal; Steingoetter, Andreas; Arnold, Myrtha; Scheuble, Nathalie; Bergfreund, Jotam; Fedele, Shahana; Liu, Dian; Parker, Helen L.; Langhans, Wolfgang; Rehfeld, Jens F.; Fischer, Peter (2022). "Lipid emulsion interfacial design modulates human in vivo digestion and satiation hormone response". Food & Function. 13 (17): 9010–9020. doi: 10.1039/D2FO01247B . PMC   9426722 . PMID   35942900.
  9. Mwangi, William Wachira; Lim, Hui Peng; Low, Liang Ee; Tey, Beng Ti; Chan, Eng Seng (June 2020). "Food-grade Pickering emulsions for encapsulation and delivery of bioactives". Trends in Food Science & Technology. 100: 320–332. doi:10.1016/j.tifs.2020.04.020. S2CID   218967470.
  10. Binks, B. P.; Fletcher, P. D. I. (2001). "Particles Adsorbed at the Oil−Water Interface: A Theoretical Comparison between Spheres of Uniform Wettability and "Janus" Particles". Langmuir. 17 (16): 4708–4710. doi:10.1021/la0103315. ISSN   0743-7463.
  11. Dinsmore, A. D. (2002). "Colloidosomes: Selectively Permeable Capsules Composed of Colloidal Particles". Science. 298 (5595): 1006–1009. Bibcode:2002Sci...298.1006D. CiteSeerX   10.1.1.476.7703 . doi:10.1126/science.1074868. ISSN   0036-8075. PMID   12411700. S2CID   2333453.
  12. Joris Salari (12 May 2011). "Pickering emulsions, colloidosomes &micro-encapsulation". Slideshare.
  13. Poortinga, Albert T. (2008). "Microcapsules from Self-Assembled Colloidal Particles Using Aqueous Phase-Separated Polymer Solutions". Langmuir. 24 (5): 1644–1647. doi:10.1021/la703441e. ISSN   0743-7463. PMID   18220438.
  14. Anderton N, Carlson CS, Matsumoto R, Shimizu RI, Poortinga AT, Kudo N, Postema M (2022). "On the rigidity of four hundred Pickering-stabilised microbubbles". Japanese Journal of Applied Physics. 61 (SG): SG8001. Bibcode:2022JaJAP..61G8001A. doi: 10.35848/1347-4065/ac4adc . S2CID   245915590.
  15. Anderton N, Carlson CS, Matsumoto R, Shimizu RI, Poortinga AT, Kudo N, Postema M (2022). "First-cycle oscillation excursions of Pickering-stabilised microbubbles subjected to a high-amplitude ultrasound pulse". Current Directions in Biomedical Engineering. 8 (2): 30–32. doi: 10.1515/cdbme-2022-1009 . S2CID   251981644.