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Emulsion

An emulsion is a thermodynamically unstable mixture of two or more immiscible liquids, in which one liquid is dispersed as droplets of microscopic or ultramicroscopic size within the other, appearing macroscopically homogeneous but microscopically heterogeneous. These systems require emulsifying agents, such as , to stabilize them by reducing interfacial tension and preventing droplet coalescence or separation. Emulsions are classified primarily by the nature of their continuous and dispersed phases: oil-in-water (O/W) emulsions feature oil droplets suspended in water, as seen in and , while water-in-oil (W/O) emulsions have water droplets dispersed in oil, exemplified by and . More complex forms, such as multiple emulsions (e.g., water-in-oil-in-water), also exist for specialized uses like controlled release. Preparation typically involves mechanical agitation or high-shear processes to achieve droplet sizes ranging from nanometers to micrometers, with stability influenced by factors like , , and emulsifier concentration. Emulsions play a critical role across diverse industries due to their ability to combine incompatible phases effectively. In the food sector, they enhance texture, stability, and in products like sauces, ice creams, and dressings. In pharmaceuticals and , they facilitate , improve , and form bases for creams and lotions. Industrial applications extend to paints, adhesives, and processing, where emulsions enable efficient and reaction control.

Etymology and Fundamentals

Etymology

The term "emulsion" originates from the Latin verb emulgere, meaning "to milk out," a reference to the process of extracting milk and the resulting milky appearance of mixtures where one liquid is dispersed in another, as seen in natural examples like milk itself. This etymological root reflects the early association of the concept with dairy products, where fat globules are suspended in water, and the word entered scientific and medical discourse in the early 17th century through French émulsion around 1610, initially describing such oil-and-water mixtures. By the 19th century, as emerged, the term evolved in chemical contexts to denote a colloidal of one immiscible liquid dispersed as droplets within another, formalized through foundational work by Thomas Graham around 1860, who distinguished from true and highlighted as a key subclass.

Definition and Classification

An is a type of , which refers to a heterogeneous where particles of one substance, ranging in size from 1 nm to 1 μm, are dispersed evenly throughout another substance without dissolving, resulting in a under certain conditions. In the context of , this colloidal system specifically involves the dispersion of droplets of one liquid within another immiscible liquid, driven by the need to minimize unfavorable interactions at their . Emulsions are defined as thermodynamically unstable mixtures of two or more immiscible liquids, where one liquid—the —forms small droplets distributed throughout the other liquid—the . This instability arises primarily from the high between the immiscible liquids, which represents the excess per unit area at their boundary and favors to reduce the total interfacial area. Conventional macroemulsions, the most common type, feature droplet sizes typically ranging from 0.1 to 100 μm, which are visible under a and contribute to the system's opacity. Emulsions are primarily classified based on the nature of the dispersed and continuous s. Oil-in-water (O/W) emulsions have droplets dispersed in a continuous aqueous , such as , while water-in- (W/O) emulsions have water droplets in a continuous , like . Multiple emulsions, such as water-in--in-water (W/O/W), involve nested dispersions where smaller droplets of one liquid are encapsulated within larger droplets of another, enabling controlled release applications. Special cases include nanoemulsions, with droplet sizes below 100 nm, which remain thermodynamically unstable but achieve kinetic stability through high energy input during formation, and microemulsions, which are thermodynamically stable, isotropic systems with droplet sizes around 10–100 nm that form spontaneously due to low interfacial tension induced by .

Physical Characteristics

Appearance

Emulsions typically exhibit a milky or opaque appearance as a result of the , where dispersed droplets scatter visible , creating a cloudy visual effect when a passes through the . This scattering occurs because the droplets are larger than the of visible (approximately 400–700 nm), leading to multiple scattering events that prevent from transmitting directly and instead diffuse it in various directions. The specific visual traits vary depending on the emulsion type. Oil-in-water (O/W) emulsions, such as , often appear and fluid due to the scattering of light by oil droplets dispersed in an aqueous continuous phase. In contrast, water-in-oil (W/O) emulsions, like or , present a creamier or more solid-like and appearance, with water droplets scattered in a continuous oil phase that contributes to a denser, less translucent look. Over time, processes like creaming or can alter this opacity, potentially leading to clearer layers as droplets aggregate and rise or settle. Several factors influence the overall appearance of emulsions. Droplet size plays a key role: larger droplets (typically >100 ) enhance and opacity, while smaller ones (e.g., <100 in nanoemulsions) reduce intensity, resulting in greater clarity or transparency. Additionally, the concentration of the dispersed phase affects visual properties; as it increases up to the close-packing limit of about 74% volume fraction, the emulsion becomes more opaque due to higher density from closely packed droplets.

Key Properties

Emulsions exhibit a range of rheological behaviors depending on their composition and concentration. Dilute emulsions, where the volume fraction of the dispersed phase (φ) is low, typically display Newtonian flow, characterized by a constant viscosity independent of shear rate. In contrast, concentrated emulsions often behave as non-Newtonian fluids, showing shear-thinning properties where viscosity decreases under increasing shear rates due to droplet deformation and alignment. The overall viscosity of an emulsion increases with the dispersed phase volume fraction; for dilute suspensions, this relationship is described by the Einstein equation: \eta = \eta_0 (1 + 2.5 \phi) where η is the emulsion viscosity, η₀ is the viscosity of the continuous phase, and φ is the volume fraction of the dispersed phase (valid for φ < 0.05). Interfacial properties play a critical role in emulsion formation and maintenance. Emulsifiers adsorb at the oil-water interface, significantly reducing surface tension from typical values of around 50 mN/m to as low as 1-10 mN/m, which facilitates droplet breakup during emulsification. For charged emulsions, the zeta potential of droplets, arising from ionized groups or adsorbed ions, influences electrostatic repulsion between droplets; values greater than |30| mV typically indicate sufficient stability against coalescence by providing a repulsive barrier. Thermal and electrical properties of emulsions vary markedly with the type of emulsion. Oil-in-water (O/W) emulsions are generally conductive due to the aqueous continuous phase, which allows ion mobility, whereas water-in-oil (W/O) emulsions are non-conductive as the oil phase insulates the dispersed water droplets. Density differences between phases drive buoyancy effects, with dispersed droplets rising (creaming) or sinking (sedimentation) based on whether their density exceeds or is less than that of the continuous phase, influencing phase separation tendencies. Optically, these density gradients can contribute to light scattering and turbidity variations, though emulsions often appear opaque due to refractive index mismatches at interfaces.

Stability Aspects

Instability Mechanisms

Emulsions are thermodynamically unstable systems that tend to separate into their constituent phases over time due to various physical processes driven by gravity, interfacial forces, and diffusion. The primary instability mechanisms include creaming or sedimentation, flocculation, coalescence, , and phase inversion, each contributing to the breakdown by altering droplet distribution or integrity. Creaming occurs when less dense droplets rise to the surface, while sedimentation involves denser droplets settling at the bottom, both governed by gravitational forces in emulsions where the dispersed phase density differs from the continuous phase. The velocity of this movement for individual spherical droplets in dilute emulsions follows : v = \frac{2r^2 (\rho_1 - \rho_2) g}{9 \eta} where v is the settling or creaming velocity, r is the droplet radius, \rho_1 and \rho_2 are the densities of the dispersed and continuous phases, g is gravitational acceleration, and \eta is the continuous phase viscosity. Larger droplets cream faster due to the quadratic dependence on radius, exacerbating separation in polydisperse systems. Flocculation refers to the reversible aggregation of droplets without merging, primarily due to attractive van der Waals forces overcoming repulsive barriers between droplets. This process forms loose clusters that can accelerate creaming by increasing effective droplet size while maintaining individual droplet integrity. Coalescence involves the irreversible merging of flocculated droplets through the drainage and rupture of the thin liquid film separating them, often initiated by van der Waals attractions. The rate depends on film stability, with higher interfacial tension and viscoelastic films slowing the process. Ostwald ripening arises from the diffusion of dispersed phase molecules from smaller to larger droplets, driven by differences in solubility caused by curvature effects. The Laplace pressure, \Delta P = \frac{2\gamma}{r}, where \gamma is the interfacial tension and r is the droplet radius, is higher in smaller droplets, increasing their internal pressure and solubility according to the Kelvin equation. This leads to gradual growth of larger droplets and shrinkage of smaller ones, broadening the size distribution over time. Phase inversion is the transition from an oil-in-water (O/W) to a water-in-oil (W/O) emulsion or vice versa, triggered by changes in composition, such as increasing the dispersed phase volume fraction beyond a critical point (typically around 0.74 for catastrophic inversion). Transitional inversion occurs when emulsifier affinity shifts, often with temperature, altering the curvature of the interfacial film. Environmental factors significantly influence these mechanisms by modulating inter-droplet interactions. Elevated temperature reduces continuous phase viscosity and accelerates , enhancing diffusion rates in and flocculation while promoting coalescence through increased kinetic energy. Variations in pH affect the charge on emulsified interfaces, altering electrostatic repulsion; for instance, at the isoelectric point, reduced repulsion facilitates flocculation and coalescence. Higher ionic strength screens electrostatic charges, compressing the double layer and weakening repulsion, which promotes flocculation and accelerates creaming in charged emulsions.

Monitoring and Prediction Methods

Monitoring emulsion stability relies on a suite of experimental techniques that probe droplet size distribution, aggregation tendencies, and interfacial properties. Turbidity measurements, utilizing light scattering principles, quantify the optical density of emulsions to infer droplet size distributions and detect instability through changes in scattering intensity; for instance, increased turbidity signals flocculation or coalescence as larger droplets form. Optical and electron microscopy provide direct visualization of droplet morphology and flocculation events, allowing observation of processes like bridging or coalescence at the microscale, often enhanced by image analysis for quantitative droplet sizing. Rheometry assesses viscosity and viscoelastic responses, where elevations in shear viscosity or the onset of non-Newtonian behavior indicate droplet aggregation, offering insights into structural changes during storage. Zeta potential analysis, commonly performed via electroacoustic methods, evaluates electrostatic repulsion by measuring electrophoretic mobility; absolute values exceeding 30 mV typically signify robust charge-based stability against coalescence. Prediction of emulsion shelf life employs accelerated testing and theoretical modeling to forecast long-term behavior from condensed experiments. Accelerated shelf-life protocols, such as temperature cycling to hasten diffusion-driven creaming or centrifugation to mimic gravitational separation, enable extrapolation of stability timelines using , reducing real-time testing durations from years to weeks. Mathematical frameworks like model colloidal interactions by summing attractive van der Waals forces and repulsive electrostatic potentials, with the total interaction energy expressed as V_{\text{total}} = V_{\text{vdW}} + V_{\text{elec}} where a high energy barrier (often >20 kT) predicts resistance to aggregation. Population balance equations further simulate droplet size evolution by accounting for birth and death rates of droplets due to breakage, coalescence, and Ostwald ripening, solving integro-differential forms to project distribution shifts over time. Post-2020 advancements introduce non-invasive and automated tools for enhanced monitoring and forecasting. Ultrasonic spectroscopy facilitates real-time, contactless assessment of droplet size and concentration by analyzing sound wave attenuation and velocity, detecting phase separation or flocculation without sample perturbation, particularly useful for opaque industrial emulsions. AI-driven image analysis processes microscopic or macroscopic visuals via convolutional neural networks to predict stability in real time, classifying destabilization patterns like creaming with accuracies exceeding 90% by training on annotated datasets of droplet dynamics. Recent machine learning models, such as interpretable frameworks trained on multi-laboratory literature data, have been developed to predict lipid emulsion stability in parenteral nutrition as of November 2025, offering generalizable predictions across diverse clinical formulations.

Components and Processes

Emulsifiers

Emulsifiers are surface-active agents, primarily , that enable the formation of emulsions by adsorbing at the between immiscible liquids, such as oil and water, to stabilize dispersed droplets. These amphiphilic molecules feature both hydrophilic (water-attracting) and lipophilic (oil-attracting) components, allowing them to bridge the two phases. The (HLB) scale, developed by William C. Griffin in 1949, quantifies this property on a numerical range from 0 (highly lipophilic) to 20 (highly hydrophilic); for instance, emulsifiers with HLB values greater than 8 are typically used for oil-in-water (O/W) emulsions, while those below 6 suit water-in-oil (W/O) types. Emulsifiers are categorized into natural and synthetic types, with polymers and particle-based stabilizers serving as additional classes for enhanced stabilization. Natural emulsifiers, such as —a mixture extracted from soybeans or egg yolks—offer and are widely used in food and pharmaceutical applications due to their mild nature. Emerging natural approaches include Pickering emulsions, stabilized by solid particles like protein nanoparticles or nanocrystals, which provide irreversible adsorption and improved environmental . Synthetic emulsifiers include nonionic like Tween 80 (, HLB ≈ 15), which promotes O/W emulsions, and Span 80 (, HLB ≈ 4.3), favored for W/O systems; these provide precise control over emulsion properties but may raise concerns regarding long-term safety. Polymeric emulsifiers, exemplified by —a microbial —contribute steric stabilization by creating a thick, entangled layer around droplets, preventing aggregation through physical hindrance rather than charge effects. The core functions of emulsifiers involve lowering interfacial tension (γ) to allow droplet formation and creating protective barriers against instability. Adsorption of emulsifiers at the interface follows the Gibbs adsorption isotherm, which relates surface excess (Γ) to changes in tension: \Gamma = -\frac{1}{RT} \frac{d\gamma}{d \ln C} Here, R is the gas constant, T is the absolute temperature, and C is the emulsifier concentration in the bulk phase; this equation demonstrates how increased adsorption reduces γ, easing the mechanical energy required for emulsification. Additionally, emulsifiers assemble into viscoelastic interfacial films that encase droplets, imparting steric repulsion or mechanical strength to inhibit coalescence—the merging of droplets into larger ones. Selecting an appropriate emulsifier requires evaluating compatibility with the emulsion's phases to ensure rapid and complete interfacial coverage, as mismatches can lead to ineffective stabilization. In regulated sectors like food production, emulsifiers must secure approval, such as Generally Recognized as Safe (GRAS) status from the U.S. Food and Drug Administration, confirming their safety for intended use without extensive toxicity data. Environmental considerations are increasingly pivotal, with a shift toward biodegradable alternatives—like plant-derived proteins or biosurfactants—to reduce persistence in ecosystems and align with sustainability goals, addressing limitations of traditional synthetics.

Emulsification Mechanisms

Emulsification involves the or physicochemical disruption of immiscible liquids to form droplets of one dispersed in another, typically requiring emulsifiers to reduce interfacial tension and promote droplet breakup while aiding initial stabilization. The process balances disruptive forces against cohesive interfacial forces, with the goal of achieving desired droplet sizes and uniform distribution. High-energy and low-energy approaches differ in their reliance on external input versus internal behavior. High-energy methods apply intense mechanical forces to break larger droplets into smaller ones, often producing emulsions with droplet diameters ranging from nanometers to micrometers. High-pressure homogenization forces the through narrow valves or orifices under pressures of 500–2,000 bar (7,250–29,000 ), generating , , and that reduce droplets to 0.1–10 μm. This technique is widely used in settings for its in creating fine, uniform emulsions. Ultrasonication employs high-intensity waves (typically 20 kHz) to induce acoustic , where collapsing bubbles generate localized and shock waves that disrupt droplets, yielding sizes as small as 100 depending on energy input and duration. Microfluidization directs the through fixed-geometry interaction chambers under (up to 20,000 ), where colliding streams produce intense forces in narrow channels, resulting in monodisperse droplets often below 1 μm and narrower size distributions compared to conventional homogenization. Low-energy methods leverage spontaneous or thermally induced changes, minimizing external mechanical input and relying on emulsifier properties for droplet formation. inversion temperature () involves heating the mixture to alter the emulsifier's hydrophile-lipophile balance (HLB), causing a temporary inversion from oil-in-water to water-in-oil or vice versa, followed by rapid cooling to trap fine droplets (typically 20–200 nm) in the desired configuration. Spontaneous emulsification occurs via displacement, where a water-miscible containing oil and emulsifier is injected into a continuous aqueous , leading to rapid , , and into nano-sized droplets (10–100 nm) without significant agitation. Key process parameters influence droplet breakup and emulsion quality. Energy input governs disruption, quantified by the We = \frac{\rho v^2 d}{\gamma}, where \rho is the continuous , v is the , d is the droplet , and \gamma is the interfacial ; values exceeding a critical (often 4–12 depending on the ) enable inertial forces to overcome for breakup. The order of addition affects initial droplet formation: for oil-in-water emulsions, the oil (dispersed) is typically added gradually to the aqueous (continuous) under stirring to prevent coalescence. Scale-up from laboratory to industrial presents challenges, including inconsistent mixing and leading to larger droplets or , as well as difficulties in maintaining uniform energy dissipation across larger volumes, often requiring adjusted equipment like anchor stirrers to achieve turbulent flow ( >10,000).

Practical Applications

Food and Nutrition

Emulsions are integral to , enabling the incorporation of fats and oils into aqueous-based products to achieve desirable sensory attributes and nutritional benefits. In the , oil-in-water (O/W) emulsions predominate, dispersing hydrophobic within a continuous aqueous to form stable mixtures essential for everyday consumables. These systems not only influence and but also facilitate the delivery of essential nutrients, making them a cornerstone of processed and natural foods alike. Prominent examples of food emulsions include , a classic O/W system comprising 70–80% oil droplets stabilized by the in yolk, which acts as a natural emulsifier to prevent and ensure a smooth, viscous consistency. exemplifies a natural O/W emulsion, with approximately 3.5% present as globules ranging from 0.2 to 15 μm in diameter, enveloped by a phospholipid-protein that maintains in the aqueous phase. represents a more complex partially coalesced emulsion, where globules (typically 10–16% of the mix) adsorb to air-water interfaces during freezing, enabling overrun levels of 50–100% that impart lightness and creaminess to the final product. Emulsions enhance food by creating creamy textures and uniform distribution, which improve sensory appeal without altering core flavors, as seen in dressings and spreads. They also boost nutrient , particularly for fat-soluble vitamins such as A, D, E, and K, by increasing their and absorption in the through . Additionally, homogenization processes in products reduce globule size to below 1 μm, minimizing creaming and thereby extending by up to several weeks while preserving product uniformity. Nutritionally, low-fat emulsion formulations often employ modified starches, such as octenyl (OSA)-modified variants, to replicate the and stability of full-fat systems, allowing reduced content (e.g., 30–50%) without compromising in products like or sauces. Regulatory concerns arise with synthetic or allergen-containing emulsifiers; for instance, soy , a common additive derived from soybeans, can trigger IgE-mediated reactions in sensitive individuals due to residual soy proteins, prompting labeling requirements under frameworks like the U.S. Food Allergen Labeling and Consumer Protection Act. Post-2010 trends in the food sector emphasize clean-label alternatives, favoring natural emulsifiers like , , or unmodified starches to meet consumer demands for transparency and minimal processing, with market growth for such ingredients projected at 7–8% annually through 2035.

Healthcare and Pharmaceuticals

Emulsions play a vital role in healthcare and pharmaceuticals, particularly as vehicles for and nutritional support. Intravenous lipid emulsions, such as Intralipid, are widely used for in patients unable to receive adequate calories enterally, providing s and energy-dense formulations typically containing 10–30% oil from sources like or . Intralipid specifically consists of 20% emulsified with egg phospholipids and glycerin, administered via intravenous infusion to prevent deficiency. In topical applications, oil-in-water (O/W) emulsions form the basis of creams and lotions, such as moisturizers, where the external aqueous phase facilitates easy spreading and absorption while delivering oil-soluble active ingredients to the skin. Nanoemulsions enhance by improving the of poorly water-soluble compounds, such as , a chemotherapeutic agent with inherently low aqueous limiting its oral absorption. These submicron droplets (typically 20–200 ) increase and permeation across biological barriers, achieving up to 70% oral for in optimized formulations compared to less than 8% for conventional preparations. Controlled release is another key benefit, achieved through droplet encapsulation where drugs are entrapped within emulsion cores, enabling sustained delivery and reducing dosing frequency; for instance, nanoemulsion-loaded alginate capsules have demonstrated prolonged release of lipophilic actives over hours to days. Advancements in emulsion technology include self-emulsifying systems (SEDDS), isotropic mixtures of oils, , and cosurfactants that spontaneously form fine O/W emulsions upon dilution in gastrointestinal fluids, significantly boosting oral of lipophilic drugs by up to 20-fold in some cases. Regulatory standards ensure safety for injectables, with the (USP <729>) stipulating that intravenous lipid emulsions must have a volume-weighted mean droplet below 500 nm and no more than 0.05% of fat globules exceeding 5 μm to minimize risks like . In vaccine development, squalene-based emulsions like MF59 serve as adjuvants in , enhancing immune responses; post-2020 research has elucidated mechanisms such as uric acid release from muscle cells to amplify immunogenicity, supporting broader applications in seasonal and pandemic flu formulations.

Firefighting and Safety

Emulsions play a critical role in , particularly through foam formulations designed for suppressing Class B fires involving flammable liquids such as and polar solvents. Aqueous film-forming foams (AFFF), a type of emulsion-based suppressant, utilize to create a thin aqueous that spreads across the surface, suppressing vapors and preventing ignition or re-ignition by acting as a physical barrier to oxygen. The primary mechanisms of AFFF involve emulsification, where the foam blanket incorporates oil into water droplets, smothering the fire by excluding air and providing evaporative cooling to reduce fuel temperatures below ignition points. This emulsification process disrupts the fuel's continuity, while the foam's structure enhances coverage over irregular surfaces like spill areas. For alcohol-resistant variants (AR-AFFF), designed for polar fuels, expansion ratios typically reach up to 8:1 when proportioned at 3% concentration, allowing efficient deployment with lower water volumes compared to standard foams. Environmental concerns have driven significant updates in AFFF composition, with -based emulsifiers phased out due to their environmental persistence and risks. EU REACH regulations, including Commission Regulation (EU) 2025/1988 adopted in October 2025, restrict in firefighting foams, entering into force on October 23, 2025, with full prohibition applying from October 23, 2030, and labeling requirements starting October 23, 2026. Alternatives include protein-based foams, derived from natural hydrolysates for stable blanketing without fluorination, and fluorotelomer-based foams using shorter-chain chemistries to reduce persistence while maintaining film-forming efficacy. These foams are increasingly applied in response scenarios, where rapid deployment suppresses ignited spills on water or land, minimizing spread and environmental damage.

Industrial and Chemical Uses

Emulsions play a pivotal role in , particularly through , a process where monomers are dispersed in an aqueous phase and polymerized using radical initiators to form stable particles. This method is widely used to produce paints, which consist of dispersions like or styrene- copolymers that provide and when applied to surfaces. Similarly, synthetic rubbers such as rubber (SBR) are manufactured via free radical in water, enabling the creation of high-molecular-weight with controlled particle sizes for applications in tires and adhesives. The aqueous environment in these processes facilitates heat dissipation and reduces , allowing for efficient production at industrial scales. In industrial applications, emulsions enhance recovery through surfactant-polymer (SP) flooding, where lower interfacial tension between and , and polymers increase solution to mobilize trapped in reservoirs. This technique can improve recovery factors by up to 25% in heterogeneous formations by forming stable emulsions that block high-permeability zones and redirect flow. Emulsions are also essential in fluids, typically oil-in- formulations that provide to reduce and cooling to dissipate heat during operations like milling and turning. These fluids prevent and improve by forming a lubricating film at the tool-workpiece interface while flushing away chips. Beyond these, emulsions find use in cosmetics as oil-in-water systems, such as lotions, where oil droplets are dispersed in a continuous aqueous to deliver moisturizing agents while ensuring a non-greasy feel and easy spreadability on skin. emulsions, consisting of droplets stabilized in water with emulsifiers, are applied in road paving for tack coats and surface treatments, promoting between layers and enabling cold-mix applications that reduce energy consumption. Recent eco-friendly innovations include bio-based emulsifiers derived from renewable sources like or biosurfactants, which are increasingly used in to stabilize dye dispersions, improve color uptake, and minimize environmental impact by replacing petroleum-based alternatives.

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