Condensed matter physics |
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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, [1] while others extend the definition to include substances like aerosols and gels. The term colloidal suspension refers unambiguously to the overall mixture (although a narrower sense of the word suspension is distinguished from colloids by larger particle size). A colloid has a dispersed phase (the suspended particles) and a continuous phase (the medium of suspension). The dispersed phase particles have a diameter of approximately 1 nanometre to 1 micrometre. [2] [3]
Some colloids are translucent because of the Tyndall effect, which is the scattering of light by particles in the colloid. Other colloids may be opaque or have a slight color.
Colloidal suspensions are the subject of interface and colloid science. This field of study began in 1845 by Francesco Selmi, [4] [5] [6] [7] who called them pseudosolutions, and expanded by Michael Faraday [8] and Thomas Graham, who coined the term colloid in 1861. [9]
Colloid: Short synonym for colloidal system. [10] [11]
Colloidal: State of subdivision such that the molecules or polymolecular particles dispersed in a medium have at least one dimension between approximately 1 nm and 1 μm, or that in a system discontinuities are found at distances of that order. [10] [11] [12]
Colloids can be classified as follows:
Medium/phase | Dispersed phase | |||
---|---|---|---|---|
Gas | Liquid | Solid | ||
Dispersion medium | Gas | No such colloids are known. Helium and xenon are known to be immiscible under certain conditions. [13] [14] | Liquid aerosol Examples: fog, clouds, condensation, mist, steam, hair sprays | Solid aerosol Examples: smoke, ice cloud, atmospheric particulate matter |
Liquid | Foam Example: whipped cream, shaving cream | Emulsion or Liquid crystal Examples: milk, mayonnaise, hand cream, latex, biological membranes , liquid biomolecular condensate | Sol Examples: pigmented ink, sediment, precipitates, solid biomolecular condensate | |
Solid | Solid foam Examples: aerogel, floating soap, styrofoam, pumice | Gel Examples: agar, gelatin, jelly, gel-like biomolecular condensate | Solid sol Example: cranberry glass |
Homogeneous mixtures with a dispersed phase in this size range may be called colloidal aerosols, colloidal emulsions, colloidal suspensions, colloidal foams, colloidal dispersions, or hydrosols.
Hydrocolloids describe certain chemicals (mostly polysaccharides and proteins) that are colloidally dispersible in water. Thus becoming effectively "soluble" they change the rheology of water by raising the viscosity and/or inducing gelation. They may provide other interactive effects with other chemicals, in some cases synergistic, in others antagonistic. Using these attributes hydrocolloids are very useful chemicals since in many areas of technology from foods through pharmaceuticals, personal care and industrial applications, they can provide stabilization, destabilization and separation, gelation, flow control, crystallization control and numerous other effects. Apart from uses of the soluble forms some of the hydrocolloids have additional useful functionality in a dry form if after solubilization they have the water removed - as in the formation of films for breath strips or sausage casings or indeed, wound dressing fibers, some being more compatible with skin than others. There are many different types of hydrocolloids each with differences in structure function and utility that generally are best suited to particular application areas in the control of rheology and the physical modification of form and texture. Some hydrocolloids like starch and casein are useful foods as well as rheology modifiers, others have limited nutritive value, usually providing a source of fiber. [15]
The term hydrocolloids also refers to a type of dressing designed to lock moisture in the skin and help the natural healing process of skin to reduce scarring, itching and soreness.
Hydrocolloids contain some type of gel-forming agent, such as sodium carboxymethylcellulose (NaCMC) and gelatin. They are normally combined with some type of sealant, i.e. polyurethane to 'stick' to the skin.
A colloid has a dispersed phase and a continuous phase, whereas in a solution, the solute and solvent constitute only one phase. A solute in a solution are individual molecules or ions, whereas colloidal particles are bigger. For example, in a solution of salt in water, the sodium chloride (NaCl) crystal dissolves, and the Na+ and Cl− ions are surrounded by water molecules. However, in a colloid such as milk, the colloidal particles are globules of fat, rather than individual fat molecules. Because colloid is multiple phases, it has very different properties compared to fully mixed, continuous solution. [16]
The following forces play an important role in the interaction of colloid particles: [17] [18]
The Earth’s gravitational field acts upon colloidal particles. Therefore, if the colloidal particles are denser than the medium of suspension, they will sediment (fall to the bottom), or if they are less dense, they will cream (float to the top). Larger particles also have a greater tendency to sediment because they have smaller Brownian motion to counteract this movement.
The sedimentation or creaming velocity is found by equating the Stokes drag force with the gravitational force:
where
and is the sedimentation or creaming velocity.
The mass of the colloidal particle is found using:
where
and is the difference in mass density between the colloidal particle and the suspension medium.
By rearranging, the sedimentation or creaming velocity is:
There is an upper size-limit for the diameter of colloidal particles because particles larger than 1 μm tend to sediment, and thus the substance would no longer be considered a colloidal suspension. [19]
The colloidal particles are said to be in sedimentation equilibrium if the rate of sedimentation is equal to the rate of movement from Brownian motion.
There are two principal ways to prepare colloids: [20]
The stability of a colloidal system is defined by particles remaining suspended in solution and depends on the interaction forces between the particles. These include electrostatic interactions and van der Waals forces, because they both contribute to the overall free energy of the system. [21]
A colloid is stable if the interaction energy due to attractive forces between the colloidal particles is less than kT, where k is the Boltzmann constant and T is the absolute temperature. If this is the case, then the colloidal particles will repel or only weakly attract each other, and the substance will remain a suspension.
If the interaction energy is greater than kT, the attractive forces will prevail, and the colloidal particles will begin to clump together. This process is referred to generally as aggregation, but is also referred to as flocculation, coagulation or precipitation. [22] While these terms are often used interchangeably, for some definitions they have slightly different meanings. For example, coagulation can be used to describe irreversible, permanent aggregation where the forces holding the particles together are stronger than any external forces caused by stirring or mixing. Flocculation can be used to describe reversible aggregation involving weaker attractive forces, and the aggregate is usually called a floc. The term precipitation is normally reserved for describing a phase change from a colloid dispersion to a solid (precipitate) when it is subjected to a perturbation. [19] Aggregation causes sedimentation or creaming, therefore the colloid is unstable: if either of these processes occur the colloid will no longer be a suspension.
Electrostatic stabilization and steric stabilization are the two main mechanisms for stabilization against aggregation.
A combination of the two mechanisms is also possible (electrosteric stabilization).
A method called gel network stabilization represents the principal way to produce colloids stable to both aggregation and sedimentation. The method consists in adding to the colloidal suspension a polymer able to form a gel network. Particle settling is hindered by the stiffness of the polymeric matrix where particles are trapped, [26] and the long polymeric chains can provide a steric or electrosteric stabilization to dispersed particles. Examples of such substances are xanthan and guar gum.
Destabilization can be accomplished by different methods:
Unstable colloidal suspensions of low-volume fraction form clustered liquid suspensions, wherein individual clusters of particles sediment if they are more dense than the suspension medium, or cream if they are less dense. However, colloidal suspensions of higher-volume fraction form colloidal gels with viscoelastic properties. Viscoelastic colloidal gels, such as bentonite and toothpaste, flow like liquids under shear, but maintain their shape when shear is removed. It is for this reason that toothpaste can be squeezed from a toothpaste tube, but stays on the toothbrush after it is applied.
The most widely used technique to monitor the dispersion state of a product, and to identify and quantify destabilization phenomena, is multiple light scattering coupled with vertical scanning. [28] [29] [30] [31] This method, known as turbidimetry, is based on measuring the fraction of light that, after being sent through the sample, it backscattered by the colloidal particles. The backscattering intensity is directly proportional to the average particle size and volume fraction of the dispersed phase. Therefore, local changes in concentration caused by sedimentation or creaming, and clumping together of particles caused by aggregation, are detected and monitored. [32] These phenomena are associated with unstable colloids.
Dynamic light scattering can be used to detect the size of a colloidal particle by measuring how fast they diffuse. This method involves directing laser light towards a colloid. The scattered light will form an interference pattern, and the fluctuation in light intensity in this pattern is caused by the Brownian motion of the particles. If the apparent size of the particles increases due to them clumping together via aggregation, it will result in slower Brownian motion. This technique can confirm that aggregation has occurred if the apparent particle size is determined to be beyond the typical size range for colloidal particles. [21]
The kinetic process of destabilisation can be rather long (up to several months or years for some products). Thus, it is often required for the formulator to use further accelerating methods to reach reasonable development time for new product design. Thermal methods are the most commonly used and consist of increasing temperature to accelerate destabilisation (below critical temperatures of phase inversion or chemical degradation). Temperature affects not only viscosity, but also interfacial tension in the case of non-ionic surfactants or more generally interactions forces inside the system. Storing a dispersion at high temperatures enables to simulate real life conditions for a product (e.g. tube of sunscreen cream in a car in the summer), but also to accelerate destabilisation processes up to 200 times. Mechanical acceleration including vibration, centrifugation and agitation are sometimes used. They subject the product to different forces that pushes the particles / droplets against one another, hence helping in the film drainage. Some emulsions would never coalesce in normal gravity, while they do under artificial gravity. [33] Segregation of different populations of particles have been highlighted when using centrifugation and vibration. [34]
In physics, colloids are an interesting model system for atoms. [35] Micrometre-scale colloidal particles are large enough to be observed by optical techniques such as confocal microscopy. Many of the forces that govern the structure and behavior of matter, such as excluded volume interactions or electrostatic forces, govern the structure and behavior of colloidal suspensions. For example, the same techniques used to model ideal gases can be applied to model the behavior of a hard sphere colloidal suspension. Phase transitions in colloidal suspensions can be studied in real time using optical techniques, [36] and are analogous to phase transitions in liquids. In many interesting cases optical fluidity is used to control colloid suspensions. [36] [37]
A colloidal crystal is a highly ordered array of particles that can be formed over a very long range (typically on the order of a few millimeters to one centimeter) and that appear analogous to their atomic or molecular counterparts. [38] One of the finest natural examples of this ordering phenomenon can be found in precious opal, in which brilliant regions of pure spectral color result from close-packed domains of amorphous colloidal spheres of silicon dioxide (or silica, SiO2). [39] [40] These spherical particles precipitate in highly siliceous pools in Australia and elsewhere, and form these highly ordered arrays after years of sedimentation and compression under hydrostatic and gravitational forces. The periodic arrays of submicrometre spherical particles provide similar arrays of interstitial voids, which act as a natural diffraction grating for visible light waves, particularly when the interstitial spacing is of the same order of magnitude as the incident lightwave. [41] [42]
Thus, it has been known for many years that, due to repulsive Coulombic interactions, electrically charged macromolecules in an aqueous environment can exhibit long-range crystal-like correlations with interparticle separation distances, often being considerably greater than the individual particle diameter. In all of these cases in nature, the same brilliant iridescence (or play of colors) can be attributed to the diffraction and constructive interference of visible lightwaves that satisfy Bragg’s law, in a matter analogous to the scattering of X-rays in crystalline solids.
The large number of experiments exploring the physics and chemistry of these so-called "colloidal crystals" has emerged as a result of the relatively simple methods that have evolved in the last 20 years for preparing synthetic monodisperse colloids (both polymer and mineral) and, through various mechanisms, implementing and preserving their long-range order formation. [43]
Colloidal phase separation is an important organising principle for compartmentalisation of both the cytoplasm and nucleus of cells into biomolecular condensates —similar in importance to compartmentalisation via lipid bilayer membranes, a type of liquid crystal. The term biomolecular condensate has been used to refer to clusters of macromolecules that arise via liquid-liquid or liquid-solid phase separation within cells. Macromolecular crowding strongly enhances colloidal phase separation and formation of biomolecular condensates.
Colloidal particles can also serve as transport vector [44] of diverse contaminants in the surface water (sea water, lakes, rivers, fresh water bodies) and in underground water circulating in fissured rocks [45] (e.g. limestone, sandstone, granite). Radionuclides and heavy metals easily sorb onto colloids suspended in water. Various types of colloids are recognised: inorganic colloids (e.g. clay particles, silicates, iron oxy-hydroxides), organic colloids (humic and fulvic substances). When heavy metals or radionuclides form their own pure colloids, the term " eigencolloid " is used to designate pure phases, i.e., pure Tc(OH)4, U(OH)4, or Am(OH)3. Colloids have been suspected for the long-range transport of plutonium on the Nevada Nuclear Test Site. They have been the subject of detailed studies for many years. However, the mobility of inorganic colloids is very low in compacted bentonites and in deep clay formations [46] because of the process of ultrafiltration occurring in dense clay membrane. [47] The question is less clear for small organic colloids often mixed in porewater with truly dissolved organic molecules. [48]
In soil science, the colloidal fraction in soils consists of tiny clay and humus particles that are less than 1μm in diameter and carry either positive and/or negative electrostatic charges that vary depending on the chemical conditions of the soil sample, i.e. soil pH. [49]
Colloid solutions used in intravenous therapy belong to a major group of volume expanders, and can be used for intravenous fluid replacement. Colloids preserve a high colloid osmotic pressure in the blood, [50] and therefore, they should theoretically preferentially increase the intravascular volume, whereas other types of volume expanders called crystalloids also increase the interstitial volume and intracellular volume. However, there is still controversy to the actual difference in efficacy by this difference, [50] and much of the research related to this use of colloids is based on fraudulent research by Joachim Boldt. [51] Another difference is that crystalloids generally are much cheaper than colloids. [50]
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.
A gel is a semi-solid that can have properties ranging from soft and weak to hard and tough. Gels are defined as a substantially dilute cross-linked system, which exhibits no flow when in the steady state, although the liquid phase may still diffuse through this system.
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.
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.
A dilatant material is one in which viscosity increases with the rate of shear strain. Such a shear thickening fluid, also known by the initialism STF, is an example of a non-Newtonian fluid. This behaviour is usually not observed in pure materials, but can occur in suspensions.
Zeta potential is the electrical potential at the slipping plane. This plane is the interface which separates mobile fluid from fluid that remains attached to the surface.
In physical chemistry, the Derjaguin–Landau–Verwey–Overbeek (DLVO) theory explains the aggregation and kinetic stability of aqueous dispersions quantitatively and describes the force between charged surfaces interacting through a liquid medium. It combines the effects of the van der Waals attraction and the electrostatic repulsion due to the so-called double layer of counterions. The electrostatic part of the DLVO interaction is computed in the mean field approximation in the limit of low surface potentials - that is when the potential energy of an elementary charge on the surface is much smaller than the thermal energy scale, . For two spheres of radius each having a charge separated by a center-to-center distance in a fluid of dielectric constant containing a concentration of monovalent ions, the electrostatic potential takes the form of a screened-Coulomb or Yukawa potential,
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.
In materials science, the sol–gel process is a method for producing solid materials from small molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon (Si) and titanium (Ti). The process involves conversion of monomers in solution into a colloidal solution (sol) that acts as the precursor for an integrated network of either discrete particles or network polymers. Typical precursors are metal alkoxides. Sol–gel process is used to produce ceramic nanoparticles.
Coacervate is an aqueous phase rich in macromolecules such as synthetic polymers, proteins or nucleic acids. It forms through liquid-liquid phase separation (LLPS), leading to a dense phase in thermodynamic equilibrium with a dilute phase. The dispersed droplets of dense phase are also called coacervates, micro-coacervates or coacervate droplets. These structures draw a lot of interest because they form spontaneously from aqueous mixtures and provide stable compartmentalization without the need of a membrane—they are protocell candidates.
Particle agglomeration refers to the formation of assemblages in a suspension and represents a mechanism leading to the functional destabilization of colloidal systems. During this process, particles dispersed in the liquid phase stick to each other, and spontaneously form irregular particle assemblages, flocs, or agglomerates. This phenomenon is also referred to as coagulation or flocculation and such a suspension is also called unstable. Particle agglomeration can be induced by adding salts or other chemicals referred to as coagulant or flocculant.
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.
Sedimentation potential occurs when dispersed particles move under the influence of either gravity or centrifugation or electricity in a medium. This motion disrupts the equilibrium symmetry of the particle's double layer. While the particle moves, the ions in the electric double layer lag behind due to the liquid flow. This causes a slight displacement between the surface charge and the electric charge of the diffuse layer. As a result, the moving particle creates a dipole moment. The sum of all of the dipoles generates an electric field which is called sedimentation potential. It can be measured with an open electrical circuit, which is also called sedimentation current.
A colloidal crystal is an ordered array of colloidal particles and fine grained materials analogous to a standard crystal whose repeating subunits are atoms or molecules. A natural example of this phenomenon can be found in the gem opal, where spheres of silica assume a close-packed locally periodic structure under moderate compression. Bulk properties of a colloidal crystal depend on composition, particle size, packing arrangement, and degree of regularity. Applications include photonics, materials processing, and the study of self-assembly and phase transitions.
Colloidal silicas are suspensions of fine amorphous, nonporous, and typically spherical silica particles in a liquid phase. It may be produced by Stöber process from Tetraethyl orthosilicate (TEOS).
Adsorption of polyelectrolytes on solid substrates is a surface phenomenon where long-chained polymer molecules with charged groups bind to a surface that is charged in the opposite polarity. On the molecular level, the polymers do not actually bond to the surface, but tend to "stick" to the surface via intermolecular forces and the charges created by the dissociation of various side groups of the polymer. Because the polymer molecules are so long, they have a large amount of surface area with which to contact the surface and thus do not desorb as small molecules are likely to do. This means that adsorbed layers of polyelectrolytes form a very durable coating. Due to this important characteristic of polyelectrolyte layers they are used extensively in industry as flocculants, for solubilization, as supersorbers, antistatic agents, as oil recovery aids, as gelling aids in nutrition, additives in concrete, or for blood compatibility enhancement to name a few.
The Stöber process is a chemical process used to prepare silica particles of controllable and uniform size for applications in materials science. It was pioneering when it was reported by Werner Stöber and his team in 1968, and remains today the most widely used wet chemistry synthetic approach to silica nanoparticles. It is an example of a sol-gel process wherein a molecular precursor is first reacted with water in an alcoholic solution, the resulting molecules then joining together to build larger structures. The reaction produces silica particles with diameters ranging from 50 to 2000 nm, depending on conditions. The process has been actively researched since its discovery, including efforts to understand its kinetics and mechanism – a particle aggregation model was found to be a better fit for the experimental data than the initially hypothesized LaMer model. The newly acquired understanding has enabled researchers to exert a high degree of control over particle size and distribution and to fine-tune the physical properties of the resulting material in order to suit intended applications.
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.
A depletion force is an effective attractive force that arises between large colloidal particles that are suspended in a dilute solution of depletants, which are smaller solutes that are preferentially excluded from the vicinity of the large particles. One of the earliest reports of depletion forces that lead to particle coagulation is that of Bondy, who observed the separation or "creaming" of rubber latex upon addition of polymer depletant molecules to solution. More generally, depletants can include polymers, micelles, osmolytes, ink, mud, or paint dispersed in a continuous phase.
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