In chemistry, a colloid is a phase separated mixture in which one substance of microscopically dispersed insoluble or soluble particles is suspended throughout another substance. Sometimes the dispersed substance alone is called the colloid;[1] 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). Unlike a solution, whose solute and solvent constitute only one phase, a colloid has a dispersed phase (the suspended particles) and a continuous phase (the medium of suspension) that arise by phase separation. Typically, colloids do not completely settle or take a long time to settle completely into two separated layers.
The dispersed-phase particles have a diameter between approximately 1 and 1000 nanometers.[2] Such particles are normally easily visible in an optical microscope, although at the smaller size range (r < 250 nm), an ultramicroscope or an electron microscope may be required. Homogeneous mixtures with a dispersed phase in this size range may be called colloidal aerosols, colloidal emulsions, colloidal foams, colloidal dispersions, or hydrosols. The dispersed-phase particles or droplets are affected largely by the surface chemistry present in the colloid.
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. The cytoplasm of living cells is an example of a colloid, containing many types of biomolecular condensate.
Colloidal suspensions are the subject of interface and colloid science. This field of study was introduced in 1845 by Italian chemist Francesco Selmi[3] and further investigated since 1861 by Scottish scientist Thomas Graham.[4]
The dispersed-phase particles have a diameter between approximately 1 and 1000 nanometers.[2] Such particles are normally easily visible in an optical microscope, although at the smaller size range (r < 250 nm), an ultramicroscope or an electron microscope may be required. Homogeneous mixtures with a dispersed phase in this size range may be called colloidal aerosols, colloidal emulsions, colloidal foams, colloidal dispersions, or hydrosols. The dispersed-phase particles or droplets are affected largely by the surface chemistry present in the col
The dispersed-phase particles have a diameter between approximately 1 and 1000 nanometers.[2] Such particles are normally easily visible in an optical microscope, although at the smaller size range (r < 250 nm), an ultramicroscope or an electron microscope may be required. Homogeneous mixtures with a dispersed phase in this size range may be called colloidal aerosols, colloidal emulsions, colloidal foams, colloidal dispersions, or hydrosols. The dispersed-phase particles or droplets are affected largely by the surface chemistry present in the colloid.
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. The cytoplasm of living cells is an example of a colloid, containing many types of biomolecular condensate.
Colloidal suspensions are the subject of interface and colloid science. This field of study was introduced in 1845 by Italian chemist Francesco Selmi[3] and further investigated since 1861 by Scottish scientist Thomas Graham.[4]
Because the size of the dispersed phase may be difficult to measure, and because colloids have the appearance of solutions, colloids are sometimes identified and characterized by their physico-chemical and transport properties. For example, if a colloid consists of a solid phase dispersed in a liquid, the solid particles will not diffuse through a membrane, whereas with a true solution the dissolved ions or molecules will diffuse through a membrane. Because of the size exclusion, the colloidal particles are unable to pass through the pores of an ultrafiltration membrane with a size smaller than their own dimension. The smaller the size of the pore of the ultrafiltration membrane, the lower the concentration of the dispersed colloidal particles remaining in the ultrafiltered liquid. The measured value of the concentration of a truly dissolved species will thus depend on the experimental conditions applied to separate it from the colloidal particles also dispersed in the liquid. This is particularly important for solubility studies of readily hydrolyzed species such as Al, Eu, Am, Cm, or organic matter complexing these species. Colloids can be classified as follows:
Based on the nature of interaction between the dispersed phase and the dispersion medium, colloids can be classified as: Hydrophilic colloids: The colloid particles are attracted toward water. They are also called reversible sols. Hydrophobic colloids: These are opposite in nature to hydrophilic colloids. The colloid particles are repelled by water. They are also called irreversible sols.
In some cases, a colloid suspension can be considered a semi-homogeneous mixture. This is because the distinction between "dissolved" solution and "particulate" suspension matter can be sometimes a matter of approach, which affects whether or not it is homogeneous or heterogeneous.
Interaction between particles
The following forces play an important role in the interaction of colloid particles:[10][11][12]
- Excluded volume repulsion: This refers to the impossibility of any overlap between hard particles.
- Electrostatic interaction: Colloidal particles often carry an electrical charge and therefore attract or
Based on the nature of interaction between the dispersed phase and the dispersion medium, colloids can be classified as: Hydrophilic colloids: The colloid particles are attracted toward water. They are also called reversible sols. Hydrophobic colloids: These are opposite in nature to hydrophilic colloids. The colloid particles are repelled by water. They are also called irreversible sols.
In some cases, a colloid suspension can be considered a semi-homogeneous mixture. This is because the distinction between "dissolved" solution and "particulate" suspension matter can be sometimes a matter of approach, which affects whether or not it is homogeneous or heterogeneous.
Interaction between particles
The following forces play an important role in the interaction of colloid particles:[10][11][12]
- Excluded volume repulsion: This refers to the impossibility of any overlap between hard particles.
- Electrostatic interaction: Colloidal particles often carry an electrical charge and therefore attract or repel each other. The charge of both the continuous and the dispersed phase, as well as the mobility of the phases are factors affecting this interaction.
- van der Waals forces: This is due to interaction between two dipoles that are either permanent or induced. Even if the particles do not have a permanent dipole, fluctuations of the electron density gives rise to a temporary dipole in a particle. This temporary dipole induces a dipole in particles nearby. The temporary dipole and the induced dipoles are then attracted to each other. This is known as van der Waals force, and is always present (unless the refractive indexes of the dispersed and continuous phases are matched), is short-range, and is attractive.
- Steric forces between polymer-covered surfaces or in solutions containing non-adsorbing polymer can modulate interparticle forces, producing an additional steric repulsive force (which is predominantly entropic in origin) or an attractive depletion force between them. Such an effect is specifically searched for with tailor-made superplasticizers developed to increase the workability of concrete and to reduce its water content.
Preparation
There are two principal ways to prepare colloids:[13]
- Dispersion of large particles or droplets to the colloidal dimensions by milling, spraying, or application of shear (e.g., shaking, mixing, or <
In some cases, a colloid suspension can be considered a semi-homogeneous mixture. This is because the distinction between "dissolved" solution and "particulate" suspension matter can be sometimes a matter of approach, which affects whether or not it is homogeneous or heterogeneous.
The following forces play an important role in the interaction of colloid particles:[10][11][12]
- Excluded volume repulsion: This refers to the impossibility of any overlap between hard particles.
- Electrostatic interaction: Colloidal particles often carry an electrical charge and therefore attract or repel each other.
There are two principal ways to prepare colloids:[13]
- Dispersion of large particles or droplets to the colloidal dimensions by milling, spraying, or application of shear (e.g., shaking, mixing, or high shear mixing).
- Condensation of small dissolved molecules into larger colloidal particles by precipitation, condensation, or redox reactions. Such processes are used in the preparation of colloidal silica or gold.
Stabilization (peptization)
The stability of a colloidal system is defined by particles remaining suspended in solution at equilibrium.
Stability is hindered by aggregation and sedimentation phenomena, which are driven by the colloid's tendency to reduce surface energy. Reducing the interfacial tension will stabilize the colloidal system by reducing this driving force.
The stability of a colloidal system is defined by particles remaining suspended in solution at equilibrium.
Stability is hindered by aggregation and sedimentation phenomena, which are driven by the colloid's tendency to reduce surface energy. Reducing the interfacial tension will stabilize the colloidal system by reducing this driving force.
Aggregation is due to the sum of the interaction forces between particles.[14]Stability is hindered by aggregation and sedimentation phenomena, which are driven by the colloid's tendency to reduce surface energy. Reducing the interfacial tension will stabilize the colloidal system by reducing this driving force.
Aggregation is due to the sum of the interaction forces between particles.[14][15] If attractive forces (such as van der Waals forces) prevail over the repulsive ones (such as the electrostatic ones) particles aggregate in clusters.
Electrostatic stabilization and steric stabilization are the two main mechanisms for stabilization against aggregation.
- Electrostatic stabilization is based on the mutual repulsion of like electrical charges. In general, different phases have different charge affinities, so that an electrical double layer forms at any interface. Small particle sizes lead to enormous surface areas, and this effect is greatly amplified in colloids. In a stable colloid, mass of a dispersed phase is so low that its buoyancy or kinetic energy is too weak to overcome the electrostatic repulsion between charged layers of the dispersing phase. The electrostatic repulsion between suspended colloidal particles is most readily quantified in terms of the z
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). All the above-mentioned mechanisms for minimizing particle aggregation rely on the enhancement of the repulsive interaction forces.
Electrostatic and steric stabilization do not directly address the sedimentation/floating problem.
Particle sedimentation (and also floating, although this phenomenon is less common) arises from a difference in the density of the dispersed and of the continuous phase. The higher the difference in densities, the faster the particle settling.
- The gel network stabilization represents the principal way to produce colloids stable to both aggregation and sedimentation.[16][17]
The method consists in adding to the colloidal suspension a polymer able to form a gel network and characterized by shear thinning properties. Examples of such substances are xanthan and Electrostatic and steric stabilization do not directly address the sedimentation/floating problem.
Particle sedimentation (and also floating, although this phenomenon is less common) arises from a difference in the density of the dispersed and of the continuous phase. The higher the difference in densities, the faster the particle settling.
The method consists in adding to the colloidal suspension a polymer able to form a gel network and characterized by shear thinning properties. Examples of such substances are xanthan and guar gum.
Particle settling is hindered by the stiffness of the polymeric matrix where particles are trapped.[16] In addition, the long polymeric chains can provide a steric or electrosteric stabilization to dispersed particles.
The rheological shear thinning properties find beneficial in the preparation of the suspensions and in their use, as the reduced viscosity at high shear rates facilitates deagglomeration, mixing and in general the flow of the suspensions.
Destabilisation
Unstable colloidal dispersions can form either flocs or aggregates as the particles assemble due to interparticle attractions. Flocs are loose and flexible conglomerates of the particles, whereas aggregates are compact and rigid entities. There are methods that distinguish between flocculation and aggregation, such as Flocs are loose and flexible conglomerates of the particles, whereas aggregates are compact and rigid entities. There are methods that distinguish between flocculation and aggregation, such as acoustic spectroscopy.[18] Destabilization can be accomplished by different methods:
- Removal of the electrostatic barrier that prevents aggregation of the particles. This can be accomplished by the addition of salt to a suspension or changing the pH of a suspension to effectively neutralise or "screen" the surface charge of the particles in suspension. This removes the repulsive forces that k
Unstable colloidal suspensions of low-volume fraction form clustered liquid suspensions, wherein individual clusters of particles fall to the bottom of the suspension (or float to the top if the particles are less dense than the suspending medium) once the clusters are of sufficient size for the Brownian forces that work to keep the particles in suspension to be overcome by gravitational forces. 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.
Monitoring stability
Multiple light scattering coupled with vertical scanning is the most widely used technique to monitor the dispersion state of a product, hence identifying and quantifying destabilisation phenomena.[19][20]
Accelerating methods for shelf life prediction
The kinetic process of destabilisation can be rather long (up to several months or even years for some products) and it is often required for the formulator to use further accelerating methods in order to reach reasonable development time for new product design. Thermal methods are the most commonly used and consists in increasing temperature to accelerate destabilisation (below critical temperatures of phase inversion or chemical degradation). Temperature affects not only the viscosity, but also interfacial tension in the case of non-ionic surf
The kinetic process of destabilisation can be rather long (up to several months or even years for some products) and it is often required for the formulator to use further accelerating methods in order to reach reasonable development time for new product design. Thermal methods are the most commonly used and consists in increasing temperature to accelerate destabilisation (below critical temperatures of phase inversion or chemical degradation). Temperature affects not only the 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. However, some emulsions would never coalesce in normal gravity, while they do under artificial gravity.[23] Moreover, segregation of different populations of particles have been highlighted when using centrifugation and vibration.[24]
As a model system for atoms
In physics
In physics, colloids are an interesting model system for atoms.[25] 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. In addition, phase transitions in colloidal suspensions can be studied in real time using optical techniques,[26] and are analogous to phase transitions in liquids. In many interesting cases optical fluidity is used to control colloid suspensions.[26][27]
Crystals
The stability of a colloidal system is defined by particles remaining suspended in solution at equilibrium.
