Colloid

SEMimage of a colloid.

Acolloidis amixturein which one substance consisting of microscopicallydispersedinsolubleparticlesissuspendedthroughout another substance. Some definitions specify that the particles must be dispersed in aliquid,while others extend the definition to include substances likeaerosolsandgels.The termcolloidal suspensionrefers unambiguously to the overall mixture (although a narrower sense of the wordsuspensionis 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 1nanometreto 1micrometre.

Some colloids aretranslucentbecause of theTyndall effect,which is thescatteringof light by particles in the colloid. Other colloids may beopaqueor have a slight color.

Colloidal suspensions are the subject ofinterface and colloid science.This field of study began in 1845 byFrancesco Selmi,who called them pseudosolutions, and expanded byMichael FaradayandThomas Graham,who coined the termcolloidin 1861.

IUPACdefinition

Colloid:Short synonym forcolloidalsystem.

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.

Classification

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 beimmiscibleunder certain conditions.	Liquidaerosol Examples:fog,clouds,condensation,mist,steam,hair sprays	Solid aerosol Examples:smoke,ice cloud,atmospheric particulate matter
	Liquid	Foam Example:whipped cream,shaving cream	EmulsionorLiquid crystal Examples:milk,mayonnaise,hand cream,latex,biological membranes,liquidbiomolecular condensate	Sol Examples:pigmented ink,sediment,precipitates,solidbiomolecular condensate
	Solid	Solid foam Examples:aerogel,floating soap,styrofoam,pumice	Gel Examples:agar,gelatin,jelly,gel-likebiomolecular condensate	Solid sol Example:cranberry glass

Homogeneous mixtures with a dispersed phase in this size range may be calledcolloidal aerosols,colloidal emulsions,colloidal suspensions,colloidal foams,colloidal dispersions,orhydrosols.

• 
  Aerogel
• 
  Jello cubes
• 
  Colloidalsilica gelwith lightopalescence
• 
  Whipped cream
• 
  A dollop of hair gel
• 
  Creamsare semi-solid emulsions of oil and water. Oil-in-water creams are used for cosmetic purpose while water-in-oil creams for medicinal purpose
• 
  Tyndall effectin anopalite:
  it scatters blue light making it appear blue from the side, but orange light shines through.
  opalis a gel in which water is dispersed in silicacrystals
• 
  Milk-emulsionof liquidbutterfatglobules dispersed in water
• 
  Mist

Hydrocolloids

Hydrocolloidsdescribe certainchemicals(mostlypolysaccharidesandproteins) that are colloidally dispersible inwater.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 fromfoodsthroughpharmaceuticals,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 withskinthan 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.

The term hydrocolloids also refers toa type of dressingdesigned to lock moisture in the skin and help the natural healing process of skin to reduce scarring, itching and soreness.

Components

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.

Compared with solution

A colloid has adispersed phaseand a continuous phase, whereas in asolution,thesoluteandsolventconstitute only one phase. A solute in a solution are individualmoleculesorions,whereas colloidal particles are bigger. For example, in a solution of salt in water, thesodium chloride(NaCl)crystaldissolves, 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.

Interaction between particles

The following forces play an important role in the interaction of colloid particles:

• 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:A repulsive steric force typically occurring due to adsorbed polymers coating a colloid's surface.
• Depletion forces:An attractive entropic force arising from an osmotic pressure imbalance when colloids are suspended in a medium of much smaller particles or polymers called depletants.

Sedimentation velocity

Brownian motion of 350 nm diameter polymer colloidal particles.

The Earth’sgravitational fieldacts upon colloidal particles. Therefore, if the colloidal particles are denser than the medium of suspension, they willsediment(fall to the bottom), or if they are less dense, they willcream(float to the top). Larger particles also have a greater tendency to sediment because they have smallerBrownian motionto counteract this movement.

The sedimentation or creaming velocity is found by equating theStokes drag forcewith thegravitational force:

$m_{A}g=6\pi \eta rv$

where

$m_{A}g$is theArchimedean weightof the colloidal particles,

$\eta$is theviscosityof the suspension medium,

$r$is theradiusof the colloidal particle,

and$v$is the sedimentation or creaming velocity.

The mass of the colloidal particle is found using:

$m_{A}=V(\rho _{1}-\rho _{2})$

where

$V$is the volume of the colloidal particle, calculated using the volume of a sphere$V={\frac {4}{3}}\pi r^{3}$,

and$\rho _{1}-\rho _{2}$is the difference in mass density between the colloidal particle and the suspension medium.

By rearranging, the sedimentation or creaming velocity is:

$v={\frac {m_{A}g}{6\pi \eta r}}$

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.

The colloidal particles are said to be insedimentation equilibriumif the rate of sedimentation is equal to the rate of movement from Brownian motion.

Preparation

There are two principal ways to prepare colloids:

• Dispersionof large particles or droplets to the colloidal dimensions bymilling,spraying,or application of shear (e.g., shaking, mi xing, orhigh shear mi xing).
• Condensation of small dissolved molecules into larger colloidal particles byprecipitation,condensation,orredoxreactions. Such processes are used in the preparation of colloidalsilicaorgold.

Stabilization

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 andvan der Waals forces,because they both contribute to the overallfree energyof the system.

A colloid is stable if the interaction energy due to attractive forces between the colloidal particles is less thankT,where k is theBoltzmann constantand T is theabsolute 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 asaggregation,but is also referred to asflocculation,coagulationorprecipitation.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 mi xing. Flocculation can be used to describe reversible aggregation involving weaker attractive forces, and the aggregate is usually called afloc.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.Aggregation causes sedimentation or creaming, therefore the colloid is unstable: if either of these processes occur the colloid will no longer be a suspension.

Examples of a stable and of an unstable colloidal dispersion.

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. The charge of colloidal particles is structured in anelectrical double layer,where the particles are charged on the surface, but then attract counterions (ions of opposite charge) which surround the particle. The electrostatic repulsion between suspended colloidal particles is most readily quantified in terms of thezeta potential.The combined effect of van der Waals attraction and electrostatic repulsion on aggregation is described quantitatively by theDLVO theory.A common method of stabilising a colloid (converting it from a precipitate) ispeptization,a process where it is shaken with an electrolyte.
• Steric stabilization consists absorbing a layer of a polymer or surfactant on the particles to prevent them from getting close in the range of attractive forces.The polymer consists of chains that are attached to the particle surface, and the part of the chain that extends out is soluble in the suspension medium.This technique is used to stabilize colloidal particles in all types of solvents, including organic solvents.

A combination of the two mechanisms is also possible (electrosteric stabilization).

Steric and gel network 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,and the long polymeric chains can provide a steric or electrosteric stabilization to dispersed particles. Examples of such substances arexanthanandguar gum.

Destabilization

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 to reduce theDebye screening length(the width of the electrical double layer) of the particles. It is also accomplished by changing the pH of a suspension to effectively neutralise the surface charge of the particles in suspension.This removes the repulsive forces that keep colloidal particles separate and allows for aggregation due to van der Waals forces. Minor changes in pH can manifest in significant alteration to thezeta potential.When the magnitude of the zeta potential lies below a certain threshold, typically around ± 5mV, rapid coagulation or aggregation tends to occur.
• Addition of a charged polymer flocculant. Polymer flocculants can bridge individual colloidal particles by attractive electrostatic interactions. For example, negatively charged colloidal silica or clay particles can be flocculated by the addition of a positively charged polymer.
• Addition of non-adsorbed polymers calleddepletantsthat cause aggregation due to entropic effects.

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 withviscoelasticproperties. Viscoelastic colloidal gels, such asbentoniteandtoothpaste,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

Measurement principle of multiple light scattering coupled with vertical scanning

The most widely used technique to monitor the dispersion state of a product, and to identify and quantify destabilization phenomena, is multiplelight scatteringcoupled with vertical scanning.This method, known asturbidimetry,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.These phenomena are associated with unstable colloids.

Dynamic light scatteringcan 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.

Accelerating methods for shelf life prediction

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,centrifugationand 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.Segregation of different populations of particles have been highlighted when using centrifugation and vibration.

As a model system for atoms

Inphysics,colloids are an interesting model system foratoms.Micrometre-scale colloidal particles are large enough to be observed by optical techniques such asconfocal 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 tomodelthe behavior of a hard sphere colloidal suspension.Phase transitionsin colloidal suspensions can be studied in real time using optical techniques,and are analogous to phase transitions in liquids. In many interesting cases optical fluidity is used to control colloid suspensions.

Crystals

Main article:Colloidal crystal

A colloidal crystal is a highlyorderedarray of particles that can be formed over a very long range (typically on the order of a few millimeters to one centimeter) and that appearanalogousto their atomic or molecular counterparts.One of the finestnaturalexamples of this ordering phenomenon can be found in preciousopal,in which brilliant regions of purespectralcolorresult fromclose-packeddomains ofamorphouscolloidal spheres ofsilicon dioxide(orsilica,SiO₂).These spherical particlesprecipitatein highlysiliceouspools inAustraliaand elsewhere, and form these highly ordered arrays after years ofsedimentationandcompressionunderhydrostaticand gravitational forces. The periodic arrays of submicrometre spherical particles provide similar arrays ofinterstitialvoids,which act as a naturaldiffraction gratingforvisiblelightwaves,particularly when the interstitial spacing is of the sameorder of magnitudeas theincidentlightwave.

Thus, it has been known for many years that, due torepulsiveCoulombicinteractions,electrically chargedmacromoleculesin anaqueousenvironment can exhibit long-rangecrystal-like correlations with interparticle separation distances, often being considerably greater than the individual particle diameter. In all of these cases in nature, the same brilliantiridescence(or play of colors) can be attributed to the diffraction andconstructive interferenceof visible lightwaves that satisfyBragg’s law,in a matter analogous to thescatteringofX-raysin crystalline solids.

The large number of experiments exploring thephysicsandchemistryof 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.

In biology

Colloidalphase separationis an important organising principle for compartmentalisation of both thecytoplasmandnucleusof cells intobiomolecular condensates—similar in importance to compartmentalisation via lipid bilayermembranes,a type ofliquid crystal.The termbiomolecular condensatehas been used to refer to clusters ofmacromoleculesthat arise via liquid-liquid or liquid-solidphase separationwithin cells.Macromolecular crowdingstrongly enhances colloidal phase separation and formation ofbiomolecular condensates.

In the environment

Colloidal particles can also serve as transport vector of diverse contaminants in the surface water (sea water, lakes, rivers, fresh water bodies) and in underground water circulating in fissured rocks (e.g.limestone,sandstone,granite). Radionuclides and heavy metals easilysorbonto colloids suspended in water. Various types of colloids are recognised: inorganic colloids (e.g.clayparticles, silicates,iron oxy-hydroxides), organic colloids (humicandfulvicsubstances). 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 theNevada Nuclear Test Site.They have been the subject of detailed studies for many years. However, the mobility of inorganic colloids is very low in compactedbentonitesand in deep clay formations because of the process ofultrafiltrationoccurring in dense clay membrane. The question is less clear for small organic colloids often mixed in porewater with truly dissolved organic molecules.

Insoil science,the colloidal fraction insoilsconsists of tinyclayandhumusparticlesthat are less than 1μm indiameterand carry either positive and/or negativeelectrostatic chargesthat vary depending on the chemical conditions of the soil sample, i.e.soil pH.

Intravenous therapy

Colloid solutions used inintravenous therapybelong to a major group ofvolume expanders,and can be used for intravenousfluid replacement.Colloids preserve a highcolloid osmotic pressurein the blood,and therefore, they should theoretically preferentially increase theintravascular volume,whereas other types of volume expanders calledcrystalloidsalso increase theinterstitial volumeandintracellular volume.However, there is still controversy to the actual difference inefficacyby this difference,and much of the research related to this use of colloids is based on fraudulent research byJoachim Boldt.Another difference is that crystalloids generally are much cheaper than colloids.