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Microencapsulation Technologies

Microencapsulation technology has been used commercially since the 1950s when it became established
as the basis for carbonless copy paper and is now used widely within the food processing, paper,
pharmaceutical, agrochemical and cosmetic/persona; care industries. Similarly the technology has
played a significant role in new developments in the textile industry and has been used for example to
impart a range of long-lasting finishes to textile materials including, fragrances, antimicrobials,
insecticides, fire retardants and temperature control phase change materials. Micro-encapsulation has
also been the major force behind the rise of Cosmeto-textiles delivering moisturising agents, vitamins
and anti-wrinkle/anti-ageing active ingredients onto the skin.

Microencapsulation is a process by which very tiny droplets or particles of liquid or solid material are
surrounded or coated with a continuous film of a polymeric material. The ingredient to be
encapsulated is usually referred to as the core material, however, can also be called the internal
phase, active, encapsulate, payload or fill. The coating of the microcapsule is generally referred to as
the wall material with shell, external phase and in some cases membrane also commonly used. The
shape of the capsule is generally governed by the physical nature of the core material for example if
the core material is a solid or crystalline material then the resulting capsule may be irregularly shaped.
However, if the core material is a liquid, a simple spherical capsule containing a single droplet of active
ingredient may be formed.

Microcapsules range in size from 100s of microns, down to single microns although 10-40microns is
probably most common. Nanocapsules are also available with sizes around or below 1 micron. Typically
the core content will be around 80% by weight although anything up to 95% is possible.
Follow the links below to find out more about the major microencapsulation technologies and also
other technologies used to store and control release active ingredients:

Chemical Based Microencapsulation Technologies

Coacervation

Coacervation

Interfacial Polymerisation

In-situ Polymerisation

Liposomes

Inclusion Complexation

Sometimes called phase separation this technology is considered as the oldest true encapsulation technology
first developed by the National Cash Register Company for carbonless copy-paper. Microencapsulation by
coacervation, involves the phase separation of one or more hydrocolloids from the initial solution and the
subsequent deposition of the newly formed coacervate phase around the active ingredient suspended or
emulsified in the same reaction media. After being hardened, the wall of the microcapsules forms a crosslinked structure, thus the microcapsules have good thermal and moisture-resistant properties and can be
used for controlled release applications. Coacervation generally involves a number of steps which are carried
out under continuous agitation

1. Disperse the oil phase in a solution of a surface active hydrocolloid.


2. Precipitate the hydrocolloid onto the oil phase by lowering the solubility of the hydrocolloid (add a nonsolvent or change pH or temperature)
3. Induce the formation of the polymer-polymer complex by addition of a second complexing hydrocolloid.
4. Cross-link to stabilise the microcapsule
5. Dry the material to form microcapsules with sizes in the range 10-250microns
Although many materials (e.g. alginates, chitosan, starch, and methyl cellulose) can be used the most
commonly used are mixtures of proteins and anionic polysaccharides. Perhaps the most well-known example
is gelatin and gum arabic.
At pH values above 6 both these materials are miscible, however when the pH is lowered below gelatins
isoelectric point the net charge on the gelatin becomes negative and it then interacts with the positively
charged gum arabic. The active ingredient, e.g. dye dissolved in an oil phase is first emulsified at about 40%
in 10%w/v gelatin. The mixture is then added to about 2 parts gum arabic solution, maintaining the pH of the
system above 5. As the pH is lowered to 4.5, microcapsules form from coacervate material positively charged
gelatin and negatively charged gum arabic depositing around the oil droplets. After wall formation the wall is
hardened by cross linking with for example glutaraldehyde or alternatively using transglutaminase.

Interfacial Polymerisation
This technique is based on the classical technology involved in interfacial polycondensation polymerisation
which is widely used to produce synthetic fibres such as polyester, nylon and polyurethane and is
characterized by wall formation via the rapid polymerization of monomers at the surface of the droplets or
particles of dispersed core material. A multifunctional monomer is dissolved in the core material, and this
solution is dispersed in an aqueous phase. A reactant to the monomer is added to the aqueous phase, and
polymerization quickly ensues at the surfaces of the core droplets, forming the capsule walls. Interfacial
polymerization can be used to prepare bigger microcapsules, but most commercial interfacial polymerization
processes produce smaller capsules in the 20-30 micron diameter range, or even smaller 3-6 micron diameter

range for carbonless paper ink.

In interfacial polymerization, the two reactants in a polycondensation meet at an interface and react rapidly.
The basis of this method is the classical Schotten-Baumann reaction between an acid chloride and a
compound containing an active hydrogen atom, such as an amine or alcohol, polyesters, polyurea,
polyurethane. Under the right conditions, thin flexible walls form rapidly at the interface.

In-situ polymerisation
In situ polymerization is a chemical encapsulation technique very similar to interfacial polymerization. The
distinguishing characteristic of in situ polymerization is that no reactants are included in the core material.
All polymerization occurs in the continuous phase, rather than on both sides of the interface between the
continuous phase and the core material, as in interfacial polymerization. Examples of this method include
urea-formaldehyde (UF) and melamine formaldehyde (MF) encapsulation systems. Typically an oil-phase is
emulsified in water using water-soluble polymers and high shear mixers yielding a stable emulsion at the
required droplet size. A water-soluble melamine resin is added and dispersed. The pH is then reduced by the
addition of acid initiating the polycondensation which yields cross-linked resins that deposit at the interface
between the oil droplets and the water phase. During hardening of the wall material the microcapsules form
and the aqueous dispersion of polymer-encapsulated oil droplets is produced.

Liposomes
A liposome is a tiny vesicle generally made from phospholipids which spontaneously form when disrupted in
water, with diameter ranging from 25nm to 10microns. Both hydrophobic and hydrophilic active ingredients
can be entrapped. The vesicles are made of a bilayer similar to that of a cell membrane hence orient
themselves so that the inner and outer phase is hydrophilic. The central core can therefore contain water
soluble active ingredients with hydrophobic ingredients being trapped within the bilayer. In a similar way
micelles can be formed to entrap hydrophobic materials in the central core.

Inclusion Complexation
Inclusion complexation involves the use of cyclodextrins which are a group of structurally related natural
products formed during bacterial digestion of cellulose (Martin Del Valle, 2004). These cyclic oligosaccharides
consist of (-1,4)-linked -D-glucopyranose units and contain a lipophilic central cavity and a hydrophilic
outer surface. Cyclodextrin inclusion is a molecular phenomenon in which usually a single guest molecule
interacts with the cavity of a cyclodextrin molecule to become entrapped and form a stable association.
Molecules or functional groups of molecules which are less hydrophilic than water can be included in the
cyclodextrin cavity in the presence of water. In order to become complexed, the "guest molecules" should fit,
at least partly, into the cyclodextrin cavity. The cavity size as well as chemical modifications to the
cyclodextrin defines the affinity of the various guest molecules. In the case of some low molecular weight
molecules, more than one guest molecule may fit into the cavity.

Physical Microencapsulation Technologies

Spray Coating

Centrifugal Extrusion

Spinning Disk
Extrusion

Annular Jet

Spray Drying

Prilling

Spray Coating
Coating technologies have been used for many years to prepare pharmaceutical capsules in the traditional
macro scale. The particles are tumbled in a pan or other device while the coating material is applied
producing capsules we have all used at one time or another. Building on this technique Air-Suspension
Coating/Fluidised Bed Coating (a more specific version is called Wurster Coating) of particles by solutions or
melts gives better control and flexibility for microcapsule production. Particles of the active ingredient,
spheres or granules are coated while suspended in an upward-moving air stream. They are supported by a
perforated plate having different patterns of holes inside and outside a cylindrical insert. Just sufficient air is
permitted to rise through the outer annular space to fluidize the settling particles. Most of the rising air
(usually heated) flows inside the cylinder, causing the particles to rise rapidly. At the top, as the air stream
diverges and slows, they settle back onto the outer bed and move downward to repeat the cycle. The
particles pass through the inner cylinder many times in a few minutes.

In the food industry the Wurster process has been used to encapsulate/coat vitamins, minerals and functional
food ingredients for example to mask an undesirable flavour or improve stability and shelf life. The coating
possibilities are relatively unlimited for example it is possible to coat a hydrophilic active ingredient with a
hydrophobic polymer, or a hydrophobic active ingredient with a hydrophilic wall material at various
thicknesses for process optimisation. With irregular shaped crystals it is likely that the coated particles
would also be irregular in shape, although trials would have to be completed to be certain. Particles can be
prepared with potential diameters of less than 50microns upwards.

Centrifugal Extrusion
The centrifugal extrusion process is a liquid co-extrusion process utilising nozzles consisting of concentric
orifices located on the outer circumference of a rotating cylinder. A liquid core material is pumped through
the inner orifice and a liquid wall material through the outer orifice forming a co-extruded rod of core
material surrounded by the wall material. As the device rotates, the extruded rod breaks into droplets which
form capsules. The rotational speed affects the capsule size which can be a little as 150microns in diameter
and the active ingredients can be encapsulated to up to 80% per weight. Typical wall materials include
gelatin, alginate, carageenan, starch, cellulose derivatives, gum arabic, fats and waxes or polyethylene
glycol. Flavour oils for example are easily encapsulated using this methodology.

Spinning Disk
Similarly to centrifugal extrusion this spinning disk system uses
rotational forces to create droplets. Typically the active
ingredient is suspended in a wall material and dropped onto the
rotating disk which throws the droplets out towards the
circumference of the disk where the wall material solidifies
through drying or chilling. As the spinning rate can be carefully
controlled the disk process is able to yield narrow particle size
distributions, and produce matrix particles of between 5 and
3000 microns.

Annular Jet
The technique involves two concentric jets, the inner containing the active ingredient and the outer
generally molten wall material which solidifies when exiting the jet. The duel fluid stream naturally breaks
into droplets which form the basis of the microcapsule, which depending on configuration can be matrix

particles or core-shell in formation. Later adaptations


have added a vibrational nozzle to help control the
droplet size giving a more uniform product with lower
microcapsule sizes down to sub-micron diameters. The
liquid can consist of any liquids with limited viscosities
e.g. solutions, emulsions, suspensions, melts etc. The
soldification can be initiated by any common gelation
system (e.g. sol-gel processing, melt) or by using an
external additional binder system, (e.g. in a slurry).

Spray Drying
Traditionally the most common method of
microencapsulation of food ingredients. To
prepare materials for spray drying the wall
material (e.g. maltodextrin, modified starch,
gum or a combination of these is hydrated. The
flavour or ingredient to be encapsulated is
added to the carrier and homogenised or
thoroughly mixed using a equivalent technique
to create small droplets. Typically the ratio of
carrier to flavour would be 4:1, however in
some applications higher flavour loads can be
used. The mixture is fed into the spray dryer
where it is atomised through a nozzle or
spinning wheel. Hot air flowing in either a cocurrent or counter current direction contacts
the atomised droplets and evaporates the
water producing a matrix particle containing
small droplets of flavour. The dried particles
are generally collected in a separate chamber
through a cyclonic air stream.

There are many variants of the technique utilising a wide range of wall materials. Spray drying is carried out
internally in virtually all major and medium size flavour companies where the encapsulated flavours, spices
etc are either sold as spray dried individual active ingredients or as part of a formulated blend.

Prilling
Prilling sometimes called spray chilling, spray cooling or spray congealing is similar to spray drying in that the
active ingredient is dispersed in a liquefied coating or wall material and atomised. However in these cases
the mixture is atomised into cool or chilled air which solidifies the wall material around the active
ingredient. In some cases two fluid nozzles can be used. Microcapsules or matrix particles can be produced
generally from 10-400microns in diameter utilising a wide range of wall materials including waxes,
hydrogenated vegetable oils and polymers. This technology has been applied to agrochemicals and drugs but
can also be used for flavours and fragrances. As the melting point of the wall material can be carefully
selected it is possible to develop control release formulations for a given active ingredient.

Prilling systems are capable of high throughput for major industrial application and contract manufacture
capability is fairly widespread.

Extrusion
Encapsulation by extrusion involves dispersion of the active ingredient in a molten wall material often a
carbohydrate such as starch or maltodextrins. The process can also be called melt-extrusion, glass
encapsulation, melt-encapsulation or the Durarome process. The mixture is forced through a die producing a
solid filament as the material cools in air or by falling into a dehydrating liquid such as isopropyl alcohol. The
filaments are then milled and sieved to the desired particle size. Generally the product contains 8-20%
flavour load, although the capsules size are in general fairly large (~500microns)

A typical commercially available product range utilises sugar as a wall material and with careful selection of
the glass transition temperature can produce glassy matrix particles stable at room temperature which
protect the flavours from oxidation. As the coating is sugar based they are particularly suited to sweet
applications.

Gel Based Technologies

Hydrogels
The first synthetic Hydrogels were developed in the 1950s and since those days have been researched and
developed as food additives, controlled release pharmaceuticals, biomedical implants, tissue constructs for tissue
engineering, and also in regenerative medicines, diagnostics, in the separation of biomolecules or cells, in
biosensors, as barrier materials to regulate biological adhesions.
Hydrogels are hydrophilic polymeric network of three dimensional cross linked structures that absorb substantial
amount of water. When cross-linked water solubility is reduced because of ionic interaction and hydrogen
bonding. It also provides required mechanical strength and physical integrity to the Hydrogels. Hydrogels can
absorb water nearly 10-20 times its molecular weight and hence become swollen. Some examples of Hydrogels
include contact lenses, wound dressing, and superabsorbents.
The ability to swell can be controlled and used to release active ingredients in a controlled and targeted way.
Hydrogels can also be found naturally for example agarose, hylaronan and cellulosic polymers. The materials are
biocompatible and easy to modify and release of the active ingredients can be precipitated by change in pH,
temperature or even change in the concentration of a specific substance in the vicinity of the hydrogel.
Conventional Air Freshener Gel Systems

Fragrances, insect repellents and other


active materials can be controlled
released into the environment from gel
based systems. Typical air freshener
systems are made from cellulose
derivatives, carrageen or similar gel
matrices and the fragrance is released as
gel dries out on exposure to the air. These
systems generally contain around 5-8%
fragrance and last a few weeks. The gel is
prepared as a liquid and metered into
plastic or glass moulds which are sealed
ready for use.

the
gel

Higher fragrance concentration can be achieved in sodium stearate type gels systems. Typically used in public
health applications, these products can contain around 30% fragrance. Although there are specialist gel systems
where the fragrance concentration can be higher than 90%.

Plastic Technologies

Fragrances, flavours, insect repellents and other hydrophobic liquid active ingredients can be compounded or
infused into a whole variety of plastics for subsequent moulding into consumer and industrial products. The
loading in the concentrate is usually around 40% and
in final application between 1 and 5%. Anything higher
than this is generally uneconomic.
In some case finished products can be dipped in the
fragrance which is absorbed effectively into the
finished product. The active ingredient diffuse out
through the surface of the plastic and is released into
the atmosphere at a rate which depends on air flow,
temperature
etc.
Application are very broad and include air fresheners,
in car and in the home, gum shields, medical devices
(flavoured tongue depressors), infant teething mugs,
and even animal toys (chocolate flavoured dog
chews).

Some specialist systems for adding the active ingredient into plastics are available including liquid injection
systems which allow formation of microcapsule within the plastic to further control the release.

Natural Preformed Microcapsule Systems

Yeast Microencapsulation Technology


The most widely known and commercially available systems utilise yeast cells, either bakers or brewers
yeast as preformed microcapsules. The commercial products are usually made up of yeast coated or
partially coated with maltodextrin, gelatin or a similar material although purely yeast cell based systems
are possible.
They are primarily sold as heat stable flavoured systems for food products, breads, fries etc, although
research has been conducted with drugs, pesticides, anti-microbials and many other active ingredients.
As single yeast cell is approximately 8-10microns in diameter and comprises and lipid membrane which
provides selectivity for the microencpasulaiton system (only low molecular weight liquid lipophilic active
ingredients can be encapsulated successfully) and an outer glucan/mannan cell wall which gives the
microcapsule system great strength in process.
The active ingredient when mixed under the right conditions diffuse into the yeast cell and remain there
until the external conditions promote release, for example when the yeast cell touches a moist mucous
membrane, mouth or nose or a strong solvent for the active ingredient.

Overall advantages:

Low cost
High Loading

Heat Stable
Natural

Other Natural Systems


A range of other natural systems have been examined as preformed microcapsules for example spores, pollen
grains, starch granules. However, as yet none of these systems have practical applications.