Encapsulation core material

In this context. Let et al. suggested that the composition of the interface may be more important than the total surface area itself. In recent years, research focused on modification of the oil-water-interface with the aim of physical stabilization of the interface during dehydration and/or modification of the release of the encapsulated core material. A well-described system is stabilization of the interface through bilayer formation using lecithin as emulsifier and chitosan as oppositely charged polymer for bilayer formation. - Due to the cationic surface of the droplet, surface repulsion... 

Polymer coacervation can occur in either aqueous or organic liquids. Coacervation in aqueous liquids and the related processes are mainly used to encapsulate water-immiscible liquids or water-insoluble solid particles. On the other hand, coacervation in organic liquids, or sometimes called phase separation in organic liquids, is used to encapsulate core materials that are not miscible or soluble in the organic liquids. It may be induced by the addition of a nonsolvent to the polymer solution or by the addition of an incompatible polymer based on polymer-polymer incompatibility. This chapter will only discuss the coacervation in aqueous liquids. 

Many terms have been used to describe the contents of a microcapsule active agent, actives, core material, fill, internal phase (IP), nucleus, and payload. Many terms have also been used to describe the material from which the capsule is formed carrier, coating, membrane, shell, or wall. In this article the material being encapsulated is called the core material the material from which the capsule is formed is called the shell material. 

Classification of the many different encapsulation processes is usehil. Previous schemes employing the categories chemical or physical are unsatisfactory because many so-called chemical processes involve exclusively physical phenomena, whereas so-called physical processes can utilize chemical phenomena. An alternative approach is to classify all encapsulation processes as either Type A or Type B processes. Type A processes are defined as those in which capsule formation occurs entirely in a Hquid-filled stirred tank or tubular reactor. Emulsion and dispersion stabiUty play a key role in determining the success of such processes. Type B processes are processes in which capsule formation occurs because a coating is sprayed or deposited in some manner onto the surface of a Hquid or soHd core material dispersed in a gas phase or vacuum. This category also includes processes in which Hquid droplets containing core material are sprayed into a gas phase and subsequentiy solidified to produce microcapsules. Emulsion and dispersion stabilization can play a key role in the success of Type B processes also. 

Complex Coacervation. This process occurs ia aqueous media and is used primarily to encapsulate water-iminiscible Hquids or water-iasoluble soHds (7). In the complex coacervation of gelatin with gum arabic (Eig. 2), a water-iasoluble core material is dispersed to a desired drop size ia a warm gelatin solution. After gum arabic and water are added to this emulsion, pH of the aqueous phase is typically adjusted to pH 4.0—4.5. This causes a Hquid complex coacervate of gelatin, gum arabic, and water to form. When the coacervate adsorbs on the surface of the core material, a Hquid complex coacervate film surrounds the dispersed core material thereby forming embryo microcapsules. The system is cooled, often below 10°C, ia order to gel the Hquid coacervate sheU. Glutaraldehyde is added and allowed to chemically cross-link the capsule sheU. After treatment with glutaraldehyde, the capsules are either coated onto a substrate or dried to a free-flow powder. 

Polymer—polymer iacompatibiHty encapsulation processes can be carried out ia aqueous or nonaqueous media, but thus far have primarily been carried out ia organic media. Core materials encapsulated tend to be polar soHds with a finite degree of water solubiHty. EthylceUulose historically has been the sheU material used. Biodegradable sheU materials such as poly(D,L-lactide) and lactide—glycoHde copolymers have received much attention. In these latter cases, the object has been to produce biodegradable capsules that carry proteias or polypeptides. Such capsules tend to be below 100 p.m ia diameter and are for oral or parenteral administration (9). 

Figure 4a represents interfacial polymerisation encapsulation processes in which shell formation occurs at the core material—continuous phase interface due to reactants in each phase diffusing and rapidly reacting there to produce a capsule shell (10,11). The continuous phase normally contains a dispersing agent in order to faciUtate formation of the dispersion. The dispersed core phase encapsulated can be water, or a water-immiscible solvent. The reactant(s) and coreactant(s) in such processes generally are various multihmctional acid chlorides, isocyanates, amines, and alcohols. For water-immiscible core materials, a multihmctional acid chloride, isocyanate or a combination of these reactants, is dissolved in the core and a multihmctional amine(s) or alcohol(s) is dissolved in the aqueous phase used to disperse the core material. For water or water-miscible core materials, the multihmctional amine(s) or alcohol(s) is dissolved in the core and a multihmctional acid chloride(s) or isocyanate(s) is dissolved in the continuous phase. Both cases have been used to produce capsules. 

Figure 5 illustrates the type of encapsulation process shown in Figure 4a when the core material is a water-immiscible Hquid. Reactant X, a multihmctional acid chloride, isocyanate, or combination of these reactants, is dissolved in the core material. The resulting mixture is emulsified in an aqueous phase that contains an emulsifier such as partially hydroly2ed poly(vinyl alcohol) or a lignosulfonate. Reactant Y, a multihmctional amine or combination of amines such as ethylenediamine, hexamethylenediamine, or triethylenetetramine, is added to the aqueous phase thereby initiating interfacial polymerisation and formation of a capsule shell. If reactant X is an acid chloride, base is added to the aqueous phase in order to act as an acid scavenger. 

A key feature of encapsulation processes (Figs. 4a and 5) is that the reagents for the interfacial polymerisation reaction responsible for shell formation are present in two mutually immiscible Hquids. They must diffuse to the interface in order to react. Once reaction is initiated, the capsule shell that forms becomes a barrier to diffusion and ultimately begins to limit the rate of the interfacial polymerisation reaction. This, in turn, influences morphology and uniformity of thickness of the capsule shell. Kinetic analyses of the process have been pubHshed (12). A drawback to the technology for some apphcations is that aggressive or highly reactive molecules must be dissolved in the core material in order to produce microcapsules. Such molecules can react with sensitive core materials. 

Figure 4c illustrates interfacial polymerisation encapsulation processes in which the reactant(s) that polymerise to form the capsule shell is transported exclusively from the continuous phase of the system to the dispersed phase—continuous phase interface where polymerisation occurs and a capsule shell is produced. This type of encapsulation process has been carried out at Hquid—Hquid and soHd—Hquid interfaces. An example of the Hquid—Hquid case is the spontaneous polymerisation reaction of cyanoacrylate monomers at the water—solvent interface formed by dispersing water in a continuous solvent phase (14). The poly(alkyl cyanoacrylate) produced by this spontaneous reaction encapsulates the dispersed water droplets. An example of the soHd—Hquid process is where a core material is dispersed in aqueous media that contains a water-immiscible surfactant along with a controUed amount of surfactant. A water-immiscible monomer that polymerises by free-radical polymerisation is added to the system and free-radical polymerisation localised at the core material—aqueous phase interface is initiated thereby generating a capsule sheU (15). 

Figure 4d represents in situ encapsulation processes (17,18), an example of which is presented in more detail in Figure 6 (18). The first step is to disperse a water-immiscible Hquid or soHd core material in an aqueous phase that contains urea, melamine, water-soluble urea—formaldehyde condensate, or water-soluble urea—melamine condensate. In many cases, the aqueous phase also contains a system modifier that enhances deposition of the aminoplast capsule sheU (18). This is an anionic polymer or copolymer (Fig. 6). SheU formation occurs once formaldehyde is added and the aqueous phase acidified, eg, pH 2—4.5. The system is heated for several hours at 40—60°C.

A unique feature of in situ encapsulation technology is that polymerization occurs ia the aqueous phase thereby produciag a condensation product that deposits on the surface of the dispersed core material where polymerization continues. This ultimately produces a water-iasoluble, highly cross-linked polymer capsule shell. The polymerization chemistry occurs entirely on the aqueous phase side of the iaterface, so reactive agents do not have to be dissolved ia the core material. The process has been commercialized and produces a range of commercial capsules. 

Solvent Evaporation. This encapsulation technology involves removing a volatile solvent from either an oil-in-water, oil-in-oil, or water-in-oH-in-water emulsion (19,20). In most cases, the shell material is dissolved in a volatile solvent such as methylene chloride or ethyl acetate. The active agent to be encapsulated is either dissolved, dispersed, or emulsified into this solution. Water-soluble core materials like hormonal polypeptides are dissolved in water that contains a thickening agent before dispersion in the volatile solvent phase that contains the shell material. This dispersed aqueous phase is gelled thermally to entrap the polypeptide in the dispersed aqueous phase before solvent evaporation occurs (21). 

The second step is to disperse the core material being encapsulated in the solution of shell material. The core material usually is a hydrophobic or water-knmiscible oil, although soHd powders have been encapsulated. A suitable emulsifier is used to aid formation of the dispersion or emulsion. In the case of oil core materials, the oil phase is typically reduced to a drop size of 1—3 p.m. Once a suitable dispersion or emulsion has been prepared, it is sprayed into a heated chamber. The small droplets produced have a high surface area and are rapidly converted by desolvation in the chamber to a fine powder. Residence time in the spray-drying chamber is 30 s or less. Inlet and outlet air temperatures are important process parameters as is relative humidity of the inlet air stream. 

Liquid food ingredients encapsulated are typically oil-soluble flavors, spices (see Flavors and spices), and vitamins (qv). Even food oils and fats are encapsulated (63). These core materials normally are encapsulated with a water-soluble shell material appHed by spray drying from water, but fat shell formulations are used occasionally. Preferred water-soluble shell materials are gum arabic, modified starch, or blends of these polymers with maltodextrins. Vitamins are encapsulated with 2ero bloom strength gelatin by spray drying. 

An important class of materials that originates from the precursor core-shell particles is hollow capsules. Hollow capsules (or shells ) can be routinely produced upon removal of the core material using chemical and physical methods. Much of the research conducted in the production of uniform-size hollow capsules arises from their scientific and technological interest. Hollow capsules are widely utilized for the encapsulation and controlled release of various substances (e.g., drugs, cosmetics, dyes, and inks), in catalysis and acoustic insulation, in the development of piezoelectric transducers and low-dielectric-constant materials, and for the manufacture of advanced materials [14],... 

In interfacial polymerization, monomers react at the interface of two immiscible liquid phases to produce a film that encapsulates the dispersed phase. The process involves an initial emulsification step in which an aqueous phase, containing a reactive monomer and a core material, is dispersed in a nonaqueous continuous phase. This is then followed by the addition of a second monomer to the continuous phase. Monomers in the two phases then diffuse and polymerize at the interface to form a thin film. The degree of polymerization depends on the concentration of monomers, the temperature of the system, and the composition of the liquid phases. 

The term aqueous phase separation is often more simply described as oil-in-water microencapsulation. The two encapsulation processes described above are examples of this oil-in-water encapsulation. In this process the core material is the oil and it should be immisible in the continuous phase, namely water. A commercial example of aqueous phase separation would be the microencapsulation of an oily flavor such as sour cream with a gelatin wall. These microcapsules would then be dispersed in a dry cake mix. The mechanism of release would be during the moist baking cycle of the cake, moist-heat causing the capsule walls to first swell and then rupture. 

In this contribution a novel fluidized-bed coating process is introduced to encapsulate heat-sensitive materials with particle sizes below 100 pum. Supercritical carbon dioxide is used as solvent for the coating material as well as carrier fluid for the core material. The behaviour of the high pressure fluidized-bed was investigated for different process parameters and materials. It is shown that the fluidization starts at lower fluid velocities if the pressure is increased and it was possible to fluidized particles with a mean size below 10 xm. The coating of glass beads with stearyl alcohol was carried out and layers with a thickness of 1-8 xm were achieved. 

In another approach, the polymer is precipitated from the continuous phase onto on stable nanodroplets in an inverse miniemulsion [109], In this case, a miniemulsion with the liquid core material is formed in a continuous phase that consists of a mixture of a solvent and a nonsolvent for the polymer. That way, PMMA nanocapsules encapsulating an antiseptic agent could be produced. 

Spray drying is the most commonly used method in the food industry. Bioactive ingredients microencapsulated by this method include fats and oils, flavours, essential oils and other oil-soluble bioactives. Water-soluble bioactives can also be encapsulated by spray drying, where the encapsulant forms a matrix structure rather than a film surrounding the core. This process typically involves the dispersion of the core material into a solution of the encapsulant (e.g., protein, carbohydrate) and atomization of the mixture into the drying chamber. This leads to evaporation of the solvent... 

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