Microencapsulation technology

Complex coacervation & hydrog

Ben Sales and David Palmer introduce ISPs microencapsulation technologies*

he science of microencapsulation has been used in industry for many years, the greatest commercial volumes currently being in carbonless copy paper and agricultural chemicals. In recent years there has been an increase in the number of companies seeking microencapsulated actives for consumer markets. Microencapsulation offers users the ability to control the release of active ingredients as well as to isolate and protect these actives from the surrounding formulation. Encapsulation also makes it possible to combine incompatible ingredients in a formulation. This can be as straightforward as formulating lipophilic material into clear aqueous systems or meeting more challenging demands, such as incorporating otherwise incompatible sunscreens. In this article, we describe two different encapsulation techniques practised by ISP as well illustrating how these ever-evolving technologies can provide new benefits to the formulator.

8 7 Cumulative distribution

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Complex coacervation
ISP Microcaps specialises in the technique of complex coacervation. This involves the formation of a continuous capsule wall around a lipophilic water-immiscible core. The capsule wall is formed of two oppositely charged polymers (typically gelatin and gum acacia) in an aqueous solution, that interact together to form a coacervate polymer (the word coacervate comes from the Latin meaning to heap together) that wraps around the lipophilic droplet to form the wall. The key parameter in forming the capsule wall is the rate of pH change. Lowering the pH below the isoelectric point of the amphoteric gelatin causes it to become cationically charged. The gelatin then interacts with the anionic polymer and forms the coacervate. Changing pH at the optimum rate is essential for controlling the capsule wall thickness. Different anionic polymers can be used to form capsules with different qualities. After wall formation, the capsule walls are cross-linked. The wall consequently has excellent long-term and thermal stability, which allows this type of capsule to be put into many different types of systems.

Figure 1 - Size distribution of beads produced via JetCutter

The JetCutter process in action

Another advantage of this technology is that the active/core material is typically 85-95% of the capsule. This type of encapsulation system can therefore be an efficient method of delivering an active ingredient. Shear or pressure is typically used as a release mechanism for the internal active, although enzymatic release is also possible. By using complex coacervation, it is possible to produce capsules as small as 1 micron, depending on the type of homogeniser used. One of the key challenges when forming capsules smaller than 50 microns is to avoid agglomeration of small individual capsules into large clusters. Again, this is achieved by precise pH control. Capsules can be made up to 2,000 microns, although low viscosity in the oil may restrict the maximum diameter achievable. At above 2,000 microns, capsules may become too fragile to process. Typically, the microcapsules formed using complex coacervation are incorporated in the form of an aqueous microcapsule slurry. Capsules with an average diameter below 50 microns may also be spray-dried to form a free-flowing powder for use in non-aqueous systems. The complex coacervation encapsulation technique is traditionally based on the stabilisation of lipophilic water-immiscible materials. Recent development work has now made it possible to encapsulate some water-soluble actives using the same technique by forming a water-in-oil (W/O) emulsion. It is then possible to process this emulsion as a routine oil phase, thereby allowing the inclusion of up to 45% (W/W) water in the microcapsules. Water-soluble actives, such as l-ascorbic acid (Vitamin C), can be dissolved in the water phase, emulsified and encapsulated, allowing the microcapsules to be added to formulations. This avoids the incompatibilities normally caused by unstable ingredients and provides controlled release of the active ingredient. The high viscosity of the emulsion allows a greater maximum size capsule to be produced by comparison with normal oilbased encapsulation. The customisation of most parameters is possible during the encapsulation process and this can greatly influence the breakage characteristics of the finished microcapsules. Careful control of microcapsule size, core contents, wall thickness and the degree of cross-linking can result in a microcapsule robust which is enough to survive filling and processing, but will still March 2008 Speciality Chemicals Magazine

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Microencapsulation technology

gel encapsulation technology

break when required to release the active ingredient within the capsule. The choice of anionic polymer can also greatly influence the breakage characteristics and other physical properties of the finished microcapsule.

JetCutter technology
ISP has recently added the patented JetCutter technology as an alternative means of microencapsulation. Beads are produced by pumping component materials at high velocity as a solid jet of fluid. The fluid jet is then cut into cylindrical segments using a rotating JetCutter tool. Driven by surface tension, the cut cylindrical segments form spherical droplets and fall into a bath of hardening solution. The resulting chemical reactions process the droplets into gelled beads. Droplet generation using the JetCutter technique is based on the mechanical impact of the cutting wire on the liquid jet. The size of the droplets can be adjusted within a range of 200 microns up to several mm. The main size-influencing parameters are the nozzle diameter, the flow rate through the nozzle, the number of cutting wires and the rotation speed of the cutting tool. The cutting process (pictured opposite) causes a small initial material loss as a cylindrical segment the height of the diameter of the cutting wire is pushed out of the jet, where it can be collected and recycled. If all process parameters are adjusted correctly, these losses can be reduced to 1% or less. This means that more than 99% of the processed fluid is transferred directly into the beads. The process gives beads with a particularly narrow size distribution (Figure 1). In principle, any fluid that can be solidified instantaneously can be processed and the means to achieve this can be a purely physical reaction (such as a temperature shift to harden a molten material), a chemical reaction (like the ionic interaction between polymers and counter ions) or a combination of the two. The typical bead matrix consists of a polymer in an aqueous phase, resulting in hydrogel particles.

A typical material used for the process is sodium alginate, a naturally-derived polysaccharide consisting of guluronic and mannuronic acids. Droplets of a sodium alginate aqueous solution, typically of 1-4%, depending on the viscosity and type of alginate, and the required particle strength, are processed into a solution of 2% calcium chloride. Upon entering the collection bath the calcium ions diffuse into the alginate solution, thereby hardening the matrix and forming a solid hydrogel system. Maturated beads are harvested from the hardening bath after approximately 48 hours. The key to the process is that the matrix formed within the beads can be used to trap active materials. When carrageenan is used as the matrix, droplets are processed at elevated temperature. Hardening the droplets is achieved by the combined influence of lowering the temperature and increasing the ionic strength. Other matrix systems to have been tested successfully are chitosan (dissolved in acid and precipitated in caustic soda), modified cellulose (gelated in the presence of high levels of potassium ions), pectates (gelated by bivalent ions such as calcium and/or high levels of sugars), Gellan gum (reacting to ionic strength) and molten butters or fats hardened by cooling.

Comparing technologies
Complex coacervation and JetCutter technologies offer key benefits which complement each other. Where visible capsules or beads are prepared using coloured pigments, both technologies can offer a remarkable aesthetic to an end formulation. These discreet particles can offer a visual cue for the encapsulated active. Of the two technologies, complex coacervation is most suitable for the encapsulation of lipophilic materials as well as low molecular weight or volatile actives. JetCutter is better suited to delivering insoluble materials, such as powdered actives, pigments and clays. The use of hydrogels, such as sodium alginate, is also more suitable for the encapsulation of temperature-sensitive materials. Both technologies allow the incorporation of a high percentage of pigment into the capsule or bead. Up to 25% pigment can be incorporated using either. The encapsulate can then be used as a means of delivering a striking visual colour change when broken, for example indicating damage to a coating or confirming controlled release of an active. In personal care, the capsules can be used to deliver pigmentation to the skin to give a tanning effect
* - Dr Ulrich Jahnz and Dr Peter Wittlich also contributed to this article

Both technologies can be used to produce pigments

For more information, please contact: ISP Microcaps UK Ltd Units 8-9 Stepnell Reach 541 Blandford Road Poole Dorset UK BH16 5BW Tel: +44 1202 627350 E-mail: palmerd@ispcorp.com Website: www.ispcorp.com

Speciality Chemicals Magazine March 2008 www.specchemonline.com

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