Surfactants

Microemulsion technology for surfactants

A UK company has embarked on a mission to launch a game-changing surfactant technology for the industrial chemical cleaning market. John Harrison of Surface Active Solutions explains more
pecialist cleaning applications in industry are now facing increased levels of scrutiny, due to the effect that chemical product efficiency and design have on technical performance and company economics. In addition, more stringent SHE legislation is driving the need for more specialised and more effective cleaning agents to be produced. The Surfactant Technologies (STL) Group of the UK has developed a revolutionary set of chemical materials, using microemulsion technology that is based on optimised surfactant design. The work has been funded to date by the Royal Society of Edinburgh, Scottish Enterprise and the Scottish Executive, in conjunction with Napier University. The term surfactant is a contraction of surface-active agent, a phrase coined in 1950. A surface-active substance reduces the surface tension of a liquid in which it is dissolved. This effect derives from the fact that surfactants are amphipathic in their molecular structure, i.e. their molecules are composed of two groups of opposite solubility tendencies, as shown in Figure 1. When molecules of this structure are introduced to an oilwater interface they align themselves at that interface, with the hydrophilic group being solubilised into the aqueous phase and the hydrophobic group being solubilised into the organic phase. If the surfactant molecular structure is linear, as in the case of sodium dodecyl sulphate (SDS), this results in the formation of a planar monolayer of surfactant molecules at the interface. With more active shearing and mixing, these types of surfactants are able to form oil-in-water (O/W) and water-in-oil (W/O) dispersions by forming droplet structures called micelles of one phase dispersed within the other. If the structure of the surfactant molecule is designed precisely so that it has a flexible cone or wedge shape and possesses the correct hydrophile-lipophile balance (HLB) and other such characteristics to match the relative oil and water substrates, as can be achieved with Aerosol-OT (AOT), then the surfactant film may spontaneously adopt a natural radius of curvature of the interface, which has a direction and magnitude without any need for an energy input.

Table 1 - Technical differentiation between emulsions & microemulsion systems

Emulsions Thermodynamically unstable Inefficient molecular packing Direct oil/water contact at the interface Interfacial surface tension 20-50mNm-1 Multiple phase only Micelle diameter 20nm + Cloudy colloidal systems

Microemulsions Thermodynamically stable Efficient molecular packing No direct oil/water contact at the interface Interfacial surface tension 10-4 -20mNm-1 May be single or multiple phase Micelle diameter 3-20nm Optically transparent (Isotropic)

Hydrophobic 'tail' group

O Hydrophobic 'head' group Hydrophobic 'tail' group O O S O ONa O O S O Na O

O O

Hydrophobic 'head' group Figure 1 - Molecular structure of SDS a typical linear surfactant (left) and AOT, a structured surfactant (right)

The reduction in surface free energy due to surfactant saturation and the preference for adopting a radius of curvature are sufficient to explain this ability. The equilibrium interfacial free energy in such systems is extremely low and the combined surface free energy of the micellar structures - though slightly positive - is counterbalanced by the entropy of dispersion of the structures within the continuous phase. There is therefore a very fine balance between surface energy and dispersion entropy, with these unique systems forming when the surfactant is capable of lowering the surface free energy to values that can be compensated for by the dispersion entropy. The surfactant design and the structure of the interface must therefore be very specific for this type of chemical system, which is known as a microemulsion. A microemulsion is defined as a system of oil, water and amphiphile that is a single-phase, optically isotropic and thermodynamically stable liquid solution. Microemulsions were not recognised as a special form of dispersion before the work of Schulman in 1943 and microemulsion systems were only named as such in 1958. They usually behave like Newtonian fluids; their viscosity is comparable to that of water, even at high droplet concentrations. A number of features distinguish microemulsion systems from emulsions (Table 1). Microemulsions, as described above, are thermodynamically stable and are self-organising. As such, they do not require an input of energy to form, unlike emulsion systems. This is due to a specific molecular design in which virtually all of the surfactant is located at the oil-water interface, providing very efficient molecular packing parameters of microemulsion-forming surfactants at that interface. This is not the case in emulsions, where molecular packing is not efficient and the surfactant only partially coats the interface, leaving gaps. The uncoated surfaces are therefore directly exposed to the continuous phase. This is thermodynamically unfavourable; the droplets aggregate by coalescing at their exposed surfaces, increasing the surface area to volume ratio and hence minimising oil-water contact. The outcome of extensive droplet coalescence is therefore bulk-phase separation. In microemulsions, there are no uncoated surfaces and thus there is no driving force for coalescence and phase separation. The phase separation of an emulsion can be relatively slow; emulsions can be created in which the phases only separate completely after several weeks or even months. Nevertheless the fundamental distinction between emulsion and microemulsion systems remains. Indeed, the interesting properties of November 2004 Speciality Chemicals Magazine

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Surfactants
microemulsions, both in general and in this specific context, derive from the thermodynamic properties arising from the total oil-water exclusion at the interface that in turn arises from the interfacial close packing of the surfactant molecules. Internal structures within microemulsion systems can vary greatly, depending upon relative component amounts, concentrations and other characteristics. They may be spherical, spheroid or cylindrical rod or worm-like micelles and they may exist in hexagonal, cubic or lamellar phases. Alternatively, a range of bi-continuous phases may exist. In each case, the relative oil and water domains that form in microemulsion systems are usually so small (about 10-20 nm or less in diameter) that they do not scatter light. In emulsion systems, the structures are large enough to scatter light and as such they appear as cloudy colloidal solutions in comparison. The gross physical differences between microemulsion and emulsion systems can be determined by visual examination - microemulsions show no tendency to phase separate and are usually optically transparent, whereas emulsions are opalescent or turbid and the phases inevitably separate. The two can also be distinguished by measuring the surface tension at the oil-water interface. The surface tension at plain oil-water interfaces is typically of the order of 50 mNm-1. Emulsions formed by mixing oil, water and non-microemulsion-forming surfactants are typically characterised by interfacial surface tensions of the order of 20-50 mNm-1, whereas microemulsions are characterised by far lower surface tensions or ultra-low interfacial surface tensions, typically below 20 mNm-1, and can be of the order of 10-3 to 10-6 mNm-1, these latter values reflecting the absence of direct oilwater contact at the interface. It is in part due to these properties that microemulsion systems are much more efficient in their cleaning, mobilising and emulsion destabilisation capabilities when compared to normal emulsion-forming surfactant systems - hence their applicability to super-efficient water-based industrial cleaning applications, which the STL Group is patenting. As shown in Figure 3, surfactant behaviour can be quantified in terms of triangular phase diagrams. Traditionally, emulsionforming surfactants have been used in conjunction with other surface active agents such as alcohol, glycol and/or glycol ether components, which may act as co-surfactants, enhancing the O/W microemulsion-forming properties of the surfactant. As long as these constituents are held at a constant ratio, they can be treated as a single component for the purpose of constructing the phase diagram. The apexes of the phase diagram each correspond to one of the components in pure form: oil, water/brine or surfactant at the stated ratio. Any point on one of the axes corresponds to a mixture of two of those components in a defined ratio (given in %wt). Any point within the phase diagram corresponds to a mixture of the three components in a defined ratio.
oil aq

Figure 3 - Ternary/pseudoternary phase diagram for a Winsor IV single phase O/W and W/O microemulsion forming system

oil

aq

Figure 2 - Structure of normal and inverse micelles formed in microemulsion systems

Note: Multiple phase systems (WI, WII, WIII) may also be produced.

The physical state of the mixture at equilibrium can be mapped on to the phase diagram. For example, the phase diagram in Figure 3 is characterised by a prominent single-phase microemulsion region, known as a Winsor IV system. Outside the Winsor IV region is an area that corresponds to equilibrium multi-phase regions commonly known as Winsor I, II or III regions. Alternatively the region may be a gel, a liquid crystal or another type of multi-phase system. It can be argued that the modes of operation of aqueous microemulsions are very different from those of emulsion systems. Whereas emulsion-forming surfactants often operate only to displace or partially to disperse oil, O/W microemulsionforming surfactants not only displace and disperse oil acting as a detergent but may also disperse the oil acting as an emulsifier, to the extent of completely dissolving or solubilising the oil or water into the continuous solvent medium. This process of microemulsification has proven to be particularly effective in hard surface cleaning applications in the oil and gas industry. The applications exploit a number of features whereby, just as an aqueous solution of an O/W microemulsion-forming surfactant system can absorb oil from a bulk oil phase, thus forming an O/W microemulsion, the same solution absorbs oil from an oil-coated solid surface or fine solid particulates with the same result without forming stable emulsion wastes. Furthermore, in the O/W microemulsion environment, any oil is effectively encapsulated within the surfactant monolayer and is therefore no longer in direct contact with the original surface or solid. Oil-contaminated surfaces may therefore be rendered completely water-wet as a result of the microemulsification process. In effect, it can be envisaged that the contaminating oil is simply dissolved and solubilised within the aqueous solvent via the process of microemulsification. In addition, if O/W microemulsion systems themselves are used in a cleaning operation the modes of action of both a microemulsion-forming surfactant and an organic solvent may be combined to increase cleaning capability still further. In this fashion the STL Group has demonstrated that the synergies of this combination of modes of action may even outperform pure organic solvents or pure surfactant systems when used independently in their cleaning capabilities for many industrial cleaning applications. The mode of action of the cleaning systems outlined herein may therefore be threefold: firstly the penetration of the contaminating oil layer through the solvent microemulsion mechanism, then the microemulsification of the oil components into the aqueous phase and finally the water-wetting of the underlying solid surfaces through the surfactant/detergent action. November 2004 Speciality Chemicals Magazine www.specchemonline.com

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Another advantage of these systems is that microemulsions tend to increase in their cleaning efficiency when the active ingredient (AI) concentrations are increased, unlike emulsion systems, which often demonstrate no increase in cleaning efficiency on increasing concentrations above their critical micellar concentration (CMC). In turn, lower volumes of higher AI concentrations may be used in microemulsion-based cleaning formulations than in emulsion-based systems. Due to their increased efficiency microemulsion systems may also be used to much greater effect at much lower AI concentrations when compared to normal emulsion forming surfactant systems. These capabilities have significant ramifications in terms of reducing waste, saving time and costs and associated health and safety aspects. As outlined above, these characteristics mean that the cleaning action of O/W microemulsion-forming systems and O/W microemulsion systems is different from that of conventional surfactant formulations. At higher active matter concentrations, the major mode of cleaning action is by miscible displacement instead of immiscible displacement. At lower concentrations, as aqueous rinsing is employed, immiscible displacement is also used in the cleaning action. These O/W microemulsion (forming) formulations therefore offer a combination of cleaning modes of action, supplying a multifaceted approach to the cleaning applications addressed. For further information, please contact: Kevin Dorrian Acumen PR Tel: +44 131 624 1155 E-mail kevin.dorrian@ acumen-pr.com As stated above, it is known from prior work in the field that co-surfactants are often required within formulations in order to enhance the oil-solubilising capacity of O/W microemulsion surfactant systems. It is recognised that combinations of surfactant and co-surfactant are more efficient than using either of these two constituents on their own. However, the use of an emulsifying agent in conjunction with an alkyl alcohol and/or an ethylene glycol co-solvent and/or a mutual glycol ether solvent may not be allowable in many industry applications as they may be classified as a volatile organic compound (VOC) content, with ramifications on health and safety guidelines, not to mention environmental legislation. For example, in the UK inks and printing sectors, a VOC is classified as an organic solvent with a boiling point of <200C, a closed cup flash point of typically <80C and a vapour pressure of <0.1mmHg. The STL Group has overcome this limitation with new surfactant designs which are microemulsion-forming systems in their own right and which do not require the use of VOC-type co-surfactant components. In the past, problems have often been encountered when diluting such ternary microemulsion systems in the field. As the concentrate is diluted with water or brine, impractical regions are often encountered in the phase diagram, such as gel regions, liquid crystals, mesomorphous phases and multiple phase windows, and the simple act of dilution may therefore result in phase separation of the microemulsion system. This is not the case with STL surfactants and the products can be used at any concentration as desired. If designed well, microemulsion systems may be boosted by other chemistries that can have roles to play during specific industrial processes. Additional complexing agents, flocculating agents, builders, corrosion inhibitors, viscosifiers and biocides can all be incorporated into formulations without reducing the levels of performance or disrupting microemulsion stability. In addition and where necessary, microemulsion products can be designed to perform and withstand extreme changes in environmental variables - for example to be temperature-stable from 0C to >200C and to be used in saturated calcium chloride brines. The STL Group has therefore managed to produce a commercially sound and environmentally robust range of practical and highly efficient industrial solutions to meet the needs of specific industry applications.

Difference between emulsion & microemulsion systems

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November 2004 Speciality Chemicals Magazine