URAL. OF COLLON AND INTERFACE ScIENCR 197, 142-150 (1998) ‘axnicts no, C3975222 Influence of Interfacial Properties of Lipophilic Surfactants on Water-in-Oil Emulsion Stability Foyeke ©. Opawale and Diane J. Burgess" Deparment of Pharmaccuteal Sciences, Untveraty of Connectci, Stors, Connecticut 06209 ‘Received June 12,1997; acceped October 9, 1997 “The purpose of this study i to investigate interfacial properties of lipophilic nonionic surfactants ofthe sorbitan fatty acid ester type (Spans 20, 80, 83, and 8S) withthe aim of selecting appro- rate emulsifiers for water-in-oil (W/O) emulsions under differ- nt condidons. terface tension and heology were investigated at planar mineral oll/double distilled water interface using a Wilhelny plate method and an osellatory ring surface rheometer, respectively. The effects of bulk concentration, temperature and ‘the presence of sat in the aqueous phase onthe interfacial proper- tis of surfactant lms were determined. The relationship between interfacial fim properties and W/O emulsion stability inthe pres- ‘ence of salt was assessed by visual observation of phase separation on storage. All the surfactants exhibited viscolastic properties with the exception of Span 85. Interfacial assocation of inverse rmicelles and/or surfactant multilayer formation are probably responsible for the observed viscoelasticity. Addition of sodium chloride tothe aqueous phase and increase in temperature infh- enced the viscoelastic properties. Emulsion stability to phase sepa- ration decreased in the presence of salt. The interfacial rheology data were predictive of emulsion stability for the systems studied, ‘Key Words: Spans; water-in-oil emulsion; interfacial rheology: {interfacial tension; emulsion stability. INTRODUCTION Emulsions systems have minimal thermodynamic stability and tend to phase separate. The primary driving force for phase separation is droplet interfacial free energy (1). Inclusion of a surface-active substance which concentrates at the oil-water interface imparts a degree of stability to these systems by low xing interfacial tension. In addition, reduction in interfacial {tension facilitates emulsion formation and prevents immediate droplet recoalescence during preparation (1). However, for Jong-term emulsion stability to coalescence and hence phase separation, the strength of the interfacial film formed by @ surface-active substance has been reported to be more important than its effect on interfacial tension (1-3). "To whom comespondeace shouldbe addressed at Department of Phar- macetteal Sciences, School of Pharmacy U-92, University of Connecticut, ‘372 Fairfield Road, Stor, CT 06269. Fax: (860) 486-4908, Email: ‘@ourgess@@aconnvmn uconn. el, oma.579788 $2500 Capra © 998 by Aeatense Fess Al ihe of oped nay form reserved Interfacial rheology has been used to quantify the film strength of adsorbed emulsifier layers at fluid interfaces (4— 6). Both mechanical (solid-like) and flow (liquid-like) properties can be measured using this technique. Several studies have been reported on the characterization of emulsi- fier film strength for water-soluble emulsifiers, used to stabi- lize oil-in-water (O/W) emulsions (6-8). For example, ‘macromolecules (such as proteins) have been reported to be effective stabilizers of O/W emulsions as a consequence of their ability to form strong interfacial films (6~8). However, {ew studies have been conducted on oil-soluble surfactants, such as sorbitan fatty acid esters (Spans), which are typi- cally used in the preparation of water-in-oil (W/O) emul- sions. Span surfactants are effective at reducing interfacial tension (9) and investigations performed on Spans 80 and 83, in separate studies, indicated that they possess apprecia- ble interfacial viscoelasticity (10, 11). There has not been 1 detailed interfacial rheological investigation of Span sur- factants or of any other lipophilic surfactants. Such studies, are important since it has been reported that interfacial rheo- logical film strength is an important contributor to W/O ‘emulsion stability (12). For example, there is a controversy in the literature over the effect of electrolytes, such as sodium, chloride on the film properties of Span surfactants at the primary W/O interface in multiple emulsions (1316) Some reports indicate that electrolytes rigidify these interfa- cial films (13, 14), whereas others suggest thatthe presence of salt results in interfacial film breakdown (15, 16). ‘The purpose of this present study is to investigate the theological properties of sorbitan fatty acid esters ata planar rineral oil/water interface. Specifically, the effects of so- dium chloride and temperature are investigated. An oscilla- tory ring-surface theometer which operates under the surface shear mode was used to measure interfacial rheology at the ‘mineral oil/water interface. These measurements can pro- ‘vide information on the intramolecular and intermolecular forces acting at the interface as well as the kinetics of interfa- cial film formation (6) MATERIALS AND METHODS. Span 20 (sorbitan monolaurate), Span 80 (sorbitan monooleate), Span 83 (sorbitan sesquioleate), Span 85 (sor- weINTERFACIAL, PROPERTIES OF LIPOPHILIC SURFACTANTS phase at the bottom of the container or by complete break- down into two phases with a layer of surfactant in between. RESULTS AND DISCUSSION Interfacial Tension ‘The mineral oil/water interfacial tension remained con- stant with time (52.93 + 0.81 mN/m, 25°C) indicating purity of the oil with respect to surface-active components. Appar ent CMC values of Span surfactants in oil in the presence cof a water phase were calculated from the break in the in- terfacial tension vs log concentration plots (Fig. 1). The apparent CMC values of Spans 80, 83, and 85 occurred at, 0.026, 0.024, and 0.262% w/v, respectively (Table 1). The CMC of Span 20 was indeterminable as no clear break in the interfacial tension vs log concentration plot was apparent. Span 20 can also be used to prepare O/W emulsion and therefore its affinity forthe aqueous phase may be a com cating factor. The relatively high apparent CMC of Span 85 is probably a result ofthe bulkiness of this molecule and its higher oil solubility (HLB value of 1.8) compared to the other Spans. Figure 2 is a representation of the structures of the Span surfactants. The sorbitan ring may vary as indi- cated. Span 85 has thee oleic acids on the sorbitan ting (Fig, 2) and these fatty acid groups appear to hinder interfacial adsorption and molecular interaction. The sorbitan rings of Spans 20 and 80 have single substitutions of lanric and oleic acid, respectively. Span 83 is a 2 to 1 mixture of the monooleate (single oleic acid) and dioleate (double oleic acid). The interfacial tension values continued to decrease as the concentration was increased above the apparent CMC values, although the rate of decrease was less (Fig. 1). Re- Guction in interfacial tension above the apparent CMC is ‘unusual. However, this phenomenon has been reported pre- viously for asphaltene dissolved in heptol and was speculated to be the result of multilayer adsorption (18). The Gibbs ‘adsorption equation was used to calculate the area occupied ‘per molecule in the monomolecular film regions for Spans 80, 83, and 85 (i.e, just below the apparent CMC values), Activity corrections were neglected as a change in activity is not expected with these nonionic surfactants (19). The apparent CMC and molecular area values in the monomolec- ular film regions are given in Table 1. The molecular area ‘was calculated to determine the concentration of surfactant necessary to form a condensed monolayer at the emulsion droplet interface, This information is helpful in determining the role of surfactant concentration in emulsion stability. Interfacial Rheology Effect of bulk concentration. The adsorbed nonionic sur- factant films exhibited viscoelastic properties with the excep tion of Span 85 (Fig. 3). Span 85 gave a constant interfacial elasticity value of 11.10 + 3.88 mN/m atthe bulk concentra- tions studied (1, 2.5, and 5% w/v), which are well above 145 the apparent CMC value of Span 85. The very low interfacial elasticity observed for Span 85 was attributed to the bulki- ness and low interfacial activity of this molecule. Conse- quently, no further interfacial theology studies were con- ducted on Span 85. The interfacial elasticity values of Spans 004 {= +0076 40.0168, max dev ze, 0.900, y= +0017 40.0120, mex dvs B96, P0908 ‘018 "ys 0.0876! 46.3564, max Sov OTE-4, 740.81 teil, newt | y= S014 +6164 max dos 55:6, 20.907 obs cae) mes om oss FIG. 4, Analysis of the second-order itecfcil film kinetics of (a) ‘Span 80 and (b) Spen 83,INTERFACIAL PROPERTIES OF LIPOPHILIC SURFACTANTS two phases at the third week. The Span 80 emulsions were ‘more stable to salt effects than the Span 83 emulsions, which ig in agreement with the interfacial elasticity data. 149 TABLE 3 Effect of Sodium Chloride on the Stabitity of W/O Emulsions (8% wiv Spans, n = 2) to Phase Separation (60°C) PANS) ts al ae ‘a bite WOOO wake ee =e ° © ¢ c c Os € € v wv | 04 é wv wv $ 03 € w 3 $ i pebeeesasenssd | a re : al a israw'0) t eferverecesesescces al xa “a a mci va it alee ° c c c © oes c c € ¢ on c € € ¢ 05 c € c c S14 c s c e “Tamer “The rites) FIG. 7. The effect of temperature onthe interacial elasticities of (a) ‘Span 20 (b) Spun 80, and (c) Span 83 atthe mineral o/ water ners. (38 o/, mean values,n = 3). The eror bars ae within the symbol. ‘valuation: C, reaming, W, thre layers, S, two pases ‘CONCLUSIONS Interfacial rheology appears to be useful in the character- ization of the film properties of Span surfactants. ‘The lipo- philic surfactants investigated formed viscoelastic films at {he water-il interface with the exception of Span 85. Interfa- cial film formation may involve adsorption of monomers, and/or micelles, molecular rearrangement, multilayer forma- tion and intermolecular interactions. The interfacial tension data also showed evidence of multilayer formation for Spans 80 and 83. The interfacial elasticities of Spans 20, 80, and ‘83 were influenced by bulk concentration, the presence of salt in the aqueous phase, and temperature. ‘The interfacial behavior of these surfactants varied as a result of differences in molecular structure and hydrophobicity, Span 20 exhibited anomalous behavior in the presence of salt when compared to the other surfactants. The interfacial elasticity of Span 20 increased initially with increase in salt concentration and then decreased at higher salt concentrations. This was attrib- tuted to the relatively polar nature of this surfactant. Spans 80 and 83 were less sensitive to increase in temperature than Span 20 and this also was considered to be a result of the polarity of Span 20. Interfacial rheological measurements are useful in predicting W/O emulsion stability, since film strength and emulsion stability followed the same trends. For example, surfactants which formed strong interfacial films in the presence of salt formed more stable emulsions than those which formed weak interfacial films. The use of high salt concentrations (>1 M) in emulsion formulation is ‘not recommended as this decreases the elastic behavior of the interfacial film and therefore emulsion stability. Maximizing, interfacial film strength by increasing surfactant concentra- tion, using low or no salt in the aqueous phase, and/or