The Effect of Shear and Oil/Water Ratio on the Required Hydrophile-Lipophile Balance for Emulsication

Jana Vander Kloeta and Laurier L. Schramma,b,*

a

Chemistry Department, University of Calgary, Calgary, AB, Canada, T2N 1N4, and bPetroleum Recovery Institute, Alberta Research Council, Calgary, AB, Canada, T2L 2A6

ABSTRACT: Required hydrophile-lipophile balance (HLB) values were examined in terms of the nature of kerosene water, both oil-in-water (O/W) and water-in-oil (W/O), emulsions formed using Span 80/Tween 80 surfactant blends. Both the nature of the emulsication method and the oil/water ratio were critical in determining the resulting emulsion type. Both high- and low-shear conditions were investigated. Under high shear, low internal phase emulsions formed using the surfactant mixtures that corresponded to the required HLB values for emulsication involving kerosene (6 for W/O and 14 for O/W). However, at low shear, high internal phase (concentrated) emulsions resulted. Furthermore, depending on the oil/water ratio, some of the high internal phase emulsions were opposite to the type expected, given the HLB of the surfactant blend used. From these results, it appears that the emulsication technique (applied shear and oil/water ratio) used can be of greater importance in determining the final emulsion type than the HLB values of the surfactants themselves. Paper no. S1223 in JSD 5, 1924 (January 2002). KEY WORDS: Effect of shear, emulsification methods, emulsion-forming requirement, hydrophile-lipophile balance (HLB), technical-grade nonionic surfactants.

The hydrophile-lipophile balance (HLB) concept was first introduced by Griffin (1) as an empirical scale to describe the balance of the size and strength of the hydrophilic and lipophilic groups in an emusier molecule. In Griffins proposed HLB system (1) both surfactants and oil phases could be classified. The latter are described in terms of a required HLB value for their emulsification. In this sense, every oil phase has two required HLB values, one each for water-in-oil (W/O) and oil-in-water (O/W) emulsication. Griffins original work (1) focused on the creation of O/W emulsions. In order to evaluate the required HLB for O/W emulsion formation, a bottle test series was created using a 50:50 oil/water ratio (by weight) and 15% surfactant (of the oil phase) that was predissolved in the oil phase. A stable emulsion was judged to occur for bottles where no oil or water separated over a period of at least 24 h. The surfactant mixture HLB that created the stable emulsion was taken to correspond to the required HLB value for O/W emulsi*To whom correspondence should be addressed at Saskatchewan Research Council, 15 Innovation Blvd., Saskatoon, SK, Canada S7N 2X8. E-mail: schramm@src.sk.ca Copyright 2002 by AOCS Press

cation of the oil phase employed. In a later publication (2) from ICI Americas (Bridgewater, NJ), Griffins method was modified through the use of an oil/water ratio of 20:80 or smaller and a surfactant concentration that was 1020% by weight of the oil phase. Low internal phase emulsions were then formed as the continuous phase was added under propeller agitation. In both of these publications, only a few required HLB values for W/O emulsification were reported. Most of the published work done by Griffin (1) and ICI (2) to determine required HLB values was carried out with the nonionic ICI surfactant series of Spans and Tweens. Whereas the HLB classification of surfactants has been the focus of many researchers, only a few groups have examined required HLB experimentally, in terms of emulsion inversion points (35), turbidity (6), and conductivity (7). At the present time, there appear to be no published reports of attempts to repeat Griffins work. Both Griffins (1) and ICIs (2) studies introduced relatively high shear into the oil/water/surfactant systems. Low internal phase emulsions typically result when high-shear conditions are used for emulsication, and low-shear mixing can lead to high internal phase, or concentrated, emulsions (8). Several conditions are needed to form a concentrated emulsion. First, it is generally accepted that low-shear mixing is required while the internal phase is slowly added to the continuous phase (811). Second, the surfactants used to create the emulsion need to be able to form elastic lms (8,11). The formation of concentrated emulsions has been linked to surfactantoil phase interactions (9) and therefore to oilwater interfacial tension and the potential for surfactantsurfactant interactions (12). The combined inuence of these factors may encourage the inversion of low internal phase to concentrated emulsions during the emulsication process. Many industrial processes exist in which the formation of low internal phase or concentrated emulsions needs to be controlled, whether in terms of formation, stability, destruction, or prevention. Examples range from asphalt emulsions to personal-care products to food products. Success in emulsion control requires achieving the right physical chemistry and also the right uid mechanics. The focus of the present work is on the formation of low internal phase and concentrated emulsions made with kerosene/ water, Span/Tween surfactant systems. The emulsion types created from the use of different oil/water ratios and shear
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J. VANDER KLOET AND L.L. SCHRAMM

intensities applied in the emulsification process are compared to the surfactant blend HLB employed.

EXPERIMENTAL PROCEDURES
The surfactants chosen were Span 80 and Tween 80 (ICI Surfactants, used as received). These sorbitan monooleates fall into the category of elastic film-forming surfactants (11). Span 80 (HLB 4.3) and Tween 80 (HLB 15) were blended using different weight percentages to produce mixtures of varying HLB ranging from 5.4 to 13.9. Kerosene was chosen as the reference oil phase since kerosene was one of the few oil phases Griffin had examined in terms of required HLB values for both W/O and O/W emulsication, which allowed for verification of the emulsion preparation method. Triple-distilled, deionized water was used as the aqueous phase. The method used to determine the required HLB values for emulsication was essentially that of ICI (2). Emulsions formed under low shear were created using a magnetic stir plate/stir bar combination; this kind of mixing involves maximal shear rates in the range 10 to 103 s1 (13). Emulsions formed under high shear were created using a Waring blender; this kind of mixing involves maximal shear rates in the range 104 to 105 s1 (13). The produced emulsions were examined under an optical microscope (Jenalumar; Zeiss, Jena, Germany) after being placed, dropwise, on glass slides that had been pretreated with Desicote (Beckman, Fullerton, CA) to render the glass surfaces hydrophobic. This was necessary to inhibit the water droplets in W/O emulsions from coating the glass surface (14). A stable emulsion was judged to occur for bottles where no oil or water separated over a period of at least 24 h; the emulsions meeting this stability criterion actually tended to be stable for several days. All HLB values obtained were the result of at least two separate experiments. The error associated with all required HLB values determined in this work was 1.

RESULTS AND DISCUSSION

Various combinations of kerosene, deionized water, and the Span 80/Tween 80 blends were tested to find the best method for creating accurate and reproducible emulsion series. Initially, the kerosene/water ratio was kept at 50:50; the surfactant, as a percentage of the oil phase, was held

constant at 15%. Five methods of agitation were tested: vortex, stirring, blender, wrist-action shaker, and stirring during addition of water. With the exception of the last method, the various Span80/Tween 80 mixtures were blended rst with kerosene (as advised by Griffin) followed by the addition of the deionized water, and then the agitation method was applied. The only alteration in the stirring during addition method was that the water addition and applied shear occurred simultaneously. The high shear introduced by vortex and blender methods required only short application times, less than 2 min, whereas stirring and wrist-action shaking were employed for 10 min. The longer mixing times for stirring and wrist-action shaking were needed to ensure emulsion homogeneity. Of the five methods tested, stirring during the addition of water appeared to give the best results for required HLB determinations for both W/O and O/W emulsions. The formation of both W/O- and O/W-type emulsions, through lower internal (or dispersed) phase quantities, was encouraged by adjusting the kerosene/water ratio to 80:20 and 20:80, respectively. Table 1 outlines some of the variations made with these ratios to further pinpoint the exact order of combination necessary for successful emulsification within the HLB series. All these trials were performed by the stirring under addition method. The results of trials 1 and 2 successfully correlated with the correct required HLB values for each of W/O and O/W emulsification, respectively. In both of these trials, the surfactant was premixed with the dispersed phase, and the continuous phase was added under stirring. When surfactant was added to the continuous phase (trials 3 and 4) before addition to the dispersed phase, no stable emulsions developed. Similarly, if surfactant was added to the internal phase (trials 5 and 6) and then mixed into the continuous phase, success in obtaining the required HLB was not possible due to the instability of the potential emulsions. The W/O and O /W emulsions created from trials 1 and 2 were very viscous and exhibited long-term stability. Figure 1 illustrates a typical bottle series done to determine the W /Oand O /W-required HLB (trials 1 and 2 of Table 1, respectively). The experimental details for the bottle series in Figure 1 are given in Table 2 and are discussed below. In bottles 16 (Fig. 1), 12 g of deionized water was premixed with 1.8 g of a Span 80/Tween 80 emulsifier blend followed by the addition of 48 g of kerosene. For bottles

TABLE 1 Test Emulsication Procedures for Required HLBa Determinations Water (%) 20 80 20 80 20 80 Kerosene (%) 80 20 80 20 80 20 Surfactant (% of oil phase) 15 15 15 15 15 15 Surfactant premixed with Water Kerosene Kerosene Water Water Kerosene Phase added under stirring Kerosene Water Kerosene Water Water Kerosene Stable emulsion formed Yes Yes No No No No

Trial 1 2 3 4 5 6
a

HLB, hydrophilic-lipophilic balance.

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FIG. 1. Required hydrophilic-lipophilic balance (HLB) determination for water-in-kerosene and kerosene-in-water emulsions (details in text).

711, 12 g of kerosene was premixed with 1.8 g of a Span 80/Tween 80 emulsifier blend followed by the addition of 48 g of deionized water. The oil/water ratio was changed in the middle of the bottle series (Fig. 1) since preliminary results had shown that at higher HLB values with an oil/water ratio 80:20, or at lower HLB values with an oil/water ratio 20:80, no stable emulsions resulted. Figure 1 shows that creamy, stable emulsions were formed in bottles 2 and 3 (emulsifier blend HLB 6 1) and bottle 10 (emulsifier blend HLB 14 1). Although Figure 1 shows an apparently homogeneous emulsion in bottle 5, that this sample was unstable went undetected by the camera. Given that bottles 2 and 3 each had an oil/water ratio of 80:20, these emulsions were first presumed to be W/O. Conversely, it was initially assumed that bottle 10 was an O/W emulsion. Several 23 g samples of the stable emulsion produced in bottle 2 were diluted with either water or kerosene to determine which phase was the continuous phase (14,15). That the emulsion diluted spontaneously with water and not kerosene was surprising. The reverse observation was noted for the bottle 10 emulsion, which diluted spontaneously with kerosene and not water. These results indicated that the bottle 2 emulsion was actually O/W and the bottle 10 emulsion W/O. Given this unexpected result, fresh emulsions were made incorporating a blue dye (food coloring, Food Club, Scott Bathgate Ltd., Winnipeg, Canada) into the aqueous phase (the dye was completely insoluble in the kerosene). This allowed for microscopic examination of the emulsion to substantiate the assignments of kerosene or water as the external (continuous) emulsion phase. Microscopic examination of the emulsions conrmed the results of the dilution tests.

The unexpected emulsions were high-internal phase, or concentrated, emulsions. The explanation for this behavior can be understood in terms of the shear applied in the emulsion formation and the description that follows. Effect of shear and oil/water ratios on the required HLB for kerosene. Figure 2 illustrates what would normally be the expected HLB behavior, without regard to either the shear used to create the emulsions or the oil/water ratio. To assess the difference in emulsication between low- and highshear mixing, a number of kerosene/water/surfactant series were produced using a Waring blender. In these experiments, oil/water ratios were altered while using only the two surfactant mixtures (HLB 6 1 and HLB 14 1) that corresponded to the required HLB values for kerosene. Table 3 gives a summary of these experiments. All samples listed in Table 3 were prepared by first mixing the surfactant with the designated phase, followed by a one-step addition of the other phase. The two phases were then blended for 15 s. The emulsion formation method used for the original kerosene/water reference system involved adding the 80% phase to the 20% phase under stirring. Therefore, preparation of the samples of Table 3 was repeated by slowly introducing the added phase with a 40 mL glass syringe via a hole in the lid during the 15-s blending period. The results were identical to those in Table 3, attesting to the importance of high shear over stepwise addition of one phase into another. The emulsion information provided by these tests is mapped in Figure 3. This phase diagram nearly matches the expected emulsification behavior of Figure 2. Thus, the required HLB assignment system remained valid across the phase map at high shear.

TABLE 2 Experimental Description for Bottle Tests Shown in Figure 1 (kerosene/deionized water, Span 80/Tween 80 systems) Bottle 1 2 3 4 5 6 7 8 9 10 11
a

Oil/aq. ratio %/% [g/g] 80:20 [48:12] 80:20 [48:12] 80:20 [48:12] 80:20 [48:12] 80:20 [48:12] 80:20 [48:12] 20:80 [12:48] 20:80 [12:48] 20:80 [12:48] 20:80 [12:48] 20:80 [12:48]

Surf. HLBa 4.3 5.4 6.4 7.6 8.6 9.7 10.7 11.8 12.9 13.9 15

Wt. surfactant (g) (15% of 20% phase) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8

Surfactant premixed with Water Water Water Water Water Water Kerosene Kerosene Kerosene Kerosene Kerosene

Phase added under stirring Kerosene Kerosene Kerosene Kerosene Kerosene Kerosene Water Water Water Water Water

For abbreviation see Table 1.

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FIG. 2. The expected emulsion tendencey as a function of HLB and oil/water ratio for kerosene/water emulsions (based on the definition of required HLB values for kerosene). O/W, oil-in-water; W/O, water in oil; for other abbreviation see Figure 1.

FIG. 3. Observed emulsion tendency as a function of HLB and oil/water ratio for kerosene/water emulsions prepared under high shear (Waring blender) (data from Table 3). For abbreviations see Figures 1 and 2. TABLE 3 Emulsions Formed by Means of a Waring Blender (kerosene/water, Span 80/Tween 80 combinations)a Kerosene/water ratio 20:80 80:20 50:50 20:80 80:20 50:50
a

Span 80/Tween 80 ratio 10:90 10:90 10:90 80:20 80:20 80:20

HLB 13.9 13.9 13.9 6.4 6.4 6.4

Surfactant premixed with Kerosene Water Kerosene Kerosene Water Kerosene

Emulsion formed O/W Unstable O/W Unstable W/O Unstable

O/W, oil-in-water; W/O, water-in-oil; for other abbreviation see Table 1.

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TABLE 4 Emulsions Formed by the Stirring Under Addition Method (kerosene/water/Span 80/Tween 80 combinations)a Kerosene/water ratio 20:80 80:20 50:50 20:80 80:20 50:50
a

Span 80/Tween 80 ratio 10:90 10:90 10:90 80:20 80:20 80:20

HLB 13.9 13.9 13.9 6.4 6.4 6.4

Surfactant premixed with Kerosene Water Kerosene Kerosene Water Kerosene

Emulsion formed W/O + O/W/O O/W O/W W/O O/W + W/O/W W/O

O/W/O, oil-in-water-in-oil; W/O/W, water-in-oil-in-water; for other abbreviations see Tables 1 and 3.

A number of kerosene/water/surfactant series were then produced using the low-shear method (Table 4). In the lowshear case, the emulsion tendency deviated from the expected required HLB behavior. Figure 4 is the phase diagram for the systems of Table 4. Two things are immediately obvious upon comparison of Figures 3 and 4. First, at the kerosene/water ratio 50:50, the formed-emulsion tendency was predicted by the classical required HLB approach, regardless of high or low shear applied to the system. This reaffirms Griffins work cited earlier, that is, for high HLB values O/W emulsions resulted, for low HLB values W/O emulsions resulted, and required HLB values for emulsication could be assigned unambiguously. Second, at oil/water ratios of 20:80 or 80:20, the low shear had a marked effect on the formed-emulsion tendency. Where unstable emulsions were expected, namely, at HLB 6, oil/water ratio 20:80 and at HLB 14, oil/water ratio 80:20, highly concentrated emulsions formed. This is reasonable given that the conditions for concentrated emulsion formation were met under these experimental conditions. The most interesting emulsions formed at HLB 14,

oil/water ratio 20:80 and at HLB 6, oil/water ratio 80:20. Both of these combinations also formed concentrated emulsions, as seen in Figure 4, but in these cases the emulsion types were contrary to what would be expected given the HLB values. Under these conditions, a small amount of multiple emulsion samples appeared alongside the concentrated emulsions. The formation of double emulsions is reasonable since multiple emulsions have been identified as the intermediate steps in phase inversion (16,17). The appearance of multiple emulsions in the work presented here also points to the insufficiency of low shear to force these intermediate emulsions through to their nal concentrated emulsion forms. Depending on the phase volume ratios employed, the emulsification technique used apparently can be of greater importance in determining the nal emulsion type than the HLB values of the surfactants themselves. The HLB classification for oil phases in terms of the required HLB values is seemingly very dependent on the emulsification conditions and process for some phase volume ratios. When an emulsification procedure involves high shear, or when a 50:50 phase volume ratio is used, in-

FIG. 4. Observed emulsion tendency as a function of HLB and oil/water ratio for kerosene/water emulsions prepared under low shear (stirring under addition method) (data from Table 4). O/W/O, oil-in-water-in-oil; W/O/W, water-in-oil-in-water; see Figures 1 and 2 for other abbreviations. Journal of Surfactants and Detergents, Vol. 5, No. 1 (January 2002)

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J. VANDER KLOET AND L.L. SCHRAMM

terpretations based on the classical HLB system appear to remain valid. However, at other phase volume ratios and especially under low-shear emulsification conditions, inverted, concentrated emulsions may form at HLB values that were not predicted. Future work should involve investigating the effects of mixing time and energy.

11.

12.

ACKNOWLEDGMENTS
The authors wish to express their thanks and appreciation to the Natural Sciences and Engineering Research Council of Canada, Syncrude Canada Ltd., and the Petroleum Recovery Institute of Alberta Research Council Inc. for funding and other support of this research.

13. 14.

15. 16.

REFERENCES
1. Griffin, W.C., Classication of Surface-Active Agents by HLB, J. Soc. Cosmetic Chem. 1:311 (1949). 2. The HLB System, ICI United States, Inc. (now ICI Americas, Inc.), Wilmington, 1976. 3. Marszall, L., Emulsion Inversion Point and Required HLB of Oil-in-Water Emulsions, Cosmet. Toilet. 91:21 (1976). 4. Marszall, L., Emulsion Inversion Point as an Accelerated Method for Evaluating Required HLB, Cosmet. Toilet. 92:32 (1977). 5. Marszall, L., Cloud Point and Emulsion Inversion Point, Fette Seifen Anstrich. 79:41 (1977). 6. Frenkel, M., R. Shwartz, and N. Garti, Turbidity Measurements as a Technique for Evaluation of Water-in-Oil Emulsion Stability, J. Dispersion Sci. Technol. 3:195 (1982). 7. Prinderre, R., P. Piccerelle, E. Cauture, G. Kalantzis, J.P. Reynier, and J. Joachim, Formulation and Evaluation of O/W Emulsions Using Experimental Design, Int.. J. Pharm. 163:73 (1988). 8. Lissant, K.J., in Emulsions and Emulsion Technology, Part I, Marcel Dekker, New York, 1974. 9. Chen, H.H., and E. Ruckenstein, Effect of the Nature of the Hydrophobic Oil Phase and Surfactant in the Formation of Concentrated Emulsions, J. Colloid Interface Sci. 145:260 (1991). 10. Cameron, N.R., and D.C. Sherrington, Non-aqueous High 17.

Internal Phase Emulsions, J. Chem. Soc., Faraday Tran. 92:1543 (1996). Aronson, M.P., and M.F. Petko, Highly Concentrated Waterin-Oil Emulsions: Inuence of Electrolyte on Their Properties and Stability, J. Colloid Interface Sci. 159:134 (1993). Kirikou, M., and P. Sherman, The Influence of Tween 40/Span 80 Ratio on the Viscoelastic Properties of Concentrated Oil-Water Emulsions, J. Colloid Interface Sci. 71:51 (1979). Hiemenz, P.C., and R. Rajagopalan, Principles of Colloid and Surface Chemistry, 3rd edn., Marcel Dekker, New York, 1997. Schramm, L.L. (ed.), Emulsions, Fundamentals, and Applications in the Petroleum Industry, American Chemical Society, Washington, DC, 1992. Briggs, T.L., Experiments on Emulsions, J. Phys. Chem. 18:34 (1914). Brooks, B.W., and H.N. Richmond, Dynamics of LiquidLiquid Inversion Using Non-Ionic Surfactants, Colloids Surf. 58:131 (1991). Brooks, B.W., and H.N. Richmond, Phase Inversion in Nonionic Surfactant-Oil-Water SystemsII. Drop-Size Studies in Catastrophic Inversion with Turbulent Mixing, Chem. Eng. Sci. 49:1065 (1994). [Received September 25, 2000; accepted August 24, 2001]

Jana Vander Kloet is a recent M.Sc. graduate (2000) in colloid and interface chemistry from the University of Calgary, Canada, where she studied the interfacial characteristics and other physical properties of bituminous froth emulsions systems. She earned her B.Sc. (Hon.) from McMaster University (1995). Her research interests include the areas of emulsifiers and demulsifiers in petroleum industry applications. Dr. Laurier L. Schramm is president and CEO at the Saskatchewan Research Council and adjunct professor of chemical engineering at the University of Calgary, both in Canada. His research interests lie in colloid and interface science and the petroleum industry applications of suspensions, emulsions, foams, surfactants, and polymers. In these areas he has published seven books and over 100 other scientific publications including 17 patents, most of which have been adopted into commercial practice.

Journal of Surfactants and Detergents, Vol. 5, No. 1 (January 2002)