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Langmuir 1998, 14, 260-263

Formation of Microemulsions in Mixed Ionic-Nonionic Surfactant Systems

Hironobu Kunieda,*, Kazuyo Ozawa, Kenji Aramaki, Akihiro Nakano,, and Conxita Solans
Graduate School of Engineering, Yokohama National University, Tokiwadai 79-5, Hodogaya-ku, Yokohama 240, Japan, and Departomento de Tensioactivos, CID, CSIC, Jordi Girona 18-26, 08034 Barcelona, Spain Received April 21, 1997. In Final Form: October 21, 1997X
Phase behavior of a mixed surfactant, sodium dodecyl sulfate + lipophilic poly(oxyethylene) dodecyl ether, in a brine-decane system was investigated at a constant brine/decane weight ratio equal to 1. Solubilization capability of the mixed surfactant reaches its maximum and microemulsion is formed when the surfactant is changed from hydrophilic to lipophilic in a given system. In the present system, lamellar liquid crystal (LC) intrudes in the single-microemulsion region, and three-phase microemulsions are not formed. The mixing fraction of nonionic surfactant in the total surfactant in the midst of the LC present region increases with increasing oil content due to the high solubility of nonionic surfactant in oil. The partition of nonionic surfactant molecules between the oil and the bilayer in the LC phase is analyzed by using the geometrical relationship of the phase equilibria in the phase diagrams, taking into account the solubility. The monomeric solubility of nonionic surfactant in oil is much less than that of an ordinary cosurfactant like hexanol, and the mixing fraction of nonionic surfactant in the bilayer decreases with increasing salinity. The interlayer spacing of the midlamellar liquid crystal between the two microemulsion regions was measured by small-angle X-ray scattering. The average effective cross-sectional area per surfactant is about 0.37 nm2 and is unchanged upon dilution. It is considered that there is a strong attractive interaction between the ionic group and the nonionic hydrophilic moiety of surfactants.

Introduction Most ionic surfactants are strongly hydrophilic and form aqueous micelles when dissolved in water. By combining with lipophilic amphiphiles often called cosurfactants, the mixed surfactant tends to dissolve in oil. Three-phase microemulsions are formed in a brine/ionic surfactant/ cosurfactant/oil system at certain mixing ratio of ionic surfactant/cosurfactant.1-5 Since the relative hydrophilelipophile balance (HLB) of the mixed surfactant in a given system is optimum in the midst of the three-phase region, the composition is also called the HLB composition. When the microemulsion coexists with excess water and oil phases, the solubilization capability reaches its maximum and ultralow interfacial tensions are attained due to critical solution phenomena of microemulsion.6,7 Threephase microemulsion is also called middle-phase microemulsion, bicontinuous microemulsion, or surfactant phase in which water and oil microdomains are in bicontinuous structure8 and surfactant molecules are adsorbed at the microinterface.9
* Corresponding author. Yokohama National University. Present address: JO Cosmetics Corp., Komatsudai 1-603-36, Hanyu 348, Japan. CSIC. X Abstract published in Advance ACS Abstracts, December 15, 1997.
(1) Winsor, P. A. Solvent Properties of Amphiphilic Compounds; Butterworths: London, 1954; p 68. (2) Healy, R. N.; Reed, P. L. In Improved Oil Recovery by Surfactant and Polymer Flooding; Shah, D. O., Schechter, R. S., Eds.; Academic Press: New York, 1977; p 383. (3) Kunieda, H.; Shinoda, K. Yukagaku 1980, 29, 676. (4) Kunieda, H. J. Colloid Interface Sci. 1988, 122, 138. (5) Kunieda, H.; Nakamura, K.; Uemoto, A. J. Colloid Interface Sci. 1994, 163, 245. (6) Kunieda, H.; Shinoda, K. Bull. Chem. Soc. Jpn. 1982, 55, 1777. (7) Kunieda, H. J. Colloid Interface Sci. 1987, 116, 224.

In the previous studies, middle-chain alcohols have been mainly used as cosurfactants. The cosurfactant is mainly partitioned between the surfactant layer and the oil domain inside the microemulsion phase. Since the solubility of the cosurfactant in the oil domain is fairy large, the apparent solubilizing capability of the mixed surfactant (ionic surfactant + cosurfactant) is low. To avoid the loss of cosurfactant, a long-chain alcohol should be used. However, since lamellar liquid crystal is formed over a wide range of temperatures in a mixed ionic surfactant and higher-alcohol system, it is difficult to form isotropic fluid microemulsions.11 The combination of ionic surfactant and lipophilic poly(oxyethylene) type nonionic surfactant is considered to be a good candidate to produce microemulsions. Although the phase diagrams of water/ ionic surfactant/nonionic surfactant/oil systems were reported,12-14 the detail phase behavior of ionic-nonionic microemulsion systems has not been studied. In this context, the phase behavior of mixed sodium dodecyl sulfate and lipophilic poly(oxyethylene) type nonionic surfactant in water-decane was investigated. Experimental Section
Materials. Sodium dodecyl sulfate (SDS) was obtained from Sigma Co., and homogeneous nonionic surfactants, bis(oxyethylene) dodecyl ether (C12EO2) and tris(oxyethylene) dodecyl ether (C12EO3) were obtained from Nikko Chemicals Co. Extra pure grade n-decane was obtained from Tokyo Kasei Kogyo Co., and
(8) Olsson, U.; Shinoda, K.; Lindman, B. J. Phys. Chem. 1986, 90, 4083. (9) Kunieda, H.; Nakano, A. J. Colloid Interface Sci. 1995, 170, 78. (10) Kunieda, H.; Aoki, R. Langmuir 1996, 12, 5796. (11) Kunieda, H.; Nakamura, K. J. Phys. Chem. 1991, 95, 1425. (12) Sagitani, H.; Friberg, S. E. Bull. Chem. Soc. Jpn. 1983, 56, 31. (13) Shinoda, K.; Kunieda, H. J. Colloid Interface Sci. 1973, 42, 381. (14) Mori, F.; Lim, J. C.; Miller, C. A. Prog. Colloid Polym. Sci. 1990, 82, 114.

S0743-7463(97)00411-3 CCC: $15.00 1998 American Chemical Society Published on Web 01/20/1998

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Figure 1. Phase diagrams of the 1 wt % NaCl(aq)/SDS/C12EO3/decane (4), 3 wt % NaCl(aq)/SDS/C12EO3/decane (O), and 5 wt % NaCl(aq)/SDS/C12EO3/decane (0) systems in a dilute region at 35 C. I and II indicate isotropic one-phase and twophase regions, respectively. LC means the region in which lamellar liquid crystal is present.
extra pure grade NaCl was obtained from Junsei Chemicals Co. These chemicals were used without further purification.

Figure 2. Phase diagrams of the 1 wt % NaCl(aq)/SDS/C12EO2/decane (4), 3 wt % NaCl(aq)/SDS/C12EO2/decane (O), and 5 wt % NaCl(aq)/SDS/C12EO2/decane (0) systems at 35 C. I and II indicate isotropic one-phase and two-phase regions, respectively. LC means the region in which lamellar liquid crystal is present.

Procedures Density of Surfactant in a Liquid State. The densities of a SDS aqueous solution and a propanol + water solution (propanol:water ) 1:4) were measured as a function of SDS concentration at 35 C. The values are extrapolated to 100% SDS. The average molar volume of SDS is 258 ( 2 cm3/mol. The molar volume of C12EO3 (347.3 cm3/mol) was directly obtained by using its density. By measuring the densities of the C12EOn series, the volume of one dodecyl group was determined to be 0.354 nm3. Small-Angle X-ray Scattering. Interlayer spacing of lamellar liquid crystal was measured using small-angle X-ray scattering (SAXS) performed at a power of 2.25 kW from a Siemens generator, model Krystalloflex 760 at 35 C. The collimation was carried out with a Kratky camera from MBraun and the scattering was detected with a linear position sensitive detector OED 50M from MBraun. Relative intensity was represented as a function of diffusion vector q. The available range of q was from 4 10-4 to 3 10-2 nm. The samples were covered by plastic films for the SAXS experiment (Mylar seal method). Lamellar liquid crystalline phase was also distinguished by the SAXS peaks. The ratio of interlayer spacing from the first and second peaks is 1:1/2 for the lamellar type. The type of liquid crystal was also identified by a polarizing microscope. Results and Discussion Three-Phase Behavior of NaCl(aq)/SDS/C12EO2 or C12EO3/Decane Systems. Phase diagrams of NaCl(aq)/ SDS/C12EO2 and C12EO3/decane systems are shown in Figures 1 and 2, respectively. The brine/oil weight ratio is unity. The weight fraction of total surfactant in the system (x) is plotted horizontally, and the weight fraction of nonionic surfactant in total surfactant (W1) is plotted vertically.

Surfactant forms an aqueous micellar solution phase at low W1, and the aqueous micellar phase coexists with an excess oil phase in the lower II region. However, a reverse micellar solution phase is formed and coexists with an excess water phase at high W1 in the upper II region. When the phase behavior is changed and the hydrophile-lipophile property of the mixed surfactant is just balanced in the given system, a single-phase microemulsion is formed even in a dilute region. In a brine/ ionic surfactant/middle-chain alcohol/oil system, a threephase region consisting of microemulsion, excess water, and excess oil phase appears beyond the solubilization limit.10 However, in the present systems, instead of three coexisting phases, a lamellar liquid crystal is present between the two microemulsion regions as is shown in Figures 1 and 2. Microemulsions on both sides of the LC region show flow birefringence, and it is considered that the structure of the microemulsion itself resembles that of a lamellar liquid crystal. Emulsions are very stable in this LC present region, and we could not accurately identify the number of phases except confirming the existence of liquid crystal. The lower limit of the single LC region was not determined because of its narrowness. In the dilute area of the LC region, water and oil phases were separated, but the separation was incomplete. Hence, it is considered that there is a three-phase region consisting of lamellar liquid crystal, water, and oil phases. The compositions giving the two microemulsion regions are shifted to lower W1 values with increasing salinity. When the oxyethylene chain length of nonionic surfactant is increased, the compositions are also shifted to lower W1 values. This tendency is similar to that of an ordinary ionic microemulsion system.10 When the nonionic surfactant and the salinity are fixed, the microemulsion region is shifted to a higher W1 with decreasing x, as is shown in Figures 1 and 2 due to the partitioning of surfactant in the oil domain and that of the bilayer of liquid crystal.10 Analysis of Phase Behavior. As described above, on decreasing the total surfactant concentration, the W1 values for the microemulsions and the LC region are

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deviated to the nonionic surfactant-rich region. This type of distortion of the microemulsion region or three-phase body is quite common in a mixed surfactant system because surfactant molecules are distributed between water domain, oil domain, and the interface inside the microemulsion.14-20 Lipophilic cosurfactant, or nonionic surfactant, is fairly soluble in oil. As a result, with increasing oil content, cosurfactant molecules tend to shift from the surfactant layer to the oil domain inside the microemulsion. Hence, more cosurfactant is needed to keep the HLB composition in the surfactant layer upon dilution. If it is assumed that the monomeric solubilities of hydrophilic surfactant in water and oil and of lipophilic surfactant in water are negligible, then the following equation holds concerning the center of one- or threephase regions of the three-phase microemulsion

W1 ) S1S +

S1S2S 1 -1 R 1 - S1 ow x

(1)
Figure 3. The weight fraction of nonionic surfactant in total surfactant (W1) for the midst of the LC region plotted against 1/ - 1 in the 1 wt % NaCl(aq)/SDS/C EO /decane (0), 3 wt % x 12 3 NaCl(aq)/SDS/C12EO3/decane (O), and 5 wt % NaCl(aq)/SDS/ C12EO3/decane (4) systems at 35 C. The value of x is the weight fraction of total surfactant in the systems.
Table 1. S1 and S1S in the Mixed Surfactant Systems at 35 C surfactant 1a C12EO3 C12EO3 C12EO3 C12EO2 C12EO2 C12EO2 hexanolb hexanol hexanol water or aqueous soln (wt % NaCl) 1 3 5 1 3 5 1 3 5

where W1 is the weight fraction of lipophilic surfactant or cosurfactant (nonionic surfactant) in the mixed surfactant and S1 is the solubility of lipophilic surfactant 1 in oil. S2S is the mixing fraction of surfactant 2 (ionic surfactant) in the total surfactant at the microwater or microoil interface inside the microemulsion (S1S + S2S ) 1). Row is the weight fraction of oil in water + oil, and x is the weight fraction of total surfactant in the system, respectively. In the present system, however, a three-phase body does not appear as is shown in Figures 1 and 2. Instead, a lamellar liquid crystal is present between two one-phase microemulsion regions. Moreover, the number of phases present in the LC region and the compositions of each phase are also unknown. However, as stated before, since it was observed that water and oil phases are present in the dilute region of LC (Figures 1 and 2), there is a threephase region consisting of LC, water, and oil phases in the LC region. Hence, it is considered that the same equation for a three-phase microemulsion in a mixed surfactant system can be applied to the present LC region. In fact, such three- or four-phase regions are reported in other ionic surfactant systems.21,22 The monomeric solubility of SDS in water and the solubility of SDS in oil are extremely low, and these values decrease in the presence of salt or other amphiphilic compounds. Hence, all the SDS molecules can be considered to form bilayers of lamellar liquid crystal. However, although the critical micelle concentration of C12EO2 in water is much less than SDS, in general, the monomeric solubility of C12EO2 in oil (S1) is not negligibly low. As a result, it can be assumed that only the nonionic surfactant is distributed between the bilayer and the oil. It is also assumed that the water part of the lamellar liquid crystal is regarded as pure water, and the composition of the oil part is the same as that in excess oil phase. Then, concerning the center of LC present region, eq 1 may hold. In the present case,
(15) Kunieda, H.; Shinoda, K. J. Colloid Interface Sci. 1985, 107, 107. (16) Kunieda, H.; Sato, Y. In Organized Solutions; Lindman, B., Friberg, S. E., Eds.; Marcel Dekker: New York, 1992, pp 67-88. (17) Kunieda, H.; Ushio, N.; Nakano, A.; Miura, M. J. Colloid Interface Sci. 1993, 159, 37. (18) Kunieda, H.; Yamagata, M. Colloid Polym. Sci. 1993, 271, 997. (19) Kunieda, H.; Yamagata, M. Langmuir 1993, 9, 3345. (20) Kunieda, H.; Nakano, A. J. Colloid Interface Sci. 1995, 170, 78. (21) Kegel, W. K.; Lekkerkerker, H. N. W. Colloids Surf., A 1993, 76, 241. (22) Hackett, J. L.; Miller, C. A. SPE Reservoir Eng. 1988, 3, 791.

oil n-decane n-decane n-decane n-decane n-decane n-decane dodecane dodecane dodecane

S1 0.0307 0.0227 0.0184 0.0447 0.0292 0.0247 0.197 0.0783 0.0490

S1S 0.703 0.598 0.525 0.526 0.462 0.407 0.223 0.306 0.319

a Surfactant 2 is SDS. b The values for SDS-hexanol systems are at 25 C.10

S1S is the mixing fraction of nonionic surfactant in the bilayer of LC. The center of the LC present region in Figure 1 (the broken curve) is plotted against 1/x - 1, and the result is shown in Figure 3. The straight lines are obtained, and it is considered that eq 1 holds not only in the three-phase microemulsion but also in the LC region in the present system. From Figure 3, we can estimate the solubility of C12EO3 in oil part. We calculated the monomeric solubility of nonionic surfactant using eq 1 and the data in Figures 1 and 2. The obtained values are shown in Table 1. The S1 is considerably smaller than with the result in the NaCl(aq)/SDS/ hexanol/decane system.10 At high salinity, the solubility, S1, tends to decrease in a manner similar to that of an ordinary cosurfactant system. S1S is also decreased at higher salinity because SDS becomes relatively less hydrophilic upon addition of salt. In other words, in order to keep a balanced state of the mixed surfactant layer at the water-oil interface, the amount of lipophilic nonionic surfactant should be decreased. This is also in good agreement with the results of the C12EO3/commercial alkyl ethoxy sulfate system.14 However, in the latter system, there is a three-phase body, which does not appear in the

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Langmuir, Vol. 14, No. 2, 1998 263

Figure 4. Phase diagram of the 3 wt % NaCl(aq)/SDS/C12EO3/decane system at 35 C. The brine/decane weight ratio is unity. The line A corresponds to the broken curve in Figure 1.

present system. The S1S value for C12EO3 is higher than the S1S value for C12EO2 or hexanol, because C12EO3 is more hydrophilic than the latter two. In the present discussion, we assume that aqueous salt solution can be treated as pseudo one component, which means that the salinity is always constant in each phase. However, it is possible that the salt/water ratios are different in excess water phase and microemulsion phase or lamellar liquid crystal. In order to improve the above theory, we have to consider the distribution of inorganic salt within each phase. Interlayer Spacing of Lamellar Liquid Crystal between Two Microemulsion Regions. According to the phase behavior analysis in the former section, 2.27 wt % of C12EO3 is dissolved in oil in the center of the LC present region, and the mixing fraction of C12EO3 is 0.598 in the bilayer of the liquid crystal in the NaCl(aq)/SDS/ C12EO3/decane system. A phase diagram of the 3 wt % NaCl(aq)/SDS/C12EO3/ decane system was constructed at an equal weight ratio of brine and decane at 35 C and is shown in Figure 4. The concentrated region of SDS was not investigated because SDS is in a solid state. The single-phase microemulsion region is extended from the C12EO3 apex to the brine/decane corner. Along the microemulsion region, lamellar liquid crystal is present over a wide range of composition. If we assume that the bilayer composition is unchanged and the solubility of nonionic surfactant in the oil part of the LC phase S1 is constant in the center of the LC region in Figure 1, then the bilayer composition would be unchanged on line A in Figure 4. In other words, if we measure the interlayer spacing of lamellar liquid crystal along this line by means of SAXS, and the composition of bilayer is considered to be unchanged, then the following relation should hold

Figure 5. The interlayer spacing of lamellar liquid crystal (0) and effective cross-sectional area per one surfactant molecule in the bilayer (O) are plotted against 1/S on the line A in Figure 4. S is the volume fraction of the mixed surfactant bilayer in the system.

is the volume fraction of mixed surfactant of the bilayer of the LC phase in the system, O is the volume fraction of oil in the system, and F1 and Fo are the densities of nonionic surfactant and decane, respectively. The second term in eq 3 represents the volume fraction of nonionic surfactant in the oil part of the LC phase. Equation 3 is derived from a simple volume balance in the LC phase, taking into account the above assumptions. The SAXS result on line A is shown in Figure 5. We plotted the measured interlayer spacing against the reciprocal of the volume fraction of the mixed surfactant in the bilayer of the LC phase. Since the straight line is obtained, the above relation may approximately hold. The average effective cross-sectional area per one surfactant molecule in the bilayer, aS, can be calculated by,

aS ) Vs/dSL

(4)

d ) 2dS/ S ) S S S1 F 0 1 - S1 F1 O

(2) (3)

where Vs is the molar volume of the mixed surfactant and L is the Avogadro constant. The aS is also indicated in Figure 5. The aS value is constant and is equal to 0.37 nm2. We also measured the interlayer spacing of the lamellar liquid crystal in 50 wt % C12EO3 solution, and the same value of aS was obtained at 35 C. However, SDS alone forms hexagonal liquid crystals in water at the same concentration. The effective cross-sectional area per SDS in the hexagonal phase is much larger than the above value.23 Since the charge density in the mixed surfactant layer decreases, the lateral attractive interactions increase in the present ionic-nonionic surfactants, compared with ionic surfactant alone. Besides, the present nonionic surfactants have long lipophilic chains compared with ordinary cosurfactants, and the cohesive energy of lipophilic changes is strong. For this reason, the bilayer structure is maintained even in a very dilute region. Acknowledgment. The authors thank Mr. J. Caelles for the SAXS measurements.
LA9704112
(23) Amaral, L. Q.; Gulik, A.; Itri, R.; Mariani, P. Phys. Rev. A: At., Mol., Opt. Phys. 1992, 46, 3548.

where d is the interlayer spacing measured by SAXS, dS is the effective length of surfactant in the bilayer, S is the volume fraction of mixed surfactant in the system, S