Proceeding of 2nd International Conference on Mathematics and Natural Sciences (ICMNS) 2008

ELLIPSOID TO WORM-LIKE MICELLE STRUCTURE TRANSITION REVEALED BY SMALL-ANGLE NEUTRON SCATTERING TECHNIQUE
1Neutron Scattering Laboratory Center for Technology of Nuclear Industrial Materials National Nuclear Energy Agency of Indonesia (BATAN) Kawasan Puspiptek Serpong, Tangerang 15314, Indonesia

Arum Patriati1, Edy Giri Rachman Putra1

Abstract. The micelle structure transition on the self-assembly sodium dodecyl sulfate (SDS) in water by addition of sodium chloride (NaCl) salt has been revealed by a small-angle neutron scattering (SANS) technique. At a fixed concentration of 0.3 M SDS it was found that the inter correlation peak of Bragg diffraction on SANS distribution profiles disappear gradually as the salt concentration increased from 0.02 M to 0.6 M. It indicated that there is screening effect on the present of salt due to decreasing of repulsion force between charge head groups of the SDS molecule. Furthermore, it leads to decrease the free energy on micellization in which the molecules of SDS assembled easily to form a large size micelle. The major axis of micelle increases from 22 to more than 250 as an ellipsoidal micelle transform into a cylindrical (worm-like) micelle. This worm-like micelle structure was obtained for the first time using a 36 m SANS BATAN spectrometer (SMARTer). Keywords: Self-assembly, micelle, small-angle neutron scattering

1 Introduction
The growth of ionic micelle in aqueous micellar solution was determined at least of two factors conducted to the free energy changes, i.e. the repulsion force between head groups of the micelle in which would decrease the free energy and the restructuring hydrogen bonding of water that associated with increasing of entropy1. The repulsion between head groups of the ionic surfactant could be neutralized by ions which have opposite charge to the head groups of the surfactant, called counter ions. Salt addition will increase the number of counter ions in the solution. Consequently, it decreases the repulsion between charge head groups and leads to the growth of micelle. The effect of salt addition is not only depended to the concentration of the salt but also determined by the type of the counter ions2,3,4. The type of counter ions will determine the affectivity of screening effect as the variation of the hydrated size. The tendency in covering the charge on the micelle is enhanced by a small hydrated size of counter ions. The previous works of the effect of salt addition using small angle neutron scattering (SANS) spectrometer in BATAN (SMARTer) shows that the micelle transform from spherical to ellipsoid micelle for both variation of concentration and the type of counter ions2,3. The transition of spherical to ellipsoidal micelle by variation of salt concentration is probably due to salt addition to the surfactant solution in low range concentration. Since the present of salt in the surfactant system reduces the repulsion between head groups, the micelle will tend to grow and form a large size micelle. Then, it is expected that the ellipsoidal micelle forms a larger micelle by addition of high concentration salt. In this work, sodium dodecyl sulfate (SDS) as anionic surfactant at a fixed high concentration is prepared to store an enough amounts of surfactant molecules. The inter correlation peak of Bragg diffraction will appear at high concentration of SDS. Whereas, to enhance the tendency of SDS molecules to form a long-size micelle, sodium chloride (NaCl) salt is added from low to high concentration. The present of NaCl will reduce the repulsion between sulfate head groups and leads the growth of micelle. As increasing the size of micelle at a fixed surfactant concentration, the inter correlation peak disappears due to increasing of inter micellar distance5.

2 Experimental Section
Reagents. Analytical grade of SDS, NaCl, and 99.9% deuterium oxide (D2O) were purchased from Aldrich. These chemical were used without further purification. D2O was used as a solvent to enhance contrast as required for SANS experiment. At fixed 0.3M SDS, a various amounts of NaCl were added to obtain a final salt concentration of 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6 M.

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Proceeding of 2nd International Conference on Mathematics and Natural Sciences (ICMNS) 2008

Small-Angle Neutron Scattering. SANS experiments were carried out on SMARTer at neutron scattering laboratory (NSL) BATAN in Serpong, Indonesia. Each sample was measured on two detector distances, 1.5 m and 3 m, to cover a momentum transfer Q range of 0.02 to 0.25 -1, with the neutron wavelength was 3.9 . A 5 mm thick of sample is contained in quartz cell and then exposed to neutron beam for 1 hour. During the experiment, each sample was held at 30 C to avoid a clouding effect. Scattering intensities of the samples are corrected for incoherent scattering; i.e. background of detector, quartz cell and solvent scattering; and sample transmission by GRAPS data reduction program6. Data Analysis. The growth of micelle can be investigated by a SANS technique since the size of micelle lies on range 1 nm to 100 nm. The size determination by SANS technique is based on the measurement of the elastic neutron scattering intensity as a function of scattering angle, which is transformed as momentum transfer7. The momentum transfer Q is the resultant between incident ki and scattered ks wave vectors, and its modulus is given by

(1) where is scattering angle and is the wavelength of neutron. By substituting equation (1) into Braggs Law of diffraction, thus very useful expression is given as.

Where d is a distance. Here, the intensity I(Q) of small angle scattering as a function of Q for a monodisperse interacting micelle system can be expressed as (2) where n denotes the number density of micelles, m and s are the scattering length densities of the micelle and the solvent, respectively. The term (m-s) is called contrast factor. V is the volume of a micelle. The aggregation number N of the micelle related to the micellar volume V by the relation V = Nv, where v is the volume of a surfactant monomer. For ellipsoid and cylinder shape it is calculated by N = 4Ra2Rb/3v, where Ra and Rb are respectively minor and major axis. P(Q) is the intraparticle structure factor and depends on the shape and size of the particles. S(Q) is the interpaticle stucture factor and is decided by the interparticle distance and the particle interaction. For elipsoid micelle with axis 2a, 2a, and 2az, P(Q) is formulated by (3) where x = Qa[cos2 + z2sin2] and is the angle between the scattering vector and the direction of the symetry axis of ellipsoid. Whereas cylinder micelle with diameter 2a, and heigth 2h,

(4) Where j1 is the cylindrical Bessel function of order 1. Meanwhile, for isotropic system S(Q) can writen as,

(5) where g(r) is the probability of finding another particle at a distance r from a reference particle centered at the origin.

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The data is analyzed by screen Coulomb model provided by NIST data analysis8. The model is calculated based on equation (3), (4), and (5). Here, it is determined the fractional charge and the major axis, since the minor axis is fixed at 16.7 . This is the same as the length of the extended hydrophobic chain of SDS molecule based on the Tanfords formulation9.

3 Result and Discussion

The inter correlation peak appears on SANS distribution profile of 0.3M SDS, and gradually disappear as increasing on salt addition, Figure 1. Those peaks occur due to inter micellar interaction in the system as a repulsion between micelle surfaces and give contribution on structure factor S(Q). The repulsion between micelles makes the micelle having the average distance between them to establish the stable system. The Qmax value of inter correlation peak conducted to average distance between micelles d as given in Equation (2).

Figure 1. SANS distribution profile of 0.3 M SDS/D2O system at a various concentration of NaCl at 30C

When up to 0.1 M of NaCl is added into the 0.3 M SDS solution, the peak broadens without significant shift of Qmax position. The inter correlation peak becomes broad and shift on Qmax position at addition of more than 0.2 M NaCl and noticeably disappears at 0.4 M NaCl. The relation between Qmax value and the concentration of present salt is showed in Figure 2. The shifted of Qmax to low value shows that there is an increment on average distance between micelles as a consequence of decreasing of the repulsion force.

Figure 2. The inner correlation peak position of 0.3 SDS as a function of NaCl

The broadening of the correlation peak is a result of screening effect on repulsion force between micelles10. The repulsion between sulfate head groups screened out by Na+ion from salt added into solution, and finally, decreasing those repulsion force. The broadening peak also shows that the micelle grows, since the Qmax intensity of the addition NaCl up to 0.3 M gradually increase. In this salt concentration range, the effect of the NaCl addition is utilized to screen out

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Proceeding of 2nd International Conference on Mathematics and Natural Sciences (ICMNS) 2008

the strong repulsion force between sulfate head groups existing in the solution. Consequently, the growth of the micelles is not thoroughly significant.

Figure 3. The Micelle structure transformation from 0.2 M to 0.4 M NaCl addition indicated by SANS distribution profile changes

The micelle structure transformation can be noticeably seen as the SANS distribution profile pattern is dramatically change from 0.3 M to 0.4 M NaCl, Figure 3, where the inter correlation peak disappeared at 0.4 M NaCl. It can be described that by the present salt concentration in the 0.3 M SDS solution, the repulsion between sulfate head groups has been neutralized, indicated by low fractional charge , see Table 1. Furthermore, the addition of higher salt concentration has stronger effect in the system and leads to the growth of long-size micelle. The micelle transform from ellipsoid to cylindrical micelle. The SANS distribution profile by addition of NaCl in range 0.4 M to 0.6 M become similar with dilute micellar concentration, figure 4. Here, the intensity of SANS spectra is only determined by P(Q), since the inter particle interaction becomes weak, therefore S(Q) 1.

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Proceeding of 2nd International Conference on Mathematics and Natural Sciences (ICMNS) 2008

Table 1. Micellar parameter of 0.3 M SDS as varying NaCl concentration. The minor axis fixed at Ra = 16.7 .

The intensity of SANS distribution profile of 0.3 M SDS significantly increases in addition of more than 0.3 M NaCl. From Equation (3), for dilute solution, the increasing of intensity indicates the increasing of micelle volume. Because of increasing the micelle volume, the number of micelle reduces. Consequently, the system of 0.3 M SDS solution seems to be dilute and the pattern of SANS distribution profile tends to appear as a dilute-like pattern, Figure 4. At a fixed minor axis of the micelle, the most probable structure of micelle, by increasing of micelle volume, is ellipsoid to cylindrical micelle. This assumption is based on the basic natural behavior of SDS molecules in a micellar solution system. The hydrophobic chains will tend to get close each other inside the micelle to prevent from contact with water. At a fixed Ra, the length of micelle increases as increasing the intensity of SANS distribution profile at low Q with salt addition. This is appropriate with the fitting results of SANS distribution profile by NIST program which obtain a low chi square value on ellipsoid structure model up to 0.3 M NaCl addition in SDS solution. Meanwhile, the addition of more than 0.3 M NaCl, give a best fitting result on cylinder structure model. The major axis (Rb) is calculated in a fixed minor axis (Ra) at 16.7 , the calculated length of stretch SDS molecules8. The result of major axis (Rb) and the axial ratio (Rb/Ra), obtained from this experiment is given in Table 1. The increasing of Rb value leads on increasing of aggregation number, N, which is the average number of surfactant molecules assembled in one micelle. The aggregation number increase as increasing of NaCl concentration, Figure 5.

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Proceeding of 2nd International Conference on Mathematics and Natural Sciences (ICMNS) 2008

Figure 4. The pattern of SANS distribution profile addition of NaCl salt from 0,4 M to 0,6 M.

The relation of aggregation number with the concentration of NaCl added into 0.3 M SDS solution clearly shows the effect of salt addition on the growth of micelles. The micelles grow dramatically in addition of more than 0.3 M NaCl due to the repulsion between sulfate head groups has been entirely neutralized.

Figure 5. The relationship between aggregation number with NaCl concentration in 0.3 M SDS micelle solution

The Na+ions from NaCl in solution would stay near the micellar surface and neutralize the micellar surface charge, particularly, neutralize the sulfate head groups of SDS, and then, reduce the optimum head group area, a0. Consequently, the packing parameter will increase that lead to form a larger micelle1,11. The increasing of packing parameter is a result as a balance between the tendency of sulfate head groups to get closer due to decreasing of electrostatic repulsion and stretching inside of the hydrocarbon tail groups as a consequence of decreasing a0 value. The balance of those two factors produces a minimum free energy as a basic driving force behind the self-assembly process [12], as it is assume that repulsion force is the most significant factor which is determining the free energy change in the ionic surfactant system [1]. This decreasing of free energy change as increasing the salt concentration leads the SDS molecules to form a large size of micelle, i.e. transition of ellipsoidal to cylindrical micelle. Since the SDS molecules, in the form of micelle, were bounded by electrostatic forces, the cylindrical micelles are not rigid as a rod-like micelle. However they tend to form a worm-like micelle.

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4 Conclusion
Addition of low to high concentration NaCl salt in concentrated SDS solution leads in micelle structure transition. The present of salt reduces the repulsion force between sulfate head groups. The effect of the repulsion force reduction is decreasing of packing parameter as a condition to reach minimum free energy on micellization where the SDS molecules tend to assemble and form a large micelle. The ellipsoidal micelle elongates and transforms to a cylindrical micelle as increasing of NaCl.

Acknowledgment
The authors would thank to Y. A. Mulyana of Neutron Scattering Laboratory for helping the SANS experiment setting preparation.

References
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R.J. Hunter (2001), Foundation of Colloids Science, Oxford University Press. E.G.R. Putra and A. Ikram (2006), Nanosize structure of self-assembly sodium dodecyl sulfate: A study bt small angle neutron scattering (SANS), Indonesian J. of Chem. 6, 2, 117-120. E.G.R. Putra and A. Ikram (2008), Nanostructure and growth of cetyltrimethylammonium bromide micelles determination using small angle neutron scattering (SANS) technique, J. Nucl. Related Techn. 10, 1 in printing. S. Kumar, S.L. David, V.K. Aswal and P.S. Goyal (1997), Growth of sodium dodecyl sulfate micelles in aqueous ammonium salts, Langmuir, 13, 6461-6464. S.S. Berr, R.M. Jones (1988), Effect of added sodium and lithium chlorides on intermicellar interaction and micellar size of aqueous dodecyl sulfate aggregates as determined by small-angle neutron scattering, Langmuir, 4, 1247-1251. C. Dewhurst (2001 2007), GRASP: Graphical Reduction and Analysis SANS Program for Matlab, http://www.ill.eu/fileadmin/users_files/Other_Sites/lssgrasp/grasp_main.html, Institut Laue Langevin. P.S. Goyal, Small Angle Neutron Scattering, RCA/IAEA Workshop on Small Angle Neutron Scattering, BARC-Bombay, India, April 1995. S.R. Kline (2006), Reduction and analysis of SANS and USANS data using IGOR Pro, J. Appl. Cryst. 39, 895-400. C. Tanford (1980), The Hydrophobic Effect: Formation of Micelle and Biological Membranes, Willey, New York. V.K. Aswal, P.S. Goyal, S.V.G. Menon, B.A. Dasannacharya (1995), Role of inter-micellar interaction on micellar growth, Physica B, 213&214, 607-609. C.A. Dreiss (2007), Wormlike micelles: where do we stand? Recent development, linear rheology and scattering techniques, Soft Matter, 3, 956-970. R.A.L. Jones (2002), Soft Condensed Matter, Oxford University Press.

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ARUM PATRIATI Neutron Scattering Laboratory Center for Technology of Nuclear Industrial Materials National Nuclear Energy Agency of Indonesia (BATAN) E-mail: arum@batan.go.id EDY GIRI RACHMAN PUTRA Neutron Scattering Laboratory Center for Technology of Nuclear Industrial Materials National Nuclear Energy Agency of Indonesia (BATAN) E-mail: giri@batan.go.id

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