<?xml version="1.0" encoding="UTF-8"?><!DOCTYPE article  PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd"><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" dtd-version="3.0" xml:lang="en" article-type="research article"><front><journal-meta><journal-id journal-id-type="publisher-id">SNL</journal-id><journal-title-group><journal-title>Soft Nanoscience Letters</journal-title></journal-title-group><issn pub-type="epub">2160-0600</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/snl.2012.21002</article-id><article-id pub-id-type="publisher-id">SNL-16573</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Chemistry&amp;Materials Science</subject></subj-group></article-categories><title-group><article-title>
 
 
  Light Scattering and SAXS Study of AOT Microemulsion at Low Size Droplet
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>oheil</surname><given-names>Sharifi</given-names></name><xref ref-type="corresp" rid="cor1"><sup>*</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Masoud</surname><given-names>Amirkhani</given-names></name></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Jahanbakhsh</surname><given-names>Mashaiekhy Asla</given-names></name></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Mohamad</surname><given-names>Reza Mohammadi</given-names></name></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Othmar</surname><given-names>Marti</given-names></name></contrib></contrib-group><author-notes><corresp id="cor1">* E-mail:<email>soheil.sharifi@gmail.com(OS)</email>;</corresp></author-notes><pub-date pub-type="epub"><day>31</day><month>12</month><year>2011</year></pub-date><volume>02</volume><issue>01</issue><fpage>8</fpage><lpage>12</lpage><history><date date-type="received"><day>February</day>	<month>5th,</month>	<year>2011</year></date><date date-type="rev-recd"><day>May</day>	<month>27th,</month>	<year>2011</year>	</date><date date-type="accepted"><day>April</day>	<month>18th,</month>	<year>2011</year></date></history><permissions><copyright-statement>&#169; Copyright  2014 by authors and Scientific Research Publishing Inc. </copyright-statement><copyright-year>2014</copyright-year><license><license-p>This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/</license-p></license></permissions><abstract><p>
 
 
  We study collective diffusion coefficient (D
  <sub>c</sub>) of Water-in-oil nanoemulsions (L
  <sub>2</sub> phase) stabilized by AOT and dispersed in n-Decane oils by dynamic light scattering (DLS). At constant water concentration we vary the oil concentration and there is clear evidence for a changing collective diffusion coefficient of the droplets in AOT nanoemuslion. The collective diffusion coefficient in AOT nanoemulsions is studied from relaxation investigations with dynamic light scattering. Also, we study the collective diffusion coefficient (D
  <sub>c</sub>) of droplets with add the TBAC to the droplets of AOT nanoemulsion. We discuss the results with study structural investigations with small-angle x-ray scattering. The results of this study suggest that the formation of non-spherical aggregates at low concentration of droplets can describe the behavior of the collective diffusion coefficient at AOT nanoemulsion.
 
</p></abstract><kwd-group><kwd>Nano-droplet; Microemulsions; Light scattering; SAXS; Diffusion</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>Brownian motion is a subject of renewed interest since the development of photon correlation spectroscopy (PCS) in the last decade. The dynamic properties of microemulsions and colloidal systems is studied by measuring the relaxation of concentration fluctuations, [1,2]. The relaxation time of the fluctuations can be expressed in a diffusion coefficient, which is called the collective diffusion coefficient (D<sub>c</sub>), in the limit of infinite dilution. The study of the collective diffusion coefficient of microemulsion is an interesting topic in soft matter physics. The microemul- sions are thermodynamically stable mixtures of water, oil, and surfactant with nano-metric size of droplets to the solvents (H<sub>2</sub>O or Oil). In the case of water/surfactants (droplet) to the nanopolar solvents (oil), microemulsions have L<sub>2</sub> phase and oil/surfactant inside the water solutions is L<sub>1</sub> phase of microemulsions. In our samples, the composition of each system is determined by the molar ratio X of water to surfactant molecules.</p><disp-formula id="scirp.16573-formula58582"><label>(1)</label><graphic position="anchor" xlink:href="2-4600011\fb078744-06bc-4c13-9012-eafc6de8e830.jpg"  xlink:type="simple"/></disp-formula><p>and the droplet mass fraction (mf),</p><disp-formula id="scirp.16573-formula58583"><label>(2)</label><graphic position="anchor" xlink:href="2-4600011\d411f608-d95e-48e8-959f-67c7f34e53c3.jpg"  xlink:type="simple"/></disp-formula><p>which varies by the respective mass of the components water (<img src="2-4600011\4ea23e65-d7be-4a74-97a4-9501e7a701a4.jpg" />), decane (m<sub>Dec</sub>), and AOT. In this work, the microemulsion system is located in the L<sub>2</sub> region at studied temperatures and compositions investigated. Most works on collective diffusion coefficient of droplets and interactions of droplets have been done mainly on charged macromolecules, [3-15], for example bimolecular, [3-10], as DNA, proteins and amino acids, micelles, [<xref ref-type="bibr" rid="scirp.16573-ref11">11</xref>], and polymer latexes, [<xref ref-type="bibr" rid="scirp.16573-ref15">15</xref>], in water (as polar solvent) at low ionic strength. The strong, long range electrostatic interactions between the particles or droplets in these systems lead to remarkable structure effects. Only in the higher number densities or droplet concentration of microemulsions where the inter-particle separation is in the order of the particle dimensions hydrodynamic interactions can be observed.</p><p>In previous study of the collective diffusion coefficient in C<sub>12</sub>E<sub>5</sub>/H<sub>2</sub>O/Decane microemulsion, the collective diffusion coefficient as function of droplet mass fraction has positive slop at the low droplet mass fraction (dilute regime mass fraction below 0.1) that describes an attractive interaction between droplets. It is well known that C<sub>12</sub>E<sub>5</sub>/- H<sub>2</sub>O/Decane microemulsion at constant surfactant-oil mass ratio of 1.08 with the different mass fractions has shown behaviors as the hard sphere droplets, [16-20]. The Collec- tive diffusion coefficient as function of mass fraction in the C<sub>12</sub>E<sub>5</sub>/H2O/Decane microemulsion has positive behavior and only depends to the inter-particle interaction of hard sphere droplet. The mixture of PEG with C<sub>12</sub>E<sub>5</sub>/H<sub>2</sub>O/- Decane microemulsion shown that addition of PEG causes slow down of the collective diffusion coefficient D<sub>c</sub>. The measured D<sub>c</sub> data for the droplets in the presence of PEG are modeled using the Asakura-Oosawa theory of depletion, [<xref ref-type="bibr" rid="scirp.16573-ref20">20</xref>], but D<sub>c</sub> in the AOT/H<sub>2</sub>O/Decane microemulsions has different behavior. Structure and phase behavior of AOT microemulsions are well investigated of a liquid of droplets on a nanometer scale, [<xref ref-type="bibr" rid="scirp.16573-ref21">21</xref>]. A study shown, for AOT/H<sub>2</sub>O/Decane microemulsion, at the low droplet mass fractions (0.01 &lt; mf &lt; 0.1 transition from dilute to semi-dilute regime) and molar ratio 40 the collective diffusion coefficient has a linear function of mass fraction. It is well known that at high water concentration with the molar ratio of X = 40 the collective diffusion coefficient D<sub>c</sub> depends on the droplet mass fraction (droplet concentration) due to inter-particle interactions, [<xref ref-type="bibr" rid="scirp.16573-ref22">22</xref>]. This study is an attempt to understand the collective diffusion coefficient behavior of AOT/H<sub>2</sub>O/Decane microemulsion at low water concentration (molar ratio, X = 6.7). The most study in this range of water concentration that shown droplet of the microemulsion has spherical behavior, [23,24]. In the present work, we studied the behavior of the collective diffusion coefficient at the molar ratio 6.7 and low mass fraction (0.01 &lt; mf &lt; 0.08), by means of DLS and SAXS techniques. Also, we study effect of TBAC on the D<sub>c</sub> in the AOT/H<sub>2</sub>O/Decane microemulsion.</p></sec><sec id="s2"><title>2. Experimental</title><sec id="s2_1"><title>2.1. Methods and Materials</title><p>Sodium-2-diethylhexyl sulfosuccinate, or AOT 99% (an Alfa product), was dried in vacuum. Deionized and distilled water were employed to prepare the samples for the light scattering and SAXS measurements and solutions of the mix TBAC with microemulsions. The microemulsions were prepared by mixing of surfactants AOT, H<sub>2</sub>O, and oil (Decane) and waiting for several minutes until the samples were single phase and optically clear. Decane 99% (Aldrich) and tetrabutylammonium chloride (TBAC) and n-decane were obtained from Sigma-Aldrich. The composition of the AOT/H<sub>2</sub>O/Decane microemulsion is given by the two parameters X and mf. The mixing of TBAC with microemulsions is described with the molar ratio of TBAC to AOT, Equation (3).</p><disp-formula id="scirp.16573-formula58584"><label>(3)</label><graphic position="anchor" xlink:href="2-4600011\186191eb-4aff-41bc-9440-76e62b3f8b13.jpg"  xlink:type="simple"/></disp-formula><p>The experimental solutions were prepared at temperature 293.15 K. The microemulsions were prepared by weighting appropriate amounts of AOT dissolving in decane then by adding water into the solution. Finally, all samples were filtered by using 0.2-pm Teflon filters (Gelman). The Small-angle X-ray scattering measurements were performed using the pinhole SAXS instrument at the University of Aarhus. The instrument consists of an X-ray camera (NanoSTAR, Bruker AXS) with a rotating anode X-ray (Cu Kα radiation) source, cross-coupled G&#246;bel mirrors, collimation using three pinholes and an evacuated beam path, and a 2D position-sensitive gas detector (HiSTAR). In the current experiments the small pinholes were used, giving a range of scattering vectors as 0.0084 ≤ Q<img src="2-4600011\03b1e9bf-c5e2-46b6-a6e9-bf38ca329599.jpg" /> ≤ 0.35, where Q = <img src="2-4600011\49249bc0-cfad-4177-87e3-2eefa8be4742.jpg" />sin<img src="2-4600011\83c89c17-4d91-4748-b628-41e6d07fcd35.jpg" /> is the modulus of the wave vector, θ is the scattering angle, and λ = 1.542 &#197; is the X-ray wavelength. The sample was held in a 1 mm glass capillary at room temperature. Data was acquired as a function of the scattering vector modulus <img src="2-4600011\e3a2f2d2-bf9d-469b-8f7b-50c517643992.jpg" /> where 2θ is the angle between the incident and scattered photons. Dynamic light scattering measurements were performed on filtered samples using ALV CGS-8f/DLS Instruments Series A6160-V1052 at Ulm University. The scattering angle was maintained at 90˚, and the temperature was kept at 293.15 K for the microemulsion samples.</p></sec></sec><sec id="s3"><title>3. Results</title><p>Microemulsions were formulated by mixing AOT with water and n-Decane at the fixed molar ratio of water to AOT (X = 6.7) at the different mass fraction (0.01 &lt; mf &lt; 0.07 dilute regime). The dynamic behavior of the AOT/- H<sub>2</sub>O/Decane microemulsion was probed with dynamic light spectroscopy. The correlation function of the scattered light intensity showed a single exponential decay at all concentrations, <xref ref-type="fig" rid="fig1">Figure 1</xref>. (A). All the correlation functions in this work were fitted by a single stretched exponential function, [1,2].</p><disp-formula id="scirp.16573-formula58585"><label>(4)</label><graphic position="anchor" xlink:href="2-4600011\c6ea9a0a-1b47-423b-a127-c040a267dcd7.jpg"  xlink:type="simple"/></disp-formula><p>That <img src="2-4600011\867dea12-b5f1-408f-8f6f-9494a998371e.jpg" /> and the collective diffusion coeffi- cient D<sub>c</sub> was extracted as a function of the droplet mass fraction as shown in <xref ref-type="fig" rid="fig1">Figure 1</xref>(b). The collective diffusion coefficient measurements were carried out on dilution series of microemulsion samples at fixed temperature 293.15 K and molar ratio 6.7 with two different molar ratio of TBAC (0.0 and 0.049 molar/l). In the <xref ref-type="fig" rid="fig1">Figure 1</xref>, the collective diffusion coefficient show a liner behavior with negative slop between 0.01 &lt; mf &lt; 0.07. By increasing TBAC content relaxation time decreases, <xref ref-type="fig" rid="fig1">Figure 1</xref>(a) and the diffusion coefficient increases, <xref ref-type="fig" rid="fig1">Figure 1</xref>(b).</p><p>In this experiment, SAXS is used for the determination of the structure of AOT/H<sub>2</sub>O/Decane microemulsions at 293.15 K. The SAXS methods are useful for studies the structure of reverse micelles. This is because the scattering of X-rays of wavelengths of a few angstroms through small angles provides a Q range (as defined by Equation 2) which is particularly appropriate for the determination of both</p><p>the size of discrete reverse micelles and their interactions. From the angular dependence of the scattered X-ray intensity <img src="2-4600011\e684d47a-2617-4e18-b0b2-6452b7378c4b.jpg" /> we have</p><disp-formula id="scirp.16573-formula58586"><label>(5)</label><graphic position="anchor" xlink:href="2-4600011\567f5cf1-eec8-4285-ae8e-14370a4b65fb.jpg"  xlink:type="simple"/></disp-formula><p>where</p><disp-formula id="scirp.16573-formula58587"><label>(6)</label><graphic position="anchor" xlink:href="2-4600011\6feb5aba-fd3f-4790-94b1-a94159f52896.jpg"  xlink:type="simple"/></disp-formula><p>Q is the wavelength and θ is the scattering angle. <img src="2-4600011\264d0c36-8c8f-436c-ae2d-2f8e3187f850.jpg" />is referred to the form factor, which gives information on the dimensions of an individual reverse micelle, and <img src="2-4600011\711de84f-e7b2-4eb9-9197-54601e8ec47d.jpg" /> is the structure factor, which provides information on inter-micelle interaction. We will consider the nature of the interactions between micelles. Information on interactions can be obtained from structure factor. The scattered intensity as a function of Q from samples presented in the <xref ref-type="fig" rid="fig2">Figure 2</xref>, which the lines are fits to a power law,</p><p><img src="2-4600011\4ff30cec-e8e5-4828-a174-9b36501228de.jpg" />, with properties of a cylindrical object. At small Q, the scattering is only sensitive to the overall dimension of the scattering particles, and we expect from Guinier’s law, <img src="2-4600011\a286bc72-b648-40f3-8ed9-a625245543b4.jpg" />, where ξ is correlation length. The microemulsions with molar ration 6.7 and different droplet mass fractions were collected for these experiments. The SAXS data is measured from the high concentration sample (mass fraction 0.1) to the dilute sample. <xref ref-type="fig" rid="fig2">Figure 2</xref> shows the small angle X-ray scattering intensities for AOT/H<sub>2</sub>O/Decane as a function of Q at the molar ratio 6.7 and different mass fraction.</p><p><xref ref-type="fig" rid="fig2">Figure 2</xref>, depict that intensity as a function of Q at the high droplet mass fraction (mf = 0.1) and Q range of 0.02 &lt; Q (1/&#197;) &lt; 0.1 has linear behavior. At low Q, we used Guinier’s law, <img src="2-4600011\b832b266-8e26-48c8-a4d1-2dd990ca9fca.jpg" />, that results presented in the <xref ref-type="fig" rid="fig3">Figure 3</xref>&quot; target=&quot;_self&quot;&gt; <xref ref-type="fig" rid="fig3">Figure 3</xref>. Our results show, the correlation length <img src="2-4600011\60399d61-c53a-469a-8a91-a62ebdb45ce4.jpg" /> change from 23 &#197; to 50 &#197; with the increase of droplet mass fraction (<xref ref-type="fig" rid="fig3">Figure 3</xref>). The most important observation from <xref ref-type="fig" rid="fig2">Figure 2</xref> is increasing of the correlation length with the increase of droplet mass fraction. We also study the effect of adding TBAC to the AOT/H<sub>2</sub>O/Decane microemulsion with SAXS experiment. 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