Journal of Colloid and Interface Science 411 (2013) 152–161

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Journal of Colloid and Interface Science

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Physicochemical investigation of mixed surfactant microemulsions:

Water solubilization, thermodynamic properties, microstructure, and
dynamics
Soumik Bardhan a, Kaushik Kundu b, Swapan K. Saha a,⇑, Bidyut K. Paul b,⇑
a
Department of Chemistry, University of North Bengal, Darjeeling 734 013, India
b
Surface and Colloid Science Laboratory, Geological Studies Unit, Indian Statistical Institute, 203, B.T. Road, Kolkata 700 108, India

a r t i c l e i n f o a b s t r a c t

Article history: In this contribution, we report on a systematic investigation of phase behavior and solubilization of water
Received 10 July 2013 in water-in-heptane or decane aggregates stabilized by mixtures of polyoxyethylene (20) cetyl ether
Accepted 20 August 2013 (Brij-58) and cetyltrimethylammonium bromide (CTAB) surfactants with varying compositions in conju-
Available online 3 September 2013
gation with 1-pentanol (Pn) at fixed surfactant(s)/Pn ratio and temperature. Synergism in water solubi-
lization was evidenced by the addition of CTAB to Brij-58 stabilized system in close proximity of
Keywords: equimolar composition in both oils. An attempt has been made to correlate composition dependent water
Synergism
solubilization and volume induced conductivity studies to provide insight into the solubilization mech-
Conductance percolation
State of water
anism of these mixed systems. Conductivity studies reveal the ascending curve in water solubilization
Thermodynamic parameter capacity-(Brij-58:CTAB, w/w) profile as the interdroplet interaction branch indicating percolation of con-
Temperature-insensitive microemulsion ductance and the descending curve is a curvature branch due to the rigidity of the interface in these sys-
Droplet diameter tems. The microstructure of these systems as a function of surfactant composition has been determined
by dynamic light scattering (DLS) and Fourier transform infrared spectroscopy (FTIR) measurements. FTIR
study reveals increase and decrease in relative population of bound and bulk-like water, respectively,
with increase in Brij-58:CTAB (w/w). DLS measurements showed that the droplet hydrodynamic diame-
ter (Dh) decreases significantly with the increase in Brij-58:CTAB (w/w). Further, the interfacial compo-
sition and energetic parameters for the transfer of Pn from bulk oil to the interface were evaluated by
the dilution method. Formation of temperature-insensitive microemulsions and temperature invariant
droplet sizes are evidenced in the vicinity of the equimolar composition. The results are interpreted in
terms of a proposed mechanism.
Ó 2013 Elsevier Inc. All rights reserved.

1. Introduction distinctly different from bulk water in physicochemical properties,

such as microviscosity, acidity, and polarity [8,9] and are very
Microemulsions are thermodynamically stable organized important in areas such as the catalysis of small molecules [9,10]
assemblies comprising of isotropic mixtures of surfactant, oil, and biopolymers [8,11], enhanced oil recovery [12], and models
water with or without cosurfactant [1]. These organized assem- for the study of hydration in membranes and cells [10]. All these
blies have been receiving a lot of theoretical as well as experimen- applications depend crucially on the water solubilization capacity,
tal investigations from time to time due to their potential which changes in response to the environmental conditions/vari-
applications in various fields, viz. aqueous chemical reactions [2], ables, for example, the chemical structure and physicochemical
vehicles for drug delivery [3], membrane mimetic systems [4], sep- properties of the amphiphile(s), the nature of the oil phase, the
aration and extraction processes of both metal ions and proteins temperature, and the presence of electrolytes [13].
[5,6], and nanoparticle and polymer syntheses [7]. Microemulsions It is well known that the organization of amphiphiles at the
consist of a hydrophilic core and a hydrophobic corona. Due to the interface of a microemulsion plays an important role in solubiliza-
polar nature of the core in microemulsions, water can be easily sol- tion of water in nanoscopic water pool and warrants an in-depth
ubilized into these micellar solutions. The solubilized water is study of solubilization mechanism for understanding of the phase
behavior as well as microstructure of the ordered phases in water/
amphiphile(s)/oil systems. Nowadays, mixing of surfactants is a
⇑ Corresponding authors. Fax: +91 33 2577 3026. preferred practice in surfactant industry due to associated perfor-
E-mail addresses: [email protected] (S.K. Saha), [email protected] mance advantages (synergism) and the inherent difficulty in
(B.K. Paul).

0021-9797/$ - see front matter Ó 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2013.08.034
 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161 153

preparing chemically new surfactants. Among different types of surfactant (non-ionic/ionic) w/o microemulsions [water/polyoxy-
possible mixed surfactant systems, ionic/non-ionic mixed systems ethylene (20) cetyl ether (Brij-58)/cetyltrimethylammonium bro-
are most frequently making their appearance in commercial and mide (CTAB)/1-pentanol (Pn)/heptane (Hp) or decane (Dc)] as a
non-commercial products as they provide more flexible physico- function of different mixing ratios of Brij-58:CTAB (5:0 ? 0:5, w/
chemical properties in terms of detergency, solubilization and syn- w) at 303 K. Both of these surfactants are chosen in such a way that
ergistic performance, which are key parameters in the formulation they possess similar hydrocarbon tail (comprising 16 carbon atoms
of cosmetic and medicinal products [14,15]. Synergism in water in the linear hydrocarbon chain), but they differ in charge type and
solubilization was previously reported for a non-ionic/anionic size of the polar head groups, so that the possible interaction be-
microemulsion system designed for pharmaceutical applications, tween the hydrocarbon chains of two surfactants gets minimized
using mixtures of AOT [sodium bis(2-ethylhexyl)sulfosuccinate] [50]. In this report, we intend to address non-ionic (Brij-58)/ionic
and Arlacel-20 (sorbitan laurate) at different proportions [16]. Also, surfactant (CTAB) mixtures at different compositions that exhibit
it was reported earlier that the solubilization capacity of non-ionic synergism in solubilization of water in w/o mixed surfactant micro-
microemulsions increased upon addition of ionic surfactants [17– emulsions. An attempt has also been made to correlate the solubili-
21], which was attributed to the inhibition of the undulations in zation capacity of water as a function of mixed surfactant
the surfactant layer and the consequent gain in surface area composition with percolation of conductance to underline the
[22,23]. The cosurfactant (short chain lipophilic n-alkyl alcohols) microstructure of these mixed surfactant microemulsions. In addi-
plays an important role by blending with surfactant(s) and parti- tion, solubilization mechanism is suggested in terms of the model
tions between the coexisting aqueous and oleic phases to control proposed by Shah et al. [51,52] (based on curvature of the mixed
the bending elasticity of the interfacial layer offering stability to amphiphilic film separating oil and water and interaction between
the dispersion as well as affecting the droplet dimensions of the microemulsion droplets). Further, microstructure, internal dynam-
microemulsion systems [24]. In order to quantify the composition ics (dynamics of the confined water), and interfacial composition of
of the interfacial layer and the distribution of surfactant and cosur- the mixed interfacial film of these systems have been characterized
factant between the oil/water interface, a simple but elegant meth- by means of the phase study, DLS, FTIR measurements and dilution
od (the Schulman method of cosurfactant titration of the oil/water method as a function of different mixing ratios of surfactant(s). An
interface or the dilution method, which is accomplished by adding in-depth analysis on thermodynamic properties of these micro-
oil at a constant water and surfactant level to destabilize an other- emulsions based on results obtained from the dilution method at
wise stable w/o microemulsion and restabilizing it by adding a req- different temperatures (303, 308, 313, 318 and 323 K) has also been
uisite amount of cosurfactant with constant composition of the presented. An attempt has been made to rationalize the results in a
interface and continuous phase) has been employed by a number comprehensive manner. The results are expected to enrich the basic
of workers [25–38]. understanding of the role of the amphiphiles (both surfactants and
Numerous studies have been reported for understanding of the cosurfactant) and oils (of different chain lengths) on the formation,
interaction and dynamics of the microemulsion droplets in single stabilization, and characterization of the mixed surfactant micro-
and mixed surfactant systems using various techniques, such as emulsions, which is seldom, reported literature.
small-angle X-ray scattering (SAXS), dynamic light scattering
(DLS), pulsed-gradient spin-echo nuclear magnetic resonance 2. Experimental
(PGSE-NMR), steady-state fluorescence spectroscopy, conductance,
and viscosity measurements [39–43]. Of these, electrical conduc- 2.1. Materials
tivity provides a convenient, useful, and accessible tool for probing
the microstructure of microemulsions. Of the different physical Polyoxyethylene (20) cetyl ether (Brij-58, >98.5%) and cetyltri-
properties of microemulsions, percolation of conductance is strik- methylammonium bromide (CTAB, >99%) were products of Fluka,
ing; where many fold (100–1000 times) increase in conductance Switzerland and Sigma–Aldrich, USA, respectively. 1-Pentanol
can take place after a threshold volume fraction of the dispersant (Pn, >98%), heptane (Hp, >99%), and decane (Dc, >99%) were prod-
(water) at a constant temperature or after a threshold temperature ucts of Lancaster, England and Merck, Germany, respectively. The
at a constant composition [44]. Dynamic light scattering is a useful chemicals were used as received. Eosin blue and Sudan IV were
method for detecting the droplet size of microemulsions up to very from Aldrich, USA, and further purified by re-crystallization from
small dimensions, when the scattering contrast (refractive index) 1:1 aqueous methanol. Dyes were dried at 50 °C under vacuum be-
is strong enough for a successful application of this method. Re- fore use. Doubly distilled water of conductivity less than 3 lS cm1
cently, it was shown that DLS can be applied up to very small par- was used in the experiments.
ticle dimensions below 1 nm in size [45]. In order to get a clear
understanding of various interactions in the droplet core, including 2.2. Methods
the type of H-bonding which is operative within the water pool, an
excellent and non-invasive technique viz., Fourier transform infra- 2.2.1. Sample preparation and phase behavior
red spectroscopy (FTIR) has been introduced. Several authors were The samples comprising mixed surfactants (Brij-58 and CTAB)
significantly contributed to the understanding of the water dynam- at different proportions, cosurfactant (Pn), oil (Hp and Dc), and
ics in w/o microemulsion system by studying the state of water water with constant surfactant and cosurfactant mass ratio (S/
using FTIR method [28,46]. CS = 1:2) were formulated in a screw cap glass vials. The samples
In view of these reports, very recently, we have reported the were monophasic, transparent, and stable for over several months.
interfacial composition, thermodynamics of alkanol transfer pro- Phase behavior of the chosen systems was constructed at a fixed
cess, solubilization behavior, transport and microstructural proper- temperature (303 K) using thermostated water bath (accuracy,
ties, and the dynamics of confined water of mixed surfactant (ionic ±0.1 K). The repeat experiments were found to be reproducible
and non-ionic) w/o microemulsions under different physicochemi- with an error limit of ±1%.
cal conditions, by employing the dilution method, conductivity, vis-
cosity, DLS, and FTIR measurements [29,30,47–49]. In continuation 2.2.2. Optical transparency
of our previous studies, we contemplate to undertake studies on the The homogeneity and optical isotropy of mixed microemulsions
formation and precise characterization vis-à-vis the nature of the formed were examined by a cross-polarizer and visual examina-
oil/water interface and water in the confined environment of mixed tion at 303 K.
154 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161

2.2.3. Water solubilization 3. Results and discussion

The initial composition of mixed surfactants (Brij-58 and CTAB
at different proportions), cosurfactant (Pn), and oil (Hp and Dc) for 3.1. Phase behavior
water solubilization studies were 23% (w/w), 46% (w/w), and 31%
(w/w), respectively. The surfactant and cosurfactant mass ratio The pseudo-ternary phase behavior of Brij-58/CTAB/Pn/Hp/
was used 1:2 (w/w). Water was added to each solution in steps water system as a function of different mass ratios of mixed surfac-
with a Hamilton micro-syringe, and solubilization capacity was tant (=5:0 ? 0:5) at fixed surfactant and cosurfactant mass ratio
measured after homogenization as a function of water (wt%) at (=1:2) and at 303 K has been described in Supplementary Material
303 K [28]. (Section 2) with the help of phase diagrams (Fig. S1).

2.2.4. Dye solubilization experiment 3.2. Water solubilization capacity

Dye solubilization experiment [48,51] was performed to esti-
mate the phase separation phenomenon in single (Brij-58 or CTAB) The water solubilization capacity of w/o mixed surfactant
and mixed surfactants (Brij-58 and CTAB) microemulsion by water microemulsions is one of the important parameters not only from
soluble dye Eosin blue and oil soluble dye Sudan IV at 303 K. the view point of its wide applications, but also it determines the
size of the water core, the rigidity or flexibility of the oil/water
interface, and morphology of the surfactant aggregates. Further,
2.2.5. Conductivity measurements studies emphasized on understanding of the factors that govern
The conductivity measurements were performed using Mettler solubilization phenomenon in these systems, are of fundamental
Toledo (Switzerland) digital conductivity bridge (accuracy ± 1%). importance [53,54].
The temperature was kept constant within ±0.1 K by circulating The solubilization of water in mixed Brij-58:CTAB/Pn/Hp (Dc)
thermostated water, through a jacketed vessel containing the solu- microemulsions as a function of composition of mixed surfactants
tion. The electrical conductivity of the selected mixed microemul- at 303 K has been presented in Fig. 1. It is evident from Fig. 1 that
sions was measured at 303 K. The repeatability and the accuracy of w/o single Brij-58 (Brij-58:CTAB = 5:0, w/w) can solubilize water
the measurements were ±0.3% and ±1%, respectively. up to 17 and 15 wt% in Hp and Dc, respectively, at constant surfac-
tant/cosurfactant ratio (1:2, w/w). While Brij-58 has been blended
2.2.6. Dilution method with spectrophotometric measurements with CTAB at different proportions (for example, Brij-58 and
Details of the dilution method were provided in our previous re- CTAB = 4:1; 3:2; 2:3; 1:4, w/w), the water solubilization capacity
ports [29,30,37,38]. The procedure of this experiment at different increases up to a maximum value at a certain composition of the
physicochemical conditions with theoretical backgrounds (i.e., ba- mixed surfactants (Brij-58:CTAB = 2:3, w/w), beyond which (Brij-
sics of the dilution method and evaluation of thermodynamic 58:CTAB = 1:4 and 0:5, w/w) the solubilization capacity further de-
parameters) has been presented in Supplementary Material creases with increasing CTAB. A plausible explanation for this
(Section 1). trend in composition-dependent solubilization phenomenon in
mixed microemulsions is not straightforward. However, solubiliza-
tion of water in w/o microemulsion system depends upon many
2.2.7. DLS measurements
factors, for example, type of surfactant (as major amphiphile)
DLS measurements were carried out using a Zetasizer Nano
and cosurfactant (or a second surfactant as auxiliary amphiphile),
ZS90 (ZEN3690, Malvern Instruments Ltd, UK). A He–Ne laser of
size of the polar head group and hydrocarbon moiety of both
632.8 nm wavelength was used, and the measurements were made
amphiphiles, the composition, oil type, etc. [53–55]. But the main
at a scattering angle of 90° at 303 K. Temperature was controlled
driving force of such solubilization is the spontaneous film curva-
by inbuilt Peltier heating–cooling device (±0.1 K). Refractive index
ture (H0) (the curvature that the amphiphilic film would like to at-
of each solution was recorded with an ABBE type refractometer, as
tain) and the elasticity of the amphiphilic film [52]. If the
it was required as an input in determining the size of the micro-
interfacial curvature and the bending elasticity are fixed, solubili-
emulsion droplet by DLS technique. Viscosity data, as obtained
zation can be maximized by minimizing the interfacial bending
from viscosity measurements, were used in processing DLS data.
Samples were filtered thrice using Milipore™ hydrophobic mem-
brane filter of 0.25l pore size. Hydrodynamic diameter (Dh) of
the microemulsion droplets was estimated from the intensity 16
autocorrelation function of the time-dependent fluctuation in 50

intensity. According to Stokes–Einstein equation, Dh is defined as

[49]
wt% of water (φ)

14
40
HLB mix

Dh ¼ kB T=3pgD ð1Þ

where kB, T, g, and D indicate the Boltzman constant, temperature,

30 12
viscosity, and diffusion coefficient of the solution, respectively. To
check the reproducibility of the results, at least 6 measurements
were done.
20
Hp 10
2.2.8. FTIR measurements Dc
FTIR absorption spectra were recorded in the wave number
(5 : 0) (4 : 1) (3 : 2) (2 : 3) (1 : 4) (0 : 5)
range of 400–4000 cm1 with a Shimadzu 83000 spectrometer (Ja-
pan) using a CaF2-IR crystal window (Sigma–Aldrich) equipped Brij-58 : CTAB
with Presslock holder with 100 number scans and spectral resolu- Fig. 1. Water solubilization capacity (wt% of water) and HLBmix of mixed Brij-58/
tion of 4 cm1 at 303 K. Deconvolution was carried out with the CTAB/1-pentanol/Hp or Dc microemulsions as a function of different mass ratios of
help of Origin 6.0 software. mixed surfactant at 303 K (Hp: filled triangle and Dc: open circle).
 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161 155

stress of the rigid interface and the attractive interdroplet interac- et al. [21] reported on the effect of ionic surfactant (sodium laurate)
tion among droplets [56]. The solubilization of a microemulsion of on the solubilization capacity of w/o microemulsions derived from
a fluid interface can be increased by increasing the interfacial rigid- sucrose ester (water/sucrose dodecanoate/decane). According to
ity and decreasing the natural radius. Alcohol (cosurfactant) is also them, increase in the solubilization of water by the addition of ionic
an essential factor in promoting interfacial fluidity for the forma- surfactant was attributed to the increase in repulsion between sur-
tion of microemulsion [51–54]. It can be seen from Fig. 1 that factant layers. At high concentration of ionic surfactant, enhance-
water solubilization capacity reaches maxima at the close proxim- ment in solubilization of water was lost due to the screening of
ity of the middle range composition of Brij-58 and CTAB (i.e., in be- charged groups.
tween 3:2 and 2:3, w/w) in both oils. These results clearly indicate Further, it is evident from Fig. 1 that Dc-based system shows
that the addition of CTAB to the non-ionic microemulsion (water/ significantly lower water solubilization capacity compared to Hp-
Brij-58/Pn/Hp or Dc) results in obtaining synergism (or maximiza- based system. Actually increasing oil chain length would gradually
tion) of water solubilization at a specified composition (mentioned reduce the cohesive interaction between the hydrocarbon chains of
earlier). The maximization of solubilization capacity of water in amphiphiles present at the interface and decrease the interfacial
mixed microemulsions can be interpreted as a result of counteract- rigidity, due to decreasing oil penetration. This is in turn decrease
ing effects of the attractive interdroplet interaction of the fluid the water solubilization capacity in Dc [51,52].
interfaces and bending stress of the rigid interfaces [52]. According In the present study, phase separation upon the addition of ex-
to Israelachvili, the molecular packing is determined by a balance cess water in Brij-58/CTAB/oil(s)/water microemulsion systems
between the repulsive force of hydrophilic moieties and the attrac- has been examined by employing dye solubilization process in
tive forces of lipophilic moieties [57]. Since non-ionic, Brij-58 has both oils [48,51,54]. The objective for the dye solubilization exper-
20 POE in hydrophilic moieties, its effective cross-sectional area iment is to investigate whether the solubilization process is gov-
per hydrophilic unit should be larger than that of an ionic CTAB erned by the curvature effect or the interdroplet interaction
[48,58]. Hence, the repulsion between the hydrophilic groups is re- effect [53]. A brief description of dye solubilization experiment
duced when a part of Brij-58 is replaced by CTAB, which results in a has been presented in Supplementary Material (Section 3).
more dense packing of mixed surfactants at the interface [59]. This
is why the added CTAB induces rigidity to the surfactant layer in 3.3. Conductivity measurements
Brij-58 microemulsions.
Further, attainment of maximum water solubilization using a It is known that electrical conductivity measurements can be
mixture of ionic/non-ionic surfactants can be explained in the light used to predict qualitatively the interaction between the droplets
of hydrophilic–lipophilic balance (HLB) of individual surfactants. and thus stability of microemulsion. For example, appearance of
The HLB is one of the most common methods to correlate surfac- an electrical percolation process indicates the existence of large
tant structure with their effectiveness as emulsifiers. The HLB va- attractive interaction between droplets [28,53,58].
lue of a surfactant indicates how surfactant behaves in a solution In this section, an attempt has been made to correlate the max-
and also represents the capability of surfactant solution to solubi- imum water solubilization with percolation of conductance to
lize other substances [60]. Huibers and Shah [61] reported earlier underline the microstructure of these mixed surfactant micro-
that the best solubilization for the mixture occurs when HLB values emulsions. If the droplets are of non-interacting hard sphere type,
of its components lie in 9–13 regions. Further, they mentioned that no significant increase in conductance occurs with increasing
good solubilization occurs when HLB of the surfactant mixture falls water content at constant temperature or with increase in temper-
in a certain HLB region, which should be neither very water soluble ature at fixed water content. But if the interfaces of the droplets are
nor oil soluble. As a result of attainment of these conditions, the fluid enough to coalesce during these collisions followed by mate-
surfactants are more favorable to partition at the interface. In such rial exchange and fusion, a sharp rise in conductance is evidenced
a case, solubilization for the mixtures is better than that of either [53]. In the present investigation, conductance studies have been
component. Hence, HLB of the present systems at the mixed com- carried out for mixed surfactant microemulsion systems wherein
positions (i.e., HLBmix) has been evaluated using the concept of solubilization maxima (in the vicinity of equimolar composition,
Acosta et al. [62], i.e., at Brij-58:CTAB = 2:3 and 3:2, w/w) are observed. The samples
from both sides of the corresponding maxima, i.e., from the
HLBmix ¼ ðX 1 HLB1 þ X 2 HLB2 Þ ð2Þ
ascending branches and the descending branches are chosen.
where X1 and X2 are the mole fraction of surfactant 1 and surfactant The conductivity of mixed water/Brij-58/CTAB/Pn/Hp or Dc
2 in the mixture, respectively. HLB1 and HLB2 are the hydrophilic– microemulsion systems at different compositions (Brij-
lipophilic balance of surfactant 1 and surfactant 2, respectively. In 58:CTAB = 5:0; 4:1; 3:2; 2:3; 1:4; 0:5, w/w) [S:CS = 1:2 (w/w)] at
these calculations, HLBs of CTAB [63] and Brij-58 [64] are 10 and 303 K as a function of wt% of water has been determined and de-
16, respectively. A graphical illustration of HLBmix versus Brij- picted in Figs. S2A–S2F. Samples chosen from the ascending branch
58:CTAB (w/w) has been represented in Fig. 1. It is evident from (i.e., at Brij-58:CTAB = 5:0 ? 2:3, w/w) exhibit a nonlinear sharp
Fig. 1 that maximum water solubilization occurs at HLBmix equals enhancement in conductivity with the addition of water, which
to 12–13 regions. According to Huibers and Shah [61], synergism signifies the volume-induced percolation in conductance
in maximum water solubilization in w/o microemulsion was ob- (Figs. S2A–S2D). The critical value for sharp enhancement in con-
served at HLBmix equals to 9 for a mixture of nonylphenylethoxylate ductivity with the addition water is considered as volume-induced
surfactants (C9PhE1.5 and C9PhE12) in cyclohexane. Further, syner- percolation threshold (/p). Such percolation in the present systems
gistic effect must cause the majority of the two surfactants to pref- (i.e., at ascending branch of Fig. 1) shows that the interface of the
erentially partition at the interface that allows larger interfacial droplets is fluid enough to coalesce during the collisions followed
area and thus high levels of solubilization [65]. While microemul- by material exchange and fusion. Further, it is evident that /p in-
sions were composed of equal amounts of surfactants, the synergis- creases (i.e., percolation process is retarded) with decrease in con-
tic effect reported to be more pronounced [65]. In this report, the tent of Brij-58 or increase in content of CTAB. On the other hand, no
synergistic effect has been achieved at Brij-58 and CTAB mass ratio sharp enhancement in conductivity vis-à-vis percolation phenom-
of 2:3 and 3:2. Similar result was reported by Fanun for water/pro- enon is observed in the descending branch of the solubilization
pylene glycol/sucrose monolaurate/ethoxylated mono-di-glyceride/ maximum (i.e., at Brij-58:CTAB = 1:4 ? 0:5, w/w) (Figs. S2E–S2F).
peppermint oil/ethanol microemulsion systems [65]. Rodríguez Further, at a composition of Brij-58:CTAB = 0:5, w/w, i.e., single
156 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161

CTAB-derived microemulsion systems, a bell-shaped conductivity Table 1

profile with flattened maxima is obtained in both oils (Fig. S2F). Thermodynamic parameters of transfer of Pn from Hp (or, Dc) to the interface of
microemulsion containing 2 ml oil, 0.5 mmol of surfactant and at fixed water content
Further, discussion in this aspect has been dealt in Supplementary (2.75  102 mol) with varying compositions (Brij-58:CTAB, w/w) and temperatures.a
Material (Section 4).
Temperature (K) DG0t (kJ/mol) DH0t (kJ/mol) DS0t (J/mol/K)
3.4. Dilution method Brij-58:CTAB = 5:0
303 2.61 (2.43) 15.74 (10.10) 51.98 (33.36)
The interfacial composition of water/Brij-58/CTAB/Pn/Hp or Dc 308 2.94 (2.66) 17.14 (12.12) 55.68 (39.37)
313 3.25 (2.90) 18.49 (14.07) 59.12 (44.99)
microemulsion systems with different mixing ratios of the surfac- 318 3.63 (3.21) 19.81 (15.97) 62.33 (50.24)
tants (Brij-58:CTAB = 5:0, 4:1, 3:2, 2:3, 1:4 and 0:5, w/w) at a fixed 323 4.00 (3.51) 21.08 (17.80) 65.29 (55.15)
amount of mixed surfactants (5  104 mol) and water content Brij-58:CTAB = 4:1
(2.75  102 mol), and at five different temperatures of 303 K, 303 1.20 (1.63) 35.71 (21.41) 117.86 (70.68)
308 K, 313 K, 318 K, and 323 K has been evaluated by the dilution 308 1.76 (1.96) 31.14 (17.76) 101.13 (57.68)
method. From the data collected, graphs were constructed by plot- 313 2.26 (2.29) 26.72 (14.22) 85.40 (45.46)
318 2.71 (2.49) 22.44 (10.79) 70.61 (33.98)
ting na/ns against no/ns according to Eq. (S2). Representative illus-
323 3.05 (2.69) 18.29 (7.47) 56.68 (23.18)
tration is shown in Fig. S3 (Supplementary Material). The
Brij-58:CTAB = 3:2
calculated values of compositional variations of amphiphiles (sur-
303 2.68 (2.13) 3.03 (1.60) 10.02 (5.31)
factants and Pn) at the interface (nia =ns ) at surfactant compositions 308 2.78 (2.18) 3.78 (0.75) 12.31 (2.48)
mentioned above with varying temperatures are illustrated in 313 2.89 (2.23) 4.51 (0.05) 14.45 (0.15)
Figs. S4A and S4B. The distribution of the cosurfactant (Pn) be- 318 3.02 (2.25) 5.22 (0.85) 16.45 (2.64)
tween the oil and the interface imparts stability to the dispersion. 323 3.15 (2.27) 5.91 (1.61) 18.32 (4.97)

The distribution constant (Kd) at different temperatures lead to the Brij-58:CTAB = 2:3
evaluation of energetic of the transfer process. To gain insight into 303 3.66 (2.34) 6.44 (2.70) 21.20 (8.89)
308 3.62 (2.33) 6.35 (3.08) 20.57 (9.98)
the thermodynamic stability of these systems as a function of 313 3.57 (2.32) 6.26 (3.45) 19.97 (11.01)
different mixing ratios of the surfactants and oil chain length, stan- 318 3.53 (2.29) 6.18 (3.80) 19.39 (11.95)
dard Gibbs free energy change of transfer of alkanol from oil to the 323 3.49 (2.27) 6.09 (4.15) 18.85 (12.83)
interface (DG0t ) has been computed according to Eq. (S4) and pre- Brij-58:CTAB = 1:4
sented in Figs. S4A and S4B (Supplementary Material) and Table 1. 303 4.89 (3.73) 14.34 (10.49) 47.28 (34.61)
Figs. S4A and S4B represent three-dimensional profiles of nia =ns and 308 4.67 (3.63) 19.41 (9.55) 62.97 (30.99)
313 4.44 (3.53) 24.32 (8.64) 77.65 (27.58)
DG0t as a function of both the compositions and temperatures in
318 4.03 (3.47) 29.07 (7.76) 91.38 (24.37)
Hp and Dc, respectively. 323 3.63 (3.40) 33.68 (6.90) 104.22 (21.35)
It reveals from Figs. S4A and S4B and Table 1 that DG0t values for
Brij-58:CTAB = 0:5
these systems are negative at experimental temperatures and indi- 303 6.76 (5.21) 29.88 (16.91) 98.55 (55.77)
cate that water/Brij-58/CTAB/Pn/Hp or Dc microemulsion systems 308 6.39 (5.04) 29.04 (15.22) 94.22 (49.39)
form spontaneously no matter which oil or composition was used. 313 6.02 (4.87) 28.22 (13.59) 90.12 (43.39)
The observed DG0t (kJ/mol) values vary in the range of – (1.5–6.8). 318 5.68 (4.76) 27.44 (12.01) 86.22 (37.74)
323 5.34 (4.65) 26.67 (10.48) 82.52 (32.41)
Similar variations were also reported by our group earlier for
mixed anionic/non-ionic and cationic/non-ionic surfactant-based a
The error limits of DG0t , DH0t and DS0t are ±3%, ±5% and ±8%, respectively.
systems stabilized in both hydrocarbon (Hp or Dc) as well as polar
lipophilic oil (IPM) [29,30].
can be surfactant specific, which was reported earlier by Bisal et al.
3.4.1. Influence of composition, temperature, and oil on nia =ns and [68]. Similar types of results were also reported by Moulik et al.
DG0t [31], Hait and Moulik [25], Kumar and Kabir-ud-Din [67], Paul
It is evident from Figs. S4A and S4B that both of the values of and Nandy [36] and De et al. [27].
nia =ns and DG0t are found to be higher for (single) CTAB-stabilized Further, it has been observed that the values of nia =ns and DG0t
systems (Brij-58:CTAB = 0:5, w/w) compared to (single) Brij-58 did not follow any straight-forward trend as a function of mixing
stabilized systems (Brij-58:CTAB = 5:0, w/w) in both oils at all tem- ratios of the surfactants for any of these systems (Figs. S4A and
peratures. The differential behavior of the surfactants toward the S4B). It has been observed that nia =ns value first decreases upon
above phenomenon may reflect the degree of favorable/unfavor- the addition of CTAB to Brij-58 stabilized systems (mixed Brij-
able interaction between the surfactant(s) and the alkanol [25] 58:CTAB = 5:0 ? 4:1, w/w) and after that increases gradually
and can be explained in the following way: it was reported that (mixed Brij-58:CTAB = 4:1 ? 0:5, w/w) in both oils at all tempera-
the interaction between Brij-58 and Pn is of dipole–dipole or di- tures. In other words, nia =ns values show minima at composition
pole-induced dipole or London dispersion type, because of the Brij-58:CTAB = 4:1 (w/w). The interfacial population of cosurfac-
presence of uncharged or neutral hydroxyl groups (Pn) and POE tant vis-à-vis stability of the mixed microemulsion systems is
chains (Brij-58), whereas the interaction between CTAB and Pn is mainly determined by the repulsions between head groups, includ-
of ion–dipole type because of the presence of uncharged or neutral ing electrostatic origin for quaternary ammonium head groups and
hydroxyl groups (Pn) and charged quaternary ammonium groups steric origin for oxyethylene head groups [69]. When CTAB is ini-
[NðCH3 Þþ 3 ]. Ion–dipole interaction is very strong compared to di- tially added into Brij-58 stabilized systems, the steric repulsion be-
pole–dipole or dipole-induced dipole or London dispersion interac- tween head groups of Brij-58 decreases with increasing content of
tions [66]. Therefore, the association between Pn and CTAB is much CTAB (XCTAB), but the introduction of quaternary ammonium head
more favorable than Pn and Brij-58. As Pn molecules are slightly groups of CTAB to Brij-58 surfactant molecules brings about a lar-
deprotonated, which assist Pn to associate strongly with cationic ger electrostatic repulsion between the charged head groups and
CTAB than non-ionic Brij-58, and result in stronger association be- subsequently decreases the area required per surfactant head
tween Pn with CTAB[13]. As a result, both nai /ns and DG0t for CTAB- group, allowing the mixed systems to adopt a conformation with
stabilized systems are higher compared to Brij-58 stabilized sys- smaller curvature [70]. As a result, nai /ns values of the mixed sys-
tems. Hence, it can be concluded that the interfacial alkanol affinity tems increase from Brij-58:CTAB = 4:1 ? 0:5, w/w. However, at
 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161 157

Brij-58:CTAB = 5:0, w/w (single Brij-58), the electrostatic repulsion been illustrated as Fig. 2A and B in Hp and Dc, respectively. These
is absent and nia =ns is mainly controlled by steric repulsion be- curves are not straightforward upon the addition of ionic surfac-
tween head group of Brij-58 [70]. Hence, it can be concluded that tant (CTAB) to the non-ionic surfactant (Brij-58) under various
the effective binding between CTAB and/or Brij-58 and Pn at the physicochemical conditions.
interface increases in the order of composition, (Brij-58:CTAB, w/
w): 4:1 < 3:2 < 2:3 < 1:4, which corroborates well with the degree 3.4.2.1. Pure Brij-58 and CTAB microemulsion systems. For pure CTAB
of spontaneity of the transfer process. system (Brij-58:CTAB = 0:5, w/w), the overall transfer process is
It reveals from Figs. S4A and S4B that both nia =ns and DG0t exothermic at all experimental temperatures with negative entro-
values increase with increase in temperature for pure Brij-58 py change (order) in both oils. So, Pn causes release of heat during
(Brij-58:CTAB = 5:0, w/w) and Brij-58 rich (Brij-58:CTAB = 4:1, w/ transfer process. Consequently, the negative entropy change may
w) stabilized systems, whereas reverse trend is observed for pure be due to more organization of the interface and its surroundings.
CTAB (Brij-58:CTAB = 0:5, w/w) and CTAB rich (Brij-58:CTAB = 1:4, Therefore, the interface composed of Pn and CTAB is to some extent
w/w) stabilized systems in both oils. This phenomenon can be ex- orderly. Such negative enthalpy and entropy changes were ob-
plained as follows. The effect of temperature on the solubility and served by Wang et al. [34] for water or aqueous HCl/cetyltrimeth-
hydration of ionic surfactant is opposite to that of non-ionic surfac- ylammonium chloride (CTAC)/alkanol/diesel oil, De et al. [27] for
tant. With increase in temperature, dissociation of the ionic head water/DTAB/alkanol/Hp and Digout et al. [35] for CPC derived
group increases and the ionic surfactant becomes more hydrophilic microemulsion systems stabilized in different chain length of
at higher temperatures [71]. A higher degree of dehydration cosurfactants (Bu, Pn, Hx) and oils (pentane/octane/decane). Hait
around the head group region of the non-ionic surfactant apprecia- and Moulik [25] and Mohareb et al. [33] reported that the sponta-
bly imparts to the molecules an increase in hydrophobicity, there- neity of the process of alkanol transfer associated with positive
by leading to unsuitable molecular geometry at higher DH0t and DS0t values for CTAB/1-butanol/IPM/water system. The ob-
temperatures [72,73]. Addition of alcohol (herein, Pn) effectively served difference in thermodynamic properties for CTAB-stabilized
changes the originally unfavorable packing geometry of the surfac- system may be due to the basic difference in type of oils used (for
tant molecules and produces a stable surfactant/alcohol mixed example, ester of fatty acids [25,33] and long chain alkanes in the
interfacial film [26]. Hence, with increasing temperature, nai /ns val- present study). For pure Brij-58 stabilized system (Brij-
ues increase for pure Brij-58 and Brij-58 rich stabilized systems. 58:CTAB = 5:0, w/w), the process is endothermic with absorption
However, an interesting result has been observed in the vicinity of heat at all experimental temperatures with positive entropy
of equimolar composition (i.e., Brij-58:CTAB = 3:2 and 2:3, w/w) change (disorder) in both oils. The non-ionic surfactant produces
that both nia =ns and DG0t are found to be invariant with increase insignificant ion-dipolar effect with the alkanol showing endother-
in temperature, i.e., temperature-insensitive microemulsions have mic transfer from bulk oil to the interface [33]. The desolvation of
been formed in both oils. The increased lipophilicity of Brij-58 is head group of Brij-58 during the transfer of Pn in the oil is respon-
suppressed by the increased hydrophilicity of CTAB at elevated sible for both positive enthalpy and entropy change [38]. Similar
temperatures, and in consequence, no variation in both of these observation was also reported by De et al. [27] for Tween-20/Bu
parameters has been found in vicinity of equimolar composition. or Pn/Hp/water and Kundu et al. [29] for Brij-58 or Brij-78/Pn/Hp
Temperature-insensitive microemulsion formation in the vicinity or Dc/water microemulsion systems. However, Bardhan et al.
of equimolar composition is further confirmed by the analysis of [30] reported an opposite behavior of pure Brij-35-based systems
the results of other thermodynamic parameters (DH0t and DS0t ) stabilized in IPM. The opposite behavior toward temperature of
and has been dealt in subsequent paragraph. ionic and non-ionic surfactants might be responsible for such
DG0t values are more negative in Hp continuum than Dc contin- variation in enthalpy and entropy values with temperature [74].
uum at all compositions of the mixed surfactant microemulsions, The negative entropic change of pure CTAB systems is due to the
indicating the process to be more favorable for the former than better organization of the interface and its surroundings. The
the latter. It is suggested that an effective binding (or, a strong inter- interfacial film composed of Pn and CTAB indicates more ordered
action) between amphiphiles (Brij-58/CTAB) and alkanol (Pn) at the at all experimental temperatures than Brij-58 stabilized systems,
interface, indicating spontaneity of the transfer process becomes which corroborated well with the spontaneity of the transfer
more favored in lower chain length of oils. It may be due to larger process.
penetration of Hp (C7) due to shorter chain length than Dc (C10) into
the mixed interfacial film of these systems. It is quite likely that the 3.4.2.2. Mixed compositions of Brij-58 and CTAB microemulsion
interfacial fluidity may increase with increase in oil chain length systems. At compositions in between two extremes (i.e., Brij-
and thereby increasing alcohol partitioning at the interface. Such 58:CTAB = 4:1, 3:2, 2:3 and 1:4, w/w) in both oils, DH0t and DS0t val-
an increase in interfacial fluidity results in inelastic collisions be- ues are found to be both positive and negative, respectively, at all
tween droplets, leading to formation of transient dimmers and en- studied temperatures. It has been observed from Fig. 2A and B that
hances apparent interdroplet interaction for Dc-based systems. At both DH0t and DS0t values are positive at Brij-58 rich composition
sufficiently strong interdroplet interaction, the microemulsion (Brij-58:CTAB = 4:1 and 3:2, w/w) and negative at CTAB rich com-
droplets stabilized in Dc are less stabilized compared to Hp-based position (Brij-58:CTAB = 2:3 and 1:4, w/w) in both oils (with some
systems [52]. Similar observations were reported by Moulik et al. exception at Brij-58:CTAB = 3:2, w/w in Dc). A positive contribution
[31], Paul and Nandy [36], Mitra et al. [38], and Kundu et al. [29]. toward DH0t can be interpreted as the energy required to release the
structural water from the hydration layer around the hydrophilic
3.4.2. Enthalpy and entropy of the transfer process domain. An additional contribution arises from the liberation of
Due to nonlinear dependence of (DG0t /T) on (1/T) (Fig. S5, Sup- water molecules from the water cage around the hydrophilic moi-
plementary Material) in terms of a two degree polynomial ety of the surfactants. The negative contribution toward DH0t is
equation, at each composition of surfactant(s) (Brij- identified with the transfer of the surfactant tail from water to
58:CTAB = 5:0 ? 0:5, w/w), five values of DH0t and DS0t at five tem- liquid hydrocarbon state in the interfacial layer and restoring the
peratures have been evaluated according to Eqs. (S7) and (S8) and hydrogen bonding structure of the water around the surfactant
presented Table 1. Three-dimensional profiles on the dependence head group [75]. However, insignificant changes in these
of DH0t and DS0t as a function of both the compositions (Brij- thermodynamic parameters with temperature have been observed
58:CTAB = 5:0 ? 0:5, w/w) and temperatures (303 K?323 K) have in the vicinity of equimolar composition (Brij-58:CTAB = 3:2 and
158 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161

Fig. 2. Plot of DH0t and DS0t versus different mass ratios of mixed surfactant (Brij-58 and CTAB) for w/o microemulsion systems comprising 5  104 mol of total mixed
surfactant, 2.75  102 mol water, 2 ml of heptane (Plot: A) and decane (Plot: B) stabilized by 1-pentanol at five different temperatures [303 K (open triangle), 308 K (open
square), 313 K (open circle), 318 K (open star), 323 K (open pentagon)].

2:3, w/w), leading to the formation of isenthalpic and isentropic 3.5.1. Effect of composition on Dh
microemulsion systems. Similar observation was also reported It reveals from DLS measurements that Dh decreases signifi-
earlier for mixed surfactant microemulsion systems [29,30,37,76]. cantly with the increase in cationic surfactant (CTAB) in the mixed
Further, it has been observed that both DH0t and DS0t values are more systems (Brij-58:CTAB = 5:0 ? 0:5, w/w) in both oils at each tem-
positive or more negative in Hp stabilized systems compared to Dc perature. It can be argued as follows. The droplet sizes of the mixed
stabilized systems at all compositions. The difference in enthalpic surfactant microemulsion systems (herein, water/Brij-58/CTAB/Pn/
and entropic behaviors between these two oils may be attributed Hp or Dc) is mainly governed by the repulsion between head
to the difference in alkyl chain length between two oils, as reported groups of the surfactants (viz. steric origin for oxyethylene head
earlier [29,37]. It is apparent that different phenomena associated groups and electrostatic origin for quaternary ammonium head
with the transfer process of Pn, viz., changing aggregation number, groups) and also by the packing parameters of the surfactants
solvation–desolvation of non-ionic surfactant, electrostatic and ste- forming the mixture. As discussed above, the initial effect of
ric interactions between hydrophilic head groups of CTAB and Brij- introducing an ionic surfactant into a non-ionic surfactant-based
58, steric and other non-specific processes contribute their shares system results in increase in electrostatic repulsive interactions
to DH0t and DS0t values [77]. Hence, it can be inferred that the overall between head groups and, thus decrease the droplet size [78,79].
mixed surfactant microemulsion forming systems can end up with From packing parameter consideration, it can be explained as
both absorption or release of heat and with ordered or disordered follows. The droplet size of microemulsion depends upon the
state, depending on their chemical compositions (i.e., the constitu- flexibility of the interface, which in turn is related to the surfactant
ent surfactant(s) with their configuration, content, and type of oil) packing parameter (P) given by the relation, P = v/al, where ‘‘v’’ and
and thermal condition. ‘‘l’’ are the volume and the length of hydrophobic chain,
A linear thermodynamic correlation between enthalpy (DH0t )
and entropy (DS0t ) for these systems at 303–323 K (with correlation
16
of coefficients of 0.9999 at each temperature) has been observed. 16
A
Such figures are not exemplified here. The compensation tempera- 14
Dh/nm

tures (Tcomp) at each experimental temperature are presented in 14 12

Table S1. It was reported that the compensation temperatures 10

(Tcomp) are minorly deviated from the experimental temperatures 8

12
[25,29,31,35]. The linear correlation suggested that a mutual 6
Dh/nm

balance is established between enthalpy and entropy during the (5 : 0) (4 : 1) (3 : 2) (2 : 3) (1 : 4) (0 : 5)

alkanol transfer process from the oleic phase to the oil/water 10 Brij-58 : CTAB
interface. The extraordinary correlation between enthalpy and en-
tropy is mainly due to the experimental errors than to chemical
8 303K
variations [36]. 308K
313K
318K
6
323K
3.5. Dynamic light scattering (DLS) measurement

(5 : 0) (3 : 2) (2 : 3) (1 : 4)
The hydrodynamic diameter (Dh) or droplet size of water/Brij- (4 : 1) (0 : 5)

58/CTAB/Pn/Hp or Dc microemulsions was measured by employing Brij-58 : CTAB

the dynamic light scattering (DLS) technique at different tempera-
Fig. 3. Plot Dh as a function of mixed surfactant composition for water/Brij-58/
tures (303, 308, 313, 318 and 323 K). The same compositions were CTAB/Pn/Hp or Dc microemulsion systems comprising 5  104 mol of total mixed
chosen for DLS measurements as employed for the dilution meth- surfactant, 2.75  102 mol of water, 2 ml of Hp or Dc (Inset A) at different
od. The results are depicted in Fig. 3. temperatures (303 K ? 323 K).
 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161 159

respectively, and ‘‘a’’ the area of polar head group of the surfactant. bond network dynamics regardless of the nature of the interface in
For a mixed surfactant microemulsion (herein, Brij-58/CTAB), the w/o microemulsion [85]. But still significant differences in respect
effective packing parameter (Peff) can be expressed according to of the dynamical nature of water in reverse micelle or w/o micro-
the following relation as obtained by Evans and Ninham [80]: emulsion have been reported for ionic and non-ionic surfactants.
Levinger et al. [86,87] reported that the solvation dynamics of
Peff ¼ ½ðxv =alÞA þ ðxv =alÞB =ðxA þ xB Þ ð3Þ
anionic surfactant (AOT)-based reverse micelle are slower than
where xA and xB are the mole fractions of CTAB and Brij-58 present non-ionic surfactant (Brij-30)-based reverse micelle from ultrafast
at the interface, respectively. It was reported earlier that head group solvation dynamics measurements. This difference in solvation
area of Brij-58 and CTAB are 1.81 and 0.50 nm2[26,29]. Hence, v/al dynamics may be attributed to the difference in interaction be-
of Brij-58 is smaller than that of CTAB. It follows from Eq. (3) that tween water and charged and uncharged head groups of the sur-
Peff reaches a higher value than that of P due to the presence of CTAB factants [46]. An interesting question that emerges from these
at the mixed interface, and consequently, the mixed systems attain reports is that whether one can tune the dynamics of the confined
lower droplet size than the single Brij-58/oil(s) system. water in w/o microemulsions by mixing of two surfactants with
different charge types. Hence, in order to get a clear picture about
3.5.2. Effect of oil on Dh the dynamics of the confined water vis-à-vis type of hydrogen
It can be observed from Fig. 3 and Fig. 3 (inset A) that droplet bonding network within the water pool of w/o mixed microemul-
sizes in Dc continuum are larger compared to Hp continuum and sion systems (water/Brij-58:CTAB/Pn/Hp) as a function of mixed
can be explained in the following way. It is easier for the solvent surfactant composition (Brij-58:CTAB = 5:0 ? 0:5, w/w) at fixed
with smaller molecular volume (herein, Hp) to penetrate into the water content (2.75  102 mol), surfactant and cosurfactant mass
hydrocarbon chains of the surfactant(s) existing at the interfacial ratio (1:2) and temperature (303 K), we employ a simple non-inva-
film of the w/o microemulsions and, consequently, increases the sive technique viz. Fourier transform infrared spectroscopy (FTIR).
packing parameter (P = v/al) of the surfactant and decrease the In any reverse micelle or w/o microemulsion formulation, the O–H
diameter of the microdroplets [81]. Similar observation was also stretching vibration is a good probe to get an insight into the states
reported earlier by Liu et al. [58] . of water trapped or confined inside the micellar core. A number of
studies have been explored the properties of encapsulated water in
3.5.3. Effect of temperature on Dh a range of sizes and types of w/o microemulsions by FTIR measure-
Again, it is evident from Fig. 3 that droplet size (Dh) has been ment [28,46,47,85,88]. Small amount of Pn has been used as struc-
found to decrease with increase in temperature in pure Brij-58 ture forming cosurfactant in the present study as mentioned
(Brij-58:CTAB = 5:0, w/w) and Brij-58 rich (Brij-58:CTAB = 4:1, w/ earlier. Recently, different states of water species have been re-
w) compositions, whereas a reverse effect of temperature on drop- ported in single surfactant (CTAB or polyoxyethylene (10) oleyl
let size has been observed for pure CTAB (Brij-58:CTAB = 0:5, w/w) ether-based) and mixed surfactant [CnTAB + C16E20 (1:1),
and CTAB rich (Brij-58:CTAB = 1:4, w/w) compositions of the sys- n = 12 ? 18] w/o microemulsions in presence of cosurfactant (alk-
tems in both oils. Further, a negligible effect of temperature on anol) [28,47]. However, the influence of alkanol vibration on the
droplet size has been observed in close proximity of equimolar intensity of O–H stretching vibration of confined water cannot be
composition of the mixed surfactants (Brij-58:CTAB = 2:3 and ignored. To get rid of the IR intensity due to O–H stretching vibra-
3:2, w/w). This trend can be explained in the following way. It tion of Pn molecule, the spectra of Pn at same concentration have
has been observed that nia =ns values (i.e., compositional variation been subtracted from the spectral intensity of O–H stretching band
of Pn at the interface) increase with increase in temperature in at corresponding x, and the differential spectra have been ana-
Brij-58 rich compositions (Brij-58:CTAB = 5:0 and 4:1, w/w), lyzed [47]. Different types of hydrogen bonded water molecules
whereas reverse trend is observed for CTAB rich compositions exist in reverse micelles or w/o microemulsions and can broadly
(Brij-58:CTAB = 0:5 and 1:4, w/w). However, in the vicinity of equi- be classified into two major classes, namely, head group bound
molar composition (Brij-58:CTAB = 3:2 and 2:3, w/w), nia =ns has and bulk-like water molecules, as reported earlier by both FTIR
been found to be invariant with increase in temperature in both and solvation dynamic techniques [46,47,88]. Hence, the differen-
oils (Fig. S4). Pn molecules are mainly located at the micellar inter- tial spectra obtained in the present study as described above have
face due to their negligible solubility in water [29]. The total inter- been deconvoluted into two peaks at 3500 and 3300 cm1, cor-
facial area becomes larger as alcohol molecules are incorporated at responding to the O–H stretching frequency of the surfactant head
the mixed surfactants interface, which results in increase in the group bound and bulk-like water molecules (droplet core water),
number of droplets and subsequently, the droplet size shrinks. respectively [46,47]. A representative result is depicted in Fig. S6
[82]. Further, droplet size depends on the packing parameter (P) (Supplementary Material). Since no coupling effects have been
of the surfactant(s). The addition of alcohol reduces the average considered, precise calculation of the fractions of different water
cross-sectional area of the surfactant head group, and conse- species cannot be achieved from the present results [89]. However,
quently, effective packing parameter (Peff) becomes larger. This the values are used for comparative purpose as a measure of the
leads to increase in the interface curvature and Dh decreases. relative abundance of different water species [28,89].
Hence, the accommodation of larger Pn molecules at the interface It is evident from Fig. S6 that the proportion of bound and
leads to decrease in droplet size [83]. Similar observation was re- bulk-like water in mixed microemulsion system (Brij-
ported earlier by Zhang et al. [83] for water/AOT/Bu or Pn/IPM 58:CTAB = 5:0 ? 0:5, w/w) has been found to be affected upon
microemulsion systems. The polydispersityindex (PDI) has been increase in content of CTAB. Further, the decrease in the hydrody-
observed in the range between 0.1–0.2, which indicates a monodis- namic diameter (Dh) [15.9 nm (5:0) ? 6.4 nm (0:5)] has been
persity of the systems [84]. Hence, the reported w/o mixed micro- observed at the prevailing condition as evident from the DLS mea-
emulsions can be exploited as templates for synthesis of the surement. It is evident from Fig. S6 that the variation of Gaussian
nanoparticle of different sizes. profiles (area fraction) of the normalized spectra of different water
species (bound and bulk-like water molecules) that the bulk-like
3.6. FTIR measurement water and its relative proportion decrease considerably, passing
from 58% to 43% with the increase in CTAB content (Brij-
It is well known that the nanoscopic confinement of water 58:CTAB = 4:1 ? 0:5, w/w) vis-à-vis decrease in droplet size from
droplets as well as their sizes has major impact on water hydrogen 15.9 nm to 6.4 nm. Meanwhile, contribution of the bound water
160 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161

increases from a proportion of 42–57%. In a previous report, FTIR been argued that the interaction between head group (POE as un-
spectra of mixed surfactant (AOT/Brij-30) reverse micelles in isooc- charged) of Brij-58 and water is comparatively weaker than the
tane was deconvoluted into two curves peaks at 3300 and interaction between charged head group [NðCH3 Þþ 3 ] of CTAB and
3500 cm1, with the relative contribution of the former peak (at water. From the analysis of nia =ns (compositional variation) and
3300 cm1) to be the most prominent one, which indicates the DG0t values (obtained from the dilution method), it can be con-
presence of a large fraction of bulk-like water in non-ionic rich cluded that the effective binding between CTAB and/or Brij-58
(Brij-30) composition compare to anionic rich (AOT) composition and Pn at the interface increase in the order: 4:1 < 3:2 < 2:3 < 1:4
[46]. On the whole, the features of the FTIR spectra obtained in (w/w). Both nia /ns and DG0t values increase with increase in tem-
the present report corroborate well with the reported system perature for pure Brij-58 and Brij-58 rich systems, whereas reverse
(AOT/Brij-30), although structural variation in polar head groups trend is observed for pure CTAB and CTAB rich systems in both oils.
of AOT and CTAB exists significantly. Hence, it can be inferred that The phenomenon has been explained from the view point of oppo-
the water molecules interact less strongly with the non-polar head site temperature dependence on the solubility and hydration of io-
group in comparison with the ionic head group [46]. In a similar nic and non-ionic surfactants. Both of these properties, have been
experiment, Brubach et al. [85] reported that proportion of differ- found to be invariant with increase in temperature (indicating for-
ent water species significantly changes with the variation of drop- mation of temperature-insensitive microemulsions) in both oils in
let size (x = 1.51 ? 25.3, Dh = 9.4 nm ? 20.9 nm) in non-ionic the vicinity of equimolar compositions (Brij-58:CTAB = 3:2 and 2:3,
fluorocarbon w/o microemulsion. Further, it was reported that w/w). Such types of microemulsion formulations have been found
the hydroxyl stretch absorption spectra, vibrational population to be useful in various commercial and technological processes
relaxation times, orientational relaxation rates, and spectral diffu- [92]. The overall transfer process for pure Brij-58 and CTAB sys-
sion dynamics as a function of the water nanopool size result in tems indicates endothermic and exothermic with positive and neg-
changes from those of bulk properties toward the bound nature ative entropy changes, respectively, in both oils. However, at
as the system moves toward the smaller water nanopool compositions in between two extremes, both DH0t and DS0t values
(x = 60 ? 2, diameter = 28 nm ? 1.7 nm) for AOT reverse micelles are positive at Brij-58 rich compositions and negative at CTAB rich
[88]. Hence, it can be concluded that both the parameters, viz., compositions in both oils. Interestingly, insignificant changes in
change in mixed surfactant composition (Brij-58:CTAB = 5:0 ? 0:5, these parameters with temperature have been observed in the
w/w) and droplet size (Dh = 15.9 nm ? 6.4 nm) significantly affect vicinity of equimolar composition (=3:2 and 2:3, w/w), leading to
the dynamics of the confined water vis-à-vis type of hydrogen formation of isenthalpic and isentropic microemulsion systems.
bonding network within the water pool in mixed surfactant Similar to many self-organizing systems, the DH0t and DS0t values
microemulsions. well compensate each other. It reveals from DLS measurements
that Dh decreases remarkably with the increase in CTAB content
in the mixed systems at each temperature in both oils. On the other
4. Conclusions hand, Dh has been found to decrease with increase in temperature
in pure Brij-58 and Brij-58 rich stabilized systems, whereas the re-
In this report, phase behavior, water solubilization capacity, verse effect of temperature on Dh has been observed in pure CTAB
conductivity, method of dilution, DLS, and FTIR techniques were and CTAB rich stabilized systems in both oils. Temperature invari-
employed for understanding of the physicochemical properties ant droplet sizes have also been evidenced in the vicinity of the
and microstructures of a water-in-oil microemulsion system equimolar composition. Also, all these physicochemical parame-
comprising of Brij-58 and CTAB, and Pn stabilized in Hp or Dc with ters have been found to be influenced by oil chain length. The
varying composition (Brij-58:CTAB = 5:0 ? 0:5, w/w). adjustable size of the microemulsion droplets along with the Gibbs
Phase studies reveal that a single phase (1a) clear microemul- free energy change (DG0t ) [93,94] could be used for predicting the
sion region has been found to increase with the increase in the ra- size of the nanoparticles in mixed surfactant w/o microemulsions,
tio of Brij-58 and CTAB in both oils at 303 K. The single phase if used as templates. Very recently, it was reported that successful
region is larger for Hp stabilized systems compared to Dc stabilized inclusion of 2D allotrope of carbon in CTAB/isooctane/n-hexanol/
systems. The addition of CTAB in Brij-58/Pn/Hp or Dc microemul- water microemulsions without compromising the stability of the
sion system induces synergism in water solubilization capacity in system can increase the activity of surface-active enzymes
the vicinity of equimolar composition (Brij-58:CTAB = 3:2 and enormously by modulating the amount of cosurfactant at the
2:3, w/w). The conductivity of mixed surfactant water/Brij-58/ interface [95]. Further, Singh et al. [96] reported that quantum dots
CTAB/Pn/Hp or Dc microemulsions with varying composition of (QDs), which possess potential applications in white light emitting
surfactant(s) as a function of wt% of water at 303 K reveals that devices can be synthesized successfully in CTAB/cyclohexane/1-
the samples chosen from the ascending branch (Brij- butanol/water microemulsion systems and the optical properties
58:CTAB = 5:0 ? 2:3, w/w) of the solubilization capacity versus of QDs can be tuned by changing the experimental parameter, x
compositions (Brij-58:CTAB, w/w) profile exhibit volume-induced (i.e., molar ratio of water to surfactant). In view of these, the
percolation in conductance, whereas no percolation phenomenon evaluation of all these physicochemical and thermodynamic
has been observed in the descending branch (Brij- parameters of the present systems could be used as prospective
58:CTAB = 1:4 ? 0:5, w/w). Hence, it can be concluded that templates for increasing the activity of surface-active enzymes
ascending and descending curves indicate the interdroplet interac- and synthesis of QDs.
tion branch (Rc) and the curvature branch (Ro), respectively. The
above findings from conductivity measurements also corroborate
well with dye solubilization experiments. Understanding of the
relationship between microstructure and solubilization capacity Acknowledgments
of microemulsions is important for preparation and optimization
of microemulsions for protein purification process [90] and also The financial support in the form of an operating research grant
for efficient use in drug delivery [91]. Further, FTIR measurements to B.K.P. and Senior Research Fellowship to K.K. from the authority
show that bulk water (3300 cm1) and bound water of Indian Statistical Institute, Kolkata, India, is thankfully acknowl-
(3550 cm1) gradually decreases and increases, respectively, edged. S.B. thanks UGC, New Delhi, India, for Financial assistance
with increasing CTAB content to Brij-58 stabilized systems. It has and UGC-BSR Research Fellowship.
 S. Bardhan et al. / Journal of Colloid and Interface Science 411 (2013) 152–161 161

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