Using dielectric relaxation spectroscopy and small-angle neutron scattering techniques, we present a quantitative analysis of the influence of short-chain (ethanol) and long-chain (octanol) alcohol molecules on the elastic bending constants of AOT [sodium-1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate]-stabilized reverse microemulsions. A significant increase in the elastic bending rigidity, κ, of the AOT surfactant layer (30.7%) is observed with the inclusion of octanol, whereas a decrease in κ amounting to 11.2% is obtained in the presence of ethanol. The experimentally elusive saddle-splay modulus, κ¯, of alcohol-loaded microemulsions is determined using a novel approach. Notably, the ratio κ¯/κ lies in the range 2<κ¯/κ<0, which is acceptable for spherical microemulsion droplets. Further, the presence of ethanol molecules causes a decrease in the percolation threshold temperature owing to an increase in the fluidity of the surfactant monolayer at the oil–water interface. On the other hand, the addition of octanol molecules shifts the percolation threshold to higher temperatures implying a further reinforcement of the surfactant film.

1.
C.
Stubenrauch
,
Microemulsions: Background, New Concepts, Applications, Perspectives
(
Wiley
,
Chichester, UK
,
2009
).
2.
D. O.
Shah
,
Improved Oil Recovery by Surfactant and Polymer Flooding
(
Elsevier
,
2012
).
3.
B. K.
Paul
and
S. P.
Moulik
, “
Uses and applications of microemulsions
,”
Curr. Sci.
80
,
990
1001
(
2001
), available at https://www.jstor.org/stable/24105809?seq=1.
4.
P. M.
Geethu
,
I.
Yadav
,
S. K.
Deshpande
,
V. K.
Aswal
, and
D. K.
Satapathy
, “
Soft confinement effects on dynamics of hydrated gelatin
,”
Macromolecules
50
,
6518
6528
(
2017
).
5.
B.
Farago
,
D.
Richter
,
J. S.
Huang
,
S. A.
Safran
, and
S. T.
Milner
, “
Shape and size fluctuations of microemulsion droplets: The role of cosurfactant
,”
Phys. Rev. Lett.
65
,
3348
(
1990
).
6.
J. S.
Huang
,
S. T.
Milner
,
B.
Farago
, and
D.
Richter
, “A study of dynamics of microemulsion droplets by neutron spin echo spectroscopy,” in Physics of Amphiphilic Layers (Springer, 1987), pp. 346–352.
7.
E.
Van der Linden
,
S.
Geiger
, and
D.
Bedeaux
, “
The Kerr constant of a microemulsion for a low volume fraction of water
,”
Physica A
156
,
130
143
(
1989
).
8.
W.
Meier
, “
Kerr effect measurements on a poly (oxyethylene) containing water-in-oil microemulsion
,”
J. Phys. Chem. B
101
,
919
921
(
1997
).
9.
R.
Wipf
,
S.
Jaksch
, and
B.
Stühn
, “
Dynamics in water–AOT–n-decane microemulsions with poly (ethylene glycol) probed by dielectric spectroscopy
,”
Colloid Polym. Sci.
288
,
589
601
(
2010
).
10.
S.-H.
Chen
,
S.-L.
Chang
, and
R.
Strey
, “
Structural evolution within the one-phase region of a three-component microemulsion system: Water–n-decane–sodium-bis-ethylhexylsulfosuccinate (AOT)
,”
J. Chem. Phys.
93
,
1907
1918
(
1990
).
11.
B.
Kuttich
,
P.
Falus
,
I.
Grillo
, and
B.
Stühn
, “
Form fluctuations of polymer loaded spherical microemulsions studied by neutron scattering and dielectric spectroscopy
,”
J. Chem. Phys.
141
,
084903
(
2014
).
12.
B. P.
Binks
,
J.
Meunier
,
O.
Abillon
, and
D.
Langevin
, “
Measurement of film rigidity and interfacial tensions in several ionic surfactant-oil-water microemulsion systems
,”
Langmuir
5
,
415
421
(
1989
).
13.
P. M.
Geethu
,
I.
Yadav
,
V. K.
Aswal
, and
D. K.
Satapathy
, “
Enhancement in elastic bending rigidity of polymer loaded reverse microemulsions
,”
Langmuir
33
,
13014
13026
(
2017
).
14.
S.
Bhattacharya
,
J. P.
Stokes
,
M. W.
Kim
, and
J. S.
Huang
, “
Percolation in an oil-continuous microemulsion
,”
Phys. Rev. Lett.
55
,
1884
(
1985
).
15.
H. F.
Eicke
,
M.
Borkovec
, and
B.
Das-Gupta
, “
Conductivity of water-in-oil microemulsions: A quantitative charge fluctuation model
,”
J. Phys. Chem.
93
,
314
317
(
1989
).
16.
D. S.
Mathew
and
R.-S.
Juang
, “
Role of alcohols in the formation of inverse microemulsions and back extraction of proteins/enzymes in a reverse micellar system
,”
Sep. Purif. Technol.
53
,
199
215
(
2007
).
17.
J.
Lang
,
N.
Lalem
, and
R.
Zana
, “
Quaternary water in oil microemulsions. 1. Effect of alcohol chain length and concentration on droplet size and exchange of material between droplets
,”
J. Phys. Chem.
95
,
9533
9541
(
1991
).
18.
L. M. M.
Nazário
,
T. A.
Hatton
, and
J. P. S.
G. Crespo
, “
Nonionic cosurfactants in AOT reversed micelles: Effect on percolation, size, and solubilization site
,”
Langmuir
12
,
6326
6335
(
1996
).
19.
S.-Y.
Choi
,
S.-G.
Oh
,
S.-Y.
Bae
, and
S.-K.
Moon
, “
Effect of short-chain alcohols as co-surfactants on pseudo-ternary phase diagrams containing lecithin
,”
Korean J. Chem. Eng.
16
,
377
381
(
1999
).
20.
M.
Van Dijk
,
J.
Joosten
,
Y.
Levine
, and
D.
Bedeaux
, “
Dielectric study of temperature-dependent aerosol OT/water/isooctane microemulsion structure
,”
J. Phys. Chem.
93
,
2506
2512
(
1989
).
21.
J. S.
Pedersen
, “
Analysis of small-angle scattering data from colloids and polymer solutions: Modeling and least-squares fitting
,”
Adv. Colloid Interface Sci.
70
,
171
210
(
1997
).
22.
V. K.
Aswal
and
P. S.
Goyal
, “
Small-angle neutron scattering diffractometer at Dhruva reactor
,”
Curr. Sci.
79
,
947
953
(
2000
), available at https://www.jstor.org/stable/24104808.
23.
I.
Breßler
,
J.
Kohlbrecher
, and
A. F.
Thünemann
, “
Sasfit: A tool for small-angle scattering data analysis using a library of analytical expressions
,”
J. Appl. Crystallogr.
48
,
1587
1598
(
2015
).
24.
M. J.
Stephen
, “
Mean-field theory and critical exponents for a random resistor network
,”
Phys. Rev. B
17
,
4444
(
1978
).
25.
M.
Lagues
, “
Electrical conductivity of microemulsions: A case of stirred percolation
,”
J. Phys. Lett.
40
,
331
333
(
1979
).
26.
G. S.
Grest
,
I.
Webman
,
S. A.
Safran
, and
A. L. R.
Bug
, “
Dynamic percolation in microemulsions
,”
Phys. Rev. A
33
,
2842
(
1986
).
27.
C.
Cametti
,
F.
Sciortino
,
P.
Tartaglia
,
J.
Rouch
, and
S.-H.
Chen
, “
Complex electrical conductivity of water-in-oil microemulsions
,”
Phys. Rev. Lett.
75
,
569
(
1995
).
28.
Y.
Feldman
,
N.
Kozlovich
,
I.
Nir
, and
N.
Garti
, “
Dielectric relaxation in sodium bis (2-ethylhexyl) sulfosuccinate–water–decane microemulsions near the percolation temperature threshold
,”
Phys. Rev. E
51
,
478
(
1995
).
29.
F.
Bordi
,
C.
Cametti
,
J.
Rouch
,
F.
Sciortino
, and
P.
Tartaglia
, “
Cluster formation in water-in-oil microemulsions at percolation: Evaluation of the electrical properties
,”
J. Phys. Condens. Matter
8
,
A19
(
1996
).
30.
H.
Kataoka
,
T.
Eguchi
,
H.
Masui
,
K.
Miyakubo
,
H.
Nakayama
, and
N.
Nakamura
, “
Scaling relation between electrical conductivity percolation and water diffusion coefficient in sodium bis (2-ethylhexyl) sulfosuccinate-based microemulsion
,”
J. Phys. Chem. B
107
,
12542
12548
(
2003
).
31.
S. K.
Mehta
Kawaljit
, “
Phase diagram and physical properties of a waterless sodium bis (2-ethylhexylsulfosuccinate)-ethylbenzene-ethyleneglycol microemulsion: An insight into percolation
,”
Phys. Rev. E
65
,
021502
(
2002
).
32.
W.
Helfrich
, “
Elastic properties of lipid bilayers: Theory and possible experiments
,”
Z. Naturforsch. C
28
,
693
703
(
1973
).
33.
M.
Gradzielski
,
D.
Langevin
, and
B.
Farago
, “
Experimental investigation of the structure of nonionic microemulsions and their relation to the bending elasticity of the amphiphilic film
,”
Phys. Rev. E
53
,
3900
(
1996
).
34.
P. G.
De Gennes
and
C.
Taupin
, “
Microemulsions and the flexibility of oil/water interfaces
,”
J. Phys. Chem.
86
,
2294
2304
(
1982
).
35.
W.
Meier
, “
Poly (oxyethylene) adsorption in water/oil microemulsions: A conductivity study
,”
Langmuir
12
,
1188
1192
(
1996
).
36.
R.
Wipf
,
M.
Kraska
,
T.
Spehr
,
J.
Nieberle
,
H.
Frey
, and
B.
Stühn
, “
Interaction between a water-in-oil microemulsion and a linear-dendritic poly (propylene oxide)–polyglycerol block copolymer
,”
Soft Matter
7
,
10879
10888
(
2011
).
37.
B.
Kuttich
,
A.-K.
Grefe
, and
B.
Stühn
, “
Changes in the bending modulus of AOT based microemulsions induced by the incorporation of polymers in the water core
,”
Soft matter
12
,
6400
6411
(
2016
).
38.
M.
Nagao
,
H.
Seto
,
T.
Takeda
, and
Y.
Kawabata
, “
Effects of temperature and pressure on phase transitions in a ternary microemulsion system
,”
J. Chem. Phys.
115
,
10036
10044
(
2001
).
39.
H.
Kellay
,
B.
Binks
,
Y.
Hendrikx
,
L.
Lee
, and
J.
Meunier
, “
Properties of surfactant monolayers in relation to microemulsion phase behaviour
,”
Adv. Colloid Interface Sci.
49
,
85
112
(
1994
).
40.
P. M.
Geethu
,
I.
Yadav
,
E.
Mani
,
V. K.
Aswal
, and
D. K.
Satapathy
, “
Saddle-splay modulus of reverse microemulsions: Experimental determination using small-angle neutron scattering and dielectric relaxation spectroscopy
,”
Phys. Rev. E
98
,
052604
(
2018
).
41.
S. A.
Safran
, “
Fluctuations of spherical microemulsions
,”
J. Chem. Phys.
78
,
2073
2076
(
1983
).
42.
S. T.
Milner
and
S. A.
Safran
, “
Dynamical fluctuations of droplet microemulsions and vesicles
,”
Phys. Rev. A
36
,
4371
(
1987
).
43.
S.
Safran
, “
Saddle-splay modulus and the stability of spherical microemulsions
,”
Phys. Rev. A
43
,
2903
(
1991
).
44.
R. H.
Templer
,
B. J.
Khoo
, and
J. M.
Seddon
, “
Gaussian curvature modulus of an amphiphilic monolayer
,”
Langmuir
14
,
7427
7434
(
1998
).
45.
M.
Tomšič
and
A.
Jamnik
, “Simple alcohols and their role in the structure and interactions of microemulsion systems,” in Microemulsions (CRC Press, 2008), pp. 174–215.
46.
L. M.
Nazário
,
J. P.
Crespo
,
J. F.
Holzwarth
, and
T. A.
Hatton
, “
Dynamics of AOT and AOT/nonionic cosurfactant microemulsions. An iodine-laser temperature jump study
,”
Langmuir
16
,
5892
5899
(
2000
).
You do not currently have access to this content.