Colloid & Polymer Science Colloid & Polymer Sci 263:156-159 (1985)

A system with non-aqueous birefringent microemulsions

S. E. Friberg and C. S. Wohn

Chemistry Department, UMR, Rolla, MO 65401

Abstract:Non-aqueous birefringent microemulsions were found in a system ofp-xylene,

glycerol, triethanolammonium oleate and oleic acid. The microemulsions showed long
term stability once formed, but failed to form spontaneously when the components were
contacted. After partial separation by centrifugation, no signs of spontaneous reforma-
tion were found.

Key words:Non-aqueous microemulsions, birefringent microemulsions, lyotropic liquid

crystals, glyceroMn-p-xylene microemulsions, glycerol inverse micelles.

Introduction ary oil recovery. The question of the structure and sta-
Colloidal association structures in water-flee sys- bility Of such systems is a fascinating problem.
tems have recently attracted considerable interest. We have recently found a system containing non-
aqueous birefringent microemulsions and we consid-
Evans and collaborators [1, 2] have investigated micel-
lar formation of surfactants in ethylammonium nitrate ered our results concerning their stability to be of suf-
and hydrazine and Ionescu [3] found micellization of ficient interest to merit publication of a research note.
acylcarnitine in glycerol. Lyotropic liquid crystal with The system investigated was glycerol, triethanolam-
non-aqueous solvents have been introduced by Fri- monium oleate, oleic acid and p-xylene.
berg and collaborators [4-7] and studied by Evans [8].
McIntosh et al. [9] have analyzed association struc-
tures of lecithin and glycerol emphasizing their biolo- Experimental
gical importance. The p-xylene was Aldrich, 99 %, the glycerol was Aldrich Gold
Microemulsions in which a non-aqueous polar Label, 99.5 % and the triethanolammonium oleate (TEAO) was
made by contacting equimolar amounts of oteic acid, Fisher puri-
compound replaces water have independently been fied, and triethanolamine, Fisher certified. All chemicals were used
introduced by Friberg [10] and by Lattes [11]. as received.
Another novelty in the area are birefringent micellar The solubilization of glycerol in the p-xylene/TEAO solution
solutions [12,13] or microemulsions [14,15]. They was determined by titration with mixing, using a vibromixer at
30 ~ The viscosity of the solutions was measured using Cannon-
were introduced by Hoffman in 1978 [12], who attri- Fenske capillary viscometers at 30 ~ covering the range of viscosi-
buted their properties to the presence of giant micelles, ties encountered.
while Taupin and collaborators [14,15] discussed the The stability of the microemulsions part of the system was inves-
structure of birefringent microemulsions. The ques- tigated by long term storage at 30 ~ and by examination of the
tion of stability of such systems has recently been transport direction of layers in partially separated or incompletely
homogenized samples at the same temperature.
raised by Fontell [16] who expressed doubt as to the
birefringent solutions possessing thermodynamic sta-
bility. With regard to the fact that the compositions
were found at the limit of the solubility area, Fontell Results and discussion
[16] cautioned against an inadvertent path into the Our earlier results in aqueous systems [18] have
two-phase region containing a liquid crystallinephase. introduced the relation between liquid crystals and
Birefringent phases have also been observed by Miller microemulsions; hence, our primary efforts were
and collaborators [17] in their investigations on terti- limited to finding the lamellar liquid crystalline phase
M870
Fribergand Wohn,A system with non-aqueous birefringentmicroemulsions 157

OLEIC ACID 40-

30-
ILl

o o~ ~
I--
~2o
I.-
z
W
('~ RINGENT(,I)
10

I ~ ~ BIREFRINGENT(X)
GLYCEROL TEAOL BIREFRIN(ENT(O)
I i J
Fig. 1. The liquidcrystallinephasein the systemglycerol,triethanol 0 5.0 10.0 15.0 20.0
ammonium oleate (TEAOL) and oleicacid (OLA) GLYCEROL,WEIGHT 96

Fig. 3. The viscosityversusglycerolcontentfor solutionswith dif-

in the system of the three structure-forming compo-
nents: the glycerol, the triethanol ammonium oleate
and the oleic acid. The lamellar liquid crystalline phase
reached in a large crescent-formed area from the tri-
ethanol ammonium oleate corner towards the glycerol
corner reaching to 75 % by weight of glycerol (fig. 1).
The basis for the microemulsion system was chosen
with a triethanol ammonium oleate/oleic acid ratio of
2,57 in order to obtain the largest possible extension of
the liquid crystalline area (marked in fig. 1). This
choice was made against our earlier observation [18] of
the close relation between W / O microemulsions and
the lamellar liquid crystals.
Combining the compositions along the line in figure
1 with p-xylene gave the p-xylene/surfactant isotropic
solution area with solubilized glycerol according to
figure 2. The marked part to the left of the region is not
ferent triethanol ammonium oleate/p-xylene weight ratios.
TEAOL/p-xylene O 0.11; X 0.18; 9 0.25
a separate phase. Instead, the striped part shows the
extent of bluish solutions and the zig-zag marking indi-
cates the birefringent solutions.
The viscosity of solutions with a TEAO/p-xylene
ratio of 0.11, 0.18 and 0.25 versus the glycerol fraction
are given in figure 3. The sudden increase of viscosity
when the composition entered the birefringent region
is a conspicuous feature.
The stability of well mixed samples is illustrated in
figure 4. All three samples appeared as a homogenous
birefringent solution at the beginning of the storage
time, figure 5. After 30 days, an upper transparent lay-
er started separating in sample 3 and the birefringent
part retracted according to the diagram in figure 4.

P-XYLENE 1.0

SAMPLE
z
/ 00.8
I-
O
ev 0 . 6

I.-.-
"r
o 0.4
LU
7-

0.2
GLYCEROL TEAOL

t t I I I
Fig. 2. The areafor hydrocarboncontinuousmicroemulsionsin the 0 28 56 84 112 140
system glycerol, p-xylene and triethanol ammonium oleate at TIME,DAYS
30 ~ The stripedareamarksbluishisotropicsolutions,the zig-zag
markingsshow birefringentsolutions.The compositionsindicated Fig. 4. The relativeheight of the birefringentlayer versus time for
by 1,2,3 refer to figure3 three samplesmarked in figure 1
158
Fig. 5. The birefringent microemulsions were easily detected between crossed polarizers
Similar behavior was observed in sample 1 after 71
days. Sample 2 remained identical during the 4 month
period. The separated phase in sample 3 was identified
as a liquid crystalline phase with lamellar structure
from its optical pattern (fig. 6).
In order to obtain further information about the
potential thermodynamic stability of sample 2, two
samples of this composition were carefully mixed to
obtain the single birefringent liquid and partially sepa-
rated by centrifugation to form two layers with the
birefringent one at the bottom. The height of the bire-
fringent layers in the two samples was different. Stor-
age at 30 ~ for a two month period gave no changes in
layer thickness to indicate a spontaneous reformation
of the birefringent microemulsion. A further test was
made in the following manner. Samples of composi-
tion 2 were less thoroughly mixed so that the birefrin-
gent layer did not occupy the entire sample at the
Fig. 6. The optical pattern in polarized light of the separated phase from samples 1 and 3 was typical of a lamellar liquid crystalline phase
Colloid and Polymer Science, Vol. 263 9No. 2 (1985)
beginning of the experiment. The changes in height of
the layers with time was observed at 30~ No
increase of the thickness of the birefringent was
observed.
Conclusions
Birefringent microemulsions were observed in a
non-aqueous system and showed excellent long term
stability once formed. For the sample which separated
spontaneously with time, the rate of separation was
accelerated. It suddenly stopped at the formation of a
lamellar liquid crystal (fig. 3).
No case of spontaneous formation from compo-
nents was found and awaiting further experimental
information, a conclusion of thermodynamic instabil-
ity of the microemulsions investigated appears most
Fribergand Wohn, A system with non-aqueous birefringent microemulsions 159

reasonable. The birefringent solutions may, until fur- 10. Friberg SE, Podzimek M (1984) Colloid Polym Sci 262:252
ther evidence, be considered as a kinetically stable state 11. Rico I, Lattes A, Nouveau Journal De Chimie (in press)
12. Hoffman H, Ulbricht W, TagessonB (1978)J Phys Chem 113:17
of a lamellar liquid crystal and a p-xylene/TEAO solu- 13. Hoffman H, Tagesson B (1978) Ibid 113:110
tion with solubilized glycerol. Such a conclusion by 14. Dvolaitzky M, Ober R, BillarJ, Taupin C, Charvolin J,
no means implies the structure of these microemul- Hendricks Y (1981) C R Acad Sc Paris 292:45
sions with a long term stability to be without interest. 15. di Meglio JM, Dvolaitzky M, Ober R, Taupin C (1983) C R
Acad Sc Paris 296:405
16. Fontell K, Lindman B (1983) J Phys Chem 87:3289
17. Benton WJ, Miller CA, Fort Jr T (1982)J Dispersion Sci Tech-
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Cryst 72:183 Curators' Distinguished Professor
8. Evans DF, Kaler EW, Benton WJ (1983) J Phys Chem 87:533 University of Missouri-Rola
9. Mclntosh TJ, McDaniel RV, Simon SA (1983) Biochim Biophys 142 Schrenk Hall
Acta 731:109-114 Rolla, Missouri 65401, USA