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Microemulsiones No Acuosas Birrefringentes

Microemulsiones No Acuosas Birrefringentes

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& 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
Non-aqueous birefringent microemulsions were found in a system ofp-xylene,glycerol, triethanolammonium oleate and oleic acid. The microemulsions showed longterm stability once formed, but failed to form spontaneously when the components werecontacted. After partial separation by centrifugation, no signs of spontaneous reforma-tion were found.
Key words:
Non-aqueous microemulsions, birefringent microemulsions, lyotropic liquidcrystals, glyceroMn-p-xylene microemulsions, glycerol inverse micelles.
Colloidal association structures in water-flee sys-tems have recently attracted considerable interest.Evans and collaborators [1, 2] have investigated micel-lar formation of surfactants in ethylammonium nitrateand hydrazine and Ionescu [3] found micellization ofacylcarnitine in glycerol. Lyotropic liquid crystal withnon-aqueous solvents have been introduced by Fri-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-gical importance.Microemulsions in which a non-aqueous polarcompound replaces water have independently beenintroduced by Friberg [10] and by Lattes [11].Another novelty in the area are birefringent micellarsolutions [12,13] or microemulsions [14,15]. Theywere introduced by Hoffman in 1978 [12], who attri-buted their properties to the presence of giant micelles,while Taupin and collaborators [14,15] discussed thestructure of birefringent microemulsions. The ques-tion of stability of such systems has recently beenraised by Fontell [16] who expressed doubt as to thebirefringent solutions possessing thermodynamic sta-bility. With regard to the fact that the compositionswere found at the limit of the solubility area, Fontell[16] cautioned against an inadvertent path into thetwo-phase region containing a liquid crystalline phase.Birefringent phases have also been observed by Millerand collaborators [17] in their investigations on terti-
ary oil recovery. The question of the structure and sta-bility O such systems is a fascinating problem.We have recently found a system containing
birefringent microemulsions and we consid-ered our results concerning their stability to be of suf-ficient interest to merit publication of a research note.The system investigated was glycerol, triethanolam-monium oleate, oleic acid and p-xylene.
The p-xylene was Aldrich, 99 %, the glycerol was Aldrich GoldLabel, 99.5 % and the triethanolammonium oleate (TEAO) wasmade by contacting equimolar amounts of oteic acid, Fisher puri-fied, and triethanolamine, Fisher certified. All chemicals were usedas received.The solubilization of glycerol in the p-xylene/TEAO solutionwas determined by titration with mixing, using a vibromixer at30 ~ The viscosity of the solutions was measured using Cannon-Fenske capillary viscometers at 30 ~ covering the range of viscosi-ties encountered.The stability of he microemulsions part of he system was inves-tigated by long term storage at 30 ~ and by examination of thetransport direction of layers in partially separated or incompletelyhomogenized samples at the same temperature.
Results and discussion
Our earlier results in aqueous systems [18] haveintroduced the relation between liquid crystals andmicroemulsions; hence, our primary efforts werelimited to finding the lamellar liquid crystalline phase
Friberg and Wohn, A system with non-aqueous birefringent microemulsions
Fig. 1. The liquidcrystallinephase n the systemglycerol, riethanol ammonium oleate (TEAOL) and oleicacid (OLA)in the system of the three structure-forming compo-nents: the glycerol, the triethanol ammonium oleateand the oleic acid. The lamellar liquid crystalline phasereached in a large crescent-formed area from the tri-ethanol ammonium oleate corner towards the glycerolcorner reaching to 75 % by weight of glycerol (fig. 1).The basis for the microemulsion system was chosenwith a triethanol ammonium oleate/oleic acid ratio of2,57 in order to obtain the largest possible extension ofthe liquid crystalline area (marked in fig. 1). Thischoice was made against our earlier observation [18] ofthe close relation between
microemulsions andthe lamellar liquid crystals.Combining the compositions along the line in figure1 with p-xylene gave the p-xylene/surfactant isotropicsolution area with solubilized glycerol according tofigure 2. The marked part to the left of the region is not
o o ~~
I i J
0 5.0 10.0 15.0 20.0GLYCEROL,WEIGHT 96
Fig. 3. The viscosityversus glycerolcontentfor solutions with dif- ferent triethanol ammonium oleate/p-xylene weight ratios.TEAOL/p-xylene O
X 0.18; 9 0.25a separate phase. Instead, the striped part shows theextent of bluish solutions and the zig-zag marking indi-cates the birefringent solutions.The viscosity of solutions with a TEAO/p-xyleneratio of 0.11, 0.18 and 0.25 versus the glycerol fractionare given in figure 3. The sudden increase of viscositywhen the composition entered the birefringent regionis a conspicuous feature.The stability of well mixed samples is illustrated infigure 4. All three samples appeared as a homogenousbirefringent solution at the beginning of the storagetime, figure 5. After 30 days, an upper transparent lay-er started separating in sample 3 and the birefringentpart retracted according to the diagram in figure 4.
Fig. 2. The area for hydrocarboncontinuousmicroemulsions n thesystem glycerol, p-xylene and triethanol ammonium oleate at30 ~ The striped areamarks bluish sotropicsolutions, he zig-zagmarkings show birefringent olutions. The compositions ndicatedby 1,2,3 refer to figure 3
00.8I-Oev 0.6I.-.-"r
t t I I I
0 28 56 84 112 140TIME,DAYS
Fig. 4. The relative height of the birefringent ayer versus time forthree samples marked in figure 1
Colloid and Polymer Science, Vol. 263 9No. 2 (1985)
Fig. 5. The birefringent microemulsions were easily detected between crossed polarizers
Similar behavior was observed in sample 1 after 71days. Sample 2 remained identical during the 4 monthperiod. The separated phase in sample 3 was identifiedas a liquid crystalline phase with lamellar structurefrom its optical pattern (fig. 6).In order to obtain further information about thepotential thermodynamic stability of sample 2, twosamples of this composition were carefully mixed toobtain the single birefringent liquid and partially sepa-rated by centrifugation to form two layers with thebirefringent 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 inlayer thickness to indicate a spontaneous reformationof the birefringent microemulsion. A further test wasmade 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 thebeginning of the experiment. The changes in height ofthe layers with time was observed at 30~ Noincrease of the thickness of the birefringent wasobserved.
Birefringent microemulsions were observed in anon-aqueous system and showed excellent long termstability once formed. For the sample which separatedspontaneously with time, the rate of separation wasaccelerated. It suddenly stopped at the formation of alamellar liquid crystal (fig. 3).No case of spontaneous formation from compo-nents was found and awaiting further experimentalinformation, a conclusion of thermodynamic instabil-ity of the microemulsions investigated appears most
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

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