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Since their introduction in 1943 by Hoar and Schulman (1), microemulsions have attracted considerable attention in view of their use in many industrial products and their potential application in enhanced tertiary oil recovery. Various investigations have been carded out to study the formation and stability of such systems, and various techniques have been employed for their characterization. Several review articles (2-5) and monographs
~Present address: The Wellcome Foundation Ltd., Berkhamsted, Herts HP4 2D4, U.K. 2 Author to whom correspondence should be addressed. 31
(6, 7) are now available for the description of a number of microemulsion systems and the methods used for their study. The latter indude phase diagrams, scattering techniques, conductivity and dielectric studies, viscosity measurements, NMR investigations, and interfacial tension measurements. Moreover a number of theories have been put forward in recent years to explain the origin of thermodynamic stability of such systems and these have been recently reviewed (5). However, in spite of this amount of research, which expanded rapidly in the last decade or so, there is still some controversy about the nature of such systems. The most recent NMR self-diffusion studies by Lindman et al. (8) have
0021-9797/84 $3.00 Copyright 1984by AcademicPress,Inc. All fightsof reproductionin any form reserved.
312
dearly shown that such systems can vary from the so called bicontinuous (with flexible and highly disorganized internal interfaces and no definite separation into hydrophilic and hydrophobic domains) to thermodynamically stable "dispersions" with definite droplet cores. In the first case, there is no justification for the use of the term "microemulsion" to describe such systems and these are better referred to as "thermodynamically stable isotropic solutions" (9). On the other hand, in the latter case, the term "microemulsion" or "swollen micellar system" may still be appropriate. In the present two papers, we will describe some systematic investigations on microemulsions using a quaternary system of water, xylene, sodium alkyl benzene sulfonate (to be referred to as NaDBS), and hexanol. NaDBS was selected as the surfactant since it can be easily purified and it is stable to hydrolysis in solution. For a systematic study of microemulsion composition, it is essential to establish the phase diagrams of the system under investigation. From these one can identify the extent of the microemulsion region and its relation to other phases. One of the objectives of the present investigations was to establish the effect of temperature and therefore studies were made at 25, 37, and 50C. Since the ternary phase diagrams of the system water-NaDBS-heXanol have not been established previously, we found it necessary first to establish such phase diagrams. The various phases formed were identified qualitatively using phase contrast and polarizing microscopy. Quantitative analysis of some of the phases formed was attempted using low angle X-ray diffraction. The amount of water solubilized in the inverse mieelle region was determined as a function of total surfactant concentration and the r a t i o o f surfactant to cosurfactant (hexanol). This is then followed by an investigation of the quaternary system and in particular the extent of the microemulsion in each system. Characterization of the w/o microemulsions was carried out using light scattering, conductivity, and viscosity (Part II) (10) measurements.
Jqurnal of Colloid aod Interface Science, Vol. 100, No. 2, August 1984
Materials Water. All water was twice distilled from an all glass apparatus and its surface tension was 72 ___0.2 m N m -~ at 25 + 0.1C. Xylene. Analar grade material (ex Koch Light) was used as received. The N M R spectrum showed the material to be a mixture of ortho, meta, and para isomers and containing a few percent ethyl benzene. Surfactant. The surfactant was a commercial product, Nansa 1106, supplied by Albright and Wilson (Whitehaven). Although this material is usually referred to as sodium dodecyl benzene sulfonate, the linear hydrocarbon chain consists of a distribution from C9 to C 1 4 as shown below.
Carbon chain length Wt% <9 9 10 11 12 13 14 1 16 21 20 18 17 7
This distribution of alkyl chain length gives the surfactant a Krafft point well below room temperature and therefore the surfactant aqueous solution remained clear in all investigations. The commercial material which was supplied as a 30% aqueous solution, contained a maximum of 0.8% unsulfonated material and 0.5,0.8% sodium sulfate. The surfactant was extracted from the aqueous solution using toluene. The water was distilled off from the mixture together with some of the toluene as a n azeotropic mixture. The surfactant was then isolated from the toluene solution by vacuum distillation. The sodium sulfate was removed by dissolving the surfactant in chloroform, followed by removal of any solubilized water by addition of oven dried magnesium sulfate. Both sodium sulfate and magnesium sulfate are filtered offand the chloroform was removed under vacuum at 50C. The surfactant was purified by repeated recrystallization from propan-2-ol. The purified surfactant was dried and stored in a vacuum oven. The material
313
Each phase, unless transparent, was observed under phase contrast and between crossed nicols using either a Zeiss or a Leitz microscope fitted with a 10 eyepiece, 16X objective lens, and a Reichart Kam-ES camera. The appearance of each phase under the microscope was noted and in some cases a photograph was taken. To determine whether the phases were oil or water continuous, a dye test was used. A drop of the phase under investigation was placed on a clean microscope slide and a small amount of two dyes, Waxoline red (n-hexanol soluble) and Lissamine Scarlet (water soluble), was placed at two separate edges of the droplet. Continuity of the fluid phases was readily determined by observing which dye dissolved in the droplet. However, in the case of highly viscous phases, mixing had to be aided by a small spatula, thus making assessment difficult. For investigations at 37 and 50C, a hot stage was fitted to the microscope.
Assessment of Samples
The different phases were assessed visually and by optical and polarizing microscopy.
L ~ t
25c
>
Watel,000/I
L~I
t'=v -v I ._.1 j r =
, -', ,"
1~000 NaDBS
Water 0
"L1
'~Slid"~00NaDBS
C
d
Hexanol 0 1OO
Hexanot 0 100
s o c
X
o > ~0 r
> ~ .... 25C
LI+L~+L
'
L~
/ / ~
; .
~ "~ !
\0 NaDBS 100
100 Water 0
"
10\~)0NaDBS
PHASE DIAGRAMS OF A TERNARY AND QUATERNARY SYSTEM TABLE I Designation and Nomenclatureof the Observed Phases
Designation Basic structure Alphabetical notation
315
Water continuous isotropic liquid Oil continuous isotropic liquid Neat phase Middle phase, normal Middle phase, reversed Optically isotropic, normal Optically isotropic, normal
Normal micelles Reversed micelles Lamellar, double layers Two-dimensional hexagonal Two-dimensional hexagonal Face centered cubic Primitive cubic
Lj D E F FCC PC
fraction line positions were measured using a Hilger and Watts measuring device with a precision of 0.05 mm. The values of the scattering angle 0 were calculated from the diffraction patterns and the d-spacings followed from the Bragg equation, i.e., nX = 2d sin 0 [1]
where )~ is the wavelength of the incident Xray beam and n is an integer. RESULTS
hexanol axis is determined by the solubility of hexanol in water (<2 wt%) (15). With increase of temperature, the extent of the L~ region along the water-NaDBS axis increases as a result of the increase of solubility of NaDBS with increase of temperature ( ~ 40% at 37C and ~ 4 3 % at 50C), whereas the extent along the water-hexanol axis does not change significantly since the amount of hexanol that is solubilized in the L~ region does not increase with increase of temperature.
Ternary System
The phase diagrams for the ternary system studied are shown in Figs. l a-c at the three temperatures investigated, namely 25, 37, and 50C. These diagrams show the typical phases previously described by many authors (1114). It should be mentioned, however, that dotted boundaries shown on the phase diagrams are more uncertain than those shown with a continuous line. A qualitative description of the phases observed and the nomenclature used (11) is given in Table I. Below a brief description of the various regions is given.
L1 + L2 Region
This region appears at low NaDBS concentrations (<2 wt%) when the a m o u n t o f
FIG. 1. Phase diagrams of the ternary system water-sodium alkyi benzene sulfonate(NaDBS)-hexanol at three differenttemperatures.
Journal of Colloid and Interface Science, Vol. 100, No. 2, August 1984
316
BAKER ET AL.
hexanol in the L region exceeds its solubilization limit (>2%). It should be mentioned that there is some uncertainty in the hexanolrich end of this region since the part with a dotted boundary cannot have a tie line between L2 and L1 without it crossing the L2 + LC region. This is clearly forbidden by the phase rule. Therefore such boundaries drawn by the dotted line are only to be considered approximate.
However, since both NaDBS and hexanol are hygroscopic, traces of water must have been present and, these are used in the formation of such liquid crystalline phases. As the temperature is increased, the extent of the F-phase decreases and the amount of water that can be solubilized is reduced to approximately 15 wt% at 37 and 50C. Similar observations were made by Ekwall and Mandell (19) for the ternary system water-sodium caprylate-decanol.
PHASE DIAGRAMS OF A T E R N A R Y A N D Q U A T E R N A R Y SYSTEM TABLE II Observed and Theoretical Ratios of d-spacings for Three Samples of Liquid Crystalline Phases
Sample No. NaDBS Composition hexanol (wt%) Water Ratio of d-spacings (expt) Structure
317
Theoretical ratio
1 2 3
5 5 30
5 12,5 10
90 82.5 60
X-Ray Results
Low angle X-ray diffraction offers the best method for the quantitative identification of the various liquid crystalline phases. However,
full analysis of all the regions would extensive obtained no means measurements in the present exhaustive and a few points were selected. Thus, and
therefore,
the results
TABLE IIl X-Ray Diffraction Results--Line Spacings are in ,~ (a) Face Centered Cubic and Lamellar
Sample composition (wt%) Sample No. NaDBS hexanol Water ( I 11 ) Face centered cubic (200) (220) 3111 t/ (A) n= 1 Lamellar n=2 n=3 a (A)
1 2 3 4
5 5 15 20
5 12.5 10 15
90 82.5 75 65
-----
91 90 90 90
5 6 7 8a 9 10 11
30 40 50 50 60 60 70
10 20 10 30 0 20 0
60 40 40 20 40 20 30
50.3 . . --. --
25.3 . . --. --
-. . . .
58.4 . .
--
39.1
. . .
. . .
. . .
78 81 81
80
12 13
70 80
10 10
20 10
33.0 32.5
26.7 26.0
16.3 --
13.2 --
46 46
-.
29.8 .
14.5 .
56
318
BAKER ET AL.
confirm some of the observations made by microscopy. The structure of the samples was determined by comparing the ratio of the calculated d spacings to those expected from theory. As an illustration, some examples obtained with three samples are given in Table II. The results obtained with the various other samples are given in Table III, along with the unit cell dimensions which were calculated for each structure from the following equation, a
dhkl -Vh 2 + k 2 + l 2
[2]
where h, k, l are the Miller indices and a gives the distance between the centers of adjacent units (11, 21). The points corresponding to the compositions in Table III, along with the identified structures are shown in a temary phase diagram in Fig. 2. In some cases the X-ray results confirm the observations made by microscopy but there are a number of discrepancies. For example, at a sample composition of 80 wt% NaDBS, 20 wt% water 10 wt% n-hexanol (sample 13), the X-ray data suggest that a primitive cubic structure exists. If this was so,
the sample should be transparent, highly viscous, and isotropic. In fact the sample was turbid and showed strong birefringence between crossed nicols. The reason for this discrepancy is unclear, but it may be that other phases are dispersed in this primitive cubic structure. The unit cell dimensions a given in Table III give the distance between the centers of adjacent units, i.e., the sum of the radii of two surfactant molecules plus any material (water or n-hexanol) contained inside or between the units. The results in Table III show an increase in the unit cell dimensions in the order primitive cubic ~ reversed hexagonal < lamellar < face centred cubic. Since the units in the primitive cubic and reversed hexagonal are essentially close-packed the unit cell dimension in this case should correspond to approximately twice the length of a surfactant molecule. The unit cell dimension obtained in these cases was "--46 A corresponding to a surfactant chain length of ~ 2 3 A. This value is in close agreement with the value of ~ 2 1 A calculated from the bond lengths. From the unit cell dimensions of the other liquid crystalline phases, the thickness of the
~ -~+E
8 -F 9 -E
II
t l
10- D
,X.)
,,
2,
?iiir, o
L 1+L2+2
Water
100 0
. . L~
"
11 f-
""
FIG. 2. Ternary phase diagram (at 25C) showingthe identifiedstructures from X-ray data.
Journal of Colloid and Interface Science, Vol. 100, No. 2, August 1984
319
10-
o - 2sc
s
0'5
110
FIG. 3. Data from the ternary phase diagrams. Solubilizationof water as a function of total surfactant (NaDBS + hexanol) concentration. water layer was calculated using a value of 21 A for the surfactant chain length. Thus, the thickness of the water layer between cylinders in the hexagonal (E) phase is 16.6 A, between the layers in the lamellar (D) phase is 38/~, and between spheres in the FCC phase is 8 A. These values are in close agreement with those reported by previous authors (1 l, 21, 22). Since the unit cell dimension, and hence the thickness of the water layer, does not increase with an increase in the water content (e.g., samples l, 7, and 10 in Table II) it seems likely, from the limited amount of data obtained by X-ray diffraction, that the present system forms a non-expanding lamellar (D) phase (11, 23). This result is rather surprising for an ionic surfactant/alcohol mixture, although this may be caused by the aromatic head group.
I0
c~ "6
s
"5 :S
'
~o
go
6'0
ab
FIG. 4. Data from the ternary phase diagrams. Solubilizationof water as a function of molar ratio of NaDBS to hexanoL
Journal of Colloid and Interface Science. Vol. 100, No. 2, August 1984
Xylene~5wt ~o NaDBS
t~ 3 7C
25Oc
L2
< ?-
LI+E
=>
0 " Water~5wt ~oNaDBS Xy#ene+5w~ lO0
NaOBS
E ~-Gel
>
Water=~Swt~ NaDBS
HexanoI-PSwt~ NaDBS
po
>
5 0C
--
25C
\ \
0 100 Hexanol-l-5wt~ NaDIrS Water+ 5wt~oNaDBS
LI~-E
M~-EILC
WaterU-5wt~ NaPeS
10 0
~0
1oo Hexanol+5wt~oNaDBS
321
L2 region is considered here in more detail, by considering the amount of water solubilized to the total surfactant (i.e., NaDBS + n-hexanol) concentration and to the ratio of NaDBS to n-hexanol. Figure 3 shows the number of moles of water per mole of total surfactant solubilized in the L 2 region at 25 and 50C, as a function of the total surfactant concentration (the data for 37C are not shown to avoid overcrowding of the graph, since the values lie between those at 25 and 50C). The results show that solubilization does not change appreciably with temperature and the maximum water solubilization (approximately 11 mole of water per mole of total surfactant) occurs at a critical molar concentration of NaDBS + n-hexanol of ~0.3. Above the latter value, the amount of water solubilized decreases rapidly. When the amount of water solubilized per mole of total surfactant is plotted versus mole ratio of n-hexanol to NaDBS (Fig. 4), a sharp maximum is found at a ratio of n-hexanol to NaDBS of 4.5:1. This shows that the molar ratio of the two surfactants is critical for maximum solubilization of water. Furthermore, the values of this optimum ratio do not change significantly with temperature. The results obtained in this study also show that the maximum amount of water solubilized exceeds that required for the hydration of NaDBS and n-hexanol ( ~ 5 and 3 molecules, respectively) (11, 12) indicating that at least in this part of the L2 region water aggregates must be present. The most likely structure is that of an inverse micelle made up of n-hexanol and NaDBS molecules with a molar ratio of 4.5:1 and swollen with water (11, 12).
Figs. 5-8(a-c) at three different temperatures, namely 25, 37, and 50C. The influence of temperature on the extent of the transparent region (i.e., L2 + M) is shown in Figs. 5d to 8d for the four systems investigated. Each phase diagram is plotted in a two-dimensional triangle in the same manner as those described by Friberg and co-workers (24, 25). Since the NaDBS concentration is fixed for each set of phase diagrams, the comers of the triangles represent the other three components, i.e., nhexanol, water, and xylene plus x wt% NaDBS, where x is the NaDBS concentration for that particular set of diagrams. In other words, the points in the phase diagrams are obtained by multiplying each particular composition by 100/(100 - x). This was done in order to enlarge the variable components to fill the whole of the equilateral triangles. However, in the discussion of the phase diagrams all concentrations of ingredients mentioned refer to actual composition, i.e., corrected values. At each concentration ofNaDBS, a number of different phases were identified and labeled using the same nomenclature as with the ternary phase diagram (Table I). It should be mentioned that the phase boundaries are only approximate; accuracy of the location varies between 1 and 5%. Moreover, in the present study, the regions containing liquid crystalline phases were not fully investigated and the phases in the regions were grouped together under the general headings of gel or E/LC (emulsion containing liquid crystalline phase). Below a brief description of the various regions is given.
Isotropic L1 Phase
This extends over a very limited area in the high water content part of the phase diagrams and is, in general, capable of solubilizing only a small amount of xylene or n-hexanol. However, the amount of xylene solubilized increases with increase in NaDBS concentration
Quaternary System
The phase diagrams for the four component systems, containing fixed concentrations of 5, 10, 15, and 20 wt% NaDBS, are shown in
F1G. 5. Phase diagrams for the quaternary system at three different temperatures. Total concentration of NaDBS is 5 wt%.
Journal of ColloM and Interface Science, Vol. 100, No. 2, August1984
Xylene+10wt O/oNaDBS
t~
25C
/
LI+E M
e~ N
LI+E
L2-PGel
>-
L2-~Gel
EILC L1
G~ , 10
E/LC
i
100 He xanol -t-lOwtC~NaDBS
L ,ao7/~,,+~,c
~0
>
100 Hexanol~lOwt~oNaOBS
=ml]m=-
Weter-PlOwt /o NaDB$
XY l e n e ~ l O w t /o NaDB S O 100
O
- -
t-n rn >
C 50C
E L2~-E ILC
25C
..... ~o~
~.S--,~
__.
=oo 1~.~
1000 Water-]-lOwt/o NaDB S
'
,\
L1-PE
L1 10 ~,
"
. mm~Bm-
0 H e x a n o H 1Owt% NaDBS
"
323
and temperature, reaching a maximum of 15 wt% at 15 wt% NaDBS and 50C. On further increase of the NaDBS concentration to 20 wt% the solubilization of xylene is reduced to approximately 5 wt%. The solubilization of n-hexanol does not show an increase with increase of NaDBS concentration or temperature and remains constant at approximately
1-2 wt%.
NaDBS, it becomes very difficult to detect. This vague distinction between the Lz and M regions disappears completely at 20 wt% NaDBS which shows (Fig. 8) a large region of colorless, isotropic solution. The extent of the L2 region at 5 and 10 wt% remains essentially the same as the temperature is increased (Figs. 5 and 6), but the extent of the microemulsion region is reduced. The range of n-hexanol concentrations over which the microemulsion region remains stable is also reduced with increase of temperature (Figs. 5d and 6d). In contrast, at 15 wt% NaDBS, both the extent of the L2 and M regions increase slightly with an increase of temperature (Fig. 7d). Finally, at 20 wt% NaDBS there does not seem to be any significant change in the extent of the transparent region with an increase of temperature (Fig. 8d).
LI + Le Region
This region appears in the 5 and 10 wt% NaDBS phase diagrams (Figs. 5 and 6), at all temperatures, when the water content increases beyond the solubilization limit in the L2 region. In both cases, the extent of the L~ + Le region increases with increase of temperature. In contrast, this region only appears at 37 and 50C in the 15 wt% NaDBS system and no such region exists at 20 wt% NaDBS.
FIG. 6. Phase diagrams for the quaternary system at three different temperatures. Total concentration o f NaDBS is 10 wt%.
Journal of Colloid and Interface Science, Vol. 100, No. 2, August 1984
X y]ene
EILC
////',,\
EILC
~~
25C b ~ 37Oc LI+EILC
z
L1 10 Water+15wt~NaDBS i~ Xylene+15wt~oNaDBS 0 100 > 0 100 Hexanot+15wt~NaDBS
>
O Water+15wt ~ NaDBS
im~
~o n p m > ~
2 5C
c d
,/
\,___,0%
..... 37C
LI+E~LC
Gel
10
i~
100
Hexanol
0 Wate~+15wt ~ NaDBS
325
is difficult to explain since all samples were made by mixing the two phases with simple agitation. Increasing the n-hexanol concentration beyond the solubilization limit in the L1 r e g i o n also results in the formation of two phase regions. For example at 5 wt% NaDBS the L1 + E region is formed whereas at 10 wt% NaDBS the Lx + E/LC region is formed (Figs. 5 and 6). From the observed textures in the latter region, the liquid crystalline phase appears to be a neat of D phase. The L1 + E/ LC region also appears at 15 and 20 wt% NaDBS when either the n-hexanol or xylene is increased beyond its solubilization limit. These results demonstrate that a minimum amount of surfactant is required to form a liquid crystalline phase in an emulsion, as previously found by Friberg and Mandell (27).
L 2 q- E
fringence and the observed textures at 10 wt% NaDBS indicate that these consist of predominantly D phase.
M + E, M + E/LC
Binary phases of microemulsion in equilibrium with either E or E/LC appear in the vicinity of the M region. In all cases, the amount of emulsion in the M + E region k, quite small and this region changes to M + Lt with an increase of temperature. The textures observed in the M + E/LC region (mosaic and oily streaks) indicate that in all cases, this region consists of the D phase. The latter also constitutes most of the gel region in equilibrium with the M phase at 15% NaDBS (Fig. 7).
Gel Regions
Various other gel regions (apart from those described above) can be distinguished in the phase diagrams. For example, in the 5 wt% NaDBS there is a large E + gel region (Fig. 5) whereas at 10 wt% NaDBS this region, E/ LC + gel (Fig. 6), consists of a mixture of emulsions and gels of high viscosity; the emulsions are located mainly at low water content and the gels in the high water content part of the region. In the 15 and 20 wt% NaDBS systems (Figs. 7 and 8) the gel region appears transparent at a high water content and more turbid in the lower water content part of the region. At each concentration of NaDBS, the textures are very similar in these gel regions as proved using phase contrast and polarizing microscopy.
By gradually increasing the xylene concentration, while maintaining that of n-hexanol at a low level, inversion of the system into a w/o emulsion takes place above a critical concentration of xylene which depends on surfactant concentration and temperature. As the xylene concentration is further increased at 5 wt% NaDBS the inverse emulsion is found in equilibrium with the L2 phase. At 10, 15, and 20 wt% NaDBS the inverse emulsion remains in equilibrium with the L2 phase at higher xylene concentrations but contains a liquid crystalline phase. The 1-2 phase also appears in equilibrium with gel and emulsion/LC phases (see Figs. 5-8). The L2-gelregions appear when the water content is increased beyond the L~ + L2 phase. Throughout most of these regions, the samples are viscous and either very weakly or nonbirefringent. In contrast the E/LC phase in the [.2 + E/LC region shows stronger bire-
FIG. 7. Phase diagrams for the quaternary system at three different temperatures. Total concentration of NaDBS is 15 wt%. Journal of Colloidand InterfaceScience, Vol. 100,No. 2, August1984
L~ t~ C~ r
b ~
3 7C
z p >
LI~E/LC L1 10 O " Water +20w t % NaDBS " ml~ " O 100 H exanol+2Owt % NaDBS
LI+EILC
0 Water +20wt%
m~
"
0 100
Hexano ~+ 20 wtlo NBDBS
NaDBS
>
__
25C
L2
LI~EILC
Gel
~x
1 0 0 ~ O War e r-l-2Owt % Na DBS
.M~
"
"
'
H e x ano I -t- 20 w tOIoN a DB S
W a t e r 2 O w t lo NaDBS
PHASE D I A G R A M S OF A T E R N A R Y A N D Q U A T E R N A R Y SYSTEM
lOOwt ~ NaDBS
327
Xylene
Water
,q~
Hexanol
as illustrated in Fig. 9 for the results obtained at 25C. A similar representation can be made for the other temperatures. The front of the tetrahedron represents the ternary water-nhexanol-xylene systems and the corners of the triangle represent the pure components. The fourth corner of the tetrahedron represents pure NaDBS. An expanded scale is used for the NaDBS composition to allow a clear representation of the transparent regions. This diagram clearly shows the increase of the extent of transparent regions as the surfactant concentration is increased. In Fig. 10 a distorted tetrahedron is used to show the effect of the xylene concentration on the extent of the transparent region. The right-hand side triangle represents the ternary water-NaDBS-n-hexanol system and the corners of the triangle the pure components. In this case the fourth corner of the tetrahedron represents pure xylene. The data for this diagram were interpolated from the phase diagrams shown in Figs. 5-8 by noting the composition at the extremities of the transparent region for each NaDBS concentration. The same procedure described for Figs. 5-8 was used for expanding the composition of the variable components to fill the whole triangle at each xylene composition.
FIG. 8. Phase diagrams for the quaternary system at three different temperatures. Total concentration of NaDBS is 20 wt%.
Journal of Colloid and InterfaceScience, Vol. 100, No. 2, August1984
328
Xylene
BAKER ET AL.
10 ( ~ . ~
75
Water
"~
NaDBS
served by Cooke and Schulman (28) and this led these workers to draw a clear distinction between inverse micelles and microemulsions. The total surfactant concentration at which the maximum solubilizafion of water occurs is shifted to lower values as the xylene content is increased. With an increase of the temperature to 50C (Fig. 12) a small reduction in the maximum amount of water incorporated occurs at 25C and 75 wt% xylene, although the value at 50 wt% xylene remains (essentially) constant. Figure 13 shows that the maximum solubilization of water occurs at an optimum ratio of n-hexanol to NaDBS which depends on the xylene content. The ratios observed were 4.0, 3.0, and 2.0:1 at 0, 25, and 50 wt% xylene,
respectively. A similar dependence on the concentration of oil phase was observed by Sj6blom and Friberg (25). When the temperature is increased to 50C, the ratios change slightly and the corresponding values are approximately 5.0, 2.5, and 2.0:1.
DISCUSSION
A comparison of the phases described in the quaternary system can be made with those for the three component system. For example, the same type of liquid crystalline phases, two phase regions and a large extent of the I-2 region are observed in both the three and four component systems. This shows that the four component system is an extension of the three component one. This can be clearly seen if
2c
~=
~.-25 .-so
.-
Owt%xyte.e
75
,,
I
o Moles NaDBS . 1'.o
Hexan ol
FIG. 11. Solubilization of water as a function of total surfactant (NaDBS + heano|) concentration at various xylene concentrations (25C).
Journal of Colloid and Interface Science, Vol. 100, No. 2, August 1984
PHASE D I A G R A M S OF A T E R N A R Y A N D Q U A T E R N A R Y SYSTEM
329
-75
..
~
0
j
' 0"5 1~0
Moles N a D B S + Hexanol
FIG. 12. Solubilization of water as a function of total surfactant (NaDBS + hexanol) concentration at various xylene concentrations (50C).
one follows the sequence of the changes that occur with an increase in n-hexanol concentration at a fixed level of NaDBS. For example, at 10 wt% NaDBS (Fig. 6) the sequence of the phase transition observed at vanishingly small xylene concentrations is Lx ---* Lt + E/LC ---* E/LC+gel~L2+gel~L2+Ll ~L2as the concentration of n-hexanol is increased. The corresponding sequence with a zero concentration of xylene, i.e., in the ternary system (Fig. 1) is L1 --~ L1 + LC ---, LC ~ L2
+ LC ~ L2 + LI ~ L2 with increasing nhexanol concentration. The phase diagrams can be used to describe the phase changes which may appear during the preparation of microemulsions by the titration technique. For example, Schulman and co-workers (26, 28-30) observed that the titration of an o/w emulsion with an alcohol resulted in the formation of a highly viscous phase, later thought to be lamellar liquid crystalline phase (26), before finally con-
2 5 w t ~ Xylene
5Owt ~ Xylene
lO
n0
z
:E
10
20
30
lb
'
2b
:O'
1)
'
2'0
'
3~3
20~
25C
~ lO
10
20
30
'
~b
'
2'0
10
20
30
FIG. 13. Solubilization of water as a function of molar ratio of hexane NaDBS at various xylene concentrations (25 and 50C),
Journal of Colloid and Interface Science, Vol. 100, No. 2, August 1984
330
BAKER ET AL. It should be mentioned that using the present surfactant system, water in xylene microemulsions with a high water content, reaching ~ 5 5%, could be prepared using reasonably low NaDBS levels, namely, 10 and 15 wt%. Such high water volume fractions cannot be reached with the potassium oleate system, in which, m a x i m u m of only ~ 3 0 wt% water can be incorporated (25). An important point which emerges from the present investigation is the effect of temperature. It is generally accepted that microemulsions ionic surfactants are not very sensitive to temperature variation. However, the present results clearly show that this is not the case, at least when relatively low concentrations of NaDBS (< 15 wt%) are used (see Figs. 5d and 6d) when the extent of the microemulsion region is significantly reduced by increase of temperature. ACKNOWLEDGMENTS The authors are indebted to Mr. C. A. Hart for his help with the microscopicinvestigations.They are alsograteful for the ICI management for their support for Dr. R. C. Baker for carrying out this work at Jealott's Hill for his thesis. REFERENCES I. Hoar, T. P., and Schulman, J. H., Nature (London) 152, 102 (1943). 2. Prince, L. M., J. Soc. Cosmet. Chem. 21, 193 (1970). 3. Rosano,H. L., J. Soc. Cosmet. Chem. 25, 609 (1974). 4. Shindoa, K., and Friberg, S., Adv. Colloid Interface Sci. 4, 281 (1975). 5. Tadros,Th. F., in "Solution Behaviourof Surfactants" (K. L. Mittal, Ed.). Plenum, New York, in press. 6. Prince,L. M., "MicroemulsionsTheoryand Practice." Academic Press, New York, 1975. 7. Robb, I., "Microemulsions." Elsevier, Amsterdam, 1982. 8. Lindman, B., Stilbs, P., and Moseley,M. E., J. Colloid Interface Sci. 83, 569 (1981). 9. Danielsson, I., and Lindman, B., Colloids Surfaces 3, 391 (1981). 10. Baker, R. C., Florence, A. T., Ottewill, R. H., and Tadros, Th. F., J. Colloid Interface Sci. 100, 332 (1984). 11. Ekwall,P., in "Advancesin Liquid Chrystals" (G. H. Brown, Ed.), Vol. 1. Academic Press, New York. 12. Ekwall,P., Mandell, L., and FonteU, K., Mol. Crystals Liquid Crystals 8, 157 (1969).
verting to a w/o microemulsion. The phase diagrams in Figs. 5-8 dearly show that small additions of n-hexanol produce a gel or highly viscous emulsion which, above 5 wt% NaDBS is liquid crystalline in nature. At 10, 15, and 20 wt% NaDBS, this liquid crystalline phase appears to be lamellar throughout most of its extent, but above 40-50% water, the observed textures suggest that the middle (E) phase is present. This seems rather surprising since, in the three component system, a m i n i m u m of about 25-30 wt% NaDBS is required to form the E phase. However, the observed textures are rather difficult to identify and were not confirmed by any other technique. Further addition of alcohol results in the formation of a w/o microemulsion, providing that the water concentration is not too high. The phase diagrams given in Fig. 5 also show why a sharp end point is observed when using the titration technique, since the amount of n-hexanol required to form a microemulsion is very critical. Figure I0 clearly illustrates that the microemulsion region is an extension of the L2 region. This result is in agreement with observations made by Friberg and co-workers (24, 25, 31) for other systems. It was the type of phase behavior shown in Fig. 10 that led Friberg and co-workers (24, 26, 32) to consider microemulsions to be swollen inverse micellar systems. The results shown in Figs. 11-13 clearly show the role played by xylene in the solubilization of water in the microemulsion region. First, a lower n-hexanol:NaDBS ratio is required for optimum solubilization of water in the presence of xylene, i.e., less n-hexanol is required. Moreover, the systems containing 25 and 50 wt% xylene are capable of incorporating twice as m a n y moles of water per mole of total surfactant when compared to that obtained without xylene (i.e., ternary system). These results indicate that, although there is a gradual transition from the L2 to the microemulsion region, the structures m a y be different, especially at the extremes of the two regions.
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PHASE DIAGRAMS OF A TERNARY AND QUATERNARY SYSTEM 13. Mustafa, R. M. A., Hassan, M. A., and Fikrat, H. T., Canad. J. Pharm. Sci. 14, 43 (1979). 14. Ekwall, P., Mandell, L., and Fontell, K., Acta Chem. Scand. 22, 697 (1968). 15. Kertes, A. S., and Lai, W. C., Colloids Surfaces 1, 197 (1980). 16. Ekwall, P., and Mandell, L., Acta Chem. Scand. 21, 1612 (1967). 17. Ekwall, P., J. Colloid Interface Sci. 29, 16 (1968). 18. Rosevear, F. B., J. Amer. Oil Chem. Soc. 31, 628 (1954). 19. Mandell, L., and Ekwall, P., Acta Polytech. Scand. 74, 1 (1968). 20. Brown, G. H., Doane, J. W., and Neff, V. D., "A Review of the Structure and Physical Properties of Liquid Crystals." Butterworths, London, 1971. 21. Luzzati, V., Mustacchi, FI., and Skoulis, A., Disc. Faraday Soc. 25, 43 (1958). 22. Tiddy, G. J. T., and Wheeler, B. A., J. Colloid Interface Sci. 47, 59 (1974). 23. McBain, J. W., and Marsden, S. S., Acta Crystallogr. 1, 270 (1948).
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24. Friberg, S., and Burasczenska, I., Progr. ColloidPotym. Sci. 63, 1 (1978). 25. Sj6blom, E., and Friberg, S., J. Colloid Interface Sci. 67, 16 (1978). 26. Prince, L. M., "Microemulsion Theory and Practice." Academic Press, New York, 1977. 27. Friberg, S., and Mandell, L., J. Amer. Oil Chem. Soc. 47, 149 (1970). 28. Cooke, C. E., and Schulman, J. H., J. Stereochem. 59, 283 (1955). 29. Hoar, T. P., and Schulman, J. H., Nature (London) 152, 102 (1943). 30. Bowcott, J. E., and Schulman, J. H., in "Surface Chemistry," p. 231. Munksgaard, Copenhagen, 1965. 31. Rance, D. G., and Friberg, S., J. Colloid Interface Sci. 60, 207 (1977). 32. Friberg, S., and Buraczewska, I., in "Micellisation, Solubilisationand Microemulsions" (K. L. Mittal, Ed.), Vol. 2, p. 791. Plenum, New York, 1977. 33. Sj6blom, E., and Friberg, S., J. Colloid Interfce Sci. 67, 16 (1978).
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