High resolution NMR has been used in the investi
gation of the structure of microemulsion systems. Changes in the chemical shifts of the constituent groups of the components of the system give information concerning the different chemical environments of these groups; the bandwidths of the resonances give an indication of the mobility of the groups concerned.
Kumar and Balasubramanian (64,65) used ”4l NMR to
investigate systems formed by adding water to Triton X-1G0 plus hexanol in cyclohexane. They found that the initial addition of water led to the formation of reverse micelles with a decrease in the mobility of the ethylene oxide
chains. At low concentrations most of the water was bound to the ethylene oxide groups. This surfactant
1.5 «4. Cont’d.
hydration increased as water was added levelling off to a value suggesting a limiting ratio of one molecule of water bound per two oxyethylene units. This is a much lower value than that which has been found in most cases for normal micelles (section 1.1.2). As the water concentration increased "free" water pools were formed indicated by a change in the chemical shift of
the-OH signal from its initial high value of 5-8
'X
tothe normal bulk water value of around 5 -0 T.
Detergentless microemulsions can be formed from
hexane, water and 2-propanol; NMR showed that "bulk"
water was present in these systems (66).
Hansen and Mast investigated the system sodium dodedyclbenzenes sulphonate, water and xylene using NMR. This showed that xylene was solubilized in surfactant micelles, initially distributed along the surfactant molecules and only above a certain higher con centration accumulating in the core of the micelle. Sur factant line width variations were attributed to in
creased mobility of the surfactant chains when xylene molecules were distributed between them. The surfactant, and xylene chemical shifts showed no discontinuity in going from the one-phase solubilized system to the two- phase macroemulsion, indicating continuity of the
molecular environment.
Shah used NMR in studying the system hexadecane,
1.5 • ^ • Cont'd .
potassium oleate and hexanol, Kith added water (6?* 68,69)- He measured chemical shift and band width
for the water, methylene and methyl protons as a function of the ratio of water to oil. As the water content
was increased there was a transition from a W/0 micro- emulsion to a reversed hexagonal liquid crystal phase, then to a lamellar liquid crystal phase and then to an 0/W microemulsion. The chemical shift of the water protons changed significantly and by different amounts in the two liquid crystalline phases. The bandwidth increased in the liquid crystalline phases for all the protons measured, though by different amounts due to the reduced mobility.
1.5.5- SELF-DIFFUSION
The pulsed field gradient NMR technique for measuring self diffusion coefficients is outliined in section 2.2. Lindrnan et al (?0) have used this technique and also a tracer technique using radioactive labelling, to measure self diffusion coefficients in isotropic liquid regions
of the systems 0E^ -water-hexadecane and sodium
octylbenzene sulphonate-pentanol-sodium chloride-water- decane. In the nonionic surfactant system at high water contents they found diffusion coefficients typical of a normal micellar solution; in the ionic surfactant system normal micelles only appeared to occur to a very limited extent at very high water contents. Diffusion coefficients
1.5.5. Cont'd.
typical of reversed micellar solutions were found in the nonionic surfactant system at high hexadecane contents and in the ionic surfactant system only at
very high decane contents. Both systems exhibited large regions at high coneentrations of both hydrocarbon and water where diffusion coefficients indicated bicontinuous structures with high self-diffusion coefficients for both hydrocarbon and water. No distinct transition from a normal to a reversed structure was found.
Larche et al (53) used self-diffusion measurements (made by the open-ended capillary tube method with
radioactive tracers) and conductivity measurements in
their study of the system sodium p-octylbenzene sulphonate-
1-pentanol-water (+0.3wt% Nacl) - decane. By maintaining
a constant alcohol: surfactant ratio (2.1) they worked in a pseudo-ternary system which exhibited a large iso tropic liquid region. At high water content similarly low values of surfactant and decane self-diffusion co efficients and a high value for the sodium ion self diffusion coefficient were in agreement with an O/tf microemulsion. At low water content the sodium ion, chloride ion, water and surfactant exhibited similarly low self-diffusion coefficients (of the order of
1x 10 ^ nT s ^ ) whilst the decane had a higher self
diffusion coefficient (8x10 ^ ^ m^s ^ ) in agreement vrith a W/0 microemulsion structure. At intermediate volume fractions of water all the diffusion coefficients were
1.5.5- Cont’d.
greater than the surfactant diffusion coefficient which remained almost constant; there was a continuous change from values appropriate to an 0/W structure to those of a W/0 structure. The authors suggest an intermediate bicontinuous structure comparing the instantaneous structure with that of porous media. The continuous variation of the conductivity from low values
( <0.05 Sm a) in the W/0 region to high values ~1.0 Sm ^ ) in the 0/W region is in agreement with this,
1.5.6 . ELECTRICAL CONDUCTIVITY
Conductivity measurements have been used in the investigation of several microemulsion systems, both oil-continuous and water-continuous. Such measurements can be a convenient way of determining the nature of the continuous phase.
Kumar and Balasubramanian (60) measured conductivity in the Triton X-100-alcohol-water ^clohexane system.
The water was doped with potassium chloride for these measurements; the alcohols used were pentanol, hexanol and octanol, similar results being obtained for all. The conductivity was measured for increasing amounts of water added to a fixed volume of solution of surfactant and alcohol in cyclohexane. For a Triton X-100: alcohol
ratio of
^:2
the initial low conductivity of about 0.5m Smremained virtually the same until just before phase
1.5-6. Cont’d.
separation occurred to form macroemulsions, when it rose s t e e p l y . The authors state that there is no ap
preciable barrier to conduction in the macroemulsions ■which would be the case if these are 0/W emulsions. The conductivity changed by a factor of about 100 from
the initial oil-continuous phase to the final macroemulsion.
For the surfactant:alcohol ratio
k:l
the variationof conductivity with added water is more complex (Fig.1.9)• The initial low conductivity of about 0.5m Sm ^ (as
before) rose prior to the phase transition to the ani sotropic phase. The conductivity then fell, the
explanation given being that the effect of the increase in the medium viscosity outweighs the effect of the relatively easy conduction pathways in the lamellar/
cylindrical micellar configuration; however, the viscosity of the medium is not necessarily related to the con
ductivity. Beyond the anisotropic region macro
emulsions were again formed and the conductivity rose as in the system with the surfactant;alcohol ratio of 3 :2 .
Smith et al (6l) measured conductivity in their investigation of the system 2-propanol-water-hexane, which they found to exhibit an oil-continuous micro emulsion region. They proposed structures for regions covering most of the phase diagram on the basis of con ductivity and ultracentrifugation data. The conductivity increased steadily through the microemulsion region as the propanol content was increased; this behaviour was ascribed to an increasing amount of water in the continuous
'ft
% % KCL exeU«4
Fig. 1.9* Variation of the conductivity of the micellar dispersion as a function of aqueous KC1 uptake into a 20%
solution of Triton X-100 - alcohol (ratio 4:1 ) in cyclohexane. Single arrow indicates transition to anisotropic phase and double arrow indicates region.
of phase separation pentanol; x*** hexanol;
o o e o octanol. (from ref.60.)
So
Fig. 1.10.' The pseudo three component phase map of Tween 60- n-pentanol -water -hexadecane. The arrows denote
compositions employed for the conductivity measurements, (from ref.71)*
1•5•6. Cont’d .
phase (rather than in the reverse micelles). The conductivities measured in this region ranged from
about 10
MSm
^ to about 200ydSm
^ according to thewater content and propanol content of the sample. Mackay and Agarwal (?) have measured the con
duct ivity of a number of 0/W microemulsions containing added electrolyte in the systems surfactant-n-pentanol- water-oil where the oil was hexadecane or Nujol and the nonionic surfactants were various Tweens. They studied
the Tween 60-n-pentanol-water-hexadecane system in more detail. They replaced the water with 0.1M sodium chloride solution fir the conductivity measurements. For a constant emulsifier:oil ratio (see Fig. 1.10) they found that the equivalent conductance (A ) obeyed the relation
A = A " (1 - a
comp0)n -- 1.1
where
0
comp is the disperse phase volume estimatedfrom the composition and density of the microemulsion and ’a 1 and 'n' are parameters to be found for the system. The systems obeyed the relation well except
at the highest values of / corap . The clear region extends*
to the emulsifier-oil axis so it is suggested that these deviations from the linearity of the above expression are a result of a transition from the 0/W micellar
solution (i.e. the microemulsion) to some other isotropic
phase. The maximum values of o rnp were 0.80 and 0.85;
1.5.6. Cont'd •
the maximum disperse phase volume for monodisperse hard spheres in 0.74 so that it is not surprising
if the microemulsion breaks down at these phase volumes. The ’a 1 values were generally found to be about
1.2. Mackay and Agarwal discussed the meaning of the
'a* term and thought the most likely possibility to be that the effective phase volume with respect to con
ductivity measurements differed from
0
comp and was infact larger than °
0
comp so that0 =
a0
comp where0
is the effective phase volume. This could be accounted for on the basis that some of the water should be included as part of the drop, in the form of water of hydration of the ethylene oxide groups. If the bound water/ surfactant ratio is constant then constant ’a' values result. Calculations of the quantity of water involved gave values of 1-2 moles of water per ethylene oxide group). The authors suggest that the presence of pentanol in the system may account for the constancy of the fa ’ value for different Tweens.The 'n' values were constant at constant emulsifier oil ratios but decreased on increasing the oil concen
trations ranging from about 1.5 to 1.1. A tentative
explanation of the change in fn f values is given, based on the behaviour of the alcohol in the system.
1.5.6. Cont’d.
The results were compared with theoretical
equations for macroemulsions (the Maxwell and Bruggeman equations - chapter 2 ) and also with the usual be
haviour of macroemulsions. The conductivity measured in the present system was considerably lower than that which would be expected if the theoretical equations were obeyed or if the system behaved as a macroemulsion. Converting the equation 1.1 to the same form as the
Bruggeman equation (Equation 2.1) gives:
= (
1
-0)2,3
-1.2
m
where K is the conductivity of the emulsion and K the
conductivity of the continuous phase;
0
is the dispersephase volume. The exponent is 2.5 instead of 1.5 as in the Bruggeman equation.
No mention is made of the impurities occurring in the commercial surfactants used and whether these are likely to affect the results in any way.
Roux and Viallard (72) measured conductivity in dilute (0.002M) aqueous solutions of nonionic sur
factants (polyoxyethylene nonylphenyl ethers of varying oxyethylene chain length), to wThich methyl benzoate was added. At about 0.5% (v/v) ester transparent
solutions were obtained which they described as a micro- emulsions. Sedimentation velocity measurements indicated the presence of large aggregates. The location of the
1.5-6. Cont’d.
ester in the aggregates is not discussed. These micro emulsions are much more dilute than man3r systems so described.
Conductivity was related to changes in viscosity in the micellar solutions and the emulsions (occurring at lower ester concentration) and the microemulsions.
Shah et al have measured electrical resistance
(reciprocal of conductance) in the same systems for which they recorded the NMR (67»68,69) (Section 1.5*^-)-
Since their system contained an ionic surfactant, doping with a salt was not necessary. Electrical resistance was measured as water was added to the mixture of hexa- decane, hexanol and potassium oleate. The resistance dropped initially as water was added to the system.
(Fig l.ll). They accounted for this on the basis of "molecular solubilization" of water in the hexadecane - hexanol-potassium oleate mixture, NMR supporting this interpretation. The resistance then remained fairly
constant throughout the W/0 microemulsion region, in which the interface between the oil and water is the main
barrier controlling ion transport between the electrodes. The resistance then dropped abruptly as the system became birefringent on the formation of a liquid
crystalline region. The sharp decrease in resistance within the birefringent region appears to coincide with
the change from a reversed hexagonal to a lamellar phase
____ j] TiTi7n7mfiTaiT<7iIi7ni B lr t f 'r r iN jin t W» i -Xo si r
9
•> « 4u 4- 4) 1*6 0*1Fig, 1.11. Variation in electrical resistance, optical clarity and. birefringence of a system consisting of 1cm of hexadecane, 0«4cm? ofhexanol and 0*2g of potassium oleate as water is added, (from ref.69).
1•5•6. Cont1d •
which the authors discuss in relation to their NMR data. The resistance then increases again; this is at
tributed to the disruption of lamellar structures. It then decreases as the 0/W microemulsion is formed. Throughout this system the resistance changes by a
k
factor of 10 ; the difference between the resistance of the W/0 and the 0/W mi croemulsions is a factor of; between 10^ and 10^.