Small angle neutron scattering near Lifshitz lines: Transition from weakly

structured mixtures to microemulsions

K.V. Schubert, R. Strey, S. R. Kline, and E. W. Kaler

Citation: The Journal of Chemical Physics 101, 5343 (1994); doi: 10.1063/1.467387
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 Small angle neutron scattering near Lifshitz lines: Transition from weakly
structured mixtures to microemulsions
K.-V. Schubert
Department of Chemical Engineering. University of Delaware. Newark. Delaware 19716
R. Streya)
Max-Planck-1nstitut fur Biophysika/ische Chemie. Postfach 2841. 37018 Gottingen. Germany
S. R. Kline and E. W. Kaler
Depanment of Chemical Engineering. University of Delaware. Newark. Delaware 19716
(Received 22 April 1994; accepted 31 May 1994)
We have studied the phase behavior, wetting transitions, and small angle neutron scattering (SANS)
of water, n-alkane, and n-alkyl polyglycol ether (C;E) systems in order to locate the transition
between weakly structured mixtures and microemulsions, and to provide a measure for the
transition. We first determined the wetting transition by macroscopic measurements and then
measured the location of the Lifshitz lines by SANS. Starting with wel1-structured mixtures
(exhibiting nonwetting middle phases and wel1-expressed scattering peaks, features that qualify
them as microemulsions) the wetting transition was induced by increasing the chain length of the
alkane or by changing the oil/water volume ratio, and then the Lifshitz line was crossed. Further,
starting with systems past the disorder line (weakly structured mixtures that display wetting middle
phases and no scattering peaks), local structure was induced by either increasing the surfactant
concentration or decreasing the oil/water volume ratio or the temperature. In each case a Lifshitz
line was crossed. Analyzing the scattering experiments quantitatively, allows determination of the
amphiphilicity factor, which is a measure of the strength of the surfactant. The results suggest there
is a sequence of roughly parallel surfaces within the three-dimensional composition-temperature
space. As the amphiphilicity factor increases, first a disorder surface is encountered, then a Lifshitz
surface, and finally a wetting transition surface. How and to what extent these surfaces move in the
one-phase region toward smal1er surfactant concentrations, and intersect there with the body of
heterogeneous phases, depends on a number of factors that are discussed in some detail.

I. INTRODUCTION phase behavior is comparable in all mixtures (Ref. 3 is a

good introduction for newcomers to the field). On the micro-
Amphiphilic molecules (surfactants) adsorb at the water/ scopic level, however, one may expect differences in struc-
oil interface and reduce the interfacial tension by several ture.
orders of magnitude. This feature allows formation of ther- Long-chain surfactant molecules form an interfacial film
modynamically stable dispersions, called microemulsions. separating polar and nonpolar domains, and in this way the
The nature of the surfactant' orders the mixtures on a micro- surfactant molecules order the domains into a variety of
scopic scale, but leaves them macroscopically homogeneous. structures. The size and arrangement of the domains is a
In recent years it has become evident that the essential prop- function of many variables including concentration, tempera-
erties of a large variety of different microemulsion systems, ture, and the water-to-oil ratio. The microstructure has been
often five-component mixtures containing brine and ionic examined by various techniques 6,7 such as conductivity,6,8
surfactant in combination with a cosurfactant and oil, can be smal1 angle scattering,6,9-14 NMR,6,IS,I6 freeze fracture elec-
found in easier-to-study ternary systems. A polar solvent (A), tron microscopy (FFEM),6,I7-20 viscosity,6 fluorescence
a nonpolar solvent (B) (typically a hydrocarbon), and a quenching,2I,22 and ultrasonic absorption. 6,23
single surfactant (C) suffice. Shinoda2 demonstrated that the Short-chain amphiphiles display a decreasing degree of
typical phase behavior can be generated by using nonionic ordering with decreasing chain length. On the other hand,
surfactants and temperature. Kahlweit and co-workers (Refs. still the same phase behavior is observed, so the role of the
3-5, and references therein) studied such ternary systems surfactant molecules in determining the phase behavior and
systematically using as surfactants the family of the n-alkyl microstructure needs to be clarified. Aside from the funda-
polyglycol ethers (denoted as C;E). Interestingly, the generic mental interest of such less structured fluids, such mixtures
pattern of the macroscopic isotropic phases is the same for offer interesting potential applications as solvents of interme-
both long-chain and short-chain nonionic surfactants. For in- diate polarity for chemical reactions. Further, the knowledge
stance, a phase inversion is observed as function of tempera- of the phase behavior3,4 of the ternary systems and the
ture or hydrocarbon chain length. Further, the effect of dif- known effects of additives should make the extraction of the
ferent additives (e.g., electrolytes, or other polar solvents) on products easy to handle.
As the chain length of surfactants is decreased, middle
Author to whom all correspondence should be addressed.
phase microemulsions become able to wet the water/oil in-
terface for thermodynamic reasons. 24 Widom has suggested
,I

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 5344 Schubert et af.: Transition from mixtures to microemulsions

Experimentally, further decreasing the amphiphilicity

(but with fa still slightly negative) leads to a crossover
from a nonwetting to wetting surfactant-rich
phase,6,10,24,27,32,34,36,37-40 so that phase (c) spreads at the in-

>-
tricriticat points ~ terface between phases (a) and (b). In the vicinity of this
...... transition there is a Lifshitz line4' (defined by c, =0, so that
:~
fa=O). Further decreasing amphiphilicity leads to the disor-
:E
0. disorder tine - - - - - - - - -- + 1 der line42 where fa= 1. Both the Lifshitz and the disorder
:E line are detectable using small angle neutron scattering
0.
E (SANS). While these lines do not correspond to macroscopic
o
phase transitions, they may be taken as demarcation lines for
Ol
C Lifshitz tine ----------- o the transition from weakly structured mixtures to genuine
(f)
oQ) microemulsions. Further decreasing amphiphilicity, and posi-
'- tive values of fa' leads to tricritical points. 5,24,27,32,43
U
Q)
good" microemutsions These observations motivated us to further examine the
U
scattering behavior of mixtures close to the wetting transi-
lamellar phase -1
tion. Since Schubert and Strey27 found that the wetting tran-
sition occurred closer to the Lifshitz line than to the disorder
line, we wanted to investigate whether the Lifshitz line al-
FIG. 1. A schematic diagram of observations of microemulsion systems as a ways correlates with the wetting behavior of the solutions. If
function of the amphiphilicity factor (for further discussion see the text).
this is so, the coincidence would suggest that the Lifshitz line
is the more general marker of the onset of microemulsion
structure. Further, we wanted to determine whether the scat-
that microemulsions could be differentiated from less- tering peak moves towards q =0 close to the wetting transi-
structured mixtures by this feature. 25 However, such a defi- tion as predicted by theory,26 or whether it first moves to-
nition limits microemulsions to cases in which the wards larger q values and then develops at around q=O, as
surfactant-rich phase is in equilibrium with excess phases, the experiments of Langevin and co-workers 10,11,44 indicate.
because only then a nonwetting-+wetting transition can be We chose to study the following systems, which permit
observed experimentally. Gompper and Schick suggested
the crossing of wetting transitions and Lifshitz lines along
that the wetting transition is connected to a change in the
several experimental paths. Here, the mass fraction a of the
real-space correlation function of the microemulsions in the
oil in the mixture of water (A) and oil (B) is denoted by
vicinity of a disorder line?6 The real-space correlation func-
tions are readily measured using small-angle scattering meth- a=mb/(ma + mb) in wt %, where mi is the mass of compo-
ods, and scattering experiments can be performed regardless nent i. The oiVwater volume ratio c/> is defined by
of the number of phases in equilibrium with the microemul- c/>=c/>b/(c/>a+c/>b)' where c/>i is the volume fraction of com-
sion. In a previous paper Schubert and Strey27 investigated ponent i, and the overall surfactant concentration y is calcu-
the scattering behavior of microemulsions with varying am- lated from y=mJ(ma+mb+mJ in wt %. We first studied
phiphilic strengths in order to quantify the degree of ordering symmetric microemulsions (c/>=0.5) in the systems
in the solutions and to compare the findings with theoretical D20-n-alkane-C6Ez using different n-alkanes with carbon
predictions?5.26,28-3o The analysis of the small angle neutron numbers k ranging from k=8 (n-octane) to k=22 (n-
scattering spectra permitted extraction of the coefficients of a docosane). The wetting transition for these symmetric micro-
Landau-Ginzburg order parameter expansion. 9 The param- emulsions is located between k=20 (nonwetting) and k=22
eters in tum could be combined into an amphiphilicity factor (wetting). We then studied the scattering behavior of the sys-
fa(=C,/(4a2c2)'I2, for details see below) that allows deter- tem water-n-hexadecane (k= l6)-C6E2 as a function of oil
mination of the amphiphilic strength on a uniform scale in- content. In this family the symmetric microemulsion (c/>
dependent of the individual microemulsions studied. Figure =0.5) does not wet the water/oil interface. Increasing the
1 illustrates the use of this amphiphilicity scale, which is
oil/water volume ratio leads to the wetting transition (at
consistent with recent theories?'
c/>=0.72), and, as shown below, crosses the Lifshitz line.
For very strong amphiphiles (with high amphiphilicity
Next, the scattering patterns for water-n-octane-C 4E, mix-
and an amphiphilicity factor fa close to -1) the lamellar
liquid crystal is the dominating phase in the phase tures (c/>=0.5) were measured as function of surfactant con-
diagram. 32 ,33 A slight decrease in amphiphilicity leads to an centration in order to determine, if local structure forms
isotropic phase, which is a strongly structured ("good") mi- when the surfactant concentration increases in disordered so-
croemulsion. If such a microemulsion exists as a surfactant- lutions. Such local structures were also examined as a func-
rich phase (c), it does not wet the interface between the polar tion of temperature in solutions of water-n-octane-C4E\
excess phase (a) and nonpolar excess phase (b), as discussed ( y= 60 wt %). Local structure also depends on c/> in the
by Widom,25 but rather forms a lens at the alb interface. D20-n-octane-C4 E\ system, and a Lifshitz line exists even
Photographs of such lenses are shown in Refs. 6, and 34-36. in the binary water-C4E\ mixtures. 45

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 Schubert et al.: Transition from mixtures to microemulsions 5345

II. SCATTERING THEORY for the amphiphilicity factor defined in Eq. 6. fa is an indi-
rect "measure" because it is based on the behavior of the
Analyzing scattering spectra of nearly molecular ternary
correlation function '}{ r). For - I <fa < I the correlation
mixtures within the small-scale region, as it has been termed
function displays oscillatory behavior. At the disorder line
by Safran,4<l in the previous study,27 it was found that experi-
(fa = 1) the solution loses its quasiperiodical order and the
mental spectra could be precisely fitted with the Teubner-
interfaces (or what is left of them) become uncorrelated. The
Strey form. 9 That form is used again here with the fits for
correlation function at large distances changes from an oscil-
each spectrum given as a solid line in the Figures below. The
latory to a monotonic behavior. The spectrum obtained then
normalized differential scattering cross-section /(q) is9
also decays monotonically with q. At the Lifshitz line (fa =0,
87TC2( rh/~ that is when C 1 =0) the lowest order gradient term in the
/(q)= Q2+Clq2+C2q4 , (1) Landau-Ginzburg order parameter expansion changes its
sign from negative to positive. Cl =0 is the defining charac-
if)
where < = <Pa<Pb(llp?, with (llp) being the difference in teristic of a Lifshitz point. 41
scattering length densities between media a and b. The co- Experimentally, it was found that the macroscopic wet-
efficients Q2 ,CI 'C2 stem from a Landau-Ginzburg order pa- ting transition occurs on the microemulsion side of the Lif-
rameter expansion of the local free energy density including shitz line, which is as predicted by Gompper and Schick26 on
gradient terms and are adjustable parameters. c I <0 causes a the microemulsion side of the disorder line. In the meantime
peak at nonzero wave vector in the scattering spectrum. Fou- theoretical work using various approaches has appeared also
rier transformation of a simple real-space correlation func- predicting the Lifshitz and disorder lines. 52 - 58 A useful re-
tion '}{r) leads to the functional form of Eq. (1) with view of the current theoretical understanding is given by
Gompper and SchickY
y(r)= sin(kr) ex p ( -~) (2) The scattering curves for the system I6Fx, to be dis-
kr ~
cussed below, are increasingly dominated by critical scatter-
and k = 2 7T/ d. This correlation function combines two well- ing as conditions approach those of the critical endpoint.
known features of microemulsions, namely the alternation of Therefore, they were fitted with a Teubner-Strey equation
water and oil-containing domains due to the orientation of augmented with a critical scattering relation
the surfactant molecule (the sidedness)1 and the absence of a (Ornstein-Zernike)59 effective at low q. The fitting equation
long-range order. There are two lengths then reads

~= [
I (Q2)
- -
1/2
+-
C[ ]-112 (3)
2 C2 4C2
l(q) (7)
and

~ =[~ (Q2)
27T 2 C2
112 _~]-1I2
4C2
(4) where ~oz is the correlation length accounting for the effect
of critical scattering. Gompper and Schick28 provide a ratio-
The length d is a measure of the quasiperiodic repeat dis- nale for the functional form of Eq. 7 and show how, in an
tance between polar and nonpolar molecules9 as in a lamellar incompressible fluid, there will be two independent scatter-
phase, but the correlation function is isotropic and represents ing functions, and that any observed scattering function will
no long range order because of the exponential in Eq. (2). simply be a linear combination of the two. They calculated
The correlation length ~ can be thought of as a measure of the two independent scattering functions for their model of a
the dispersion of d. 47 ,48 "balanced" microemulsion and found that one scattering
The experimental spectra we fit to the expression function was of the TS form [Eq. (1)] and the other was of
I the OZ form. This will be the case for the experiments dis-
l(q)= +b (5) cussed here as long as the samples are on the microemulsion
Q2+Clq2+C2q4 ,
side of the disorder line. On the other side of the disorder
where b represents a (mainly) incoherent background deter- line, the scattering will be described by two OZ forms. The
mined from the scattered intensity at large q. The coherent correlation length in one of them diverges as the critical end-
part of the scattering intensity at q =0 is IIQ2' Because the point is approached, while the correlation length in the other
length d diverges at the disorder line [that is when will not. Thus, the functional form of Eq. (7) is justifiable,
C[ =(4Q2C2)1/2] we can define an amphiphilicity factor fa and is not ad hoc as it might appear.
Model fits to the scattering spectra were obtained using
(6) nonlinear least-squares optimization with minimization of
fa ( 4a 2C2)1I2
the K error. Due to the uneven distribution of the data points
which can be calculated given the values of the three fitted along the individual scattering spectra, the resulting fit pa-
parameters of Eq. (5). Note that any inaccuracy in the abso- rameters were finely readjusted by careful visual inspection
lute intensity calibration drops out when calculating the ratio of each scattering curve. This procedure yields nearly perfect
fa. There are different expressions for amphiphilicity,49-51 in descriptions of the data points (see Figs. 4-8 beloW). The
terms of ~ and d; in those terms the disorder line corresponds typical errors are ±2% for Q2' ±4% for CI' and ±8% for C2'
to 27Tljd=0 and the Lifshitz line to 27Tljd= 1,51 as is the case so the approximate error for fa is ± 10%.
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 5346 Schubert et al.: Transition from mixtures to microemulsions

III. EXPERIMENT TABLE 1. The mnemonic sample nomenclature (first column) is composed
of the number of carbon atoms in the hydrophobic part of the surfactant i (14
A. Materials or 16), and either the number of carbon atoms of the hydrocarbon k, the
oil/water volume ratio 4> or the surfactant concentration 'Y. For each sample
All n -alkanes used in this study were purchased from the weight fractions a and 'Y are given.
Merck, Darmstadt (Germany) with a purity >99%. D20 (de-
gree of deuteration >99.9%) was from Cambridge Isotope Sample System a 'Y 4>
Laboratory (Cambridge, MA). 2-Buthoxy ethanol
16K08 D2O-C sH,s-C 6E:z 38.94 34.00 0.5
[H-(CH2)c(OCH2CH 2h-OH; C4 E 1] was from Aldrich 16K 10 D20-CIOH2Z-C6E2 39.64 39.76 0.5
(spectrophotometric grade, 99+%), and diethyleneglycol 16KI2 D20-C I2H26 -C 6E2 40.52 46.20 0.5
monohexylether (C 6 E2) was purchased from Fluka (Neu 16KI4 D20-C'4H30-C~2 40.84 54.70 0.5
VIm, Germany) with a purity >98%. The cloud points at the 16KI6 DzO-C'~3CC~2 41.10 61.84 0.5
16KI8 D20-C,sH3S-C~2 41.16 67.20 0.5
critical compositions of the binary systems of water-CiEj
16K20 D2O-C2oH4Z- C6E2 41.26 71.40 0.5
were always checked in order to monitor any surfactant deg- 16K22 D20-CZ2H46-C~2 41.35 73.40 0.5
radation. When necessary, they were purified using the puri-
fication technique 3PHEX. 60 The solvents were used without 16F90 D2O-C sH,s-C 6E:z 86.38 44.20 0.9
16F85 D2O-C sH,s-C 6E2 80.00 51.05 0.85
further purification. 16F80 D20-C sH 'S-C~2 73.68 55.38 0.75
Volume fractions ¢x were calculated assuming ideal 16F70 D2O-CgH,g-C 6E2 62.06 60.20 0.7
mixing using the known densities (gIcm 3 ) at 20°C for D20 16F75 D2O-C sH,s-C 6E2 67.87 58.64 0.65
(1.105), n-octane (0.703), n-decane (0.730), n-dodecane 16F60 D2O-C sH,s-C 6E2 51.45 62.14 0.6
(0.751), n-tetradecane (0.762), n-hexadecane (0.775), 16F50 D2O-C sH,s-C 6E2 41.10 61.84 0.5
n-octadecane (0.777), n-eicosane (0.779), n-docosane 14F50 DzO-C sH,s-C4E, 39.94 54 0.5
(0.780), C4 E 1 (0.903), and C6E2 (0.932). 14F40 DzO-C sH,s-C4E, 29.76 54 0.4
14F30 DzO-CsH ,s-C4E, 21.45 54 0.3
14F20 D2O-C sH,s-C4E, 13.72 54 0.2
B. Phase diagram determination and sample 14FlO D zO-C sH,s-C 4E, 6.58 54 0.1
preparation 14FOO DZO-C4 E, 0 54 0
A useful procedure for studying the phase behavior of 14G52 DzO-C sH,s-C4E, 38.9 52 0.5
ternary systems is based on the observation of the two- 14G54 D2O-C sH,s-C4E, 38.9 54 0.5
dimensional phase diagrams constructed by erecting vertical 14G55 D2O-C sH,s-C 4E, 38.9 55 0.5
sections through the phase prism. 3 Here such sections 14G57 DzO-CsH ,s-C4 E, 38.9 57 0.5
14G60 DzO-C sH,s-C4 E, 39.0 60 0.5
through the phase prism were measured at a constant oil/ 14G65 D2O-C sH,s-C4E, 38.8 65 0.5
water volume ratio ¢ as function of surfactant concentration I4G75 D2O-C sH,s-C4E, 38.9 75 0.5
y and temperature T. All phase diagrams in this study were
determined using D20 instead of H20. A more detailed de-
scription of phase diagram determinations was published
previously.27 There are also details of the sample preparation 0.008 to 0.6 A-I, with the mean neutron wavelength ~=5 A
described. 27 All samples were studied in bulk contrast, so with an accuracy of better than 1%. The wavelength spread
that only one solvent was deuterated (D 20) and all other was a~/~= 15%. The collimation path was chosen such that
compounds were hydrogenated. the sample-to-detector distance was approximately equal to
the sample-to-source distance. Samples I6F90, I6F85, and
I6F80 were measured with three sample-to-detector dis-
C. Mnemonic sample nomenclature
tances, 12.0 and 4.0 m (detector on axis) and 1.3 m (detector
The large number of samples requires an unambiguous 25 cm off axis). In all other cases two distances or only one
labeling. We use the following mnemonic nomenclature: distance (for 14FOO) had to suffice (thUS some of the scatter-
Each sample is characterized by the number of carbon atoms ing curves have different lengths). All samples were mea-
in the hydrophobic part of the surfactant i=4,6 (e.g., 14 for sured in 1 mm Hellma QS cells with Teflon stoppers. The
C4 E 1), and either the chain length of the hydrocarbon k used method of temperature control and the cell holder were de-
(see Figs. 2 and 4) (e.g., KlO for n-decane), the oil/water scribed earlier.27 Care was taken that the measurements were
volume ratio ¢ (e.g., F50 for ¢=0.50) (see Figs. 3 and 5), or made on homogeneous samples.
the total surfactant concentration y (e.g., G55 for y=55
wt %) (see Fig. 6). For example, the sample D20-CsH1S E. Raw data treatment
(k=8)-C 6 E2 is referred to as I6K8. The sample is then
Detector sensitivity was determined by measurement of
uniquely characterized because temperature and oil/water
the incoherent scattering of H20 at a short sample-to-
volume ratio are fixed. Table I summarizes this nomenclature
detector distance with sufficiently good statistics. Bad pixels
and gives all sample compositions.
of the 64X64 cm2 two-dimensional detector and the pixels
around the beam stop and the rim of the detector were elimi-
D. SANS measurements
nated by applying a software mask. The raw data were nor-
The scattering experiments were carried out using the malized, radially averaged, and masked using the standard
NG3 spectrometer at the National Institute of Standards and software provided by NIST. The data were put on absolute
Technology (NIST) in Gaithersburg, MD. q ranged from scale by measuring the scattering of a silica standard pro-

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 Schubert et al.: Transition from mixtures to microemulsions 5347

80r-----~------.-----~------.-~--~
80r------r------~~--~------.-----,

020 -C k H2k • 2 -C 6 E z

60 :2 60
T/"C
TIDe
0.5

20

OL-----~------~------~------~----~
40 50 60 70 80
30 40 50 60 70 80
y/wt%
y/wt%

FIG. 2. Vertical sections through the phase prisms of D20-n-alkanes-C6E2 .

The mixtures contain equal volume fractions of water and oil (4)=0.5). FIG. 3. Vertical sections through the phase prisms of
Increasing the chain length of the hydrocarbon leads to decrease in the D 20-n-hexadecane-C 6E2 with varying oil/water volume ratio. Increasing
efficiency of the surfactant, and the three-phase region moves to higher the oil content (from 4>=0.50 to 4>=0.90) produces a systematic shift in
temperature. For n-hexadecane (k = 16) parts of the three-phase body are temperature for the middle phase microemulsion region as the critical end
indicated by dashes lines. A complete fish diagram for this system with point at T u =55.5 °C is approached. The middle phase wets for 4»0.72.
a=50 wt 'K is given in Ref. 36. The middle phase does not wet the interface
between the two excess phases for all k less than 20.

tion located between k=20 (nonwetting) and k=22 (wet-

ting).
vided by NIST. The scattering of an empty cell was sub-
The system D20-n-hexadecane-C6E2 is well suited for
stracted from each spectrum after taking the appropriate
studying the effect of the oil/water ratio on the wetting prop-
transmission factors into account. Data sets from each dis- erties of the middle phase. The trajectory (dashed line) of the
tance were independently placed on absolute scale and over- middle phase (c) can be seen from the variations of the fish
lapped without any scale adjustment. The data points at the
tails in Fig. 3. Increasing oil content above 4>=0.5 leads to a
lowest q values measured at each sample-to-detector dis-
reduction of the surfactant concentration needed to make a
tance were not used. Smearing effects at low q for each single phase, accompanied by the characteristic shift6 in tem-
sample-to-detector distance were critically examined and
perature towards Tu' The transition from nonwetting to wet-
found to be insignificant. The measurements were extended
ting is at 4>=0.72 (±0.03).
to sufficiently large q to obtain precise estimates for the flat
The vertical section through the phase prism at equal
background scattering. Two samples (I4G52 and I6K8) had
volumes of water and oil (4)=0.5) for the
been measured previously at the Institute Laue-Langevin H20-n-octane-C4E, system has recently been published. 32
(ILL) in Grenoble, France (referred to as B4-0 and B6-0 in
Replacing H20 with DzO results in a shift down in tempera-
Ref. 27). The NIST data that we obtained in the present study
ture by about 3 K and is taken into account in our measure-
overlap those from ILL obtained previously by Schubert and ments. We investigated samples as function of surfactant
Strey 27 within 10% on absolute scale.
concentration much larger than the fish tail concentration,
and so are far from phase boundaries. Additionally, we stud-
ied samples at constant y and temperature as function of
IV. RESULTS
increasing water content. Figure 3 shows that samples with
A. Phase diagrams decreasing 4> (ranging from 4>=0.5 to 4>=0) at constant high
surfactant concentrations will remain homogeneous if the
All phase diagrams in this study were determined using
temperature is kept constant. We also studied the scattering
D20 instead of H20. The one phase temperature interval was
behavior of a single sample (I4G60) as a function of tem-
determined for each sample prepared.
perature. Figure 1 in Ref. 32 shows that the sample always
In Fig. 2 vertical sections through phase prisms for sys-
was far from phase boundaries.
tems D20-n-alkane-C6 Ez(4)=0.50) are shown. We confine
ourselves to the relevant portions of the "fish tails." Only for
k = 16 is the extent of the three-phase body partially indicated
(for a complete "fish diagram" for a=50 wt % see, e.g., B. Water-n-alkanes-C s E2 : the effect of oil chain
length (16Kx)
Refs. 36 and 40). With increasing chain length of the hydro-
carbon the surfactant becomes less efficient (e.g., for k=8 a In Fig. 4 the bulk contrast scattering spectrum of the
surfactant concentration of around 33 wt % is required to D 20-n -octane-C6E2 sample is shown as the top curve on
solubilize equal amounts of water and oil, whereas for k= 16 absolute scale. All spectra are presented on a double log
around 62 wt % is needed). Also, with increasing chain scale and displaced from each other by dividing them by
length of the oil the fish tail moves to higher temperatures. factors of 2, 4, 8, etc. The solid lines through the data points
Both effects contribute to the occurrence of a wetting transi- are the fits of the Teubner-Strey formula [Eq. (5)]. The fit
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 5348 Schubert et al.: Transition from mixtures to microemulsions

curves describe the spectra quantitatively and, therefore, con-

tain all the essential information obtainable from such a
curve. The fit parameters are summarized in Table II. Previ-
ous SANS measurements27 allow calculation of the am-
phiphilicity factor for I6K08 (in Ref. 27 it is called B6-0) of
fa = -0.58, in very good agreement with the current value of
I(q) -0.62 (see Table II). Increasing the chain length of the oil
[em -1] 1 :""111___ k8 leads to a decrease of the coherent scattering intensity, while
~~ma""~~~;;~10 the incoherent background determines the scattering inten-
0.1 t--EJJl-----.....:
~~mB. . . . . .__~. . . 16
:"'11---12
14
sity at large q. The decrease in intensity reflects the fact that
increasing surfactant concentration leads to a decrease in the
f ---<::9BII!II_ _ _"';::~ 18 length scale d, and the contrast supplied by the D20. On
r 20
approaching the wetting tranSItion [located between
0.01 r-----------;;;;~ 22 n-eicosane (k=20) and n-docosane (k=22)] it is evident that
0.01
the scattering peak does not move continuously towards
q=O. Instead, qrnax moves towards larger q (from
qrnax=0.055 A-\ for n-octane to qrnax=0.12 A-\ for
n-docosane) and persists through the wetting transition. For
FIG. 4. Bulk contrast spectra of D20-n-alkane-C6~ mixtures with the
hydrocarbon chain length k as a parameter. Compositions correspond to the all systems the amphiphilicity factor fa [see Eq. (6)] remains
fish tails of Fig. 2. The top curve represents the scattering spectrum for the negative, whereas d and ~ [calculated from Eqs. (3) and (4)]
sample with n-octane on an absolute scale. This spectrum quantitatively decrease systematically as a function of the chain length of
reproduces the center curve in Fig. 4(b) in Ref. 27. The overlap of the data
from different sample-to-detector distances is achieved without adjustment
the hydrocarbon.
of the individual parts of the curves. The solid lines are fits according to Eq.
(5). The curves are separated by factors of 2 from one curve to the next. For c. Water-n-hexadecane-C6 E2 : the effect of oil
further discussion see the text.
content (ISFx)
These mixtures allow the wetting transition to be ap-
proached by varying the water-to-oil ratio. 44 The scattering
spectra are fitted using the Eq. (7), because critical scattering
occurs on approach to the critical endpoint. In Fig. 5, again

TABLE II. Fit parameters according to Eq. (5), with ~ and d calculated from Eqs. (3) and (4). The parameter
fa is a measure for the amphiphilicity and is calculated from Eq. (6), fa=O corresponds to the Lifshitz line,
fa = 1 to the disorder line.

Sample T (0C) a2 CI C2 b H".) d (A) fa

I6K08 5.0 0.038 -9.54 1566 0.75 32.74 99.6 -0.62

16K 10 13.0 0.103 -17.03 1790 0.81 26.61 80.0 -0.63
I6K12 21.4 0.140 -14.16 1308 0.81 20.14 70.8 -0.52
16KI4 29.1 0.343 -20.85 1231 0.87 15.60 56.1 -0.51
16K16 37.8 0.885 -33.44 1315 0.89 12.27 45.2 -0.49
16KI8 48.8 1.426 -31.48 1139 0.90 9.63 40.1 -0.39
16K20 59.5 2.391 -35.78 1163 0.90 8.17 36.1 -0.34
16K22 72.6 3.677 -26.00 966 0.91 6.44 32.4 -0.22

I4G52 15.0 0.112 19.5 477 0.81 7.48 +1.33

14G54 15.0 0.222 14.2 529 0.82 7.68 105.4 +0.65
14G55 15.0 0.292 12.0 569 0.83 7.76 80.8 +0.46
I4G57 15.0 0.830 -4.99 741 0.86 8.15 46.3 -0.11
14G60 15.0 0.955 -7.02 750 0.87 8.03 44.2 -0.14
14G65 15.0 2.480 -37.0 882 0.89 7.90 32.7 -0.40
14G75 15.0 11.52 -142.9 1191 0.94 7.22 22.3 -0.61

14G60 5.0 1.06 -11.9 744 0.88 8.20 41.5 -0.22

14G60 15.0 0.96 -7.02 750 0.87 8.03 44.2 -0.14
14G60 25.0 0.82 1.60 665 0.86 7.43 48.3 +0.03
14G60 30.0 0.73 7.48 575 0.85 6.89 52.1 +0.18

14F50 15.0 0.220 14.2 529 0.82 7.68 105.4 +0.65

I4F40 15.0 0.225 9.21 529 0.80 8.26 81.4 +0.42
14F30 15.0 0.255 7.89 594 0.75 8.54 74.9 +0.32
14F20 15.0 0.430 4.51 402 0.70 7.23 53.9 +0.17
14F1O 15.0 0.540 3.39 331 0.64 6.63 47.3 +0.12
14FOO 15.0 1.010 -4.18 337 0.61 6.42 35.9 -0.12

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 Schubert et al.: Transition from mixtures to microemulsions 5349

DZO-C16H34-C6E2 DzO-CaHla-C4El
10r=~~~~~--~~~~

-----_..,.90 <!>

I(q)

[em
-I
1 r~--
---...._ _~. 85

....",:: --...._ . .
t--€SiIIIII-_ _ _~---_~.75
0.1 L
t---elII!!IIIII---"":: .70
.60
80 [em
I(q)
-I
]

0.1
==: [8ft

~. 50
0.01 '--.--~-~-'-'--~-~~~
0.01

FIG. 5. Bulk contrast spectra of D20-n-hexadecane-C6~ mixtures as a FIG. 6. Bulk contrast spectra of D20-n-octane-C4 E, mixtures at 15°C as a
function of the oiVwater volume ratio </>. Compositions correspond to the function of the surfactant concentration 'Y. The top curve quantitatively re-
fish tails of Fig. 3 The solid lines are fits of Eq. (7). The structural scattering produces the bottom curve in Fig. 4(b) in Ref. 27. For the sample 14G57, c,
peak vanishes with increasing oil content, while critical scattering evolves has become negative and the Lifshitz line has been crossed.
close to q =0. For further discussion see the text.

havior. Temperature is constant at 15°C, and the spectra are

on a double log scale, the <;6=0.90 sample is given on abso- shown in Fig. 6. The top curve is given on absolute scale, the
lute scale. The neighboring compositions are again displaced subsequent curves are again displaced by factors of 2. In-
by factors of 2. With increasing oil content (from bottom to creasing surfactant concentration leads to a decrease in in-
top in Fig. 5) the characteristic peak vanishes, while at the tensity at low q. At the same time a faint peak develops at
same time the scattered intensity at low q increases. The fit finite q, and for sample I4G57 CI has become negative (see
parameters are summarized in Table III. fa decreases and the Table II). Thus it is possible to induce formation of structure
Lifshitz line (fa=O) is passed between samples I6F80 and in disordered systems by increasing the surfactant concentra-
16F85. For comparison, the macroscopically observable wet- tion. Quantitatively, the Lifshitz line falls between the
ting transition is at <;6=0.72. The approach to the Lifshitz line samples I4G55 and 14G57 (cf. Table 11). Further increasing
can be seen in the spectra: The peak at large q (clearly seen surfactant concentration causes the total intensity to decrease
for <;6=0.50, 0.60, 0.70 in Fig. 5) disappears. At q =0 the because of the decreasing contrast. The values of fa and d
intensity rises for increasing <;6 (clearly seen for <;6=0.80, decrease with increasing surfactant concentration, while ~
0.85, 0.90), and in parallel fa becomes positive. It is worth remains nearly constant.
noting that the samples I6F85 and 16F90 are located on the
amphiphilicity scale between the Lifshitz line and the disor- E. Water-n-octane-C 4 E1 : the effect of temperature
der line. (14G60)
The results of the preceding paragraph show that sample
D. Water-n-octane-C 4 E1 : the effect of surfactant I4G60 has a negative C l' The possible analogy between re-
concentration (14Gx)
gions of negative C 1 and more ordered mesophases (see Sec.
Here we examined mixtures of D20-n-octane-C4E 1 V) suggests that the region of negative Cl should depend on
past the disorder line (fa> 1) in order to investigate the effect temperature (see e.g., Ref. 33). Thus sample I4G60 was ex-
of increasing surfactant concentration on the scattering be- amined at temperatures from 5 to 30°C (Fig. 7, Table 11).

TABLE III. Fit parameters for DP-C'~34-C~2 according to Eq. (7). d and g are calculated from Eqs. (3) and (4), and fa from Eq. (6).
Sample T (OC) loz goz a2 c, C2 b g (A) d (A) fa

16F90 55.0 9.78 56.10 3.59 39.19 2496 1.03 6.61 51.2 +0.21
16F85 54.1 5.41 41.41 2.80 18.35 2323 1.00 7.19 50.7 +0.11
16F80 51.9 2.97 28.63 2.58 -37.45 2658 0.97 9.11 45.5 -0.23
16F75 50.5 1.50 19.99 2.23 -50.58 2584 0.96 10.10 44.9 -0.33
16F70 48.1 0.95 16.14 1.97 -50.76 2385 0.95 10.52 44.8 -0.37
16F60 43.4 0.56 12.50 1.60 -68.20 2302 0.95 13.13 43.8 -0.57
16F60 43.4 0 0 0.95 -16.40 1097 0.92 9.55 46.3 -0.25
16F50 37.8 0.40 10.50 1.22 -62.10 1998 0.88 14.75 44.3 -0.63
16F50 37.8 0 0 0.89 -33.44 1315 0.89 12.27 45.2 -0.49

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 5350 Schubert et al.: Transition from mixtures to microemulsions

V. DISCUSSION

Investigations of the phase behavior of ternary mixtures

of water, n-alkanes, and n-alkyl polyglycol ethers (C;E)
show that the amphiphilic strength of the surfactants depends
on various factors. Principal considerations4.z5.z6.55 and re-
sults from preceding investigations z7 indicate that the chain
I( q)
length of the surfactant and the nature of the polar solvent
[ern-I] 1 are the most important variables. However, the composition

::
of the mixtures, the chain length of the hydrocarbon (or the
nature of the oil itselt),43 and temperature are useful tuning
: parameters as well. IO · 11 In particular it is possible to shrink
the three-phase body with decreasing amphiphilicity for
aqueous systems beginning with C6Ez .4.5,24,27 For sufficiently
0.1
0.01 weak surfactants a transition in the wetting behavior is ob-
served before the three-phase body disappears at a tricritical
point. The middle phase (c) for the system
H20-n-octane-C4E 1, for instance, wets the alb interface,
FIG. 7. Bulk contrast spectra of the DzO-n-octane-C4E 1 sample (I4G60) as whereas if C6E2 replaces C4E" phase (c) does not wet. 27
a function of temperature T. Increasing temperature weakens the structure Replacing water by other polar protic substances strongly
(cf. Table II) and C I becomes positive. affects the amphiphilicity.5,24,27,32,61-64 For instance, addition
of formamide to a water-based "good" rnicroemulsion in-
The structure becomes more stable as the temperature de- duces a wetting transition, and eventually drives the system
to a tricritical point. 5,24.z7 The accompanying change in mi-
creases, and increasing temperature drives the sample across
the Lifshitz line. Note at 25°C fa is close to zero. crostructure in these systems is interpreted as a transition
from weakly to more structured solutions. 4,27,28.3I.54

F. Water-n-octane-C 4 E1 : The effect of water content A. Effect of hydrocarbon chain length (ISKx)
(14Fx) Changing the hydrocarbon chain length produces rela-
Finally, we studied these samples as a function of de- tively small changes in amphiphilicity (see Table 11). In
creasing ¢ at constant surfactant concentration and tempera- water-n-alkane-C;Ej systems, longer hydrocarbon chain
ture. The goal was to investigate whether the scattering peak lengths give three-phase bodies at higher temperatures and
appears on approach to the binary system DZO-C4E 1. The larger surfactant concentrations (see Fig. 2). The scattering
peak appears only for the pure binary system I4FOO (that is behavior changes in accord with the increased surfactant
¢=O, see Fig. 8 and Table 11). Fitting Eq. (5) shows that g concentration, and the spectra become less pronounced (see
changes only slightly with ¢, while d decreases with de- Fig. 4). The amphiphilicity factor fa varies slowly, and re-
creasing ¢. The samples containing oil are between the dis- mains negative (see Table II) through the wetting transition.
order and Lifshitz lines. This result is not unexpected, because, coming from good
microemulsions (for which fa <0) the Lifshitz line (where
fa=O) occurs after the wetting transition. The value of
fa= -0.33 at the wetting transition seems to indicate the
presence of a still quite good microemulsion. Concomit-
tantly, we observed that on approach to the wetting transition
the scattering peak did not move continuously towards q =0
as one might have expected from theory.26 Instead, in support
of the observations of Langevin et al.,l0,l1,44 the scattering
I( q) peak moved to larger q. This is because the surfactant con-
[ern
-1
] centration increases with longer alkyl chain hydrocarbons, so
the maxima move to larger q. At the same time, the mutual
0.1 miscibility between long-chain alkanes and amphiphiles
decreases. 3 Accordingly, the attractive interaction between
the three components decreases, and so the three-phase body
grows.
0.01 L-_~~~~"'"'--_~~~~.....J
0.01
B. Effect of oil content (ISFx)
Figure 3 and Table III show that the oil content taken up
FIG. 8. Bulk contrast spectra of DzO-n-octane-C4 E t mixtures as a function
by the middle phase microemulsion is a strong function of
of the oil/water volume ratio <p. Increasing water content strengthens the temperature. In other words, the volume fraction of water
structure. domains in the microemulsions decreases with increasing
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 Schubert et al.: Transition from mixtures to microemulsions 5351

temperature. For that reason, the coherence of the micro- TABLE IV. Amphiphilicity factors for samples spanning the wetting transi-
structure is expected to be weakened as one approaches the tion. The first three entries stem from a previous study (Ref. 27) and have
critical endpoint. As already reported, the wetting transition the following nomenclature: Samples are bulk contrast (B) with a surfactant
chain length i =4-8 and a given wt % of formamide. For example, esE, and
is located at </J=0.72. The scattering spectra (see Fig. 5) re- 85 wt % of formamide in the water/formamide mixtures is indicated as
veal the accompanying changes in microstructure. fa in- BS-S5. Note that an amphiphilicity factor of fa = -0.33 is consistent with all
creases with increasing </J as the samples move towards the five wetting transitions.
Lifshitz line, which is located close to sample I6F85 (see
Nonwetting Wetting
Table III). The value of </J there is larger than that of the samples samples
fa fa
macroscopically observable wetting transition, in qualitative
agreement with theoretical predictions. 26 ~ decreases and d B6-0 -0.5S B4-0 +1.61
BS-S5 -0.53 BS-IOO +0.41
increases slightly, as already observed in Ref. 27. From
B6-0 -0.58 B6-50 -0.11
theory26 one might have expected a much stronger change of 16K20 -0.34 16K22 -0.22
d because the system is moving towards the disorder line. 16F70 -0.37 16F75 -0.33
However, due to the relatively small steps made here along
the amphiphilicity scale, the disorder line is not reached and
d increases only slightly. Calculating qrnax from the relation

qrnax
=[(27T)2_
d g2]112 (8) interesting to note how strongly d moves as function of tem-
perature, at constant composition, indicating how fragile the
shows that the scattering peak moves to smaller q, and the structures are.
peak becomes less pronounced on approach to the wetting
transition, in agreement with theory.26 The scattering inten-
sity increases at q =0 on approach to the critical endpoint,
E. Effect of water content (14Fx)
and fa becomes positive (the Lifshitz line is crossed). This is
discussed further below. The spectra shown in Fig. 8 demonstrate, and the nu-
merical values of fa in Table II quantify, that structure begins
to evolve as the water content is increased (decreasing </J). In
C. Effect of surfactant concentration (14Gx) fact, the local structure is most expressed in the binary sys-
A different situation is encountered for the system tem water-C 4E 1 , and there is a domain of negative c 1 for
D20-n-octane-C4 E 1 measured as a function of surfactant high y and low T. This is the region where long chain sur-
concentration. SANS data previously obtained 27 showed that factants typically display lyotropic mesophases (see, e.g.,
the sample with </J=0.50 and y=52 wt % has fa= + 1.6, and Refs. 65 and 66). A more detailed study of the structure in
so is located past the disorder line. Here we reproduced the the binary system water-C4 E 1 is in preparation. 67
same surfactant concentration and found fa = + 1.3, which is
a sufficient agreement. Further increasing the surfactant con-
centration allowed examination of the region between the
disorder line and Lifshitz line. After passing the Lifshitz line, F. Nonwetting_wetting transitions
fa becomes negative and a scattering peak appears (see Fig. In the previous pape~7 a number of non wetting
6 and Table II). Here the formation of microstructure is in- -wetting transitions were induced by applying formamide
duced by increasing the surfactant concentration in a weakly to reduce the amphiphilicity. In Table IV we have collected
structured system. the results from all five systems studied up to now. The latter
The idea of inducing ordering behavior by simply in- two cases were examined with smaller amphiphilicity steps.
creasing the surfactant concentration is implicit in all of the The numerical values show that an amphiphilicity factor of
work of Gompper and Schick summarized in the excellent fa = -0.33 for the wetting transition is consistent with the
article. 31 Their phase diagrams show that by increasing the results. The wetting transition is located on the microemul-
surfactant concentration the disorder and/or Lifshitz lines are sion side of the Lifshitz line, which is, as predicted by
crossed whether or not the surfactant is strong enough to theory,26 on the microemulsion side of the disorder line. And
produce lamellar phases. The latter point is explicitly seen in it is in agreement with recent Monte Carlo calculations by
Lerczak et al. 54 Schmid and Schick51 which show the oil/water interface to
be wet in a system between the disorder and Lifshitz lines.
Theory predicts26 that the scattering peak moves to q =0
D. Effect of temperature (14G60)
on approach to the wetting transition. Langevin et at.
Sample 14G60 displays a peak at 15°C. The peak disap- observed 1o ,II,44 that the peak first moves towards higher q
pears upon raising the temperature to 30 °C, but is strength- values and then develops around q =0. Here we found that
ened by decreasing the temperature to 5 °C (Fig. 7 and Table the wetting transition is located on the microemulsion side of
II). This demonstrates a particularly simple method for cross- the Lifshitz line and that at the wetting transition the samples
ing the Lifshitz line in the one-phase region. Extended mea- stilI show a scattering peak. On approach to the Lifshitz line
surements as function of temperature, </J, and y would permit the scattering peak moved in to q =0 while critical scattering
mapping of the Lifshitz surface within the phase prism. It is developed near q =0 (see Fig. 5 and Table III).

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 5352 Schubert et al.: Transition from mixtures to microemulsions

c c
/'
'~\------------------/?-r
T
\ 2 ;7
\ /'
t \
~
:;..;"

8 B

.. y
FIG. 9. (a) Schematic picture of the Lifshitz domains (Cl<O) at large sur-
factant concentration for short-chain CiEj . Increased extension of the Lif-
shitz domain with increasing amphiphilicity is indicated by the dashed line.
(b) Schematic picture of the extension of the lamellar phase La for long-
chain surfactants (see, e.g., Ref. 32). FIG. 10. Schematic picture of the Lifshitz domain (Cl<O) in the binary
system water-short-chain CiEj .

G. Lifshitz surfaces and domains

microemulsions,32 shows that the domain with c 1<0 is lo-
In summary, we have compiled evidence that a Lifshitz cated in the region of the phase diagram where mesophases
surface exists within the accessible three-dimensional form with long-chain amphiphiles [see Refs. 3,32,65,66 for
composition-temperature space (the phase prism). typical experimental phase diagrams and compare with Figs.
For short-chain su/factants this surface lurks in the 9(a) and 9(b) and 10]. Accordingly, the region inside the
phase prism and one might visualize its shape as an ovoid Lifshitz surface could be thought of as the precursor of the
[Fig. 9(a)]. Inside this ovoid c 1<0, so that the spectra from lamellar phase La' which tends to form ordered interfaces
such solutions show a scattering peak at nonzero q. This with strongly negative Cl (sharp scattering peaks, ~__ oo).
conclusion is supported by the observation of structure for- This holds for the binary side of the phase prism as well (Fig.
mation (crossing the Lifshitz line, Cl becoming negative) in 10) where a Lifshitz line is also observed.67 In synopsis of
mixtures with a weakly structured wetting middle phase (c) the results discussed and Table II we can construct a sche-
induced by increasing the surfactant concentration, by de- matic fish diagram in which the homogeneous region (fish
creasing temperature or by increasing the water content (see tail) contains an interesting sequence of structures. The
Figs. 6-8 and Table II). sample with the lowest 'Y studied (14052) is past the disorder
For long-chain surJactants [exhibiting nonwetting line (fa> 1). Increasing 'Y, causes the disorder line (fa = 1) to
middle phases (c)] a Lifshitz surface must exist as a function be passed, and two samples (14054 and 14055) are located
of the chain length of the hydrocarbon. By increasing the between the disorder line and the Lifshitz line because their
number of carbon atoms of the oil we decreased the am-
phiphilicity of the surfactant and observed the
°
fa are between 1 and (see Table 11). Further increasing 'Y
causes the Lifshitz line to be crossed and a weak scattering
nonwetting--wetting transition, which is the precursor of the peak evolves. With sample 14060 it is possible to then cross
Lifshitz line, but we did not reach the Lifshitz line in this the Lifshitz line with increasing T (but not with decreasing T
experiment (see Fig. 4 and Table II). With increasing tem- as one might have expected if the analogy between the loca-
perature, phase (c) moves from the polar side of the phase tion of the lamellar phase and the region of negative c 1 were
diagram to the nonpolar side. On either side it is possible to complete). The reason for this might be that the stabilization
cross the Lifshitz line (see Fig. 5 and Table III) because the of structures at low temperatures is relatively strong. Figure
formation of structure will be weakened as the volume frac- 11 shows schematically the sections at constant water/oil ra-
tions of the dispersed structures becomes smaller. The local tio for a long-chain surfactant (top) and for a short-chain
structure may still persist in the sense that there is a locally surfactant (bottom). The dashed line indicates how the
strongly varying polarity. However, due to the dilution, the hatched c 1<0 region expands as the amphiphilicity in-
interdomain interactions will be weakened and the structure creases.
will become less ordered. Oiven the preceding discussion and the numerical data in
We observe that, coming from the weak microemulsion the Tables I-IV, we suggest that the Lifshitz surface is only
side, the Lifshitz line is a precursor for the wetting transition, one of a set of (approximately) parallel surfaces occurring in
and for long-chain surfactants the Lifshitz surfaces cover the following sequence with increasing amphiphilicity: a dis-
most of the three-phase body [see dashed line in Fig. 9(a)]. order surface at fa = 1, a Lifshitz surface at fa =0, and a
This means that the microemulsion phase does not wet the wetting transition surface fa = -0.33. The set of surfaces
water/oil interface except for compositions very close to the may be visualized as moving collectively towards smaller
critical endpoints. If the amphiphilicity is reduced, the Lif- surfactant concentration with increasing amphiphilicity.
shitz surface has to retract towards the amphiphile-rich cor- There the surfaces sequentially intersect with the surface of
ner of the phase prism [see Fig. 9(a)]. Comparison of the the body of heterogeneous phases, thereby defining lines of
approximately known region of the Lifshitz surface within intersections on the surface of that body. For a schematic
the isothermal phase diagrams with phase diagrams of good representation of the body of heterogeneous phase the reader

J. Chem. Phys., Vol. 101, No.6, 15 September 1994

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 Schubert et at.: Transition from mixtures to microemulsions 5353

100 100
T
I ~oz
t [em
oz
-1
1
10 10

I =! E -1.1
oz a
A/B=1I1 ---y
0.1 ~~~.....",j_~~w.......L--'''---'-~......J 0.1
2 0.001 0.01 0.1 1
€

T 3 FIG. 12. Critical scattering intensity loz and correlation length goz as func-
tion of distance from the upper critical endpoint at T.=328.7 K. Note the

t power law behavior with E=(T.-DIT. and ~=2 A.

1 critical behavior for </>=0.6 and 0.5. The numerical values

for fa are affected but are not changed qualitatively.
A/B=1I1 ---y Solutions in the vicinity of critical points as well as good
microemulsions strongly scatter light in the visible range, so
they have a characteristic bluish tint. The preceding analysis
FIG. II. Schematic section through the phase prism. The top diagram re-
calls the situation encountered for long-chain surfactants, including the La raises the question of which part of the scattered intensity for
pha~e stable at high r (see, e.g., Ref. 33). The bottom diagram envisions the good microemulsions stems from the nearness of the critical
eltpansion of the Lifshitz domain from a short-chain to a medium-chain endpoints, which for good microemulsions often are only a
surfactant. few degrees apart (see, e.g., Ref. 33). Therefore, the distance
from the endpoint is typically of the order of 1 K. For the
is referred to Ref. 3. One can then visualize the point at system considered here the critical scattering loz and struc-
which the trajectory of the middle phase (c) intersects the tural scattering Im= l/a2 at q=O are about equal in magni-
wetting surface, as defining the water/oil ratio of the wetting tude (see Table III). In the limit of long surfactant chains
(i~12) one can expect loz~/m' because 1m exceeds easily
transition. This is the only locus where the wetting transition
values of 104 cm-I,6.13 while loz stays of the order of or
can be observed experimentally because all three phase have
below 102 cm- 1 (cf. Fig. 12). Accordingly, the contribution
to coexist in order to see the transition. On the other hand,
scattering investigations can be performed over the entire of critical scattering to the overall scattering intensity of
symmetric good microemulsions is small.
one-phase region of the phase prism.

H. Critical scattering VI. CONCLUSIONS

Analysis of the I6Fx data gives the value of the critical The quantitative analysis of small angle neutron scatter-
contribution loz to I(q) and the Omstein-Zemike correlation ing spectra permits the location of individual samples on a
length ~z (Fig. 12). Even though these experiments were not scale of relative amphiphilicity and, thus, to quantify the
designed to test critical scaling relations, it is clear that both relative location of various lines and related surfaces in the
loz and ~z are consistent with power law behavior. In par- phase diagrams. Gompper and Schick26 predicted that a dis-
ticular, the exponent for the intensity, /-t, is approximately order line should be observable, and for somewhat more
twice that of the correlation length, v, which is consistent structured mixtures, a wetting transition, characterized by the
with the exact relation /-t=(2- TJ)v and the fact that TJ for the scattering peak moving to q =0 should also exist. In a previ-
universality class of this transition is small (1/'0.04). The ous paper the amphiphilic strength of the surfactant was
critical contributions have been evaluated including only weakened by replacing water by formamide. 27 The scattering
data for </>~70. However, a critical component could also be peak disappeared as predicted. That paper also shows that the
present in the scattering for </><70. In this case the data could Lifshitz line is located closer to the wetting transition than
be re-evaluated in an iterative process including critical ex- the disorder line. The results lead to the schematic Fig. I.
ponents and amplitudes from Fig. 12. This procedure reduces Thus the question was whether the Lifshitz line could serve
the number of parameters associated with critical scattering as a measure for the border line between weakly structured
from 10 (loz and ~z for five samples) to five parameters (lo, mixtures and microemulsions. Theory31 indicated that there
~, Tu, /-t, and v) linked by the power law behavior. We do should be a link between the macroscopic wetting transition
not do this analysis, but include in Table III the effect of and the change in the local microscopic structure.

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 5354 Schubert et al.: Transition from mixtures to microemulsions

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