Colloids and Surfaces
A: Physicochemical and Engineering Aspects 203 (2002) 55 – 66
www.elsevier.com/locate/colsurfa
Winsor behaviour of sucrose fatty acid esters: choice of the
cosurfactant and effect of the surfactant composition
Anne-Sophie Muller a, Juliette Gagnaire a,*, Yves Queneau a,
Marc Karaoglanian b, Jean-Paul Maitre b, Alain Bouchu b
a
Laboratoire de Sucrochimie, UMR 143 CNRS, c/o Eridania Béghin-Say, CEI, BP 2132, 27 bd du 11 No6embre 1918,
69603 Villeurbanne Cedex, France
b
Eridania Béghin-Say, Di6ision Béghin-Say, Laboratoire R&D Lyon, CEI, BP 2132, 27 bd du 11 No6embre 1918,
69603 Villeurbanne Cedex, France
Received 4 April 2001; accepted 2 October 2001
Abstract
The behaviour of various sucrose fatty acid esters blends in pseudoternary mixtures {water/methyl stearate/sucrose
ester+propanol or ethanol} was explored. The qualitative and quantitative analysis of the phases gave information
on the distribution of the surfactant and the oil in the polyphasic systems. It was seen that the transitions between
Winsor systems of type I–III can be obtained by using propanol as cosurfactant. Transition from a Winsor I
behaviour to a Winsor II behaviour was observed, depending on the substitution degree of the sucrose ester. Marked
differences can also be seen by this method between sucrose esters blends containing same contents of monoesters, but
differing by the content of minor products, especially soaps. The Winsor behaviour can thus be used as a ‘fingerprint’
to distinguish different sucrose ester batches. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Sucrose; Sugar; Surfactant; Winsor; HLB; Soap
1. Introduction
The fatty acid esters of sucrose are used for
their good emulsifying and toxicological properties [1–3] in the field of food additives [4,5] and
cosmetics [6,7]. Their surface properties depend
on the substitution degree of the sucrose polar
head by the fatty chains. Commercial sucrose
* Corresponding author. Tel.: + 33-4-7244-2989; fax: + 334-7244-2991.
E-mail addresses: [email protected] (J. Gagnaire),
[email protected] (Y. Queneau).
esters are mixtures of mono and polysubstituted
products (Fig. 1) [5,8]. The content of monosubstitued sucrose ester is usually used to identify the
sucrose ester blend and to give an idea of its
hydrophilicity. The higher the proportion of monoesters, the higher the hydrophilicity of the sucrose ester blend is. Usually, no precision is given
for the distribution of the polysubstituted products (diesters and over) included in the blends. A
HLB scale has been attributed to the sucrose ester
blends [5,8,9], adapted from one of the Griffin
scales, from 0 to 20 [10]. The HLB is approxi-
0927-7757/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 0 1 ) 0 1 0 6 7 - 6
56
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
phase diagrams without [27,28] or with alcohols
[29–41], rheological behaviour of solutions and
emulsions [42–48] have been studied. Preparation
of vesicles with sucrose esters has also been described [49–51]. In this paper, we used water–
oil–alcohol– sucrose ester pseudoternary mixtures
in order to compare the solution properties of
various blends of sucrose esters. Wider knowledge
has been developed on the quaternary systems
water–oil –surfactant–alcohol, especially in application to enhanced oil recovery [52]. These studies
have led to a good understanding of the relations
between the nature of the surfactant, oil, alcohol
and composition parameters and the phases pattern (especially the multiphasic behaviour often
named Winsor I–III [53]) within pseudoternary
diagrams. The transitions from one kind of multiphasic system to another have been rationalised
by the introduction of the R-ratio, whose change
from RB 1 to R=1 and then R\1 can be interpreted by the variation of the lipophilic and hydrophilic interactions between the components
[52–55]. In the specific case of the polyethylene
oxide surfactants, the simple variation of the temperature leads to the progressive change of the
phase pattern in a manner that can be related to
the change in the polar head hydration. In the
case of sucrose esters, such progression does not
occur [40,41], since the hydration of the sugar
polar heads should be different, as it is the case
for alkylpolyglucosides [56,57]. In order to work
out the appropriate conditions for the observation
of a classical Winsor phase sequence, and especially in order to obtain triphasic systems (Winsor
III) as a tracer of the ‘optimal formulation’ (R=
1), we used the variation of the alcohol length as
a parameter. When the water-to-oil mass ratio is
equal to 1, the transitions between different multiphasic systems are generally more varied. Therefore, the different blends of sucrose esters have
Fig. 1. Structure of fatty acid sucrose esters. Commercial
blends are mixtures of regioisomers and substitution degrees.
mately equal to 20× [weight percent of monoesters in the blend/100] and is used as a nomenclature for the sucrose ester blends (Table 1).
Whatever the length of the fatty chain (from
laurates to stearates, for example from L16 to
S16), a HLB of 16 is attributed to blends containing 80% of mono-sucrose esters. In our laboratory, an adaptation of the experimental
emulsification method described by Griffin [11] to
assess the HLB was applied to commercial and to
our own sucrose esters blends in comparison to
commercial polyethylene oxide surfactants. The
‘emulsion scale’ was made by mixtures of oils of
gradual RHLB. The large emulsifying capacities
of sucrose esters, compared with polyethyleneoxide surfactants were confirmed, but not the HLB
range [12]. This concept being quite debatable—
although widely used—, we looked for a more
accurate method for the description of the properties of sucrose esters.
Experimental data are available concerning different aspects of the surfactant properties of sucrose esters. Hydrophilicity and emulsifying
properties [9,13–22], surface properties [23– 27],
Table 1
Monoesters content in sucrose ester blends
Sucrose ester
S370
S570
S770
S970
S1170
S1670
P1570
P1670
Monoesters (supplier, %wt.)
Monoesters (HPLC, % wt.)
20
20
30
32
40
39
50
49
55
58
75
80
70
70
80
80
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
been compared on the basis of their phase behaviour by keeping the water-to-oil mass ratio
equal to 1. The number, the volume and the
composition of the phases were registered for each
sucrose ester sample, each time the mass of sucrose ester+alcohol was increased. The sucrose
ester/alcohol ratio was constant equal to 1/2.
Three other sugar-based surfactants, an alkylpolyglucoside, dodecylglucoside (DGlc) and two
sorbitan esters (Span 20 and Span 60), were compared in the same way. The sorbitan esters were
chosen free from ethylene oxide groups, since it
has been shown that the properties (e.g. water
titration) of grafted ones related to non-grafted
ones cannot be compared with the same scale [58].
2. Experimental
2.1. Products and sample preparation
A set of sucrose esters covering the whole range
of substitution degree, and bearing two kind of
chain length was purchased from Ryoto, S370,
S570, S770, S970, S1170, S1670 (stearates), P1570
and P1670 (palmitates), the number 70 referring
to as the 70% purity of the chain length. The
contents in monoesters of these blends given by
the supplier [5] and measured by high performance liquid chromatography (HPLC) are reported in Table 1.
Others blends with high contents in monoesters
were synthesised and purified in our laboratory,
according to a method described elsewhere [59].
They were named following the Ryoto nomenclature, as a function of their content in monoesters
and the chain length (either stearic or palmitic,
equally of 70% purity), S16-A, S16-B, S16-C,
S16-D, P15-A, P15-B, P16-A, P16-B, the letters
A, B, C, D corresponding to the different batches.
Their composition in monoesters, diesters and
fatty acid were determined by HPLC analysis on
a Nucleosil C8-grafted column (L 25 cm, ID 4,6
mm; 30 °C), coupled to an isocratic pump (Shimadzu LC-20) and a refractive index detector
(Shimadzu RID-6). The eluent was a mixture
THF –methanol–water 40– 40 – 20 (v/v) + 0.5 ml
l − 1 of acetic acid. The compositions in mo-
57
noesters and fatty acid are reported in detail in
the discussion, Table 3. Acid values were measured according to a standard method by
acidobasic titration with KOH [60]. The acid
value of a blend containing y% by weight of
palmitic/stearic acid will be approximately equal
to 2y.
Span 60 and Span 20 were purchased from
Aldrich and are mixtures of esterified sorbitan
containing mainly sorbitan monostearate and sorbitan
monolaurate,
respectively,
without
polyethoxylated grafting. A sample of DGlc was
supplied by Cerestar and contained a mixture of
polyglucosides of DP=1 –4 (mass spectroscopy
data). The oil phase was methyl stearate (SMe,
technical, 70/30 wt.% mixture of methyl stearate
and methyl palmitate) or methyl palmitate (PMe,
95%). Ethanol, propanol-1 and butanol-1 (for
analysis) were purchased from Carlo Erba. The
water used was de-ionized water. All surfactant
blends were used without further purification.
2.2. Phase diagram
The pseudoternary phase diagram fatty methyl
ester/water/sucrose ester+alcohol was explored
at the points containing 10, 20, 30, 40, 50 and
60% of sucrose ester+ alcohol in the sample, by
keeping the water-to-oil ratio equal to 1. The
samples were prepared by weighing adequate
quantities of water, oil, and of a solution of
sucrose ester in alcohol (mixture 1/2, by weight) in
a 5 ml cylindrical vial sealed with a Teflon-faced
silicone septum. The total mass of the sample was
7 g. The sample was heated to 45 °C in an oven,
was shaken until complete dissolution and mixing
of the components, and then allowed to rest at
45 °C without stirring, until it reached equilibrium, with clear phases (sometimes up to 3
weeks). If they had not reached equilibrium during this period, they were described as ‘emulsion’.
Approximate periods for full decantation were
noted. The height of the phases (‘H oil’ and ‘H
aq’), their aspect at 45 °C and at room temperature (after crystallisation) were registered and an
aliquot of each phase was taken through the
septum with a syringe, at 45 °C, and analysed by
HPLC with the method described above. The
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
58
Table 2
Macroscopic description of the samples obtained in the diagrams {sucrose esters+alcohol/water/fatty acid methyl ester}
Symbol
Macroscopic aspect at equilibrium
Partition of the constituents
Interpretation
1 (+)
Two clear phases at 45 °C. Two
crystallised phases at r.t.a
Two clear phases at 45 °C. Upper phase
only crystallised at r.t.
Three clear phases at 45 °C. Upper and
intermediate phase crystallised at r.t.
One clear phase at 45 °C, crystallised at
r.t.
Two clear phases at 45 °C, both are
crystallised at r.t.
Three clear phases at 45 °C with a very
small intermediate phase, all crystallised at
r.t.
Monophasic stable opalescent system
High ethanol content, two clear phases at
45 °C. Lower phase crystallised at r.t.
With ethanol, one opalescent stable phase
High ethanol content, one clear phase
Systems not at the equilibrium (emulsions,
full and partial)
Surfactant is mainly in the lower phase
Winsor I or 26
Surfactant is mainly in the upper phase
Winsor II or 2(
Surfactant is mainly in the intermediate
phase
–
Winsor III or 3
Surfactant is partitioned in both phases
Two ‘surfactant phases’ in
equilibrium
2 (2)
3 ()
4 ()
5 (−)
6 ()
7 (“)
8 (")
9 ()
10 (
)
11 (×)
a
Winsor IV or 1
Surfactant is mainly in the lower phase
–
Lower phase contains near all constituents, Inversion of the density
oil included
of the phases
–
–
‘Solubilisation’
–
r.t., Room temperature. The fatty acid methyl ester is crystallised at r.t., when pure or into a microemulsion.
latter enabled the quantification of sucrose monoesters and diesters, fatty acid methyl esters and
fatty acids (palmitic and stearic, under the
unionised or soap form). Except for samples containing 50 and 60% of {sucrose ester+ ethanol},
for which the density of the phases was inverted
(see Table 2 and Figs. 7, 8 and 10), the oily phase
correspond the upper phase and the aqueous
phase to the lower phase. The samples were described according to the Winsor classification of
multiphasic systems when possible (Table 2). No
investigation of the microscopic organisation has
been made on these samples.
2.3. Calculations
The analyses provided the mass composition of
each phase, for monoesters and fatty acid methyl
esters. The composition of the phase € in monoesters (S) is given by the ratio:
wt.% (S, €)
weight of monoesters measured in the aliquot
=
×100
weight of the aliquot
referred to as wt.% (S, oil), for the oily phase and
wt.% (S, aq) for the aqueous phase.
The composition of the whole sample in monoesters is given by:
wt.% (S, global)
=
weight of monoesters introduced in the samples
× 100
weight of the whole sample (7 g)
Two deviations from the whole sample composition have been constructed from these variables,
named ‘phase composition deviations’:
wt.% (S, oil) − wt.% (S, global)
wt.% (S, global)
and
wt.% (S, aq) − wt.% (S, global)
wt.% (S, global)
and the difference between them:
wt.% (S, aq) − wt.% (S, oil)
wt.% (S, global)
and the same variable was used for methyl
stearate:
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
wt.% (SMe, oil)− wt.% (SMe, global)
wt.% (S, global)
and
wt.% (SMe, aq) −wt.% (SMe, global)
wt.% (SMe, global)
The partition of monoesters and fatty acid
methyl esters was calculated by taking into account the volume (or the height) of the phases:
p(S, oil) =
wt.% (S, oil)
Hoil
×
× 100
wt.% (S, global) Hoil + Haq
p(S, aq) =
wt.% (S, aq)
H aq
×
× 100
wt.% (S, global) H oil +H aq
The difference of density between the phases
was not taken into account, since the sums p (S,
oil) +p (S, aq) were approximately equal to
100%, justifying this approximation.
3. Results and discussion
3.1. Phases obser6ed for the different sucrose
ester blends
Preliminary explorations of sucroester+ alcohol/water/fatty acid methyl ester diagrams, with a
sample of S16, showed that by using butanol-1 or
pentanol-1 as alcohol, in various surfactant-to-alcohol ratio, only Winsor II-type biphasic systems
were obtained, although S16 can be considered as
a quite hydrophilic surfactant. In order to enforce
the formation of Winsor I or Winsor III, that is,
to decrease the R-ratio, more hydrophilic alcohols
have been used, propanol-1 and ethanol. The kind
of multiphasic and monophasic systems obtained
with these two alcohols and with the different
blends of sucrose esters are described in Table 2.
In Figs. 2–4, are reported the sequence of the
systems observed for each surfactant, when the
surfactant+alcohol ratio is increased stepwise
along the water=oil median. When the propanol1 was used, the observation of the classical Winsor I –III behaviours was possible (Figs. 2 and 3).
If we take into account, not only the type of
multiphasic system (I–III) but also the volumes of
the phases, we can see that each surfactant has a
specific succession, that can be used as a ‘finger-
59
print’. It depends on the monoesters content of
the blend but it depends also on the composition
in minor products, since large differences are observed for sucrose ester blends containing the
same amounts of monoesters (Fig. 2 and Table 3).
Comparisons between the various samples of
hydrophilic sucrose esters (Fig. 2) can be made on
the basis of the distribution of the Winsor I–III
systems. The more hydrophilic blends have
mainly a Winsor I behaviour, whereas the formation of Winsor II systems show a tendency to be
more hydrophobic. Sucrose ester blends in which
the residual fatty acid is at least partially in soap
form showed a more hydrophilic behaviour (e.g.
S16-C, P16-B, S16-D), while blends containing no
soap, in which the fatty acid is essentially in
unionised form showed more hydrophobic behaviour (P16-A, P15-A, S16-A). The amount of
residual soap is assessed by the difference between
the acid value, measuring the fatty acid form and
the HPLC data, measuring globally fatty acid and
soap species (Table 3). In the sample S16-D, the
monoesters content is the lowest of this series,
while the behaviour is a full Winsor I, hydrophilic
behaviour. This can be ascribed to the high content of soap in this sample (out of norms for users
[61,62]). Comparison between S16-A and S16-B is
particularly significant. With this sucrose ester,
pH adjustment during the purification led to two
different samples S16-A and S16-B. The difference
observed in the behaviour can be attributed to the
form, ionised (soap, S16-B) or unionised (fatty
acid, S16-A) under which the residual fatty acid is
transformed during purification. These results
show that the residual soap content has a strong
effect on the phase behaviour of the sucrose esters. It is possible that other residual products
(salts, solvents) also act on it, since the trace
amounts of the soap included in the blend should
be sensitive to salinity. That could explain further
differences. Such a sensitivity of the behaviour to
the presence of very little amounts of an anionic
surfactant has been observed in the case of alkylpolyglucosides [63].
With P16-A and S16-A, the formation of Winsor III systems, along with a very rapid decantation in all the samples, indicated a point of
‘optimum formulation’, corresponding to a R-ratio=1 [52]. A small change of the sucrose ester
69
70
5
1.5
Monoesters distributiona
%wt. Monoesters in the blendb
Acid valuec
Global %wt. fatty acid+soap in the blendb
80
80
4
1.5
P16–A
80
80
nd
1
P1670 with PMe
78
80
1.5
Traces
S16–A
70
70
nd
1.5
P1570 with PMe
78
80
0.6
traces
S16–B
79
75
3
2.5
S16–C
70
70
nd
1.5
P1570
70
70
4.1
3.5
P15–B
80
80
nd
2
S1670
80
80
nd
1
P1670
75
70
2.4
2.5
P16–B
75
60
3.4
5
S16–D
b
Distribution of the monoesters among the whole sucrose esters species. It does not take into account species other than sucrose esters.
%wt. Of monoesters or fatty acid in the bulk blend, measured by HPLC (C8-grafted column). With this method, the fatty acid quantification includes both the fatty acid and the soap form.
c
The acid value gives a quantification of only the unionised form of the fatty acid (titration with KOH). The acid value of a blend containing y% by weight of stearic/palmitic acid will be approximately equal to 2y.
a
P15–A
Surfactant
Table 3
Monoesters and fatty acid contents of the different sucrose ester blends of low substitution degree
60
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A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
composition (monoester content), of the ionised
state of the residual fatty acid (S16-B), the surfactant chain length or the oil length (P1670 with
either methyl palmitate 95% or tech. methyl
stearate) led to a deviation from this optimum
point. For the samples containing 10% {sucrose
esters+ propanol}, the longest decantation period
(more than 3 weeks) were observed for the blends
containing the larger amount of residual soap
(S16-D and P15-B), while the shortest periods (15
min to 6 h) were observed for the blends containing only the unionised form of the residual fatty
acid (P15-A, P16-A, S16-A). This correlation is
the most obvious one, since for other samples, the
measurement of the decantation period was not
precise enough to enable further interpretation.
The phase sequences obtained for the sucrose
esters of higher substitution degrees, for the sorbi-
61
tan esters and the dodecylglucoside, in the presence of propanol-1, showed a progression from
mainly Winsor I behaviour (DGlc and S1670) to
mainly Winsor II behaviour (S370, sorbitan
stearate) (Fig. 3). S570, S770, S970 showed an
intermediate behaviour with mainly biphasic systems composed of two ‘surfactant-phases’ (type
5). The formation of such biphasic systems can be
due to the presence in the blends of a high proportion of both hydrophilic monosucrose esters
and hydrophobic polysubstitued sucrose esters.
Their different distribution between the oil phase
and the water phase (Table 4) leads to the formation of two microemulsions in equilibrium. The
partition of the surfactant in either the oil phase
(Winsor II) or the aqueous phase (Winsor I) no
longer takes place in the case of these intermediate sucrose esters.
Fig. 2. Map of the Winsor systems obtained for sucrose esters of low substitution degree, on the median of the pseudoternary
diagram {sucrose esters +propanol/water/fatty acid methyl ester} at 45 °C. Symbols are described in Table 2. Water-to-oil ratio is
1. Surfactant-to-propanol ratio is 1/2. The oil is a technical methyl stearate (70/30 mixture stearate/palmitate), except when specified
‘with PMe’ (95% pure methyl palmitate). The surfactants have been coarsely ranked in five categories of similar behaviour, from the
more hydrophobic one (on the left) to the more hydrophilic one (on the right). The relative volumes of the phases are added above
each symbol (volume upper phase/volume lower phase).
62
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
Fig. 3. Map of the Winsor systems obtained for sucrose esters of different substitution degrees and three other sugar surfactants,
on the median of the pseudoternary diagram {sucrose ester + propanol/water/methyl stearate} at 45 °C. For symbols, see Table 2.
The relative volumes of the phases are added above each symbol (volume upper phase/volume lower phase).
With ethanol, the ‘map’ showed other kind of
systems, which cannot be described with the Winsor classical sequence (Fig. 4), probably due to the
high miscibility of ethanol in water. First, we
noticed an inversion of the density of the oily
phase and the aqueous phase occurred when the
sucrose ester+ethanol content ]50%, and the
lower phase contained all the surfactant and oil.
3.2. Phases compositions
The composition of the phases of all biphasic
samples were reported in Figs. 5– 10, in order to
support the type of Winsor system attributed to
each one. In Winsor I systems, the content of
surfactant in the aqueous phase is much higher
than the content in the oily phase, and it is the
opposite for the Winsor II systems. Moreover, it
was observed that both the distribution of the
monoesters (Figs. 5 and 7) and the relative enrich-
ment of the phases in monoesters (Figs. 6 and 8)
and in methyl stearate (Figs. 9 and 10) followed a
consistent progression along the series.
Two methods are used to represent the distribution of monoesters in the biphasic samples. In
Figs. 5 and 7, we represented the global distribution of monoesters between the oily and the
aqueous phase, along with the heights of the
phases. With propanol-1 as cosurfactant (Fig. 5),
we can see mainly the effect of the volume of the
phases on the distribution of monoesters, and
marked divergences were found only with S370
and S1670. The intermediate sucrose esters (S970,
S770, S570) show a partition of monoesters in
both phases, progressing continuously along the
series. In Fig. 6, we represented the weight content of monoesters (in percent) of the oily or the
aqueous phase. The variable used (phase composition deviation) aims to represent how the phases
became richer or poorer in monoesters, in relation
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
to the whole composition of the sample. This
variable represents the dissymmetry between the
phase compositions. Both figures showed the progression along the sucrose ester series from a
typical Winsor I behaviour, with the surfactant
located in the aqueous phase (S1670) to a typical
Winsor II behaviour (S370), with the surfactant
located in the oily phase.
With ethanol as alcohol, only S1670 show a
marked Winsor I behaviour (Figs. 7 and 8). The
differences between the more hydrophobic sucrose
esters are less marked. In this case, the ethanol
63
can bring about a levelling, because of its solubilisation effects.
In Figs. 9 and 10, the progression of the phases
enrichment (phase composition deviations) in
methyl stearate is reported. In the case of ethanol,
the progression remained consistent if the data
corresponding to the upper and the lower phases
for the samples containing 50 and 60% {sucrose
ester+ ethanol} are swapped round in the
graphic. This demonstrate the occurrence of an
inversion of the density of the phases in the case
of samples enriched in ethanol (type 8, Table 2),
Fig. 4. Map of the ‘Winsor systems’ obtained for sucrose esters of different substitution degrees, on the median of the pseudoternary
diagram {sucrose esters + ethanol/water/methyl stearate} at 45 °C. For symbols, see Table 2. The relative volumes of the phases are
added above each symbol (volume upper phase/volume lower phase).
Table 4
Distribution of monoesters and diesters in some biphasic samples
%wt. {sucrose ester+propanol}
{Area ratio monoester/diesters in the oily phase}
/{Area ratio monoester/diesters in the aqueous phase}
Area ratio monoesters/diesters in the initial sucrose ester blend
30%
20%
S770
S970
S1170
1.0/2.6
0.7/2.0
1.8/2.2
1.0/3.0
2.7/3.7
2.5/3.1
2.0
2.2
3.0
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
64
along the median of a pseudoternary diagram
sucroester+ propanol/water/methyl stearate enabled a fine differentiation of the different sucrose
ester blends depending on their composition. This
study showed that propanol is a suitable alcohol
for the observation of the classical Winsor behaviour in the sucrose esters family. The analysis
of the phases showed the non-linearity of the
behaviour related to the monoester composition,
and thus showed the effects of polysubstituted
Fig. 5. Distribution (p) of the monoesters ( = S) and heights
(H) between the oily and the aqueous phase in biphasic
samples with propanol (in relation with Fig. 3). For the
definition of p, see the Section 2. The dotted lines are guides
for the eyes to follow the global progression of the phase
composition along the sucrose ester series.
Fig. 7. Distribution (p) of the monoesters ( = S) between the
oily and the aqueous phase in biphasic samples with ethanol
(in relation with Fig. 4). For the definition of p, see the Section
2.
Fig. 6. Phase composition deviations in monoester ( =S) of
the oily and the aqueous phase, in biphasic samples with
propanol (in relation with Fig. 3). For the definition of the
variables, see the Section 2. The dotted line is a guide for the
eyes to follow the global progression of the dissymmetry of the
phase composition along the sucrose ester series.
since the upper phase corresponds to the aqueous
phase and the lower phase to the oily phase.
4. Conclusion
The characterisation of the Winsor systems
Fig. 8. Phase composition deviations in monoester ( =S) of
the oily and the aqueous phase, in biphasic samples with
ethanol (in relation with Fig. 4). For the definition of the
variables, see the Section 2.
A.-S. Muller et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 203 (2002) 55–66
65
Acknowledgements
Financial support from CNRS and the Ministére de l’Education Nationale (convention REACTIF-98T0166) is gratefully acknowledged.
References
Fig. 9. Phase composition deviations in methyl stearate ( =
SMe) of the oily and the aqueous phase, in biphasic samples
with propanol (in relation with Fig. 3). For the definition of
the variables, see the Section 2.
Fig. 10. Phase composition deviations in methyl stearate ( =
SMe) of the oily and the aqueous phase, in biphasic samples
with ethanol (in relation with Fig. 4). For the definition of the
variables, see the Section 2.
sucrose esters. This effect is not taken into account in the usual HLB scale. The different results
obtained, depending on the sucrose ester batch,
suggested that the residual fatty acid or soap have
a significant effect on the behaviour. That encourages to investigate more in detail the influence of
the minor components of the blends on the sucrose ester behaviour.
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