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Nešto Oko Osmoze
Nešto Oko Osmoze
Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd
a r t i c l e i n f o a b s t r a c t
Article history: We describe a gelation process based on the osmotically driven water flux between the two aqueous
Received 14 September 2013 compartments of double emulsions. We first prepare fluid water-in-oil-in-water (W/O/W) double
Accepted 11 November 2013 emulsions whose external aqueous phase contains hydrocolloids and/or proteins at moderate concen-
tration. The initial osmotic pressure in the innermost droplets is considerably larger than that in the
Keywords: external phase. An inward water transfer (swelling) is thus likely to occur in order to restore osmotic
Double emulsions
equilibrium. In the initial state, the globules are large and so the transfer is slow because of the limited
Osmotic pressure
exchange surface area. The emulsions are then submitted to a short and intense shear that provokes
Swelling
Coalescence
globule breakup, in order to increase the rate of water diffusion. As a consequence, the initially fluid
Gelling materials undergo a sudden rheological transition. During that process, the hydrocolloids and/or proteins
are concentrated in the continuous phase until a point that a gel is formed. The final rheological prop-
erties can be tuned from weak to strong gels depending on the initial composition. The inner droplet
fraction strongly increases during the swelling process and dropleteglobule coalescence occurs above a
critical volume fraction that determines the maximum swelling capacity and thus final state of the
system. The proposed approach demonstrates a simple, yet versatile and adaptable solution for making
texturized emulsions with reduced fat content and limited amount of hydrocolloids/proteins.
Ó 2013 Elsevier Ltd. All rights reserved.
0268-005X/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodhyd.2013.11.009
12 M. Delample et al. / Food Hydrocolloids 38 (2014) 11e19
the globule size and accelerate the swelling process. The applied 2.4. Rheological measurements
shear had to be strong enough to provoke globule breakup,
while avoiding as much as possible the concomitant shear- When a small shear stress, s, is applied to a solid, the resulting
induced delivery of the inner droplets reported in many previ- deformation, G, is proportional to s, with s ¼ GG, where G is the elastic
ous studies (Muguet et al., 2001; Stroeve & Varanasi, 1984). The shear modulus. For materials which do not store perfectly the energy,
conditions were optimized in terms of applied shear rate to G can be generalized as the sum of two contributions. The in-phase
obtain gels with the highest possible rheological moduli within contribution G0 is linked to the stored energy while the p/2 out-of
the shortest period of time after the shear was applied. This phase contribution G00 is related to the dissipated energy. For com-
issue will be further commented at the end of Section 3.4. The plex systems, the relative contributions may be frequency-dependent.
following conditions were finally adopted: gap ¼ 100 mm, shear Oscillatory rheological experiments were performed with an AR-G2
rate ¼ 5000 s1, residence time of the emulsion in the cell rheometer from TA-Instruments. The experiments were performed
gap ¼ 5 s. at a frequency of 1 Hz, a strain of 0.5% (linear regime) and at T ¼ 4 C,
using a cone and plate geometry with the following characteristics:
Table 1 indicates the initial composition of the systems prepared cone diameter ¼ 60 mm, cone angle ¼ 2 00 1800 and a gap of 56 mm.
in the course of this study. Once fabricated, the double emulsions Since the double emulsions were shear-sensitive, all possible pre-
were stored at 4 C for several weeks. This temperature was cautions were taken in order to obtain reproducible data. To diminish
selected because it corresponds to usual storage conditions for the “preshear” when loading the samples, the emulsions were loaded
dairy products and also because the kinetic stability was consid- into the rheometer very carefully; the sample compression during
erably prolonged compared to room temperature. loading was the minimal possible and was always done at the smallest
rate. The lateral parts of the sample were covered by fluid silicon oil to
2.3. W/O/W emulsion characterization avoid evaporation. All rheological measurements were repeated three
times and the deviation between experiments did not exceed 20%.
The emulsions were observed using phase contrast methods on
an Olympus BX51 microscope (Zeiss, Germany) equipped with a 2.5. Density measurements
video camera. Water droplet size distributions of the primary W/O
emulsions were measured by static light scattering, using a Coulter Unless otherwise specified, the concentrations and droplet/
LS 230 apparatus. The measuring cell was filled with sunflower oil globule fractions will be expressed on a weight percentage basis.
containing 1 wt.% PGPR, and a small volume of the sample was The density of all liquids used in the present study (oil, aqueous
introduced under stirring. Measurements were performed at room solutions) were measured at different concentrations in order to
temperature. The volume weighted average diameter was obtained convert weight fractions into volume fractions, when necessary. To
from Mie theory. The average diameter of oil globules could not be this end, we used a DMA 4500 density meter from ANTON PAAR
measured using light-scattering because measurements required a (Austria) whose precision is 5.105 g cm3.
strong dilution of the emulsions. Since in our experiments, the final
solute concentration in the inner droplets was unknown, it was not 3. Results and discussion
possible to match the osmotic pressures in order to avoid water
transfer phenomena that would modify the globule size and/or 3.1. Influence of the initial inner droplet fraction at constant oil
induce coalescence phenomena. The volume-averaged diameter of volume fraction
the globules was thus estimated by direct microscope observations.
Images were recorded and the dimensions of about 50 droplets One of the aims of this study is to fabricate W/O/W double
were measured. emulsions with the lowest possible oil content. Indeed, low calorie,
Table 1
Initial compositions of the W/O/W emulsions formulated within this study (before swelling); SC ¼ sodium caseinate; GA ¼ gum Arabic; X ¼ Xanthan; SA ¼ sodium azide;
fi,0 ¼ fraction of inner droplets in the globules; foil ¼ oil fraction; fg,0 ¼ globule fraction; fe,0 ¼ fraction of the external aqueous phase. All fractions are expressed on a weight
percentage basis.
fg,0
a
Internal aqueous phase Oil phase
b a
1 5.5% 9.1% NaCl (20%) 0.1% 5% Sunflower oil (97%) þ 94.5% SC (10%) þ SA (0.02%)
2 6% 16.7% 0.2% PGPR (3%) 94%
3 7.5% 33.3% 0.5% 92.5%
4 10% 50% 1.0% 90%
5 5.25% 4.8% D-Glucose (40%) 0.1% 94.75%
6 6.25% 20% 0.5% 93.75%
7 7.5% 33.3% 1.0% 92.5%
8 11.25% 55.6% 2.5% 88.75%
9 10% 50% NaCl (20%) 1.0% 90% SC (7.0%) þ SA (0.02%)
10 SC (7.5%) þ SA (0.02%)
11 SC (8.0%) þ SA (0.02%)
12 11.25% 55.6% D-Glucose (40%) 2.5% 88.75% SC (7.0%) þ SA (0.02%)
13 SC (7.5%) þ SA (0.02%)
14 SC (8.0%) þ SA (0.02%)
15 20% 50% NaCl (20%) 2% 10% 80% SC (10%) þ SA (0.02%)
16 NaCl (10%) 1% GA(10%) þ X(2%) þ SA (0.02%)
a
with respect to the total mass of the double emulsion.
b
with respect to the corresponding phase.
14 M. Delample et al. / Food Hydrocolloids 38 (2014) 11e19
X
pi ¼ Ci RT (1)
Fig. 3. Variation of the rheological moduli G0 et G00 as a function of the initial droplet
volume fraction; inner solute ¼ D-glucose (emulsions n 5e8) (a); NaCl (emulsions n
1e4) (b). The initial compositions of the emulsions are provided in Table 1. Open
symbols correspond to a solution with 10 wt.% SC and 5 wt.% oil dispersed in it.
4s
Dp ¼ (3)
dd
Vw ¼ Vi þ Ve (4)
Fig. 4. Variation of the rheological moduli G0 et G00 as a function of the initial SC
concentration in the external phase; inner solute ¼ D-glucose (emulsions n 8, 12, 13, Vi and Ve being the volumes of the internal and of the external
14) (a); NaCl (emulsions n 4, 9, 10, 11) (b). The initial compositions of the emulsions aqueous phases respectively. The set of equations (1)e(4) can be
are provided in Table 1. solved numerically in order to determine the composition of the
system at osmotic equilibrium. Considering the conditions adopted
in the present study (s z 2 mN/m (Marze, 2009), dd 5 mm), both
In principle G0 and G00 are expected to depend on the final pi and pe are at least two orders of magnitude larger than Laplace
concentration of SC in the external phase, on the globule fraction pressure (4s/dd) at equilibrium. Thus, the equilibrium condition can
and on the interactions between the globules. The coupling be- be simply expressed as pi z pe.
tween these variables and their dependence on fi,0 and [SC]0 is non In Fig. 6, we report the theoretical variation of the concentration
trivial and makes any theoretical prediction cumbersome. Here- of SC in the external phase after osmotic equilibration, under the
after, we propose an analysis based on simplifying e yet realistic e different initial configurations that were probed in the previous
assumptions aiming at better understanding the phenomena that sections: variable inner droplet fraction at constant oil volume
control the final material properties. fraction (Fig. 6-a) and variable SC concentration in the external
phase at constant globule and inner droplet fraction (Fig. 6-b). The
inserts show the variation of the inner droplet fraction after os-
motic equilibration, defined as:
Vi
fi ¼ (5)
Vi þ Voil
where Voil is the volume of the oil phase. Because of the very low
osmotic pressure of the external phase compared to the internal
one in the initial conditions, the extent of swelling predicted by this
model is remarkably high as revealed by the very large equilibrium
values of [SC] and fi (solid lines).
Unfortunately, it was not possible to directly measure [SC] in our
double emulsions because of their very large viscosity. Collecting
the continuous phase required a long and high-speed centrifuga-
tion step, which inexorably led to globule compression and partial
destruction of the double structure with significant release of the
inner droplets. In order to assess the pertinence of this approach,
we measured the variation of G0 and G00 in aqueous solutions con-
taining a well-defined amount of SC, and 0.02 wt.% SA (Fig. 7).
Samples with high SC concentrations were difficult to homogenize
and the upper explored limit was 20 wt.%. Assuming that the
rheological properties of the double emulsions are determined by
the continuous phase, the plot of Fig. 7 can be considered as a
Fig. 5. Macroscopic images of the double emulsions n 9 (a) and n 4 (b). The arrow calibration curve. We are aware that this is an oversimplifying
indicates the gravity direction. The initial compositions are provided in Table 1. approach as the globules also contribute to the rheological
M. Delample et al. / Food Hydrocolloids 38 (2014) 11e19 17
where the subscript “0” refers to the initial state. The final con-
centration of SC in the continuous phase is then straightforwardly
derived. We tried to fit the experimental data of Fig. 6 using f* as
the unique free parameter. The obtained values for f* are reported
in Fig. 8 (versus fi,0 (a) or [SC]0 (b)). Considering the previous re-
marks about the overestimation of [SC], the ordinate of the graphs
represent an upper limit for f*. However, it should be underlined
that the obtained values are very similar to those deduced from
direct measurements by Leal-Calderon et al. (2012) for similar W/O
globules (same oil type and same PGPR concentration).
In Fig. 8-a, f* exhibits a slight but regular increase with fi,0
probably reflecting the variation of the average inner droplet size.
Fig. 7. Variation of G0 and G00 for aqueous solutions containing 0.02 wt.% SA and As explained in the materials and methods section, for a given
different SC concentrations. solute (NaCl or D-glucose), all the W/O emulsions derive from the
18 M. Delample et al. / Food Hydrocolloids 38 (2014) 11e19
2s dg hc g_
Ca ¼ ¼ (7)
PL 2s
In the explored conditions, the applied capillary number lies in a
range between 0.7 and 3 which is sufficient to induce breakup but
low enough to limit the extent of dropleteglobule coalescence.
Some experiments were conducted with the composition of
emulsion n 8 (Table 1) at variable shear rates during step 3:
g_ ¼ 1000, 5000 and 14,200 s1. Almost the same final G0 value was
obtained at 4 C for the two lowest shear rates but we visually
observed that it took longer time, about 30 min, to reach the gelled
state like that described in Fig. 1-b at room temperature for
g_ ¼ 1000 s1. This was due to the fact that average globule size was
larger (50e60 mm) leading to lower exchange surface area and
consequently slower water diffusion. At the opposite, the final G0
value at 4 C was nearly 2-fold lower for the emulsion sheared at
g_ ¼ 12,500 s1, reflecting significant droplet release during the
fragmentation stage.
moduli G0 and G00 rise sharply with concentration, providing further Effect of emulsifier 1 on water permeability. Journal of Colloid and Interface
Science, 104(2), 587e591.
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We hope this study will provide a useful guidance for the
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