Colloids and Surfaces A 536 (2018) 96–103

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Colloids and Surfaces A

journal homepage: www.elsevier.com/locate/colsurfa

Formulation of a water-in-oil emulsion encapsulating polysaccharides to T

improve the efficiency of spraying of plant protection products
⁎ ⁎
Danièle Claussea, , Jean Louis Lanoiselléa,b, , Isabelle Pezrona, Khashayar Saleha
a
Sorbonne Universités, Université de Technologie de Compiègne, EA TIMR 4297 UTC/ESCOM, Rue du Dr Schweitzer, 60200 Compiègne, France
b
Univ. Bretagne Sud, FRE CNRS 3744, IRDL, F-56300 Pontivy, France

G RA P H I C A L AB S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: W/O emulsions were formulated with a vegetable oil and a water phase containing a polysaccharide and glycerol
Polysaccharide release in order to reduce the loss of a phytosanitory product during its spraying on plants and therefore the amount
Vegetable oil used. Different kinds of polysaccharides were tested (CMC, guar and xanthan) and two kinds of surfactants were
Lecithin used (lecithin and PGPR). The stability of the emulsions was determined by different techniques: bottle test,
PGPR
optical microscopy, laser granulometry and differential scanning calorimetry – whose principle is based on the
Cynthiorex
DSC
correlation between the freezing temperature of the droplets and their radius. From the experiments performed
by varying different parameters, a formulation of a suitable emulsion was developped: 3% of CMC in the water
phase, 50–70% V/V of water, 10–12% of PGPR. The release within a few minutes of the required amount of CMC
in water checked by conductivity was obtained by adding another surfactant commercially named Cynthiorex.

1. Introduction supported by the Pole of Industry and Agro Resources of Picardie –

The study reported in this article is part of a project named
VEGEPHY. The aim is to analyse the use of VEGEtable oils to spray
PHYtosanitory (plant protection) products to avoid diseases caused by
the virus Y transmitted by greenflies. An adjuvant was found to avoid
the disease but problems with the spraying itself were identified. These
problems are coming from the drift, the rebound of the droplets on the
leaves, the leaching of the product, the evaporation of the droplets and,
overall, the falling presence of residues of plant protection molecules in
the soil. The Fig. 1 gives a schematic overview of the problems en-
countered.
To try to solve these problems an EUREKA European project in-
volving French and Belgian partners was set up. The project was also
Champagne Ardenne in France. The leader of the project is the CCL
company (Comptoir Commercial de Lubrifiants) located at Le Meux
(France). The final users are CCL and the Comité Nord – Plants de
Pomme de Terre (Achicourt, France) in charge to test the formulated
products on the seed potato growing operation. For that purpose, areas
of treated and untreated vegetables were managed. And from time to
time, observations of the two plots of lands are done. The vegetables
concerned in the project are more precisely potatoes. Four research
laboratories belonging to public establishments were involved in the
project: The Université de Technologie de Compiègne – France (UTC)
for the design of the formulation, the Université Picardie Jules Verne
(UPJV) d’Amiens – France for the action of the virus Y, the center
Agrobiotech de Gembloux (FUSAgx) – Belgium for the spraying, the

⁎
Corresponding authors at: Sorbonne Universités, Université de Technologie de Compiègne, EA TIMR 4297 UTC/ESCOM, Rue du Dr Schweitzer, 60200 Compiègne, France.
E-mail addresses: daniele.clausse@utc.fr (D. Clausse), jean-louis.lanoiselle@univ-ubs.fr (J.L. Lanoisellé).

http://dx.doi.org/10.1016/j.colsurfa.2017.07.032
Received 29 September 2016; Received in revised form 22 June 2017; Accepted 8 July 2017
Available online 10 July 2017
0927-7757/ © 2017 Elsevier B.V. All rights reserved.
D. Clausse et al.
Fig. 1. Schematic overview of the spraying of a water solution of polysaccharide on
plants.
center Wallon de Recherche Agronomique (CRAW) of Gembloux –
Belgium for the studies of the residues. Other Belgian industrials part-
ners for the available chemical components were also in the project:
Vandeputte for the oleochemicals, Mosselman for the surfactants.
Finally, the Belgian company Redebel was in charge of studying the
toxicity, the ecotoxicity and the regulation.
In this article the results obtained by the UTC for introducing the
polysaccharides in the water to be sprayed are described. This was
achieved first by formulating water in oil emulsions wherein the
polysaccharides are trapped in the water droplets. The properties of
these emulsions were tested by using classical techniques such as bottle
test, optical microscopy, laser microscopy and a more sophisticated one
based on the correlation between the radius of the droplets and their
freezing temperatures. The last part of the study is dealing with the
release of the polysaccharide in the water to be sprayed. This article
aims at giving an overview of the study and results obtained at the UTC,
emphasis being put on the main results showing the difficulties to get
reliable results on such a large and complex study dealing with emul-
sions formulated to be stable for the encapsulation and to be broken for
obtaining the release of the polysaccharide. More details on the ex-
periments can be found in theses and previous papers devoted to this
study [1–7].
2. Formulation of the W/O emulsions entrapping polysaccharides
2.1. Materials and methods
First, kind and amount of polysaccharides required to obtain sui-
table properties regarding the viscosity and the granulometry of the
spray were determined [1]. However the required amount cannot be
put directly in the water tank in the fields, otherwise lumps form. To
overcome this difficulty, it was proposed to formulate water in oil
emulsion in which polysaccharides are trapped in the water droplets
[4]. This can be achieved by making the emulsion in laboratory at
suitable temperature and operating conditions. A vegetable oil as ra-
peseed oil methyl ester was proposed to replace mineral oils. A first
screening of surfactants was made and Lecithin and the PolyGlycerol
PolyRicinoleate (PGPR) were retained as surfactants. These products
were obtained from the companies given thereafter.
Guar gum was supplied by Rhodia (Cranbury, NJ, USA) and xanthan
gum by CP Kelco (Atlanta, GA, USA). Carboxymethylcellulose (CMC)
was provided by Roeper GmbH (Hamburg, Germany). These poly-
saccharides were available as powder. Liquid glycerol of 98% purity
supplied by Thermo Fisher Scientific (Illkirch, France) was added in
order to facilitate the dispersion of polysaccharides in water, and pre-
vent the formation of lumps. Rapeseed methyl ester was provided by
Mosselman (Ghlin, Belgium). Powdered lecithin (Emulmetik 300) was
provided by Lucas Meyer Cosmetics (Champlan, France). The
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Colloids and Surfaces A 536 (2018) 96–103
PolyGlycerolPolyRicinoleate (PGPR 4150) in liquid form was supplied
by Palsgaard (Juelsminde, Denmark).
2.2. Emulsification
The water and oil phases were prepared separately as followed.
2.2.1. Water phase
The polysaccharide was dissolved into glycerol under gentle stirring
(200 rpm) with a magnetic stirrer at the laboratory temperature
(22 ± 2 °C) for 2 min. The shearing speed was then increased to
1000 rpm while introducing the demineralized water in the beaker
glass. Agitation was continued for 1 h to form a homogeneous disper-
sion. The solution was allowed to stand for 2 h prior to the emulsifi-
cation to ensure complete dispersion prior to homogenization.
2.2.2. Oil phase
The surfactant was introduced into the oil and the solution was
stirred at 300 rpm by using a hot plate magnetic stirrer equipped with a
temperature control system for precise control of the solution up to
70 °C for 1 h.
2.2.3. Emulsification of the two phases
The first step of the experiments was the preparation of a coarse
emulsion using a rotor stator system (VMI-Raynery Turbotest,
Montaigu, France). The water phase was dispersed drop by drop using a
50 mL syringe pipette into 500 mL of oil phase under shear 1000 rpm,
at room temperature (22 ± 2 °C) in 5 min. The shearing rate was then
increased to 2000 rpm and maintained at this speed for another 5 min.
Afterwards 1000 mL of coarse emulsion were introduced into the
feeding hopper of the high pressure homogenizer (GEA-Panda Plus
2000, Niro Soavi homogenizer). The first valve was closed to set the
pressure at 4.5 ± 0.5 MPa (10% of total pressure was maintained over
the second valve). The emulsion then passed through the valve, dis-
charged to the output side. This single pass product was stored in a
1000 mL beaker glass.
Emulsion was then recycled into the homogenizer. The second valve
was closed to adjust the pressure of the homogenizer until desired
pressure was obtained (45 MPa). The single pass product was refilled
into the feeding hopper. These processes were repeated until the
minimum size of the droplets was achieved (five times passed through
the valves).
3. Characterization of the emulsions
The emulsions were characterized immediately after their prepara-
tion and also versus time in order to check their stability. A rather good
stability is required when the emulsions are stored before being com-
mercialized and the criterion was two years for the emulsions entrap-
ping polysaccharides. Although this time was thought to be too long,
ageing times were performed. Ageing times were set up in agreement
with the recommendation by the Collaborative International Pesticides
Analytical Council [8] for liquid formulation devoted to plant protec-
tion uses. The emulsions containing the polysaccharides either CMC or
guar were stored at 54 °C for 14 days. Those containing xanthan, be-
cause of its sensitivity to temperature above 40 °C were stored at 35 °C
for 84 days. Another ageing test is to submit the emulsions to freezing
and melting cycles in order to get pieces of information about the re-
sistance of the film against coalescence. Freezing induces an expansion
of the water volume and the birth of dendrites and this may have an
influence on the surrounding film of the droplets that could introduce
coalescence of the droplets and by the way a destabilization of the
emulsion.
D. Clausse et al.
3.1. Fresh emulsions characterizations
Fresh emulsions were observed using a labophot-2 Nikon optical
microscope (Tokyo, Japan), to observe the way the droplets were dis-
persed (separated or flocculated) and to estimate their size. A drop
taken from the mother emulsion and diluted in about 1 mL of rapeseed
methyl ester to allow a better observation was placed on a glass and
covered with a microscope slide to optimize the observation. The esti-
mate of the droplet size of emulsion allows to choose the right size of
lens for the determination of the droplet size distribution, by laser
granulometry.
The droplets size analysis was realized using a Malvern Mastersizer
granulometer (Laser Granulometer, Orsay, France), at room tempera-
ture (20 °C).
Few drops of emulsion were diluted in about 200 mL of rapeseed
methyl ester into the granulometer sampler, in order to get about 20%
of obscuration rate, and analysed by the laser diffraction technique.
Another more sophisticated technique was used to get more in-
formation about the way the water phase is dispersed. This technique
referred as the calorimetric or DSC (Differential Scanning Calorimetry)
was utilized in numerous studies to get this kind of information.
Research works dealing with this technique can be found in [9]. The
information given by this technique is based on the correlation between
the sizes of the droplets and their freezing temperatures that are de-
termined through the freezing energies registered by DSC (Differential
Scanning Calorimetry). To do so, an emulsion sample (a few mm3) is
poured in a crucible and introduced in the head of the calorimeter. In
order to get the freezing and the melting of the droplets a regular
cooling and heating is performed between 20 °C and −60 °C when the
droplets are made of water and solute. The chosen lowest temperature
may be less than −60 °C depending on the solute concentration. Due to
nucleation phenomenon the freezing of the droplets does not occur at
the freezing point, 0 °C for pure water under atmospheric pressure, but
at a temperature that could be around −40 °C for micro-sized droplets
submitted to a cooling performed at 2 °C/min. Even if the droplets are
monodispersed they do not freeze all at −40 °C but the temperatures
are not erratic and a maximum of droplets freeze around a mean tem-
perature. At the contrary, melting of pure water droplets occur at 0 °C
without delay. Therefore, two signals are registered by the DSC, one
during cooling with a peak at −40 °C and another one during heating
that starts at 0 °C. Fig. 2 gives the drawing of these signals B and C that
are taken as references for characterizing the emulsion under study.
Any freezing signal between −40 °C and 0 °C shows a less good
emulsification, the limit being observed when the emulsion is com-
pletely broken when two separated bulk phases, water and oil ones, are
present. A test performed with bulk water of same volume, a few mm3,
gives a freezing temperature around −10 °C, signal A. It is worth to
note that this signal has a different shape for the signal B showing a bell
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Colloids and Surfaces A 536 (2018) 96–103
shape. It shows a dissymmetry with a sharp increase of the released flux
as far as all the bulk water freezes rapidly at a sole temperature.
Moreover, this temperature can change from one sample to another one
but it is more probably found between −10 °C and −20 °C.
These signals are modified when a solute is dissolved in water as it is
the case when polysaccharides and glycerol are present in the water
droplets. Water does not melt totally at 0 °C but a progressive melting is
observed and the freezing signal is found at a lower temperature.
3.2. Emulsion stability
The stability was essentially followed by a simple bottle test and by
microscopy and by DSC, this last technique appearing as the most
performing technique because the emulsions are opaque and rather
viscous depending of the amount of dispersed water.
3.2.1. Bottle test
This test is easy to set up. It only needs a transparent graduated tube
wherein around 10 mL of emulsion are poured. A simple observation
versus time permits to have an idea of the emulsion state. The complete
destabilization of the emulsion is characterized by the presence of two
phases: a supernatant oil phase and a bulk water one. Between one
phase characterizing a homogeneous emulsion and two phases showing
the complete destabilization, intermediate states are shown by the
presence of three phases: an oil phase in the top of the tube, a bulk
water phase in the bottom and an emulsified one in the middle.
Following the ratio of the emulsified phase volume versus the total
volume of the sample permits to get an idea of the state of the emulsion.
3.2.2. Microscopy test
From time to time a sample emulsion is taken from the mother
emulsion and observed using the microscopic techniques described in
the section devoted to fresh emulsions.
3.2.3. DSC test
A DSC test is performed from time to time on emulsions stored at
room temperature or stored in an oven and introduced in the head of
the calorimeter. The resulting signal shows a destabilization of the
emulsion when freezing curves are shifted towards highest tempera-
tures, the complete destabilization being observed when a signal similar
to A (Fig. 2) is obtained.
For ageing tests such freezing and melting cycles are repeated on the
same sample. In the case of a resistant film, the mean freezing tem-
perature observed during the second and subsequent cycles will give
the same value. Otherwise less resistant films will give higher tem-
peratures due to the coalescence phenomenon which give birth to
bigger droplets. This technique was been used by some authors to es-
timate the stability of emulsions at the beginning of their shelf life
Fig. 2. Freezing and melting signals (B and C) of micro-sized droplets
of water in oil emulsion, freezing and melting signals (A and C) for
bulk water.
D. Clausse et al.
[10–12].
4. Release of the polysaccharides
4.1. Materials and methods
To obtain the release of the polysaccharides trapped in the droplets
a surfactant named Cynthiorex PMH an ethoxylated fatty alcohol,
supplied by Mosselman (Ghlin, Belgium) was chosen. From studies
performed with different demulsifiers, it appeared that it was the one
that was the most performing. The evolution of the emulsion after the
introduction of the Cynthiorex was followed by DSC through the shift of
the freezing signal of the droplets. Before destabilization a bell shape
freezing signal was expected similar to signal B (Fig. 2) and after de-
stabilization a signal showing a sharp slope similar to signal A (Fig. 2)
at a higher temperature was expected. The release was also detected by
conductivity of the emulsion versus time. This technique is based on the
fact that before the introduction of the Cynthiorex, the entire emulsion
shows a conductivity equals to zero. After the breakdown of the
emulsion due to the introduction of the Cynthiorex and dilution in
water, the presence of the released polysaccharides in water induces a
conductivity different of zero due to the ionization of the poly-
saccharides that yields negative charges COO−. The conductivity was
measured using a conductimeter type CDM 092 (Radiometer, Denmark)
with an electrode/automatic control and an ATP probe.
5. Results
5.1. Formulation and characterization of the emulsions entrapping
polysaccharides
More of the studies were performed with CMC as polysaccharide,
guar and xanthan showing unsatisfactory results for the stability and
the spraying and the action on the plants to be treated. Lecithin and
PGPR were retained as possible surfactants and the studies reported
thereafter were undertaken in order to detect the most performing one.
Various water/oil ratios in the emulsion were also considered in order
to obtain the maximum of polysaccharides trapped in a minimum vo-
lume of emulsion.
First the results obtained with the two surfactants: lecithin and
PGPR surfactants (lecithin and PGPR) will be reported. Afterwards the
optimization of the ratio of water and oil will be examined. This ratio
being fixed and the percentage of CMC as well, the influence of the
concentration of the surfactant on the emulsion stability will be ex-
amined.
Fig. 3. Microscopy and granulometry of dispersed droplets of fresh emulsions. 3A Lecithin, 3B PGPR.
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Colloids and Surfaces A 536 (2018) 96–103
5.1.1. Effect of the surfactant on the droplet size distribution of fresh
emulsions
Microscopic observations of fresh emulsions prepared with CMC in
the water phase and lecithin as surfactant in the oil phase show a po-
pulation of polydisperse drops agglomerated together (Fig. 3A). The
laser particle size analysis gives a maximum of volume percentage at
20 μm. These emulsions were more viscous (dynamic viscosi-
ty = 0.48 Pa s at 20 °C for 6%(w/w) lecithin, and 3% (w/w) CMC) than
those prepared with PGPR (dynamic viscosity = 0.12 Pa s) showing a
better dispersion (Fig. 3B) and which have a maximum of volume
percentage of about 4 mm, in the same conditions.
According to literature [13,14] the viscosity is due to a strong as-
sociation of water droplets together, seen on Fig. 3A for emulsion with
lecithin. These results were confirmed by the DSC studies (Fig. 4). DSC
of emulsion prepared with lecithin gave a freezing signal of dispersed
phase with a maximum (T*) of around −24 °C, whereas emulsion
prepared with PGPR gave T* of −32 °C. According to the correlation
(T* – droplet radius) these results show that the droplets were the
smallest with PGPR in agreements with the microscopic tests.
The PGPR is known to decrease rapidly and significantly the inter-
facial tension compared to lecithin [15,16]. From preliminary experi-
ments performed with the Du Nouÿ ring method, we have noticed that
with 6% (w/w) of PGPR in the rapeseed methyl ester, the interfacial
tension formed with water was less than 1 mN/m, whereas it was 10
times higher with 6% (w/w) of lecithin, in the same conditions. These
data showed only a tendency as far as the technique used was not fully
adapted for such low interfacial tension. Nevertheless, that could ex-
plain the differences in the mean diameters of droplets obtain with
PGPR and lecithin.
5.1.2. Effect of the surfactant and its concentration on the stability of
emulsion stored at 20 °C
The effect of surfactant concentration from 4 to 10 w/w on emulsion
stability of emulsions stored at 20 °C was studied using the bottle test
technique
After 31 days of storage, a supernatant oil phase was observed for
emulsions prepared with lecithin for all concentration studied. The
volume of the emulsified phase increased however with lecithin con-
centration. One explanation could be the steric stabilization occurred
by the lecithin between droplets which slows down the sedimentation.
Another hypothesis is that the increase of the viscosity of the external
phase with the lecithin concentration could slow down the sedi-
mentation as well. Emulsions prepared with PGPR have shown better
stability with the exception of one made with 4% (w/w) of PGPR which
showed a low bulk water phase at the bottom of the bottle. In addition,
no supernatant oil phase has appeared as the one obtained with le-
cithin. These results corroborate those obtained by Sherze et al. [16].
D. Clausse et al.
These authors have also obtained significant phase separation for W/O
type emulsions containing gelatine and/or NaCl in the water phase and
prepared with lecithin, compared to those that they have prepared with
PGPR under the same conditions.
The results reported in Sections 5.1 and 5.2. are given as illustration
of a large amount of experiments that were performed and gave a
justification for the choice of the surfactant PGPR for formulating such
emulsions. Therefore, one of the objectives was reached, namely the use
of vegetable oils instead of mineral oils for making the emulsions.
Nevertheless more studies with this surfactant were undertaken in
order to reach an acceptable stability (two years) and a release of the
polysaccharides in the water tank in field conditions (a few minutes at
temperatures that could vary between 10 and 20 °C). Some examples of
the studies undertaken are reported thereafter.
5.1.3. Effect of the polysaccharide type on the stability of emulsions
stabilized with PGPR, under accelerated ageing tests
Accelerated ageing tests were done on emulsions prepared with
different polysaccharides, the amount of PGPR being 4% w/w and the
amount of water 50% (v/v).
The succession of freezing and thawing of emulsions containing
CMC showed an evolution of the crystallization temperature of the
droplets (Fig. 5A). A peak characteristic of a bulk phase, which reflects
the presence of large drops, and so, the destabilization of the system,
appears during the second cycle and the area of the bulk phase peak
increases in the third cycle. This means that the emulsion was desta-
bilized gradually over the experiments. Nevertheless, the peak of
crystallization of the dispersed phase has not completely disappeared
after three cycles (peak around −32 °C).
For emulsions prepared with guar, a peak at −18 °C can be already
seen for freshly prepared emulsions, in addition to the crystallization of
the dispersed phase, which is noticed at about −32 °C (Fig. 5B). In fact,
the peak at −18 °C could be due to the presence of a few numbers of
large drops in the emulsion and not necessarily to a complete destabi-
lization of the emulsion. The temperature at −18 °C was also found as
the mean freezing temperature of mm3 droplets. After a second cycle of
freezing-thawing, the crystallization peak at −32 °C has disappeared
leaving place to a shoulder at the peak found at −18 °C. This implies an
increase of the sizes of the droplets that were freezing around −32 °C
during the first cycle.
For emulsions prepared with xanthan, the crystallization peak of the
dispersed phase disappears totally in the second cycle giving way to a
peak of bulk phase at about −15 °C, as shown in Fig. 5C.
These results show that the interfacial film of emulsions prepared
with CMC, for a given concentration of PGPR was more stable to a cycle
of freezing-thawing than the one prepared with guar, or with xanthan.
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Colloids and Surfaces A 536 (2018) 96–103
Fig. 4. Freezing curves obtained with lecithin and PGPR.
It could be expected that emulsions prepared with CMC will be more
stable that those containing guar or xanthan.
Ageing tests performed by heating the emulsions in a thermostated
oven have confirmed the results obtained from succession of cycles of
freezing-thawing. Emulsions prepared with CMC were found to be more
stable than those prepared with guar, and those containing xanthan
were found to be the less stable. Furthermore, bottle tests performed
with different amounts of PGPR for different polysaccharides show that
the more stable emulsions were obtained with CMC and an amount of
PGPR higher than 4%.
5.1.4. Influence of the amount of the volume ratio water/oil
These experiments were performed on emulsion made with the
surfactant PGPR (4% w/w in the oil phase), 3.5% wt/wt of CMC in the
water phase, 10% of glycerol and various values of the ratio water/oil
between 50 and 80%. The relatively high amount of PGPR was chosen
to satisfy the stability for such high amount of water. Indeed, DSC tests
performed on emulsions maintained at 54 °C for 14 days have shown
that 12% was not enough.
Some of the results obtained by bottle and DSC tests are given as
examples in Fig. 6. In this figure, {0} represents the fresh emulsion for
all percentages of the dispersed phase (60–80% v/v) at t = 0 day; no
visual destabilization was detected. However, after an accelerated
ageing test, 14 days at 54 °C, instability was pointed out for emulsions
containing ϕ = 60% v/v (Fig. 6A {1}), which shows a bulk water phase
at the bottom, an emulsified phase in the middle and a separated oil
phase at the top. A separated oil phase was also seen for ϕ = 70% v/v
(Fig. 6A {2}), but no bulk water phase at the bottom of the tube. The
best stability was obtained for ϕ = 75% v/v (Fig. 6A {3}) and for
ϕ = 80% v/v (Fig. 6A {4}). These results are in agreement with those
obtained with the DSC test. The corresponding freezing curves obtained
on emulsions maintained either at 20 °C, plain lines, or at 54 °C, dashed
lines, are reported Fig. 6 B.
The exothermic peaks of fresh emulsions (solid lines) show a max-
imum referred to as the mean freezing temperature around
T* = −29 °C for ϕ = 60% v/v (Fig. 6B – line 1) and around
T* = −35 °C for respectively ϕ = 70, 75 and 80% v/v (Fig. 6B – lines
2, 3 and 4). The lowest freezing temperature at −50 °C is due to the oil
solidification. Furthermore, the DSC curves show a freezing signal for
the dispersed droplets with a rather narrow distribution for ϕ = 75 and
80% v/v, and a large one for ϕ = 60 and 70% v/v. This is in favour of a
best stability for the emulsions prepared with ϕ = 75 and 80% v/v in
agreement with the found values of T*. The accelerated ageing test at
54 °C during 14 days (dotted lines) results in a shift of the mean
freezing temperatures to higher ones. At around −18 °C, a signal of
crystallization characteristic of a bulk water phase (see Fig. 2 for the
D. Clausse et al.
Fig. 5. Freezing signals obtained during 3 cycles of cooling and heating for CMC (A), guar
(B) and xanthan (C).
shape, a difference in the temperature is not abnormal as far as the
freezing of a single sample is a stochastic event) is observed for ϕ = 60
and 70% v/v (Fig. 6B – lines 1 & 2) indicating that a destabilization has
begun. For ϕ = 75 and 80% v/v (Fig. 6B – lines 3 & 4), rather small
variations of the freezing signals of the droplets were observed, 4 °C for
ϕ = 80%, and 3 °C for ϕ = 75%, but without the presence of a signal
showing a bulk phase as it is for ϕ = 60% and ϕ = 70%. These results
are in accordance with the bottle test observation showing a beginning
of destabilization for the emulsions prepared with ϕ = 60 and 70% v/v
of dispersed phase and a better stability for ϕ = 75 and 80% v/v.
The melting signals are different from the ones observed for pure
water, essentially due to the presence of the glycerol. The ice formed
during cooling melts progressively during heating as it is expected for
the melting of solute-water solutions. As expected as well, the melting
signals are the same whatever the percentage of water in the emulsion
because there is no delay for the melting.
In conclusion of this study it can be noticed that increasing the
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Colloids and Surfaces A 536 (2018) 96–103
amount of water in the emulsion leads to a better stability in experi-
mental conditions used in this study.
An explanation of the higher stability of emulsions at ϕ = 75–80%
v/v against sedimentation could be the fact that the volume fraction of
the dispersed phase is above the packing maximum. The droplets are
thus packed close to each other and the sedimentation rate, which was
caused by the hydrodynamic interaction between the droplets [17] is
then reduced.
Nevertheless, the amount of 75% was retained. Under these condi-
tions, the rheology characteristics of the formulation are the best for the
process.
5.1.5. Conclusions
From this study on the characterization of the emulsions entrapping
polysaccharides, an optimum formulation was obtained containing
3.5% of CMC, 10% of glycerol, in 75% of dispersed water and 14% of
PGPR in the continuous phase made of vegetable oil.
The success of entrapping polysaccharides is conditioned by the
release of them when the emulsions are used in the water tank. First the
emulsion which is W/O has to be diluted in water and the droplets have
to burst to liberate the CMC which is not supposed to go through the oil
membrane. Some illustrative results obtained for liberating the poly-
saccharide are given in the next section.
5.2. Release of the CMC
Fig. 7 reproduces the freezing curves obtained by DSC of emulsions
without and with Cynthiorex. The exothermic peaks reveal that the
freezing temperature moved significantly to a higher temperature with
the presence of demulsifier. That means that the emulsion is broken.
These results were confirmed by studying the release by conductivity.
From Fig. 8, it can be deduced that the release is nearly total after
around 15 min. This result is satisfactory for the process that does not
need too long time for obtaining the release when the emulsion is di-
luted in the tank.
6. Conclusions
This article describes a part of the works made to introduce a
polysaccharide in the water tank in field conditions. This cannot be
achieved directly due to the formation of lumps. It was proposed to
formulate W/O emulsions encapsulating a water solution of poly-
saccharide prepared in laboratory conditions that render this operation
possible. The present article describes some of the experiments made to
formulate such an emulsion. Focus are put on the stability of such
emulsions as far as they have to be stored for later use on the fields. This
involves a release step which has to be as short as possible. The results
obtained are acceptable as far the release is achieved quickly thanks to
the addition of a chemical product, the Cynthiorex. Therefore, two
surfactants are needed: one for making the emulsion in a vegetable oil
as required, and PGPR is the more suitable with regards to the emulsion
stability, and another one, the Cynthiorex, for the reverse effect. This
study shows also that performing DSC tests on such emulsions which
are opaque and therefore difficult to study by optical techniques is a
good way to obtain reliable pieces of information.
Acknowledgement
This work was carried out as part of the European project VEGEPHY
lead by the Comptoir Commercial des Lubrifiants (Le Meux, 60200
Compiègne, France) and supported by EUREKA and the Industry and
Agro-Ressources (IAR) biorefining cluster of the Picardie and
Champagne-Ardenne regions (France). Thanks also to ESA for sup-
porting a general study on emulsion stability (FASES project).
D. Clausse et al. Colloids and Surfaces A 536 (2018) 96–103

Fig. 6. Bottle and DSC tests for emulsions containing 60–80% of water, 3.5% of CMC, 10% of glycerol, and submitted to ageing tests of 14 days at 54 °C.

Fig. 7. Freezing curves of emulsions without Cynthiorex (solid lines)

and with Cynthiorex (dashed lines).

Fig. 8. Conductivity versus time of emulsion regularly agitated. The

dashed line is the conductivity expected for a solution containing the
total amount of CMC entrapped in the droplets.

102
D. Clausse et al.
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