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Chemical Engineering Research and Design

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

The application of a multi-scale approach to the

manufacture of concentrated and highly
concentrated emulsions

Diego Pradilla, Watson Vargas, Oscar Alvarez ∗

Grupo de Diseño de Producto y de Proceso (GDPP), Departamento de Ingeniería Química, Universidad de los Andes,
Carrera 1 N 18A-12, Edificio Mario Laserna, Piso 7, Bogotá, Colombia

a b s t r a c t

In this work, a multi-scale approach is applied to the emulsification process of concentrated emulsions. Whereas
a vast number of studies have focused on either formulation or processing (Mason et al., 1997; Pal, 1999; Dimitrova
and Leal-Calderon, 2004; Derkach, 2009; Capdevila et al., 2010), we propose a transversal study that includes those
variables and also covers aspects of the rheological behavior, the droplet size and the near infra-red spectra (NIRS).
The analysis on oil-in-water (O/W) and water-in-oil (W/O) emulsions yielded results that depend on the energy
incorporated during the emulsification process. First, depending on the tip velocity and pumping capacity of the
impeller, a certain amount of energy can be incorporated to a given formulation (i.e., concentration of the dispersed
phase). Second, as a consequence, the properties (rheology and droplet size) (Zölzer and Eicke, 1993; Ewoldt and
McKinley, 2007; Evans et al., 2009) of the resulting emulsion are set and mathematical relationships are established.
Finally, it is possible to visualize via NIRS not only the changes in concentration (Aske et al., 2002; Sjöblom et al.,
2003; Araujo et al., 2008) but also the influence of the changes in droplet size and couple all three aspects.
The novelty of these results rests on the treatment of the energy as a transversal variable to the scales studied
instead of handling only the formulation variables.
© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Emulsions; Mixing; Rheology

1. Introduction a surfactant that stabilizes the droplets by ensuring a short

Emulsions are a type of colloidal system in which droplets of
a liquid are dispersed in a second immiscible liquid. Emul-
sions are widely used in a variety of industrial applications:
cosmetics, food, pharmacy, coatings, oil recovery and the so-
called liquid explosives (Jager-Lézer et al., 1998; Clausse et al.,
1999; Dimitrova and Leal-Calderon, 2001,2004; Sjoblom, 2001;
Tadros, 2004; Pal, 2006; Masalova and Malkin, 2008; Capdevila
et al., 2010; Bouyer et al., 2011; Masalova et al., 2011). These
products are non-equilibrium systems, which means that they
are thermodynamically unstable and consequently two vari-
ables must be considered for their formation: energy (which
must be incorporated through the emulsification process) and
range repulsive interaction at the interface (Dimitrova and
Leal-Calderon, 1999; Datta et al., 2011). Highly concentrated
emulsions also known as high internal phase ratio emul-
sions (Pal, 1996,1998a,b,1999,2006; Clausse et al., 2007) and
concentrated emulsions are of special interest because of the
complexity of their rheological behavior resulting from the
increasing relevance of the interactions between the droplets
as they come closer to one another. In most cases, this proxim-
ity causes the spherical droplets to change in shape and take
the shape of polyhedrons.
A multi-scale approach could be defined as a way of creat-
ing a link between what happens within a system (in this case,
an emulsion) and its performance as a finished product. The

∗
Corresponding author. Tel.: +57 1 3394949x3935; fax: +57 1 3324334.
E-mail addresses: d-pradil@uniandes.edu.co (D. Pradilla), wvargas@uniandes.edu.co (W. Vargas), oalvarez@uniandes.edu.co
(O. Alvarez).
Received 28 February 2014; Received in revised form 6 October 2014; Accepted 23 October 2014
http://dx.doi.org/10.1016/j.cherd.2014.10.016
0263-8762/© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: Pradilla, D., et al., The application of a multi-scale approach to the manufacture of concentrated and highly
concentrated emulsions. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.10.016
CHERD-1723; No. of Pages 11
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practical use of such link (or links) has been acknowledged by size and G is the value of the elastic modulus in the linear
some authors using several field specific examples (Jager-Lézer viscoelastic region. Eqs. (1) and (2) indicate how the elasticity
et al., 1998; Sagis, 2011; Charton et al., 2013). and the average droplet size change with respect to the incor-
Recently, Sagis (2011) pointed out that the dynamic behav- porated energy for W/O emulsions when the concentration of
ior of the interfaces of high surface to volume ratio systems, the dispersed phase is between 92 and 96 (wt%).
such as emulsions (also dispersions of vesicles, dispersion of The second part of this work, studies how average droplet
nanocapsules, etc.) is responsible for the macroscopic dynam- size affects the near infrared spectra (NIR) of O/W emulsions.
ics. Therefore, a study solely focused on the molecular scale Similarly, the effect of the concentration of the dispersed
(i.e., surface active material adsorption, desorption kinetics, phase on the different trends will also be studied for concen-
diffusion mechanisms, surface rheology, etc.) would not suf- trations of 30–80 (wt%).
fice if the goal of the study was to evaluate overall performance According to Sjøblom (Aske et al., 2002; Sjöblom et al., 2003),
of a product in different scenarios. In fact, interactions at the when the near infrared spectra (NIR) spectra of a water-in-oil
molecular scale are only a part of what defines the behavior emulsion is obtained, the water droplets within the emulsion
of emulsions. will scatter portions of the incoming light with an intensity
Analogously, at the macroscopic level, as highlighted by that follows Eq. (3):
Dimitrova and Leal-Calderon (2004), Babak et al. (2001) and
more recently by Derkach (2009), several factors affect the Id r6
behavior of emulsions: the volume fraction of the dispersed ∝ 2 4 (3)
I0 x 
phase, the droplet size, the polydispersity of the droplets, the
temperature and the emulsification process. This behavior
where r is the droplet radius, x is the sample thickness,  is
is usually studied using rheological measurements such as
the wavelength and Id /I0 is a measurement of the extinction
steady-state flow experiments to determine the viscosity as
of light. This means that for two water-in-oil emulsions that
a function of the shear rate and thus observing both the shear
have the same formulation but differ in their droplet size dis-
thinning behavior and the yield stress (Pal, 1999) -and oscil-
tributions, the emulsion with bigger droplets will scatter light
latory experiments in which the elastic and viscous moduli
with a greater total intensity than the emulsion with smaller
(G and G ) are obtained (Mason et al., 1997; Fa et al., 2004).
droplets. This will shift the spectra toward areas of higher
Also, the droplet size and droplet size distribution are usu-
absorbance for the emulsion with greater average droplet size.
ally obtained through optical microscopy or light diffraction
Araujo et al. (2008) observed similar changes in the NIR spectra
techniques.
of water-in-crude oil emulsions due to changes in the average
The overall goal of this work is to use a novel multi-scale
droplet size and concentration of water. However, the trends
approach, which analyzes the coupled effects between, first,
of the different spectra were opposite to those reported previ-
the formulation and the composition variables of a product
ously (Aske et al., 2002; Sjöblom et al., 2003).
(i.e., an emulsion), second, the process through which the
Finally, the third part of this work will use creep tests
product is made and third, the properties that the product
to study concentrated and highly concentrated W/O emul-
exhibits. These properties can be studied using a multi-level
sions and analyze the behavior of the compliance modulus,
method, meaning that the responses at different levels can be
J(t), when the concentrations of the dispersed phase and
analyzed. In this sense, the product will have properties at the
the applied stress within the linear viscoelastic region are
macroscopic level, described in this case by the rheology of the
changed.
system, the microscopic level, related to the average droplet
Creep testing has been commonly used to determine the
size, and the molecular level, represented in this case by the
yield stress at which some materials may fracture or to deter-
combinations and overtones in a near infrared spectrum. This
mine the viscosity of soft materials at low shear rates (Tadros,
novel approach allows the simultaneous study of aspects at
2004). Typically, oscillatory measurements are used to obtain
the three mentioned levels, covering the main variables that
reliable results in the short-time/high frequency domain and
influence emulsion preparation.
creep measurements are used to obtain information in the
The first part of this work establishes the relationships
long-time/low-frequency domain. However, creep testing can
between the energy incorporated through the emulsification
also be used to obtain information about the viscoelastic
process, the concentration of the dispersed phase and the
nature of concentrated and highly concentrated emulsions
properties at the three levels, using three different types
(Zölzer and Eicke, 1993; Baravian and Quemada, 1998; Jager-
of impellers to prepare oil-in-water (O/W) emulsions with
Lézer et al., 1998; Ewoldt and McKinley, 2007). Therefore, the
concentrations ranging from 80 to 90 (wt%). Using a simi-
information obtained through a creep experiment contains
lar approach, Alvarez et al. (2010) established a relationship
essentially the same information as oscillatory measure-
between the energy incorporated through the emulsification
ments, and accordingly, changes in the morphology of the
process and the macroscopic properties (the rheology) of
droplets can also be observed using a different technique.
water-in-oil (W/O) emulsions. They also established a second
relationship that relates the energy incorporated to the micro-
scopic structure of the system (the average droplet size). The 2. Materials and methods
relationships are shown in the following equations:
2.1. Materials
G ∝ E0.6
v (1)
Highly concentrated oil-in-water (O/W) and water-in-oil (W/O)
Rm ∝ E−0.3
v (2) emulsions were prepared with mineral oil (USP-grade), mili-Q
de-ionized water and two non-ionic surfactants provided by
In these equations, Ev corresponds to the energy incorporated Croda: Span 80® (Sorbitan Monooleate), oil soluble, HLB 4.3,
through the emulsification process, Rm is the average droplet and Tween 20® (polisorbate 20), water soluble, HLB 16.7.

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Table 1 – Relevant dimensions of the mixing system.
Impeller Impeller Tank Height of
diameter diameter the finished
[mm] [mm] emulsion
[mm]*
“PB”: Pitch Blade 45◦ 104 133 48
“HF”: Hydrofoil 85 108 48
“PR”: Propeller 65 83 48
∗
Relative to the bottom.
2.2. Methods
2.2.1. Formulation
Stability tests showed that 4 (wt%) of total concentration of the
surfactant mixture was the most suitable for the study. At this
value, the phase separation vs. time data showed a maximum
indicating the most stable system. This corresponds to a mass
ratio of Tween 20® to Span 80® for O/W emulsions of 7/3 and
78/5 for W/O emulsions. The corresponding final HLB values
are 15 and 5 respectively.
Drop tests were performed after each preparation to verify
the continuous phase.
Part I: O/W emulsions were prepared in a concentration
range of 80–90 (wt%).
Part II: O/W emulsions were prepared in a concentration
range of 30–80 (wt%).
Part III: W/O emulsions were prepared in a concentration
range of 75–85 (wt%). W/O emulsions were chosen for this part
because their elastic response in the linear viscoelastic region
is more strongly pronounced than that of O/W emulsions.
2.2.2. Emulsification process
Before the preparation of the emulsions, the surfactants were
added to the corresponding soluble phase separately: Span 80®
was pre-mixed with oil and Tween 20® was pre-mixed with
water.
Part I: A semi-batch process was used to prepare all emul-
sions. This process consisted of three steps: In the first
step, the continuous and the dispersed phase were pre-
homogenized separately for 15 min at 300 rpm. In the second
step, the dispersed phase was added to the continuous phase
at a slow, constant rate using a peristaltic pump (Fischer Sci-
entific, flow rate = 0.5 ml/s). In the third step, the emulsion was
homogenized for 10 min at the same tip velocity (1.7 m/s).
These three steps were performed in a mixing device (Light-
nin LabMaster L1U10F) that allowed for the torque to be
recorded as a function of time, and from this data, it was pos-
sible to calculate the power generated. The area under the
power-time curve was later calculated (via integration); this
value corresponds to the energy consumed per unit volume
for each emulsion.
Three different types of impellers were used: a pro-
peller, a 45◦ pitch blade turbine and a hydrofoil turbine. The
impeller-to-tank diameter ratio was kept constant at 0.78. The
off-bottom clearance was defined by placing the impeller at
the liquid-air interface prior to the incorporation of the dis-
persed phase. The total final height of the emulsion was also
kept constant at 48 mm relative to the bottom of the tank to
avoid head pressure effects on the impeller. Table 1 shows rel-
evant dimensions of the mixing system. The tip velocity was
also fixed at a constant value and a thermometer was used
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3
Table 2 – The characteristic peaks of an emulsion.
Values taken from (Sjöblom, Aske et al., 2002).
Absorption band Wavelength
region [nm]
O H first overtone 1400–1450
O H combinations 1900–1975
C H second overtone 1125–1225
C H combinations first overtone 1350–1450
C H first overtone 1625–1775
C H combinations 1950–2450
to measure the temperature at all stages of the emulsification
process. The variation was less than 1 ◦ C in all experiments.
Part II: The procedure described in Part I was used with a
minor change: only the propeller was used.
Part III: The procedure described in Part I was used with a
minor change: only the propeller was used.
2.3. Characterization
All measurements were performed 30 min after preparation to
allow the emulsions to adequately stabilize. High reproducibil-
ity was achieved by testing duplicates for each emulsion.
The experimental error was no higher than 10%. The char-
acterization consisted of three parts: rheology, near infrared
spectroscopy and droplet size measurement.
2.3.1. Rheology
Part I: A controlled-stress rheometer (ARG2, TA instruments)
equipped with a 20 mm-parallel plate geometry was used to
perform 2 oscillatory tests at a constant gap of 1 mm and
constant temperature of 20 ◦ C with a maximum deviation of
±0.1 ◦ C. An extra set of oscillatory tests was carried out while
varying the gap size (500–1500 ␮m) to ensure that there was
no wall-slip. These results were not included in the analysis.
The first oscillatory test was a frequency sweep with a
pre-shear of 1 min at 1 s−1 , followed by the frequency step
of 1–100 rad/s. The second oscillatory test was a stress sweep
with a pre-shear of 1 min at 1 s−1 , followed by the stress step
of 1–100 Pa. These tests allowed for the obtention of the value
of the elastic modulus (G ) in the linear viscoelastic region. In
our case, this means that G is independent of both the stress
and the frequency, thus the value reported corresponds to the
average in the plateau region. No creaming or other signs of
instability were observed during the experiments.
Part II: No rheological measurements were performed.
Part III: A controlled-stress rheometer (ARG2, TA instru-
ments) equipped with a 20 mm-parallel plate geometry was
used to perform creep tests at a constant gap of 1 mm and
constant temperature of 20 ◦ C, with a maximum deviation of
±0.1 ◦ C. An extra set of oscillatory tests was carried out while
varying the gap size (500–1500 ␮m) to ensure that there was
no wall-slip. These results were not included in the analysis.
The creep tests were carried for 300 s without recovery, and
the stress varied from 1 to 125 Pa.
2.3.2. Near infrared spectroscopy (NIRS)
Part I: The absorbance of the emulsions was measured in the
near infrared region (1100–2500 nm) using a smartprobe ana-
lyzer spectrophotometer (FOSS). The sample size was 12 ml.
Table 2 shows the different characteristic peaks and their cor-
responding functional groups.
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The parameter chosen to characterize the O/W emulsions

was the maximum located at 1625–1775 nm, which corre-
sponds to the first overtone of the C H (stretching vibrations).
This is a good representation of the oil droplets dispersed in
the continuous phase for the O/W emulsions. This parameter
has the advantage of being dependent on the concentration
of the absorbing group and largely independent of the rest of
the molecule, avoiding induced noise from other groups (Kelly
and Callis, 1990).
Part II: The procedure described in Part I was used without
any changes for this section.
Part III: No spectroscopy measurements were performed.

2.3.3. Average droplet size and droplet size distribution

Part I: The droplet size distribution was obtained using a Mas-
tersizer 3000 (Malvern Instruments), which uses the laser
diffraction technique to perform droplet size measurements Fig. 1 – Elastic modulus (G in the linear viscoelastic region:
in the range from 0.01 to 3500 ␮m. The governing principle 0.1–100 [rad/s] and 0.1–100 [Pa]) as a function of the energy
for these measurements is the Mie theory. To avoid multi- incorporated (homogenization step) to the system for O/W
ple scattering, adequate ranges of obscuration were selected emulsions with a concentration of the dispersed phase in
according to the laser specifications. All measurements were the range of 80–90 (wt%) prepared using three different
performed under the same conditions. impellers: 45◦ Pitch blade, Hydrofoil and Propeller. (The
Mie theory considers the diffraction, refraction and absorp- concentration values in ascending order are 80%, 82%, 85%,
tion events that occur when a beam of light impacts a particle. 87% and 90%).
For this reason, the optical parameters must be known. The
dispersant, which carries the particles or droplets to the mea-
elasticity of the system affects the amount of energy neces-
surement area, must not interact in any way with the droplets
sary for homogenization, that is, when the concentration of
to avoid changes in size; for this reason, water was the dis-
the dispersed phase increases, the energy incorporated also
persant for O/W emulsions (Sjöblom et al., 2003; Araujo et al.,
increases as long as the other variables related to the process
2008).
are kept constant (i.e., the geometry of the mixing system and
From the intensity reports, which are related to the vol-
the tip velocity of the impeller).
ume that the particles occupy, various mean diameters can be
The relationship between the rheological behavior of
obtained. One of these is the volume mean diameter, D[4,3],
concentrated and highly concentrated emulsions and the
which is the mean diameter used in this work.
average droplet size (droplet size distribution) has also been
Part II: The procedure described in Part I was used without
the subject of numerous publications (Jager-Lézer et al., 1998;
any changes.
Pal, 1998a,b; Malkin et al., 2004; Mougel et al., 2006; Pal,
Part III: No droplet size measurements were performed.
2006; Derkach, 2009; Capdevila et al., 2010). A comparison of
Figs. 1 and 2, confirms that when the elasticity of the system
3. Results and discussion

3.1. Part I: multi-scale approach

The first part of this discussion focuses on describing and

understanding the possible relationships between the energy
incorporated through the emulsification process and the
macroscopic properties, the microscopic structure and the
molecular response of oil-in-water emulsions. It is important
to highlight the fact that the energy incorporated through
the emulsification process corresponds to the energy that is
required to homogenize the product after the dispersed phase
has been added. In the preparation of concentrated and highly
concentrated emulsions, this stage requires more energy than
the incorporation step (Alvarez et al., 2010).
Different publications have reported that when the vol-
ume fraction of the dispersed phase increases, the elasticity
of the concentrated and highly concentrated emulsions also
increases (Salager, 1996; Langevin, 2000; Dimitrova and Leal-
Calderon, 2004; Pal, 2006). This increase in the elasticity is Fig. 2 – Average droplet size (D[4,3] ␮m) as a function of the
directly related to the degree of packing of the droplets, which energy incorporated (homogenization step) to the system
promotes the interactions among them. The consequence for O/W emulsions with a concentration of the dispersed
of the interactions between the droplets is an increase of phase in the range of 80–90 (wt%), prepared using three
the elastic modulus in the linear viscoelastic region. The different impellers: 45◦ Pitch blade, Hydrofoil and Propeller.
emulsions prepared for this work exhibited the behavior just (The concentration values in descending order are 80%,
described as shown in Fig. 1. Evidently, an increase in the 82%, 85%, 87% and 90%.)

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Table 3 – Values of the elastic modulus (G ), average droplet size (D[4,3]) and energy consumption for direct oil-in-water
emulsions with different concentrations of the dispersed phase prepared with three impellers: Pitch blade “PB”,
Hydrofoil “HF” and Propeller “PR”. Same data plotted in Figs. 1 and 2.
wt% Impeller Energy [J/ml] G [Pa] D[4,3] ␮m
80 PB 1.00 ± 0.06 3.85 ± 0.07 17.55 ± 0.07
HF 2.10 ± 0.06 5.62 ± 0.82 14.30 ± 0.56
PR 4.80 ± 0.06 9.37 ± 0.76 10.60 ± 0.07

82 PB 1.05 ± 0.01 5.86 ± 0.98 14.05 ± 0.49

HF 2.11 ± 0.02 7.78 ± 0.65 10.80 ± 0.28
PR 4.89 ± 0.03 10.16 ± 1.05 8.91 ± 0.39

85 PB 1.33 ± 0.06 14.97 ± 1.71 8.32 ± 0.67

HF 2.66 ± 0.07 22.75 ± 4.03 6.51 ± 0.50
PR 6.01 ± 0.28 29.14 ± 5.57 4.81 ± 0.03

87 PB 1.46 ± 0.12 31.00 ± 0.56 5.11 ± 0.11

HF 2.99 ± 0.16 35.25 ± 1.90 4.47 ± 0.15
PR 7.05 ± 0.04 53.75 ± 1.24 3.78 ± 0.06

90 PB 2.87 ± 0.04 169.47 ± 10.92 2.50 ± 0.26

HF 5.33 ± 0.09 220.11 ± 5.07 1.80 ± 0.17
PR 12.24 ± 0.17 322.57 ± 91.11 1.27 ± 0.04

(represented by the elastic modulus G ) increases, the average
droplet size (D[4,3]), decreases. This leads to the conclusion
that increased energy consumption causes a decrease in
the average droplet size. This conclusion is also valid when
the concentration of the dispersed phase increases (see also
Table 3 for direct value comparison).
Moreover, it can be observed that the changes at the macro-
scopic level (indicated by the rheological properties) and the
microscopic level (indicated by the droplet size) due to the
energy incorporated during the emulsification process, are
also evident in the molecular response of the emulsions. Fig. 3
shows how the absorbance of the first overtone of the C H
bond interactions behaves as a function of the incorporated
energy. This increment is a result of two conditions: first, an
increase in the phase volume of oil causes an increase in the
absorbance of its characteristic peak (Gossen et al., 1993; Frake
Fig. 3 – Total measured absorbance of the 1st overtone of
CH-bond interactions as a function of the energy
incorporated (homogenization step) to the system for O/W
emulsions with a concentration of the dispersed phase in
the range of 80–90 (wt%) prepared using three different
impellers: 45◦ Pitch blade, Hydrofoil and Propeller. (The
concentration values in ascending order are 80%, 82%, 85%,
87% and 90%.)
et al., 1998; Sjöblom et al., 2003), this is directly proportional to
the elasticity of the system and the amount of energy needed
for homogenization. Second, changes in the average droplet
size cause shifts in the overall spectra of the emulsions. This
result will be further studied in a later section of the present
article.
The effect of any variable related to the process can be
evaluated through the relationships described previously (Eqs.
(1) and (2)). Such a variable can be, for instance, the type of
impeller: pitch blade, hydrofoil or propeller. If the concen-
tration of the dispersed phase is fixed at a given value (see
Figs. 1–3 and Table 3), it can be seen that the values of the
elastic modulus, G , the average droplet size, D[4,3], and the
absorbance of the first overtone are similar and do not seem
to depend on the type of impeller used for preparation (i.e., all
the values of G are within the same order of magnitude). For
better clarity and to avoid misinterpretations caused by solely
looking at Figs. 1 and 2, the data used to construct these figures
are shown in Table 3. From this table, it can be observed that
all the values of the elastic modulus are within the same order
of magnitude, which means they are comparable. Something
similar happens when looking at the values of the average
droplet size. However, it is also clear that the energy consump-
tion does, in fact, depend on the type of impeller. The values
of energy consumption for the propeller are always signifi-
cantly higher compared to the hydrofoil and the pitch blade.
This is a direct consequence of the relevance of the pumping
capacity as will be addressed further on this section. This also
means that there is a similar rheological behavior associated
with a similar microscopic structure and molecular response
for different energy consumption values.
To attempt an explanation of this result, it is important to
highlight two facts: first, the variables related to the geom-
etry of the mixing system were kept constant; that is, the
impeller-to-tank diameter, the total final emulsion height and
the location of the impeller inside the mixing tank were kept
constant. The tip velocity was also kept constant to assure
that the same shear was given by impellers with different
diameters. Second, the stage of the emulsification process that
demands the most energy is the homogenization step (Alvarez
et al., 2010).
A very important factor that influences this stage is the
ability that each impeller has to move the fluid across the

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Table 4 – The calculated pumping capacity for the three
impellers used in this study (pitch blade, hydrofoil and
propeller) shown in Fig. 1.
Type of impeller Pumping capacity (m3 /min)
Eq. (4)
“PB”: Pitch Blade 45◦ 0.34
“HF”: Hydrofoil 0.17
“PR”: Propeller 0.10
mixing tank. This ability can be measured through the so-
called pumping capacity, which can be calculated using Eq.
(4) from reference Hemrajni and Tatterson (2004):
Q = Nq ND3
Q represents the circulation of the fluid within the mixing
tank, Nq is the dimensionless pumping number, N is the
mixing velocity in rpm and D is the impeller diameter. The
dimensionless pumping number can be calculated or found
in different handbooks; for instance, the values used for the
“PB” and “HF” impellers in this study were found in (Bakker
and Gates, 1995) and the value for the “PR” impeller was found
in (Comments by Murray, 1948) and (Procházka and Landau,
1961). It is important to highlight that these values are valid
for laminar flow.
Table 4 shows the calculated pumping capacity for the sys-
tem described in Figs. 1–3. It is evident that the values are
different for the three impellers used; therefore a possible
explanation for why the curves in Fig. 1 do not overlap is
that each impeller uses the energy incorporated through the
mixing system differently. A portion of the energy is used for
droplet formation as expected, whereas the other portion of
the energy is used for fluid circulation.
From Fig. 1 and Table 3, it can be concluded that the
impeller with greatest pumping capacity is the one that
exhibits the lowest energy consumption for the studied emul-
sions. Similarly, there is a qualitative relationship between
the energy consumed and the pumping capacity: a low
pumping capacity partially accounts for the increase in energy
consumption when emulsions with similar properties are
obtained. An impeller that has a high pumping capacity value
will allow for a better circulation of the fluid within the mixing
tank for concentrated and highly concentrated emulsions.
Different authors (Salager, 1996; Tadros, 2004; Alvarez et al.,
2010; Capdevila et al., 2010) have implicated the tip velocity
as a key factor in the emulsification process, mainly because
this factor can control the amount of shear available for
droplet formation. If we now take into consideration the
results presented in Figs. 1–3, a novel methodology can be used
for the preparation of concentrated and highly concentrated
emulsions. This methodology (the multi-scale approach) may
be used to manufacture emulsions with certain desirable
characteristics while minimizing the energy consumption by
controlling the tip velocity and selecting an impeller that
yields the highest pumping capacity. These parameters may
be used as criteria for scale-up processes.
If we now look more closely at the relationships between
the incorporated energy and the rheological behavior (that is,
the microscopic structure and the molecular response), we can
follow an approach similar to the one proposed by Alvarez
(Alvarez et al., 2010) and establish equations similar to Eqs.
(1) and (2). In Fig. 1, two trends proposed are represented by
the dotted lines: when the concentration range is 80–85 (wt%),
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concentrated emulsions. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.10.016
the slope of the straight line that best fits the three curves
(three impellers) has a value of 4 (R2 = 0.99). Similarly, when the
concentration goes up to 85–90 (wt%), the slope of the straight
line that best fits the three impellers has a value of 3 (R2 = 0.99).
These two trends can be described through the proportional
relationships in Eqs. (5) and (6):
G ∝ E4v (5)
G ∝ E3v (6)
It is that the slope of the straight line decreases as the con-
centration of the dispersed phase increases. When this occurs,
the rheological properties associated with the incorporated
(4) energy decreases. Therefore the energy might split into three
paths once it has been incorporated during the emulsification
process: first, energy is required for droplet formation; second,
energy is required to circulate the fluid across the mixing tank;
and third, when the droplets are small enough to come into
contact with one another, the interactions between them is
more relevant, therefore they dissipate energy due to droplet-
droplet contact (high packing and change in morphology).
We can now look for proportional relationships that are
similar to those established in Eqs. (5) and (6) for the aver-
age droplet size and the energy (dotted lines in Fig. 2). For
the concentration range of 80–85 (wt%), the straight line that
best fits the three impellers has a slope of −2.5 (R2 = 0.99), and
similarly, the slope of the straight line that best fits the three
impellers for concentrations in the range of 85–90 (wt%) has
a value of −1.5 (R2 = 0.99). Eqs. (7) and (8) describe these rela-
tionships and once again, the trend of the slope is evident:
as the concentration increases, the slope of the line tends to
decrease.
D ∝ E−2.5
v (7)
D ∝ E−1.5
v (8)
These results provide a clearer insight into the relationship
between the process, the product and properties of con-
centrated and highly concentrated emulsions and how the
energy is related to the different formulation and composition
variables. Eqs. (7) and (8) show that for systems that are mod-
erately concentrated (80 wt%), where the elasticity is low and
the droplets are somehow larger, the relationship between the
elastic modulus (or the average droplet size) and the energy
is strongly correlated, but when the concentration increases
to 90 wt%, this relationship becomes less relevant, indicating
that highly concentrated systems require much more energy
to be circulated across the mixing tank.
The last relationship that can be established using the
multi-scale approach is that between the incorporated energy
and the properties at the molecular level represented by the
near infrared spectra of the emulsions. Fig. 3 shows the behav-
ior of the absorbance of the first overtone of the C H bond
interactions as a function of the incorporated energy. The con-
centration range is the same as those reported in Figs. 1 and 2.
When the concentration increases, the absorbance
increases. This result was expected and has been studied by
Sjöblom et al. (2003): When there is an increase in the amount
of any substance, the characteristic peaks that best describe
it will increase because of the increase in the number of
bonds that vibrate. When Fig. 3 is evaluated with Figs. 1 and 2,
it can be noted that the increase in the absorbance is also
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Fig. 4 – Near infrared spectra of oil-in-water emulsions
with a concentration of the dispersed phase of 30 (wt%).
Average droplet size also shown (D[4,3] ␮m).
related to a decrease in the average droplet size; therefore,
this technique is also able to quantify changes in elasticity
and the morphology of droplets and can also be used for this
purpose.
If we now look for relationships between the absorbance of
the first overtone (the oil droplets) and the incorporated energy
(dotted lines in Fig. 3), Eqs. (9) and (10) can be established:
AbsC H ∝ E−0.17
v (9)
AbsC H ∝ E−0.10
v (10)
These equations also have a good fit for the slopes of the
straight lines (R2 = 0.99), and once again, it can be seen that
the slope decreases as the concentration increases.
These results provide better insight about the behavior of
these types of colloidal systems and how the process, the
product and the properties are related. As stated recently
by Capdevila et al. (2010), for concentrated and highly con-
centrated systems such as O/W and W/O emulsions, the
formulation and composition variables are of paramount
importance in product design and product scale-up because
of the highly non-Newtonian nature of these fluids.
3.2. Part II: near infrared spectroscopy and droplet size
The second part of the discussion focuses on describing and
understanding the possible relationship between the changes
in the average droplet size of the O/W emulsions and the
molecular response represented by the near infrared spec-
trum. To accomplish this, O/W emulsions with the same
concentration of the dispersed phase were prepared by vary-
ing the tip velocity (different shear) to generate different
droplet size distributions.
The near infrared spectra of O/W emulsions with a 30 (wt%)
concentration of the dispersed phase is presented in Fig. 4
along with the values for the average droplet size, D[4,3]. The
only difference between the emulsions is the average droplet
size meaning that the formulation is constant.
When the incident light beam meets particles in its way,
two main phenomena may occur: first, the particles can absorb
the light, and the molecular bonds within the particles will
vibrate at a frequency similar to that of the incoming light.
Second, the particles can scatter the light, and the particles
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concentrated emulsions. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.10.016
7
will cause the beam of light to change its trajectory at some
angle. These two phenomena may occur simultaneously, or
one may dominate over the other, and this influences the
total absorbance measured by the device. There are several
other phenomena that make smaller contributions to the total
measured absorbance, such as diffraction, partial absorption,
back scattering and multiple scattering, but they will not be
included in the following analysis (Bohren and Huffman, 1983;
Aske et al., 2002; van de Hulst, 2012).
The predominance of one phenomenon over the other
depends, primarily, on the size and shape of the particle that
interacts with the beam of light. Araujo et al. (2008) reported
a trend in the behavior of the near infrared spectra of water-
in-crude oil emulsions with different average droplet sizes.
They established that the total measured absorbance of the
spectra of emulsions with smaller average droplet sizes was
higher than the total measured absorbance of the spectra of
emulsions with larger average droplet sizes. The behavior of
spectra 3, 4 and 5 in Fig. 4 is similar to the reported trend.
This trend is attributed to the predominance of the light
absorption phenomenon by the oil particles in this droplet
size range. If the average droplet size is within or close to the
value of the wavelength (Rayleigh limit), or in other words,
when the volume of the particle approaches 0, the extinction
of light due to absorption is proportional to V/ whereas the
extinction of light due to scattering is proportional to 4 V2 (van
de Hulst, 2012) where V is the volume of the particle and 
is the wavelength. For spectra 3, 4 and 5 in Fig. 4, in which
the average droplet size is approximately 2–7 ␮m, the domi-
nant phenomenon is light absorption, which thus contributes
more to the total measured absorbance. This is because the
size range of the droplets is very similar to the wavelength of
the incoming light (1–2.5 ␮m).
Analogously, spectra 1 and 2 in Fig. 4 correspond to emul-
sions having an average droplet size of at least one order
of magnitude higher than the incident wavelength (diameter
10 ␮m). Within this range, the predominant phenomenon
is light scattering. As pointed out by van de Hulst (2012), the
incident beam of light, which forms a plane wave front with
infinite extent, may be thought to consist of separate rays of
light that pursue their own path. This allows the rays actually
hitting the particle and rays passing along the particle to be
differentiated and therefore these rays are said to be localized.
When this occurs, the probability of multiple beams of light
hitting one particle is much greater for large particles than for
small particles because, in the latter case, neither absorption
nor scattering or diffraction are likely to occur. This causes an
increase in the total measured absorbance simply because the
scattered light leaves the particle at angles that make it dif-
ficult to reach the detectors. Because the scattering particles
are homogeneous, absorbing and spherical, there is no dou-
ble fraction or dichroism of any kind (van de Hulst, 2012). The
above theoretical implications hold very well for particles and
mediums with refractive index close to 1 as in this study.
Of note in the spectra shown in Fig. 4, is the behavior when
average droplet size changes in either region. In the first region
(spectra 3–5 in Fig. 4), where the average droplet size can be
compared to the wavelength of the incident light and light
absorption dominates, if the average droplet size decreases,
the total measured absorbance increases; this trend is similar
to that reported by Araujo et al. (2008). In the second region
(spectra 1 and 2 in Fig. 4), where the average droplet size is
much higher than the wavelength and light scattering dom-
inates, if the average droplet size decreases then the total
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8 chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx
Fig. 5 – Near infrared spectra of oil-in-water emulsions
with a concentration of the dispersed phase of 50 (wt%).
Average droplet size also shown (D[4,3] ␮m).
measured absorbance also decreases; this trend is similar to
that reported by Sjöblom et al. (2003) and Kallevik et al. (2000).
With these results it is possible to observe a change in the
behavior of the spectra depending on whether light absorption
or light scattering is the dominant phenomenon. This change
in the behavior is due to the changes in the average droplet
size.
Even more interesting than the change in the behavior of
the spectra of O/W emulsions due to the changes in the aver-
age droplet size is how these two trends are influenced by the
concentration of the dispersed phase. Fig. 5 shows the spectra
of O/W emulsions of a given concentration of the dispersed
phase of 50 (wt%) with different average droplet sizes. In this
case, it is possible to see the same trends described above,
where spectra 6 and 7 in Fig. 5 are comparable to spectra 1 and
2 in Fig. 4. In this case, when the average droplet size decreases,
the total measured absorbance also decreases. Similarly, spec-
tra 8 and 9 in Fig. 5 are comparable to spectra 3–5 in Fig. 4, and
show that when the average droplet size decreases, the total
measured absorbance increases.
Finally, when the concentration of the dispersed phase
increases, the average droplet size decreases. This causes the
droplets to be closer to one another to the point that some or
all of them are no longer spheres and become polyhedral (Pal,
1996). This is true for emulsions with an 80 (wt%) concentra-
tion of the dispersed phase; these spectra are shown in Fig. 6.
The average droplet size is also shown. It is clear from Fig. 6
that the two trends described for diluted and moderately con-
centrated emulsions are still identifiable, and the behavior of
spectra 11 and 12 in Fig. 6 are comparable to spectra 6 and 7 in
Fig. 5 or spectra 1 and 2 in Fig. 4. Similarly, spectra 10 and 13
in Fig. 6 are comparable to spectra 8 and 9 in Fig. 5 or spectra
3–5 in Fig. 4.
However, the distinction between the two regions in Fig. 6
is not as evident as in Fig. 5 or Fig. 4. This is due to the
change in the morphology of the oil droplets, and this change
requires a completely different theoretical analysis of how
the light behaves once it meets a particle with non-spherical
shape (van de Hulst, 2012). This is mainly because knowl-
edge of the specific shape or morphology of the particle, in
addition to the homogeneous nature of its optical constants,
allows for the construction of a mathematical problem (field
equations and constitutive models) that involve defined
known-boundary conditions. Because a spherical particle
of one material is thought to be isotropic, the method for
Please cite this article in press as: Pradilla, D., et al., The application of a multi-scale approach to the manufacture of concentrated and highly
concentrated emulsions. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.10.016
Fig. 6 – Near infrared spectra of oil-in-water emulsions
with a concentration of the dispersed phase of 80 (wt%).
Average droplet size also shown (D[4,3] ␮m).
solving the field equations is relatively straightforward. If the
boundary conditions are not defined, the constitutive models
become highly problematic to solve. There are methods for
solving the equations using approximations; however, the
results deviate from the results for a spherical particle simply
because of the changes in the methods for solving the equa-
tions and because the spherical problem is a limiting case
(Bohren and Huffman, 1983; van de Hulst, 2012). When dealing
with non-spherical particles (or a mixture of both spherical
and non-spherical particles), the equations become specific,
where each case must be treated differently (which yields
different constitutive models) and some approximations
must be considered. It is highly unlikely that a constitutive
model for each particle within the medium (i.e., emulsion)
can be produced and solved.
It is important to note that near infrared spectroscopy
can be used to establish two different trends depending on
the predominance of one phenomenon over the other (light
absorption or light scattering); this behavior depends on the
changes in the average droplet size. The relevance of this find-
ing is that this technique can be used together with statistical
calibration methods, such as partial least squares, to adapt
it as a quick on-line quality measurement for industries in
which it is necessary to know in advance the droplet size or
the average droplet size of the product (e.g., cosmetics or bev-
erage emulsions). It has been shown here that the two trends
described for the near infrared spectra are independent of the
concentration of the dispersed phase; this result can also be
used for industries that deal with highly concentrated systems
(e.g., petrochemical or food emulsions).
3.3. Part III: creep tests and viscoelasticity
For the last part of this work, we will again focus on the
rheological behavior of concentrated and highly concentrated
emulsions. We will show one method of relating the changes
that occur at the microscopic level (i.e., changes in the struc-
ture/morphology of the droplets) and the response at the
macroscopic level (i.e., rheological properties) using creep test-
ing. The results will be also related to the viscoelastic nature
of the emulsions.
Creep tests were used to study water-in-oil emulsions
where the concentration of the dispersed phase was between
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Fig. 7 – Compliance modulus J(t) as a function of time
obtained through creep tests (imposed stress 50 Pa) for
water-in-oil emulsions having a concentration of the
dispersed phase from 70 to 85 (wt%). The value of the
imposed stress is within the linear viscoelastic region
(0.1–100 [rad/s] and 0.1–100 [Pa]).
Fig. 8 – Compliance modulus J(t) as a function of time
obtained through creep tests for water-in-oil emulsions at
different values of the imposed stress () 1–125 [Pa]. The
concentration of the dispersed phase is fixed at 85 (wt%).

70 and 85 (wt%). Fig. 7 shows the compliance modulus J(t) as a

function of time, and it is clear from this figure that the dura-
tion of the experiments was sufficient to reach the terminal
regime. When this regime is attained, it is possible to identify
the three typical regions of a viscoelastic material proposed by
Tadros (2004): the elastic response (at low times), the retarded
viscoelastic response (at intermediate times) and the steady
state viscous response (at latter times).
When the concentration of the dispersed phase is higher
than 70 (wt%), it is possible to observe the so-called “ringing”
phenomenon (perfectly reproducible damped oscillations)
located at intermediate times, more specifically, at the
retarded viscoelastic response (Fig. 7). This phenomenon has
been reported in some publications (Zölzer and Eicke, 1993;
Baravian and Quemada, 1998; Ewoldt and McKinley, 2007), and
it is a result of the coupled effect between the elasticity of the
sample and the inertia of the instrument. When the concen-
tration of the dispersed phase is 70 (wt%), which is below the
maximum packing fraction for spherical droplets, the oscil-
lations are not present and the behavior of the compliance
modulus is smooth as expected. However, when the concen-
tration increases, the phenomenon is evident. This suggests
that ringing is a consequence of three variables. The first vari-
able is the inertia of the instrument, which is unavoidable in
controlled stress rheometers. The second variable is the elas-
ticity of the sample, which is a result of the increase in the
concentration of the dispersed phase.
Highly concentrated water-in-oil emulsions are systems in
which the elastic response clearly dominates the viscoelastic
nature of the emulsion. Fig. 9 shows that the elastic modulus
(G ) is at least two orders of magnitude higher than the loss
Fig. 9 – (a) Elastic and loss moduli (G and G ) obtained
modulus (G ). The third variable is the changes in morphology
through a frequency sweep for a water-in-oil emulsion with
(droplet deformation) as the concentration increases which
a concentration of the dispersed phase of 85 (wt%) showing
cause an increase in the interaction forces as the droplets
the linear viscoelastic region. The frequency sweep was
come closer to one another when the droplets reach the
performed at a fixed stress of 1 Pa (b). Elastic and loss
maximum packing fraction. In this sense, ringing can be
moduli (G and G ) obtained through a stress sweep for a
thought of as a manifestation of the viscoelastic nature
water-in-oil emulsion with a concentration of the dispersed
of concentrated and highly concentrated W/O emulsions.
phase of 85 (wt%) showing the linear viscoelastic region.
It is important to highlight that the behavior depicted in
The stress sweep was performed at a fixed frequency of
Figs. 8 and 9 for an emulsion with a concentration of the
1 rad/s. For both figures 20 points per decade per duplicate
dispersed phase of 85 (wt%) is similar (data not shown) if the
were taken.
concentration is lower, for instance: 70 (wt%). This means

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that all the emulsions in this study are analyzed within the
linear viscoelastic region where the elastic modulus (G ) is
independent of the stress (and in this particular case, also
independent of the frequency).
If the analysis was to be taken further and if creep data
were to be transformed into oscillatory data (G and G ), it
would be necessary to separate the response associated to the
inertia of the instrument. This goes beyond the scope of this
work. However the calculations and the appropriate rheologi-
cal models have been previously reported elsewhere; see for
instance (Zölzer and Eicke, 1993; Baravian and Quemada, 1998;
Ewoldt and McKinley, 2007).
Fig. 8 shows an interesting result that supports the fact
that ringing is a manifestation of the viscoelastic nature of
W/O emulsions, where the compliance modulus is plotted as
a function of time with various values for the imposed stress
and a fixed concentration of 85 (wt%). When the imposed
stress in the creep experiment is low (i.e., 1 Pa) the oscilla-
tions are diffused and not reproducible; similarly, when the
imposed stress is high (i.e., 125 Pa) ringing not present. In this
figure, it should be noted that ringing becomes clear and repro-
ducible in a stress range that corresponds to the stress range
of the linear viscoelastic region, where the elastic response
of the emulsion (i.e., the elastic modulus) is independent
of the stress (and in our case, also independent of the fre-
quency). It is important to emphasize that in our case, the
stress range applied during the creep tests must be within the
linear viscoelastic region otherwise the response of the emul-
sions would not primarily be elastic. This was corroborated
through oscillatory tests to determine the linear viscoelas-
tic region presented in Fig. 9a, which shows a frequency and
Fig. 9b, which shows a stress sweep for W/O emulsions with a
concentration of the dispersed phase of 85 (wt%).
4. Conclusions
Research on concentrated and highly concentrated emul-
sions has been traditionally focused on relating formulation
variables (i.e., amount of surfactant, concentration of the
dispersed phase) to limited aspects of their properties (Jager-
Lézer et al., 1998; Derkach, 2009; Capdevila et al., 2010;
Masalova et al., 2011). The main results of this type of approach
have led to the development of some scale-up parameters
based on traditional dimensionless and characteristic num-
bers. However, the main flaw of this analysis is that it fails
to establish adequate relationships for non-Newtonian fluids.
In this study, a first attempt to tackle this issue through the
use of a multi-scale approach is made (Alvarez et al., 2010).
Relationships between the energy incorporated through the
emulsification process and the properties at three different
levels were established (Eqs. (5)–(10)): first, the macroscopic
level represented by the elastic modulus G , second, the micro-
scopic level represented by the average droplet size D[4,3] and
third, the molecular level represented by the near infrared
spectrum.
In this sense, an intertwined connection between the
energy incorporated, the formulation of the given system and
the properties is proposed as a way of producing emulsions
with given characteristics. The description of how the energy
incorporated influences the properties depending on the dif-
ferent formulation gives a novel insight on product design.
This behavior, represented in Figs. 1–3, can be used to pro-
duce tailor-made emulsions given a fixed formulation; or, in
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concentrated emulsions. Chem. Eng. Res. Des. (2014), http://dx.doi.org/10.1016/j.cherd.2014.10.016
the same sense, to have a preliminary notion of the proper-
ties (elastic modulus, viscosity, average droplet size) of the
emulsion after preparation.
Furthermore, it was established how the energy incor-
porated through the emulsification process depends on two
variables: first, the tip velocity by which droplet formation is
set through shear and second, the pumping capacity of the
impeller which determines the circulation of the emulsion
on the mixing tank. This novel result leads to a new way of
considering emulsion manufacture. Instead of solely consid-
ering the design of an impeller for a given application, it is
proposed to choose an impeller with the suitable pumping
capacity that allows a fixed formulation to produce an emul-
sion with desired properties. For instance, if the droplet size
distribution is a key parameter of a given product, Figs. 1–3 can
be used to select the appropriate impeller based on the energy
required.
Through the use of a multi-scale approach, it was also
possible to extract relevant information about the different
properties of O/W and W/O emulsions. First, although near
infrared spectroscopy (NIRS) can be used to track changes in
the amount of a given substance, for instance oil (Aske et al.,
2002; Sjöblom et al., 2003; Araujo et al., 2008) it was possible to
elucidate the influence of the droplet size in the spectra of the
emulsions. Figs. 4–6 show that the predominance of two phe-
nomena depending on how close the average droplet size is to
the incident wavelength causes different trends in the spectra.
These two phenomena are light absorption and light scatter-
ing. Second, the phenomenon commonly known as “ringing”
(Zölzer and Eicke, 1993; Ewoldt and McKinley, 2007; Evans et al.,
2009) was observed for W/O emulsions. This is attributed not
only to the decrease in droplet size but also to the phys-
ical deformation (packing) that droplets undergo when the
concentration of the dispersed phase increases. Furthermore,
ringing is only present at a specific range of applied stress.
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