Influence of ethyl cellulose in a multicomponent mixture (sorbitan monopalmitate-vegetable oils) on physicochemical properties of organogels

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Vol. 19, No. 2 (2020) 953-968
Ingeniería de alimentos
Revista Mexicana de Ingeniería Química
CONTENIDO
Volumen 8, número 3, 2009 / Volume 8, number 3, 2009
213 Derivation and application of the Stefan-Maxwell equations
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Stephen Whitaker
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J.R. Medina, R.L. Romero y G.A. Pérez
Influence of ethyl cellulose in a multicomponent mixture (sorbitan
monopalmitate-vegetable oils) on physicochemical properties of organogels
Influencia de etilcelulosa en una mezcla multicomponente (monopalmitato de
sorbitan-aceites vegetales) sobre las propiedades fisicoquímicas de organogeles
M. García-Andrade1, R.F. González-Laredo1, N.E. Rocha-Guzmán1, W. Rosas-Flores1, M.R. Moreno-Jiménez1,
E.A. Peña-Ramos2, J.A. Gallegos-Infante1*
1Tecnológico Nacional de México-Instituto Tecnológico de Durango, Unidad de Posgrado, Investigación y Desarrollo
Tecnológico (UPIDET), Dpto. de Ingenierías Química y Bioquímica, Blvd. Felipe Pescador 1830 Ote. Col. Nueva Vizcaya,
Durango, Durango, México, C.P. 34080
2Centro de Investigación en Alimentación y Desarrollo A.C. (CIAD), Carretera Gustavo Enrique Astiazarán Rosas, No. 46,
Hermosillo, Sonora, México C.P. 83304
Received: August 22, 2019; Accepted: November 14, 2019
Abstract
The modification of vegetable oils from liquid to solid state gel type is achieved by organogelation, where the first phenomenon
experienced is nucleation that can be spectrophotometrically evaluated and obtain thermodynamic properties. The objective of
this work was to evaluate the solid formation from nucleation to macroscopic properties of the mixture: sorbitan monopalmitate
and ethyl cellulose in canola, olive and coconut vegetable oils. Nucleation kinetics, solid growth analysis, oscillatory rheology
characterization, thermal properties by differential scanning calorimetry and microstructural formation by optical microscopy
were evaluated. Non-isothermal nucleation kinetics indicated short induction times for canola and prolonged ones for coconut.
The inclusion of ethyl cellulose involved a more compact solid formation in the systems without modifying the growth
parameters, the coconut organogel was more sensitive to thermal changes. Non-isothermal nucleation kinetics are useful for
determining the thermodynamic properties of organogels and the closest to thermodynamic equilibrium, being decisive the
inclusion of ethyl cellulose, which does not influence formation speed and solid growth. The multicomponent gels obtained
showed that the structural differences depend on the concentration of the mixture that includes ethyl cellulose, presenting more
compact structures and thereby more resistant gels.
Keywords: Nucleation, organogelation, ethyl cellulose, vegetable oils.
Resumen
La modificación de aceites vegetales de estado líquido a sólido tipo gel, se logra por organogelación, el primer fenómeno
experimentado es la nucleación que puede evaluarse espectrofotométricamente y obtener propiedades termodinámicas. El
objetivo de este trabajo fue evaluar la formación sólida desde nucleación hasta propiedades macroscópicas de la mezcla:
monopalmitato de sorbitan y etilcelulosa en aceites vegetales de canola, oliva y coco. Se evaluaron cinéticas de nucleación,
análisis de crecimiento sólido, caracterización por reología oscilatoria, propiedades térmicas por calorimetría diferencial de
barrido y formación microestructural por microscopía óptica. Las cinéticas de nucleación no isotérmica indicaron tiempos de
inducción cortos para canola y tiempos prolongados en coco. La inclusión de etilcelulosa involucró una formación sólida más
compacta en los sistemas, sin modificar los parámetros de crecimiento el organogel de coco resultó más sensible a cambios
térmicos. Las cinéticas de nucleación no isotérmica son útiles para establecer las propiedades termodinámicas de organogeles y
el más cercano al equilibrio termodinámico, siendo determinante la inclusión de etilcelulosa; misma que no influye en velocidad
de formación y crecimiento sólido. Los geles obtenidos mostraron que las diferencias estructurales dependen de la concentración
de la mezcla que incluye etilcelulosa, presentando estructuras más compactas y geles más resistentes.
Palabras clave: Nucleación, organogelación, etilcelulosa, aceites vegetales.
*Corresponding author. E-mail:agallegos@itdurango.edu.mx
Tel. 52- 618-8186936 ext 111
https://doi.org/ 10.24275/rmiq/ Alim801
issn-e: 2395-8472
Publicado por la Academia Mexicana de Investigación y Docencia en Ingeniería Química A.C. 953

García-Andrade et al./Revista Mexicana de Ingeniería Química Vol. 19, No. 2 (2020) 953-968
1Introduction
The organogels are defined as semi-solid materials
resulting from the immobilization of an organic liquid
in a three-dimensional network formed by a gelling
or structuring agent (organogelator) that is randomly
entangled in the form of fiber or platelet (Toro-
Vazquez et al.,2013).
The conversion of oils into gels generally involves
altering the chemical characteristics of the liquid,
(Daniel and Rajasekharan, 2003).The organic liquids
involved in the elaboration of organogels have specific
characteristics, such as their chemical composition.
Several vegetable oils have been used to obtain
organogels, for instance canola oil is a vegetable
oil that contains 7.49% saturated fatty acids (SFA)
and 92.51% of polyunsaturated fatty acids (PUFA)
(Kim et al., 2014); olive oil, 13.29% of SFA, 81.28%
of monounsaturated fatty acids (MUFA) and 5.43%
of PUFA (Utrilla et al.,2014); and coconut oil than
contains 93.33% of SFA, 5.33% of MUFA and
2% of PUFA (USDA, 2018). These vegetable oils
are an example of oils with different saturated and
unsaturated fatty acid levels, whose function is to act
as solvents.
Most supramolecular gels consist of two parts,
namely the solvent and the gelator, however, the
concept of multi-component supramolecular gels, in
which more than one component is added to the
solvent, offers a facile way (e.g., by changing the ratio
of the different components) to tailor the properties
of the gel. The simplest multi-component gels consist
of two components added to the solvent and are the
most widely studied to date (Buerkle and Rowan,
2012). Solvent-gelator interactions play a key role in
mediating organogel formation, which determines the
macroscopic properties of the gel (Zhu and Dordick,
2006).
An ideal gel has an almost pure elastic response
behavior. The elastic modulus should be much
higher than the viscous modulus and independent of
frequency.
Table 1. Fatty acids composition of the vegetable oils.
Fatty Acid Canola % Olive % Coconut %
C6:0 - - 0.23±0.00a
C8:0 - - 4.04±0.01 a
C10:0 - - 4.02±0.02 a
C12:0 - - 38.76±0.13a
C14:0 0.04±0.00b- 17.96±0.07a
C16:0 4.06±0.00c10.55±0.01b14.13±0.10a
C16:1 0.20±0.00b0.78±0.01 a0.13±0.00c
C17:0 0.02±0.03c0.06±0.00b0.09±0.00a
C17:1 0.14±0.00 a0.10±0.00b-
C18:0 1.78±0.00c3.48±0.03b4.53±0.05a
C:18:1 TRANS - - 0.38±0.01
C:18:1 CIS 59.76±0.05b77.14±0.05 a12.47±0.31c
C:18:2 TRANS 3.24±0.00 a1.90±0.00b
C18:2 CIS 19.23±0.05 a4.51±0.04b
C18:3 9.05±0.06 a0.68±0.01c2.92±0.06b
C:20 0.61±0.00 a0.41±0.00b0.13±0.00c
C:20:1 1.23±0.00 a0.24±0.00b0.06±0.00c
C:20:2 0.06±0.00 a- -
C22:0 0.33±0.00 a0.11±0.00b-
ΣSFA 6.87±0.05c14.66±0.01b83.94±0.40a
ΣMUFA 61.35±0.05b78.27±0.03a13.05±0.33c
ΣPUFA 31.77±0.11 a7.10±0.05b2.99±0.06c
ΣTotal 100 100 100
Abbreviations SFA: saturated fatty acids; MUFA: monounsaturated fatty
acids; PUFA: polyunsaturated fatty acids.
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Table 2. Kinetic and thermodynamic parameters of organogels obtained through non-isothermal nucleation adapted
to the Fisher-Turnbull model.
Organogel EC%-
SMP%
ti(min) Ti(ºC) ∆T(Tm−Tn) J (min−1)∆Gn (J/nucleus)
Canola 0-10 15.29±0.05c37.5±0.70a42.5±0.70b0.0654±0.00 a-2.27E-26±4.08E-27a
0-12 15.41±1.53 c31.0±1.41b49.0±1.41 a0.0651±0.00a-2.32E-26±3.49E-27a
4-10 19.74±0.12 b35.5±2.12 ab 44.50±2.12ab 0.0506±0.00 b-1.75E-26±1.52E-27a
4-12 19.43±0.31b37.5±0.70 a42.50±0.70b0.0514±0.00 b-1.76E-26±8.70E-27a
8-10 22.58±0.01ab 36.5±0.70 a43.50±0.70 b0.0448±0.00 b-1.26E-26±1.09 E-27a
8-12 20.58±0.11a39.5±0.70 a40.50±0.70b0.0485±0.00b-1.16E-26±1.14E-27a
Olive 0-10 18.41±0.11a32.0±0.00 cd 48.0±0.00 ab 0.0542±0.00 b-4.53E-26±7.67E-27a
0-12 15.51±0.49ab 29.5±0.70d50.5±0.70 a0.0645±0.00 ab -3.73E-26±7.35E-27a
4-10 17.58±0.11ab 33.5±0.70bc46.50±0.70bc 0.0568±0.00ab -1.84E-26±1.45E-27a
4-12 16.91±1.76 ab 38.5±0.70 a41.50±0.70d0.0594±0.00ab -1.80E-26±3.58E-28a
8-10 18.50±0.00 a33.5±0.70 bc 46.50±0.70bc 0.0540±0.00b-2.98E-26±9.27E-27a
8-12 14.83±0.70 b35.5±0.70 b44.50±0.70c0.0675±0.00a-2.26E-26±1.31E-27a
Coconut 0-10 17.66±2.35 cd 35.5±2.12 a44.5±2.12 a0.0571±0.00 ab -3.74E-26±3.38E-26a
0-12 16.91±0.35d30.0±0.00 a50.0±0.00 a0.0591±0.00a-3.57E-26±3.06E-26a
4-10 23.83±0.46 a31.5±2.12 a48.50±2.12 a0.0419±0.00 c-1.75E-26±5.54E-28a
4-12 19.41±0.35 bcd 35.0±1.41 a45.00±1.41a0.0515±0.00 abc -1.52E-26±5.94E-28a
8-10 22.41±0.12 ab 30.5±0.70 a49.50±0.70 a0.0447±0.00bc -1.46E-26±4.23E-27a
8-12 21.58±0.35abc 34.5±0.70 a45.50±0.70 a0.0468±0.00abc -1.46E-26±3.98E-27a
Abbreviations: sorbitan monopalmitate (SMP), ethyl cellulose (EC), induction time (ti), nucleation rate (J), nucleation-free
energy change (∆Gn).
However, when gel networks are formed with
imperfections, the response of the polymer gel
depends on frequency, i.e., both the storage and
loss moduli increase with frequency. The polymer
gel can be tested at various time scales by using
the oscillation mode in rheological experiments. At
low frequencies, both the gel and polymer solution
are rearranging by the Brownian motion. Thus, the
measured properties are dominated by the elastic
deformation equilibrium of the gel network (Zhang et
al., 2018). Numerous oleogelator systems have now
been identified with great promise for mimicking the
physical characteristics of traditional fats, and several
of these systems have also shown to be effective fat
replacers in certain food systems. However, the range
of physical properties, which can be achieved using
oleogelators, are often fairly limited due to either
the nature of the gelator or the process/conditions
necessary to achieve gelation. In this regard, ethyl
cellulose (EC) offers a unique set of physical
and chemical properties as an oil-structuring agent,
allowing the resulting oleogels to be used in a
wide variety of applications. More specifically, the
polymeric nature of EC produces gels with unique
properties that can be tuned and altered to specific
requirements (Davidovich-Pinhas et al., 2016). Ethyl
cellulose has the ability to modify the crystallization
behavior of a low molecular weight oleogelator, while
increasing the plasticity of the polymer network, to
form a synergistic oleogelator system (Gravelle et al.,
2017).
The gelation process that involves EC and
gel properties are similar to those of polymer
hydrogels, being the nature of the solvent the main
difference (Gravelle et al.,2016). The EC has a
semicrystalline structure with crystalline domains
within an amorphous background (Davidovich-Pinhas
et al., 2014a), therefore, this characteristic is important
because the self-assembly of crystalline particles or
fibrils are created from a low molecular weight gelator
(Garti and Marangoni, 2011).
The gelation of edible oils using EC is achieved by
dispersing the polymer in the liquid oil and heating
above the glass transition temperature of EC. This
temperature is approximately 140 °C, but it has been
found to depend on the polymer molecular weight
(Davidovich-Pinhas, et al., 2014b). The gelation
mechanism and gel structure of EC-based oleogels
are not fully understood and therefore, it is not easy
to explain the origin of this behavior (Davidovich-
Pinhas et al., 2014a). Additionally, these types of
gels arise upon the formation of non-covalent junction
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zones, and are thus termed ‘physical’ gels. Physical
gels are characterized by a unique network behavior
arising from the nature of the junction zones, which
can fluctuate in size, number, position, and time, and
are also strongly affected by environmental conditions.
Such systems exhibit interesting gelation kinetics,
which never achieves a final equilibrium state due
to secondary chain extension, formation or breaking
of junction zones, and rearrangement or stacking
of the already formed junction zones (Lefebvre and
Doublier, 1998).
Eventually, depending on the proper interaction
between solute-solute and solvent-solute, the gelation
(Patel, 2017) and the existence of larger assemblies
occur as a result of the increase in hydrophobic
interactions (Sánchez-Juárez et al., 2019). The
phenomena of the formation of fat crystal networks
are similar to the colloidal gel formation (Sciortino
et al., 2005; Lu and Weitz, 2013). Those primary
particles assemble together to form aggregates, which
leads to the formation of a complex network of
particles in the solution. Similarly, in the formation
of organogels as in the case of fat crystallization, the
nucleation starts either because of the mass transfer
or heat transfer in the system, where the stable
nuclei start to form through aggregation of crystallites.
The growth of primary particles occurs until they
attach to each other, which ultimately lead to the
complex cluster formation that is dispersed into the
liquid oil (Joshi et al., 2018). Gelator combinations
may modify the structural arrangements of the gel
network, which could thus influence the functional
properties of the bulk material. Polymer gelators
may be particularly amenable to this strategy, as
plasticizing agents are regularly used to manipulate
the intermolecular junction zones of such networks.
In a recent study, it was investigated the effect of
incorporating the polymer oleogelator ethyl cellulose
into a structured oleogel with a 7:3 mixture of stearyl
alcohol (SO) and stearic acid (SA); the addition of EC
reduces the brittleness and increases the plasticity of
the bulk material, demonstrating the ability of EC to
modify the crystallization behavior of a low molecular
weight oleogelator (Gravelle et al. 2017). The use of
surface active molecules as sorbitan monopalmitate
(hydrophobic non-ionic molecule) could be favorable
to the ethyl cellulose gels systems because it may form
solid fiber matrix in non polar solvents under cooling
(Kantaria et al., 1999).
Davidovich-Pinhas et al. (2015) have
characterized the effects of surfactant addition on
the mechanical strength of ethyl cellulose/canola oil
oleogels in order to examine the role of both the
“head” and “tail” groups on the final gel properties.
They observed that the interaction behavior could
arise from an additional organized structure formation
in the presence of surfactant molecules, which can
self-assemble due to their amphiphilic nature. The
presence of surface-active species such as high-
melting monoglycerides assists in promoting the
nucleation by forming stable nuclei, which can act
as a template for other TAG molecules to grow
on. The segregated crystalline phase thus formed
organizes into flocs, which are linked together via
weak forces to form a continuous network (Patel,
2015). Consequently, the objective of this work was to
relate the influence of the conditions of formation
of the first solid nucleus with the macroscopic
properties of the material (rheological and thermal) in
a multicomponent mixture using edible oils (canola,
olive and coconut), sorbitan monopalmitate, with and
without ethyl cellulose.
2Materials and methods
2.1 Materials
Sorbitan monopalmitate (SMP) and ethyl cellulose
(EC) at viscosity 10 cP, molecular weight 28.6 Kda,
5% in toluene/ethanol 80:20 v/v and 48% ethoxyl,
were obtained from Sigma Aldrich (St. Louis MO.,
USA), and three vegetable oils (canola, olive and
coconut) were bought at local supermarket of Durango
(Durango, Mexico), stored at (20 °C) until use.
2.2 Methods
2.2.1 Fatty acid profile determination
Methylation of the fatty acids in vegetable oils
was performed as described (AOAC 969.33 method),
analyzed by gas chromatography using a Hewlett
Packard 6890 Series (Palo Alto, CA, USA) with
a flame ionization detector (FID) and an auto-
sampler 6890 m and Supelco SP2560 capillary column
(100 m ×0.25 mm). Temperatures of the injection
port was maintained at 250 °C and at the detector
was maintained at 300 °C. The identification of fatty
acids was performed according to the retention time,
and the elution pattern showed the FAME standards
(Supelco 37 FAME mix). The quantification was
performed by integrating the area under the curve
of peaks and was expressed as the percentage of
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total fatty acid present in the sample. Additionally,
the amounts of saturated fatty acids (SFAs), mono-
unsaturated fatty acids (MUFAs), and polyunsaturated
fatty acids (PUFAs) were calculated.
2.2.2 Preparation of organogels
Organogels with EC were obtained as follows: oils
were heated to 140 °C and separately EC was added up
to 4 and 8% (w/w); the mixture was stirred for 10 min,
and allowed to cool at 80 °C to add SMP up to 10 and
12% (w/w) for each concentration of EC, remaining
under stirring during 20 min. Organogels without EC
were only heated to 80 °C and the SMP was added at
10 and 12% and kept that way for 20 min, after all the
samples were placed in glass tubes and stored 24h at
5 °C.
2.2.3 Non-isothermal nucleation kinetics
Kinetics of non-isothermal nucleation of organogels
was performed in a Jenway 6705 spectrophotometer
(OSA, UK), controlling the temperature with a
Techian water bath (OSA, UK), starting at 80 °C up to
approx. 18 °C. Before starting the kinetics the sample
was maintained at 80 °C for 20 min. After this time the
measurement started in the spectrophotometer from
80 °C, generating a temperature differential (∆T/∆t)
induced by the water bath and measuring the 550 nm
absorbance every 10s for 60 min (Toro-Vazquez and
Gallegos-lnfante, 1996; Terech et al., 2000). The
induction time of nucleation (ti), nucleation rate (J)
and nucleation free energy (∆Gn) were determined by
the use of Fischer-Turnbull model already described
(Rogers and Marangoni, 2009) as follows:
J=1
ti (1)
The cooling rate (φ) as the temperature change
ratio ∆T(T0−Ti) with respect to the change in time
(i.e., ∆t=(t0−ti))
φ=∆T
∆t(2)
The determination of effective supercooling (β),
which incorporates a thermodynamic component:
supercooling in nucleation (∆Tc) and a kinetic
component in the form of a non-isothermal nucleation
induction time (φ)
β=∆Tc
p2φ
(3)
The determination of the previous time-
dependent supercooling parameters finally provides
the nucleation-free energy
∆Gn =mkβ
(∆T)2(4)
2.2.4 Modeling and analysis according to the
Avrami equation
The Johnson-Mehl-Avrami equation was used to
modelling the spectrophotometrical data by the use of
following equation:
q(t)=exp(−k∗tN) (5)
This is known as the Avrami equation, where (N)
is the exponent of Avrami, (k) is an associated constant
with the global phase transition speed, (t) the time and
q(t) is the fraction without crystallizing at the time (t)
(Avrami, 1939). An integer value of N represents the
formation of bar-shaped crystals (1-D), disc-shaped
crystals (two-dimensional 2-D) and spherical crystals
(3-D), respectively. A non-integer value indicates
the formation of irregularly shaped crystals. The
parameters Nand Kwere determined through a
non-linear regression by the use of Rosenbrock and
Quasi-Newton method into Statistica software, v 12.0
(StatSoft, OK, 2013). The model was tested for each
processing condition of the organogels.
2.2.5 Polarized light microscopy
Micrographs of organogels were obtained through an
AxioLab Carl Zeiss polarized light optical microscope
(Champaign, IL) equipped with a color digital video
camera (AxioCam ERC 55). The obtained images
were analyzed by Zen 2.3 Lite image software
(Germany). Samples of gels were placed prior to
analysis and tested at room temperature (25 °C) on
the glass slide, obtaining micrographs on the 40X
lens and magnification 400X of the samples under all
processing conditions.
2.2.6 Rheological tests
Dynamic rheology test was performed with a
controlled strain rheometer Discovery Hybrid
Rheometer 3 (TA Instruments, USA) equipped with
parallel plate geometry (diameter 40 mm and gap
1500 µm) with a Peltier system for the thermal control
of the sample. Preliminary strain sweep tests were
carried out to determine the linear viscoelastic regime
(LVR): in this region a frequency sweep test was
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performed in the frequency range 0.01-100 rads−1
at 25 °C, and a temperature sweep in the range of
18-90 °C and 90-18 °C at 5 °C min−1Each sample
was prepared independently and the results presented
are the average values of the rheological properties
measured for each one.
2.2.7 Differential Scanning Calorimetry (DSC)
The thermal properties of the organogels were
measured with a TA Instruments Differential Scanning
Calorimetry (DSC), Model Q2000 with a refrigerated
cooling system RCS90 (New Castle, DE, USA).
The instrument was calibrated with indium, 8-10 mg
of organogel samples were weighted into aluminum
pans and sealed hermetically. A heating cycle was
performed (8 to 80 °C, at 10 °C min−1). Thermograms
were analyzed with the software provided with
the equipment. Analyses were performed in two
replicates.
2.2.8 Statistical analysis
All experiments were performed by two replicates and
data analyzed by standard statistics methods ANOVA
in the software Statistica (Data Analysis Software
system, StatSoft, Inc, Tulsa −USA) v.7.
3Results and discussion
3.1 Non-isothermal nucleation kinetics
Data obtained into the non-isothermal kinetics
experiments are shown in Figure 1. Nucleation start
is defined as the point at which curves rise from
the base line, this time was shorter in the canola
organogel, followed by olive and coconut. However,
the inclusion of the EC polymer in the mixture showed
a differentiated nucleation mechanism that involved
longer times to carry out the nucleation, influencing
the different triglyceride mixtures present in the oils.
Specifically, the content of saturated fatty acids in
the oils, canola (6.87±0.05%), olive (14.66±0.01%)
and coconut (83.94±0.40%) have influenced longer
induction times, as well as the available interactions of
the gelling molecule and the lipid. Thus, oil polarity
and unsaturation degree exert effect on its ability to
form H-bonds with organogelator molecules (Gravelle
et al., 2016). They showed that increase concentration
of EC, leads to a organogels’ assembly with low
degree of self-supported crystalline structure (Figure
2). This result is opposite to reported by Cerqueira et
al. (2017). This can be explained from the fact that
EC forms a hydrogen bond stabilized polymer network
in the oil, however the presence of SPM inhibits
the interaction between EC and oil, diminishing
the hydrogen bond and alter the balance between
polymer-solvent and polymer-polymer interactions in
the system plays a major role on the network structure
and gel properties (Davidovich-Pinhas et al., 2015).
The parameter of thermodynamic guiding force
(∆T) is the difference between the equilibrium melting
temperature of the material (Tm) and the nucleation
temperature (Tn). This difference of temperature (i.e.,
Tm−Tn) induces major mobility in canola oil in
comparison to coconut and olive oils. However, it
is not sufficient for the generation of the first solid
core despite having the greatest molecular movement
impulse; although the temperature differential is larger
by including the EC in the mixture, it originated the
largest number of nuclei per minute (J) in organogels
with olive oil.
Fig. 1. Change in solid content as a function of time
for the non-isothermal.
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Coconut oil begins the formation of nuclei at
a longer time, propitiating an explanation related
to the majority composition of saturated fatty acids
83.94±0.40% given that the triacylglycerols often
crystallize in one of the metastable states because
they have lower activation energy of nuclei formation.
At the molecular level, the more saturated and
uniform are the TAGs, more stable is the polymorphic
form formed upon nucleation, while the presence
of a kink such as cis-unsaturated fatty acids results
in the formation of less stable polymorphic forms
(Grotenhuis et al.,1999; Cisneros et al., 2006).
3.2 Modeling and analysis according to the
Avrami equation
Parameters of Avrami model are shown into the
Table 3. Organogels made with olive oil and higher
concentration of EC and SMP showed high kvalue
According to results shown in table 3, the parameter
(N) of the Avrami model predicts a 1D growth in
the organogels assuming a formation from sporadic
nuclei (e.g., needles, bars) because the number of
nuclei increases linearly with time at all processing
conditions of organogels. Although Nshould be
an integer, fractional values are usually obtained,
even in cases where the model fits well. Deviations
from integer values for Nhave been explained as
simultaneous development of two or more types of
crystals, or similar crystals from different types of
nuclei (i.e., sporadic vs. instantaneous). At all tested
conditions, organogels displayed the same behavior
with good fitting to the Avrami model and non-integer
values, independently of the type of oil and type of
mixture. An exception was the condition involving
coconut oil and EC4% -SMP10% with Nvalue of
2.68±0.71 that could indicate differences in crystal
growth geometry and the type of nucleation, because
it is a function of the number of dimension in which
growth take place, reflecting the details of fat crystal
nucleation and growth mechanism (Cristian, 1975).
Despite the good fit of the Avrami model, this value is
contrary to the morphology shown in the micrography,
where Nvalue resembles a plastic fat, since it is
greater than 2, attributable probably to the presence of
coconut oil showing an order similar to the packing
of a plastic grease, which may lead to a granular
microstructure composed of a large number of small
and more dense crystals.
Generally, low values of Nand high values of kare
associated with an increased rate of crystallization and
a more instantaneous nucleation process with shorter
induction times, which in turn, would yield smaller
and more numerous crystals (Meng et al., 2014).
Table 3. Parameters of rate and crystal growth in organogels from the Avrami model.
Organogel EC%-
MPS%
k(min−1)NR2
Canola 0-10 0.0001295±0.00a1.27±0.01a0.99
0-12 0.0001316±0.00a1.30±0.02a0.96
4-10 0.0154787±0.01a1.46±0.07a0.98
4-12 0.0101120±0.01a1.71±0.42a0.98
8-10 0.0022822±0.00a1.94±0.01a0.98
8-12 0.0278446±0.02a1.33±0.17a0.95
Olive 0-10 0.0056292±0.00b1.65±0.10a0.98
0-12 0.0001316±0.00b1.46±0.03a0.97
4-10 0.0083574±0.01b1.81±0.50a0.98
4-12 0.0269681±0.01b1.30±0.07a0.97
8-10 0.0529352±0.02ab 1.10±0.21a0.92
8-12 0.09893854±0.03a1.00±0.08a0.97
Coconut 0-10 0.0114379±0.01a1.67±0.50a0.97
0-12 0.0000403±0.00a1.55±0.03a0.97
4-10 0.0003759±0.00a2.68±0.71b0.98
4-12 0.0433361±0.00a1.2±0.04a0.98
8-10 0.0067232±0.01a1.78±0.33a0.99
8-12 0.0133901±0.01a1.58±0.31a0.97
Abbreviations: sorbitan monopalmitate (SMP), ethyl cellulose (EC),
velocity (k), dimensionality of growth (N).
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Fig. 2. Optical light microscopy polarized in dark field of organogels with mixtures (ethyl cellulose (EC) - sorbitan
monopalmitate (SMP) in Canola, Olive and Coconut oil organogels.
This behavior was presented only in olive oil
systems, indicating an instant nucleation process,
while the other two oils show the formation of
crystalline growth as a sporadic nucleation with
similar crystals of different types of nuclei.
3.3 Polarized microscopy
The morphology arrangement was studied for a better
understanding of the influence of EC concentration
in organogel formation as a mixture using SMP. The
morphology of solids was observed under a polarized
light microscope. Figure 2 shows the increase of
birefringence at lower concentrations of EC. The
changes in the crystalline morphology are related to
the concentrations of the mixture and the type of
oil; in addition, the arrangement is fibrillar needle
type, corresponding to what was predicted through the
Avrami model. There is a marked difference in the
fibers of organogels since the polymer is not included,
given that the size is much greater regardless of the
oil, the size of the fiber decreased proportionately
with increased EC concentrations. However, the solid
formation had a very long needle shape, which is a
desirable feature for gel formation (Terech and Weiss,
1997 Burkhardt et al., 2009).
When a crystalline structure was not observed,
it was associated to the cooling of the phase of the
solution, which resulted in reduced solubility of the
gellant in the solvent and, consequently, a reduction of
affinity with the solvent (vegetable oil). Such spacings
are possibly due to the fact that hydrogen bonds are
not available for gelation; however; between these
spacings is where the needle-like fibers are observed.
This is a product of the gelator molecules that come
out of the solution for aggregates, interacting through
junctions and points to form a three-dimensional
network that immobilizes the liquid components. This
formation is related to the effect exerted by the SMP,
characterized by the formation of rods with increasing
tubular length (Jibry et al., 2006).
3.4 Rheological Properties
3.4.1 Frequency sweep (ω)
All samples were analyzed in the regimen of the linear
viscoelastic region (LVR). In organogels that involve
the use of EC polymer, it has been demonstrated
the strong influence of the solvent composition on
the mechanical properties of organogels, therefore,
the influence of solvent polarity can be attributed to
the presence/absence of chemical species capable of
forming hydrogen bonds with the polymer network
(Gravelle et al., 2016). About the influence of SMP
into the system, it has been reported that it forms
a viscous solutions in edible oils whose viscosity
increases when increasing the concentration of the
gelator, where the threshold concentration to form a
gel is 10%, causing a firm and opaque gel (Murdan et
al., 1999). The SMP behavior was modified by adding
EC polymer. Obtained organogels with SMP and EC
showed higher G’s. Regardless of the type of oil used
and concentrations of the mixture, its behavior was gel
type (i.e., G’ >G”) (see Figure 3).
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Fig. 3. Dynamic viscoelastic properties: Storage modulus (G’) and loss modulus (G”) for canola, olive and coconut
oil organogels added with ethyl cellulose (EC) over a frequency range of 0.01 to 100 rads−1at 25 °C.
However, the difference between values of G’
and G” was minimum for coconut oil SMP and EC
organogels, and higher for organogels obtained with
canola oil. These behaviors could be related with
the hydrophilic interactions between SMP, EC and
vegetable oils that stabilize polymer network and
increase mechanical properties of the gel network.
However, this increase is related with the type of
vegetable oil, Laredo et al., (2011) demonstrated that
the use of oil with high level of insaturation render
strong gels, similar results have been reported by Dey
et al. (2011) and Zetzl et al. (2012) and they agree with
the results found into the present work.
Data were adjusted to the power law (G’ =Kωn)
and obtained parameters are shown in Table 4. These
results indicate the influence of the oil, SMP and
EC in the mechanical behavior of oleogels. Several
reports about the influence of EC/oil (Laredo et
al., 2011; Gravelle et al., 2018) have shown higher
resistance of gel with increase concentration of EC,
and no influence with the type of vegetable oil. These
results were opposite to the found in the present
work a possible explanation about the influence of
vegetable oil could be done by the use of solubility
theory, it has reported that in oleogel systems, which
are structured via hydrogen bonds, the hydrogen
bonding δhparameter of Hansen solubility theory
alone can dominate the “quality” of the combined
solvent (Rogers and Marangoni, 2016). This behavior
was demonstrated by Gravelle et al. (2018) for EC/oils
blends, showing that higher mechanical properties are
obtained when δhdistance between the elements of
the blend were shorter. Thus, following this idea, the
presence of SMP in the blend modifies the mechanical
structure of the obtained oleogels in combination with
EC and vegetable oil.
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Table 4. Power-law model G’=Kωn parameters calculated for describing the behavior of G’ values in canola, olive
coconut oils organogels.
Organogel Mixture
EC-SMP%
Parameter (K) PasnParameter n R2
Canola 0-10 44.56±4.29k0.09±0.03bcd 0.95
0-12 67.55±11.92i jk 0.09±0.04bcd 0.95
4-10 308.50±61.64hi 0.14±0.04bcd 0.96
4-12 480.93±28.48 f gh 0.24±0.04bcd 0.94
8-10 1086.04±9.33e0.11±0.00bcd 0.9
8-12 4246.70±72.46c0.06±0.01cd 0.95
Olive 0-10 58.32±3.38 jk 0.21±0.15bcd 0.98
0-12 64.34±2.98i jk 0.29±0.03ab 0.99
4-10 291.32±82.95hjj 0.21±0.05bcd 0.99
4-12 440.81±2.57gh 0.27±0.06abc 0.99
8-10 190.10±39.54i jk 0.25±0.06abcd 0.98
8-12 701.93±56.69 f0.26±0.03abc 0.98
Coconut 0-10 62.74±18.14i jk 0.14±0.00bcd 0.99
0-12 51.54±20.34 jk 0.24±0.04bcd 0.99
4-10 686.12±49.54 f g 0.18±0.00bcd 0.94
4-12 3733.31±126.42 j0.04±0.01d0.97
8-10 5561.50±75.60b0.18±0.00bcd 0.93
8-12 8496.35±144.65a0.46±0.01a0.94
Abbreviations: sorbitan monopalmitate (SMP), ethyl cellulose (EC).
Obtained results show that more elastic gels
are those made with coconut oil, even without the
mixture (EC-MPS), which is reflected in the larger
differences of K followed by canola and olive.
This mechanical characteristic is attributed to the oil
chemical composition, viz. in coconut the interaction
is exerted by the components of the oil, mostly
saturated fatty acids (83.94±0.40%), while in canola
oil, rich in PUFA (31.77±0.11%) and in olive oil, rich
in MUFA (78.27±0.03%).
3.4.2 Temperature sweep
The organogels made with canola, olive and coconut
oils at all experimental conditions of MPS and EC
showed a sol-gel phase transition at temperatures
ranging from about 42 to 47 °C, (Figure 4). It was
observed a sinusoidal or stepped increase in Tan δ
with temperature increase; consequently, this behavior
indicated the formation of an additionally organized
structure formed by the gellant SMP (Davidovich-
Pinhas et al., 2015). Stepped sol-gel transitions have
been associated with the formation of secondary
structures, such as helices (Braudo et al., 1991;
Miyoshi et al., 1996), double helices (Mangione et
al., 2003) and crystallization (Rocha et al., 2013). The
nature of these structures in organogels with EC is not
fully understood, however, the ability of surfactants
to self-assemble and create a crystal structure in the
presence of hydrocarbon chains is already known
(Sánchez et al., 2011).
Depending on the interfacial structure of the
fibers (or networks), several interactions can develop
between adjacent fibers at the nodes (or junction
zones) of the networks, showing in this way that the
sol-gel temperatures are dependent on concentration
of the structuring agent and type of oil. The sol-gel
transition was estimated as the temperature at which
the transition occurs between the loss modulus and
storage modulus, that is, the crossover temperature
(G =G ") (Figure 5).
Sol-gel transition is the same regardless of the
type of oil used. The addition of the polymer
increases this temperature considerably; however,
there is no statistically significant difference between
the inclusion of 4 and 8% of EC, whose temperature
range was 54-59 °C, achieving a transition to a
lower temperature by not including the polymer at
48-52 °C. The change of sol-gel influences all the
factors involved in the elaboration of materials, whose
temperature intervals are shorter in this transition for
the organogel with coconut oil between 41 and 46 °C.
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Fig. 4. Temperature sweep. Tan delta for heating (full symbols) and cooling (empty symbols) for canola, olive and
coconut oil organogels added with ethyl cellulose (EC).
Fig. 5. Temperature G’=G” in heating and cooling from a temperature sweep in canola, olive and coconut oils
organogels added with ethyl cellulose (EC).
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Organogels with olive and canola oils experience
this transitions in a range of temperatures between 49
and 56 °C, but without statistical difference between
them. The mixture used suggests that at a lower
concentration of the gellant, this temperature tends
to be higher, suggesting that the concentration used
influences the transition temperature of the materials
regardless of the concentration used of the polymer.
3.5 Differential scanning calorimetry
(DSC)
In the present study, surfactant characteristics were
observed for the determination of the thermodynamic
properties of organogels. Specifically, in the melting
process of the material, at a range of 8-90 °C in a
single heating cycle, it was observed the impact of the
polymer on the different mixtures of organogels.
The start of melting was observed at higher
temperatures for organogels from olive oil, following
by canola and coconut oils. This behavior could be
related to the structural arrangement shown by canola
and coconut oils that retards absorption of heat caused
by the heating to which they are subjected and to the
distribution of non-covalent bonds in the materials.
The EC polymer is determinant for such effects and
although it is not added in the mixtures, this start is
an indication of a higher T onset. Therefore, EC is
an inducer of the most important thermal transition
regardless of the type of oil, but depending on the
concentration used of the polymer in any of the
concentrations used.
The maximum temperature or the temperature
considered as that from the maximum peak that refers
to the point of complete melting of the material has
significance in the type of oil and the presence of
EC. Such behavior reflects that there is a higher
temperature (Tm) and a greater thermal resistance in
those organogels made with olive oil followed by the
ones with canola and coconut oils, who showed the
lowest melting T (i.e., the lowest thermal resistance
and the highest sensitivity to heat absorption). The
end of structure loss is influenced by the type of oil
and concentration of polymer, being the highest T
for canola, followed by olive and coconut oils. The
materials without polymer have the lower T end; also
it was observed higher T end with higher polymer
concentration.
Table 5. Thermal parameters (Temperature of melting-Tm, enthalpy of melting ∆H.
Organogel Start (°C) Onset (°C) Tm (°C) Stop (°C) ∆Hm(J g−1)
EC-SMP%
Canola
0-10 38.39±0.19a40.45±0.95 a46.94±0.02a52.63±0.14b1.43±0.00b
0-12 37.18±0.10a40.18±0.73 a46.54±0.14ab 52.49±0.04b1.31±0.18b
4-10 30.96±1.85b33.33±0.62bc 45.41±0.14ab 52.03±0.09 b1.75±0.00b
4-12 26.92±0.15b32.01±0.60 c44.73±0.98b54.95±0.22a1.44±0.07b
8-10 31.43±0.19c28.82±0.91d 45.61±0.39ab 54.98±0.15 a2.76±0.51a
8-12 32.67±0.65b35.67±0.04b46.45±0.27ab 52.21±0.35b1.96±0.26ab
Olive
0-10 41.83±1.05a42.09±0.70a46.91±0.84a50.01±0.45b0.80±0.25c
0-12 40.34±0.04ab 41.53±0.40ab 47.46±0.59a49.94±0.45 b1.92±0.28ab
4-10 33.34±0.40c38.53±0.07cd 46.64±0.00a51.92±0.04a1.80±0.02ab
4-12 32.31±0.04c39.11±0.27c46.56±0.31a51.54±0.00a2.06±0.41ab
8-10 33.35±1.90c37.17±0.33d46.78±0.19a51.89±0.19a2.52±0.13a
8-12 37.4±0.19b40.10±0.6bc 46.46±0.12 a51.39±0.09a1.41±0.03bc
Coconut
0-10 35.41±0.19a35.86±0.74ab 44.00±0.16a49.12±0.09c1.00±0.08a
0-12 35.44±0.04a38.81±1.42a44.42±0.50a48.73±0.15bc 1.28±0.00a
4-10 34.80±0.34b35.54±0.52b43.64±0.12a50.25±0.60bc 0.75±0.02a
4-12 34.34±0.50b35.63±0.64b43.45±0.71a52.95±0.04a1.33±0.40a
8-10 32.18±0.08c34.87±0.14b44.41±0.62a50.68±0.80b1.57±0.80a
8-12 32.11±0.04c33.36±0.51b44.12±0.62a48.90±0.09c1.66±0.45a
Abbreviations: sorbitan monopalmitate (SMP), ethyl cellulose (EC).
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The area under the curve of the materials has an
equal behavior in the organogels of canola and olive
oils, being different for coconut, where it is smaller.
However, the addition of polymer (EC) indicates that
there is no difference in this parameter between 0
and 4%, but if it increases to 8% of EC, following
the pattern as the concentration increases, this value
is also increasing. Similar behavior was observed in
organogels with sesame oil and sorbitan monostearate
(Singh et al., 2015).
Conclusions
Non-isothermal nucleation kinetics obtained by a
simple test (e.g., spectrophotometrically) was a useful
tool to determine the thermodynamic properties
from the origin of the organogel (i.e., nucleation).
These parameters indicate what type of oil is
capable of initiating the phenomenon at longer or
shorter times and which is more favorable and
closer to the thermodynamic equilibrium, emphasizing
that for this case the inclusion of ethyl cellulose
is determinant. However, this inclusion does not
modify the speed of formation and directionality
of nuclei growth according to the Avrami model,
indicating an instant nucleation process in olive oil
systems, while canola and coconut oils systems show
the formation of crystalline growth as a sporadic
nucleation with similar crystals of different types of
nuclei. The multicomponent gels obtained showed that
the structural differences depend on the concentration
of the mixture, presenting more compact structures
at higher concentrations of ethyl cellulose according
to their microstructure, where the crystals are closer
ones and the inclusion of EC limits their growth by an
inhibitory effect of the SMP gelling agent.
Acknowledgements
Author M. Garcia-Andrade is very thankful for
graduate scholarship and the financial support received
from the Basic Science Program, grant number
241241 from CONACyT (National Council of Science
& Technology), Mexico.
Nomenclature
C Centigrade
kcristal growth rate
Kconsistency index (Pa.sn)
DSC differential scanning calorimetry
EC ethyl cellulose
Tmequilibrium melting temperature of material, °C
G’ elastic or storage modulus, Pa
q(t) fraction without crystallizing at the time
nflow behavior indices (dimensionless)
Hhours
Tiinduction time, minutes
t0initial time, minutes
LVR línear viscoelastic región
Min minutes
Navramy exponent
Pa pascal, N* s−2
Jrate nucleation: nucleus per minute
SMP sorbitan monopalmitate
SSeconds
TTime
G” viscous or loss modulus, Pa
WWeigth
Greek simbols
∆Gn change free energy nucleation
φcooling rate
∆T temperature differential
∆t time differential
βSupercooling
tanδtangente delta
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