Fuel 239 (2019) 403–412

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Full Length Article

Lipid nanostructures as surfactant carriers for enhanced oil recovery T

a,⁎ b a
Jônatas C.S. Rosestolato , Aurora Pérez-Gramatges , Elizabeth R. Lachter ,
Regina S.V. Nascimentoa
a
Instituto de Química – Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909 Rio de Janeiro, RJ, Brazil
b
Departamento de Química – Pontifícia, Universidade Católica do Rio de Janeiro, Gávea, 22451-900 Rio de Janeiro, RJ, Brazil

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: The main challenge faced by enhanced oil recovery processes (EOR) is to further increase production of the residual
Hydrophobic nanoparticle oil trapped within the reservoir porous media beyond conventional recovery methods. Chemical EOR processes,
Surfactant release such as surfactant flooding, could be employed to dislocate the residual oil to a production well through the re-
Nanocarriers duction of the water/oil (w/o) interfacial tension. Surfactant Flooding is an efficient method, but a large part of the
Interfacial tension
injected surfactant is lost by adsorption on the rock surface before reaching the oil site, turning it often economically
Enhanced oil recovery (EOR)
unfeasible. This work aimed to evaluate the potential of lipid nanostructures as surfactant nanocarriers for the EOR
Unconsolidated porous media
process. In this new concept, nanocarriers formed by hydrophobic nanoparticles (NPs), should be able to store and
carry the surfactant molecules through the reservoir porous media, releasing the surfactant only at the w/o in-
terface, triggered by the nanocarriers solubilization. The released surfactant did lead to a w/o interfacial tension
reduction, improving the recovery factor. Nanoparticles were produced through nano-emulsification techniques
with beeswax (BW) as the lipid structure and nonylphenol ethoxylate (NPE10) as surfactant. The nanocarriers were
characterized by dynamic light scattering (DLS), scanning electron microscopy (SEM), differential scanning ca-
lorimetry (DSC) and surfactant entrapment in the nanocarriers. Interfacial tension (IFT) measurements and Fourier
transform infrared spectroscopy (FTIR) analysis were used to evaluate the surfactant release and unconsolidated
sandpack column tests were conducted to evaluate the transport behavior of the NPs system. The results did de-
monstrate that the nanocarriers should be able to permeate through the porous media and release the surfactant at
the w/o interface, reducing the IFT to values compatible with the ones obtained when employing solely the sur-
factant solution. The effect of the nanoparticles production process, temperature and salt concentration on the
efficiency of the nanoparticles in the delivery of the surfactant at the oil/water interface was evaluated and the
results showed the great potential of this type of system as surfactant nanocarrier for the EOR process.

⁎
Corresponding author.
E-mail address: jonatascdsilva@gmail.com (J.C.S. Rosestolato).

https://doi.org/10.1016/j.fuel.2018.11.027
Received 18 December 2017; Received in revised form 23 October 2018; Accepted 6 November 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
J.C.S. Rosestolato et al.
1. Introduction
A great effort has been made worldwide to improve the oil recovery.
Although millions of barrels are extracted per day from the oil fields,
conventional oil recovery methods (primary or secondary) are capable
to remove only approximately 40% of the total oil initially contained in
a reservoir. The residual oil is trapped in the porous media by strong
capillary forces and demands very low interfacial tensions for its dis-
placement. Tertiary oil recovery techniques (or enhanced oil recovery –
EOR) can be implemented in order to remove oil beyond conventional
methods. In some of the EOR processes, specific chemicals are injected
and interact with the oil/water/rock system in order to create favorable
conditions for oil displacement. These interactions have a physico-
chemical nature and might reduce the water/oil (w/o) interfacial ten-
sion (IFT), increase the viscosity of injection fluid, modify the rock
wettability or create a favorable phase behavior [1].
An important method of tertiary oil recovery is the surfactant
flooding. Surfactants have an amphiphilic structure and tend to reduce
the energy of the w/o interface. The changes on interfacial properties
improve the displacement efficiency, mobilizing the residual oil into the
production well [2]. Wu et al., for example, reported an experimental
study using different types of surfactants (cationic, anionic and non-
ionic) for an EOR process. They observed that the reduction in the in-
terfacial tension between the oil and the aqueous phase was the main
cause of faster and larger oil recovery [3]. Surfactant flooding is an
efficient oil recovery method, but surfactant molecules usually have a
strong interaction with the reservoir rock surfaces and a large part of
the injected surfactant is lost by adsorption before reaching the oil site.
The adsorption of surfactants and their high cost are of great concern
for the application of this type of chemical EOR process, turning it often
economically unfeasible [4].
Nanostructured materials have been widely used in petroleum re-
search due to their interfacial properties, mainly for their use in EOR.
Nanoparticles have the ability to modify the water/oil and oil/rock
interfaces, reducing the interfacial tension, increasing emulsion stabi-
lity, inhibiting asphaltene precipitation, and changing the rock surface
wettability [5]. Several types of nanoparticles have been used to sta-
bilize microemulsions [6,7]. Zhang et al., for example, highlighted the
use of surface-coated nanosilica that tend to strongly interact with the
water/oil interface, increasing the emulsions stability by the formation
of a monolayer on the droplets surface (Pickering emulsion) [7]. Kon-
diparty et al. proposed the use of silica nanoparticles for modifying the
reservoirs rock surface. These nanoparticles would form a structural
film between the discontinuous phase (oil) and the solid phase (rocks
surface), displacing the oil through the achievement of a structural
disjunction pressure [8]. The literature shows many other applications
of nanoparticles in EOR. However, most of these particles are of in-
organic nature and usually tend to be integrally adsorbed at the water/
oil/rock interfaces [9].
In recent years, nanomaterials have gained special attention when
employed to prevent the surfactant adsorption on the rocky reservoir
surface [10–12]. These nanomaterials have a specific structure capable
of interacting with surfactant molecules and working as nanocarriers to
avoid the surfactant losses. Romero-Zeon et al. used nanocarriers based
on the inclusion complex formed between surfactants and β-cyclodex-
trin molecules [10]. Chen et al. proposed the use of carbonaceous na-
noparticles (multi-wallet nanotubes and carbon black). The combina-
tion of the large specific area and strong affinity for the surfactant
molecules by the nanoparticles did lead to a competitive surfactant
adsorption process between the nanoparticles and the rock surface,
decreasing the surfactant losses on the rock reservoir surface [11].
Our research group is committed to developing new technologies for
interfacial properties control and oil recovery improvement [13,14].
Avila et al. the use of crosslinked polystyrene nanoparticles as surfac-
tant nanocarriers for preventing the surfactant losses that occur by
adsorption on the rock surface in enhanced oil recovery processes.
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Fuel 239 (2019) 403–412
These nanoparticles swell when in contact with the oil phase, releasing
the surfactant and reducing the water/oil interfacial tension [14].
The purpose of the present work was to develop a new type of
surfactant nanocarrier for EOR, employing lipid nanoparticles. The
studied nanocarrier presents a hydrophobic structure, capable of
storing and releasing the surfactant molecules directly at the water/oil
interface, preventing the surfactant losses by adsorption on the rocks
surface. At reservoir’s temperatures below the lipid melting point, the
surfactant release is triggered by the solubilization of the solid lipid
nanocarriers at the oil surface, based on the hydrophobic nanoparticles
character. At reservoir’s temperatures above the lipid melting point, the
nanostructure works as a surfactant nanoencapsulator in an emulsion
form, releasing the surfactant by the direct solubilization of lipid na-
nodroplets at the oil surface, promoting the reduction of the w/o in-
terfacial tension and improving the oil recovery. The design of the lipid
nanocarriers structure was inspired by processes employed in the pro-
duction of nanoparticles for drug delivery systems (Solid Lipid
Nanoparticle – SLN). The nanocarriers were obtained employing
beeswax (BW) as lipid matrix and nonylphenol ethoxylate (NPE10) as
surfactant, based on the good results of nanoparticle stability [15] and
oil recovery in EOR processes [3]. The results from this study are pre-
sented and discussed in this article, and it is proposed the use of these
structures as a model for surfactant nanocarriers with potential to be
employed in EOR processes.
2. Materials and methods
2.1. Materials
Blanched beeswax (BW) (Sigma-Aldrich) was used as the solid lipid
matrix and nonylphenol ethoxylates (NPE10 –
(C9H19)C6H4(OCH2CH2)10OH, RENEX100™ by Oxiteno, Brazil) as the
nonionic surfactant. For the interfacial tension measurements, the oil
phase was a 1:1 mixture (v/v) of n-heptane and toluene named as
heptol (both solvents were purchased from Vetec Química, Brazil).
Heptol is a hydrocarbon mixture chosen to simulate oil with aliphatic
and aromatic characteristics. Sodium chloride (Vetec Química, Brazil)
was used to prepare the saline solutions. Cellulose dialysis tubing (MW
cut-off range: 14 KDa) was obtained from Sigma Aldrich, Brazil.
Distilled water was used in all the experiments and all the materials
were used as obtained from their manufacturers, without further pur-
ification.
2.2. Preparation of the surfactant nanocarriers
The nanocarriers were prepared using a high-energy emulsification
method by ultrasonication [16]. First, the surfactant NPE10 was dis-
solved in melted beeswax at 67 °C (2 °C above the wax melting point) to
obtain a clear liquid. In a second step, hot water, at that same tem-
perature, was added to the melted wax/surfactant mixture and stirred
with a magnetic stirring bar for three minutes. The obtained pre-
emulsion was ultrasonified using a probe sonicator UP200S (Hielscher)
with power output (amplitude of 100%) for three minutes. The soni-
cator’s cavitation waves lead to the wax droplets breakage and the
subsequent nanoemulsion formation. The temperature was kept at
67 ± 0.5 °C throughout these steps by a thermostatic water bath. The
nanocarrier was obtained by the cooling of the nanoemulsion in an ice
bath. Nanocarriers were produced with the wax concentration at 1.0%
(m/v) and the surfactant concentration ranging from 0.1% to 1.0% (m/
v) in order to reach an optimized procedure.
Some of the nanoparticles suspensions were submitted to a pur-
ification process through dialysis in order to remove the free surfactant
from the nanoparticles aqueous suspension. 20 mL of the NPS suspen-
sion was placed inside the dialysis bag (cellulose membrane), which
was immersed in 200 mL of distilled water at room temperature
(∼25 °C). The outer aqueous medium was continuously changed and
J.C.S. Rosestolato et al.
monitored by UV–Vis spectrophotometer (SP220, Spectrolab) at
275 nm, characteristic wavelength of the NPE10 surfactant aromatic
ring. The dialyzed nanocarrier aqueous suspension was mentioned in
this paper as purified system.
2.3. Nanoparticles characterization
2.3.1. Particle size
Particle size (hydrodynamic diameter) and polydispersity index
(PDI) were determined by dynamic light scattering (DLS) using a
Zetasizer Nano ZS (Malvern Instrument, Germany). The nanocarriers
aqueous suspension was diluted with distilled water at an appropriate
scattering intensity and data were analyzed by a cumulant method as-
suming spherical particles. The DLS technique was used for monitoring
the effect of the surfactant concentration, the storage stability at room
temperature and the nanocarrier’s stability at different temperatures
(25–75 °C) on the nanoparticles size. Each analysis was carried out in
triplicate and the data expressed as the mean value.
2.3.2. Scanning electron microscopy – SEM
Scanning electron microscopy was used to study the surface topo-
graphy and morphology of the nanocarriers obtained. Prior to analysis,
the nanoparticles suspension was placed on aluminium stubs, dried in a
desiccator and coated with gold, using a sputter coater device (K550,
Emitech). The morphology of the dried nanoparticles was examined
using the JSM-6460 (Jeol) operated at an accelerating voltage of 15 kV.
2.3.3. Differential scanning calorimetry – DSC
Thermal behavior characterization of the wax matrix and nano-
carriers were carried out using a differential scanning calorimeter (DSC
7, Perkin Elmer). A mass of 1–2 mg of dried sample was weighted and
sealed in an aluminium pan. Thermal analysis was performed in a
heating rate of 10 °C/min and temperature range of 30–80 °C.
2.3.4. Determination of surfactant entrapment in the nanocarriers
The surfactant entrapment is the relative concentration of surfactant
loaded in the nanocarriers and was indirectly determined by measuring
the free surfactant concentration in the aqueous medium. The free
surfactant was isolated from the nanocarriers suspension by centrifugal
filtration along with 100 kDa molecular weight cut-off centrifugal filter
units (Amicon® Ultra-4, Millipore). Briefly, 2 mL of NPs suspension was
placed in the filter device and centrifuged at 3000 rpm for 40 min. The
degree of entrapment was indirectly evaluated by quantifying the sur-
factant in the supernatant by UV–Vis spectrophotometry at 275 nm
[17]. The experiments were performed in duplicates, using a previously
determined calibration curve.
2.4. Surfactant release evaluation
In order to better understand the interfacial properties, two com-
plementary methodologies were used to measure the IFT: du Noüy ring
and spinning drop. The ring method was used as a preliminary analysis,
being suitable for the measurement of high interfacial tension values.
The spinning drop tensiometer is indicated for low interfacial tension
values and also allowed for measurements at higher temperatures. The
oil phase from the interfacial tension measurements with the ring ten-
siometer was analyzed by FTIR spectroscopy to determine the presence
of beeswax and surfactant in the heptol as a consequence of the na-
noparticles solubilization and therefore surfactant release.
2.4.1. Ring method interfacial tension measurement and FTIR spectroscopy
2.4.1.1. IFT measurements by the ring method. The interfacial tension (γ)
was measured by the du Noüy ring method using a digital K9
tensiometer (Krüss, Germany). All measurements were carried out
with equal volumes (25 mL) of the aqueous and heptol phases, at
room temperature (∼25 °C), until equilibrium was reached (after 24 h).
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Fuel 239 (2019) 403–412
The γ values were obtained for different formulations for the aqueous
phase (distilled water, surfactant solution or nanocarriers suspensions)
and oil phase (heptol or beeswax solution in heptol). The surfactant
concentration used was 0.1% (m/v) (1000 ppm). The effects of the salt
concentration and of the NPs purification (dialysis process applied to
the NPs suspension to remove free surfactant from the aqueous
solution) were evaluated. The reported values are the average of
three determinations.
2.4.1.2. FTIR of oil phase. After performing interfacial tension
measurements by the ring method, an aliquot of the oil phase was
withdrawn, evaporated and the residue analyzed by Fourier transform
infrared spectroscopy (FTIR). The FTIR measurements were performed
in a Magna-IR 740 spectrometer (Nicolet, USA) in a range of
400–4000 cm−1. The observation of the beeswax characteristic bands
in the FTIR spectra would be a qualitative evaluation of the
nanoparticles solubility and of the surfactant release in the oil phase.
2.4.2. Spinning drop method
The w/o interfacial tension (IFT) for the different systems was de-
termined using the Site100 spinning drop tensiometer (Krüss, Germany)
through a built-in software system based on the Vonnegut Equation.
Before the IFT measurement, the density of all analyzed solutions was
previously determined by interpolation in a standard density curve as a
function of temperature by a DMA 35 EX densimeter (Anton Parr,
Germany). All surfactant solutions and NPs suspensions were previously
centrifuged at 3000 rpm in a traditional centrifuge for 20 min to
minimize the formation of bubbles at the tensiometer’s capillary. The
measurements were carried out until the equilibrium condition was
reached at temperatures of 30 °C and 66 °C ( ± 0.2 °C) in a constant
speed rotation between 4000 and 6000 rpm. The IFT measurements
were performed for at least 40 min and finished when the equilibrium
condition was reached, i.e., when the IFT values remained unchanged
for 10 min. The effects of salt concentration, NPs purification and
temperature on the IFT were evaluated.
In order to better understand the interfacial tension values obtained
at high temperature, cloud point of the NPE10 surfactant solutions was
investigated. The cloud point values were determined through visual
observation of the temperature transition from a clean to a turbid ap-
pearance of solution, at a surfactant concentration of 0.1% (m/v) and a
NaCl concentration between 0% and 5% (m/v).
2.5. Column test: unconsolidated porous media experiments
The transport behavior of the nanoparticle suspensions was assessed
by experiments in unconsolidated sandpack column test [18]. The
porous media apparatus consists in a liquid chromatography column
(2.5 cm i.d. and adjusted to 2.5 cm length; Kontes, Vineland, NJ) con-
nected to a peristaltic pump (Masterflex® L/S peristaltic pumps, Cole-
Parmer). The column was packed with sand of 30–100 mesh
(595–149 µm) extracted from Copacabana Beach (Rio de Janeiro,
Brazil) and sealed with two PTFE (polytetrafluoroethylene) end fittings
with 20 μm porosity. The sand used was previously washed with dis-
tilled water and calcined at 600 °C for 4 h to remove organic com-
pounds. The sand porosity was determined by the direct measurement
based on the ratio between the volume of distilled water inside the
pores and the total bulk volume of the unconsolidated sand. The por-
osity of the sand used in all experiments was 30%. After the packing,
the column was completely saturated with water and a tracer test was
performed injecting a NaNO3 solution to assess the non-reactive flow
behavior [19]. The nanoparticles transport behavior was carried out at
room temperature with the injection of 3 pore volume (PV) of distilled
water, 3 PV of surfactant solution or nanoparticle suspension, and is
finishes with the injection of 4 PV of distilled water. In the column test,
the concentration of the injected fluid was 0.1% (m/v) with a pumping
flow rate of 0.5 mL/min. Effluents were collected every ¼ PV and
J.C.S. Rosestolato et al.
analyzed in a UV–Vis spectrophotometer at 275 nm and 633 nm to
determine the surfactant and NPs concentrations, respectively. The
results were plotted as relative concentration C/C0 (ratio between the
surfactant or particle recovery and the initial concentration injected)
and expressed as a breakthrough curve as a function of the pore volume
(PV).
3. Results and discussion
This investigation presents the evaluation of lipid nanoparticles as
model surfactant nanocarriers for the EOR process. The nanoparticles
obtained were characterized in terms of size, storage stability, scanning
electron microscopy (SEM), differential scanning calorimeter (DSC) and
surfactant entrapment capacity. Interfacial tension behavior and FTIR
results were used to study the surfactant release at the oil surface,
evaluating the effect of the nanoparticles purification, salt concentra-
tion and temperature. Besides, a sandpack column test was used to
evaluate the transport behavior of the nanoparticles through un-
consolidated porous media.
3.1. Nanocarriers characterization
3.1.1. Effect of surfactant concentration and nanoparticles stability
Table 1 shows the effect of the surfactant concentration on the
particle size and polydispersity Index (PDI) for the obtained nano-
particle suspensions, as measured by dynamic light scattering, 24 h
after NPs production.
The PDI was slightly influenced by the surfactant concentration. On
the other hand, the increase in NPE10 concentration decreases the
mean particle size from 234 to 118 nm. The particle size reduction is
probably caused by the increase of the lipid droplets stability due to the
formation of a surfactant molecular film on the surface of the lipid
droplets in the nano-emulsification process [20]. It is possible to note
that the size of the nanoparticles remains constant from 0.5% (m/v) of
surfactant which is an important result for surfactant concentration
optimization. Thus, in subsequent experiments, the nanoparticles were
obtained using 1.0% (m/v) of surfactant to achieve greater surfactant
incorporation.
In relation to storage stability, the nanocarriers were characterized
regarding z-average diameter and polydispersity index. Fig. 1 shows the
particle size of the nanocarrier’s suspension during three months of
storage at room temperature (∼25 °C). After three months, the nano-
particles kept their narrow size distribution (PDI ∼ 0.27) and the same
particle size range. The good stability of nanoparticles suspension could
be attributed to the steric effect from the nonionic surfactant [21].
The nanoparticles obtained in this work show a size compatible with
similar ones from the literature. Attama et al., for example, produced
solid lipid nanoparticles with beeswax and the nonionic surfactant
polysorbate 80, showing a z-average < 200 nm and a PDI around 0.2,
with the nanoparticles being stable for more than three months [15].
Fig. 2 shows the effect of temperature on the surfactant nanocarriers
particles size in aqueous suspensions with the temperatures ranging
from 25 °C to 75 °C.
It is possible to note that the lipid nanoparticles in aqueous sus-
pension were stable at temperatures up to 75 °C, showing a small de-
crease in particle size with temperature increase. The high stability of
the nanocarriers may be caused by the steric effect of the NPE10 sur-
factant that being adsorbed on the surface of the lipid droplets, would
promote high stability even above the lipid melting point. The eva-
luation of the nanoparticles stability is fundamental for the application
of NPs in EOR processes. Alomair et al. did study the effect of different
types of nanofluids on the recovery of heavy crude oil. They concluded
that nanoparticles in the order of hundreds of nm are smaller than the
pore and the throat size of the reservoirs rock. Thus, the lipid nano-
particle suspensions developed in this work would have a suitable size
for a traditional injection and flow through the porous media [22].
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Fuel 239 (2019) 403–412
3.1.2. Scanning electron microscopy
Scanning electron microscopy (SEM) was employed to reveal the
morphology of the nanoparticles. The SEM is also a way to confirm the
particle size of NPs measured by DLS. The SEM image (Fig. 3) reveals
nanoparticles with a size below 200 nm, which is consistent with the
particle size obtained by the DLS technique. The nanocarriers show
spherical shape morphology, result of the typical nanoparticles pro-
duction from nano-emulsification processes [23]. The SEM image also
suggests a wide aggregation of the particles, but this may not ne-
cessarily represent the real dispersion state of the nanoparticles in
water suspension, since the aggregation could have occurred during the
drying process in the sample preparation for SEM analysis.
3.1.3. Differential scanning calorimetry – DSC
DSC was the technique used to investigate the thermal behavior of
NPE10/BW mixture and of the nanoparticles in endothermic process.
Fig. 4 exhibits the DSC curves of pure beeswax, blends of 30% and 50%
of NPE10 in beeswax, and lipid nanocarriers obtained with 50% of
NPE10/BW.
The analysis of the DSC curves shows that the surfactant in-
corporation into the lipid matrix results in a reduction of the lipid
melting temperature and of the process enthalpy change. This phe-
nomenon can be attributed to a disorder in the lipid matrix structure
induced by a heterogeneous composition from the surfactant in-
corporation [24]. The less ordered arrangement of the lipid molecules
creates imperfections in the structure, improving the surfactant in-
corporation and the physical stability of the lipid matrix [21]. There is
also a decrease of the melting temperature and of the process variation
of enthalpy (ΔH) for the nanoparticle, as compared to the one for the
bulk material (50% of NPE10). These changes in the NPs system’s
thermal behavior occur due to an increase of the surface/volume ratio.
Surface atoms have less cohesive energy when compared to the atoms
in the bulk, reducing the required energy to melt. This trend can be
established by the Gibbs-Thomson Equation which describes the
melting point reduction with the decrease of the particles radius [25].
Although there is an effect of the surfactant incorporation and the na-
noparticles formation on the DSC curve, the melting temperature for
the produced nanoparticles is only 6% lower than the one for the pure
lipid.
3.1.4. Determination of surfactant entrapment in the NPs
The efficiency of surfactant entrapment was determined by quan-
tifying the free surfactant in the NPs suspensions (indirect method)
through UV–Vis spectroscopy. The results show that the NPE10 con-
centration in the nanoparticles was of 0.48 g/g (wt %), showing an
incorporation of 96% (m/m) of the total surfactant used in the nano-
particles production. The great solubility of the surfactant in the lipid
medium is a reflection of the chemical environment inside the NPs. The
NPE10 molecules may be stabilized by van der Walls and hydrogen
bonding interactions with the BW matrix, increasing the surfactant
entrapment in the nanoparticle. This result of surfactant entrapment is
in agreement with other works in the literature for the incorporation of
drugs into the solid lipid nanoparticles structure [17,21]. Kher-
admandnia et al., for example, studied the incorporation of the Keto-
profen as a model drug into the SLNs prepared from a mixture of
beeswax and carnauba wax. They obtained a high entrapment of 97% of
the drug in the lipid matrix, which is compatible with our entrapment
results of the NPE10 surfactant in beeswax nanoparticles [21].
Table 1
Surfactant concentration effect: Z-average and PDI of NPs suspension for-
mulated with different surfactant concentration.
NPE10 concentration (m/v) 0.1% 0.25% 0.5% 1.0%
z-average size (nm) 234 146 119 118
Polydispersity Index (PDI) 0.29 0.22 0.24 0.26
J.C.S. Rosestolato et al. Fuel 239 (2019) 403–412

Fig. 1. Storage stability: Z-Average diameter of NPs suspension during up to Fig. 4. DSC curves for BW bulk, blends of NPE10 30% (w/w) in BW, blends of
three months of storage at room temperature. NPE10 50% (w/w) in BW, and nanocarriers obtained with NPE10 50% (w/w)
in BW.

3.2. Surfactant release at the w/o interface

This section describes the experiments carried in order to verify the

nanoparticles solubility and surfactant release at w/o interface.
Measurements of the interfacial tension using the ring method with
further FTIR spectroscopy of the oil phase were carried out in order to
determine the IFT reduction and the possible presence of BW and
NPE10 in the oil phase. The spinning drop technique was employed to
access the effect of salt concentration, NPs purification and temperature
on the interfacial tension.

3.2.1. IFT measurement using the ring method

Fig. 2. Nanocarrier’s stability: effect of temperature on particles size.
The interfacial tension (IFT) between two immiscible liquids de-
pends directly on the molecular entities present at the interface. In this
study, the interfacial tension measurements of the aqueous/oil systems
were used to investigate the nanoparticles solubilization. Table 2 lists
the IFT values obtained for different systems containing the NPE10
surfactant, mixtures of NPE10/BW and nanoparticle suspensions (pur-
ified and/or in brine). All the investigated systems (except distilled
water) had a surfactant concentration of 0.1% m/v (1000 ppm) which is
above the CMC (critical micelle concentration).
Interfacial tension measurements showed that both NPE10 and
beeswax have interfacial activity. The NPE10 surfactant (S3 system) did
reduce the IFT of water/oil interface from 35.0 to 4.2 mN/m, which is
in agreement with another work in the literature [14]. The beeswax (S4
system) also reduced the IFT to 6.1 mN/m and it could be attributed to

Table 2
Interfacial tension results for aqueous/oil systems with different formulations
by the ring method. All materials were measured at a 0.1% (m/v) concentra-
tion.
System Aqueous Phase Oil Phase IFT (mN/m)

S1 Distilled water heptol 35.0

S2 Brine* heptol 35,8
S3 NPE10 heptol 4.2
S4 Distilled water BW in heptol 6.1
S5 NPE10 BW in heptol 4.0
S6 NPE10 in brine* BW in heptol 3.8
S7 NPs water suspension heptol 12.4
S8 Purified NPs heptol 15.6
S9 NPs in brine* heptol 9.8
Fig. 3. Scanning electron microscopy (SEM) image of nanocarriers surface, S10 Purified NPs in brine* heptol <1
scale bar 0.5 µm.
* Brine: 3% (m/v) of NaCl.

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J.C.S. Rosestolato et al.
the beeswax composition. The BW is composed by an esters, alcohols
and fatty acids mixture, which plays a role as surfactant species, as-
sisting in the interfacial tension reduction [26]. Thus, besides working
as a carriage medium for the surfactant, the lipid matrix could be also
acting as a surfactant, reducing the IFT. On the other hand, the IFT
between the NPE10 aqueous solution and BW in heptol (S5 System) was
4.0mN/m, which is similar to the result obtained for NPE10 surfactant
solution and pure heptol. This fact indicates that there is no synergism
between the NPE10 surfactant and BW molecules and, probably, the
NPE10 molecules were preferentially adsorbed at the interface, in
detriment of beeswax molecules. The IFT shown by the unpurified na-
noparticle system (S7 system) was 12.4 mN/m, which is higher than the
one presented by NPE10/BW solutions. In addition, the effect of pur-
ification and of salinity on the IFT of nanocarriers was studied (S8, S9
and S10 systems). The IFT value of the purified NPs suspension was of
15.6 mN/m and the IFT of the NPs suspension in brine was of 9.8 mN/
m. Therefore, when these effects were assessed separately, both pur-
ification and salinity conditions did lead to higher IFT than the one for
NPE10/BW surfactant solution in brine (S6 System). However, when
these conditions were combined (S10 system), the IFT reached a value
below the detection limit of the ring tensiometer (< 1.0 mN/m). These
results show that the action of the nanoparticles at the interface was
directly affected by the free surfactant and the presence of ions in
aqueous phase. Since the IFT value was around the detection limit of
the ring method, the spinning drop tensiometer was used to clarify the
relation between the interfacial tension and surfactant release. The
mechanism responsible for these interesting IFT differences will be
discussed based on the following experimental results.
3.2.2. FTIR of oil phase
In order to better understand the interfacial activity, after the IFT
measurements by the ring method, an aliquot from the oil phase was
removed, the heptol was evaporated and the residual content was
analyzed by Fourier transform infrared spectroscopy (FTIR). FTIR
spectrometry was performed as a qualitative analysis to verify the
presence of beeswax and NPE10 in the oil phase. Fig. 5 allows the
comparison between NPE10 surfactant, BW lipid and residual content
of oil phase from S7 and S10 systems spectra (described in Table 2, item
3.2.1).
The beeswax is a mixture of several compounds and comprises long
chain esters, aliphatic alcohols and free acids [27]. The principal ab-
sorption band of BW appears around 1750–1735 cm−1 due to the car-
bonyl stretching of carboxylic acids and esters, while the NPE10 sur-
factant has the characteristic absorption bands of ethers that are
associated with a strong vibration band of CeOeC in the
1150–1085 cm−1 region due to asymmetrical stretching [28]. The FTIR
spectra in Fig. 5 confirm the presence of characteristics bands from BW
(C]O at 1735 cm−1) and NPE10 (CeOeC at 1110 cm−1) in the oil
phase of the IFT experiments. These results corroborate the under-
standing that lipid nanoparticle systems could migrate from the aqu-
eous phase to the w/o interface and release the beeswax and NPE10
surfactant molecules. Due to their hydrophobic and amphiphilic char-
acter, part of the beeswax and surfactant molecules can be desorbed
from the w/o interface and migrate to the oil phase, where they were
detected by the FTIR technique. The nanoparticle solubilization pro-
vides unequivocal evidence that gives support to the new concept of
surfactant nanocarriers for EOR process.
3.2.3. IFT measurement through the spinning drop tensiometer
3.2.3.1. Effect of salt concentration and NPs purification on IFT. The
effect of NaCl concentration and of the NPs purification on the dynamic
IFTs between the organic phase and the aqueous systems was
investigated. For this study, all aqueous systems were prepared with
0.1% of surfactant (m/v), which is above the CMC. Fig. 6 shows the
dynamic IFT curve between heptol and NPE10 solutions at various
salinities, containing 0% to 5% (m/v) of NaCl.
408
Fuel 239 (2019) 403–412
It can be observed that the IFT decreases progressively to reach a
plateau over time (equilibrium condition). The reduction of IFT is a
common feature in the natural replacement of solvent molecules at the
interface by surfactant molecules, which provides a typical L-shape
curve. For better visualization and comparison among results, L-shape
curves for the next experiments are presented only at the minimum
interfacial tension (IFTmim), when the equilibrium conditions are
reached. Fig. 7 shows the IFTmin between heptol and NPE10 aqueous
solution, NPE10/BW blend and nanoparticles suspension (purified or
without purification), at various salt concentrations.
It is possible to observe that there is no significant variation of IFT
for the systems of NPE10 and NPE10/BW (overlapping data). The IFT of
both NPE10 surfactant solution and NPE10/BW solution were around
0.8mN/m, showing a little increase with the salt concentration. It is
well known that electrolytes have little effect on the dynamic interfacial
tension of nonionic surfactants as compared with the ones for ionic
surfactants. Iglauer et al. in their study confirm that nonionic surfactant
formulations may be largely indifferent to salinity even with very high
NaCl concentrations (up to 20 wt%) [26]. At first sight, these IFT results
obtained with the spinning drop tensiometer are inconsistent with the
ones from the ring method. While the ring method shows IFT values of
4.2 mN/m (S3 system) for the NPE10 surfactant solution and 4.0 mN/m
(S5 system) for the NPE10/BW solutions, the spinning drop measure-
ments show an IFT of 0.8 mN/m for both systems. This difference in IFT
could be attributed to differences in the measurement technique. Yeung
et al. concluded that the IFT of two immiscible liquids depend strongly
on the experimental design and significant differences in the interfacial
tension could be observed. These variations are attributed to the par-
titioning (distribution) of surfactants between (both bulk) phases and
the interface, which imply in different IFT values depending on the
employed technique [29]. In this work, these differences in IFT results
were minimized by comparing data obtained from the same measure-
ment technique.
Fig. 7 also shows the IFT between nanocarrier suspensions and
heptol. As it can be seen, the IFT for both types of nanoparticle sus-
pensions (purified or not) were higher than the ones for the surfactant
systems (NPE10 and NPE10/BW) and decreased fast with salinity. The
addition of 5% (m/v) of NaCl reduced the IFT for the purified nano-
particle system from 10.6 to 0.91 mN/m and from 7.2 to 3.2 mN/m for
the unpurified. The reduction of the IFT values may be related with the
destabilization of the surfactant and the nanoparticles in aqueous phase
promoted by an increase of salt concentration. There is a dehydration of
Fig. 5. FTIR spectra of NPE10, BW and residual content of oil phase from S7
and S10 systems. The letters A and B identify the spectra of BW and NPE10 and
the letters C and D the spectra of S7 and S10 systems, respectively.
J.C.S. Rosestolato et al.
Fig. 6. Interfacial tension (IFT) for NPE10 solution (1000 ppm) and heptol as a
function of time, for several NaCl concentrations, at 30 °C.
Fig. 7. Minimum interfacial tension (IFTmin) between heptol and NPE10 aqu-
eous solution, NPE10/BW blend and nanoparticles suspension (with or without
purification) as a function of NaCl concentration.
the surfactant head group and the nanoparticles become relatively more
hydrophobic. Neutral electrolytes, such as NaCl, may change the sur-
factant and nanoparticle distribution in the oil and aqueous phases and
in the w/o interface due to a salting-out effect [30]. Fig. 8 illustrates the
general behavior of nanoparticles (inorganic or organic) at w/o inter-
face.
The nanoparticle relative position at the w/o interface is dependent
on the nanoparticle hydrophobicity. The increase of NPs hydro-
phobicity contributes to their major penetration in the oil phase (in-
crease of contact angle, Fig. 8), improving the NPs solubilization and
surfactant release [31]. Note that in 5% of NaCl, the purified system
shows an IFT that reaches values equivalent to the ones for NPE10
surfactant in solution, demonstrating the greater release of surfactants.
On the other hand, the unpurified NPs system shows a IFT higher than
the one for the purified system. Probably, the free surfactant present in
aqueous solution of unpurified system would form a film on the w/o
interface, hindering the nanoparticles solubilization in the oil phase.
From the above results and discussion, and similarly to the IFT and
FTIR results from the ring measurements (item 3.2.1 and 3.2.2), it is
409
Fuel 239 (2019) 403–412
possible to infer that the surfactant release occurred in all nanoparticle
systems evaluated in the spinning drop tensiometer. The variation ob-
served in IFT results may be associated to the concentration of the
components at the interface, as a result of the differentiated solubili-
zation of the nanoparticles in the oil phase.
3.2.3.2. Effect of temperature on IFT. Figs. 9 shows the dynamic
interfacial tension results for the unpurified (Fig. 9a) and purified
nanocarriers system (Fig. 9b) with NaCl concentrations of 0%, 1%, 3%
and 5% (m/v), at 66 °C. This temperature is above the lipid melting
point and the nanocarriers are, in fact, an oil/water emulsion.
Assessing the IFT curves profile, it is possible to observe that in the
unpurified system (Fig. 9a) the IFT values are reduced continuously
until a minimum IFT (IFTmin) in an L-shape. However, there is a re-
duction of the time to reach the IFTmin when compared to the results
obtained at 30 °C. While at 30 °C the IFTmin did take 120 min to be
reached (data not shown), the increase in temperature shortened the
time to around 30 min. At a higher temperature, the emulsified nano-
carriers can accelerate the lipid diffusion process into the oil phase,
increasing the solubilization rate of the surfactant nanocarriers and,
consequently, decreasing the time to achieve the equilibrium. On the
other hand, for the purified system (Fig. 9b), the IFT profiles were at a
V-shape. The IFT values rapidly reached an IFTmim and then increased
to an equilibrium interfacial tension (IFTeq). The V-shape format may
be explained by the surfactant adsorption/desorption process, a char-
acteristic of nonionic surfactants or by surfactants competition for the
interface [32–35]. This behavior is already complex when dealing with
surfactants in solution, and even more when the system involves the
release of lipids and surfactants by nanoparticle solubilization. Thus,
the IFT curves in the form of a V-shape for lipid nanocarriers may be the
result of the sum of several interfacial modifications. Initially, there is a
great solubilization of the nanoparticles, starting a great competition
between the lipid and the surfactant molecules for the interface. As time
evolves, a molecular reorganization occurs, mainly with the movement
of the lipid and the surfactant molecules from the interface to the oil
phase. Furthermore, the ethylene oxide chains of the NPE10 surfactant
might gradually reoriented themselves at the interface, occupying more
space, and favoring the increase of the IFTmin to the IFTeq values. The
combination of these phenomena would favor desorption processes for
the oil phase and, consequently, the formation of V-shape curve.
The IFTmin of NPE10, NPE10/BW solutions, and of unpurified and
purified nanoparticles suspensions with different salinities are shown in
Fig. 10, which shows that the interfacial tension of the surfactant and
NPs systems tends to be reduced with an increase in salt concentration.
Initially, the IFT of the systems with purified nanoparticles in the
absence of NaCl (19.2 mN/m) is higher than for the other evaluated
systems, which can be explained by the absence of free surfactant in
aqueous solutions and by low NPs hydrophobicity (as discussed above,
item 3.2.3). Nevertheless, with an increase of NaCl concentration, the
interfacial tension curves for purified and unpurified NPs are similar to
those for surfactants, converging to the similar interfacial tension value
(∼0.2 mN/m). This behavior could be associated with the cloud point
Fig. 8. Schematic representation of nanoparticle at water/oil interface. The
contact angle increases with nanoparticle hydrophobicity.
J.C.S. Rosestolato et al.
Fig. 9a. IFT behavior of unpurified nanoparticle in different salt concentrations
at 66 °C.
Fig. 9b. IFT behavior of purified nanoparticles with different salt concentra-
tions at 66 °C.
effect of the nonionic surfactant. Table 3 shows the experimental results
obtained for the cloud point of NPE10 surfactant at a concentration of
0.1% (m/v) as a function of salt concentration.
It is possible to see that the cloud point decreases with the increase
of electrolyte concentration. At 66 °C, the surfactant and NPs systems
were above the cloud point for samples containing NaCl concentrations
equal or greater than 1%, which explains the great IFT reduction of the
systems between 0% and 1% NaCl (Fig. 10). These results can be related
to the characteristic of nonionic surfactants. The polyoxyethylene oxide
chain of the NPE10 surfactant becomes dehydrated above the cloud
point temperature and tends to be less soluble in the aqueous phase. As
a result, the surfactant and NPs tend to leave from the aqueous phase to
the w/o interface, increasing the NPs solubilization process [36–38].
Therefore, the lipid nanoparticles responded positively to both tem-
perature and salt effects; being more efficient in the interfacial tension
reduction at higher temperatures and also with the increase of the NaCl
concentration, which are interesting features present in the oil re-
servoir.
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Fuel 239 (2019) 403–412
Fig. 10. IFTmin of NPE10 surfactant, NPE10/BW system, unpurified and pur-
ified nanoparticles as a function of NaCl concentration at 66 °C.
Table 3
Cloud point of 0.1% of NPE10 aqueous solution as a function of
NaCl concentration.
NaCl concentration (m/v) Cloud point*
0% 83 °C
1% 65 °C
3% 59 °C
5% 54 °C
* Cloud point: above this temperature the surfactant becomes
insoluble in the aqueous medium.
3.3. Column test: Unconsolidated porous media experiments
The surfactant and nanoparticles mobility was investigated through
experiments in unconsolidated sandpack porous media. Fig. 11 shows
the effluent breakthrough curve for surfactant and nanoparticles in-
jection.
The results for surfactant and NPs mobility through the porous
media were similar. The breakthrough point (initial breakthrough) is
seen at 1.25 PV for both systems and the curves show a typical S-shape,
increasing until the saturation point at 2.5 PV. Thereafter, the relative
concentration decreases as a result of the distilled water injection from
4.0 PV. The effluents mass recoveries were 93% for the surfactant and
90% for the NPs. The lower surfactant and NPs adsorption on the sand
surface can be attributed to the surfactant characteristics. In general,
nonionic surfactants, such as NPE10, have low adsorption compared to
ionic surfactants [39]. The ethylene oxide chains of the surfactant hy-
drophilic head groups have strong interaction (hydrogen bonding) with
the water molecules, resulting in an excellent stability in the aqueous
medium and, consequently, a low adsorption on the solid surface.
Beeswax NPs mobility evaluation in a column test was not found in the
literature (which highlights the originality of this work). On the other
hand, there are numerous works that perform tests in porous media
with inorganic nanoparticles like silica and magnetite [18,40]. Kmetz
et al. studied the transport of aqueous suspensions of magnetite nano-
particles in unconsolidated porous media of Ottawa sand. The mass
recovery of the magnetite in the effluent depends directly on the
measurement conditions, varying between 60 and 97% [40]. Thus, the
lipid nanoparticles made of beeswax and NPE10 surfactant showed a
transport behavior compatible with silica and magnetite nanoparticles,
J.C.S. Rosestolato et al.
Fig. 11. Measured effluent breakthrough curves obtained for injection of 0.1%
(m/v) of surfactant NPE10 and nanoparticle in an unconsolidated sand column.
The cross symbol corresponds to nonreactive tracer (NaNO3).
which emphasizes the great potential of this system as surfactant na-
nocarriers for EOR process.
4. Conclusion
In this work, the potential of a new type of surfactant nanocarrier
for enhanced oil recovery was evaluated. Organic nanoparticles (NPs)
were used as model for selective surfactant nanocarriers. These NPs,
formed by a lipid matrix, were capable of surfactant storage in their
core and of releasing the surfactant directly at the oil surface.
Nanoparticles were obtained with lipid beeswax (BW) and nonylphenol
ethoxylate (NPE10) surfactant, and successfully characterized by DLS,
SEM, DSC and surfactant entrapment. The results demonstrate that the
NPs were stable for three month with a hydrodynamic diameter smaller
than 150 nm in a spherical shape. These nanocarriers showed a storage
capacity of 96% of surfactant and exhibited high mobility in porous
media of unconsolidated sandpack column. The surfactant release was
verified by interfacial tension (IFT) measurements (ring and spinning
drop methods) and FTIR analyses of oil phase. The IFT of the nano-
carrier system was compatible with IFT values of the NPE10 surfactant
solutions, while FTIR analyses confirm the nanoparticle solubilization
by the detection of beeswax in the oil phase. The NPs purification
process, salt concentration and temperature increase did favor the in-
terfacial tension reduction due to improvements on nanoparticle solu-
bility in the oil phase.
Acknowledgements
The authors gratefully acknowledge the Instituto de Química (UFRJ,
Brazil) and the financial support in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Brazil) –
Finance Code 001 and Petrobras, Brazil.
References
[1] Donalson EC, Chilingarian GV, Ten TF. Enhanced oil recovery, I fundamentals and
analyses. Developments in Petroleum science vol. 17A. New York: Elsevier Science;
1985.
[2] Guo K, Li H, Yu Z. In-situ heavy and extra-heavy oil recovery: a review. Fuel
2016;185:886–902. https://doi.org/10.1016/j.fuel.2016.08.047.
[3] Wu Y, Shuler PJ, Blanco M, Tang Y, Goddard WA. An experimental study of wetting
behavior and surfactant EOR in carbonates with model compounds. SPE J
2008;13:26–34. https://doi.org/10.2118/99612-PA.
[4] Green DW, Willhite GP. Enhenced oil recovery. In: SPE textbook, vol 6, Texas; 1998.
[5] Hendraningrat L, Li S, Torsater O. Effect of some parameters influencing enhanced
411
Fuel 239 (2019) 403–412
oil recovery process using silica nanoparticles: an experimental investigation. In:
Exhibition in SPE reservoir characterization and simulation conference and ex-
hibition, Abu Dhabi, UAE; 2013. https://doi.org/10.2118/165955-MS.
[6] Hu Z, Nourafkan E, Gao H, Wen D. Microemulsions stabilized by in-situ synthesized
nanoparticles for enhanced oil recovery. Fuel 2017;210:272–81. https://doi.org/10.
1016/j.fuel.2017.08.004.
[7] Zhang T, Davidson D, Bryant SL, Huh C. Nanoparticle stabilized emulsions for ap-
plications in enhanced oil recovery. In: Exhibition in SPE Improved Oil Recovery
Symposium, Tulsa, OK; 2010. https://doi.org/10.2118/129885-MS.
[8] Kondiparty K, Nikolov A, Wu S, Wasan D. Wetting and spreading of nanofluids on
solid surfaces driven by the structural disjoining pressure: statics analysis and ex-
periments. Langmuir 2011;27:3324–35. https://doi.org/10.1021/la104204b.
[9] Cheraghian G, Hendraningrat L. A review on applications of nanotechnology in the
enhanced oil recovery part A: effects of nanoparticles on interfacial tension. Int
Nano Lett 2016;6:129–38. https://doi.org/10.1007/s40089-015-0173-4.
[10] Romero-Zerón LB, Kittisrisawai S. Evaluation of a surfactant carrier for the effective
propagation and target release of surfactants within porous media during enhanced
oil recovery. Part I: dynamic adsorption study. Fuel 2015;148:238–45. https://doi.
org/10.1016/j.fuel.2015.01.034.
[11] Chen C, Wang S, Kadhum MJ, Harwell JH, Shiau B. Using carbonaceous nano-
particles as surfactant carrier in enhanced oil recovery: a laboratory study. Fuel
2018;222:561–8. https://doi.org/10.1016/j.fuel.2018.03.002.
[12] Nourafkan E, Hu Z, Wen D. Nanoparticle-enabled delivery of surfactants in porous
media. J Colloid Interface Sci 2018;519:44–57. https://doi.org/10.1016/j.jcis.
2018.02.032.
[13] Gramatges AP, Matheus CRV, Lopes G, Silva JC, Nascimento RSV. Surface and in-
terfacial tension study of interactions between water-soluble cationic and hydro-
phobically modified chitosans and nonylphenol ethoxylate. Colloids Surfaces A:
Physicochem Eng Aspects 2013;418:124–30. https://doi.org/10.1016/j.colsurfa.
2012.11.035.
[14] Avila JNL, Araujo LLGC, Drexler S, Rodrigues JA, Nascimento RSV. Polystyrene
nanoparticles as surfactant carriers for enhanced oil recovery. J Appl Polym Sci
2016;133(32):43789. https://doi.org/10.1002/app.43789.
[15] Attama AA, Müller-Goymanna CC. Effect of beeswax modification on the lipid
matrix and solid lipid nanoparticle crystallinity. Colloids Surfaces A: Physicochem
Eng Aspects 2008;315:189–95. https://doi.org/10.1016/j.colsurfa.2007.07.035.
[16] Anton N, Benoit J, Saulnier P. Design and production of nanoparticles formulated
from nano-emulsion templates – a review. J Control Release 2008;128:185–99.
https://doi.org/10.1016/j.jconrel.2008.02.007.
[17] Sharma RK, Sharma N, Rana S, Shivkumar HG. Solid lipid nanoparticles as a carrier
of metformin for transdermal delivery. Int Jf Drug Delivery 2013;5:137–45.
[18] Xue Z, Foster E, Wang Y, Nayak S, Cheng V, Ngo VW, et al. Effect of grafted co-
polymer composition on iron oxide nanoparticle stability and transport in porous
media at high salinity. Energy Fuels 2014;28:3655–65. https://doi.org/10.1021/
ef500340h.
[19] Grolimund D, Elimelech M, Borkovec M, Barmettler K, Kretzschmar R, Sticher H.
Transport of in situ mobilized colloidal particles in packed soil columns. Environ Sci
Technol 1998;32:3562–9. https://doi.org/10.1021/es980356z.
[20] Attama AA, Müller-Goymanna CC. Investigation of surface-modified solid lipid
nanocontainers formulated with a heterolipid-templated homolipid. Int J Pharm
2007;334:179–89. https://doi.org/10.1016/j.ijpharm.2006.10.032.
[21] Kheradmandnia S, Vasheghani-Farahani E, Nosrati M, Atyabi F. Preparation and
characterization of ketoprofen-loaded solid lipid nanoparticles made from beeswax
and carnauba wax. Nanomed: NBM 2010;6:753–9. https://doi.org/10.1016/j.nano.
2010.06.003.
[22] Alomair OA, Matar KM, Alsaeed YH. Nanofluids application for heavy oil recovery.
In: Exhibition in SPE Asia Pacific Oil & Gas Conference and Exhibition, Adelaide,
Australia; 2014. https://doi.org/10.2118/171539-MS.
[23] Seetapan N, Bejrapha P, Srinuanchai W, Ruktanonchai UR. Rheological and mor-
phological characterizations on physical stabilityof gamma-oryzanol-loaded solid
lipid nanoparticles (SLNs). Micron 2010;41:51–8. https://doi.org/10.1016/j.
micron.2009.08.003.
[24] Attama AA, Schicke BC, Müller-Goymann CC. Further characterization of theo-
broma oil–beeswax admixtures as lipid matrices for improved drug delivery sys-
tems. Eur J Pharm Biopharm 2006;64:294–306. https://doi.org/10.1016/j.ejpb.
2006.06.010.
[25] Han F, Li S, Yin R, Liu H, Xu L. Effect of surfactants on the formation and char-
acterization of a new type of colloidal drug delivery system: nanostructured lipid
carriers. Colloids Surfaces A: Physicochem Eng Aspects 2008;315:210–6. https://
doi.org/10.1016/j.colsurfa.2007.08.005.
[26] Iglauer S, Wu Y, Shulera P, Tanga Y, Goddard III WA. Alkyl polyglycoside surfac-
tant–alcohol cosolvent formulations for improved oil recovery. Colloids Surf
APhysicochem Eng Aspects 2009;339:48–59. https://doi.org/10.1016/j.colsurfa.
2009.01.015.
[27] Doan CD, To CM, De Vrieze M, Lynen F, Danthine S, Brown A, Dewettinck K, Patel
AR. Chemical profiling of the major components in natural waxes to elucidate their
role in liquid oil structuring. Food Chem 2017;214:717–25. https://doi.org/10.
1016/j.foodchem.2016.07.123.
[28] Silverstein RM, Webster FX, Kiemle DJ. Spectrometric identification of organic
compounds. 7th ed. John Wiley Sons; 2005.
[29] Yeung A, Dabros T, Masliyah J. Does equilibrium interfacial tension depend on
method of measurement? J Colloid Interface Sci 1998;208:241–7. https://doi.org/
10.1006/jcis.1998.5807.
[30] Bai J, Fan W, Nan G, Li S, Yu B. Influence of interaction between heavy oil com-
ponents and petroleum sulfonate on the oil-water interfacial tension. J Dispersion
Sci Technol 2010;31:551–6. https://doi.org/10.1080/01932690903167475.
J.C.S. Rosestolato et al.
[31] Maestro A, Guzmán E, Ortega F, Rubioc RG. Contact angle of micro- and nano-
particles at fluid interfaces. Curr Opin Colloid Interface Sci 2014;19(4):355–67.
https://doi.org/10.1016/j.cocis.2014.04.008.
[32] Qiao W, Li J, Zhu Y, Cai H. Interfacial tension behavior of double long-chain 1,3,5-
triazine surfactants for enhanced oil recovery. Fuel 2012;96:220–5. https://doi.org/
10.1016/j.fuel.2012.01.014.
[33] Liu Z, Li Z, Song X, Zhang J, Zhang L, Zhang L, Zhao S. Dynamic interfacial tensions
of binary nonionic–anionic and nonionic surfactant mixtures at water–alkane in-
terfaces. Fuel 2014;135:91–8. https://doi.org/10.1016/j.fuel.2014.06.031.
[34] Cao J, Zhou Z, Xu Z, Zhang Q, Li S, Cui H, et al. Synergism/Antagonism between
crude oil fractions and novel betaine solutions in reducing interfacial tension.
Energy Fuels 2016;30:924–32. https://doi.org/10.1021/acs.energyfuels.5b02566.
[35] Rudin J, Bernard C, Wasan DT. Effect of added surfactant on interfacial tension and
spontaneous emulsification in alkali/acidic oil systems. Ind Eng Chem Res
412
Fuel 239 (2019) 403–412
1994;33:1150–8. https://doi.org/10.1021/ie00029a012.
[36] Bera A, Ojha K, Mandal A, Kumar T. Interfacial tension and phase behavior of
surfactant-brine–oil system. Colloids Surfaces A: Physicochem Eng Aspects
2011;383:114–9. https://doi.org/10.1016/j.colsurfa.2011.03.035.
[37] Bera A, Mandal A, Guha BB. Synergistic effect of surfactant and salt mixture on
interfacial tension reduction between crude oil and water in enhanced oil recovery.
J Chem Eng Data 2014;59:89–96. https://doi.org/10.1021/je400850c.
[38] Trados TF. Applied surfactants: principles and application. Wiley-VCH 2005.
https://doi.org/10.1002/3527604812.
[39] Rosen MJ. Surfactants and interfacial phenomena. 3rd ed. Hoboken, New Jersey:
John Wiley & Sons Inc; 2004.
[40] Kmetz AA, Becker MD, Lyon BA, Foster E, Xue Z, Johnston KP, et al. Improved
mobility of magnetite nanoparticles at high salinity with polymers and surfactants.
Energy Fuels 2016;30:1915–26. https://doi.org/10.1021/acs.energyfuels.5b01785.