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Fuel 239 (2019) 403–412

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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
Instituto de Química – Universidade Federal do Rio de Janeiro, Cidade Universitária, 21941-909 Rio de Janeiro, RJ, Brazil
Departamento de Química – Pontifícia, Universidade Católica do Rio de Janeiro, Gávea, 22451-900 Rio de Janeiro, RJ, Brazil



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: (J.C.S. Rosestolato).
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. Fuel 239 (2019) 403–412

1. Introduction These nanoparticles swell when in contact with the oil phase, releasing
the surfactant and reducing the water/oil interfacial tension [14].
A great effort has been made worldwide to improve the oil recovery. The purpose of the present work was to develop a new type of
Although millions of barrels are extracted per day from the oil fields, surfactant nanocarrier for EOR, employing lipid nanoparticles. The
conventional oil recovery methods (primary or secondary) are capable studied nanocarrier presents a hydrophobic structure, capable of
to remove only approximately 40% of the total oil initially contained in storing and releasing the surfactant molecules directly at the water/oil
a reservoir. The residual oil is trapped in the porous media by strong interface, preventing the surfactant losses by adsorption on the rocks
capillary forces and demands very low interfacial tensions for its dis- surface. At reservoir’s temperatures below the lipid melting point, the
placement. Tertiary oil recovery techniques (or enhanced oil recovery – surfactant release is triggered by the solubilization of the solid lipid
EOR) can be implemented in order to remove oil beyond conventional nanocarriers at the oil surface, based on the hydrophobic nanoparticles
methods. In some of the EOR processes, specific chemicals are injected character. At reservoir’s temperatures above the lipid melting point, the
and interact with the oil/water/rock system in order to create favorable nanostructure works as a surfactant nanoencapsulator in an emulsion
conditions for oil displacement. These interactions have a physico- form, releasing the surfactant by the direct solubilization of lipid na-
chemical nature and might reduce the water/oil (w/o) interfacial ten- nodroplets at the oil surface, promoting the reduction of the w/o in-
sion (IFT), increase the viscosity of injection fluid, modify the rock terfacial tension and improving the oil recovery. The design of the lipid
wettability or create a favorable phase behavior [1]. nanocarriers structure was inspired by processes employed in the pro-
An important method of tertiary oil recovery is the surfactant duction of nanoparticles for drug delivery systems (Solid Lipid
flooding. Surfactants have an amphiphilic structure and tend to reduce Nanoparticle – SLN). The nanocarriers were obtained employing
the energy of the w/o interface. The changes on interfacial properties beeswax (BW) as lipid matrix and nonylphenol ethoxylate (NPE10) as
improve the displacement efficiency, mobilizing the residual oil into the surfactant, based on the good results of nanoparticle stability [15] and
production well [2]. Wu et al., for example, reported an experimental oil recovery in EOR processes [3]. The results from this study are pre-
study using different types of surfactants (cationic, anionic and non- sented and discussed in this article, and it is proposed the use of these
ionic) for an EOR process. They observed that the reduction in the in- structures as a model for surfactant nanocarriers with potential to be
terfacial tension between the oil and the aqueous phase was the main employed in EOR processes.
cause of faster and larger oil recovery [3]. Surfactant flooding is an
efficient oil recovery method, but surfactant molecules usually have a 2. Materials and methods
strong interaction with the reservoir rock surfaces and a large part of
the injected surfactant is lost by adsorption before reaching the oil site. 2.1. Materials
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 Blanched beeswax (BW) (Sigma-Aldrich) was used as the solid lipid
economically unfeasible [4]. matrix and nonylphenol ethoxylates (NPE10 –
Nanostructured materials have been widely used in petroleum re- (C9H19)C6H4(OCH2CH2)10OH, RENEX100™ by Oxiteno, Brazil) as the
search due to their interfacial properties, mainly for their use in EOR. nonionic surfactant. For the interfacial tension measurements, the oil
Nanoparticles have the ability to modify the water/oil and oil/rock phase was a 1:1 mixture (v/v) of n-heptane and toluene named as
interfaces, reducing the interfacial tension, increasing emulsion stabi- heptol (both solvents were purchased from Vetec Química, Brazil).
lity, inhibiting asphaltene precipitation, and changing the rock surface Heptol is a hydrocarbon mixture chosen to simulate oil with aliphatic
wettability [5]. Several types of nanoparticles have been used to sta- and aromatic characteristics. Sodium chloride (Vetec Química, Brazil)
bilize microemulsions [6,7]. Zhang et al., for example, highlighted the was used to prepare the saline solutions. Cellulose dialysis tubing (MW
use of surface-coated nanosilica that tend to strongly interact with the cut-off range: 14 KDa) was obtained from Sigma Aldrich, Brazil.
water/oil interface, increasing the emulsions stability by the formation Distilled water was used in all the experiments and all the materials
of a monolayer on the droplets surface (Pickering emulsion) [7]. Kon- were used as obtained from their manufacturers, without further pur-
diparty et al. proposed the use of silica nanoparticles for modifying the ification.
reservoirs rock surface. These nanoparticles would form a structural
film between the discontinuous phase (oil) and the solid phase (rocks 2.2. Preparation of the surfactant nanocarriers
surface), displacing the oil through the achievement of a structural
disjunction pressure [8]. The literature shows many other applications The nanocarriers were prepared using a high-energy emulsification
of nanoparticles in EOR. However, most of these particles are of in- method by ultrasonication [16]. First, the surfactant NPE10 was dis-
organic nature and usually tend to be integrally adsorbed at the water/ solved in melted beeswax at 67 °C (2 °C above the wax melting point) to
oil/rock interfaces [9]. obtain a clear liquid. In a second step, hot water, at that same tem-
In recent years, nanomaterials have gained special attention when perature, was added to the melted wax/surfactant mixture and stirred
employed to prevent the surfactant adsorption on the rocky reservoir with a magnetic stirring bar for three minutes. The obtained pre-
surface [10–12]. These nanomaterials have a specific structure capable emulsion was ultrasonified using a probe sonicator UP200S (Hielscher)
of interacting with surfactant molecules and working as nanocarriers to with power output (amplitude of 100%) for three minutes. The soni-
avoid the surfactant losses. Romero-Zeon et al. used nanocarriers based cator’s cavitation waves lead to the wax droplets breakage and the
on the inclusion complex formed between surfactants and β-cyclodex- subsequent nanoemulsion formation. The temperature was kept at
trin molecules [10]. Chen et al. proposed the use of carbonaceous na- 67 ± 0.5 °C throughout these steps by a thermostatic water bath. The
noparticles (multi-wallet nanotubes and carbon black). The combina- nanocarrier was obtained by the cooling of the nanoemulsion in an ice
tion of the large specific area and strong affinity for the surfactant bath. Nanocarriers were produced with the wax concentration at 1.0%
molecules by the nanoparticles did lead to a competitive surfactant (m/v) and the surfactant concentration ranging from 0.1% to 1.0% (m/
adsorption process between the nanoparticles and the rock surface, v) in order to reach an optimized procedure.
decreasing the surfactant losses on the rock reservoir surface [11]. Some of the nanoparticles suspensions were submitted to a pur-
Our research group is committed to developing new technologies for ification process through dialysis in order to remove the free surfactant
interfacial properties control and oil recovery improvement [13,14]. from the nanoparticles aqueous suspension. 20 mL of the NPS suspen-
Avila et al. the use of crosslinked polystyrene nanoparticles as surfac- sion was placed inside the dialysis bag (cellulose membrane), which
tant nanocarriers for preventing the surfactant losses that occur by was immersed in 200 mL of distilled water at room temperature
adsorption on the rock surface in enhanced oil recovery processes. (∼25 °C). The outer aqueous medium was continuously changed and

J.C.S. Rosestolato et al. Fuel 239 (2019) 403–412

monitored by UV–Vis spectrophotometer (SP220, Spectrolab) at The γ values were obtained for different formulations for the aqueous
275 nm, characteristic wavelength of the NPE10 surfactant aromatic phase (distilled water, surfactant solution or nanocarriers suspensions)
ring. The dialyzed nanocarrier aqueous suspension was mentioned in and oil phase (heptol or beeswax solution in heptol). The surfactant
this paper as purified system. concentration used was 0.1% (m/v) (1000 ppm). The effects of the salt
concentration and of the NPs purification (dialysis process applied to
2.3. Nanoparticles characterization the NPs suspension to remove free surfactant from the aqueous
solution) were evaluated. The reported values are the average of
2.3.1. Particle size three determinations.
Particle size (hydrodynamic diameter) and polydispersity index
(PDI) were determined by dynamic light scattering (DLS) using a FTIR of oil phase. After performing interfacial tension
Zetasizer Nano ZS (Malvern Instrument, Germany). The nanocarriers measurements by the ring method, an aliquot of the oil phase was
aqueous suspension was diluted with distilled water at an appropriate withdrawn, evaporated and the residue analyzed by Fourier transform
scattering intensity and data were analyzed by a cumulant method as- infrared spectroscopy (FTIR). The FTIR measurements were performed
suming spherical particles. The DLS technique was used for monitoring in a Magna-IR 740 spectrometer (Nicolet, USA) in a range of
the effect of the surfactant concentration, the storage stability at room 400–4000 cm−1. The observation of the beeswax characteristic bands
temperature and the nanocarrier’s stability at different temperatures in the FTIR spectra would be a qualitative evaluation of the
(25–75 °C) on the nanoparticles size. Each analysis was carried out in nanoparticles solubility and of the surfactant release in the oil phase.
triplicate and the data expressed as the mean value.
2.4.2. Spinning drop method
2.3.2. Scanning electron microscopy – SEM The w/o interfacial tension (IFT) for the different systems was de-
Scanning electron microscopy was used to study the surface topo- termined using the Site100 spinning drop tensiometer (Krüss, Germany)
graphy and morphology of the nanocarriers obtained. Prior to analysis, through a built-in software system based on the Vonnegut Equation.
the nanoparticles suspension was placed on aluminium stubs, dried in a Before the IFT measurement, the density of all analyzed solutions was
desiccator and coated with gold, using a sputter coater device (K550, previously determined by interpolation in a standard density curve as a
Emitech). The morphology of the dried nanoparticles was examined function of temperature by a DMA 35 EX densimeter (Anton Parr,
using the JSM-6460 (Jeol) operated at an accelerating voltage of 15 kV. Germany). All surfactant solutions and NPs suspensions were previously
centrifuged at 3000 rpm in a traditional centrifuge for 20 min to
2.3.3. Differential scanning calorimetry – DSC minimize the formation of bubbles at the tensiometer’s capillary. The
Thermal behavior characterization of the wax matrix and nano- measurements were carried out until the equilibrium condition was
carriers were carried out using a differential scanning calorimeter (DSC reached at temperatures of 30 °C and 66 °C ( ± 0.2 °C) in a constant
7, Perkin Elmer). A mass of 1–2 mg of dried sample was weighted and speed rotation between 4000 and 6000 rpm. The IFT measurements
sealed in an aluminium pan. Thermal analysis was performed in a were performed for at least 40 min and finished when the equilibrium
heating rate of 10 °C/min and temperature range of 30–80 °C. condition was reached, i.e., when the IFT values remained unchanged
for 10 min. The effects of salt concentration, NPs purification and
2.3.4. Determination of surfactant entrapment in the nanocarriers temperature on the IFT were evaluated.
The surfactant entrapment is the relative concentration of surfactant In order to better understand the interfacial tension values obtained
loaded in the nanocarriers and was indirectly determined by measuring at high temperature, cloud point of the NPE10 surfactant solutions was
the free surfactant concentration in the aqueous medium. The free investigated. The cloud point values were determined through visual
surfactant was isolated from the nanocarriers suspension by centrifugal observation of the temperature transition from a clean to a turbid ap-
filtration along with 100 kDa molecular weight cut-off centrifugal filter pearance of solution, at a surfactant concentration of 0.1% (m/v) and a
units (Amicon® Ultra-4, Millipore). Briefly, 2 mL of NPs suspension was NaCl concentration between 0% and 5% (m/v).
placed in the filter device and centrifuged at 3000 rpm for 40 min. The
degree of entrapment was indirectly evaluated by quantifying the sur- 2.5. Column test: unconsolidated porous media experiments
factant in the supernatant by UV–Vis spectrophotometry at 275 nm
[17]. The experiments were performed in duplicates, using a previously The transport behavior of the nanoparticle suspensions was assessed
determined calibration curve. by experiments in unconsolidated sandpack column test [18]. The
porous media apparatus consists in a liquid chromatography column
2.4. Surfactant release evaluation (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-
In order to better understand the interfacial properties, two com- Parmer). The column was packed with sand of 30–100 mesh
plementary methodologies were used to measure the IFT: du Noüy ring (595–149 µm) extracted from Copacabana Beach (Rio de Janeiro,
and spinning drop. The ring method was used as a preliminary analysis, Brazil) and sealed with two PTFE (polytetrafluoroethylene) end fittings
being suitable for the measurement of high interfacial tension values. with 20 μm porosity. The sand used was previously washed with dis-
The spinning drop tensiometer is indicated for low interfacial tension tilled water and calcined at 600 °C for 4 h to remove organic com-
values and also allowed for measurements at higher temperatures. The pounds. The sand porosity was determined by the direct measurement
oil phase from the interfacial tension measurements with the ring ten- based on the ratio between the volume of distilled water inside the
siometer was analyzed by FTIR spectroscopy to determine the presence pores and the total bulk volume of the unconsolidated sand. The por-
of beeswax and surfactant in the heptol as a consequence of the na- osity of the sand used in all experiments was 30%. After the packing,
noparticles solubilization and therefore surfactant release. the column was completely saturated with water and a tracer test was
performed injecting a NaNO3 solution to assess the non-reactive flow
2.4.1. Ring method interfacial tension measurement and FTIR spectroscopy behavior [19]. The nanoparticles transport behavior was carried out at IFT measurements by the ring method. The interfacial tension (γ) room temperature with the injection of 3 pore volume (PV) of distilled
was measured by the du Noüy ring method using a digital K9 water, 3 PV of surfactant solution or nanoparticle suspension, and is
tensiometer (Krüss, Germany). All measurements were carried out finishes with the injection of 4 PV of distilled water. In the column test,
with equal volumes (25 mL) of the aqueous and heptol phases, at the concentration of the injected fluid was 0.1% (m/v) with a pumping
room temperature (∼25 °C), until equilibrium was reached (after 24 h). flow rate of 0.5 mL/min. Effluents were collected every ¼ PV and

J.C.S. Rosestolato et al. Fuel 239 (2019) 403–412

analyzed in a UV–Vis spectrophotometer at 275 nm and 633 nm to 3.1.2. Scanning electron microscopy
determine the surfactant and NPs concentrations, respectively. The Scanning electron microscopy (SEM) was employed to reveal the
results were plotted as relative concentration C/C0 (ratio between the morphology of the nanoparticles. The SEM is also a way to confirm the
surfactant or particle recovery and the initial concentration injected) particle size of NPs measured by DLS. The SEM image (Fig. 3) reveals
and expressed as a breakthrough curve as a function of the pore volume nanoparticles with a size below 200 nm, which is consistent with the
(PV). particle size obtained by the DLS technique. The nanocarriers show
spherical shape morphology, result of the typical nanoparticles pro-
3. Results and discussion duction from nano-emulsification processes [23]. The SEM image also
suggests a wide aggregation of the particles, but this may not ne-
This investigation presents the evaluation of lipid nanoparticles as cessarily represent the real dispersion state of the nanoparticles in
model surfactant nanocarriers for the EOR process. The nanoparticles water suspension, since the aggregation could have occurred during the
obtained were characterized in terms of size, storage stability, scanning drying process in the sample preparation for SEM analysis.
electron microscopy (SEM), differential scanning calorimeter (DSC) and
surfactant entrapment capacity. Interfacial tension behavior and FTIR 3.1.3. Differential scanning calorimetry – DSC
results were used to study the surfactant release at the oil surface, DSC was the technique used to investigate the thermal behavior of
evaluating the effect of the nanoparticles purification, salt concentra- NPE10/BW mixture and of the nanoparticles in endothermic process.
tion and temperature. Besides, a sandpack column test was used to Fig. 4 exhibits the DSC curves of pure beeswax, blends of 30% and 50%
evaluate the transport behavior of the nanoparticles through un- of NPE10 in beeswax, and lipid nanocarriers obtained with 50% of
consolidated porous media. NPE10/BW.
The analysis of the DSC curves shows that the surfactant in-
3.1. Nanocarriers characterization corporation into the lipid matrix results in a reduction of the lipid
melting temperature and of the process enthalpy change. This phe-
3.1.1. Effect of surfactant concentration and nanoparticles stability nomenon can be attributed to a disorder in the lipid matrix structure
Table 1 shows the effect of the surfactant concentration on the induced by a heterogeneous composition from the surfactant in-
particle size and polydispersity Index (PDI) for the obtained nano- corporation [24]. The less ordered arrangement of the lipid molecules
particle suspensions, as measured by dynamic light scattering, 24 h creates imperfections in the structure, improving the surfactant in-
after NPs production. corporation and the physical stability of the lipid matrix [21]. There is
The PDI was slightly influenced by the surfactant concentration. On also a decrease of the melting temperature and of the process variation
the other hand, the increase in NPE10 concentration decreases the of enthalpy (ΔH) for the nanoparticle, as compared to the one for the
mean particle size from 234 to 118 nm. The particle size reduction is bulk material (50% of NPE10). These changes in the NPs system’s
probably caused by the increase of the lipid droplets stability due to the thermal behavior occur due to an increase of the surface/volume ratio.
formation of a surfactant molecular film on the surface of the lipid Surface atoms have less cohesive energy when compared to the atoms
droplets in the nano-emulsification process [20]. It is possible to note in the bulk, reducing the required energy to melt. This trend can be
that the size of the nanoparticles remains constant from 0.5% (m/v) of established by the Gibbs-Thomson Equation which describes the
surfactant which is an important result for surfactant concentration melting point reduction with the decrease of the particles radius [25].
optimization. Thus, in subsequent experiments, the nanoparticles were Although there is an effect of the surfactant incorporation and the na-
obtained using 1.0% (m/v) of surfactant to achieve greater surfactant noparticles formation on the DSC curve, the melting temperature for
incorporation. the produced nanoparticles is only 6% lower than the one for the pure
In relation to storage stability, the nanocarriers were characterized lipid.
regarding z-average diameter and polydispersity index. Fig. 1 shows the
particle size of the nanocarrier’s suspension during three months of
3.1.4. Determination of surfactant entrapment in the NPs
storage at room temperature (∼25 °C). After three months, the nano-
The efficiency of surfactant entrapment was determined by quan-
particles kept their narrow size distribution (PDI ∼ 0.27) and the same
tifying the free surfactant in the NPs suspensions (indirect method)
particle size range. The good stability of nanoparticles suspension could
through UV–Vis spectroscopy. The results show that the NPE10 con-
be attributed to the steric effect from the nonionic surfactant [21].
centration in the nanoparticles was of 0.48 g/g (wt %), showing an
The nanoparticles obtained in this work show a size compatible with
incorporation of 96% (m/m) of the total surfactant used in the nano-
similar ones from the literature. Attama et al., for example, produced
particles production. The great solubility of the surfactant in the lipid
solid lipid nanoparticles with beeswax and the nonionic surfactant
medium is a reflection of the chemical environment inside the NPs. The
polysorbate 80, showing a z-average < 200 nm and a PDI around 0.2,
NPE10 molecules may be stabilized by van der Walls and hydrogen
with the nanoparticles being stable for more than three months [15].
bonding interactions with the BW matrix, increasing the surfactant
Fig. 2 shows the effect of temperature on the surfactant nanocarriers
entrapment in the nanoparticle. This result of surfactant entrapment is
particles size in aqueous suspensions with the temperatures ranging
in agreement with other works in the literature for the incorporation of
from 25 °C to 75 °C.
drugs into the solid lipid nanoparticles structure [17,21]. Kher-
It is possible to note that the lipid nanoparticles in aqueous sus-
admandnia et al., for example, studied the incorporation of the Keto-
pension were stable at temperatures up to 75 °C, showing a small de-
profen as a model drug into the SLNs prepared from a mixture of
crease in particle size with temperature increase. The high stability of
beeswax and carnauba wax. They obtained a high entrapment of 97% of
the nanocarriers may be caused by the steric effect of the NPE10 sur-
the drug in the lipid matrix, which is compatible with our entrapment
factant that being adsorbed on the surface of the lipid droplets, would
results of the NPE10 surfactant in beeswax nanoparticles [21].
promote high stability even above the lipid melting point. The eva-
luation of the nanoparticles stability is fundamental for the application
Table 1
of NPs in EOR processes. Alomair et al. did study the effect of different Surfactant concentration effect: Z-average and PDI of NPs suspension for-
types of nanofluids on the recovery of heavy crude oil. They concluded mulated with different surfactant concentration.
that nanoparticles in the order of hundreds of nm are smaller than the
NPE10 concentration (m/v) 0.1% 0.25% 0.5% 1.0%
pore and the throat size of the reservoirs rock. Thus, the lipid nano-
z-average size (nm) 234 146 119 118
particle suspensions developed in this work would have a suitable size Polydispersity Index (PDI) 0.29 0.22 0.24 0.26
for a traditional injection and flow through the porous media [22].

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

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
Fig. 2. Nanocarrier’s stability: effect of temperature on particles size. 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-
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.

J.C.S. Rosestolato et al. Fuel 239 (2019) 403–412

the beeswax composition. The BW is composed by an esters, alcohols It can be observed that the IFT decreases progressively to reach a
and fatty acids mixture, which plays a role as surfactant species, as- plateau over time (equilibrium condition). The reduction of IFT is a
sisting in the interfacial tension reduction [26]. Thus, besides working common feature in the natural replacement of solvent molecules at the
as a carriage medium for the surfactant, the lipid matrix could be also interface by surfactant molecules, which provides a typical L-shape
acting as a surfactant, reducing the IFT. On the other hand, the IFT curve. For better visualization and comparison among results, L-shape
between the NPE10 aqueous solution and BW in heptol (S5 System) was curves for the next experiments are presented only at the minimum
4.0mN/m, which is similar to the result obtained for NPE10 surfactant interfacial tension (IFTmim), when the equilibrium conditions are
solution and pure heptol. This fact indicates that there is no synergism reached. Fig. 7 shows the IFTmin between heptol and NPE10 aqueous
between the NPE10 surfactant and BW molecules and, probably, the solution, NPE10/BW blend and nanoparticles suspension (purified or
NPE10 molecules were preferentially adsorbed at the interface, in without purification), at various salt concentrations.
detriment of beeswax molecules. The IFT shown by the unpurified na- It is possible to observe that there is no significant variation of IFT
noparticle system (S7 system) was 12.4 mN/m, which is higher than the for the systems of NPE10 and NPE10/BW (overlapping data). The IFT of
one presented by NPE10/BW solutions. In addition, the effect of pur- both NPE10 surfactant solution and NPE10/BW solution were around
ification and of salinity on the IFT of nanocarriers was studied (S8, S9 0.8mN/m, showing a little increase with the salt concentration. It is
and S10 systems). The IFT value of the purified NPs suspension was of well known that electrolytes have little effect on the dynamic interfacial
15.6 mN/m and the IFT of the NPs suspension in brine was of 9.8 mN/ tension of nonionic surfactants as compared with the ones for ionic
m. Therefore, when these effects were assessed separately, both pur- surfactants. Iglauer et al. in their study confirm that nonionic surfactant
ification and salinity conditions did lead to higher IFT than the one for formulations may be largely indifferent to salinity even with very high
NPE10/BW surfactant solution in brine (S6 System). However, when NaCl concentrations (up to 20 wt%) [26]. At first sight, these IFT results
these conditions were combined (S10 system), the IFT reached a value obtained with the spinning drop tensiometer are inconsistent with the
below the detection limit of the ring tensiometer (< 1.0 mN/m). These ones from the ring method. While the ring method shows IFT values of
results show that the action of the nanoparticles at the interface was 4.2 mN/m (S3 system) for the NPE10 surfactant solution and 4.0 mN/m
directly affected by the free surfactant and the presence of ions in (S5 system) for the NPE10/BW solutions, the spinning drop measure-
aqueous phase. Since the IFT value was around the detection limit of ments show an IFT of 0.8 mN/m for both systems. This difference in IFT
the ring method, the spinning drop tensiometer was used to clarify the could be attributed to differences in the measurement technique. Yeung
relation between the interfacial tension and surfactant release. The et al. concluded that the IFT of two immiscible liquids depend strongly
mechanism responsible for these interesting IFT differences will be on the experimental design and significant differences in the interfacial
discussed based on the following experimental results. tension could be observed. These variations are attributed to the par-
titioning (distribution) of surfactants between (both bulk) phases and
3.2.2. FTIR of oil phase the interface, which imply in different IFT values depending on the
In order to better understand the interfacial activity, after the IFT employed technique [29]. In this work, these differences in IFT results
measurements by the ring method, an aliquot from the oil phase was were minimized by comparing data obtained from the same measure-
removed, the heptol was evaporated and the residual content was ment technique.
analyzed by Fourier transform infrared spectroscopy (FTIR). FTIR Fig. 7 also shows the IFT between nanocarrier suspensions and
spectrometry was performed as a qualitative analysis to verify the heptol. As it can be seen, the IFT for both types of nanoparticle sus-
presence of beeswax and NPE10 in the oil phase. Fig. 5 allows the pensions (purified or not) were higher than the ones for the surfactant
comparison between NPE10 surfactant, BW lipid and residual content systems (NPE10 and NPE10/BW) and decreased fast with salinity. The
of oil phase from S7 and S10 systems spectra (described in Table 2, item addition of 5% (m/v) of NaCl reduced the IFT for the purified nano-
3.2.1). particle system from 10.6 to 0.91 mN/m and from 7.2 to 3.2 mN/m for
The beeswax is a mixture of several compounds and comprises long the unpurified. The reduction of the IFT values may be related with the
chain esters, aliphatic alcohols and free acids [27]. The principal ab- destabilization of the surfactant and the nanoparticles in aqueous phase
sorption band of BW appears around 1750–1735 cm−1 due to the car- promoted by an increase of salt concentration. There is a dehydration of
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 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 Fig. 5. FTIR spectra of NPE10, BW and residual content of oil phase from S7
dynamic IFT curve between heptol and NPE10 solutions at various and S10 systems. The letters A and B identify the spectra of BW and NPE10 and
salinities, containing 0% to 5% (m/v) of NaCl. the letters C and D the spectra of S7 and S10 systems, respectively.

J.C.S. Rosestolato et al. 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. 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,
Fig. 6. Interfacial tension (IFT) for NPE10 solution (1000 ppm) and heptol as a increasing the solubilization rate of the surfactant nanocarriers and,
function of time, for several NaCl concentrations, at 30 °C. 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. 7. Minimum interfacial tension (IFTmin) between heptol and NPE10 aqu- Fig. 10, which shows that the interfacial tension of the surfactant and
eous solution, NPE10/BW blend and nanoparticles suspension (with or without
NPs systems tends to be reduced with an increase in salt concentration.
purification) as a function of NaCl 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
the surfactant head group and the nanoparticles become relatively more
aqueous solutions and by low NPs hydrophobicity (as discussed above,
hydrophobic. Neutral electrolytes, such as NaCl, may change the sur-
item 3.2.3). Nevertheless, with an increase of NaCl concentration, the
factant and nanoparticle distribution in the oil and aqueous phases and
interfacial tension curves for purified and unpurified NPs are similar to
in the w/o interface due to a salting-out effect [30]. Fig. 8 illustrates the
those for surfactants, converging to the similar interfacial tension value
general behavior of nanoparticles (inorganic or organic) at w/o inter-
(∼0.2 mN/m). This behavior could be associated with the cloud point
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 Fig. 8. Schematic representation of nanoparticle at water/oil interface. The
FTIR results from the ring measurements (item 3.2.1 and 3.2.2), it is contact angle increases with nanoparticle hydrophobicity.

J.C.S. Rosestolato et al. Fuel 239 (2019) 403–412

Fig. 9a. IFT behavior of unpurified nanoparticle in different salt concentrations Fig. 10. IFTmin of NPE10 surfactant, NPE10/BW system, unpurified and pur-
at 66 °C. 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-
Fig. 9b. IFT behavior of purified nanoparticles with different salt concentra- jection.
tions at 66 °C. 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,
effect of the nonionic surfactant. Table 3 shows the experimental results increasing until the saturation point at 2.5 PV. Thereafter, the relative
obtained for the cloud point of NPE10 surfactant at a concentration of concentration decreases as a result of the distilled water injection from
0.1% (m/v) as a function of salt concentration. 4.0 PV. The effluents mass recoveries were 93% for the surfactant and
It is possible to see that the cloud point decreases with the increase 90% for the NPs. The lower surfactant and NPs adsorption on the sand
of electrolyte concentration. At 66 °C, the surfactant and NPs systems surface can be attributed to the surfactant characteristics. In general,
were above the cloud point for samples containing NaCl concentrations nonionic surfactants, such as NPE10, have low adsorption compared to
equal or greater than 1%, which explains the great IFT reduction of the ionic surfactants [39]. The ethylene oxide chains of the surfactant hy-
systems between 0% and 1% NaCl (Fig. 10). These results can be related drophilic head groups have strong interaction (hydrogen bonding) with
to the characteristic of nonionic surfactants. The polyoxyethylene oxide the water molecules, resulting in an excellent stability in the aqueous
chain of the NPE10 surfactant becomes dehydrated above the cloud medium and, consequently, a low adsorption on the solid surface.
point temperature and tends to be less soluble in the aqueous phase. As Beeswax NPs mobility evaluation in a column test was not found in the
a result, the surfactant and NPs tend to leave from the aqueous phase to literature (which highlights the originality of this work). On the other
the w/o interface, increasing the NPs solubilization process [36–38]. hand, there are numerous works that perform tests in porous media
Therefore, the lipid nanoparticles responded positively to both tem- with inorganic nanoparticles like silica and magnetite [18,40]. Kmetz
perature and salt effects; being more efficient in the interfacial tension et al. studied the transport of aqueous suspensions of magnetite nano-
reduction at higher temperatures and also with the increase of the NaCl particles in unconsolidated porous media of Ottawa sand. The mass
concentration, which are interesting features present in the oil re- recovery of the magnetite in the effluent depends directly on the
servoir. 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. 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.
[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.
[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.
[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.
[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.
[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.
[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
[12] Nourafkan E, Hu Z, Wen D. Nanoparticle-enabled delivery of surfactants in porous
media. J Colloid Interface Sci 2018;519:44–57.
Fig. 11. Measured effluent breakthrough curves obtained for injection of 0.1% [13] Gramatges AP, Matheus CRV, Lopes G, Silva JC, Nascimento RSV. Surface and in-
(m/v) of surfactant NPE10 and nanoparticle in an unconsolidated sand column. terfacial tension study of interactions between water-soluble cationic and hydro-
The cross symbol corresponds to nonreactive tracer (NaNO3). phobically modified chitosans and nonylphenol ethoxylate. Colloids Surfaces A:
Physicochem Eng Aspects 2013;418:124–30.
which emphasizes the great potential of this system as surfactant na- [14] Avila JNL, Araujo LLGC, Drexler S, Rodrigues JA, Nascimento RSV. Polystyrene
nanoparticles as surfactant carriers for enhanced oil recovery. J Appl Polym Sci
nocarriers for EOR process.
[15] Attama AA, Müller-Goymanna CC. Effect of beeswax modification on the lipid
4. Conclusion matrix and solid lipid nanoparticle crystallinity. Colloids Surfaces A: Physicochem
Eng Aspects 2008;315:189–95.
[16] Anton N, Benoit J, Saulnier P. Design and production of nanoparticles formulated
In this work, the potential of a new type of surfactant nanocarrier from nano-emulsion templates – a review. J Control Release 2008;128:185–99.
for enhanced oil recovery was evaluated. Organic nanoparticles (NPs)
were used as model for selective surfactant nanocarriers. These NPs, [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.
formed by a lipid matrix, were capable of surfactant storage in their [18] Xue Z, Foster E, Wang Y, Nayak S, Cheng V, Ngo VW, et al. Effect of grafted co-
core and of releasing the surfactant directly at the oil surface. polymer composition on iron oxide nanoparticle stability and transport in porous
Nanoparticles were obtained with lipid beeswax (BW) and nonylphenol media at high salinity. Energy Fuels 2014;28:3655–65.
ethoxylate (NPE10) surfactant, and successfully characterized by DLS, [19] Grolimund D, Elimelech M, Borkovec M, Barmettler K, Kretzschmar R, Sticher H.
SEM, DSC and surfactant entrapment. The results demonstrate that the Transport of in situ mobilized colloidal particles in packed soil columns. Environ Sci
NPs were stable for three month with a hydrodynamic diameter smaller Technol 1998;32:3562–9.
[20] Attama AA, Müller-Goymanna CC. Investigation of surface-modified solid lipid
than 150 nm in a spherical shape. These nanocarriers showed a storage nanocontainers formulated with a heterolipid-templated homolipid. Int J Pharm
capacity of 96% of surfactant and exhibited high mobility in porous 2007;334:179–89.
media of unconsolidated sandpack column. The surfactant release was [21] Kheradmandnia S, Vasheghani-Farahani E, Nosrati M, Atyabi F. Preparation and
characterization of ketoprofen-loaded solid lipid nanoparticles made from beeswax
verified by interfacial tension (IFT) measurements (ring and spinning
and carnauba wax. Nanomed: NBM 2010;6:753–9.
drop methods) and FTIR analyses of oil phase. The IFT of the nano- 2010.06.003.
carrier system was compatible with IFT values of the NPE10 surfactant [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,
solutions, while FTIR analyses confirm the nanoparticle solubilization
Australia; 2014.
by the detection of beeswax in the oil phase. The NPs purification [23] Seetapan N, Bejrapha P, Srinuanchai W, Ruktanonchai UR. Rheological and mor-
process, salt concentration and temperature increase did favor the in- phological characterizations on physical stabilityof gamma-oryzanol-loaded solid
terfacial tension reduction due to improvements on nanoparticle solu- lipid nanoparticles (SLNs). Micron 2010;41:51–8.
bility in the oil phase. [24] Attama AA, Schicke BC, Müller-Goymann CC. Further characterization of theo-
broma oil–beeswax admixtures as lipid matrices for improved drug delivery sys-
Acknowledgements tems. Eur J Pharm Biopharm 2006;64:294–306.
[25] Han F, Li S, Yin R, Liu H, Xu L. Effect of surfactants on the formation and char-
The authors gratefully acknowledge the Instituto de Química (UFRJ, acterization of a new type of colloidal drug delivery system: nanostructured lipid
Brazil) and the financial support in part by the Coordenação de carriers. Colloids Surfaces A: Physicochem Eng Aspects 2008;315:210–6. https://
Aperfeiçoamento de Pessoal de Nível Superior (CAPES, Brazil) – [26] Iglauer S, Wu Y, Shulera P, Tanga Y, Goddard III WA. Alkyl polyglycoside surfac-
Finance Code 001 and Petrobras, Brazil. tant–alcohol cosolvent formulations for improved oil recovery. Colloids Surf
APhysicochem Eng Aspects 2009;339:48–59.
[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
[1] Donalson EC, Chilingarian GV, Ten TF. Enhanced oil recovery, I fundamentals and role in liquid oil structuring. Food Chem 2017;214:717–25.
analyses. Developments in Petroleum science vol. 17A. New York: Elsevier Science; 1016/j.foodchem.2016.07.123.
1985. [28] Silverstein RM, Webster FX, Kiemle DJ. Spectrometric identification of organic
[2] Guo K, Li H, Yu Z. In-situ heavy and extra-heavy oil recovery: a review. Fuel compounds. 7th ed. John Wiley Sons; 2005.
2016;185:886–902. [29] Yeung A, Dabros T, Masliyah J. Does equilibrium interfacial tension depend on
[3] Wu Y, Shuler PJ, Blanco M, Tang Y, Goddard WA. An experimental study of wetting method of measurement? J Colloid Interface Sci 1998;208:241–7.
behavior and surfactant EOR in carbonates with model compounds. SPE J 10.1006/jcis.1998.5807.
2008;13:26–34. [30] Bai J, Fan W, Nan G, Li S, Yu B. Influence of interaction between heavy oil com-
[4] Green DW, Willhite GP. Enhenced oil recovery. In: SPE textbook, vol 6, Texas; 1998. ponents and petroleum sulfonate on the oil-water interfacial tension. J Dispersion
[5] Hendraningrat L, Li S, Torsater O. Effect of some parameters influencing enhanced Sci Technol 2010;31:551–6.

J.C.S. Rosestolato et al. Fuel 239 (2019) 403–412

[31] Maestro A, Guzmán E, Ortega F, Rubioc RG. Contact angle of micro- and nano- 1994;33:1150–8.
particles at fluid interfaces. Curr Opin Colloid Interface Sci 2014;19(4):355–67. [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
[32] Qiao W, Li J, Zhu Y, Cai H. Interfacial tension behavior of double long-chain 1,3,5- 2011;383:114–9.
triazine surfactants for enhanced oil recovery. Fuel 2012;96:220–5. [37] Bera A, Mandal A, Guha BB. Synergistic effect of surfactant and salt mixture on
10.1016/j.fuel.2012.01.014. interfacial tension reduction between crude oil and water in enhanced oil recovery.
[33] Liu Z, Li Z, Song X, Zhang J, Zhang L, Zhang L, Zhao S. Dynamic interfacial tensions J Chem Eng Data 2014;59:89–96.
of binary nonionic–anionic and nonionic surfactant mixtures at water–alkane in- [38] Trados TF. Applied surfactants: principles and application. Wiley-VCH 2005.
terfaces. Fuel 2014;135:91–8.
[34] Cao J, Zhou Z, Xu Z, Zhang Q, Li S, Cui H, et al. Synergism/Antagonism between [39] Rosen MJ. Surfactants and interfacial phenomena. 3rd ed. Hoboken, New Jersey:
crude oil fractions and novel betaine solutions in reducing interfacial tension. John Wiley & Sons Inc; 2004.
Energy Fuels 2016;30:924–32. [40] Kmetz AA, Becker MD, Lyon BA, Foster E, Xue Z, Johnston KP, et al. Improved
[35] Rudin J, Bernard C, Wasan DT. Effect of added surfactant on interfacial tension and mobility of magnetite nanoparticles at high salinity with polymers and surfactants.
spontaneous emulsification in alkali/acidic oil systems. Ind Eng Chem Res Energy Fuels 2016;30:1915–26.