Colloids and Surfaces A 556 (2018) 253–265

Contents lists available at ScienceDirect

Colloids and Surfaces A

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

Application of functionalized silica-graphene nanohybrid for the enhanced T

oil recovery performance
⁎
Sanaz Tajika, Abbas Shahrabadia, Alimorad Rashidia, , Milad Jaliliana, Amir Yadegarib
a
Nanotechnology Research Center, Research Institute of Petroleum Industry (RIPI), P.O. Box 14665-137, Tehran, Iran
b
Department of Developmental Sciences, Marquette University School of Dentistry, Milwaukee, WI, 53233, USA

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Nanoparticles as a part of nanotechnology have drawn numerous attentions for its great potential of enhancing oil
Functionalized silica-graphene nanohybrids recovery. However, the role of nanoparticles in this field is still in its infancy and consequently has attracted much
Interfacial tension more attention in the last decade. The main objective of the current study is the experimentally investigation of
Micromodel functionalized silica-graphene nanohybrids as a novel stabilizer of water-decalin and water-asphaltene emulsions
Pickering emulsion
and its effects on enhanced oil recovery (EOR). The conventional properties of crude oil and the prepared na-
nofluids were measured to examine the EOR mechanisms. The nanofluids were prepared by synthetic brine (4 wt%
NaCl) as the base fluid at various concentrations of the functionalized nanohybrids including 0.01. 0.05, and
0.1 wt%. The phase behavior of the nanohybrids dispersions in presence of NaCl was visually observed. The results
showed that the IFT between oil and water can be reduced to about half of its initial value by employing func-
tionalized silica-graphene nanohybrids. The values of IFT decrease via increasing the concentration of nanofluids
which indicates a great potential application of the proposed nanofluid for EOR. Moreover, a visualization flooding
method (glass micromodel) was employed as a porous media to investigate the EOR mechanisms of the nanofluids.

1. Introduction oil can be recovered from the preliminary extraction steps, enhanced oil
recovery (EOR) has been widely employed for more utilization of oil
The depletion of fossil fuels has recently rung an alarming bell for reserves [1–3]. Up to now, various methods and techniques such as
more exploitation from oilfield. Due to the fact that only 50% of crude water flooding, heat treatment, injection of polymers and surfactants

⁎
Corresponding author.
E-mail addresses: sanaz_tajik@aut.ac.ir (S. Tajik), rashidiam@ripi.ir (A. Rashidi).

https://doi.org/10.1016/j.colsurfa.2018.08.029
Received 16 June 2018; Received in revised form 7 August 2018; Accepted 9 August 2018
Available online 11 August 2018
0927-7757/ © 2018 Elsevier B.V. All rights reserved.
S. Tajik et al.
have been investigated as the most prominent approaches for EOR
[4–7]. Although some of them still suffer from disadvantages such as
sophisticated instruments and low productivity. Hence, developing
novel and applicable techniques for improving the EOR performance is
in great interest. It has been widely demonstrated that after initial oil
extraction, water flooding can be applied as an efficient and economic
technique for keeping the downhole pressure [8]. However, considering
the viscosity and displacement of the crude oil, waterflooding has its
own drawbacks. Therefore, developing an appropriate alternative as the
tertiary enhanced oil recovery is still demanding. Throughout the last
decade, employing of nanofluids instead of conventional fluids led to
high performance oil and gas recovery due to their unique properties
[9,10]. For instance, economically speaking, addition of only 0.01 wt%
nanoparticles could significantly accelerate the EOR process. The pre-
sence of nanoparticles may considerably facilitate the EOR process by
enhancing the well drilling, changing the wettability of rocks, boosting
the mobility of the trapped oil and decreasing the interfacial tension
[11,12]. It should be noted that the impact of nanoparticles on the EOR
performance and oil displacement mechanism need to be further ex-
plored. The alteration of wettability is considered as a critical para-
meter which should be thoroughly investigated during EOR process
[13,14]. Moreover, the estimation of IFT values between the aqueous
and oil phases during nanofluid flooding is another effective parameter.
It has been well documented that IFT can affect the mobilization of
trapped oil through capillary forces [15,16]. Although, in the case of
complex nanofluids, comprehensive and experimental studies for cal-
culation of IFT are very rare, there are a few reports that indicate the
simultaneous using of nanoparticles and anionic surfactant would
dramatically reduce the IFT values. Among the conventional nanoma-
terials, SiO2 nanoparticles have shown high compatibility for improving
the wettability of the rocks and decreasing the IFT [17]. Hendraningrat
et al have used hydrophilic SiO2 nanoparticles as an effective additive
for improving oil recovery [18]. Their experimental studies showed that
the concentration of nanoparticles should be optimized to get the
highest oil recovery in low permeable reservoirs [19]. However, it has
been suggested that the combination of SiO2 nanoparticles with Fe2O3,
MgO, and Al2O3 will provide better results compared to bare silica
nanoparticles [20]. Various kind of organic and inorganic materials
such as solid lipid, silica, carbon, titanium dioxide, and ferric oxide
nanoparticles have been utilized for stabilization of oil-water Pickering
emulsions [21–24]. A small amount of these nanoparticles can produce
stable emulsions with suitable size distribution and superior stability.
Indeed, the addition of nanoparticles replaces the liquid-liquid inter-
faces with solid-liquid interfaces which possess less interfacial energy
[25]. Obviously, nanoparticles would assist the dispersion of im-
miscible droplets into the other liquid leading to produce facile, stable,
and cost-effective emulsifiers [26,27]. The visualization of fluid’s flow
can be investigated by using a two-dimensional porous micromodel
patterns which geometrically simulate a real rock. Generally, micro-
models provide an opportunity for a realistic observation of porous
media in oil recovery which is not possible by other techniques such as
corefloods. However, employing micromodels has been restricted due
to their lack of heterogeneous surface on which flow dynamics can be
dictated. Buchgraber and coworkers designed a two-dimensions mi-
cromodels on microfluidic devices with an analogous porosity to real
rocks for the simulation of porous media [28,29]. In the present study, a
nanohybrid containing silica nanoparticles and graphene was synthe-
sized through chemical vapor deposition method. The main advantage
of this procedure is related to the usage of silica nanoparticles as the
heterogenous catalyst which eliminates further purification and se-
paration of unreacted nanoparticles. Indeed, the silica nanoparticles
have been simultaneously used as the catalyst for growing the graphene
sheets and main part of the nanohybrid. Consequently, the obtained
nanohybrid was chemically functionalized by the evaporation of sul-
furic and nitric acid in gas phase. This technique noticeably promotes
the preparation of the functionalized silica-graphene nanohybrid owing
254
Colloids and Surfaces A 556 (2018) 253–265
to the direct functionalization. Practically, the proposed approach
eliminates the additional steps such as separating, washing, neu-
tralizing, purifying, and drying compared to other reported functiona-
lization methods. To find the best level of functionalization, the time of
exposure and proportion of sulfuric and nitric acid were thoroughly
examined and optimized. The as-prepared functionalized nanohybrid
was used as a novel additive for reducing the IFT values of the crude oil-
brine (4 wt% NaCl). Furthermore, the stability of oil in water emulsions
by adding the functionalized nanohybrid was studied by taking mi-
croscopy images for evaluating the average droplet diameters. Even-
tually, the behavior of the prepared nanofluid in porous media was
visually characterized by designing a glass micromodel.
2. Experimental
2.1. Materials
All the chemical reagents including sulfuric acid (H2SO4, 98%),
nitric acid (HNO3, 65%), hydrochloric acid (HCl 37%), citric acid-hy-
drate, sodium chloride, acetone, toluene, ethylene chloride, methanol,
trichloromethylsilane, decahydronaphthalene (decalin, > 98%), to-
luene (99.9%) and water-glass (Na2SiO3-specific gravity 1.05) were
purchased from Merck. Deionized water (18 MΩ.cm) was used
throughout the experiments. The crude oil was provided from one of
the current oil field in Iran and asphaltene separated from this crude oil.
The API specifications of the crude oil including specific gravity, visc-
osity, and density at ambient temperature were estimated to be 40.5
API, 0.64 cP, and 0.84 g/ml, respectively.
2.2. Synthesis of silica-graphene nanohybrids and their functionalization
The silica-graphene nanohybrid was synthesized according to our
previous report [30]. Briefly, the silica aerogel powder was prepared
through a sol-gel method [31]. The obtained powder was annealed at
600 °C (5 °C/min) in a horizontal quartz tube furnace and the presence
of hydrogen flow (600 sccm). After that, acetylene was used as the
carbon precursor with the flow rate of 100 sccm for 30 min. Finally, the
reactor was cooled down under nitrogen flow to room temperature.
The functionalization of silica-graphene nanohybrid was carried out
in vapor phase by a simple setup (see Fig. S1) as described by our
previous report [32]. It should be noted the silica-graphene nanohybrid
was successfully functionalized in this procedure without direct contact
of the nanohybrid with liquid phase. The functionalization process was
conducted at different time period including 24, 48, and 72 h and the
obtained products are denoted as fsg.24, fsg.48, and fsg.72, respec-
tively. Fig. 1 shows the scheme of the functionalization of the silica-
graphene nanohybrid surface.
2.3. Preparation of Pickering emulsion stabilized by functionalized silica-
graphene nanohybrids
All of the Pickering emulsions were prepared by deionized water
and synthetic brine (4 wt% NaCl) as the aqueous phase and decalin and
asphaltene in toluene as the organic phase with different ratio. The
optimization suggested that the ratio of (1:1 v: v) showed the higher
stability among the other proportions. In a typical water-oil emulsion,
0.1 wt% of the functinalized silica-graphene nanohybrid was ultra-
sonically dispersed in aqueous phase for 30 min by using ultrasonic
bath at 100 W. Subsequently, decalin (or various concentrations of as-
phaltene in toluene) was added and the mixture was further sonicated
at 100 W for 15 min. Finally, the obtained Pickering emulsion was
gently dropped on a glass slide for taking microscopic images.
2.4. Interfacial tension (IFT) measurement
For measuring the IFT values between crude oil and nanofluids the
S. Tajik et al.
Fig. 1. Scheme of the functionalization of the silica-graphene nanohybrid through treatment with a mixture of nitric and sulfuric acid vapors.
Table 1
Micromodel physical properties.
Length 6 cm
Width 4.5cm
Depth 0.1mm
Porosity 36.97%
Pore Volume 0.1 cc
Absolute permeability 11 md
DSA technique was employed. The DSA technique has been introduced
as the best method for the calculation of IFT especially for the range of
3–80 mN/m. Herein, the IFT values were calculated by a drop shape
analysis device (DSA 100, KRUSS, Germany) which works on the base
of pendant drop method. It has been shown that the DSA technique on
the basis of pendant drop would be able to determine the IFT values of
0.05 mN/m due to its full automatic procedure and high accuracy. The
dynamic IFT values were also measured through connecting the IFT
apparatus to computer and running image analysis software. The results
showed that the IFT values fluctuate as a function of time till reach to a
constant value by the passage of time which is introduced as the
equilibrium IFT in this study.
2.5. Micromodel test
The fluid flow on the porous media was directly simulated and
monitored in this study by using a glass micromodel. The micromodel
was designed by chemical etching and laser ablation method which has
been previously described in detail. Prior to begin each test, the glass
micromodel was carefully washed with toluene for removing the sur-
face contaminations and the experiments were conducted at ambient
temperature and pressure. After that, the pre-cleaned porous media was
thoroughly soaked with crude oil and the fluid was then injected at the
rate of 0.03 ml/hr. The physical properties of micromodel are shown in
Table 1. The schematic illustration of the oil-saturated micromodel and
microscopic experimental setup is presented in Fig. 2. It should be
noted that the glass micromodel was horizontally situated for all
flooding experiments. For oil-wet modeling, firstly, the pre-cleaned
glass micromodel was shortly subjected to organic solvent such as to-
luene and acetone, respectively. After that, deionized water was cir-
culated through the micromodel. Subsequently, 20% HCl solution was
injected and circulated to the glass micromodel for a short period of
time and the deionized water was again injected to the micromodel.
Next, the treated micromodel was dried at 200 °C for 15 min. After
drying the micromodel, the solution of 2% trichloromethylsilane
(TCMS) in toluene was injected and methylene chloride was then re-
peatedly pumped and circulated into the micromodel for several times.
255
Colloids and Surfaces A 556 (2018) 253–265
The procedure was followed by the injection and circulation of pure
acetone to the micromodel. At the final step, the preparation procedure
was finished by washing the micromodel with deionized water. The
treated micromodel can be used for modeling oil-wet behavior through
a porous medium. In a typical experiment, crude oil was firstly injected
to prepare an oil-saturated micromodel. Then, the NaCl solution (4 wt
%) was constantly injected into the oil-saturated micromodel at the rate
of 0.03 ml/hr till no more oil was produced. Thereafter, the as prepared
nanofluids were injected with the flow rate of 0.03 ml/hr as long as the
oil production stopped. Throughout all steps of the injection procedure,
the fluid flow behavior was recorded by a digital microscopic imaging
system and the obtained images were precisely analyzed by image
processing software to determine the variations of the phase saturation.
3. Result and discussion
3.1. Characterization of nanohybrids
The Raman spectroscopy is an appropriate technique for char-
acterization of carbon nanostructure specially graphene and its deri-
vatives. The Raman spectrum of the silica-graphene nanohybrid is
shown in Fig. 3. Accordingly, the D, G, and 2D bands were positioned at
around 1320, 1560, and 2600 cm−1, respectively. The G band is com-
monly appeared in all sp2 carbon allotropes confirming the in-plane
vibration of sp2 bonded carbon atoms. While the intensity of the D band
generally shows sp3 defects which lead to increase the number of
crumpled graphene layers. Furthermore, the relatively high intensity of
2D band around 2600 cm−1 that usually appears in the monolayer
graphene sheets further verifies the creation of single layer graphene.
Hence, it can be concluded that the silica-graphene nanohybrid si-
multaneously contains a combination of single and few layers stacked
graphene sheets.
Fig. 4 shows the TEM, HRTEM images and the related select area
electron diffraction (SAED) patterns of silica aerogel and silica-gra-
phene nanohybrid. As can be clearly seen in Fig. 4(a), size of the pri-
mary silica particles is rather uniform. The high magnification TEM
image of silica aerogel is shown in Fig. 4b; obviously, the silica aerogel
mainly composed of amorphous and disordered structures. Moreover,
the SAED pattern of silica aerogel (Fig. 4(c)) shows only diffraction
rings without any diffraction dots confirming the silica aerogel struc-
tures are amorphous. Fig. 4(d) shows the TEM image of silica-graphene
nanohybrid, in which a large number of wrinkled few-layered graphene
can be distinguished on silica aerogel. A set of highly-crumpled and
individual transparent graphene sheets confirm that these wrinkles re-
sulted from the crumpling of graphene rather than stacking, which is in
agreement with the sharp intensity of 2D band in the Raman spectra.
S. Tajik et al.
Fig. 2. The schematic illustration of the oil-saturated micromodel and microscopic experimental setup.
High resolution TEM investigation of silica-graphene nanohybrids
shows that the thin walls typically consist of only few layers of gra-
phene sheets formed on silica aerogel (Fig. 4(e)). As further evidence,
the crystalline structure of graphene on silica was verified by selected
area electron diffraction (SAED), as shown in Fig. 4(f). A ring-like dif-
fraction pattern verified the loss of ordering in the sheets [33].
X-ray photoelectron spectrum (XPS) was employed to determine the
element composition and oxidation state of the prepared silica-gra-
phene and functionalized silica-graphene nanohybrids. The wide survey
of XPS spectra reveal that all of the pristine and functionalized silica-
graphene nanohybrids only composed of carbon, oxygen, and silica as
the main elements indicating the lack of any impurity. Fig. 5 illustrates
that all of the spectra contain four distinctive peaks in the vicinity of
∼101, 151, 283, and 531 eV which are related to Si 2p, Si 2 s, C1s, and
O1s bonds, respectively. As observed, the intensity of the Si 2p, Si 2 s,
and C1s bonds remain unchanged in all samples. However, the O1s
Fig. 3. Raman spectrum of silica-graphene nanohybrid.
256
Colloids and Surfaces A 556 (2018) 253–265
bonds of the functionalized samples were noticeably intensified com-
pare to pristine silica-graphene nanohybrid. Furthermore, by increasing
the time of functionalization the intensity of O1s bands were com-
paratively raised indicating the creation of more oxygen functional
groups on silica-graphene nanohybrids (Fig. 5). The C1s spectra of si-
lica-graphene nanohybrids were fitted with four Gaussian peaks related
to CeC, CeO, C]O, and O]CeO binds (see figure S2). The values of
carbon to oxygen (C/O) ratio of the samples were calculated and
summarized in Table S1. The XPS spectra demonstrate noticeable dif-
ferences between pristine and functionalized silica-graphene nanohy-
brids as the proportion of oxygen to carbon augments by increasing the
time of functionalization from 24 to 72 h. However, by changing
functionalization time there is no distinct alteration regarding the type
of oxygen containing functional groups (see Table S1).
3.2. Phase behavior of functionalized nanohybrids dispersions in presence
of NaCl
The visual observations of stability of fsg.72 nanohybrid, as an ex-
ample, are shown in Figs. 6 and 7. The addition of electrolytes in
aqueous phase increases the thickness of the electrical double layer and
causes the destabilization of nanoparticles dispersions. Fig. 6 shows the
phase behavior of 0.1 wt% fsg.72 dispersions that are various in NaCl
concentrations. As can be seen in Fig. 6, the addition of NaCl up to 4 wt
% does not lead to destabilize the aqueous dispersion of nanohybrids.
This observation suggests that 4 wt% NaCl represents a critical salt
concentration above which nanohybrid aggregation and sedimentation
visually occurs. Moreover, Fig. 7 shows the phase behavior of fsg.72
dispersions in different NaCl and nanoparticle concentrations. These
observations show that the precipitation and sedimentation of nano-
particles occur by either increasing NaCl or nanoparticles concentra-
tion. It is obvious from Fig. 7(a–c) that the fsg.72 nanohybrid disper-
sions with 0.01, 0.05, and 0.1 wt% nanoparticle concentrations are
stable for NaCl concentration up to 4 wt%. However, for 0.15 wt%
fsg.72 nanohybrid, the small addition of NaCl even 1 wt% leads to
destabilize the aqueous dispersion and settle of nanoparticles (see
Fig. 7(d)). Therefore, regarding to these observations, the nanohybrids
concentrations up to 0.1 wt% and 4 wt% NaCl concentration were se-
lected for more investigation in this study.
S. Tajik et al. Colloids and Surfaces A 556 (2018) 253–265

Fig. 4. TEM images of (a) silica aerogel, and (d) silica-graphene nanohybrids, HRTEM images of (b) silica aerogel, and (e) silica-graphene nanohybrids and the
corresponding SAED patterns of (c) silica aerogel, and (f) silica-graphene nanohybrids.

Fig. 5. X-ray photoelectron spectra of (a) silica-graphene nanohybrid, (b)

fsg.24, (c) fsg.48, and (d) fsg.72.

3.3. Mechanism investigation of functionalized silica-graphene nanofluid in

EOR

Generally, one of the prominent mechanisms has been proposed for
enhanced oil recovery when nanoparticles add to the injected fluid is
reducing the interfacial tension between the nanofluid and oil [34]. In
fact, the adsorption of nanoparticles may occur at the oil-water inter-
face conducing the reduction of IFT [35].
Fig. 6. Phase behavior of 0.1 wt% fsg.72 nanohybrid dispersions at various
NaCl concentrations at different time span (a) 1 h and (b) 24 h after dispersion.
3.3.1. IFT measurements
The IFT values of functionalized silica-graphene nanohybrids at
different concentrations (0.01, 0.05, and 0.1 wt %) were measured

257
S. Tajik et al. Colloids and Surfaces A 556 (2018) 253–265

Fig. 7. Phase behavior of various concentrations of fsg.72 nanohybrid dispersions (a) 0.01 wt%, (b) 0.05 wt%. (c) 0.1 wt% and (d) 0.15 wt% at various NaCl
concentrations (1 h after dispersion).

Fig. 8. The effect of the concentration functionalized silica-graphene nanohybrids on the IFT values.

through DSA mechanism as previously described. Fig. 8 shows the drop phase, respectively. The IFT value between the crude oil and
variation of IFT values with increasing the concentration of the func- deionized water was calculated to be about 19.11 mN/m. As can be
tionalized nanohybrids at various functionalization time. In the ex- seen in Fig. 8, at the concentration of 0.1 wt%, the IFT value reaches to
periments, the dispersants and crude oil were applied as the bulk and ∼10.44, 9.01, and 7.13 mN/m for fsg.24, fsg.48, and fsg.72 nanofluids,

258
S. Tajik et al. Colloids and Surfaces A 556 (2018) 253–265

Fig. 11. The effect of different functionalized silica-graphene nanohybrids on

Fig. 9. Comparison of the IFT values of functionalized silica-graphene nano- the average diameter of emulsions droplets at the concentration of 0.1 wt%
hybrids in deionized water and synthetic brine (4 wt% NaCl) at the con- functionalized nanohybrids in deionized water and brine solution (24 h after
centration of 0.1 wt%. preparation of emulsions).

respectively; suggesting that the IFT value can be reduced more than
60% in the presence of functionalized silica-graphene nanohybrids. It
can be clearly observed that the IFT decreases with increasing the
concentration of the functionalized nanohybrids which can be related
to the adsorption of functionalized nanohybrids on the oil-water in-
terface. As a matter of fact, the functionalized nanohybrids create an
extra layer at the interface of the oil and nanofluid which extends the
interface through acting as an amphiphilic surfactant. Hence, the ad-
dition of functionalized nanohybrids noticeably reduces the capillary
forces and consequently increases the capillary number [36]. Further-
more, in the case of fsg.72, the IFT values reduced more than fsg.24 and
fsg.48 which can be attributed to the better dispersion and higher sta-
bility of this sample versus fsg.24 and fsg.48 due to its higher con-
centration of functional groups. Indeed, functional groups on the edge
plane and surface of the nanohybrids can impede the particle-particle
interaction through decreasing the aggregation of nanoparticles;
therefore, higher amount of nanohybrids can migrate to the oil-water
interface which reduces IFT [37]. Fig. 9 exhibits the ionic strength of
nanofluids at the concentration of 0.1 wt% functionalized silica-gra-
phene nanohybrids by comparing the IFT values in deionized water and
brine solution (4 wt % NaCl). It should be mentioned that the presence
of salt may alter the oil-water interface through changing the

Fig. 10. The microscopy images of the emulsions at the concentration of 0.1 wt% functionalized nanohybrids; (a) fsg.24, (b) fsg.48, and (c) fsg.72 in deionized water,
(d) fsg.24, (e) fsg.48, and (f) fsg.72 in brine solution. (The images were taken 24 h after preparation of emulsions).

259
S. Tajik et al.
Fig. 12. The behavior of an added droplet of emulsion in deionized water and
decalin.
hydrophilic–lipophilic balance and compressing the electrical double
layer at the same time. The consequence of these phenomena can re-
duce the solidity of the interface trough increasing the concentration of
nanoparticles at the oil-water interface which leads to the reduction of
IFT [38]. From other point of view, by adding NaCl, there is an op-
portunity for positive and negative ions to form a closer contact with
oil-water interface. As it happens, the sodium cations can easily interact
with the negative charged functional groups on the surface of functio-
nalized silica-graphene nanohybrids. Thus, the negative charged func-
tional groups will be surrounded by Na+ which reduces the double
layer thickness and increases the density of nanoparticles at the oil-
water interface leading to the reduction of IFT. Considering the pre-
sence of anions in the double layer, they can be also adsorbed to the oil-
water interface by electrostatic interactions. However, the adsorption of
chloride anions is assumed to occur at the hydrophobic-hydrophilic
interfaces which have been confirmed by molecular dynamics simula-
tion [39]. Accordingly, as can be seen in Fig. 9, the IFT values decrease
by increasing the ionic strength which highlights the augmentation of
nanoparticles at the oil-water interface. Therefore, the addition of
functionalized silica-graphene nanohybrids to the brine solution might
facilitate the EOR process. Also, the results indicate that the minimum
value of IFT can be reached at the highest concentration of nanohybrids
(0.1 wt%). Hence, it was selected as the optimum concentration of
nanofluid for further investigation of the average droplets diameter in
Pickering emulsion, and micromodel.
3.3.2. Emulsion
To reach a stable Pickering emulsion, the functionalized silica-gra-
phene nanohybrids must adsorb at the oil-water interface and occupy
an enormous interfacial area to hinder droplets coalescence. Physically,
the creation of oil-water interface in the presence of nanoparticles
needs an extra force to subdue the Laplace pressure which is provided
by ultrasonic waves [40]. Generally, the stability of droplets in Pick-
ering emulsions firmly depends on the level of adsorption energy of
nanoparticles and their surface coverage at the interface [41–43]. The
functionalized silica-graphene nanohybrids enhance the stability of
emulsions by taking the advantage of hydrophilic and hydrophobic
characteristics emanating from functional groups and silica-graphene
260
Colloids and Surfaces A 556 (2018) 253–265
nanoparticles, respectively. The partition coefficients of the functiona-
lized nanohybrids between decalin and water were experimentally
determined through dispersion of functionalized nanohybrids (0.1 wt
%) in equal volume of deionized water (Fig. 10(a–c)) and brine solu-
tion-decalin emulsions (Fig. 10(d–f)). In the case of deionized water, the
lower phase shows light-brown solution due to the partially dispersion
of functionalized silica-graphene nanohybrids (left side of Fig. 10(a–c)).
Contrary, by adding salt, an absolute thin colorless phase appears after
24 h indicating that the sodium cations attracted the functionalized
nanohybrids toward the interface by electrostatic interactions (right
side of Fig. 10(a–c)). Thermodynamically, the irreversible adsorption of
nanohybrids to the oil-water interface creates more stable emulsion.
furthermore, the high stability of emulsions by the functionalized silica-
graphene nanohybrids can be ascribed to electrostatic repulsions and
steric hindrance through the formation of some rigid shells which oc-
curs by the adsorption of nanoparticles on the interface [44,45]. Ob-
viously, spherical droplets with various diameters can be seen in
deionized water and brine emulsions. The average diameter of emulsion
droplets in deionized water was approximately estimated to be about
0.45–1.06 μm which is extremely smaller than silica-carbon nanotube
nanohybrids and functionalized graphene [27,46]. As presented in
Fig. 10, the microscopic images reveal that in deionized water, most of
the droplets possess smaller diameter with better distribution than
those of brine emulsions due to less electrostatic repulsion in the pre-
sence of salt. According to the possible interactions in the proposed
emulsions, the hydrophobic parts of nanohybrids have more tendencies
to interact with oil; however, the oxygen containing functional groups
remain in aqueous phase due to their hydrophilic properties. In spite of
the closeness of the emulsion droplets in microscopic images, uniform
distribution of emulsion droplets further emphasizes the role of func-
tional groups as a hydrophilic surfactant which improves the stability.
The effect of functionalization time on the average diameter of
emulsion droplets was also investigated. As can be seen in Fig. 11, the
average diameter of emulsion drops decreases by increasing the func-
tionalization time indicating better dispersion of nanohybrids, uniform
distribution of droplets, and higher stability of emulsions by increasing
the amount of oxygen containing functional groups. In addition, to
observe individual behavior of emulsion in deionized water and dec-
alin, an equal amount of emulsion was dropped in a constant volume of
deionized water and decalin. Generally, when a drop of oil-in-water
emulsion disperses in water, the added drop remains unchanged in oil.
By adding a drop of the as-prepared emulsions to water and decalin, it
was found that the type of emulsions was decalin in water (see Fig. 12
as an example).
Nanoparticles adsorption at the oil and water interface, regard to
their high surface area, and their emulsions, can cause efficacious
treatment on heavy oil components, due to their polar agents. As an
issue incumbent to be seen, the effect of the nanoparticles on creating
Pickering emulsion and its behavior during the increase of the con-
centration of the asphaltene, have been investigated. Figs. 13, and 14
display the microscopy images of emulsions which were prepared by
0.1 wt% functionalized nanohybrids in brine and different concentra-
tions of asphaltene in toluene with their corresponding droplet size
distribution plots, respectively. The long chain of the asphaltene mo-
lecules caused nanoparticles to migrate to the outer shell of the as-
phaltene molecules and share their hydrophibic chain, while nano-
particles hydrophilic head still remained in water, and create large scale
emulsions. On the other hand, the small size of emulsions, due to the
Brownian motion of the particles, redistributes the particles to an
equilibrium configuration with the lowest total free energy, and
minimum possible IFT. As can be seen in Fig. 14(a–c), a shift towards a
broader droplet size distribution was observed with increase in as-
phaltene concentration in all emulsions. Obviously, the average dro-
plets diameter of emulsions for all samples, due to the heavy organic
S. Tajik et al. Colloids and Surfaces A 556 (2018) 253–265

Fig. 13. The microscopy images of the emulsions at the 0.1 wt% of (a) fsg.24, (b) fsg.48, (c) fsg.72 with different concentrations of asphaltene (1). 0.01 wt%, (2)
0.1 wt%, (3) 0.5 wt%, (4) 1 wt% (The images were taken 24 h after preparation of emulsions).

261
S. Tajik et al.
Fig. 14. Histograms of the droplet size distribution as a function of asphaltene concentration: (a) fsg.24, (b) fsg.48, (c) fsg.72, and (d) average droplets diameter as a
function of asphaltene concentration (concentration of nanohybrids = 0.1 wt%).
molecules, long-chain components and their polar character, was in-
creased with increase in asphaltene concentration. Furthermore, the
concentration of the brine in the water, because of ions existed in the
water and stand along the nanoparticles and then emulsions would be
the second reason of the diameter enhancement of the emulsions. The
stability of the emulsion would decrease with increase in emulsion
droplets size.
Asphaltene precipitation and the adsorption of nanoparticles in
porous media can reduce its porosity and permeability. Additionally,
emulsion trapping thorough pore throats can reduce rock permeability.
Therefore, the emulsion droplets magnitude could be an important
issue which may damage porous media, and should be investigated in
presence of the heavy oil components to find out the worst possible
effects on the emulsion droplets diameter. As a conclusion, the con-
centration of the asphaltene has a negative effect on the emulsion sta-
bilization and droplets. However, nanoparticles investigated in this
study has not raised droplets diameter so much, and could be called that
no damage would occur during the injection because of the droplets size
of the emulsions.
4. Micromodel tests
The micromodels of water flooding and nanofluid flooding at the
concentration of 0.1 wt% functionalized nanohybrids in brine in the last
moment of the test are shown in Fig. 15(a–d). Moreover, Fig. 16(a–d)
262
Colloids and Surfaces A 556 (2018) 253–265
shows the differential pressure and oil recovery of the micromodels.
The final stage of water flooding in which the oil production is being
stopped is presented in Fig. 15(a). As it can be seen in Fig. 16(a), during
water injection, the pressure difference between injecting and produ-
cing ports, is growing up until the first droplets of injected water in
micromodel was produced. The figure also shows that the growing in-
crease of the oil production was occurred before that point, and after
that the oil production decreased gradually until it stopped. It was also
obvious that in water injection, the water flow has more tendencies for
passing through the most permeable and shortest path due to the fin-
gering phenomenon. Therefore, water flowed in the areas with the
minimum resistance in which no or low oil recovery has been achieved
and consequently reduced the EOR performance. Regarding the IFT
values between oil and water, the highest IFT values leads to the lowest
capillary number [53]. The results show that only 31% of oil can be
recovered by water flooding which is relatively poor. It means that
water partially swept oil as the oil saturation reaches to 69%, hence, a
large amount of oil was remained at the end of displacement. Conse-
quently, the recovery of the oil is increased until the reducing pressure
difference in the micromodel became stable and there was no change in
pushing force to produce more oil.
The recovery of water flooding and after that, nanofluids flooding
are conducted at the concentration of 0.1 wt% functionalized nanohy-
brids in brine. Water and nanofluids flooding experiments were carried
out with the flow rate of 0.0005cc/min. The final stage of water
S. Tajik et al.
Fig. 15. Micromodel after (a) water flooding, and nanofluid flooding of (b) fsg.24, (c) fsg.48, and (d) fsg.72. (All nanofluids were prepared in synthetic brine solution
at the concentration of 0.1 wt% functionalized nanohybrids).
flooding in a separate test, which the oil production is being stopped, is
presented in Fig. 15(a). All nanofluid tests were taken after water
flooding and secondary recovery, to investigate tertiary recovery. The
micromodels (Fig. 15(b–d)) illustrate the oil production responses
during the water flooding and nanofluids flooding of fsg.24, fsg48, and
fsg72.
Comparatively, the enhancement of macroscopic sweep efficiency in
the presence of functionalized nanohybrids can be observed by in-
creasing the amount of oxygen containing functional groups. The oil
recovery from nanofluid flooding was calculated to be about 53, 71,
and 83% for fsg.24, fsg.4, and fsg.72, respectively (see Fig. 16(b–d)),
further confirming the effect of oxygen containing functional groups on
the EOR performance. This increase in EOR performance which oc-
curred in high functionalized nanofluids must be due to those changes
which affect the injecting fluid properties and enhanced them. Ac-
cording to the IFT figures, in pervious section it can be concluded that
the amount of oxygen containing functional groups affects the inter-
facial tension between oil and water. The low interfacial tension in
highly functioned nanoparticles is due to the hydrophilicity effects of
the highly functioned nanoparticles groups, and make them amphi-
philic particles; solute in water and oil.
As a result, it can be concluded that, the higher the functional
groups embedded, the lower the interfacial tension resulted, and ob-
viously, the higher the recovery enhanced in micromodel. Apparently,
the reduction of IFT influences the contact between by passed oil and
injected fluid. When the nanofluids were injected after waterflooding;
the reduction of IFT values leads to better mobilization and more oil
production. This occurred as a result of the increase in oxygen con-
taining functional groups, embedded on the nanoparticles structural
shell. As it can be seen in Fig. 16(a–d), gradually decrease in pressure
difference in micromodels, means that there is no or negligible effect of
263
Colloids and Surfaces A 556 (2018) 253–265
viscosity enhancement on the nanofluid injected in the micromodel.
Consequently, according to our calculations and experimental ob-
servations, fsg.72 as the best functionalized nanohybrid exhibits better
EOR performances compared to fsg.48, and fsg.24, respectively.
5. Conclusion
In summary, the silica-graphene nanohybrid was prepared via CVD
method and functionalized by using a mixture of nitric and sulfuric acid
vapors. The functionalization process was carried out in different time
periods. The XPS spectra show that the augmentation of defect struc-
tures and the oxygen containing functional groups is due to the passage
of functionalization time [48]. Then, the potential application of
functionalized silica-graphene nanohybrids for enhanced oil recovery
was perfectly investigated. At first step, the effect of ionic strength and
the concentration of functionalized silica-graphene on interfacial ten-
sion between crude oil and water were studied. The results reveal that
IFT values can be reduced more than 60% in the presence of functio-
nalized silica-graphene nanohybrids. The stabilization of oil in water
emulsions was also investigated at the concentration of 0.1 wt% func-
tionalized silica-graphene nanohybrids in deionized water and 4 wt%
NaCl brine solution. The results exhibit that the electrostatic interac-
tions between positively charged sodium and negatively charged
oxygen containing functional groups may lead to better stability of the
emulsions. Finally, the micromodel visualizations demonstrate that oil
recovery noticeably enhances when nanofluid flooding occurs after
water flooding. It goes without saying that employing functionalized
silica-graphene nanohybrids even at low concentration in this study not
only improves oil recovery parameters, but also introduces an economic
alternative for nanoadditive in reservoirs.
S. Tajik et al.
Fig. 16. Oil recovery performance, differential pressure vs. injected pore volume of micromodel after (a) water flooding, and nanofluid flooding of (b) fsg.24, (c)
fsg.48, and (d) fsg.72.
Acknowledgement
This research was supported by Iran National Science Foundation
for postdoctoral fellowship with number of 96006744.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.colsurfa.2018.08.029.
References
[1] T. Austad, Water-based EOR in carbonates and sandstones: new chemical under-
standing of the EOR potential using smart water, Enhanced Oil Recov. Field Case
Stud. (2013) 301–335.
[2] J. Zuta, I. Fjelde, Mechanistic modeling of CO2-foam processes in fractured chalk
rock: effect of foam strength and gravity forces on oil recovery, SPE Enhanced Oil
Recovery Conference (2011).
[3] D.W. Green, G.P. Willhite, Enhanced Oil Recovery, Richardson, Tex.: Henry L.
Doherty Memorial Fund of AIME, Society of Petroleum Engineers, 1998.
[4] H. Pei, et al., Comparative effectiveness of alkaline flooding and alkaline–surfactant
flooding for improved heavy-oil recovery, Energy Fuels 26 (5) (2012) 2911–2919.
[5] M. Dong, S. Ma, Q. Liu, Enhanced heavy oil recovery through interfacial instability:
a study of chemical flooding for Brintnell heavy oil, Fuel 88 (6) (2009) 1049–1056.
[6] N. Lai, et al., A water‐soluble acrylamide hydrophobically associating polymer:
synthesis, characterization, and properties as EOR chemical, J. Appl. Polym. Sci.
129 (4) (2013) 1888–1896.
[7] Nielson, J.P., Recovery of oil from oil-bearing formation by continually flowing
pressurized heated gas through channel alongside matrix. 1989, Google Patents.
[8] G.A. Pope, The application of fractional flow theory to enhanced oil recovery, Soc.
Pet. Eng. J. 20 (03) (1980) 191–205.
[9] C.R. Miranda, L.Sd. Lara, B.C. Tonetto, Stability and mobility of functionalized si-
lica nanoparticles for enhanced oil recovery applications, SPE International Oilfield
264
Colloids and Surfaces A 556 (2018) 253–265
Nanotechnology Conference and Exhibition (2012).
[10] O. Torsaeter, S. Li, L. Hendraningrat, Enhancing oil recovery of Low-permeability
berea sandstone through optimised nanofluids concentration, SPE Enhanced Oil
Recovery Conference (2013).
[11] L. Hendraningrat, O. Torsæter, Metal oxide-based nanoparticles: revealing their
potential to enhance oil recovery in different wettability systems, Appl. Nanosci. 5
(2) (2015) 181–199.
[12] B. Ju, T. Fan, M. Ma, Enhanced oil recovery by flooding with hydrophilic nano-
particles, China Particuol. 4 (01) (2006) 41–46.
[13] C. Drummond, J. Israelachvili, Surface forces and wettability, J. Pet. Sci. Eng. 33 (1)
(2002) 123–133.
[14] C.C. Agbalaka, et al., The effect of wettability on oil recovery: a review, SPE Asia
Pacific Oil and Gas Conference and Exhibition (2008).
[15] K. Xu, et al., Microfluidic investigation of nanoparticles’ role in mobilizing trapped
oil droplets in porous media, Langmuir 31 (51) (2015) 13673–13679.
[16] P. Stevenson, Dimensional analysis of foam drainage, Chem. Eng. Sci. 61 (14)
(2006) 4503–4510.
[17] N.Y.T. Le, et al., Design and screening of synergistic blends of SiO2 nanoparticles
and surfactants for enhanced oil recovery in high-temperature reservoirs, Adv. Nat.
Sci. Nanosci. Nanotechnol. 2 (3) (2011) 035013.
[18] O. Torsater, S. Li, L. Hendraningrat, Effect of some parameters influencing en-
hanced oil recovery process using silica nanoparticles: an experimental investiga-
tion, SPE Reservoir Characterization and Simulation Conference and Exhibition
(2013).
[19] A. Maghzi, et al., Pore-scale monitoring of wettability alteration by silica nano-
particles during polymer flooding to heavy oil in a five-spot glass micromodel,
Transp. Porous Media 87 (3) (2011) 653–664.
[20] N. Ogolo, O. Olafuyi, M. Onyekonwu, Enhanced oil recovery using nanoparticles,
SPE Saudi Arabia Section Technical Symposium and Exhibition (2012).
[21] J. Shi, et al., Synergy of pickering emulsion and sol‐gel process for the construction
of an efficient, recyclable enzyme cascade system, Adv. Funct. Mater. 23 (11)
(2013) 1450–1458.
[22] T. Chen, P.J. Colver, S.A. Bon, Organic–Inorganic Hybrid Hollow Spheres Prepared
from TiO2‐Stabilized Pickering Emulsion Polymerization, Adv. Mater. 19 (17)
(2007) 2286–2289.
[23] C. Wu, et al., Nanoparticle cages for enzyme catalysis in organic media, Adv. Mater.
S. Tajik et al.
23 (47) (2011) 5694–5699.
[24] J. Zhou, et al., Magnetic Pickering emulsions stabilized by Fe3O4 nanoparticles,
Langmuir 27 (7) (2011) 3308–3316.
[25] X.-C. Luu, J. Yu, A. Striolo, Nanoparticles adsorbed at the water/oil interface:
coverage and composition effects on structure and diffusion, Langmuir 29 (24)
(2013) 7221–7228.
[26] S. Crossley, et al., Solid nanoparticles that catalyze biofuel upgrade reactions at the
water/oil interface, Science 327 (5961) (2010) 68–72.
[27] M. Shen, D.E. Resasco, Emulsions stabilized by carbon nanotube− silica nanohy-
brids, Langmuir 25 (18) (2009) 10843–10851.
[28] M. Buchgraber, et al., Creation of a dual-porosity micromodel for pore-level vi-
sualization of multiphase flow, J. Pet. Sci. Eng. 86 (2012) 27–38.
[29] M. Buchgraber, A.R. Kovscek, L.M. Castanier, A study of microscale gas trapping
using etched silicon micromodels, Transp. Porous Media 95 (3) (2012) 647–668.
[30] S. Tajik, B. Nasernejad, A. Rashidi, Preparation of silica-graphene nanohybrid as a
stabilizer of emulsions, J. Mol. Liq. 222 (2016) 788–795.
[31] U.K. Bangi, S.L. Dhere, A.V. Rao, Influence of various processing parameters on
water-glass-based atmospheric pressure dried aerogels for liquid marble purpose, J.
Mater. Sci. 45 (11) (2010) 2944–2951.
[32] S. Tajik, B. Nasernejad, A. Rashidi, Surface modification of silica-graphene nano-
hybrid as a novel stabilizer for oil-water emulsion, Korean J. Chem. Eng. 34 (9)
(2017) 2488–2497.
[33] A. Amiri, et al., Microwave-assisted synthesis of highly-crumpled, few-layered
graphene and nitrogen-doped graphene for use as high-performance electrodes in
capacitive deionization, Sci. Rep. 5 (2015).
[34] G. Cheraghian, L. Hendraningrat, A review on applications of nanotechnology in the
enhanced oil recovery part B: effects of nanoparticles on flooding, Int. Nano Lett. 6
(1) (2016) 1–10.
265
Colloids and Surfaces A 556 (2018) 253–265
[35] B.P. Binks, Particles as surfactants—similarities and differences, Curr. Opin. Colloid
Interface Sci. 7 (1) (2002) 21–41.
[36] M.J. Rosen, et al., Ultralow interfacial tension for enhanced oil recovery at very low
surfactant concentrations, Langmuir 21 (9) (2005) 3749–3756.
[37] M.S. Manga, et al., Measurements of submicron particle adsorption and particle film
elasticity at oil–Water interfaces, Langmuir 32 (17) (2016) 4125–4133.
[38] L. Han, et al., The interfacial tension between cationic gemini surfactant solution
and crude oil, J. Surfactants Deterg. 12 (3) (2009) 185–190.
[39] C. Tian, Y. Shen, Structure and charging of hydrophobic material/water interfaces
studied by phase-sensitive sum-frequency vibrational spectroscopy, Proc. Natl.
Acad. Sci. 106 (36) (2009) 15148–15153.
[40] K.Y. Yoon, et al., Graphene oxide nanoplatelet dispersions in concentrated NaCl and
stabilization of oil/water emulsions, J. Colloid Interface Sci. 403 (2013) 1–6.
[41] T.S. Horozov, B.P. Binks, Particle‐stabilized emulsions: a bilayer or a bridging
monolayer? Angew. Chemie Int. Ed. 45 (5) (2006) 773–776.
[42] F. Kim, L.J. Cote, J. Huang, Graphene oxide: surface activity and two‐dimensional
assembly, Adv. Mater. 22 (17) (2010) 1954–1958.
[43] J. Kim, et al., Graphene oxide sheets at interfaces, J. Am. Chem. Soc. 132 (23)
(2010) 8180–8186.
[44] P. Guo, H. Song, X. Chen, Hollow graphene oxide spheres self-assembled by W/O
emulsion, J. Mater. Chem. 20 (23) (2010) 4867–4874.
[45] H.A. Wege, et al., Long-term stabilization of foams and emulsions with in-situ
formed microparticles from hydrophobic cellulose, Langmuir 24 (17) (2008)
9245–9253.
[46] Y. He, et al., Factors that affect pickering emulsions stabilized by graphene oxide,
ACS Appl. Mater. Interfaces 5 (11) (2013) 4843–4855.
[48] M. Hashemi, et al., Functionalized R9–reduced graphene oxide as an efficient nano-
carrier for hydrophobic drug delivery, RSC Adv. 6 (78) (2016) 74072–74084.