Petroleum 3 (2017) 391e405

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Petroleum
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Emergence of nanotechnology in the oil and gas industry:

Emphasis on the application of silica nanoparticles
Muili Feyisitan Fakoya*, Subhash Nandlal Shah
Well Construction Technology Center, The University of Oklahoma, 100 E. Boyd, SEC-1210, Norman, OK 73019, USA

a r t i c l e i n f o a b s t r a c t

Article history: The application of nanotechnology in the oil and gas industry is on the rise as evidenced by the
Received 15 July 2016 number of researches undertaken in the past few years. The quest to develop more game-changing
Received in revised form technologies that can address the challenges currently facing the industry has spurred this growth.
15 February 2017
Several nanoparticles, of different sizes and at different concentrations, have been used in many
Accepted 9 March 2017
investigations.
In this work, the scope of the study covered the application of nanotechnology in drilling and
Keywords:
hydraulic fracturing fluids, oilwell cementing, enhanced oil recovery (which includes transport
Nanotechnology
Silica nanoparticles
study, and foam and emulsion stability), corrosion inhibition, logging operations, formation fines
Drilling fluids control during production, heavy oil viscosity reduction, hydrocarbon detection, methane release
Hydraulic fracturing fluids from gas hydrates, and drag reduction in porous media. The observed challenges associated with
Enhanced oil recovery the use of nanoparticles are their stability in a liquid medium and transportability in reservoir
Oilwell cementing rocks. The addition of viscosifier was implemented by researchers to ensure stability, and also,
Oil and gas surface-treated nanoparticles have been used to facilitate stability and transportability.
For the purpose of achieving better performance or new application, studies on synergistic ef-
fects are suggested for investigation in future nanotechnology research. The resulting technology
from the synergistic studies may reinforce the current and future nanotechnology applications in
the oil and gas industry, especially for high pressure and high temperature (HPHT) applications. To
date, majority of the oil and gas industry nanotechnology publications are reports of laboratory
experimental work; therefore, more field trials are recommended for further advancement of
nanotechnology in this industry. Usually, nanoparticles are expensive; so, it will be cost beneficial
to use the lowest nanoparticles concentration possible while still achieving an acceptable level of a
desired performance. Hence, optimization studies are also recommended for examination in future
nanotechnology research.
Copyright © 2017, Southwest Petroleum University. Production and hosting by Elsevier B.V. on
behalf of KeAi Communications Co., Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

* Corresponding author.
E-mail addresses: feyifakoya@ou.edu (M.F. Fakoya), subhash@ou.edu
(S.N. Shah).
Peer review under responsibility of Southwest Petroleum University.
Production and Hosting by Elsevier on behalf of KeAi
Over the years, it has been discovered that the transition from
microparticles to far-smaller particles will bring about a revo-
lution in so many industries. In fulfilling this goal, the use of
nanoparticles in various applications has resulted into new fields
of science and technology. These fields are nanoscience and
nanotechnology. Nanoscience describes the study of the phe-
nomenon and principles governing the behavior of materials at
nano-scale level [1], while nanotechnology deals with the
design, characterization, production and application of materials
and devices based on nanometer scale [2]. Similarly, nano-
particles are substances with dimensions in the order of

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access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
392 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405

1e100 nm (nm). Nanoparticles possess unique properties owing

to their small size and greater surface area per unit volume; thus,
they show a higher reactivity with other molecules. A compari-
son of the surface area to volume ratio of spherical particles of
the same material with radius of 1 mm (mm), 1 mm, and 1 nm
was presented by Ref. [3]. It is obviously from Fig. 1 that more
than a millionfold increase in surface area per unit volume will
be realized if a particle on a millimeter scale is converted to
nano-sized particles. Nanoparticles traverse several industries,
and the determination of what type to use depends on the
anticipated application.
Materials that have nanoparticles embedded in their struc-
Fig. 2. A typical chemical vapor deposition reactor (source: adapted from Ref. [5]).
tures are termed nanomaterials. Most of the qualities of the
nanoparticles are inherited by these materials, and that explains
the enhancement in their properties. The nanoparticles are
knitted into the structure of materials and bring about rein-
forcement. In conventional materials, the atoms are located in
the interior of the particles; but, for a typical nanomaterial, most
of the atoms are located on the surface of the particles. Reactions
that produce superb chemical, optical, mechanical, electrical,
thermal, magnetic properties etc., occur in nanomaterials [4].
The production of nanomaterials is mainly from six known
methods, namely: chemical vapor deposition, plasma arcing,
electrodeposition, sol-gel synthesis, ball milling, and the use of
natural nanoparticles [4]. Chemical vapor deposition involves
making nanoparticulate material from the gas phase [5], and a
Fig. 3. Vacuum arc e a type of plasma discharge (source: [7]).
schematic of the process is presented in Fig. 2. The material is
heated to form gas and then allowed to deposit as a solid on a
surface, most times under vacuum. The deposition may be direct
or by chemical reaction, forming a new product that is different
liquid phase (gel) [9]. The colloids are synthesized from ions of a
from the volatilized material. In plasma arcing, gas is made to
metal or metalloid element surrounded by different reactive li-
conduct electricity and it eventually gives up its electrons and
gands. A summary of the different stages and routes of sol-gel
thus ionizes. The resulting ionized gas is called plasma. This
synthesis is presented in Fig. 5. In ball milling, small balls
method is applicable in forming carbon nanotubes. Vacuum arcs
(which rotate around a drum) are allowed to drop under gravi-
is a type of plasma discharge [6], and a schematic of it is pre-
tational force on a solid in the drum; thereby, breaking the
sented in Fig. 3. In this figure, an arc is initiated by contacting the
structure into nanocrystallites as depicted in Fig. 6. This method
cathode, while an igniter is attached to the anode for a low-
can produce fines and uniform dispersions of oxide particles [10].
voltage and high-current self-sustaining arc generation. Subse-
The use of natural nanoparticle involves the reformation of
quently, the arc gives up ions and they accelerate toward the
existing nanoparticles into new materials when their crystallite
substrate. In the process, large droplets are filtered out before
bonds are broken. Nanomaterials are used in making insulation
deposition [7]. Electrodeposition involves a controlled place-
materials, machine tools, batteries, high power magnets, motor
ment of a layer or more on a surface. An example of a template-
vehicles, aircraft, medical implants, etc. [4].
assisted electrodeposition process is shown in Fig. 4. It is obvious
When nanoparticles are added to a fluid, the mixture be-
from this figure that the process of electrodeposition leads to the
comes a nano-fluid. Nano-fluids are dilute liquid suspensions of
placement of particles on the surface of the graphene sheet [8].
nanoparticles with at least one of their dimensions smaller than
Sol-gel synthesis describes the process of generating networks
100 nm [11]. Basically, nano-fluids consist of a base fluid and a
through the formation of colloidal suspension (sol), and the
subsequent gelation of the sol to form a network in a continuous

Fig. 1. Surface area to volume ratio of the same volume of materials (source:
adapted from Ref. [3]). Fig. 4. Active template-assisted electrodeposition (source: [8]).
 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
Fig. 5. Different stages and routes of sol-gel synthesis (source: [9]).
dispersion of tiny particles. The base fluid can be water, ethylene
glycol, surfactant-based fluids, polymeric fluids, engine oil,
mixture of two or more liquids, etc. Nano-fluids are used in
Fig. 6. Motion of the ball and powder mixture during milling (source: [10]).
393
several industries [12] and for different applications. For
instance, increasing the thermal conductivity of a liquid by sus-
pending particles in the base fluid is not a recent research area. A
theoretical basis to predict the thermal conductivity of a particle-
fluid suspension was formulated by Ref. [13]. Though, high
thermal conductivity values were predicted; but, stable sus-
pensions could not be achieved because the particle sizes in the
suspension were on a micro-scale range. This range of particle
sizes caused sedimentation, erosion, and increase in fluid pres-
sure drop. This jeopardized the use of these particulate slurries
as heat transfer fluids. With the progress in technology, particles
on a nanoscale level are now available. The idea of particulate
suspensions is now being revisited, and this time, considerable
success is being recorded. Stable (minimal sedimentation) sus-
pensions with high thermal conductivity are now formed by
nanoparticles [14e16]. Even, their thermal conductivities exceed
those predicted by theoretical calculations [17,18]. Also, pipe
erosion is reduced with the use of nanoparticles for suspension
fluids [19]. The high heat transfer capability of nano-fluids
makes them suitable for numerous engineering applications in
several industries like automotive, power plant, medical,
computer, etc. [11].
In recent years, nanotechnology is becoming increasingly
popular in the oil and gas industry. Nano-fluids find applications
in drilling, drill-in, completion, stimulation, and exploration and
exploitation of oil and gas [3]. Studies are ongoing, in different
areas of the oil and gas industry, to address several challenging
issues. This work presents a study of various applications of
nanotechnology in different areas of the oil and gas industry.
394 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
Silica nanoparticles are enjoying a wide usage in different oil and
gas industry research; hence, more emphases is placed on them
in order to show their versatility. The challenges of nanoparticles
applications, in some areas of the oil and gas industry, and the
solutions implemented by the researcher are described. Addi-
tionally, future research suggestions and some recommenda-
tions are given in order to aid the advancement of
nanotechnology in this industry.
2. Scope of nanotechnology research in the oil and gas
industry
There are various fields of disciplines, with distinct and
sometimes related practices, in the oil and gas industry; but, the
achievement of a common goal is usually the focus. For instance,
the successful production from a well requires the cooperation of
the geology, drilling, completion, and production departments.
Numerous technologies are developed regularly in various dis-
ciplines of the oil and gas industry; thus, it is not a surprise that
the aftermath of nanotechnology introduction to this industry
has witnessed a considerable spread to a good number of its
disciplines.
2.1. Drilling and hydraulic fracturing fluids development using
nanotechnology
Drilling fluids are used to transport drilled cuttings from the
wellbore to the surface during a drilling operation, though, they
perform other functions too. Similarly, hydraulic fracturing fluids
are needed to carry the proppants to the fractured zones of a
reservoir. Also, they serve other functions as well to ensure a
successful fracturing operation. A consistent effort by re-
searchers to better the development of these fluids has encour-
aged the use of nanotechnology.
According to Ref. [20], the use of nanomaterials in the
development of smart fluids will enhance the formation of thin
and tight mud cake, and also, improve the rheological and
filtration properties of these fluids. Presently, most fluids used in
the petroleum industry contain conventional macro and micro
sized particles; hence, formation damage is inevitable. Poor
quality drilling muds leave thick mud cake on the wall of the
wellbore, thereby, increasing the force required to pull the
drillstring should differential sticking occurred [21]. In the work
of Ref. [20], several water-based nano-fluids were prepared in
the laboratory with three commercially available nanoparticles
at 0.5 ppb (0.14% w/w). The stability of the nanoparticles in the
dispersing phase, and the enhancement of viscous and filtration
properties of the nano-fluid were ensured by the addition of a
regular viscosifier and a tri-functional additive. In addition,
bentonite mud sample was prepared in order to have a sample
containing micro-sized particles for comparison. They went
further to confirm the stability of the nano-fluids by measuring
their viscous and gel strength properties using a rotational
viscometer. These measurements were taken immediately after
fluid preparation, and at 18, 48 and 72 h. The closeness of the
results showed that the nano-fluids were stable, and had the
potential to meet field application requirements. The nano-
fluids, compared to the bentonite mud, had better viscous
properties. Also, they exhibited a constant gel strength (i.e. the
10 s and 10 min gel strength were identical). Though, the API
fluid loss characteristics of the nano-fluids and bentonite mud
displayed a similar trend; yet, no spurt loss was recorded for the
nano-fluids. The mud cakes produced by the nano-fluids were
thin and tightly packed, and with a thickness of less than 1 mm.
The use of nanoparticles with surfactant in brine that con-
tains internal breaker will facilitate the removal of polymer
residue from hydraulic fracture during a post-treatment stage
[22]. These internal breakers are trapped in the thread-like mi-
celles (TLM) that form the pseudo-filter cake, and in those that
leak into the formation [23]. The crosslinking of fracturing fluid
has its obvious advantage on viscosity buildup, and the use of
nanoparticles as possible crosslinker had even been reported
[24]. However, the reduction in fracture conductivity associated
with crosslinked polymer fluid still remains unsolved. The four
laboratory work of Ref. [22], named particle park flow tests (i.e.
flow tests through particulate media), involved the loading of the
flow cell with different sizes of sand proppants. In these tests, the
remedial cleanup fluid used was a mixture of 3% KCl brine,
0.072% wt. Cx40 nanoparticles (of approximately 35 nm size
inorganic crystals), 1 and 3% wt. gel-forming surfactant, and 0.18
and 0.25% wt. polymer breaker E
21. Particle park flow tests
demonstrated a considerable resistance to flow, even at low
surfactant concentration in high-permeability medium. This
result was attributed to the pseudo-filter cake formed due to the
presence of nanoparticles. The efficiency of internal breaker was
proven by examining the viscosity of effluent collected after
post-flush. The viscosity was water-like due to the degradation of
TLM structure by the internal breaker and removal of more
polymer residue. The degradation caused the rearrangement of
the structure of TLM into non-viscous spherical-shape micelle
structure as depicted in Fig. 7.
2.2. Nano-emulsions for cement spacers
Depending on the task, it is necessary to displace one fluid
system with another during drilling activities; hence, spacers are
usually placed in between fluid systems during the displacement
operation. Oil based mud (OBM) needs to be removed by spacers
when displacing cement or completion fluid to avoid contami-
nation [25].
The experimental results of Ref. [26] revealed that cement
spacers formed by nano-emulsions can effectively clean OBM
from casing-wellbore surface during cementing job, and also,
reverse the wettability of this surface in order to facilitate the
adhesion of cement slurry between the casing and the open hole.
Nano-emulsions are characterized by high surface areas and
good stability. A successful primary cement job eliminates the
additional cost associated with a remedial job. Sometimes,
problems such as channeling behind casing, contamination of
surrounding aquifer, zonal isolation problems, cement setting
time problems, etc. result from the use of convectional spacers.
Reliable cement spacers are needed to provide solid cement
bonds that will assure well integrity.
For the work of Ref. [26], nano-emulsions were prepared by a
two-step procedure that involved the mixture of 10% aromatic
solvent concentration, water, and surfactant. These novel cement
spacers were called nano-spacers, and were formed by the
addition of commercial gelling and weighting agents to nano-
emulsions. The efficiency of the prepared nano-spacers was
compared to that of commercial spacers that were currently used
in the field. The comparison was based on the results obtained
from four different laboratory tests. The first test, called metallic
grid test, indicated that a 95% mud removal performance could
be derived from nano-emulsions as compared to a maximum of
50% achievable with the tested conventional spacers. Similarly,
the wettability test conducted with nano-spacers produced a
favorable outcome compared to the common spacers. The nano-
spacers completely reverted oil-wet surfaces to water-wet. The
result of contact angle test of water droplet on a surface covered
 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
Fig. 7. Degradation of TLM structure by the internal breaker (source: [22]).
with OBM, after treating the surface with nano-spacer, showed a
drastic reduction in contact angle, from 70 to about 0 [26].
Lastly, the shear bond test demonstrated the adhesion of con-
crete to the casing wall treated with nano-spacer. A load of 92 KN
was applied to the nano-spacer-treated cell surface before the
slurry girdle could be moved - a display of adhesion of the
concrete to the surface. The amount of load applied in the case of
commercial cement spacers was lower.
2.3. Corrosion inhibition using nanotechnology
Corrosion leads to the destruction of metallic structures, and
the need to hinder this occurrence is of great importance to the
oil and gas industry. Now, some researchers are looking into
nanotechnology for the possibility of alternate or better
solutions.
Some researchers have presented the use of nanotechnology
in inhibiting corrosion [27,28]. In the experimental work of
Ref. [27], the novel nanomagnetic fluid was formulated by
dispersing ferromagnetic nanoparticles in a carrier fluid, and it
proved effective in reducing the corrosion rate of carbon steel in
an acidic medium. Acid solutions are pumped for lots of reasons
such as acid cleaning, acidizing, descaling and oil well cleaning,
etc. For most of these operations, the acids are transported
through metallic conduits, thereby exposing these metallic sur-
faces to chemical reactions that corrode them. Consequently, the
addition of corrosion inhibitors to these acids will minimize this
destructive effect. The size of the ferromagnetic nanoparticles
considered for their experiment ranges between 3 and 15 nm,
while 0.1M nitric acid (HNO3) was chosen as the acidic medium.
A gravimetric measurement, for the purpose of estimating the
weight loss, was conducted by suspending carbon steel in 0.1M
HNO3, and later, in other test solutions that were a mixture of
0.1M HNO3 and varying concentration of nanomagnetic fluid
inhibitor. Likewise, electrochemical impedance and polarization
measurement was made with 1 cm2 surface area of steel spec-
imen exposed to the test solutions (without and with several
concentrations of nanomagnetic fluid). The inhibition efficiency
(IE, %) and corrosion rate, computed from the weight loss mea-
surements, increased and decreased respectively with increasing
concentration of ferromagnetic nanoparticles. Also, the corrosion
current density, measured from the electrochemical impedance
and polarization measurement, was used to calculate the IE. The
outcome validated the results obtained from the weight loss
measurements. They concluded that ferromagnetic
395
nanoparticles inhibit corrosion by adhering to the surface of the
carbon steel, and then, form a protective layer.
2.4. Nanotechnology for logging operations
It is a normal practice to collect information about the li-
thology, reservoir fluid and rock properties, etc. during the
drilling stage or at other stages during the life of a well. The
process of this information gathering is called logging.
An innovative idea, called nanologging, was presented by
Ref. [29]. This idea was about the possibility of using nanorobots
for logging applications. The inspiration emanated from the
postulation of immune machines (nanomachines) that are able
to travel through the human blood stream to detect and destroy
bacteria and viruses. So, they believed that the modification of
this concept can find application in the petroleum industry.
Nanorobotics involves the design of robots that have dimensions
in the micrometer range, but equipped with components of
nanometer sizes. However, the conceived nanorobots will have
sizes in the order of centimeters. They gave strong arguments to
support the possibility of nanorobots rendering measurements-
while-drilling (MWD) and logging-while-drilling (LWD) tech-
nologies outdated. Since nanorobots are very small, compared to
conventional logging tools, they can get very close and deep into
the formation; thereby, promoting the acquisition of more ac-
curate real time drilling and formation parameters [29]. Ac-
cording to the authors, they will not be run as part of the drill
string nor will they be loaded as source; therefore, there will be a
great reduction in rig hours and logging costs. The nanorobot will
be equipped with nanosensors for information gathering,
nanomotors as drive mechanism, shield made of carbon alloys
for downhole protection, microprocessors to receive control in-
formation from surface computer, and electro-magnetic trans-
mitter for data transfer to the surface through electromagnetic
waves. Also, nanorobot can be transported by mud circulation
system. A special retrieval system, placed before the shale
shakers or at the surface mud return point, will catch the
nanorobots at the surface. Besides, the few risks and challenges
associated with its design and field usage were highlighted, but
can be circumvented. The risks mentioned were the incompe-
tence or negligence of personnel operating the nanorobots, and
the malfunctioning due to unexpected machine-machine inter-
action. The authors said that fail stop protocols and fail safe
design, and personnel competency are the ways to reduce these
risks. Likewise, the challenges that were mentioned about
nanorobots were their building and mass production,
396 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405

programming and co-ordination, continuous collision with fluids

in the well, and their retrieval from the well. Further research
and development in nanotechnology will help in tackling these
challenges.

2.5. Controlling formation fines during production using

nanotechnology

During production, formation fines move to near wellbore

region and plug the pores, thus, reducing production rate. These
unconfined particles, found in sandstone pore spaces, are
generally smaller than 37 mm [30]. Evidently, they will pass
through a 400 U.S. mesh screen size and will lead to screen
erosion and production pump damage [30]. Few recent studies Fig. 9. Formation fines migration in 3 months in a fracture packed with non-
have emphasized the effectiveness of nanoparticles in control- nanoparticle-treated proppants (source: adapted from Ref. [31]).

ling formation fines migration [31e37].

According to Ref. [31], nanoparticles with high surface forces,
and van der Waals and electrostatic forces can coat proppant
surfaces during a fracturing job. In the proppant pack tests, a
fracturing treatment was simulated by adding the nanoparticles
(at 1 g of nanoparticle per 1000 g of proppant) in slurry form to
the viscoelastic surfactant fracturing fluid and mixed with the
proppants simultaneously. The slurry form means that the
nanoparticles were mixed with a liquid. Afterwards, the frac-
turing fluid was broken and the mixture was poured in an acrylic
tube that had a 100 mesh screen at the bottom. A 12 inches long
proppant-pack was formed in the tube, and different type and
concentration of simulated fines solutions were ran through it.
Clean filtrate flowed out of the bottom of the proppant-pack,
indicating that the fines were captured by the nanoparticle-
treated surfaces of the proppants. In addition, effluent turbidity
tests presented high turbidity values for a non-treated proppant
bed compared to the one treated with nanoparticles. Fig. 8 il-
lustrates the movement of formation fluids and fines into the
proppant-packed fracture. In Fig. 9, though the production rate
had declined from 1000 to 100 barrels per day (bpd) over a 3-
month period; it is obvious that lots of formation fines had
migrated to the near wellbore region because the fracture was
packed with non-nanoparticle-treated proppants. Fig. 10 depicts
a scenario where the fracture was packed with nanoparticle-
treated proppants. Though, the production rate had only
declined from 1000 to 900 bpd over a 3-month period; but, the
formation fines have not flocked the near wellbore region. This is
because the fines were trapped on the surfaces of the
nanoparticle-treated proppants.
Fig. 8. Movement of formation fluids and fines at the start of production (source:
adapted from Ref. [31]).
Fig. 10. Formation fines migration in 3 months in a fracture packed with
nanoparticle-treated proppants (source: adapted from Ref. [31]).
2.6. Enhanced oil recovery (EOR) using nanotechnology:
transport study, stability control, and core flooding
Enhanced Oil Recovery is a tertiary technique that involves
the application of different methods for the purpose of
increasing the amount of crude oil that can be extracted from a
hydrocarbon reservoir. Similarly, nanotechnology has found
application in this discipline.
Several research studies have established that it is difficult to
transport colloidal dispersion in reservoir rock [38]. This
conclusion emanated from the fact that it is retained on reservoir
walls, and eventually do not get to the target location where its
application is required. Although, nanoparticles can pass through
the pore throats due to their small sizes; but, their deliverability
at the intended deep location where the oil exists needs to be
addressed. This is an important test that nanoparticles have to
pass in order to support their application in EOR. In the labora-
tory work of Ref. [39], the transport and retention properties of
aqueous dispersions of paramagnetic nanoparticles in reservoir
rock were studied. Surface treated paramagnetic iron-oxide
nanoparticles at concentration of 0.1e10% wt. were considered
for the core flood experiments.
In the work of Ref. [38], the transport and retention properties
of nanoparticles through dolomite and sandstone cores were
investigated at high salinity condition. They considered carbon
nanoparticles with/without surface treatment, and so, the effect
of surface treatment was also studied. Dolomite is known to be
positively charged owing to its large amount of divalent ions of
 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
calcium and magnesium (Ca2þ and Mg2þ), while sandstone is
negatively charged due to its predominant silica content [38].
The results of the core flood experiments (when carbon nano-
particles without surface treatment was used in the presence of
KCl, Ca2þ and Mg2þ, and seawater) revealed that nanoparticles
breakthrough was delayed. The delayed breakthrough was a
reflection of carbon nanoparticles retention on core surfaces, a
result that arose from the effect of ionic strength and divalent
ions. It has been established in literature that a high ionic
strength (at increased salt concentration) leads to the shrinkage
of the double layer of charged particles in aqueous suspensions,
and consequently, reduces their repulsive capability [38,40,41].
The retention is greater with dolomite cores than with sandstone
cores [38]. This is because of the additional attractive force that
emerged between the negatively charged carbon nanoparticles
and the positively charged dolomite surface, unlike sandstone
that has negatively charged surfaces. The breakthrough values
recorded with surface-treated carbon nanoparticles were rela-
tively higher compared to the ones obtained with untreated
nanoparticles - a confirmation of minimal retention. The surface
modification assisted in shielding the carbon nanoparticles, and
thus, inhibited charge interaction. This explains the reason
behind the use of surface-treated nanoparticles in most of the
research reported in publications.
Many industries, including the oil and gas, use emulsions for
various applications. According to Ref. [42], oil/water emulsions
were used as drilling fluids to achieve some special purposes.
Also, Ref. [43] stated that oil/water emulsions find application as
mobility control agents required to enhance the displacement
efficiency of viscous oil. Still, the use of emulsions in EOR has not
blossomed because of stability issues associated with emulsions
stabilized by colloidal solid particles. These concerns arise from
the fact that colloidal solids are only transported a short distance
in oil reservoirs (they get trapped by straining and deep-bed
filtration), thereby rendering them ineffective in supplying
good sweep efficiencies for EOR application. The effect of
different nanoparticle type and concentration on CO2 foam sta-
bility has been studied [44]. Aluminum oxide, copper oxide,
silica, and titanium dioxide nanoparticles respectively were
considered for this work at concentration of 0.1, 0.3, 0.5, and 1%
wt. Oil recovery was evaluated by the results of the displacement
tests performed at room temperature and pressure. All the
nanoparticles were able to stabilize CO2 foam at certain con-
centration; but, aluminum oxide nanoparticles showed superior
results. Moreover, all the nanoparticles displayed their best
result of foam stability and half-life at 0.1% wt.
The core flood experiments conducted by Ref. [45] involved
the use of nano-fluids in order to evaluate the recovery of heavy
oil from Berea sandstone cores. Treated formation water of 3%
wt. salinity and nanoparticles of aluminum oxide, nickel oxide,
silica, and titanium dioxide were made available for nano-fluid
preparation. A field-emission scanning electron microscope
(FESEM), with a magnification of 25,000X, was used to observe
the structure of the nanoparticles as shown in Fig. 11. The nano-
fluids were prepared by dispersing each nanoparticle in the
formation water to obtain concentration of 0.01, 0.05, and 0.1%
wt. The result of their core flood experiments revealed that the
nanoparticles of aluminum oxide and silica facilitated the re-
covery of more oil compared to the nanoparticles of nickel oxide
and titanium dioxide. The better performance of aluminum ox-
ide and silica nanoparticles was attributed to their ability to
bring about a high reduction in interfacial tension. Eventually,
the highest incremental oil recovery was achieved when a mixed
nano-fluid of aluminum oxide and silica was used at a concen-
tration of 0.05% wt., and at low salinity.
397
2.7. Heavy oil viscosity reduction using nanotechnology
The recovery methods, e.g. steam injection, of heavy oil/
bitumen usually involve the transfer of enormous amount of
energy. Improvement can be achieved through a medium that
enhances heat transfer for quick viscosity reduction. Thus, en-
ergy requirement and cost of production will be reduced. It was
demonstrated by Refs. [46,47] that the introduction of nano-
technology can improve the efficiency of thermal application
processes; hence, nano-size metals were presented as a viable
medium. In conventional methods like steam injection [48], re-
ported that the viscosity reduction of heavy oil/bitumen does not
rely solely on the supplied high temperature, but also, on some
series of chemical reactions called aquathermolysis. Similarly,
other authors explained how aquathermolysis leads to viscosity
reduction [49e53]. The inclusion of metal particles in a steam
injection process can positively impact the aquathermolysis re-
actions [54]. In furtherance to this, Ref. [55] presented the
application of nano-nickel catalyst in the viscosity reduction of
heavy oil by aquathermolysis.
To some extent, the explanation of the viscosity reduction
principles was unique to some authors, so clarification was
important. In view of this, Ref. [46] also elucidated on the
mechanisms through which nano-size metals reduce the vis-
cosity of heavy oil/bitumen. In their laboratory experiments, they
studied the effect of thermal conductivity, reactivity, and cata-
lytic effect of various sizes of 0.5% wt. nano and micron-sized
metals of iron, nickel, copper, and their different oxides on vis-
cosity reduction of several samples prepared with 14.7 API
heavy oil. The samples included untreated heavy oil, and other
mixtures of heavy oil and nano and micron-sized metals (and
their oxides) mentioned above. Viscosity measurements were
made at ambient and two elevated temperatures. The results
displayed a better viscosity reduction with nano-sized particles,
an observation attributed to their larger specific surface area.
This resulted into an improved reactivity due to an increase in
the contact area with the oil phase. Likewise, higher thermal
conductivities were accomplished with nano-sized particles. It
was concluded that the volume fraction of the nanos helped in a
faster distribution of heat during the experiments. Also, Ref. [56]
studied the reduction of heavy oil viscosity due to the addition of
surfactant-based nano-fluids. Their experiments involved the
use of copper-oxide nanoparticles and two heavy oil samples.
The prepared nano-emulsions were mixed with heavy oil sam-
ples, and the results indicated that the maximum viscosity
reduction was realized at an optimum nanoparticle concentra-
tion of 0.02% wt. Additionally, Ref. [57] used metal oxide nano-
particles of copper, iron, and nickel to investigate the viscosity
reduction of two heavy oil samples. Similarly, their results
confirmed the applicability of nanotechnology for heavy oil vis-
cosity reduction.
2.8. Hydrocarbon detection using nanotechnology
Another interesting capability of nanoparticles was revealed
by Ref. [58]. They reported the use of engineered nanoparticles in
detecting hydrocarbon in oil-field rock; so, these nanoparticles
were named nanoreporters. In their laboratory experiments, a
hydrophobic cargo was carried in aqueous solution (carrier fluid)
of the engineered nanoparticles and synthetic seawater, and
then, transported through samples of different reservoir rock.
This cargo, 2,20 ,5,5'-tetrachlorobiphenyl, was selectively released
when the carrier fluid encountered hydrocarbons. The cargo is
one of the congeners of polychlorinated biphenyl (PCB); hence, it
is also called PCB. Preliminary core flood tests, similar to that of
398 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
Fig. 11. FESEM images of (a) titanium dioxide, (b) aluminum oxide, (c) nickel oxide, and (d) silica (source: [45]).
Ref. [38], were conducted in sandstone and dolomite using hy-
drophilic carbon clusters (HCCs) nanoparticles that were surface-
treated with polyethylene glycol (PEG). It was realized that the
breakthrough values needed to be improved; thus, the surface-
treatment material was replaced with polyvinyl alcohol (PVA).
Furthermore, reducing nanoparticles aggregation was deemed
necessary; therefore, oxidized carbon black (OCB) nanoparticles
were used in place of HCCs. Better results, in terms of break-
through and nanoparticles stability, were achieved with OCB
nanoparticles that were surface-treated with PVA. Thence, OCB
surface-treated with PVA was chosen for the main experiments.
Similarly, the main experiments were a series of core flood tests
that involved the flowing of solution of PCB/PVA-OCB through
sandstone (containing 12% wt. of iso-octane), iceland spar calcite,
and dolomite (containing 0.8% wt. of crude oil). The effluent
collected when the solution was flowed through sandstone
containing iso-octane was analyzed for the presence of the cargo,
and the result indicated that a significant amount of PCB was
released. The case of dolomite containing oil revealed that 80% of
PCB was released, but very little amount was released with ice-
land spar calcite. The presence of these organic compounds (iso-
octane and crude oil) was responsible for the selective release of
PCB, but the scientific explanation remains unclear at the
moment [58].
2.9. Methane release from gas hydrates using nanotechnology
Natural gas hydrates are ice-like mixture in which the mol-
ecules of gas are trapped in the crystalline structure of frozen
water [59]. The presence of water and natural gas at a low
temperature and a high pressure favors the formation of natural
gas hydrates [60]. Gas hydrates are known to be a source of
enormous amount of methane, but the technology required to
tap this energy resource is yet to be fully developed.
A novel approach that will utilize the self-heating character-
istics of nickel ferrite (NiFe2O4) nanoparticles for the liberation of
methane from gas hydrates was presented by Ref. [61]. These
nanoparticles have their sizes in the range of 30e50 nm, and
also, are non-poisonous and environmentally friendly. The self-
heating of magnetic particles is a result of hysteresis and relax-
ation losses respectively [61]. For their laboratory experiment,
gas hydrate was artificially prepared using methane and its
dissociation was measured at atmospheric pressure and a tem-
perature range of
7 to 5  C. The aim of the experiment was to
evaluate the dissociation rate and the suitability of nanotech-
nology for methane production from gas hydrates. Their results
revealed that self-heating temperature increased rapidly at the
initial stage, and later, reached the maximum. Also, hydrate
dissociation time decreased when the strength of the magnetic
field is changed at a fixed frequency. In closure, they proposed an
approach for the field production of methane from gas hydrates.
The approach will involve the injection of air-suspended nickel
ferrite nanoparticles into the gas hydrate formation through a
horizontal injector well. The nanoparticles will pass through the
hydrate voids and get to the water cage. Then, a magnetic field
will be setup in the hydrate zone by the help of a magnetic tool
that is placed in the horizontal well. Alteration of the magnetic
field will activate the nanoparticles and cause them to increase
the temperature of the hydrate formation to about 42  C.
Therefore, the thermodynamic equilibrium will be disturbed and
this will lead to the decomposition of the water cage; eventually,
methane will be released and extracted to the surface through a
producing well as illustrated in Fig. 12.
 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
Fig. 12. Field production of methane from gas hydrates (source: adapted from
Ref. [61]).
3. Silica nanoparticles
Silica, a common name for silicon dioxide, is abundant in
nature in the form of sand or quartz. It is a compound of silicon
and oxygen with the chemical formula SiO2. Silica forms part of
the building block of numerous natural and artificial structures,
and unarguably, the advent of nanotechnology spurred new
research interests directed at exploring further capabilities of
this substance. Control of silica structure at nano-scale level was
initiated to produce silica nanoparticles [62]. The surfaces of
silica nanoparticles can be rendered non-polar when treated
with compounds like alcohols, alkoxysilanes, etc. This surface
treatment is effective in facilitating the dispersion of nanosilica
in various non-alcoholic solvents [62]. Silica nanoparticles find
usage in the manufacturing of many items such as thermal in-
sulators, humidity sensors, electronic substrates, electrical in-
sulators, etc. [63].
The petroleum industry stands to reap huge benefits from
silica nanoparticles. Majority of the application so far is in the
areas of water invasion reduction in shale, filtration and rheology
control in fluids, oilwell cementing, foam and emulsion stability
for enhanced oil recovery, and drag reduction in porous media.
Further research is ongoing to explore the versatility of these
nanoparticles in order to foster more game-changing
applications.
3.1. Application of silica nanoparticles in drilling and hydraulic
fracturing fluids
Nanoparticles, when added to water-based muds, can be used
to reduce water invasion in shale [64]. Unlike conventional
filtration loss additives, carefully selected nanoparticle sizes can
enter the tiny pore throats of shale [65]. Shale is classified as a
sedimentary rock and contains clays, quartz, silicate, and car-
bonate minerals in varying proportions. Primarily, the type of
clay in a shale formation will determine the amount of water that
will be absorbed; hence, wellbore stability concerns cannot be
underplayed. Atoka and Gulf of Mexico (GOM) shales were
selected for laboratory studies by Ref. [64]. Two categories of test
fluid samples were prepared: one was a 3% brine solution, and
the other contained 20 nm silica nanoparticles at concentration
of 5, 10, 29, and 40% wt. Using the pressure transmission tech-
nique [66], fluid samples were flowed over the top and bottom
faces of the shale samples. The rate of pressure transmission
signified the magnitude of shale permeability. It was observed
that pressure transmission through the shale sample was short-
lived when the fluid samples containing nanosilica were used
compared to the 3% brine solution. That indicated the plugging of
the shale pore throats by the nanoparticles. To further corrobo-
rate their experimental studies, four field water-based muds
were obtained and silica nanoparticles were dispersed in some
399
portions of these muds; therefore, having two sets of samples e
one without nanoparticles and the other with nanoparticles. The
same experiment described above was performed with these
samples, and it was concluded that the presence of silica nano-
particles resulted in no pressure transmission after a short
period. Again, the plugging of shale pore throats was confirmed.
Moreover, the work of Ref. [67] confirmed the reduction in
water invasion reported by Ref. [64]. For the research of Ref. [67],
experiments were conducted on several shale samples using a
water-based drilling fluid containing silica nanoparticles. Besides
fluid loss control, the nano-fluid also assured the control of fluid
rheology, lubricity, and shale stability. An investigation with
silica nanoparticles, similar to that of Ref. [67], was carried out by
Ref. [68]. They developed a Shale Membrane Test (SMT) for the
purpose of evaluating the plugging ability of nanosilica. In one of
their experiments performed with Atoka shales, a reduction in
permeability or an increase in plugging ability was observed as
nanosilica concentration increased.
In the laboratory work of Ref. [69], colloidal silica nano-
particles (at concentration of 10, 20, and 30% wt./wt.) were used
to investigate the effectiveness of nanoparticles in fluid loss
control. They concluded that the use of colloidal silica nano-
particles gives a better filtration result in polymer-surfactant
blend. The consistency in particle distribution of silicon nano-
particles can be of immense advantage in controlling the thick-
ness of drilling fluids filter cake [70]. This can offer a solution to
differential sticking problems. They claimed that a more
continuous and integrated filter cake will be formed if silicon
nanoparticles are dispersed in a drilling fluid, and the resulting
filter cake will be characterized by a low permeability and
porosity; so, the reduction in filtrate loss can be assured. They
validated their claim by conducting a simple experiment with a
standard filter press and two mud samples (one without nano-
particles, and the other with 3% by volume silicon nanoparticles).
The filter cake thickness formed by the mud with nanoparticles
reduced by 34% compared to the mud without nanoparticles.
Furthermore, Ref. [71] stated that the use of nanotechnology
can significantly reduce fluid loss in surfactant-based fluids
(SBF), polymeric fluids, and SBF-polymeric fluid blends. Thus,
fluid economy will be achieved and fracture conductivity dam-
age can be reduced in unconventional reservoirs. The experi-
mental work involved the use of 20 nm silica nanoparticles at
concentrations of 0.058, 0.24, and 0.4% wt. The filtration results
revealed excellent outcome at different concentrations of
nanosilica in the investigated fluids. Based on comparison of the
results, Blend-A nano-fluid was selected as the best. This nano-
fluid was optimized and a cost reduction of 96.6% was realized
at 0.002% wt, as regards the initial recommendation of 0.058%
wt. They concluded that the presence of silica nanoparticles
promoted the formation of a low permeability and porosity filter
cake owing to the development of a double network, three-
dimensional network structure, and complex supermicellar
structure in SBF, polymeric fluids, and SBF-polymeric fluid
blends respectively. Besides, Ref. [72] detailed the effect of
nanotechnology on the rheological behavior of SBF, polymeric
fluids, and SBF-polymeric fluid blends. Similarly, the laboratory
experiments were conducted with 20 nm silica nanoparticles.
Data gathering was done with Bohlin CS-50 rheometer within a
temperature range of 75e175  F. Generally, the experiments
showed good results, and also, the detrimental effect of nano-
technology (above a certain concentration) on these fluids were
documented. In addition, Ref. [73] used the concept of relative
viscosity to describe the rheology of hydraulic fracturing fluids
containing nanoparticles. The nano-fluids were prepared by
dispersing 20 nm silica nanoparticles in SBF, polymeric fluids,
400 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
and SBF-polymeric fluid blends. Nanoparticle concentration of
0.058, 0.24, and 0.4% wt. were converted to their corresponding
solid volume fraction of 0.0083, 0.034, and 0.055 respectively.
Their results demonstrated that Einstein and Krieger-Dougherty
equations under-predicted most of the relative viscosity values.
Using laboratory and field results, Ref. [74] demonstrated that
fluids containing silica nanoparticles can be used to stimulate
damaged wells. The stimulation involved the removal of skin
damage caused by paraffin blocks, and polymer-based filter cake
deposited on the surface of reservoir rocks. They reported that
the skin removal was the result of a disjoining pressure mecha-
nism. The disjoining pressure acts on particles at nanometer
scale. Nanoparticles assemble themselves and form a wedge-
shaped film when they come in contact with a discontinuous
phase such as oil [75], gas, paraffin, or polymer as depicted in
Fig. 13. Then, they start to force themselves in between the
discontinuous phase and the substrate. This forceful movement
is driven by Brownian motion, and electrostatic repulsion be-
tween the nanoparticles; so, the nanoparticles at the vertex are
constantly being driven forward. This imparts the disjoining
pressure, and eventually, the discontinuous phase separates it-
self from the rock surface. The concept of disjoining pressure was
discussed in the work of Ref. [76] that addresses the spreading of
nano-fluids on solid surfaces. The force, that causes the disjoin-
ing pressure, is strongest at the vertex and reduces towards the
bulk fluid (nanoparticles suspension).
3.2. Application of silica nanoparticles in oilwell cementing
Cement is needed in the oilfield for casing cementation in
order to provide mechanical support, protection from corrosive
fluids, and sealing (prevention of fluid communication between
different zones) [77,78]. Besides, cement is used for squeeze jobs,
plugging operations, etc. After a cement operation, it is
customary to allow a wait-on-cement (WOC) time for hydration
purpose. If a sufficient WOC time is not allowed, the integrity of
the cement will be negatively impacted. However, a reduced
WOC time is desirable for cost savings, especially in offshore
wells [79].
The report of Ref. [80] stated that the presence of nanosilica
and silica fume accelerated the hydration of cement because a
faster initial and final setting times were observed in cement
pastes. According to Ref. [81], nanosilica can improve the early
strength development and the final compressive strength of
cement. Also, fluid loss control is an added advantage, and the
possibility of a wide temperature application is feasible. Addi-
tionally, nanosilica shows compatibility with other cement ad-
ditive composition; consequently, facilitating the design of
desired cement properties. Measurement of compressive
strength was taken at a pressure of 3000 psi. The work of Ref. [82]
showed that a concrete prepared with chemically synthesized
nano-cement produced a high compressive strength after a few
Fig. 13. Wedge effect and disjoining pressure (source: [75]).
days of curing. The nano-cement contained nanosilica, and an
alumina source. Amorphous nanosilica was added to cement
pastes and mortars by Ref. [83], and they studied their influence
on the fresh properties of the mixtures. They reported that the
spread (propagation on flow table), setting time, and the time to
reach the maximum temperature decreased when compared to
samples without amorphous nanosilica. The use of silica nano-
particles as hydration accelerator in oilwell cement (API class H)
was investigated by Ref. [84], but at a low temperature of 59  F.
Silica nanoparticles with the smallest size (4e6 nm) and those
with higher aspect ratios proved as the most effective accelerator,
with a record of 30 and 136% improvement in cement compres-
sive strength for a period of 48 h and 7 days respectively.
3.3. Application of silica nanoparticles in enhanced oil recovery
(EOR): transport study, foam and emulsion stability, and core
flooding
In order to reap the benefits of silica nanoparticles in EOR,
their transportation and deliverability at the intended depth
need to be assessed, just as established earlier. To this end,
Ref. [85] investigated the transportability of nanoparticle dis-
persions in limestones (with low permeability: 10 and 15 mD)
and sandstone (with moderate to high permeability: 421e921
mD) cores. For the core flood experiments, 5 and 18.65% wt.
suspensions of 5 and 20 nm silica nanoparticles (surface-treated
with polyethylene glycol) were used. The injected pore volume,
nanoparticle concentration and size, and flow rate were varied
for each of the core flood experiment performed with the
sandstone cores. On the contrary, the same experimental con-
ditions were maintained for the limestone cores. During post-
flush, the injected nanoparticle dispersion was displaced with
deionized water and saline solution in the limestones and
sandstones respectively. This facilitated the measurement of the
amount of recovered nanoparticles, and the calculation of the
amount retained. A data logger system provided a means of
measuring the pressure drop as the nanoparticle dispersions
flowed through the core samples. At the end of each experiment,
apparent viscosity of the dispersion was determined from the
pressure measurement. Based on the analysis of the results, it
was concluded that concentrated dispersions of surface-treated
nanoparticles can be transported through reservoir rocks of
various permeabilities, with very small retention on pore walls.
They claimed that the mechanism behind this retention was
reversible adsorption, as opposed to straining and filtration for
colloidal dispersions. Reversible adsorption means that the
nanoparticles that were initially held on the pore walls, by weak
van der Waals attraction, were later released by Brownian
diffusion [85]. The size and surface treatment of the nano-
particles accounts for these conclusions. Similarly, Ref. [86]
studied the adsorption and transport behavior of silica nano-
particles in sandstone, dolomite, and limestone. Their results
indicated an easy passage of silica nanoparticles through the
sandstone core, while a slight adsorption was recorded when
silica nanoparticles were flooded through the limestone core. In
both cases, the permeability of the cores did not change. For the
dolomite core flooding, a high nanosilica recovery was reported;
however, the permeability of the core was changed.
Similar to other nanoparticles, the stability of emulsions and
foams stabilized by silica nanoparticles needs to be confirmed
before any potential application in EOR can be investigated. Ac-
cording to Refs. [87,88], emulsions stabilized by nanoparticles
can travel long distances within oil reservoirs. Similarly, foam
stability can be achieved in porous media [89]. The small size of
nanoparticles, compared to colloidal solids, give them an edge,
 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
and also, allow them to pass through the pore throat of reservoir
formation with relative ease [90]. This advantage makes
nanoparticle-stabilized emulsions applicable for EOR. The labo-
ratory experiments conducted by Ref. [87] required the use of
aqueous suspensions of 5 and 20 nm silica nanoparticles that
have their surfaces modified with polyethylene glycol. Other
materials used for the experiments included toluene, hexane,
decane, mineral oil, and crude oil. Preliminary scoping and phase
behavior scan tests were conducted with oil/water emulsions
prepared with silica nanoparticles in a concentration range of
0.1e10% wt. For preliminary scoping, the silica-stabilized
toluene-in-water emulsions were the most stable e they were
stable for months at ambient conditions without degeneration.
Experiments were conducted at 24 and 55  C for the phase
behavior scan tests, and it was observed that the volume ratio of
non-aqueous to aqueous phase within the emulsion increased as
nanoparticle concentration increased. Lastly, column flood ex-
periments were carried out in a glass-bead pack to simulate the
flow of toluene-in-water emulsions in porous media. The glass-
bead pack was initially saturated with deionized water, and
then, emulsions were injected at a rate of 2 cm3/min and again
displaced with deionized water. Observation of the flow of
emulsions through the porous media revealed their character-
istic sharp emulsion-bank front as illustrated in Fig. 14. A sharp
emulsion-bank front is an important requirement for sweep ef-
ficiency. Furthermore, the emulsions exhibited high apparent
viscosity, and also, did not degenerate.
The stability of emulsions stabilized by surface-coated
nanosilica was reported by Ref. [91]. The stability was achieved
for months and at high temperatures. Like Ref. [87], Ref. [92]
conducted flood experiments; but, they dwelt on CO2 flooding.
Surfactant-stabilized CO2 foams are used for mobility control
application in EOR [93]. Notwithstanding, surfactant-stabilized
CO2 foams have poor stability, and low tolerance in high
salinity and temperature conditions [91]. Their low viscosity
Fig. 14. Emulsion-bank (indicated with arrow) displacing water in glass-bead pack
forms a sharp front (source: [87]).
401
causes them to channel preferentially through layers with high
permeability, while their low density makes them susceptible to
gravity segregation. In the work of Ref. [92], 5 nm surface-treated
silica nanoparticles in the range of 0.05e1% wt. were used, and
they concluded that stable CO2 foams can be generated for use in
EOR and with improved volumetric sweep efficiency. Also, in the
research work of Ref. [94], a process for the generation of sta-
bilized CO2 using nanosilica was presented. Additionally, they
studied the effect of brine concentration, pressure, and temper-
ature on CO2 foam generation.
Using laboratory core flood experiments, Ref. [95] did inves-
tigation and concluded that certain types of polysilicon nano-
particles (PSNP) can be used to enhance oil recovery in water-wet
formation by taking advantage of their ability to alter the
wettability of rock surface. Three types of PSNP namely hydro-
phobic and lipophilic PSNP (HLPN), lipophobic and hydrophilic
PSNP (LHPN) and neutrally wet PSNP (NWPN) were used. HLPN is
known to make a water-wet rock oil-wet or increase the degree of
wettability of an already oil-wet rock [95]. Conversely, LHPN
renders an oil-wet rock water-wet or cause an already water-wet
rock to become strongly water-wet. NWPN changes either water-
wet or oil-wet rock to an intermediate state. NWPN and HLPN
were used at a concentration of 3 g/L while LHPN was used at 2 g/
L. The close monitoring of volumes during the core flood exper-
iments facilitated the measurement of important parameters like
original oil in place (OOIP), volume of oil recovered when poly-
silicon nano-fluids were used, total volume of oil recovered,
volume of oil remaining in the pore space after EOR, and effective
pore volume of each core plug. The results demonstrated that the
use of HLPN and NWPN lead to an improved oil recovery while
LHPN resulted in an insignificant recovery.
Laboratory experiments were conducted by Ref. [96] to
investigate the effectiveness of modified nanosilica in the
enhancement of oil recovery from light and intermediate oil
reservoirs. Core plugs of sandstone, and a brine composition of
5% wt. was used for all experiments. Contact angle and interfacial
tension measurements were made to determine the ideal con-
centration of nano-fluid for the injection process. They discov-
ered that the presence of nanosilica lead to a reduction in
interfacial tension, and also, oil phase contact angle measure-
ments showed a rock wettability alteration from water-wet to
oil-wet. However, interfacial tension reduction and wettability
alteration was more pronounced in the light oil reservoir; so,
better recovery results were recorded with these cores. They
concluded that the mechanisms responsible for oil recovery
enhancement were interfacial tension reduction and wettability
alteration. Also, Ref. [97] applied hydrophilic silica nanoparticles
(average size: 7 nm) in the preparation of nano-fluids, and used
Berea cores for oil recovery evaluation. Two-phase flooding ex-
periments were carried out using the transparent glass micro-
model, while core flood experiments were conducted with the
Berea cores. Their results indicated that nanoparticles can
enhance the recovery of oil.
The effect of initial rock wettability on EOR process was
probed by Ref. [98]. The investigation involved core flood ex-
periments with silica nano-fluids, and within a temperature
range of 25e80  C. Fumed hydrophilic silica nanoparticles, with
average size of 7 nm and at concentration of 0.05% wt, were used
in preparing the nano-fluids. Also, the core samples used were
from Berea sandstone. Some rectangular and transparent quartz
plates served as solid substrates in order to determine the
wettability behavior in the presence of silica nano-fluids. The
cores and quartz plates' wettabilities were turned from water-
wet to oil-wet. Their results proved that silica nano-fluids
reduced the residual oil saturation and increased the
402 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
displacement efficiency for all the wettability cases considered,
but, optimal result was achieved in the intermediate-wet
system. Besides, the displacement mechanism efficiency
improved with temperature. The contact angle measurement
revealed that the nano-fluid rendered the quartz plate more
water-wet in both wettability cases, and also, the interfacial
tension measurement of both wettability cases showed the in-
fluence of temperature.
The effect of silica nanoparticles on surfactant flooding was
studied by Ref. [99]. Their work involved the use of partially
hydrophobic nanosilica, hydrophilic fumed silica, and an anionic
surfactant. The interfacial tension measurements were carried
out with a captive drive instrument. Furthermore, the adsorption
of surfactant onto the prepared sand grains was measured. Un-
consolidated sandstone sand packs were used for the flooding
experiments e a primary oil flood for establishing connate water
conditions, a water flooding for secondary oil recovery process,
and a nanoparticle-laden surfactant flooding for tertiary recov-
ery. The results, for all the surfactant concentrations investigated,
demonstrated a general reduction in surfactant adsorption on
rock surface. This reduction is due to the presence of nano-
particles, and was higher for hydrophobic nanoparticles. The
flooding experiments confirmed that silica nanoparticles facili-
tated the recovery of additional oil during surfactant flooding,
with higher improvement in efficiency noticed with the partially
hydrophobic nanosilica.
Furthermore, Ref. [100] introduced nanotechnology into their
study of polymer flooding for the purpose of enhancing oil re-
covery. The nano-fluid used was a synthesis of acrylamide,
acrylic acid, and nanosilica functional monomer. The nanosilica
functional monomer was prepared using nanosilica (size range:
10e20 nm), and then, the nano-fluid was synthesized by free
radical polymerization. Another fluid, containing only acryl-
amide and acrylic acid, was also prepared for performance
comparison with the nano-fluid. The two fluids were character-
ized by infrared and 1H NMR (Proton Nuclear Magnetic Reso-
nance) spectroscopy, elemental analysis, and scanning electron
microscope (SEM). Intrinsic viscosity measurement of copolymer
was done with an Ubbelohde viscometer at 25  C, while rheology
and viscoelastic measurements were performed with a HAAKE
RS 600 rotational rheometer at 65  C. Core flood experiments
were done with two Berea sandstone cores at 65  C. Their results
indicated that the nano-fluid exhibited a higher apparent vis-
cosity at 500 s
1 compared to the fluid without nanosilica.
Additionally, the nano-fluid revealed a viscosity retention rate of
up to 43.7% at 95  C, displayed a better mobility control
compared to the base case, and also, enhanced the recovery of oil
by up to 20.1%.
3.4. Application of silica nanoparticles in drag reduction
High injection pressure or low injection rate has been a major
problem encountered during water injection for EOR application.
This problem is even amplified when attempting to access low
permeability reservoirs; consequently, industry practices such as
hydraulic fracturing, acidizing, etc. have been applied in such
cases to increase permeability, and possibly reduce drag.
The presence of hydrophilic silica nanoparticles, at a small
concentration, can enhance the flow of oil/water binary mixture
in a confined nano-channel [101]. The observations of Ref. [101]
showed that pressure increased with increasing displacement
when silica nanoparticles were not present; but, the presence of
silica nanoparticles facilitated the reduction in pressure with
increasing displacement. In another research, similar to that of
Ref. [95], Ref. [102] carried out core displacement experiments
(CDE); but, they focused on emphasizing the drag reduction
capability of certain types of nanoparticles. Hydrophobic nano-
particles (HNPs) of silica (12.4e13.4 nm) were used in the ex-
periments performed by Ref. [102]. The first sets of sandstone
samples were not treated with HNPs, while a dispersion of HNPs
was injected into the micro-channels of the other sets of
sandstone cores. Observations pointed out that the HNPs were
adsorbed to the hydrophilic pore walls, and they formed a
strong hydrophobic layer which initiated a slip boundary con-
dition. Thereafter, CDE were executed with water to investigate
drag reduction in all the core samples. The outcome of the re-
sults indicated that the water-phase effective permeability
increased by an average of 47% for all the HNPs-treated cores -
an evidence of reduction in flow resistance through the micro-
channels. The results were attributed to the fact that the HNPs
changed the wettability of the hydrophilic walls from water-wet
to oil-wet. They simulated the relationship between pressure
gradient and flow rate using Lattice Boltzmann Method (LBM).
The developed correlations validated their experimental results.
Also, they corroborated their results with field data of three
wells that shown a reduction in injection pressure after treat-
ment with nanoparticles.
4. Challenges and the solutions implemented
Based on the study that is carried out, two possible challenges
with the use of nanoparticles are observed. Also, solution tech-
niques were applied to assure a successful application of nano-
technology in those instances. Applications of such techniques
may help in the successful execution of future research. One of
the observed challenges has to do with the stability of nano-
particles in a liquid medium. This may be a challenge for nano-
technology applications in drilling and hydraulic fracturing
fluids. In the work of Ref. [20], stability of the nanoparticles was
ensured by the addition of viscosifier. Surface modification can
also help in the case of nanoparticles aggregation. The surface of
silica nanoparticles can be rendered non-polar when treated
with compounds like alcohols, alkoxysilanes, etc. This surface
treatment is effective in facilitating the dispersion of nanosilica
in a wide array of non-alcoholic solvents [62].
The other challenge has to do with the transportability of
nanoparticles in reservoir rocks. This may be a challenge for
nanotechnology applications in EOR. That was why some re-
searchers [38,39,85,86] investigated the transport and retention
properties of nanoparticles in some reservoir core samples.
Surface modification of nanoparticles was the solution that
facilitated their minimal retention on the core surface. For
instance, in the work of Ref. [38], the surface modification
assisted in shielding the carbon nanoparticles, and thus, inhibi-
ted charge interaction between the nanoparticles and the core
surface. This explains the reason behind the use of surface-
treated nanoparticles for EOR applications.
5. Conclusions
(1) The use of several nanoparticles in different areas of the oil
and gas industry is presented. Nevertheless, more
emphasis is placed on the application of silica nano-
particles. Generally, nanotechnology has interesting ap-
plications in drilling and hydraulic fracturing fluids,
oilwell cementing, enhanced oil recovery (which includes
transport study, and foam and emulsion stability), corro-
sion inhibition, logging operations, formation fines control
during production, heavy oil viscosity reduction,
 M.F. Fakoya, S.N. Shah / Petroleum 3 (2017) 391e405
hydrocarbon detection, methane release from gas hy-
drates, and drag reduction in porous media.
(2) Most of the applications of silica nanoparticles so far are in
the areas of water invasion reduction in shale, filtration
and rheology control in fluids, oilwell cementing,
enhanced oil recovery (which encompasses transport
study, and foam and emulsion stability), and drag reduc-
tion in porous media.
(3) The observed challenges associated with the use of
nanoparticles are their stability in a liquid medium and
transportability in reservoir rocks. The addition of visco-
sifier was implemented by researchers to ensure stability,
and also, they used surface-treated nanoparticles to facil-
itate stability and transportability.
6. Future research suggestions and recommendations
The oil and gas industry can reap huge benefits from nano-
technology in the future if new nanomaterials are developed.
Better performance and new application may be uncovered if
two or more different nanoparticles, and at different concen-
trations, are probed for the possibility of synergism in their
hybrid substances. Besides, the creation of new nano-fluids may
be possible if nanoparticles are dispersed in a mixture of
different fluid types. Consequently, studies on synergistic effects
are suggested for investigation in future nanotechnology
research. The resulting technology from the synergistic studies
may reinforce the current and future nanotechnology applica-
tions in the oil and gas industry, especially for HPHT applications.
To date, majority of the oil and gas industry nanotechnology
publications are reports of laboratory experimental works;
therefore, more field trials are recommended for further
advancement of nanotechnology in this industry. Usually,
nanoparticles are expensive; so, it will be cost beneficial to use
the lowest nanoparticles concentration possible while still
achieving an acceptable level of a desired performance. Hence,
optimization studies are also recommended for examination in
future nanotechnology research.
Acknowledgements
The authors express their profound gratitude to the Univer-
sity of Oklahoma for granting the permission to publish this
work.
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