REVIEW

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Nanotechnology Research and Development in Upstream

Oil and Gas
Peter J. Boul* and Pulickel M. Ajayan

aspect ratios (in the case of nanotubes),[7]

Research in nanomaterials has brought many performance enhancements to the enhanced surface-dependent properties
materials used in oil and gas well drilling, cementing, production, and enhanced such as thermal conductivities,[8] electrical
oil recovery (EOR). While the products of these investigations and product conductivities,[9] and the ability of some
nanoparticles (such as sub-20 nm iron
development processes vary widely in terms of technological readiness, improve-
oxides) to have superparamagnetic proper-
ments in performance with nanoparticles are being witnessed in the field at this ties.[10] Nanoparticles, as those used in
current time. Step-change innovation in the industry through advances in nano- enhanced oil recovery (EOR), have been
materials is anticipated to find a strong footing in the development of smart self- observed to display a structural disjoining
sensing cements, production technologies, EOR technologies, nanoparticle pressure effect.[11] This is recognized as a
sensors, sensor networks, and downhole power and automation. Herein, a brief dominant mechanism in surface spreading
by nanoparticles in chemical EOR applica-
overview of the applications of nanoparticles as they relate to upstream oil and
tions.[12] The structural disjoining pressure
gas is provided and where the current state of the art is in high-performance effect is believed to be responsible for
oil well construction, production enhancement, and reservoir management higher efficiencies in oil displacement in
materials is evaluated. oil wet reservoir rocks.[13]
The materials used to drill, build, and
produce oil wells are required to be chemi-
cally resilient, temperature and pressure
1. Introduction tolerant, and durable for years on end. Globally, the average
age of an on-shore oil well ranges from 20 to 30 years.[14] In some
Nanoparticles have been shown to provide many improvements high-capacity on-shore wells, production can last for 50 years or
in material performances when included in existing material more. With growing energy demands, more challenging environ-
systems used in the construction and production of oil and ments are going to be encountered when petroleum wells are
gas wells.[1] Research in petroleum well drilling, design, stimu- drilled to greater depths, leading to higher pressures, higher tem-
lation, and reservoir production management has demonstrated peratures, and more complex protruding formations with the
that nanoparticles can make industrial materials tougher,[2] well potential for more corrosive gases such as CO2 and hydrogen
completion and production processes more efficient,[3] and pro- sulfide (H2S).[15] Hence, materials in upstream oil and gas will
vide the possibility for real-time sensing of a well’s structural be engineered to increasingly higher standards to meet these
health[4] and productivity. Nanoparticles have found potential demanding well conditions. The high performance promised
by nanomaterials has in many instances met these objectives.
applications in the industry due to a variety of different favorable
Step-change disruptions to the industry with nanotechnology
physical properties they impart into materials through their high
[5] [6] are a distinct possibility and the appropriate advancements
surface area-to-volume ratios, high surface activities, high in nanomaterials for subsurface power and energy storage,[16]
sensors,[17] and structural materials[6] are being actively pursued
Dr. P. J. Boul by many research groups.
Aramco Research Center The drilling domain has as its primary drivers safety, effi-
Aramco Services Company
Houston, TX 77061, USA ciency, and speed. Wells drilled with fluids containing nano-
E-mail: peter.boul@aramcoservices.com particles such as nanosilica offer the possibility of an improved
Prof. P. M. Ajayan rate of penetration (ROP) through difficult water-reactive rock
Materials Science and NanoEngineering Department formations, such as shales.[18] Nano-zinc oxides which have been
Rice University shown to outperform standard H2S scavengers can be used in
Houston, TX 77006, USA drilling to eliminate potentially deadly H2S emissions from
The ORCID identification number(s) for the author(s) of this article certain treacherous rock formations, helping to insure the safety
can be found under https://doi.org/10.1002/ente.201901216. of drilling personnel.[19]
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Cements in well construction are also witnessing numerous
Weinheim. This is an open access article under the terms of the Creative advances in the implementation of nanoparticle designs.
Commons Attribution License, which permits use, distribution and Nanoscale magnesium oxide expansive agents mitigate pervasive
reproduction in any medium, provided the original work is properly cited. volumetric shrinkage issues in Portland cements (PCs) which
DOI: 10.1002/ente.201901216 threaten the long-term stability of the well.[6,20] Nanotubes[21]

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www.advancedsciencenews.com
and nanosilicas[22] have been shown to reinforce cements with
superior tolerance to excessive loads, corrosion resistance, and
higher strength under simulated well conditions of high temper-
atures and pressures. With the foundations for improved strain
tolerances and piezo-sensitivity in cements laid out, further engi-
neering of these materials can lead to more durable wells, with
lower risks of zonal isolation breaches and cements which can
provide information to an operator when structural stresses
within the well are excessive and problematic.
Production technology and reservoir management are antici-
pated to benefit greatly from advances in nanochemistry. Product
performance achievements have been shown in hydraulic frac-
turing, where, for example, viscoelastic surfactant-based fractur-
ing fluids display greatly improved leak-off and a higher thermal
stability upon the use of ZnO nanoparticles.[23] Free-flowing pow-
ders of emulsified acids stabilized with hydrophobic nanosilicas
present the possibility of improved high-temperature acid frac-
turing performance. The control of materials at the nanoscale
allows the engineer to design materials with molecular-scale
stimulus–responsive behavior. For example, these encapsulated
acid emulsions can be triggered with surfactant to release acid at
the demand of the operator.[5]
EOR methods involving nanoparticles have shown promise
for effects in providing a higher superior emulsion stability[24]
and for their propensity to displace hydrocarbons embedded
within porous media.[13] Multimetallic nanocatalysts have also
shown the possibility of catalytic EOR for heavy oils and bitu-
mens.[25] If these technologies come to fruition, it is anticipated
that the environment, production, and transportation costs of oil
sands could be greatly reduced.[26]
The implementation of advanced nanotechnologies in oil and
gas is expected to result in higher efficiencies and lower costs,
leading to a reduction in the carbon footprint of oil extraction
and higher safety standards. The objectives of this article are
to 1) describe oil and gas applications of nanotechnology, 2) cap-
ture the most recent advances in this topic, and 3) highlight new
and emerging areas of nanoparticle research that can contribute
to the development of new oil and gas technologies. The appli-
cation areas discussed herein are classified into four domains:
drilling, cementing, production, and EOR. In what follows, we
will give an overview of these applications and the nanomaterials
(Figure 1) that are being investigated and developed to improve
material performances.
2. Nanomaterials in Drilling Fluids
Nanoparticles have been reported to bring significantly enhanced
performance to drilling fluids and help address current chal-
lenges.[27] The large surface area-to-volume ratio results in superior
or even unexpected performances for surface-dependent nanoma-
terials. The utilization of various nanoparticles as a rheological
modifiers and fluid-loss reducers in water-based muds (WBMs),
has been studied for several years. Superior rheological properties
have been obtained using very low concentrations of nanoparticles
(<1.0 wt%). The nanometric dimensions of nanomaterials have
also been shown to be of use in plugging pore throats in shale with
greater efficacy than microparticles, leading to a significant reduc-
tion in fluid invasion as well as thinner filter cakes.[28]
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Peter J. Boul received his Ph.D. degree
in chemistry from Rice University in
2002. From 2002 to 2004, he was a
chateaubriand postdoctoral fellow at
the Institut de Science et d’Ingénierie
Supramoléculaires in Strasbourg,
France. Following a fellowship at the
University of Texas at Austin, he took
a position at NASA (Johnson Space
Center) in research and development
with a focus on nanocomposites. He is currently a senior
researcher at the Aramco Research Center (Aramco
Services Company) in Houston where his work involves
the development of advanced materials for the
construction of oil and gas wells.
Pulickel M. Ajayan received his Ph.D.
degree in materials science and
engineering from Northwestern
University in 1989. Shortly after, he
spent time at NEC Corporation in
Japan and at research laboratories at
the Laboratoire de Physique des
Solides in Orsay and the Max-Planck-
Institute fur Metallforschung in
Stuttgart. Later he joined the materials
science and engineering faculty at Rensselaer Polytechnic
Institute. Currently, he is the founding chair of the
Materials Science and Nanoengineering Department and a
professor of engineering at Rice University. His research
interests are focused on functional nanostructured
materials for a variety of applications.
During drilling operations, drilling fluids must have the rhe-
ological properties required to carry cuttings from beneath the
drill bit up the annulus of the well for separation at the well sur-
face. In addition, the fluids provide cooling for the drill bit and
reduce friction between the drill string and the formation being
drilled. At the same time, the fluids should maintain these prop-
erties while stabilizing the wellbore without causing irreversible
damage to the rock formation.[29] This is especially important
when drilling reservoir sections, where formation damage can
change the permeability which can reduce the ROP and directly
impact oil and gas production efficiency.[30]
The beneficial use of nanoparticles in drilling fluids (typically
referred to as muds or drilling muds) has been demonstrated in
all types of drilling fluid systems. The basic mud systems (in the
absence of nanoparticles) have been developed over the years to
include WBMs, oil-based muds (OBMs), and synthetic-based
muds (SBMs).[29] OBMs are typically diesel based, whereas
SBMs can be based on a variety of different but more environ-
mentally friendly fluids (including glycol, glycerins, and gluco-
sides).[29] These different drilling fluid systems have different
cost benefits and material advantages which are taken into con-
sideration when the drilling engineer selects the fluid for a given
section. For example, WBMs are often favored mud systems
when drilling through aquifer sections of wells to minimize
the environmental impact of the drilling process. In the following
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 1. The most widely reported nanomaterials that utilized research and development activities in upstream oil and gas are presented. These are
the nanomaterials and their nanoscale characteristics with their applications discussed in this Review as they pertain to drilling, cementing, production,
and EOR.
sections, we highlight some of the improvements realized with
the use of nanoparticles in the design of novel drilling fluids
(Figure 2).
2.1. Wellbore Stability
When drilling through shale-producing formations, water
invasion into the shale can weaken the wellbore and lead to diffi-
culties in drilling, such as stuck pipe and hole collapse. WBM
formulations that include nanosilicas have been shown to offer
improved shale inhibition over some of the commercially avail-
able non-nanoparticle-based shale inhibitors. Because the
extremely low permeability of shales (nano-Darcy) does not allow
the fluid to permeate the formation as more permeable rock
formation does, conventional filter-cake-forming technologies
are not options in drilling through shales with WBMs.
Formation mineralogy is important when it comes to the
design of drilling fluids for use with shales. Shale is a sedimen-
tary rock composed of silicates and aluminosilicates such as
quartz, clay minerals, carbonates, and other minerals such as
pyrite. The clay content in shales makes them reactive to
water-based drilling fluids. Different varieties of clays react
differently to water. For example, a shale with a high smectite
content will typically have a higher reactivity to water than a shale
with a higher illite content.[31]
To address some of the issues in drilling through water-
sensitive shale formations, nanosized particles can be designed
to penetrate deeper into the formation and plug the shale pores t
o stop water invasion (Figure 3). High concentrations (from 5
to 50 wt%) of nanosilicas show plugging of shale core samples
with a composition of between 17% and 20% smectite.[32]
These high concentrations of nanosilicas limit the economic via-
bility of these products in the field, so a more active kind of nano-
silica has been sought and applied for use in drilling operations.
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At concentrations below 3 wt%, nanosilicas functionalized with
alkylamines show improved inhibition activity of shale
(with 28% smectite/illite mixed layers) in WBMs. When allowed
to interact synergistically with polymers, such as polyanionic cel-
lulose, these nanosilicas show even greater efficacy, inhibiting
clays in shales from reacting when in sea water-based drilling flu-
ids.[33] These nanoparticle systems also benefit from milder, less
caustic fluid requirements over silicate muds, well known to
inhibit shales. While these silicate muds require a pH in excess
of 12, nanosilica drilling fluids can be adjusted below 10.[18]
Wellbore strengthening is a critical component sought in dril-
ling through all formations. A strong wellbore is as important for
oil or gas wells constructed through shales as it is for limestones
and sandstones. Wellbore strengthening during drilling opera-
tions has also been achieved by the use of ferric hydroxide nano-
particles. A study by Nwaoji et al. utilized these nanoparticles
as a loss circulation material (LCM) that resulted in a stronger
wellbore and minimized fluid losses.[34] The ferric hydroxide
nanoparticle formulations were exposed to sandstone core sam-
ples. Cores display ultimate compressive strength values 70%
higher than unexposed cores (comparing 16.5 and 27.5 MPa).
2.2. Filtration Control of Drilling Fluids with Nanoparticles
Rock formations which have higher permeability than typical
shales, such as sandstones and limestones, require additives
to prevent filtration of the drilling fluid into the formation.
Since drilling fluids are typically weighted such that there is a
positive overbalance between the drilling fluid and the forma-
tion’s pore pressure, a filter cake at the rock–fluid interface is
built to prevent fluid loss from the drilling mud. It is important
that this filter cake (also known as the “mud cake”) is as imper-
meable to fluid loss from the drilling fluid as possible and that it
builds this essential impermeability quickly. It is also critical for
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 2. Promising nanoparticle applications in drilling fluids. Wellbore stability and filtration control can be enhanced with nanoadditives, including
nanosilicas and GO, in drilling fluids. These properties of drilling require additives that act at the solid–liquid interface of the drilling fluid and the rock
formation being drilled. Fluid rheology is another aspect of oil and gas well drilling which is essential and benefits from nanoparticle. Nanocellulose shows
promise in this fluid property. Other essential aspects of drilling fluid design where nanoparticles show promise are cooling of the drillbit, pollution
control, and safety.
Figure 3. Wellbore stabilization with nanoparticles. Nanosilicas have been
used as agents which plug pores in rock formations and strengthen rock by
preventing the sometimes negative consequences of water reactivity, par-
ticularly as pertaining to the clay content of shales.
subsequent cementing operations that the mud cake be thin to
ease in the removal of the mud cake after drilling operations. The
well is drilled in intervals. After an interval is completed, a spacer
fluid is pushed through the annulus of the well between the
casing and formation. This fluid is flushed through the well
to displace the drilling mud, clean the annulus of drilling
mud, and remove the mud cake. A thick mud cake left on the
formation after spacer treatment and after the placement
of the cement can interfere with cement bonding to the rock
formation. This is a potential leak pathway for formation
fluids along the length of the well and a source of mechanical
weakness and debonding of the cement from the formation.
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Some nanomaterials have shown synergies with clays, such as
bentonite, to not only reduce the filtration of fluid from the dril-
ling mud into the formation but also enhance the rheological
properties of the fluid. Ferric oxide nanoparticles in bentonite
muds show promising results in this regard. Ferric oxide nano-
particles are believed to intercalate the bentonite clay platelets
displacing the complexed ions (calcium and/or sodium) at high
temperatures ultimately with the effect of increasing filtration
control. A loading of 0.5 wt% of nano-Fe2O3 provides a 22%
reduction in filter-cake thickness and a 17% decrease in filtrate
volume where the test was performed at 120
C.[35] The perfor-
mance of Fe2O3 nanoparticles from 3 to 30 nm has been tested to
show the enhanced benefit of filtration control in drilling fluids at
temperatures up to 200
C, showing a 28% decrease in filtrate
volume compared with the control without iron nanoparticles.[36]
WBMs including xanthan and graphene oxide (GO) have also
shown value for filtration control in sandstone core samples.
Comparing WBMs containing GO and commercially available dril-
ling fluids, the filter cake formed from the standard American
Petroleum Institute (API) test for fluid-loss control is approxi-
mately an order of magnitude thinner in the case of WBMs with
GO. The amount of filtrate collected during the test is also slightly
lower than with the commercially available additive.[28]
2.3. Rheological Optimization with Nanoparticles
Another drilling domain that shows promise from the use of
nanoparticles is the design of drilling fluids for harsh environ-
ments where temperatures above 120
C impact drilling fluid
shear response due to thermal degradation of the viscosifiers
in the fluid. Oxidation-resistant materials, polymers, and nano-
materials are of substantial value when drilling fluids are used
with high brine concentrations. High brine concentrations are
used in drilling fluids and completion fluids to densify the fluids
in place of solid particles, such as barite. Since barite particulates
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can irreversibly plug pore throats and reduce the permeability of
rock formations, these additives are often avoided in reservoir
sections/intervals of the well. The implementation of soluble
high-density salts (such as calcium chloride, sodium formate,
sodium bromide, and zinc bromide) is often recommended
when the effect of formation damage is important. Cuttings
from the drilling process need to be carried, suspended, and
transported by these fluids, and so yield points in excess of
1 Pa are often sought and achieved with conventional additives
such as guar gum, xanthan, and crosslinked starch. Oxidative
damage to these additives, however, becomes a significant
problem in temperatures in excess of 120
C in brines.
Cellulose nanofibers (CNFs) have shown potential as rheology
modifiers in brines. Heggset et al. have demonstrated that func-
tionalization of nanocellulose through controlled oxidation with
2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) increases
the temperature tolerance of WBMs based in cesium formate
and sodium formate brines over both standard polymers, such
as guar gum and xanthan, and nanocellulose without function-
alization.[37] CNFs as well as cellulose nanocrystals (CNCs) have
demonstrated the ability to increase yield points in WBMs con-
taining bentonite. It is believed that the CNCs form assembled
complexes with bentonite platelets to increase yield point and
fluid thixotropy, which were further enhanced through syner-
getic interactions with polyanionic cellulose.[38] When CNCs with
carboxylate (cCNC) functionalities and cationic CNCs (caCNC)
are used in low-solid WBMs, further enhancements are observed
in filtration control and rheology. It has been found that while
CNFs and CNCs show potential for rheological modification
of fluids, their use in filtration control is more modest and they
are often outperformed by other nanoparticles such as iron oxide
nanoparticles,[36] GO,[28] and nanosilica.[33]
2.4. Enhancement of Other Properties of Drilling Fluids with
Nanoparticles
Other aspects which are important in drilling include thermal
conductivity and electrical conductivity. Drilling requires a ther-
mally conductive drilling fluid to transport heat away from the
drill bit. Resistivity logging is a technique often preferred for
imaging the wellbore which requires an electrically conductive
drilling fluid. The effect of nanoparticles on the thermal and
electrical properties of drilling fluids has also been investigated.
The high surface area-to-volume ratios of nanomaterials are
believed to contribute strongly to high heat transfer rates along
with increased electron conduction. Enhancements have been
shown for nanosized tin oxide[38] and 50 nm copper/zinc oxide
in polyanionic cellulose WBMs where up to 53% increases
in thermal conductivity are observed with concentrations of
nanoparticles between 1 and 5  103%. Electrical conducti-
vity increases were also observed with the 50 nm ZnO
nanoparticles.[8]
H2S released by some rock formations during drilling is a
major safety concern for drilling operations. The primary con-
cern with H2S is the hazard that it brings to field personnel.
Exposure to 600 ppm levels of H2S is known to be fatal within
3–5 min. In addition to toxicity, H2S is extremely corrosive to
equipment used in well construction. The dominant commercial
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materials available for scavenging H2S are zinc compounds
such as zinc oxide (ZnO), zinc carbonate,[39] and iron oxide
(Fe3O4).[40] Zinc oxide consumes H2S, converting it to zinc sul-
fide. The surface area-to-volume ratio of nanosized zinc oxide
particles allows the reaction with H2S to occur with much more
favorable kinetics than bulk zinc oxide. Nanoparticle samples can
completely remove 800 ppm of H2S from mud after 15 min at
room temperature. This compares well with bulk ZnO which
removes 2.5 % of H2S in 90 min.[19]
Drilling fluid wastes are an environmental concern in the
drilling industry, and the effects of drilling activities using non-
aqueous fluids on the metal contents of marine sediments are
being addressed by some groups. It is known that the drilling
fluid discharged in the mud pit at the drilling rig can contain a
considerable amount of toxic heavy metal. Metals of this kind
are a concern when they are not contained because of their
potential to contaminate soils and permeate into ground
water.[41] Functionalized nanomagnetic particles of Fe3O4 have
been shown to provide an effective means of fishing out harm-
ful pollutants such as cadmium from WBMs and OBMs.[10]
This nanoparticle acts as a magnetic nanoadsorbent in the
removal of cadmium from drilling muds. It has at its core
nano-Fe3O4 which is decorated with polyacrylic acid chains,
which are covalently bound to the iron oxide core and function-
alized with amino groups at their ends (Figure 4).[42] When
these nanoparticles are added to a WBM with 5 ppm cadmium,
90% of the cadmium is removed from the mud within
seconds.[10]
Field trials of nanoparticle additives in drilling fluids are
under way, meeting with some success in improving the drilling
fluid performance.[43] Cost drivers are key in all sectors of the
business and lowering the cost of nanoparticles will be key to
their use in the field as they proceed into commercialization.
Figure 4. Nano-Fe3O4 particle functionalization for the removal of cad-
mium from mud pits at the rig site. Nanomagnetite is coated with poly-
acrylic acid and then covalently coupled with diethylenetriamine. Cadmium
binds to the primary amino functionalities at the surface of these
nanoparticles.
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www.advancedsciencenews.com
3. Nanomaterial-Based Enhancements in Cement
PC is a dynamic, complex, nonequilibrium composite material
with structural hierarchy existing from the nanoscale to the
macroscale.[44] It is arguably the most important material in
petroleum well construction. It seals the casing to the rock for-
mation to provide structure to the oil well and prevent the flow of
fluids from one well section or interval of the well to another.
Cementing operations start in a well after drilling a given section
of a well and after a metal pipe, known as casing, is placed in the
wellbore. To place the cement in the intended location, the
cement slurry is typically poured down through the inside of
the casing and then up through the annulus between the rock
formations and the exterior surface of the casing, where it is left
to transition from liquid to a set solid with appropriate mechani-
cal properties.[45]
The existing oil well cements used widely in the industry are
often not well suited for the extreme conditions encountered in
many well environments without specialized additive technolo-
gies. Some of the material shortcomings of oil well grade PCs
are shown in Figure 5 along with the nanomaterials which offer
solutions to the problems encountered. The limitations with
cements are principally shrinkage, strength retrogression, brittle-
ness, corrosion susceptibility, and gas migration.[45] These issues
are discussed in more detail in the sections that follow.
3.1. Autogenous Shrinkage and Nanomaterials
PCs shrink volumetrically (autogenous shrinkage) during set-
ting, sometimes leading to the formation of channels in the
cement, thereby allowing for fluid communication between
zones in the oil and gas well.[46] MgO is an additive which
expands as it is converted into magesium hydroxide
Figure 5. Tough well conditions and cement material issues can lead to debonding of the cement from the casing or the rock formation in the wellbore
and the fracturing of the bulk cement. The cement material issues are listed in this figure along with well conditions that exacerbate the material
shortcomings. Nanoparticles which have shown substantial promise in improving the properties of oil and gas well cement are nanosilicas,
calcium—silicate—hydrate (C—S—H) nanofoils, and nanomagnesia.
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(Mg(OH)2) after exposure to water in the mixed cement slurry.
The expansive properties of nanoscale MgO can be controlled
through heat-treatment conditions (typically between 500 and
1400
C) due to the influence of heat on the crystal structure
and surface area of MgO. Typically, the higher the temperature
the particles are heated to and the longer they are heated, the
slower the reaction of MgO with water. This expansion can be
further controlled through the synthesis of nanosized MgO.
In this case, the expansion rate and extent are determined by
the MgO calcining time and temperature, as well as the particle
size of the MgO.
The reactivity of MgO must be adjusted to provide maximum
expansion in the late plastic phase, at the beginnning of the hard-
ening of the cement. This is why calcium oxide (CaO) systems,
which tend to provide only early-stage expansion, are less favored
than MgO systems. Given the variety of well conditions, MgO
when used as an additive must be tailored to the temperature
and pressure conditions of the well in which it is used. About
4% of MgO calcined at 700
C, for example, has been found
to be excellent at reducing shrinkage strains in a class G PC
at 40
C. At 100
C, the same additive may not counter the effects
of autogenous shrinkage as well.[6,20] An active area of research
currently aims at providing a more generic additive solution to
act against the shrinkage problem under a wide range of well
conditions.
3.2. Nanoparticle Cement Set Accelerators and Gas Migration
Additives
Cement set accelerators are important chemical additives in oil
well cements. They offer the possibility of shortening the time
duration it takes for the cement to transition from liquid (slurry)
into the solid phase. This period of time, known as “waiting on
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cement” (WOC), incurs costs with each minute, much of which

can be mitigated with good precision cement design. Cement
accelerators are also used to reduce the risk of a phenomenon
known as gas migration which is of critical importance to zonal
isolation. Inorganic salts such as calcium chloride are often used
as cement accelerators for these cases. These accelerators, how-
ever, are known to have the negative side effect of increasing the
cement porosity. Due to its high surface activity, nanosilica has
been proposed as a good replacement material as a cement addi-
tive.[2,47] Nanosilica displays a distinct advantage to commonly
used accelerators[48] because it decreases the porosity and
increases the mechanical strength of set cement[49] by up to
Figure 6. Class H cement hydration kinetics with different accelerators
35%. The surface area-to-volume ratio of nanosilica along with (2% dosage bwoc) at 15
C represented through a) heat flow and b) cumu-
the C—S—H nucleation, growth, and seeding observed in lative heat.[2b] The various shapes of nanosilicas are found to lead to
cements laden with nanosilica makes nanosilica a valuable accel- differing cement hydration acceleration, where the smallest nanosilica
erator and fortifying nanomaterial in PC. The C—S—H forma- (5 nm diameter) and rod-shaped nanosilica demonstrate the greatest
tion is accelerated, in part, due to the acceleration of the pozzolan accelerating activity.
reaction of hydrated lime (Ca(OH)2) and SiO2.[50] For these prop-
erties, nanosilica finds potential applications in a number of dif-
ferent oil and gas well cementing scenarios including the
cementing of lower temperature zones within a well. Cement
close to the surface of wells in deep-water oil wells can be
required to be set at low temperatures from 10 to 15
C.
Nanosilica is also known to help with gas migration issues.
Gas migration can occur in cements after the cements have been
placed in the well and the hydration reactions in the cements
render weak gel strength. The gel strength development results
in the loss of the hydrostatic head provided by the cement
slurry density on the surrounding rock formation. When this
occurs, the cement becomes susceptible to the pore pressures
from the formation which can cause channeling in the cement
before the cement builds enough mechanical strength to resist Figure 7. a) The molecular structure of polycarboxylate ether (PCE) super-
the influx of fluid/gas from the formation. Nanosilica and plasticizer. b) The surface pacification of C—S—H nanofoils with PCE.
C—S—H nuclei have been shown to reduce the risk of gas
migration by shortening the time (transition time) between when
the cement is a weak gel to when it is a strong set structural with polycarboxylated ethers (PCEs) (Figure 7). PCEs are known
material.[2,47,48,50,51] as superplasticizers in the concrete industry and have remarkable
There are many different sizes and shapes of nanosilica that properties on their own for their ability to dramatically reduce the
can be synthesized or purchased commercially. The size and viscosity (disperse) of cement slurries. Nanofoil-PCE nano-
shape of the materials can have a major effect on the influence composites are prepared by the coprecipitation of sodium silicate
of the material of cement hydration. Figure 6 shows how differ- and calcium nitrate in the presence of a PCE. Larger PCE con-
ent shapes and sizes of nanosilica can influence acceleration of centrations are associated with smaller sizes of amorphous/
cement setting. The nanosilica tested imparts different setting semicrystalline C—S—H nanofoils.[53]
kinetics on the cement where smaller the silica particle, the C—S—H nanofoils of 50–60 nm serve as effective nuclei for
greater the effect on hydration and hence, the shorter WOC time. the hydration acceleration in cement.[54] Examination of the time
About 5 nm nanosilica displays the fastest setting with cigar- dependence on the compressive strength of PCs blended with fly
shaped and string-of-pearl-shaped nanosilica close behind. The ash indicates rapid early strength as measured through isother-
larger the size of the spherical nanosilica, the slower the setting mal calorimetry of different concentrations of C—S—H nano-
of the cement. The hydration of cement with nanosilica is foils, showing excellent cement acceleration characteristics
believed to follow a C—S—H seeding mechanism. The reaction (Figure 8). It has been shown that the nanofoils not only accel-
of water with the anhydrous tricalcium silicate and dicalcium erate the hydration of tricalcium and dicalcium silicates in
silicate in cement is promoted and accelerated by the presence cement but also accelerate the pozzolanic reaction between fly
of nanosilica seeds in the cement to grow in larger quantities per ash and Portlandite.[53b]
unit time due to the high surface activity of the seeding
nanoparticles.
Other promising new materials which display the ability to 3.3. Mechanical Strength and Nanomaterials
accelerate the hydration of cement and porosity/permeability
reduction[52] of set cement are the so-called C—S—H nanofoils. Mechanical shocks such as those taking place during perfora-
These promising new materials are made as stabilized complexes tions and hydraulic fracturing can impart undesired damage

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www.advancedsciencenews.com
Figure 8. Time-dependent isothermal calorimetry of fly ash-blended PCs
with different concentrations of PCE–C–S–H nanofoils.[53b]
to cements in wells.[55] The thermal environment of the cement
will often be variable during production cycles, leading to the dif-
ferential thermal expansion and compression of the casing onto
the cement. This is a well-known problem in the industry and
also leads to the development of fractures in the cement sheath.
Breaches in the cement used in well construction can lead to the
migration of hydrocarbons and water to annular spaces where
they can mix and build up pressure. As hot reservoir fluids
are produced, these trapped annular fluids will expand and often
burst or crush the casing, leading to catastrophic damage.
Consequently, when these kinds of pressure buildups occur
and are detected, the well is often shut in if remedial treatments
of the well fail. At best, failures of these kinds lead to losses in
unrealized revenue. However, loss of life is also a consequence
of operational failures of this kind, as encountered in the
Deepwater Horizon incident.[56] For these and other operational
reasons, the mechanical properties of the set cement are targeted
to have the highest possible tensile strength and the lowest
possible Young’s modulus. Nanoparticles have been shown
to provide tensile strength enhancement ranging from 15%[21]
to 40%.[7]
In addition to the enhancements observed with nanosilicas,
carbon nanotubes, due to their high aspect ratios, show some
propensity for mechanical reinforcement of cement. However,
almost all of the research reported to date with carbon nanotubes
in cements has a requirement in the procedure to sonicate the
nanomaterials for an extended period prior to mixing with the
cement. If nanotubes are added to cement-mixed water without
sonication, the resultant set cement material can actually suffer
from reduced strength.[47] This imposes a clear limitation of the
procedure and use of the material due to scale-up issues encoun-
tered when handling the quantities of materials required for field
deployments. The low concentrations of nanotubes required to
show enhancement, however, are encouraging on economic
grounds. Recently, carbon nanotubes have been grown from
the surface of the cement clinker through a chemical vapor depo-
sition (CVD) process. This method precludes the need for soni-
cation as the nanotubes are already prepositioned on the cement
grains prior to adding water. The resulting set cements utilizing
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this modified clinker have shown enhancements of 15% in ten-
sile strength.[21]
Nanosilica is believed to contribute to increased strength and
permeability reduction through the chemical reaction between
SiO2 and Ca(OH)2 dissolved in water from the cement phases
as well as the packing factor improvement due to the small size
of the silicas.[57] Nanosilica has been observed to produce a more
dense and compact cement matrix than other silicas. The capil-
lary porosity, which is defined as the total pore space occupied by
water, has been observed to be reduced over time by over 200% in
cements containing nanosilica compared with plain cements and
cements containing fumed silica.[58] Nanoindentation studies of
PCs cured under simulated wellbore conditions (80
C, 10 MPa)
have revealed stiffer, higher-density C—S—H pastes, deter-
mined by 29Si NMR to have a greater degree of silicate polymeri-
zation compared with samples without nanosilica.[59] Long-term
(28 days) NMR studies of ordinary PC pastes inclusive of nano-
silica cured under ambient conditions exhibit longer silicate poly-
mer chains than samples in the absence of nanosilica.[60]
Nanosilica has the effect of increasing the bulk compressive
strength of the set cements.[2b]
At temperatures above 150
C, the strength of cement can
decrease dramatically (strength retrogression), due to the
dynamic conversion of the amorphous C—S—H into the
higher-density crystalline product which is α-dicalcium silicate
hydrate.[61] This problem with strength retrogression is, in part,
overcome through the addition of crystalline silica. Usually, sand
is added to cement at a concentration of 35 % by weight of
cement (bwoc) to improve its strength.[62] Research has shown
that nanosilica can be added to further strengthen the cement
at high temperatures. For example, upon the addition of 4%
bwoc of nanosilica to a standard 35% bwoc sand-containing
cement, the compressive strength of the set cement has been
found to increase by 25% compared with cement without the
nanosilica.[22]
Research teams have also looked at using nanosilica to counter
corrosion, which is a major issue for cements. Cements can suf-
fer from exposure to formations which produce carbon dioxide,
H2S, or other corrosive gases. Carbon dioxide can corrode
cement by converting portlandite into calcium carbonate. If
the cement is exposed to water, the calcium carbonate can dis-
solve and diffuse out of the cement to render increased porosity
into the cement and reduced mechanical strength. The calcium
leaching rate by carbon dioxide invasion can be dramatically
reduced with nanosilica. This is because the nanosilica reduces
the porosity of the cement, transforms portlandite into the
C—S—H gel through a pozzolanic reaction, and modifies the
internal structure of the C—S—H gel, increasing the average
chain length of the silicate chains.[63]
3.4. Sensors in Cement
In addition to the use of nanomaterials to overcome durability
and sustainability issues pertaining to oil well cementing, nano-
materials are also being sought for use as sensors. Conductive
nanofibers have been shown to not only enhance the durability
and downhole suitability of aluminosilicate cements, but they
also increase the piezoresistive response of cement.[64]
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 9. A depiction of pernament sensors positioned on the outside of
casing, between the rock formation of the wellbore and the casing. The
sensors housing is imbedded in a polymeric resin such as those used
as casing centralizers. The annular space between the sensor housing
and the rock formation is filled with cement after cement placement.
Additive materials in cements, which enhance the piezorespon-
sivities in cements, offer the possibility of enhanced downhole
sensing capabilities. The structural health of the cement inside
an oil well could potentially be monitored remotely and in real
time through this technology. Figure 9 illustrates how perma-
nent sensors may be located on the outside of casing within
an oil or gas well.
While there remain obstacles to the realization of this vision,
there is much research and development effort in producing sen-
sors that can report in real time the conditions throughout the
well. Downhole energy-storage devices, such as supercapacitors,
are also being investigated to be integrated to produce autono-
mous sensing capabilities.[4] Cements can be made intrinsically
sensing capable of external load through the addition of Fe2O3,
carbon fibers, carbon black, carbon nanotubes, and carbon nano-
fibers to the cement prior to setting.[65] Recent work[66] suggests
the feasibility of predicting the tensile stress on a cement contain-
ing 0.5% CNTs with separate algorithms for elastic response in
cement as compared with strain-hardening and strain-softening
responses observed after the material undergoes plastic deforma-
tion. Much of the research in this field has been devoted to con-
struction cements and concrete but oil well cements have also
gained some attention.[67]
4. Production Applications
4.1. Reservoir Sensing
Today, the industry relies on many well-monitoring methods to
bring an understanding about how the reservoir is going to
behave while producing petroleum fluids in both short and long
terms. These methods include gathering of production data, near
well-bore logging, and sampling of reservoir rock while drilling
and reservoir simulation.[68] To produce hydrocarbons from res-
ervoirs most effectively, it is highly beneficial to increase the
understanding of the reservoir architecture including reservoir
flow paths, heterogeneities, and unswept areas of the reservoir.
Surveys from these tests can lead to greater yields from extracting
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the amount of oil in place where a change in a few percentage
points can correspond to enormous revenues. They are a power-
ful way of maximizing the yields from improved oil recovery
(IOR) and EOR techniques.
The use of interwell reservoir tracers involves setting up a
flow field in the subsurface between injection and extraction
wells where the reservoir is to be mapped in the interwell zone.
Tracers are introduced in the injection wells, with subsequent
measurements of the tracer concentrations in the extraction
wells. Existing tracer techniques include solvents (i.e., ethyl ace-
tate),[69] perfluorocarbon gases, and flourescent tracers (i.e., flu-
orobenzoic acids).[70] Toxicity and environmental concerns limit
the application of many of these chemicals. Furthermore, exist-
ing fluorescent chemical tracers display low sensitivities (often
measuring to a sensitivity limit of hundreds of ppms), often
due to fluorescence quenching and a fluorescence background
from organic residues in crude oil.[71]
Figure 10 shows the use of tracers in an interwell scenario. In
this illustration, two tracers are injected into two separate injector
wells at two different locations within a reservoir. The tracers are
collected at the production wells where the concentrations
and time of travel through the reservoir can be determined.
Tracer A and Tracer B can represent two different barcodes.
As described in the following section, barcoded nanoparticle trac-
ers can be differentiated as a difference in fluorescence signa-
ture,[71] Raman signal,[72] mass spectrum,[73] or other chemical
or physical characteristics of the tracer.
4.1.1. Nanoparticle Sensors for Reservoir Mapping
One of the ultimate goals of using these nanoparticles as reser-
voir tracers is to provide in-depth data about petroleum reser-
voirs. A long-term goal for nanoparticle reservoir tracers is
that during their journey from the water injection well to an
oil producer, the particles could provide reservoir sensing
whereby they may record temperature, pressure, salinity, or
any other important reservoir rock/fluid properties. One way
to retrieve the measured data from the particles is the recovery
of the particles at the producing wells. In addition, the nanopar-
ticles can be used as vehicles for transporting specific chemicals
to the reservoir such as wettability alteration chemicals, scale
inhibitors, and water control agents. Despite the fact that this
Figure 10. Interwell reservoir tracers are deployed through one or more
injector wells and are collected at one or more production wells.
Different kinds of tracers can be used such that they barcode for a specific
injector well origin or a specific injection time.
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
vision is ambitious, the literature has reported various applica-
tions toward making it possible.
The first oilfield-scale demonstration of the use of nanopar-
ticles as sensors for oilfield reservoirs was reported in 2011.[17]
The particles were luminescent carbon dots with a size ranging
from 5 to 10 nm.[74] To measure the particles concentration, their
response to light was utilized as they are fluorescent. Thus, their
concentration was detected with an accuracy of 0.1 ppm using a
fluorometer. Several experimental tests were used to assess the
performance of the particles. These included visual tests to inves-
tigate the stability of the particles in oilfield brines, zeta potential
measurements, and injection through porous reservoir cores
(rocks) to investigate the mobility of the particles and their recov-
ery potential. The authors reported that 96% of the particles were
recovered after injection through a carbonate reservoir rock.
After these promising lab tests, a field test was reported. The par-
ticles were injected into an oil-producing well at a concentration
of 130 ppm. After the injection, the well was shut in for 24 h and
afterward, the well was put on production where samples were
collected and transported to the lab. The field results gave a recov-
ery factor of 82%.[17]
Many fluorescent tracers that were tested thus far suffer from
the drawback that the fluorescent signal can be obscured in the
presence of polyaromatic hydrocarbon fluorescence in crude
oil.[75] For this reason, nanoparticle tracers have been in develop-
ment which display a persistent luminescent signature that
outlives the fluorescence of species from the reservoir. About
50–100 nm LGO:Cr nanoparticles show some promise as tracers
of this type. They emit strong photoluminescence at 716 nm
under ultraviolet (UV) excitation (254 nm). The fluorescence
signal from the excitation lasts for an extensive time (of the order
of minutes) and can be used to detect 1 ppb concentration of
the nanoparticles.[71] These materials are particularly interesting
for the ability to detect the persistent luminescent signal with a
portable device equipped with a charge-coupled device (CCD)
camera.
Plasmonic nanostructures have been shown to display strong
surface-enhanced Raman scattering (SERS) intensities,[76] which
make them excellent candidates in many different sensor appli-
cations.[72] Silica-encapsulated silver nanoparticles have been
shown to exhibit 10 ppb-level sensitivities to the adsorption of
fluorescein and rhodamine dyes with Raman spectroscopy.[72]
This allows one to “bar tag” or label nanoparticles with dyes
so that nanoparticles injected into the reservoir either at different
times or at different locations can have a distinct spectroscopic
signature, which assists reservoir engineers in detailing reservoir
maps. Figure 11 shows the synthesis of Fe3O4/Ag@SiO2/Ag and
Fe3O4/Ag@SiO2 nanoparticles. The nanocomposite samples are
multifunctional and designed for low-concentration detectability.
The silver nanoparticle component in these nanocomposites
gives the SERS signal for detection of the particle, whereas
the iron oxide nanoparticle component is superparamagnetic
and allows the particles to be concentrated with magnetic fields
for higher detectability.[77]
The use of nanoparticles as reservoir tracers is an exciting area
of development toward the eventual possibility of bringing
recordable stimulus–responsive nanoparticles into use for reser-
voir mapping. An appealing aspect of these technologies is that
due to the potential for high revenue in oil recovery from
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Figure 11. Synthesis of a) Fe3O4@SiO2/Ag SERS nanoparticles and
b) Fe3O4/Ag@SiO2/Ag SERS nanoparticles. Reproduced with permis-
sion.[77] Copyright 2019, American Chemical Society.
reservoir mapping, there are fewer cost constraints in the design
of nanoparticles as tracers than in many other applications of
nanomaterials in upstream oil and gas. But there are many chal-
lenges that lie ahead in the development of these technologies.
One such challenge is maintaining colloidal stability of the par-
ticles under the high saline environments that the particles are
required to endure as well as the challenging temperature and
pressure environments of the reservoir.[78] Other challenges
remain in transport through porous media at a high temperature
and pressure.
4.2. Enhanced Oil Recovery
It has been estimated that only about one-third of the original oil
in place (OOIP) in reservoirs is actually recovered. In heavy oil
reservoirs, primary and secondary production methods at their
economic limit leave behind 80–95% of OOIP.[79] EOR methods
offer the possibility of improving the production yield of wells
through a variety of techniques including chemical injection,
gas injection, thermal oil recovery (such as steam flooding),[80]
and microbial EOR.[81] In all of these methods, the injected fluid
travels from one or more injection wells through the reservoir to
displace hydrocarbons toward an oil production well. Figure 12
shows a conceptual depiction of flooding as well as the nanotech-
nology applications for EOR purposes.
Various fluids, in chemical EOR, can be used for injection and
include water alone, viscous polymer/water solutions,[82] poly-
mer/surfactant,[83] alkali–surfactant–polymer (ASP) flooding
solutions,[84] and CO2 in water foams.[85] In the following para-
graphs, we shed light on the use of nanoparticles to help improve
the existing chemical EOR technologies. After discussion of
chemical EOR, emerging technologies utilizing nanocatalysts[26]
for use in thermal EOR, in steam-assisted gravity drainage
(SAGD), are discussed. These nanocatalysts are used to enhance
recovery by upgrading heavy oils and bitumens to lighter oils.
4.2.1. Chemical EOR and Nanoparticles
Water injection is the conventional solution for secondary oil/gas
recovery but water does not wet the oils on these surfaces for
many wells including unconventional heavy oils[79] and hydrocar-
bons from porous, low-permeability oil-wet carbonate
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www.advancedsciencenews.com
Figure 12. Water-flooding and EOR inject fluids from an injection well to pass fluid through the reservoir toward a production well.
reservoirs.[86] Chemical EOR, involving the injection of fluids
containing polymers or surfactants, is an attractive EOR method
for its potential to displace unrecovered oil. Chemical EOR aims
to displace unrecovered oil by three different major methods.
These are 1) polymer flooding methods, 2) surfactant flooding
methods, and 3) foam EOR methods.[87] Nanoparticles have
found applications in all of these methods.
In polymer flooding, a water-soluble polymer is added to the
flood water to increase the water viscosity and reduce its mobility
through the permeable formation medium. This causes a reduc-
tion in the mobility ratio, leading to greater sweep efficiency. The
volumetric sweep efficiency is defined as the ratio of the volume
of oil contacted by the displacing agent to the volume of oil orig-
inally in place. Surfactant flooding uses a surface-active agent to
reduce interfacial tension (IFT) and thus reduce the capillary
forces which often trap oil in rock pores unless a sufficient vis-
cous force is applied to displace the oil. Reducing the IFT reduces
the viscous force required for oil displacement. In foam EOR, the
primary purpose is to deliver gas to the reservoir to recover oil.
Foam is the dispersion of surfactant-stabilized gas in water.[87]
A challenge in surfactant EOR, both in CO2 flooding and in
micellar solutions, is that surfactants often adsorb strongly onto
rock surfaces, destabilizing the EOR fluid dispersions and poten-
tially leading to formation damage. This results in a loss in EOR
efficiency.[88] Colloidal nanoparticles have been shown to reduce
the adsorption of surfactant molecules and in this way, increase
oil recovery in comparison with cases where water without
nanoparticles is used.[89] Altering reservoir rocks through the
use of nanoparticles has been reported to increase the amount
of oil that can be recovered from a given core by changing the
wettability from oil wet to water wet.[90] Nanoparticles are
believed to benefit from an additional mechanism of oil displace-
ment, known as the structural disjoining pressure mechanism.
In this mechanism, nanoparticles in the fluid form layered struc-
tures which contact the surface of oil-wet minerals with differen-
tial pressures applied through wedge-like films to spread the
nanofluid over the surface, detaching the oily material coatings
on the rock surface.[11]
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Nanosilica shows promise for EOR due to their availability and
lower cost in comparison with other nanoparticles. Core-flood
studies have been reported using various sizes (7, 16, and
40 nm diameters) of nanosilica at different residual oil satura-
tions.[90b] Laboratory results indicate that up to 8%, 17%, and
40%, additional oil can be recovered from Berea sandstone cores
upon the use of these fluids of 7, 16, and 40 nm nanosilicas,
respectively.[90b] Other studies have shown the salt tolerance of
nanosilica in displacement of crude oil from Berea sandstone
with an efficiency of 50% as compared with 17% for the brine
in the absence of nanosilica.[13] When nanosilica is introduced
to Berea sandstone core samples containing crude oil, the water
contact angle of the system is lowered, up to a reported 33%
decrease (from 39
to 26
).[91] The water-wetting efficiency has
also been found to increase with increasing temperatures.[91]
Nanosilica is not the only nanoparticle system capable of
improved efficiency in EOR. A recent study[90c] reports the com-
parisons utilizing 17–40 nm Al2O3, TiO2, and SiO2 for EOR pur-
poses. The authors utilized a dispersant (vinyl pyrrolidone) with
the Al2O3 and TiO2 nanoparticles and compared the perfor-
mance of those nano-based fluids with nanosilica without disper-
sant. TiO2 nanoparticles were found to give the best wettability
change as evident through contact angle measurements, and the
core-flood experiments conducted with TiO2 gave the highest
hydrocarbon recovery.[90c] Nanoparticles, however, have been
found to require additional chemistry for increasing their sus-
pension stability and disposability in brines and when migrating
through porous media. There are two approaches which have
been exploited to these ends. In one, surfactants are used with
nanoparticles to increase their efficacy, and in the other, nano-
particles are specially functionalized for increased stability.[24]
4.2.2. Stabilization of Emulsions
Multiple synergies between surfactant additives, nanoparticles,
and ions can be exploited for improved water wettability and
improved nanoparticle stability.[92] ASP EOR is a chemical
EOR technique where high pH is believed to render a soap in
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www.advancedsciencenews.com
situ in the presence of oil within the reservoir. ASP EOR has
been explored in tandem with nanosilica to increase the water
wettability of oil adsorbed onto mineral surfaces. It was found
that the wettability of sandstone core samples depends on the
coadsorption of nanoaggregate-surfactant complexes on the
sandstone core where the presence of divalent cations assists
in the wettability of the surfaces.[93]
The oil that is being recovered from the reservoir through
these tertiary production methods can often emulsify due to
mass and heat transfer, the low dynamic IFT between phases,
and chemical reactions close to the oil–water interface. The pres-
ence of microemulsions is favored for oil recovery and the state
of the art for surfactant EOR in achieving microemulsions typi-
cally uses alcohol-stabilized surfactants or branched surfactants
with a finely tuned aqueous salinity. These microemulsion
formulations are designed for stability. The chemistry must be
tuned to prevent the formation of metastable macroemulsions
which can be formed by the coalescing of microemulsion drop-
lets which lead to surfactant-rich and polymer-rich phases that
can plug the porous spaces within the rocks into which they
are injected, leading to formation damage.[84] Hydrophilic nano-
particles are used to stabilize oil in water (o/w) emulsions where
the contact angle at the oil–water interface is less than 90
. In
contrast, hydrophobic nanoparticles are used to stabilize water
in oil emulsions (w/o) and their contact angle at the water–oil
interface is more than 90
.
Stimulus–responsive nanosilica grafted with poly(2-(dimethy-
lamino)ethylmethacrylate) (DMAEMA) have been shown to sta-
bilize and break oil in water emulsions of crude oil. The switch
between stabilizing and breaking the emulsions is pH responsive
where a 0.1 wt% concentration of the nanoparticles gives a
contact angle of 62
at pH ¼ 7 and 81
at pH ¼ 2. These function-
alized nanosilica at concentrations of 0.1 wt% stabilizes emul-
sions at a neutral pH and breaks emulsions under acidic
conditions (pH ¼ 2). The stimulus–responsive nature of these
materials offers the possibility of control over the emulsification
of oil droplets such that formation damage could be mitigated.
Testing of heavy oil recovery using DMAEMA nanosilica dis-
played superior oil recovery through a sandpack at 10 wt%
OOIP as compared with less than 1% for DMAEMA in the
absence of nanosilica.[94]
4.2.3. Stabilization of Foams
Gas injection is a widely used method for enhancing oil recovery.
Gases used for injection can vary from nitrogen, air, methane,
natural gas, or CO2.[95] CO2 injection accounts for about 38 %
of EOR in the United States.[81b] CO2 flooding is often the pre-
ferred method for oil recovery for light oil with viscosities less
than 10 cP and at reservoir depths greater than 900 m. The depth
must be high so that the reservoir pressure exceeds the mini-
mum CO2/oil miscibility pressure. When heavier oils are being
pursued, the use of CO2 alone as an EOR fluid, the low viscosity,
and the resulting high mobility of the gas compared with oil
(heavy oil can present viscosities as high as 10 000 cP) result
in a phenomenon known as viscous fingering, leading to poor
sweep efficiencies.[96] The mobility of water is directly related
to the viscosity of the fluids, and this must be equal to or lower
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than the oil to afford recovery/displacement of oil. To improve
the viscosity of CO2, it can be foamed with water. The longer
the viscosity stays high, the better the sweep efficiency. Thus,
it is important to maintain foam viscosity for the longest period
of time possible. As is determined to be the case in surfactant
EOR, nanosilicas aid in reducing surfactant adsorption in foam
EOR applications. Results of a study of nanosilica in sodium
dodecyl sulfate (SDS) revealed a 75% reduction in surfactant
adsorption onto kaolinite.[97]
The stability of foams is dramatically impacted by the presence
of oil, salinity, temperature, and pressure. About 15% additional
OOIP was recovered with the use of methyl-functionalized
12 nm nanosilica to stabilize the water–CO2 foam.[98] CO2–
surfactant foams that are surface modified with nanoparticles
(such as nanosilica) display enhanced stability over surfactant-
stabilized foams. Similar to the nonfoamed surfactant EOR,
nanoparticles in CO2-foamed EOR display a lower propensity
for adsorption onto the formation and have been shown to
increase CO2 foam stability when compared with cases where
just surfactants are used. Figure 13 shows the foam half life
of SDS as compared with SDS–nanosilica. The nanosilica used
in these tests was of 20 nm diameter with a partially hydrophobic
surface (contact angle with water was 122.2
). From the oil recov-
ery efficiencies from sandpack recovery testing (Figure 13a), the
optimal synergetic effect between nanosilica occurs when the
SDS/SiO2 ratio is at 0.17 at 1.5 wt% nanosilica. The nanosilica
surfactant outperforms SDS foam under high temperatures
and pressures. Visual flooding experiments (Figure 13b) show
that the nanosilica-stabilized foams have a superior stability at
elevated temperatures, whereas the SDS surfactant-stabilized
foam shows coarsening/coalescing of the foam.[99]
Similar surfactant-nanoparticle synergies in foam stabilization
for EOR have been observed with hydrophilic nanosilica (40 nm
diameter, contact angle with water ¼ 39
) with the cationic
surfactant cetyltrimethylammonium bromide (CTAB). It was
found that increasing the ratio of CTAB/nanosilica (with an
optimum ratio of 0.033) would increase foam stability, whereas
CTAB produced a monolayer on the nanosilica rendering it more
hydrophobic. Optimum contact angles for foam stability are
between 60
and 90
. As the CTAB concentration was increased
further relative to nanosilica, the foam stabilization effect
diminished.[100]
4.2.4. Thermal EOR and Nanocatalysts
While nanoparticles are useful in enhancing oil recovery through
surfactant and emulsion chemical EOR (which applies to heavy
oils and light oils alike), thermal EOR methods for oil recovery
are also being developed with a focus on the extraction of heavy
oils and bitumens. Steam flooding is a process which involves
the injection of steam into hydrocarbon-bearing formations to
reduce the viscosity of heavy oils and bitumens as a means to
enhance recovery. Typical recovery factors for this method are
between 50% and 60%. The major limitation of steam flooding
is that it is very energy intensive and costly. SAGD is a specific
kind of steam injection which involves two horizontal wells, typ-
ically spaced with the injection well 5 m above the production
well. Steam is injected into the upper well, reducing the viscosity
www.advancedsciencenews.com
Figure 13. a) Effect of the temperature on the half life of CO2 foam with and without nanosilica stabilization. b) Structures of SDS/nanosilica and SDS
foam in porous media at a pressure of 8.0 MPa at 22
C and 80
C. Reproduced with permission.[99] Copyright 2016, American Chemical Society.
of the hydrocarbons which drain into the lower production well
and are then pumped to the surface.[80]
Because of the energy-intensive nature and environmental
footprint of steam flooding and SAGD, the injection of catalysts
is emerging as a promising technology for recovery and upgrad-
ing heavy oils with thermal EOR. Molybdenum-based nanopar-
ticles show the possibility of achieving EOR of bitumen through
in situ catalytic conversion of light oil from bitumen feedstock
within oil sands. The EOR method used for these materials
was through SAGD EOR at 3.5 MPa and 300–320 ºC.[101] The
studies revealed that enhanced recovery could be achieved
through the decomposition of heavy oil into lighter products.
The absence of a porous matrix (used in fixed-bed catalyst tech-
nologies) for these materials and their high surface area is
believed to be the reason for their higher performances over
other catalysts such as fixed-bed catalysts investigated in this kind
of EOR.[101] It has also been suggested that because nanocatalysts
may permeate through the sands or formations into which they
are injected and thus be recovered in the production well, it may
be possible to recycle nanocatalysts.[26] Furthermore, these con-
cepts in upgrading heavy oils and bitumens are not limited to
SAGD. External microwave heating is being actively investigated
with nickle nanocatalysts to reduce the viscosity of heavy oils in
EOR. A recently published report provides a proof of concept that
nickel nanocatalysts with 2.45 GHz microwaves at 2 kW can
upgrade (break C—S and C—O bonds in heavy oil sands) and
could potentially be used as an in situ method for heavy oil
upgrading.[102]
In summary, nanoparticles show promise in EOR. There are
technical challenges that remain to realize the profitability of
these technologies. Aggregation is an issue with many nanopar-
ticles due to their high surface areas and the influence of such
destabilizing conditions as temperature, pressure, salinity, and
the influence of oil or other chemical species that may be present
in the reservoir.[91] In chemical EOR, the tunability of the nano-
particle surface chemistry, when achieved at low cost, offers the
possibility of superior performance over existing surfactant
Energy Technol. 2020, 8, 1901216 1901216 (13 of 18)
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technologies. Enhancing nanoparticle efficacy through stim-
uli–responsive technologies, when harnessed with the appropri-
ate level of control, could potentially lead to superior solutions in
terms of foam stability, microemulsion stability, and overall per-
formance. In thermal EOR, nanocatalysts are interesting for their
potential in upgrading heavy oils and bitumens but there is still
considerable investigation required in how nanoparticles may be
transported through porous media under well conditions while
maintaining their stability. The catalytic activities of nanocata-
lysts are currently being developed to obtain the maximum pos-
sible recovery enhancement while limiting formation damage.
4.3. Application of Nanotechnology in the Production Domain
4.3.1. Nanoparticles and Hydraulic Fracturing
Several domains in the production sector have benefited from the
use of nanotechnology. These include the design of hydraulic
fracturing fluids, water control chemicals, fine migration preven-
tion, and acidizing. The use of nanoparticles has been
highlighted in the development of fracturing fluids where a great
deal of literature exists on this topic.[3,103] Figure 14 shows nano-
particles which have been used and show a promise in these
upstream applications. In a typical fracturing operation, a fractur-
ing fluid is used to transmit hydraulic power in the form of
dynamic stress on the rock downhole to break it down and create
fractures. Once the fracture is created, proppants/sand particles
are used to keep it open. To transport the particles into the frac-
ture, the viscosity of the fracturing fluid is increased by adding
crosslinkers. For hydraulic fracturing, ZnO nanoparticles have
been proven for use with viscoelastic surfactant (VES)-based
fluids to improve their leak-off properties. Without the addition
of ZnO, these fluids were limited in applications of a 200 mD
maximum permeability.[23] Performance enhancements through
the use of polymer-based fracturing fluids can be achieved with
nanosilica. Guar-based polymers,[104] polyacrylamide-based poly-
mers,[105] and guar polymers under high salinity conditions show
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 14. Illustration of hydraulic fracturing. Nanoparticles used in hydraulic fracturing, acidizing, scale inhibition, and water shutoff are listed. The figure
shows the use of hydraulic power (drawn as black arrows) to impart stress on regions of a rock formation to break it down and create fractures.
better performance when nanosilica was incorporated in these
fluids. Recent works[23,106] report the use of nanoparticles in
packs during hydraulic fracturing treatments. Through van
der Waals forces, the particles attach themselves to the proppant
surfaces. When the reservoir-generated fines come into contact
with the proppant-treated surface, they will be attracted and
therefore, their propagation into the wellbore and perforations
will be prevented.
4.3.2. Nanoparticles and Water Shutoff
The production domain utilizes nanoparticles for the design of
water shutoff gels. These gels are composed of a polymer and a
crosslinker that react together to form a 3D gel structure which,
in turn, should block water-producing rocks and allow more oil to
be extracted. The literature usually refers to these as confor-
mance improvement treatments (CITs). The use of nanoparticles
in formulating these chemical technologies was reported to
improve gel stability, enhance control over the gelation time,
or improve gel propagation. We give examples of these technolo-
gies hereafter. One report[107] suggests the use of silica and alu-
minum oxide nanoparticles to improve the stability of silicate
gels which inherently lack stability without an additive. The addi-
tion of SiO2 nanoparticles with a size of 12 nm was found to
decrease the gelation time of silicate-based CIT gels.
Increasing concentrations of nanosilica allows the operator to
tune the kinetics of the phase change of the liquid colloidal solu-
tion (sol) to the gel. This reaction is often referred to as a sol–gel
reaction.
Another study[108] reports the use of nanosilica particles as a
water shutoff material due to their low average size (3–100 nm)
which enables propagation through the reservoir rocks. The use
of nanosilica to improve mechanical properties of gels generated
by the crosslinking of partially hydrolyzed polyacrylamide (PHPA)
with polyethyleneimine (PEI) is reported.[109] Scanning electron
microscopy (SEM) images show that the gels prepared without
Energy Technol. 2020, 8, 1901216 1901216 (14 of 18)
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the addition of nanoparticles were thin and more rigid.[110]
Another study[111] reported the use of dextran and PEI to form
nanoparticles that can sequester chromium (Crþ3) and prolong
the gelation time.
4.3.3. Nanoparticles and Acidizing
After hydraulic fracturing or in place of hydraulic fracturing, acids
are sometimes used as stimulation fluids for well production
enhancement. In these acidizing processes, the permeability of
the production zone is increased through the etching of rock for-
mation and boring of wormholes through the rocks using acids.
On the acidizing application for well-stimulation purposes, hydro-
chloric acid (HCl) is used as a stimulation fluid to dissolve carbon-
ate (CaCO3) rocks. One of the challenges of acidizing is that the
acids may be too reactive with rock (especially carbonate rock
formations) such that they dissolve the face of the rock without
fracturing or unevenly etch wormholes into the rock. To over-
come these issues, the industry has developed different retarder
technologies to slow the acid’s reactivity. One way to retard the
dissolution reaction, between HCl and the reservoir rock, is to
emulsify the acid in diesel. With time and temperature, the emul-
sion breaks down releasing the acid, allowing it to come in contact
with the rock. The emulsion is formed by the use of a surfactant
that acts as a stabilizer at the interface between the aqueous phase
and the hydrocarbon phase. Standard surfactant-stabilized emul-
sions have limited temperature stability and therefore, are of value
to enhance the thermal tolerance of stable emulsions. In this way,
the acids can take more time to break and stimulate the reservoir
to greater depths. The Pickering emulsion concept has been
recently introduced for oil and gas stimulation applications. In this
method, the nanoparticles can be used as a physical barrier
between the acid and the diesel. Extensive lab evaluation has
revealed that use of nanoparticle additives greatly enhances the
stability of emulsified acids. Bulk thermal stability tests indicate
that emulsion stability can be improved upon with the use of
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
nanoparticles. Samples of acids emulsified with hydrophobic silica
nanoparticles show enhanced retardation for emulsion breakage at
temperatures up to 150
C.[5,112]
Microencapsulation of HCl with Pickering emulsions of
14 nm size hydrophobic nanosilica (from surface modification
with polydimethylsiloxane) has been shown to render stable
dry (acid-in-air) powders of HCl with excellent thermal stabilities
(Figure 15). These acid-in-air emulsions are preferred for water-
sensitive shales where water-reactive clays can limit the efficacy
of water-based fluids. The release of acid from these powders is
triggered by surfactants so the timing of the acid release can be
modified to a desired rate. Testing of this technology has dem-
onstrated that enhanced fracturing and uneven etching are
achieved with this chemistry.
4.3.4. Scale Inhibition with Nanoparticles
The formation of scale deposits in well production tubing is a
long-standing issue that the oil and gas industry faces. Scale
inhibitors are used to prevent scale formation. Adsorption of
the inhibitor on the reservoir rock is used as a strategy of scale
inhibition. This is achieved by squeezing the scale inhibitor
inside the reservoir rocks in the near wellbore area where adsorp-
tion of the inhibitor takes place. When the well is switched back
to production, the inhibitor (phosphonate) is slowly released with
the produced fluid. There are concerns with this approach such
as lifespan of the treatment. To address these concerns and
enable a slower release, inhibitor-precipitation methods have
been put into application, a method where an inhibitor may
be precipitated inside the rock as a metal salt. The precipitating
phosphonate/calcium complex is a result of adjusting the salt
Figure 15. a) 5 wt% HCl dyed with Nile Blue A (25 g); b) hydrophobic silica
nanoparticles (2.5 g); c) dry acid powder flowing freely through the glass
funnel; d) dry acid powder (total product weight ¼ 27.5 g); and e) sche-
matic of acid-in-air powder (white sphere represents the silica nanopar-
ticles). Reproduced with permission.[5] Copyright 2017, American
Chemical Society.
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www.entechnol.de
concentration and pH of the injected solution. Limitations with
the precipitation approach include formation damage and block-
age of pores in the rock by the precipitation of solid materials.
To further increase the lifespan of scale inhibitor treatments
and address concerns related to the blockage of pores with pre-
cipitates, a new nanotechnology-based concept was lab tested
recently.[113] Zinc and calcium metals were used to formulate
metal-phosphonate nanoparticles that are synthesized with a size
from 50 to 200 nm. Carbonate and sandstone porous media were
treated with these metal-phosphonate nanoparticles to investigate
their propagation in porous media and test their retention/release
behavior. Several experimental techniques were used to investi-
gate the performance difference between the nanoparticles of cal-
cium/methylene phosphate (diethylenetriamine-pentamethylene
phosphonic acid [DTPMP]) under different conditions. The
authors compared the pore volume (PV) to breakthrough which
is a measure of how long it took the inhibitor to be released from
the porous media. In such an experiment, the concentration of
the metal is monitored as a function of PV produced. Once the
concentration drops below a minimum threshold value (around
1 mg L1), the corresponding PV is recorded as the breakthrough
PV (Figure 16). Clearly, better control over the inhibitor release is
achieved by use of nanoparticles in carbonate rocks when com-
pared with sandstone cores.[113]
In summary, the production technology domain has made use
of nanotechnology in several applications that showed promising
results. Nanoparticle-based fracturing fluids were found to
outperform other non-nanoparticle-based fluids, and this was
verified in field applications of VES-based fluids combined with
nanoparticles.[23] Pickering emulsions represent another exam-
ple where nanotechnology provided an opportunity to design
better acidizing fluids. Some of the limitations in the field
deployment and commercialization of these nanomaterials in
production are based in cost. As the nanoparticles demonstrating
performance advantages over conventional additive technologies
are brought into larger-scale production, driving down costs, it is
anticipated that commercialization of many of these technologies
will follow.
Figure 16. PV to the breakthrough of the DTPMP nanoparticles at 70
C.
Ca-DTPMP nanoparticles are compared from reports of two different
groups with the use of the inhibitor without complexation into a
nanoparticle.[113]
© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
5. Nanotechnology in Other Oil and Gas
Applications
The earlier applications relate to the bulk use of nanoparticles in
upstream oil and gas. However, there are many indirect uses of
nanotechnology-related advances in the field. The rapid evolution
of miniaturized and high-performance electronic devices has had
a significant impact in the industry. Sensors will be ubiquitous in
oilfields and the emergence of low-dimensional and low-power
sensor networks based on nanomaterials in the future will
enable several new detection technologies at various levels of
applications in the field. Power delivery is another area where
nanotechnology will have a significant impact. Form-fitted, fully
powered sensors are important for EOR applications. Power
delivery in the form of batteries and supercapacitors will
become viable in downhole applications if new chemistries
can be developed for operations across higher-temperature win-
dows (150–200 ºC), higher pressures, and harsher environ-
ments. Recent developments have shown that these devices
can be made to operate above 150 ºC using nanostructured elec-
trodes and ionic liquid electrolytes.[16] As high temperature and
robust energy-storage devices with high energy, high power
densities, and miniaturized features become available, the indus-
try will greatly benefit in building high-precision detection
devices in several upstream technologies. Fully autonomous
and deployable sensors in EOR and other downhole operations
would be the first technologies to benefit.
6. Conclusions
Nanotechnology provides huge potential in addressing technol-
ogy challenges related to the upstream oil and gas industry with
nanomaterials and devices. Some of the clear benefits of nano-
technology include the use of nanoparticles to provide incremen-
tal improvements to existing methods and procedures in
extracting oil and gas, whereas some of the development in nano-
particles promises to be transformative. Step-change advances in
the industry through developments in nanomaterials can occur
in any of the domains of well construction, production, or reser-
voir management. With nanoparticles utilized in solving difficult
industrial problems in upstream oil and gas operations, the
benefit of nanoscale precision in product development is clear.
A recent book by Schwab[114] has vividly captured the impact of
“The Fourth Industrial Revolution” where major technological
developments across industries are driven by innovations in
manufacturing,[115] robotics,[116] sensors,[117] electronics, power,
and materials. In this ensuing technological revolution, one can
have little doubt that nanotechnology will be an essential compo-
nent through all of the technological drivers that exist in the oil
and gas and related industry.
Acknowledgements
The authors would like to thank Aramco Services Company and Saudi
Aramco for permission to publish this work. The authors acknowledge sig-
nificant contributions from Dr. Ghaithan Muntasheri in the preparation of
this manuscript and thank him for his deep insights, inspiration, and direct
contributions in several sections of the manuscript.
Energy Technol. 2020, 8, 1901216 1901216 (16 of 18)
www.entechnol.de
Conflict of Interest
The authors declare no conflict of interest.
Keywords
cements, enhanced oil recovery, nanomaterials, nanoparticles, oil wells,
production
Received: October 14, 2019
Published online: November 13, 2019
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