SPE-183301-MS

Nanotechnology for Oilfield Applications: Challenges and Impact

Hon Chung Lau, National University of Singapore; Meng Yu, Shell Exploration and Production Company; Quoc P.
Nguyen, University of Texas at Austin

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE, 7-10 November 2016.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
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consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
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Abstract
Nanotechnology is the design and application of engineered or naturally occurring nanoparticles with at
least one dimension of the order of 1 to 100 nm to accomplish specific purposes. Nanoparticles possess
three unique properties. First, their small size enables nanoparticles to be transported into formation pores
not accessible to larger particles. Second, at nanoscale, material properties are sized dependent because of
the large surface area to volume ratio. Therefore nanoparticles can be engineered to contain specific optical,
magnetic, interfacial, electrical or chemical properties to perform specific functions. Combined together,
these unique properties allow nanoparticles to be used for many purposes in the oilfield. The objective of
this paper is to conduct a critical review of the recent literature to determine the status of research and
development and field application of nanotechnology to the oilfield.
Most of the proposed applications of nanotechnology in the oilfield can be classified into the following
six areas: (1) sensing or imaging, (2) enhanced oil recovery, (3) gas mobility control, (4) drilling and
completion, (5) produced fluid treatment, and (6) tight reservoir application. Our review shows that
much of the current research is focused on the performance of nanoparticles in the reservoir. Some work
is done of the propagation of nanoparticles and very little work is done on the delivery and recovery
of nanoparticles. Lack of well-defined health, safety and environmental protocols for safe delivery and
recovery of nanoparticles can be a showstopper and more focused research is needed in this area. Our
work also shows that affordability of nanoparticles is another showstopper due to the large quantity needed
for oilfield applications and the current lack of vendors. As a remedy, we propose focused research and
development on the use of naturally-occurring and industrial waste nanoparticles for oilfield applications. Of
the six applications areas, we rank imaging, drilling through unstable zones and tight reservoir applications
as having the biggest potential impact. Using nanoparticles to detect hydrocarbon saturation in a reservoir
can significantly impact how we plan field development, such as well placement. Similarly, using nano-
enhanced drilling fluid to stabilize and drill through unstable zones can increase rate of penetration, reduce
drilling cost and minimize environmental impact. Furthermore, using specially-designed nanoparticles to
image and prop up induced and naturally occurring fractures in tight reservoirs can lead to sweet spot
identification and more prolific wells.
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Introduction
Nanotechnology is the manipulation, control and integration of atoms and molecules to form materials,
structures, components, devices, and systems at the nanoscale (Hornyak et al. 2009). One nanometer is 1
billionth of a meter (Fig. 1). A water molecule is about one-tenth of a nanometer. A glucose molecule is
about 1 nm. So a nanometer approaches the size of molecules.

Figure 1—Comparison of length scale

As materials shrink in size to nanoscale, they have properties not found in bulk materials due to the very
large surface-to-volume ratio and quantum effects. Due to quantum effects at nanoscale, material properties
such as melting point, fluorescence, electrical conductivity, magnetic permeability and chemical reactivity
are size dependent. For example, by changing the size of a particle, one can change its fluorescence color.
Nanoscale gold nanoparticles are not yellow but are red or purple in color. Also, since nanoparticles have
much larger surface areas than bulk particles, they are much more reactive when they come into contact with
surrounding materials. For example, a solid cube of material 1 cm on each side has 6 cm2 of surface area.
However, when that same volume is filled with 1 nm sized cubes, it has a total surface area of 6×107 cm2,
which is one-third larger than a football field (Fig. 2). Their very small size, quantum effects and enhanced
reactivity enabled nanoparticles to be used in applications such as targeted drug delivery, medical and dental
imaging, high strength materials, catalysis, high speed computing, environmental remediation, sunscreen,
body armor, among many others.
SPE-183301-MS 3

3
Figure 2—Total surface area of a 1 cm of material (1 cm x 1 cm x 1 cm) as a function of the length of individual cubic particle

However, application of nanotechnology to the oilfield has only been discussed in the last few years.
Figure 3 shows the number of SPE papers published on nanotechnology. It can be seen that there has
been a big increase in publications on nanotechnology in the last six years. To date, SPE publications on
nanotechnology have exceeded 2000.

Figure 3—Number of SPE paper published on nanotechnology versus time

4 SPE-183301-MS

Table 1 summarizes the various nanotechnology, nanotools and their potential oilfield applications. Nano
electronics, nano optics and nano magnetism make use of the quantum effects of nanoparticles to achieve
specialized tasks. These technologies can be used to fabricate nanotools such as nano sensors for reservoir
and flood front imaging, quantum dots for reservoir logging and ferrofluids and magnetic nanoparticles for
reservoir and fracture imaging and produced water treatment. Nano composites and fibers are very high
strength materials composed mostly of single or multi-walled carbon tubes (MWCNT), and spherical nano
molecules such as fullerenes (C60). They can be used as new materials for casing, tubings, drill bits and
proppants. Surface active nanoparticles are typically functionalized nanoparticles consisting of a nanoscale
core with their surface chemically treated to contain functional groups to perform specific tasks such as
adsorbing at the oil-water or gas-liquid interface to lower the interfacial tension (IFT). They can function
either as primary surfactants or cosurfactants in enhanced oil recovery (EOR) processes. Nanoencapsulation
is a technology whereby certain chemicals such as acid or cross-linkers for polymers are encapsulated inside
a nanoscale particle so that they can be injected deep into the reservoir. If the encapsulation degrades under
reservoir conditions such as temperature, the encapsulated chemical can be released to perform specific
function such as acidizing the reservoir or cross-linking the injected polymer. This technology may be used
for in-depth matrix stimulation, profile or mobility control.

Table 1—Examples of nanotechnology and nano tools for oilfield application

Nanotechnology Nano Tool Oilfield Application Key Challenges

Nano electronics Nano senors Reservoir and flood front imaging Long battery life under
reservoir conditions

Nano optics Quantum dots Logging Transport through reservoir

Nano magnetism Ferrofluids Reservoir/fracture imaging Development of MNP, EM sources

and receivers, data acquisition
and signal processing software

Magnetic nanoparticles Produced water treatment Scale up from lab to field

Nano composites and fibers Single wall carbon tube, New casing and tubing Constructing and testing prototype
fullerenes, multiwall carbon tube materials, drill bits, proppants

Surface active nano particles Functionalized nanoparticles EOR Transport through reservoir

Nano encapsulation Chemical-laden nanoparticles, Acid stimulation, profile Scale up from lab to field
biodegradable polymeric control, gas mobility control
nanoparticles, phase
inversion nanoencapsulation

Nano thin film Nanocomposite coatings Drill bits, drilling fluids, Construction and testing prototype
completion fluids, shale inhibition

Nano catalyst Nickel nanoparticles Catalyst for in-situ thermal Transport through reservoir, scale up
upgrading of heavy oil

Nano thin film is a technology whereby a nanoscale film is deposited on the surface of oilfield tools to
enhance its material properties, such as corrosion resistance. In addition, drilling fluids containing properly
sized nanoparticles may form a thin film on top of water sensitive shales to prevent them from collapsing
during drilling.
Because of their large surface area, nanoparticles can also function as very effective catalysts. It has been
reported that nanoscale nickel particles can be used as catalyst for the in-situ thermal upgrading of heavy
oil (Shokrlu and Babadagli 2011; El-Diasty 2015).
The aforementioned technologies will be discussed in more detail in the following sections.
SPE-183301-MS 5

Sensing and Imaging

Contrast Agent for Crosswell Electromagnetic Imaging
This technology uses magnetic nanoparticles (MNP) as contrast agents for mapping the flood front in a
reservoir. The principle behind this technology is that the speed of electromagnetic (EM) waves is slowed
down when they pass through a magnetic medium. In waterflooding, water containing MNP is injected into
the reservoir. By placing an EM wave source at the injector and an EM wave receiver at the producer, a
nearby observation well or the surface, one can do cross well EM imaging to locate the MNP and therefore
the fluid front. In this method, MNP do not have to be recovered from the reservoir. Current challenges
involve the development of MNP, hardware including EM source and receivers, software for data acquisition
and signal processing (Al-Shehri et al. 2013).
Saudi Aramco has conducted a pilot in the Ghawar field which showed that it was possible to create an
EM image between two wells 850 m apart (Rassenfoss 2012). This type of imaging has also been proposed
for imaging natural fractures in tight reservoirs (Neal and Krohn 2012). However, one restriction is that it
can only be used in a well with an openhole completion.
One service company has proposed using ferrofluids as contrast agents to image fracture geometries
(Sengupta 2012). A ferrofluid is a colloidal liquid containing nanoscale ferromagnetic or ferromagnetic
particles such as magnetite, hematite, or some other compound. The liquid becomes magnetized in the
presence of a magnetic field. This technology is still in the experimental stage.

Downhole Powerless Sensors

Nanoparticles can be designed to perform specific functions, such as sensing temperature, pressure, and
presence of hydrocarbons. They are also called nano-robots or chemical reporters. They contain sensors
do not need a supply of power. They perform their tasks through chemical or quantum effects. They can
be injected into the reservoir, recovered and analyzed. The first successful demonstration is the A-Dot
piloted by Saudi Aramco in the Ghawar field (Kosynkin 2011). The A-Dots are carbon-based fluorescent
nanoparticles designed to survive the harsh reservoir conditions and can be read and interrogated reliably
when they are recovered at the surface. They can be used as active or reactive agents doped chemically with
specific functional groups to perform specific functions, e.g. partitioning into the oleic phase or residing
at the oil-water interface. In a pilot lasting for two days, the operator recovered 90% of the injected A-
Dot, showing that the A-Dot could pass through the reservoir relatively unimpeded. Another operator has
developed the fluorescent nanobeads as an easily detectable water tracer. It is a silica based nanoparticles
containing one or more organic dyes or lanthanide-based flourophores (Agenet et al. 2012). This technology
is in the experimental stage.

Downhole Electronic Sensors

These are electronic sensors equipped with a microprocessor that can record the subsurface environment
as a function of time. They are capable of sensing borehole temperature (Alaksar et al. 2012 and 2014),
borehole pressure, borehole trajectory, formation properties, oil-water contact, etc. They need to be powered
by batteries. They are capable of transmitting the data by wireless communication to the surface and
receiving signals from the surface computer to perform specific function (Ahmad 2013). In general, these
nanoparticles have to be recovered at the surface for the data to be downloaded. In future, if the antenna can
be improved they may be able to transmit the data in real time from the subsurface so they do not need to be
recovered. A key challenge for this technology is to lengthen the life of batteries under downhole conditions
(Cookson 2014; Singh and Bhat 2006).
6 SPE-183301-MS

Enhanced Oil Recovery

Chemical EOR
The ultimate goal of chemical EOR processes is to increase the overall oil displacement efficiency,
consisting of microscopic and macroscopic displacement efficiencies. Chemical EOR processes aim at
enhancing the overall oil displacement efficiency by reducing the microscopic entrapment of oil in pores
due to capillary force, or by mobilizing the macroscopically by-passed oil after secondary recovery by
waterflood. Applications of nanoparticles in chemical EOR have been extensively studied. They are
designed to achieve onte or more of the following.

Rock wettability alteration and oil-water IFT reduction

Nanoparticles are sufficiently small to pass through pore throats in typical reservoirs and thus can access
residual oil microscopically. They reduce oil-water IFT and alter rock surface wettability due to their surface
reactivity, hence reducing the capillary force that oil phase needs to overcome to be mobilized. Numerical
and theoretical calculation studies (Wasan and Nikolov 2003; Wasan et al. 2011) revealed that nanoparticles
reduce oil adsorption on rock surface by enhancing the structural disjoining pressure (film tension) between
the oil and rock surface by forming a wedge-film structure on rock surfaces, thus releasing oil droplets
(Fig. 5).

Figure 4—Nanoparticles stabilizing foam bubbles

Figure 5—Nanoparticle wedge-film structure (after Wasan et al., 2011)

SPE-183301-MS 7

Surface modified hydrophilic silica nanoparticles have been extensively studied. They were shown
to be capable of enhancing oil recovery in coreflood experiments. Zargartalebi et al. (2015) observed
enhancement of the performance of sodium dodecyl sulfate (SDS) anionic surfactant in corefloods by
adding hydrophilic and slightly hydrophobic silica nanoparticles. Silica nanoparticles reduced the oil-water
IFT and surfactant adsorption on the rock surface. However, there is a tradeoff between nanoparticle-
enabled surfactant performance and surfactant adsorption on nanoparticle surface. Metin et al. (2012)
studied the effect of bare surface and polyethylene oxide coated silica nanoparticles on adsorption of
nanoparticles on water-decane IFT. They concluded that unmodified nanoparticles or those with an
anionic (sulfonate) or cationic quaternary ammonium (quat) do not influence the water-decane IFT. The
presence of polyethylene glycol (PEG) as a surface coating material of silica nanoparticles significantly
decreases the IFT. Metin (2016) concluded that PEG and quat/PEG modified nanoparticles adsorbed
significantly on montmorillonite. The adsorption isotherm suggests increased difficulty in binding as
nanoparticle concentration increased. Roustaei et al. (2012) reported that a surface modified silica nano
fluid improves oil recovery in sandstone corefloods by reducing oil-water IFT and altering rock wettability.
Khademolhosseini et al. (2015) reported that nanosilica and biosurfactant synergistically reduce oil-
water IFT and enhance water viscosity. Onyekonwu and Ogolo (2012) studied the ability of three
polysilicon nanoparticles in surfactant coreflood experiments and found that neutrally wet polysilicon
nanoparticles (NWPN) and hydrophobic and lipophilic polysilicon nanoparticles (HLPN) resulted in
surfactant performance enhancement. Moradi et al. (2015) conducted corefloods showing that silica
nanoparticles were able to improve water-alternating-gas (WAG) injection performance via oil-water
IFT reduction, wettability alteration and water viscosity enhancement. By conducting five-spot glass
micromodel flow tests, Yousefvand and Jafari (2015) showed that addition of nanosilica enhanced heavy oil
recovery by hydrolyzed polyacrylamide (HPAM) flooding through changing the rock to water-wet. Similar
observation was made by Maghzia et al. (2014) on enhancing heavy oil recovery by silica nanoparticle-
assisted polymer flood. In a number of field applications (McElfresh et al. 2012), aqueous stabilized
nanoparticle dispersions with 4-20 nm silica particles were shown to improve producer performances by
remediating flow assurance issues caused by heavy components, achieved via wedge film mechanism to
disengage paraffin and asphaltene from the rock surface.
Application of a number of non-silica nano particles was also studied. Suleimanov et al. (2011)
incorporated non-ferrous metal nanoparticles with sulfonate anionic surfactant to reduce oil-water IFT and
enhance water rheology. In a study conducted by Srinivasan and Shah (2014), addition of 50 nm copper
oxide nanoparticles at 0.02 wt% in the injection fluid was found to significantly reduce both heavy oil
viscosity and oil-water IFT. ZrO2 nanoparticles were found to augment the performance of both cationic
(dodecyltrimethylammonium bromide, C12TAB) and anionic SDS in surfactant floods (Mohajeri et al.
2015). Experimental work by Ershadi et al. (2015) demonstrated the effectiveness of MWCNT – silica
nanohybrid systems in altering both carbonate and sandstone wettability towards water-wet without using
a surfactant.
The performance of nanoparticles in EOR processes is strongly influenced by the stability of the particles
in the injection phase which is typically brine. Poor aqueous stability of nanoparticle dispersion impairs
the transport of nanoparticle in the reservoir. Metin et al. (2011) investigated the aqueous stability of
silica nanoparticles with a diameter of 25 nm in aqueous solutions under changing pH, salt concentration
and temperature. They observed a critical salt concentration (CSC) for a given electrolyte below which
the nanoparticles are well dispersed in an aqueous phase and above which flocculation of nanoparticles
occurs and the aggregates settle by gravity. The transport and adsorption of nanoparticles, i.e., hydrophobic
and lipophilic polysilicon (HLP), in porous media was numerically described by Ju et al. (2016). Their
model described the wettability and relative permeability changes by HLP which were instrumental in
evaluating oil recovery in corefloods. Nanoparticle flow and transportation in porous media was numerically
8 SPE-183301-MS

simulated using the multipoint flux approximation (Salama et al. 2015; Chen et al. 2016). It was revealed that
anisotropy significantly impacts nanoparticle transport behaviors. Transport and retention of paramagnetic
nanoparticles – which can potentially be used as tracers – were experimentally studied by Yu et al. (2010).
Negatively-charged citrate ligands can stabilize paramagnetic nanoparticles and lead to little nanoparticle
retention even at a high injected concentration.

Oil viscosity reduction and injection fluid viscosity enhancement

Better conformance and mobility control capability, important in improving macroscopic recovery
efficiency, is achieved via modifying the injection fluid viscosity to match that of the oil. Polymer has
been widely used to increase the water viscosity. Nanoparticles, for example copper oxide, are capable
of enhancing injection water viscosity as well (Haroun et al. 2012). Metin et al. (2011, 2012) showed
that aqueous dispersion viscosity increases as the size of silica nanoparticles decreases. The unmodified,
electrostatically stabilized silica nanoparticles exhibit higher viscosity than sulfonate coated, sterically
stabilized silica nanoparticles at a given particle size and volume fraction. Metin et al (2014) reported
that silica nanoparticle dispersion can form stable aqueous gels. Their measurements showed that silica
nanoparticle gels exhibit non-Newtonian, shear-thinning behavior which could be described by the Carreau
model depending on the particle and NaCl concentration. Based on this work, Rankin and Nguyen (2014)
studied a new concept of silica nanoparticle gels for conformance control in heterogeneous or fractured
reservoirs. They found that permeability reduction due to gelation can be achieved through even at low
concentrations of nanoparticles.
Nanoparticles can also stabilize emulsion or foam due to their surface activities, which also leads to
injection fluid viscosity enhancement. Hydrophilic silica nanoparticles and anionic CTAB surfactant were
found to stabilize oil-in-water emulsions and improve heavy oil recovery in corefloods (Pei et al. 2015).
Oil-in-water emulsions stabilized by surface-treated silica nanoparticles exhibited significant shear-thining
behavior with very high viscosity at low shear rates, making them good candidates for conformance control
agents. Experiments conducted by Sharma et al. (2015) concluded that conventional surfactant polymer
flood performance was improved by an emulsion stabilized by nanoparticle-surfactant-polymer system, due
to improved oil-water IFT and water viscosity. CO2 foam stability was found to be enhanced by coal fly ash
nanoparticles, which was used in gas mobility control applications (Singh et al. 2015, Eftekhari et al. 2015).
In addition, aluminum oxide nano particles dispersed in brine were found to reduce oil viscosity (Ogolo et
al. 2012) which could potentially be used for conformance and mobility control.

Heavy oil EOR

Recovery of heavy oil can be enhanced through reducing the oil viscosity. Nanoparticles can achieve this
through two mechanisms:
Thermal conductivity enhancement of heavy oil.. Certain nanoparticles exhibit capability of improving
reservoir thermal conductivity and specific heat, besides their ability of enhancing density and viscosity
of treatment fluids (Srinivasan and Shah 2014). Thermal processes take place in reservoir rock by
electromagnetic (EM) heating, taking advantage of injected nano metal-oxides (Fig. 6). When exposed to
high frequency EM radiations, these nanoparticles align themselves with the EM field, which results in
high frequency particle movements that heats up the surrounding environment through friction (Bera and
Babdagli 2015).
SPE-183301-MS 9

Figure 6—Electromagnetic heating for heavy oil production (after Bera and Babadagli, 2015).

In-situ upgrading of heavy oil. Nanoparticles, for example, Ni, CuO/ZnO etc., can chemically crack
heavy oil molecules to achieve heavy oil in-situ upgrading by acting as nano-scale catalyst (Shokrlu and
Babadagli). The large surface area of nanoparticles improves catalytic performances on hydrogenation and
hydrocracking reactions (Hashemi et al. 2014). Compared to micro-sized catalysts, nano-scale particles
can be easily dispersed with minimal impact on the injectivity (Shokrlu and Babadagli 2011). Guo et al.
(2015) demonstrated improved heavy oil recovery by using nano metallic catalyst, which also facilitates
rock wettability alteration. Franco et al. (2016) used bimetallic nano scaled catalyst to assist heavy oil
upgrading and continuous steam injection process.

Gas Mobility Control

Typical gas EOR processes that employ the injection of a gaseous phase such as steam or CO2 suffer from
adverse mobility ratio and gravity segregation. Viscous instability leads to poor areal sweep while gravity
segregation leads to poor vertical sweep. Foam has been used to mitigate these effects. It consists of a
discontinuous gas phase dispersed within a continuous aqueous phase. Foam bubbles are stabilized by the
presence of a surfactant which resides at the gas-aqueous interface. The presence of foam lamellae increases
the effective viscosity of the injected gas phase and thus improves the mobility ratio and reduces gravity
override.
However, surfactant propagation in a porous medium is hindered by adsorption at the rock surface and
precipitation out of solution due to divalent ion exchange with the rock. Also, the presence of oil has an
adverse effect on foam stability. A number of researchers have advocated the use of nanoparticles with a
surfactant to stabilize foam. Nanoparticles can adsorb at the gas-liquid interface depending on its wettability.
A fully water-wet nanoparticle will stay in the liquid phase. A gas-wet nanoparticle will prefer to stay in
the gaseous phase. Nanoparticles that possess both hydrophilic and hydrophobic properties will preferably
adsorb at the gas-liquid interface like a surfactant molecule (Fig. 4). However, the difference between the
two is that the energy required to detach a nanoparticle from the interface is a few orders of magnitude higher
10 SPE-183301-MS

than the thermal energy of the nanoparticle. Therefore, the adsorption of a nanoparticle on the interface is
for all practical purposes irreversible (Eftekhari et al. 2015).
Research by Sun et al. (2015) has shown that aqueous foam can be stabilized by partially hydrophobic
SiO2 nanoparticles in the presence of SDS. They deduced that the SDS molecules facilitate the adsorption
of nanoparticles at the gas-liquid interface, thus increasing the dilational viscoelasticity and hence foam
stability. Corefloods by Eftenhari et al. (2015) have shown that fly-ash nanoparticles together with alpha
olefin sulfonate (AOS) can form a stronger and more stable nitrogen foam in the presence of crude oil than
a foam stabilized by AOS only. Recent research by Singh el al. (2015) shows that fly-ash nanoparticles can
stabilize CO2 foam.
The use of fly-ash nanoparticles is particularly noteworthy as fly-ash is a byproduct of coal fired power
plants. It consists mostly of SiO2 and Al2O3 and other metal oxides. Fly-ash by itself is too large to be
injected into the oil reservoir. However, after being properly processed e.g. by thermal treatment and wet
grinding, nanosize fly-ash particles can be obtained (Singh et al. 2015). Given the relative abundance of
fly-ash, harnessing it for oilfield nano applications can potentially be very cost effective.

Drilling and Completion

Nano technology has also wide-ranging applications in drilling and completion. Drilling or completion
fluids that contain at least one additive with nano-scale particle size (1 – 100 nm) are considered nano-based
fluids. Benefiting from the huge surface area, as well as the predominance of inter-particular van der Waals
and electrical forces over gravity, nano-based fluids are expected to exhibit game-changing fluid properties
at very low concentrations. Major applications of nano-based fluids include, but are not limited to:

Fluid-loss property enhancement

Nano-scale particles can be used in drilling and fracturing fluids to achieve better wellbore stability and
fluid loss control. Pham and Nguyen (2014) experimentally evaluated the ability of 5 nm PEG-coated silica
nanoparticles to stabilize clays. They found that the addition of nanoparticles to clay dispersions containing
a fixed electrolyte concentration resulted in a greater reduction in clay swelling than was achieved by the
electrolyte alone. The addition of engineered nano-scale materials help form thin mudcake and eliminate
spurt loss (Amanullah et al. 2011). On the other hand, nano additives can enhance rheological properties
of surfactant and polymer-based nano-fluids (Fakoya and Shah 2013; Gurluk 2013). Sadeghalvaad and
Sabbaghi (2015) observed enhancement of polycrylamide assisted water-based drilling fluid rheological
and filtration properties by the addition of TiO2 particles. In the study by William et al. (2014) CuO and
ZnO nanoparticles were found to enhance the thermal, electrical and rheological properties of xanthan gum
assisted water-based drilling fluids. In experimental study and field trials, improvement in lubricity and
thermal stability of water-based drilling fluid was achieved by the addition of nano graphene (Taha and
Lee 2015).

Cement property enhancement

Vipulanandan et al. (2015) observed improvement in sensing property of smart cement by 16% through
the addition of nano-iron particles, which facilitates the monitoring of cement height during cementing
operations. Vipulanandan and Amani (2015) demonstrated enhanced protection of smart cement by nano
calcium carbonate particles against oil-based mud (OBM) contamination. Moreover, de La Roji et al. (2012)
reported that the compressive strength and elasticity, along with chemical resistance of API class G cement,
can be enhanced through nanoparticles which fundamentally change the crystallization structure of the
cement. Similarly, MWCNT was found to enhance mechanical properties of API class G cements for high
temperature, high pressure applications (Khan et al. 2016).
SPE-183301-MS 11

Fracturing fluid property enhancement

Liang et al. (2015) observed that the nano-size scale crosslinker resulted in lower polymer loading in
fracturing fluids, which was very useful in reducing formation damage for post-frac gas flow. Furthermore,
rheology and thermal stability can be enhanced by nano-silica particles (Liang et al. 2016).
Besides nano-based fluid, drilling completion engineering can also benefit from nano-coated materials
for better corrosion and erosion resistance, elastic modulus, hardness and fracture toughness. Nano-scale
coating by electrical and chemical controlled processes result in precisely defined configurations of layered
metal alloys on to a variety of substrates, producing materials suitable in harsh-condition applications in the
oilfield (Joosten et al. 2015; Tsaprailis et al. 2010; Carrejo et al. 2015; Welch et al. 2012; Paz et al. 2016).

Produced Fluid Treatment

Magnetic nanoparticles (MNP) can be used to treat produced fluids such as removing undesirable chemicals.
Ko et al. (2016) studied the use of surface modified MNP to remove EOR polymer such as HPAM from the
produced water. These nanoparticles are made with FeCl2, FeCl3 and citric acid as the core with a protective
silica coating which is functionalized with amine molecules making them positively charged. These MNP
are attracted to the negatively charged HPAM molecules. When a magnetic field is applied to the mixture, the
HPAM-MNP settles out of solution and can be separated from the water phase. By subsequently adjusting
the pH, the MNP can be made to be negatively charged. Hence the HPAM will desorb from the MNP
which can then be reused. Since magnetic field can be orders of magnitude larger than gravitational force,
this method allows faster separation of HPAM molecules from water than traditional physical separation
processes.
By functionalizing the surface of ironic MNP with different functional groups, MNP can be used to attach
to a wide variety of contaminants in produced water such as polymers, waste chemicals and oil droplets.
Subsequently, a magnetic field can be used to separate out the contaminants.
Recently, a new technology called electrochemical nanodiffusion has been proposed to treat oilfield
produced water (Whitefield 2016).

Tight Reservoir Applications

The application of nantechnology in tight reservoirs including tight gas, shale gas and shale oil has been
gaining more and more attention due to the unique advantage of nanoparticles to enter tight pores. Nano
materials can be used as in the following applications.

Fluid loss control additive for drilling fluid

Nano silica was reported to be an effective fluid loss additive in xathan-assisted water-based drilling fluid
for shale drilling applications (Srivastsa et al. 2012; Javeri et al.2011; Riley et al. 2012). Nano silica played
an important role in fluid loss control by acting as a bridging material that facilitates quick formation of
thin mud filter cake. Similarly, nano graphene was also found to be good sealing agent of the micro-nano
fractures or pores on the borehole walls of shale formation (Zhang et al. 2015). Nwaoji et al. (2013) used
in-house prepared nano particles (iron hydroxide and calcium carbonate) to strengthen wellbore in shale
formations.

Nano proppant and proppant suspension enhancement agent

Bose et al. (2015) reviewed successful fracture conductivity improvement and fluid loss reduction by
nano proppants derived from coal fly-ash. On the other hand, Xiao et al. (2013) and Zhang et al. (2015)
demonstrated that the proppant carrying capability of the viscoelastic fracturing fluid for coal bed methane
reservoirs can be enhanced by introducing nano-composite polyester fiber. It is conceivable that a new class
of proppants made of nanoparticles may be introduced which has the ability to enter the induced or natural
12 SPE-183301-MS

fractures of tight reservoirs, and then coagulate or gell up thus preventing the fractures from closing during
production.

Health, Safety and Environment

Nanotechnology has been used in many industries for years. Generally the impact of nanotechnology on
health, safety and environment (HSE) can be differentiated into two types of nanostructures (Karkare 2015).
The first is "fixed" nanoparticles. They are nanoscale particles incorporated into a substance, material or
device such as nanocomposites, nano components such as nano electronic, optical or magnetic sensors, etc.
The second is "free" nanoparticles which are individual nanoparticles present at some stage of production or
use. There seems to be a consensus that the chief HSE concern is of "free" nanoparticles which are present
in a powder form or in liquid containing nanoparticles. These particles have the potential to be released to
the environment or come into contact with human beings.
"Free" nanoparticles used in oilfield applications are likely nanoparticles injected into a wellbore or
reservoir along with drilling, completion, imaging, waterflooding or EOR fluids. They have the potential
to enter the human body by being inhaled, swallowed, or absorbed through skin. Once in the human body,
they are highly mobile and may interact with human cells. Potential risks to human include overloading
on phagocytes, cells that ingest and destroy foreign matter, and interaction with biological processes inside
the body. Due to their large surface area, nanoparticles when exposed to tissues and fluids will absorb onto
their surface some of the macromolecules they encounter. This may affect the regulatory mechanisms of
enzymes and other proteins. Research has shown that buckminsterfullerene, a spherical fullerene molecule
with formula C60, can cause brain damage in fish (Karkare 2015). Also, single walled carbon tubes have
been shown to have adverse health effects on lung cells in rats (Nabhani et al. 2010).
Hitherto, regulatory bodies such as Environmental Protection Agency, The Food and Drug
Administration in the US or the Health and Consumer Protection Directorate of the European Union
have recognized the potential for new risks associated with nanomaterials but have not issued any special
regulation regarding production, handling or labeling of them. Typically, the Material Safety Data Sheet
does not differentiate between bulk and nanoscale materials in question. In addition, current risk assessment
methods are not suited to the hazards associated with nanoparticles because they are based on exposure
expressed in mass rather than quantity or surface area. Equipment for routine detection and measurement
of nanoparticles in air, water or soil is inadequate. Currently, there are few data available on the toxicology
of nanomaterials. Consequently, extensive research on nanotoxicology needs to be conducted to form the
basis for government and international regulations.
In the meantime, best practices for the safe handling and disposal of nanomaterials for laboratory and
industrial usage have been proposed for single walled carbon nanotube powder and nanodispersions in
liquid media and nanomaterial-containing pressurized aerosols (Raja et al. 2015a, 2015b).

Discussion
Our review shows that much of the current research is focused on the performance of nanoparticles in the
reservoir. Some work is done of the propagation of nanoparticles and very little work is done on the delivery
and recovery of nanoparticles. Alos, lack of well-defined health, safety and environmental protocols for
safe delivery and recovery of nanoparticles can be a showstopper and more focused research is needed in
this area. Our work also shows that affordability of nanoparticles is another showstopper due to the large
quantity needed for oilfield applications and the current lack of vendors.
Of the six applications mentioned above, we rank reservoir imaging, drilling and tight reservoir
applications as having the highest potential impact. Using nanoparticles to detect hydrocarbon saturation
in a reservoir can significantly impact how we plan field development, such as future well placement. It
has the potential to replace 4D seismic for flood front monitoring. Conceptually, cross-well electromagnetic
SPE-183301-MS 13

imaging may present a more accurate picture of fluid distribution in the reservoir than 4D seismic imaging
or logging since seismic waves are attenuated by the overburden and logging tools have very limited depth
of investigation.
Drilling fluids enhanced by nanoparticles may allow us to drill through water sensitive zones by forming a
tight filter cake at the shale surface. If successful, this technology may remove the need to use oil-based mud
to drill through shale sensitive zones, thus adding to drilling efficiency and reducing environmental impact.
Also, new casing material made of nanomaterials such as nanocomposites or singlewalled carbon tubes
may become the next generation of light weight casing, with huge implications for reducing the loading
requirements for offshore structures, especially in deep water.
Finally, due to its small size, nanoparticles embedded in fracturing fluids can enter into the induced and
natural fractures in tight or shale reservoirs. If they can then form nano or micro-sized structures to prop up
these fractures, they may become very effective proppants.

Challenges
Our literature review shows that nanotechnology has multiple high impact applications to the oilfield.
However, most of these potential applications are still in experimental stage. Some of the key technical
challenges of nanotechnology to the oilfield are also listed in Table 1. To overcome these challenges, we
propose that concerted effort by the industry is needed in the following areas.
First, it would be beneficial for oilfield scientists and engineers to cooperate with their counterparts
in other industries where nanotechnology has made a significant impact. As nanotechnology has made
significant inroad into the medical, pharmaceutical, material science and chemical processing industries, it
is conceivable that solutions in the oilfield can be found in these industries. This type of cooperation may
yield many low hanging fruits for oilfield applications.
Second, most research and development in nanotechnology for oilfield applications are in the idea
generation and laboratory stage. To accelerate the field testing of nanotechnology, more collaboration
between academia, service companies and oil companies are needed. National oil companies can play
a significant role here in piloting nanotechnology in their oilfields at perhaps much cheaper cost than
international oil companies.
Third, it would be beneficial to investigate cheaper sources of nanoparticles since their applications
to the oilfield will probably involve large quantities. Use of natural nanoparticles or unwanted industrial
nanoparticles such as fly-ash may be particularly useful, if they can be processed for oilfield applications.
Fourth, research into the safe deployment and recovery of nanoparticles in the oilfield to give minimal
impact on HSE should be given priority. In the absence of government regulations, the establishment of
industrial best practices will be highly useful.

Conclusions
The following conclusions can be made from our literature review.
1. There has been a great increase in the interest of application of nanotechnology to the oilfield in
the last six years.
2. These applications can be divided into six areas: reservoir sensing or imaging, EOR, gas mobility
control, drilling and completion, produced fluid treatment and tight reservoir applications.
3. Although most of these applications are still in experimental stage, with commercial applications
still years away, their potential impact on the oilfield can be significant. For example, reservoir
imaging by nanoparticles may give accurate description of fluid distribution in the reservoir,
drilling fluids enhanced by nanoparticles may enable us to drill through water sensitive shales and
nanoproppants may be able to prop up induced and natural fractures in tight reservoirs.
14 SPE-183301-MS

4. To overcome key challenges, we propose concerted effort in the following areas: closer cooperation
with other industries to facilitate cross-industry applications of nanotechnology, increased
cooperation between academia, service and oil companies for faster field pilots, research into
cheaper sources of nanoparticles such as natural or industrial waste nanoparticles, and research
into the safe deployment and recovery of nanoparticles in the oilfield to minimize impact on HSE.

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