pubs.acs.

org/EF Article

Synergistic Effect of Nanoparticles and Polymers on the Rheological

Properties of Injection Fluids: Implications for Enhanced Oil
Recovery
Sarmad Al-Anssari, Muhammad Ali, Mobarak Alajmi, Hamed Akhondzadeh, Abbas Khaksar Manshad,
Azim Kalantariasl, Stefan Iglauer, and Alireza Keshavarz*

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ABSTRACT: New nanotechnology-based approaches are increasingly being investigated for enhanced oil recovery (EOR), with a
particular focus on heavy oil reservoirs. Typically, the addition of a polymer to an injection fluid advances the sweep efficiency and
mobility ratio of the fluid and leads to a higher crude oil recovery rate. However, harsh reservoir conditions, including high formation
salinity and temperature, can limit the performance of such polymer fluids. Recently, nanofluids, that is, dispersions of nanoparticles
(NPs) in a base fluid, have been recommended as EOR fluids; however, such nanofluids are unstable, even under ambient
conditions. In this work, a combination of ZrO2 NPs and the polyacrylamide (PAM) polymer (ZrO2 NPs−PAM) was used to
formulate a novel nanopolymer injection solution for EOR applications to overcome the limitations of simple PAM solutions by the
in situ reservoir conditions including high temperature and salinity. A series of measurements were comprehended at controlled pH
values to measure the stability and rheological properties of NPs−PAM combinations at different temperatures, salinities, NP
concentrations, and shear rates. It is depicted from the results that a higher salinity decreased the viscosity of the polymer
formulation. However, ZrO2 NPs−PAM combinations reduced the effect of increased salinity on viscosity, which is essential for
EOR applications. Furthermore, at low and medium shear rates, which are more relevant to the flow scenarios in oil reservoirs, ZrO2
NPs−PAM exhibited a higher viscosity than the PAM solution at the same pH and salinity. In contrast, at higher shear rates, the
viscosity of ZrO2 NPs−PAM was less than that of the sole PAM solution. Mechanistically, an increased shear rate endorsed the
adsorption of polymer molecules onto the surface of NPs, foremost to a lesser polymer concentration in the solution. Moreover,
although ZrO2 nanodispersion was unstable at all NPs and salt concentrations, ZrO2 NPs−PAM was stable over an extensive range
of salinities and temperatures. The results suggested that ZrO2 NPs−PAM is more suitable than the sole polymer or NP solutions for
EOR projects.

1. INTRODUCTION impact on CO2 trapping capacities (note that CO2 injection into
In the last decade, nanotechnology, in particular nanoparticles typical formation may also have a substantial impact on
(NPs), has received increased attention in the oil and gas wettability and asphaltene precipitation).30,31 Recent studies
industry.1−8 This includes Chemical EOR (CEOR) applica- have also shown that NPs can be used as a reversing agent for
tion,9 which are widely used to produce more oil from
CO2-wet surfaces to hydrophilic surfaces for its implications on
unconventional oil reservoirs or once water flooding produce
no more oil economically.10−12 NPs have recently been
suggested as CEOR agents that can be used as dispersion in Received: January 9, 2021
water or in combination with other chemicals such as brine, Revised: February 22, 2021
CO2, surfactants, polymers, or surfactant−polymer solu- Published: March 18, 2021
tions.13−22 In real reservoir situations, the presence of organic
acids is the main factor, which changes the wettability of typical
reservoir formation to oil-wet,23−29 which may have a significant

© 2021 American Chemical Society https://doi.org/10.1021/acs.energyfuels.1c00105

6125 Energy Fuels 2021, 35, 6125−6135
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Figure 1. Impact of nanofluid flooding and the structural disjoining pressure on the wettability, fluid distribution, and oil displacement in porous
media.
CO2-geological storage.32−34 The type and properties of
chemicals formulated with NPs usually depend on the type
and condition of the targeted oil reservoirs and the specific
application.35,36 For instance, polymer flooding, a classic
chemical EOR (CEOR) technique, was originally suggested to
be a practical alternative for water flooding in unconventional
reservoirs that contain heavy (viscous) crude oils.37,38 However,
certain reservoir conditions, such as high salinity, increased
temperature, or various heterogeneity, can dramatically reduce
the feasibility of polymer flooding.39−43 Limitations such as
chemical degradation and polymer solution instability can
drastically affect the efficiency of the polymer as an EOR
agent.44,45 Synthetic fluids that use nanosized materials, internal
breakers, and low molecular weight surface active materials can
be used to achieve the performance of cross-linked polymer
fluids and overcome the limitations of the polymer46
NPs as CEOR agents have been tested in several studies. Most
of these studies have proposed that the nano size and surface
characteristics of the NPs are the key factors during EOR.18−49
Injection of NPs into oil reservoirs can significantly affect the
rock’s wettability,50,51 the oil/water interfacial tension,52,53 and
viscosity of the displacing fluid.54 Typically, efficient EOR
processes in oil-wet reservoirs require the wettability to be
changed from hydrophobic to hydrophilic, maximum decrease
of the oil/water interfacial tension, and a high water to oil
viscosity ratio to ensure a higher mobility ratio (Figure 1).55−57
In this context, the structural disjoining pressure of NPs on the
oil/solid interface can efficiently detach oil droplets from the
rock surface.58 The activation of such a disjoining force required
the existence of an in-between edge between oil and rock, as has
been previously demonstrated in the study by Al-Anssari, et al.59
Different NPs have been studied and characterized in this
context; thus, four main NP groups were categorized, including
inorganic particles (i.e., silica-containing NPs and nonsilica
NPs), organic particles (i.e., carbon and carbon nanotubes),
magnetic particles (XFe2O4, where X is any metal atom), and
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metal oxides (i.e., Al2O3, CuO, Fe2O3, Fe3O4, Ni2O3, MgO,
SnO2, TiO2, ZnO, and ZrO2).60−62 It has been investigated by
many studies to understand the potential of using NPs as the
sole EOR agent or in combination with other chemicals.63−65 In
general, NPs can drastically change the wettability of the oil-wet
surface into a water-wet surface.66
Zirconium oxide (ZrO2) NPs have received the least attention
in petroleum research, despite their potential. Zirconia NPs have
been successfully applied in various applications including
thermal barrier coatings, drug delivery, ceramics, catalysis, fuel
cell parts, heat transfer fluid, anticorrosion parts, and trans-
mitters for high-pressure and high-temperature applications.67
In spite of the promising properties of ZrO2 NPs, this
nanopowder is not viewed as an EOR agent, potentially because
it is not common in the oil and gas industry.60 Hence, only few
studies have used ZrO2 NPs as an EOR agent. Esmaeilzadeh et
al.68 examined the influence of ZrO2 NPs on the adsorption rate
of different surfactants, including a cationic, anionic, and
nanoionic surfactant used in EOR applications. The results
depicted that the NP addition has enhanced the surface activity
and thus the surfactant adsorption on the surface at the liquid/
oil interface, which led to an extensive reduction in the interfacial
tension. Ogolo et al.69 examined the impact of ZrO2 injection
into sandstone under ambient conditions. A slight increase in oil
retrieval was detected in the existence of NPs compared with DI-
water injection. However, the increased salinity of the injected
fluid eliminated the effect of ZrO2 NPs on the recovery rate.
Further increasing the salinity reduced the recovery rate to a
value lower than that in the absence of NPs. Karimi et al.70
experimentally studied the effect of ZrO2 NPs on the wettability
of oil-wet carbonate cores via spontaneous imbibition tests. The
results showed that a significant amount of hydrocarbon could
be quickly recovered via spontaneous imbibition of ZrO2
nanosuspension into oil-saturated core plugs. Similarly, Nwidee
et al.66 revealed that ZrO2 NPs have high potential for use as
EOR agents. Using contact angle measurements, atomic force
6126 https://doi.org/10.1021/acs.energyfuels.1c00105
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Energy & Fuels
Figure 2. Molecular structure of (a) PAM, (b) partly hydrolyzed polyacrylamide, and (c) hydrolyzed polyacrylamide.
microscopy, and scanning electron microscopy, they showed
that zirconium oxide nanofluids, even at very low NP
concentrations, drastically changed the wettability of strongly
hydrophobic carbonate surfaces into hydrophilic. Recently,
Rezvani et al.71 conducted a comprehensive study of ZrO2 NPs
with regard to interfacial tensions, zeta potentials, contact
angles, and viscosity measurements. Their results showed that
the lowest oil/water interfacial tension was measured at a NP
concentration of 0.006 mol/L with a zeta potential of −55.4 mV,
indicating a stable suspension. Moreover, this formulation
significantly transformed the surface wettability from hydro-
phobic to strongly hydrophilic at the same concentration, as
showed by a substantial decrease in the contact angle. Finally,
viscosity measurements showed a substantial decrease in the oil-
phase viscosity, while no detectable change was observed in the
viscosity of the aqueous phase in the presence of low
concentration of NPs. Mechanistically, reduction in oil viscosity
in the company of ZrO2 NPs is related to the collapse of C−C
bonds in the bulky oil particles via NPs, which strengthened with
temperature.71 Thus, similar to other NPs, ZrO2 has no
substantial influence on the viscosity of the aqueous phase at
such low concentrations.16,19,38,72,73
Polyacrylamide (PAM) is a commonly used polymer in the oil
industry, particularly for enhanced oil recovery. Nonetheless, the
use of this water-soluble polymer in highly saline and high-
temperature oil reservoirs is limited due to its weak salt tolerance
and poor thermal stability.74,75 PAM is composed of acrylamide
units (Figure 2a). With increased temperature, some of the
amide groups partially (Figure 2b) or entirely (Figure 2c)
undergo hydrolysis to form carboxylic groups.76,77 The degree of
hydrolysis ranges from 0 to 1 and is quantified by the degree of
hydrolysis = y , as shown in Figure 2.
x+y
Over the last 5 years, several studies have investigated the
synergistic properties of diverse NPs and PAM on EOR
competence.18,64,74,75,78,79 Kedir et al.78 explored the mutual
influence of PAM and aluminum NPs on the rheological
properties of an injected fluid as a function of pH. The measured
viscoelastic properties of PAM−NPs were controlled by pH due
to protonation of the acidic carboxyl group. Zhu et al.74
formulated a nanohybrid complex of partially hydrolyzed PAM
linked with silica NPs to improve the rheological properties of
EOR fluids at elevated salinity (32.868 mg L−1) and temperature
(85 °C). The results displayed that the addition of silica NPs
improved the apparent viscosity of the solution and exhibited a
better shear resistance and long-term thermal steadiness.
Furthermore, core flooding tests revealed that a PAM−silica
NP formulation had a greater oil recovery factor than a regular
PAM solution. Similarly, but with different NPs, Cheraghian72
showed that a mixture of PAM−TiO2 NPs exhibited out-
standing rheological properties and a 4% higher oil recovery rate
based on core flooding tests. Giraldo et al.64 evaluated the
viscosity and thermal stability of a PAM solution in the absence
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and presence of silica NPs under inert and oxidative environ-
ments at 70 °C for 2 weeks. The results showed a lower degree of
degradation in the presence of NPs and a lack of oxidative
sources. Mechanistically, silica NPs can inhibit PAM degrada-
tion by adsorbing PAM onto the NP surface, thus improving its
thermal stability. Also, rheological measurements of PAM−silica
NPs in the temperature range of 25−70 °C revealed non-
Newtonian behavior.64 Recently, Bashir Abdullahi et al.18
combined varieties of NPs, such as titanium oxide, silicon
dioxide, and aluminum oxide, in a single NPs−PAM hybrid
dispersion and developed a unique EOR injection fluid. The
results showed that the NPs−PAM hybrid dispersion exhibited
an increased viscosity than that of the PAM solution at the same
salinity at low and medium shear rates. However, the opposite
trend was observed at a high shear rate, potentially due to the
adsorption−desorption effect of polymer molecules on the NP
surface.
Despite previous efforts in developing polymer−NPs for use
in the EOR industry, no data are available concerning the
synergistic effect of ZrO2 NPs and PAM on the stability and
rheological properties of the injection fluid for EOR
applications. Thus, this study serves as a platform to describe
and understand the physicochemical phenomena of ZrO2 NPs−
PAM formulations and their potential for EOR applications. The
influence of pH on the stability and rheological properties of the
NPs−PAM dispersion was systematically investigated at differ-
ent polymer and NP concentrations and at elevated temper-
atures.
2. EXPERIMENTAL METHODOLOGY
2.1. Materials. PAM ((C3H5NO)n water-soluble, with a molecular
mass of 107 g/mol) supplied by Sigma-Aldrich, was used to formulate
the polymer solutions. Thus, PAM was first dissolved in DI water
(Ultrapure; conductivity = 0.02 mS/cm) or NaCl solution (purity of
NaCl ≥99.5 mol %, from Scharlan) by using a magnetic stirrer at 50 °C.
Thereafter, Zirconium(IV) oxide NPs (ZrO2 nanopowder, Sigma-
Aldrich) were mixed with the polymer solution to formulate different
nanopolymer solutions (ZrO2 NPs−PAM) by using an ultrasonic
homogenizer (frequency 20 kHz, Sonics and Materials Incorporation,
USA) for 10 min (note that homogeneous stirring is not possible with a
magnetic stirrer). The general properties of ZrO2 NPs are listed in
Table 1.
2.2. Formulation of Nanofluids. Different masses of zirconium
dioxide NPs (0.00005, 0.0001, 0.00015, 0.0002, 0.0003, and 0.0004 g)
were circulated in 20 mL of brine solution using an ultrasonic
homogenizer (SONICS/Vibra Cell) to formulate ZrO2 nanofluids with
various concentrations (0.025, 0.05, 0.075, 0.1, 0.15, and 0.2 wt % ZrO2
NPs). For all NP loadings, the sonication process was continued for 10
min at 200 W to ensure efficient dispersal of the solid NPs in the base
liquid. Furthermore, a cooling bath was used to prevent the unfavorable
increase in temperature during the sonication of dispersions. This wide
range of NP concentrations was used to define that at which
concentration the ZrO2 NPs will give the best synergistic influence
with brine and PAM for efficient EOR application.
2.3. Formulation of Polymer Solutions and ZrO2 NPs−PAM
Dispersions. Various concentration ranges (0.025−0.1 wt % PAM) of
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Table 1. Properties of Zirconium Oxide (ZrO2) NPs (Sigma- salinity, PAM (0.025−0.1 wt %), and NP (0.025−0.2 wt %)
Aldrich 2019) concentrations.

surface area (m2/g) 10−25 3. RESULTS AND DISCUSSION

density (g/mL) 5.89
Enhancing the viscosity and stability of an injected polymer
boiling point (°C) 5000
solution during EOR is key to increase oil production,
particle size (nm) <100
particularly from heavy oil reservoirs, which have highly
melting point (°C) 2700
unfavorable mobility ratios during water flooding.83 The
purity (wt %) 99.5
addition of NPs to polymer solutions can potentially improve
appearance color white
these characteristics, thus significantly improving microscopic
solubility in water insoluble
and macroscopic sweep efficiencies. This work discusses how
Morphology near spherical
NPs in a polymeric solution can be used to substantially improve
molecular mass (g/mol) 123.22
the viscosity and stability of PAM solutions and the effect of
different parameters including PAM, NPs, and salt concen-
PAM were weighted and then slowly and consistently added to the base
tration, as well as the effects of temperature and shear rate.
liquid (DI water or brine) to make polymer solutions with different
concentrations. A magnetic stirrer (1500 rpm, Across International) 3.1. Zeta Potential (ζ) Measurements. The zeta
was used to slowly mix and homogenize the polymer solutions at 100 potentials of different wt % ZrO2 NPs dispersed in DI water
rpm for 48 h at ambient temperature (273 K). The formulated polymer over a wide range of pH values (4−12) were measured (Figure
solutions were then left to stand for 24 h to ensure complete hydration. 3). The pH of the dispersion was adjusted with drops of aqueous
To prevent direct contact with oxygen and other degradation agents,
the polymer solutions were covered and sealed during the preparation
and storage periods. Furthermore, each polymer solution was stirred
again at 100 rpm for 15 min before running each test. Furthermore,
ZrO2 NPs at desired concentrations were added to the polymer solution
with continuous mixing to formulate a polymer NP formulation. The
polymer NP solution was then sonicated for 10 min at 200 W in a
beaker immersed in a cooling bath.
2.4. Nanodispersion Characterization. The stability of NP
dispersions can be evaluated using several methods, including visual
monitoring, ultraviolet−visible (UV−vis) spectroscopy, average
particle size, and zeta potential measurements.80 However, zeta
potential measurements are the most reliable method for stability
evaluation (see Table 247). It is to be noted that the zeta potential sign
and magnitude influence the fluid flow behavior, adsorption−
desorption mechanisms, suspension stability, and cluster growth.47,81

Table 2. Relation between Stability and Zeta Potential Values

zeta potential range (ζ mV) stability condition
±0 → ±10 highly unstable
±10 → ±30 unstable
±30 → ±60 stable
±60 → ±100 highly stable
Thus, nanofluids were formulated with and without PAM and were
subjected to stability tests, including particle size distribution (PSD)
and zeta potential (ζ) measurements. A Zetasiser (zetasiser; Nano ZS,
Malvern Instruments) was used to measure ζ of ZrO2 NP formulations
via electrophoretic mobility measurements utilizing the Smoluchow-
ski−Helmholtz equation.82 The PSD of ZrO2 NPs was examined by
dynamic light scattering (DLS; Nano ZS, Malvern Instruments), which
is based on the Brownian motion of the dispersed NPs. Typically, DLS
determines the hydrodynamic diameter by measuring a particle’s speed
in a suspension. These measurements help in the physiochemical
understanding of the effects of pH, electrolyte composition, and
polymer molecules on the nanofluid stability. Hydrochloric (HCl
reagent, 37% from Sigma-Aldrich) and sodium hydroxide (NaOH 50%
in H2O) solutions were used to regulate the pH of the tested
formulations.
2.5. Rheological Characterization of ZrO2 NPs−PAM Dis-
persions. The influence of ZrO2 NPs and salinity on the rheology of
the PAM dispersions was investigated with a rheometer (discovery HR-
3 hybrid rheometer) equipped with a temperature controller. The
rheometer was first calibrated with typical polymer and pristine water of
known viscosities at various temperatures. The viscosities of the
different PAM formulations were then measured as a function of shear
rate (1, 10, 100, and 300 s−1) and temperature (23, 30, 40, and 50 °C),
6128
Figure 3. Zeta potentials of ZrO2 NPs suspended in DI water measured
as a function of ZrO2 concentration and pH of the dispersion.
0.2 N hydrochloric acid (HCl) or 0.1 N sodium hydroxide
(NaOH). The error in the zeta potential measurements
(standard deviation) is represented by error bars shown in
Figure 3. The highest errors were measured around the
isoelectric point (IEP), where the zeta potential values
approached zero.
As can be seen from Figure 3, the ZrO2 NPs in DI water had
positive zeta potentials in high-acidity environments (i.e., pH ≤
5). Zeta potential decreased, as pH increased. For each NP
concentration, zeta potential became zero (IEP) at a specific pH
value (e.g., for 0.01 wt % NPs, the IEP was reached at pH = 7.7).
It is to be noted that the pH values depended on the
concentration of NPs in the dispersion82,84 and the composition
(electrolyte concentration) of the base fluid.80 After reaching the
IEP, the zeta potential changed from positive to negative upon
further increasing the pH and reached its lowest value before
plateauing, and no more reduction in the zeta potential was
observed. Based on the stability classification shown in Table 2,
it is crucial to control the acidity of a zirconium dispersion for a
stable nanofluid. Interestingly, Figure 3 shows that a stable
nanodispersion can be achieved at a low pH range (≤4−5) and
high pH (≥12) depending on the NP concentration. Thus,
whether the nanofluid should be formulated at a low or high pH
is determined by the proposed application, the coagents in the
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Energy & Fuels
Figure 4. Effective particle size of NPs in a nanofluid (0.05 wt % ZrO2, pH = 4) as a function of temperature and salinity.
Figure 5. Viscosity of PAM polymer solutions as a function of PAM concentration and shear rate at ambient temperature.
dispersions, and the nature and surface properties of the treated
porous media.66,85
3.2. Nanoparticle Size Measurements. The stability of
nanofluids, including NP dispersions in DI water, brine,
surfactant, polymer, or surfactant−polymer base fluids, is crucial
for successful EOR applications.72,80,86 Thus, it is necessary to
understand the stability of NPs in reservoirs under harsh
conditions. To achieve this, the growth of an effective diameter
of zirconium NPs at different temperatures and salinities was
measured as a function of time (Figure 4).
The results acquired for the effective particle sizes are
depicted in Figure 4. The figure shows that the zirconia
nanofluid is thermodynamically unstable, even at ambient
temperature and in the absence of an electrolyte. Furthermore,
elevated temperatures and salinity can dramatically accelerate
the aggregation of NPs, which reduces the stable period to <5 h.
Mechanistically, electrolytes screen the repulsive forces between
NPs by neutralizing the surface charges of the NPs.80,86
Moreover, an increased temperature increases the dynamic
energy of the particles, which increases the number of collisions
and consequently coalescence between nanoparticles, leading to
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a higher aggregation rate, particularly when repulsive forces
between the NP are low, for example, in the presence of salt
ions.81 S-shape NP diameter−time curves were obtained for all
systems investigated, as shown in Figure 4.87
Overall, these results indicate that zirconia NPs are unstable
with regard to flocculation and aggregation when solely
dispersed in a base fluid. After a relatively short time period,
microaggregates formed in the suspensions, leading to dramatic
changes in the physicochemical properties of the nanofluids,
including a higher viscosity.37 To improve this stability, it was
hypothesized that the NP dispersion can be stabilized by
addition of the polymer; this is further discussed in detail below.
3.3. Rheological Behavior of Polymer Solutions at
Varying Share Rates. Figure 5 shows the viscosity of polymer
solutions tested for varying PAM concentrations (0.005−0.125
wt %) and shear rates (0−300 s−1).
Clearly, an increase in PAM concentration (from 0.005 to 0.1
wt %) improved the viscosity at all shear rates, which is typical
due to the self-associative nature of the PAM molecules in the
liquid phase.77,88,89 However, the rate of viscosity increase with
PAM concentration was less significant at relatively higher PAM
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Figure 6. Viscosity of ZrO2 nanofluid (dispersed in 0.05 wt % PAM solution, 25 °C) as a function of NP concentration and shear rate.
Figure 7. Effect of polymeric fluid composition on the viscosity at different shear rates.
concentrations (e.g., increasing PAM concentration from 0.05 to
0.075 wt %). Furthermore, no more significant viscosity increase
was observed when the PAM concentration increased further
from 0.1 to 0.125 wt %. Such a behavior of PAM solutions is
mainly related to the alignment of PAM molecules, which
facilitate the flow of PAM molecules and thus limits the increase
in viscosity at such concentrations.45 In addition, the PAM
solutions demonstrated typical shear-thinning behavior at all
tested concentrations, although increasing the shear rate above
150 s−1 did not significantly affect the viscosity. These results are
consistent with recently published data44,45,73,75,76,89,90 and will
serve as the basis for evaluating the effects of temperature, salt,
and NPs on the rheological properties of PAM solutions.
3.4. Influence of ZrO2 NPs on the Rheological
Properties of Polymer Solutions. In CEOR applications,
polymers provide effective sweep efficiency and mobility
control.73 However, the rheological characteristics of the
polymer solutions are dramatically affected by the specific
reservoir conditions, including formation temperature and shear
rates.75 To remedy these limitations, various ZrO2 NP
concentrations (up to 0.05 wt %,91) were added to a 0.05 wt
% PAM solution to estimate the influence of NPs on the
rheological characteristics of these formulations as a function of
shear rate (Figure 6). Such a relatively dilute polymeric solution
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(0.05% wt PAM) was used as a base fluid to highlight the
potential of zirconia NPs as a coagent to synergistically enhance
the viscosity of the solution.
Addition of ZrO2 NPs to the 0.05 wt % PAM solution slightly
increased the viscosity of the mixture, that is, a higher NP
concentration slightly increased the viscosity, as shown in Figure
6. However, at closer inspection, the results showed that no
further viscosity increase was observed upon increasing the NP
concentration above 0.03 wt %. This reflects the extraordinarily
high surface efficiency of ZrO 2 NPs, which was first
demonstrated in the study by Nwidee et al.66 Mechanistically,
NPs act as a cross-linking agent between polymer chains to form
a more rigid polymeric matrix.92 At low NP concentrations
(≤0.03 wt %), integration of NPs into the polymer network
develops a hybrid polymeric structure with new rheological
properties.93 However, at high NP concentrations (>0.03 wt %),
this (new) polymer network may have already reached its
capacity for integrating NPs and no further NPs can attach to the
framework; consequently, no further changes in viscosity are
observed.
3.5. Optimization of PAM−Nanoparticle Formula-
tions. Reducing the amount of expensive and sensitive polymer
molecules by adding alternative chemicals to achieve the same
rheological properties is a main goal of the oil industry. Thus,
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Figure 8. Viscosity of an aqueous PAM solutions at different temperatures and shear rates (1/s).
Figure 9. Influence of elevated temperature and salinity on the viscosity of the formation and injected fluids.
adding NPs to such polymeric formulations can reduce costs,
while maintaining the technical requirements of the CEOR
agent. This section therefore presents and discusses viscosity
trends for different PAM and ZrO2 NP concentrations (Figure
7).
Figure 7 depicts the complex effect of PAM and NP
concentrations on the viscosity of the polymeric formulations
at different shear rates. At relatively low shear rates (<25 s−1),
addition of NPs has only a minor effect on the viscosity of
polymer solution compared to the effect of increased polymer
concentration. In this context, increasing the polymer
concentration by 50% (from 0.05 to 0.075 wt %) increased
the viscosity by a value higher than that which was achieved via
the addition of NPs (0.01−0.05 wt % ZrO2 NPs) to the original
polymeric solution. However, at higher shear rates (>30 s−1), the
viscosity of the polymer−NP mixtures (0.05 wt % PAM + 0.03
wt % ZrO2 NPs) showed higher values than that measured for
the concentrated polymer solutions (0.075 wt % PAM, without
NP). Furthermore, at high shear rates (>80 s−1), even the
addition of a small number of NPs to the polymeric solution
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(0.05 wt % PAM + 0.01 wt % ZrO2 NPs) resulted in significantly
higher viscosities when benchmarked against a pure polymer
solution (0.075 wt % PAM). Such an increase in viscosity is
related to the impact of NPs on the structural network of the
polymer solution. Mechanistically, NPs can significantly
strengthen the structural network of the polymer system.92
Typically, increasing shear forces degrades the polymer
network.45,77 However, an NP-augmented polymer network is
apparently less affected by such an increase in shear force.
3.6. Effect of Temperature on the Rheological
Behavior of Polymer Solution. Temperature-responsive
materials, including PAM, induce reversible particle aggregation
upon heating above their lower critical solution temperature.94
Typically, at elevated temperatures, polymeric materials under-
go physiochemical fluctuations that lead to unfavorable shifts in
their rheological properties.77 Thus, this section examines the
influence of increased temperature on the rheological properties
of the PAM solution. The results of the previous Section 3.3
showed that no significant increases in viscosity were observed
when the PAM concentration was increased from 0.05 to 0.075
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wt %. Thus, the effect of different temperatures (25, 50, and 70
°C) on the rheological properties of a 0.05 wt % PAM solution at
varying shear rates (0−150 s−1) (Figure 8) was studied.
The results indicated that increase in temperature reduced the
viscosity, mainly due to the reduction of the attractive binding
energy between polymer molecules. Mechanistically, such
reduction of the binding energy leads to a dramatic reduction
in the intermolecular forces between the polar groups in the
polymer structure.64 Moreover, at increased temperature, the
amide side groups of the polymers may be subject to increased
hydrolysis,44 and the polymer molecules may reversibly
flocculate,77 which changes the polymer backbone and further
reduces solution viscosity.95 Hydrolysis can also be induced by
high shear rates (i.e., ≥ 60 s−1), which explains the minor effect
of temperature at high shear rates (>100 s−1).77 Furthermore, at
a relatively higher shear rate (≥60 s−1), the viscosity profile
approaches the upper Newtonian regime. This is mainly due to
the polymeric coils and their distortion that reaching the
maximum at such shear rates.
3.7. Effect of Reservoir Conditions on the Rheological
Behavior of PAM−NPs. Harsh temperatures and salinities in
oil reservoirs pose a challenge for polymer injection77 and
nanofluid injection.82,96 Therefore, in this section, the effect of
increased temperature and salinity on the rheological properties
of the PAM−NP mixtures was evaluated (Figure 9).
Increase in temperature (from 23 to 75 °C) reduced the
viscosity (from 179 to 133 mpa s) of the pure PAM solutions.
This effect was strengthened with increasing salinity, particularly
at elevated temperatures (≥45 °C). However, the viscosity of
the nanofluids (ZrO2 NPs dispersed in DI water or brine)
increased with salinity and temperature. Such phenomena are
mainly due to the influence of flocculation and aggregation of
NPs at increased temperature and salinity, which produce
viscous nanofluids.37 In this context, salt has dramatic screening
effects on the surface charges of polymer molecules. In such
scenarios, the viscosity of the polymeric solution tends to
decrease.44 However, when existing in the polymeric solution,
NPs will share this screening effect of salts80 with polymer
molecules and thus mitigate the impact of such an electrolyte on
the surface charges of the polymer, leading to higher viscosity.
This phenomenon explains the increases in polymeric solution
viscosity in the presence of NPs and more extensively in the
presence of salt and NPs (Figure 9). Mechanistically, the
aggregation of zirconium NPs impacts the viscosity of a
polymeric nanofluid due to the enlargement of zirconium
aggregates with time, particularly in the presence of salts. In this
context, when nanofluids undergo significant aggregation, the
effective solid volume friction is the volume fraction of
aggregates.97
4. CONCLUSIONS
In chemical EOR applications, polymers are used to provide
current sweep efficiency and mobility control under the harsh
conditions of oil reservoirs. However, no information was listed
about the synergistic influence of ZrO2 NPs and PAM on the
stability and viscosity of the polymeric solutions for EOR
applications. In this work, the effect of zirconia NPs on the
rheological properties of a PAM polymer solution was
investigated experimentally at reservoir temperatures and
salinities. It was shown that zirconia NPs increased the viscosity
of these polymeric nanofluids in saline environments and at
elevated temperatures. The viscosity of the PAM solution was
substantially increased by adding a low weight percent of NPs
pubs.acs.org/EF Article
(≤0.03 wt % ZrO2). Further addition of NPs (>0.03 wt %) did
not significantly influence the viscosity, as the adsorption
capacity of NPs into the structural network of the polymer
molecules was reached. Increasing the temperature and salinity
showed that the effect of NPs on the viscosity of the polymeric
solution was due to aggregation of NPs under such conditions.
Thus, zirconia NPs−PAM is a potential EOR injection fluid if
correctly formulated.
■ AUTHOR INFORMATION
Corresponding Author
Alireza Keshavarz − Petroleum Engineering Discipline, School
of Engineering, Edith Cowan University, Joondalup 6027,
Western Australia, Australia; orcid.org/0000-0002-8091-
961X; Email: A.keshavarz@ecu.edu.au
Authors
Sarmad Al-Anssari − Petroleum Engineering Discipline, School
of Engineering, Edith Cowan University, Joondalup 6027,
Western Australia, Australia; Western Australia School of
Mines, Minerals, Energy and Chemical Engineering, Curtin
University, Kensington 6151, Western Australia, Australia;
Chemical Engineering Department, College of Engineering,
University of Baghdad, Baghdad 10011, Iraq
Muhammad Ali − Western Australia School of Mines, Minerals,
Energy and Chemical Engineering, Curtin University,
Kensington 6151, Western Australia, Australia; orcid.org/
0000-0002-2446-3072
Mobarak Alajmi − Petroleum Engineering Discipline, School of
Engineering, Edith Cowan University, Joondalup 6027,
Western Australia, Australia
Hamed Akhondzadeh − Petroleum Engineering Discipline,
School of Engineering, Edith Cowan University, Joondalup
6027, Western Australia, Australia
Abbas Khaksar Manshad − Department of Petroleum
Engineering, Abadan Institute of Technology, Petroleum
University of Technology (PUT), Abadan 144026, Iran
Azim Kalantariasl − Department of Petroleum Engineering,
School of Chemical and Petroleum Engineering, Shiraz
University, Shiraz 71454, Iran
Stefan Iglauer − Petroleum Engineering Discipline, School of
Engineering, Edith Cowan University, Joondalup 6027,
Western Australia, Australia; orcid.org/0000-0002-8080-
1590
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.1c00105
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge the support provided from Edith
Cowan University, Australia.
■
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Energy Fuels 2021, 35, 6125−6135