Fuel 252 (2019) 622–634

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Fuel
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Full Length Article

Heavy oil recovery by surface modified silica nanoparticle/HPAM T

nanofluids
⁎ ⁎
Laura M. Corredor1, Ehsan Aliabadian1, Maen Husein , Zhangxin Chen, Brij Maini ,
⁎
Uttandaraman Sundararaj
Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Dr NW, Calgary T2N 1N4, Canada

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

Keywords: Recent studies showed that the presence of dispersed nanoparticles (NPs) can increase the efficiency of polymer
Linear and nonlinear rheology flooding. The network structure of polymer/NP hybrid dispersion has a significant impact on oil recovery. In this
Enhanced oil recovery (EOR) work, the surface of SiO2 NPs was modified by chemical grafting of octyltriethoxysilane (SiO2-OTES), oleic acid
Flow in porous media (SiO2-OAA) and stearic acid (SiO2-SAA) in an attempt to stimulate higher degree of interaction with partially
Modified nanosilica particles
hydrolyzed polyacrylamide (HPAM). Thermogravimetric analysis (TGA), differential scanning calorimetry
Polymer flooding
Hydrolyzed polyacrylamide
(DSC), and Fourier transform infrared (FTIR) spectroscopy were employed to characterize the modified silica
NPs. In addition, ζ-potential, cryo-scanning electron microscopy (cryo-SEM), and linear and nonlinear rheology
were used to evaluate the characteristics of the hybrid dispersion of HPAM/unmodified and modified SiO2 NPs.
ζ-potential measurements showed that the addition of HPAM improved the colloidal stability of the modified and
unmodified SiO2 NPs dispersed in deionized (DI) water. Moreover, the addition of HPAM reduced the size of the
NP aggregates by effective steric repulsion. Small and large shear oscillatory deformation results showed that
SiO2-OTES NPs improved the HPAM network significantly. Nevertheless, HPAM/NPs network formed with all
the different SiO2 NPs severely decreased the intra-cycle shear-thickening behavior of the polymer. Lastly, the
addition of 0.2 wt% SiO2-OTES NPs to the HPAM solution increased the ultimate oil recovery from 71.4% to
75.7% OOIP.

1. Introduction
Two classes of polymers are primarily used in polymer flooding;
namely synthetic polymers and biopolymers [1]. Partially hydrolyzed
polyacrylamide (HPAM) is the most commonly used synthetic polymer
to date [2]. HPAM solutions often suffer from viscosity loss due to harsh
reservoir conditions; including high temperature, high pressure, and
presence of chemical substances such as divalent cations and clay [3].
Xanthan gum (XG) is the most widely used biopolymer [4]. XG has been
proposed as an alternative to HPAM due to its excellent tolerance to
mechanical shearing and high salinity and temperature. Nevertheless,
XG use is relatively limited compared with HPAM due to its higher cost,
higher susceptibility to biodegradation and lower availability [5–7].
Recent studies revealed higher polymer flooding performance upon
adding silica nanoparticles (NPs) to polyacrylamide solutions for
medium and heavy oil recovery [8–12]. The best performance of these
hybrid dispersions is obtained when the NPs are uniformly dispersed in
the polymer solution [13,14]. Higher extent of dispersion can be
achieved by altering the silanol groups on the surface of the SiO2 NPs
via attaching an organic functionality, either by physical association or
chemical bonding. The principle of the physical modification method is
the preferential adsorption of a polar group of a macromolecule on the
silica surface through hydrogen-bonding or electrostatic interaction.
SiO2 NPs have been modified by physical methods with fatty acids such
as stearic acid [15], and oleic acid [16,17], and with cationic salts such
as cetyltrimethylammonium bromide [18]. Modification of the surface
by chemical reactions has received more attention, since it typically
contributes to much stronger interaction between the modifiers and the
nanosilica particles. Chemical methods involve modification either by
grafting polymers or modifying agents on the nanosilica surface
[19,20]. The resultant nanocomposites have been extensively studied
for applications such as adhesives, biomaterials, protective coatings,
microelectronics and proton exchange membranes [21]. However, their
application for EOR processes has been limited.
Ponnapati et al. [22] synthesized SiO2-ethylene oxide-based
polymer/NPs hybrids using a “grafting from” method. They reported

⁎
Corresponding authors.
E-mail addresses: mhusein@ucalgary.ca (M. Husein), bmaini@ucalgary.ca (B. Maini), u.sundararaj@ucalgary.ca (U. Sundararaj).
1
L.C. and E.A. made equal contribution to this work.

https://doi.org/10.1016/j.fuel.2019.04.145
Received 13 February 2019; Received in revised form 22 April 2019; Accepted 26 April 2019
Available online 06 May 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
L.M. Corredor, et al.
Nomenclature
ASNP zwitterionic poly[2-methacryloyloxyethylphosphorylcho-
line (MPC) – co – divinylbenzene (DVB)] shell-coated si-
lica nanoparticles
DSC Differential scanning calorimetry
EOR Enhanced oil recovery
FTIR Fourier transform infrared
HPAM Hydrolyzed polyacrylamide
KBr Potassium Bromide
LAOS Large amplitude oscillatory shear
LVR Linear viscoelastic region
MW Molecular weight
OA Oleic acid
OOIP Original oil in place
OTES Octyltriethoxysilane
PV Pore Volume
PF Polymer flooding
that the injection of the 0.5 wt% nanohybrid could mobilize residual oil
in the core, yielding 7.9% of the OOIP. Subsequent injection of brine
yielded an additional 11% of the OOIP. The enhanced performance of
the modified NPs resulted from polymer-grafted NPs clogging some
water-occupied pore throats, which increased the local pressure, and
hence mobilized the trapped oil in other pores. In another work, Choi
et al. [23] studied nanofluid-enhanced oil recovery using hydrophobic
zwitterionic poly[2-methacryloyloxyethylphosphorylcholine (MPC) –
co – divinylbenzene (DVB)] shell-coated silica nanoparticles (ASNP).
The results showed that both viscous and storage modulus of ASNP
nanofluid were approximately 2 orders of magnitude higher than that
of the bare silica nanofluid. The core flooding experiments showed that
the oil recovery was 74.1%, which was higher than water injection
(68.9%) and unmodified NP injection (72.7%). In our recent works
[24,25], we showed that the slightly hydrophobic fumed SiO2 NPs
(AEROSIL R816) are more efficient at forming a stronger network
structure with HPAM molecules than the completely hydrophilic fumed
SiO2 NPs (AEROSIL 300). Moreover, we showed that the surface
chemistry of the NPs plays a key role in the formation of 3-D elastic
structure in the polymeric nanofluids, independent of fumed SiO2 NP
aggregate size.
In porous media with a wide range of pore size distribution and
geometry, hybrid dispersions may undergo various flow conditions
[26,27]. To optimize the efficiency of the polymer flooding in EOR,
understanding the flow behavior of such systems in porous media is of
great importance. Rheometry, which deals with the deformation and
flow behavior of materials, is a robust technique that provides a valu-
able opportunity to mimic both small and large deformation in porous
media. Rheometry can capture viscoelastic properties that are affected
by both inherent properties of a polymer molecule and external para-
meters. Molecular weight [28], degree of hydrolysis [29,30], and de-
gree of branching [31] are some examples of inherent properties of a
polymer molecule. Temperature [25,32,33], salt content [25,34–36],
and shear/extensional deformation [3,37,38] are examples of external
parameters that can significantly impact the viscoelastic behavior of
such systems.
Small amplitude oscillatory shear (SAOS) flow [3,39–42], flow
curve [43–45], and extensional (shear-free) tests [46,47] are common
methods used to investigate the network structure of polymer solutions.
However, the applicability of these techniques is restricted due to some
limitations like flow instabilities [48], shear inhomogeneity [49], and
low viscosity of solution systems. Recently, large amplitude oscillatory
shear (LAOS) test has been employed to assess the viscoelastic prop-
erties of different polymer solutions [50–55]. In LAOS, the input strain
amplitude and frequency can be controlled independently and, hence, a
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Fuel 252 (2019) 622–634
S Intra-cycle strain-stiffening ratio
SA Stearic acid
SAOS Small amplitude oscillatory shear
SEM Scanning electron microscopy
SiO2-OAA Silica modified with oleic acid-Method A
SiO2-OTES Silica modified with Octyltriethoxysilane
SiO2-SAA Silica modified with stearic acid-Method A
T Intra-cycle shear-thickening ratio
WF Waterflooding
G' Storage modulus
G' Loss modulus
'
GM Minimum-strain modulus
GL' Large-strain modulus
ω Angular frequency
γ Strain
ηM' Minimum-strain rate viscosity
ηL' Large-strain rate viscosity
wide range of flow conditions can be simulated. LAOS has been applied
in polymer nanocomposites [56,57], polymer solutions [24,58], and
colloidal gels [59,60] to link nonlinear viscoelastic behavior to micro-
structural evolution under nonlinear conditions.
In the present work, three different fields (chemistry, rheology, and
petroleum science) have been merged to show how to increase oil re-
covery, which distinguishes this study from other works in the litera-
ture. In phase one, bare SiO2 NPs were chemically modified with car-
boxylic acids (SiO2-SAA and SiO2-OAA) and silane (SiO2-OTES) to
generate three differently modified SiO2 NPs. By modifying the SiO2
NPs surface, we expected to (i) increase the hydrophobicity of the NPs
and, hence, enhance their dispersivity into the polymer solution; and
(ii) tailor the interaction between the treated NPs and the polymer to
tailor the mobility of the polymer solution and, consequently, increase
the oil recovery. In phase two, the network structure of the hybrid
dispersions of HPAM/SiO2 NPs was studied using rheology. The effects
of adding modified SiO2 NPs on the linear and nonlinear viscoelastic
properties were analyzed using frequency sweep test and intra-cycle
shear-thickening behavior, respectively. In phase three, these different
hybrid dispersions were injected into a linear sand-pack to evaluate
their effectiveness in tertiary recovery. In our previous work [61], we
studied the flow curves of the SiO2-SAA, SiO2-OAA and SiO2-OTES
HPAM/XG hybrid dispersions and developed a model based on a mul-
tilayer perceptron (MLP) neural network to predict the viscosity of the
dispersions. However, that study did not include the analysis of the
linear and nonlinear viscoelastic properties of the dispersions, or their
performance in displacing oil.
To the best of our knowledge, there is no work in the literature that
systematically synthesized the modified SiO2 NPs, evaluated the effect
of hydrophobicity of the modified SiO2 NPs on the linear and nonlinear
viscoelastic behavior and the network structure of an aqueous HPAM
solution, and tested the performance of the HPAM/NP hybrid disper-
sions for heavy oil recovery as reported here.
2. Materials and methods
2.1. Materials
Fumed silica powder (7 nm) was obtained from Sigma-Aldrich
(USA). The chemicals used for the surface modification of the SiO2 NPs
were oleic acid (C18H34O2, 90%), stearic acid (C18H36O2, 95%), and
octyl(triethoxy)silane (OTES, ≥97.5%) which were obtained from
Sigma-Aldrich (USA). The solvents used in the reactions were: ethanol
(EtOH, 99%) and hydrochloric acid (ACS reagent, 37%), both obtained
from Sigma-Aldrich (USA); and cyclohexane (99.5%) and ammonium
L.M. Corredor, et al.
hydroxide (28–30 wt% solutions of NH3 in water), which were obtained
from Fisher Scientific (USA). The detailed synthesis of the surface
modified SiO2 NPs used in this work has been reported previously by
the authors [61]. n-Propanol (purity ≥ 99.5%, VWR, Canada) was used
to determine the hydrophobicity of the NPs. The displacement tests
were performed with Flopaam™ 3630 s (HPAM, hydrolysis degree
25–35%, MW ≈ 20 × 106 Dalton) obtained from SNF Floerger (USA).
All chemicals were used as received.
3. Nanoparticle characterization
A Fourier transform infrared spectrometer, FTIR (model IRaffinity-
1s, Shimadzu, Japan) was used to analyze the SiO2 NPs. The back-
ground spectrum was obtained with dry KBr, and each spectrum was
recorded over a range of wavelength of 4000–400 cm−1.
Thermogravimetric analysis/differential scanning calorimetry (TGA/
DSC) measurements were performed by heating 6 mg sample of mod-
ified/unmodified NPs from 20 to 800 °C at a heating rate of 10 °C/min
under air atmosphere (SDT Q600, TA Instruments, Inc., New Castle,
DE). For FTIR and TGA/DSC, every sample was tested three times for
reproducibility. The expected coupling mechanism between the silica
surface and silanes is represented in Fig. 1.
The hydrophobicity of the modified silica NPs was determined by
using a dispersion stability test. For this procedure, 0.1 g of each NP
type were dispersed in different mixtures of propanol/DI water (10 g)
and ultrasonicated for 1 h. After that, the samples were left to settle for
10 min, and the amount of precipitate was determined for each pro-
panol/DI water mixture.
4. Hybrid dispersion preparation
Four different concentrations of unmodified and modified SiO2 NPs
(1.0, 2.0, 3.0 and 4.0 wt%) were used to prepare hybrid dispersions. At
first, the SiO2 NPs were dispersed in DI water and ultrasonicated for 1 h.
Then, HPAM powder was added at 0.4 wt% to the aqueous dispersions
under gentle stirring for 48 h.
5. Hybrid dispersion characterization
5.1. ζ-potential measurements
ζ-potential values were measured at 20 °C with a Zetasizer Nano ZS
unit (Malvern Instruments Ltd, UK) with uncertainty of ± 1 to 6% of
the reported value. 35 specimens were tested in the ζ-potential mea-
surements (20 samples + 15 reproducibility tests). Before every
Fig. 1. Reaction route of surface modification on silica particles with (A) SA and OA, and (B) OTES [62].
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Fuel 252 (2019) 622–634
measurement, the samples were pretreated by ultrasonication for 5 min.
A digital pH meter (model AB 15 plus, Fisher Scientific, USA) was used
to measure the pH of the samples at 20 °C. The uncertainty of the pH
meter was < 0.05 of the reported value.
5.2. Cryo-SEM images
An FEI Quanta FEG 250 SEM equipped with a Gatan Alto 2500 cryo-
stage and xTm version 4.1.12.2162 software was used for the cryo-SEM
analysis. A small amount of the solution was loaded and frozen in a
nitrogen slush for sample preparation. Then, the surface of the sample
was coated with a layer of gold (around 10 nm). The images were ob-
tained using either of secondary electron or backscattered electron
detectors at an accelerating voltage of 5 to 10 kV. For cryo-SEM, 3–5
different locations were captured for each sample.
5.3. Rheological characterization
An Anton Paar MCR302 rheometer with a coaxial cylinder geometry
(measuring bob and measuring cup had radii of 13.329 mm OD and
14.463 mm ID, respectively) was used to measure the rheological
properties of the hybrid dispersions. Rheoplus/32 V3.62 software was
connected to the rheometer to record the measurements. All the rheo-
logical measurements were done at a fixed temperature (T = 35 °C). To
assure all systems were in the linear viscoelastic region for frequency
sweep measurements, a strain amplitude equal to 1% was selected
(based on strain sweep results). In the frequency sweep test, the angular
frequency varied between 0.1 and 20 rad/s. Strain amplitude sweep test
in which strain amplitude varied between 1% and 1000%, was designed
to evaluate the nonlinear viscoelasticity of the hybrid dispersions. The
angular frequency was set to 0.5 rad/s, to prevent any flow instability,
torque overload and wall-slip effects.
5.4. Flooding experiments and set up
Fig. 2 depicts a schematic of the flooding setup. It consisted of a
pump, tubing, two transfer vessels, pressure transducer, sand-pack
holder, graduated cylinders, and back pressure regulator. The sand-
pack characteristics and the injected fluid properties are listed in
Table 1. For the flooding experiments, each sand-pack was fully satu-
rated with water by imbibition method. The absolute permeability was
calculated using Darcy’s law. For this procedure, water was injected at
different flow rates and the corresponding pressure drop was recorded.
The drainage process was carried out by injecting 2 PV of oil. After that,
0.5 PV of water were injected followed by 0.5 PV of HPAM/SiO2 NPs
L.M. Corredor, et al. Fuel 252 (2019) 622–634

Fig. 2. Sand-pack flooding set up.

Table 1 3400 cm−1 which corresponded to free silanol groups on the silica
The sand-pack specifications and properties of the injected fluid. surface [64].
Properties Values The bonding of the OA and SA molecules to SiO2 NPs was confirmed
by the asymmetric and symmetric (C–H) stretching vibrations of –CH3
Core holder length 30.4 cm or –CH2 groups observed at ∼2851 cm−1 and the asymmetric and
Core holder inner diameter 2.54 cm
symmetric stretching vibrations of COO– situated at ∼1536 cm−1 and
Particle size 0.0105–0.0149 cm
Sand-pack porosity 35–40%
∼1446 cm−1, respectively [65] (Fig. 4a and b).
Sand-pack permeability 5–6.5 Darcy
Connate water saturation 3.0 ± 0.2%
Pore volume 50 ± 1.5 cm3
6.1.2. TGA measurements
Oil viscosity (T = 25 °C) 940 ± 5 cP The thermogravimetric analysis (TGA) and differential scanning
Temperature T = 23–25 °C calorimetry (DSC) curves of unmodified and modified silica NPs are
shown in Fig. 5. The TGA profile of unmodified SiO2 NPs can be divided

dispersion. Finally, 2 PV of water were injected as a post-flush until the

oil cut at the production outlet was less than 1%. All the fluids were
injected at 0.1 ml/min.
Transmittance, %

6. Results and discussion

6.1. Nanoparticle characterization

6.1.1. FTIR measurements

The FTIR spectra of unmodified and modified silica NPs after nor-
malization of the peak area are shown in Figs. 3 and 4. The normal-
ization for the FTIR spectra was performed by using peaks derived from
bonds which are not involved in the modification reactions; namely
peaks between 900 and 1300 cm−1. The bonding of the OTES molecules 4000 3200 2800 2200 1600 1000 400
to SiO2 NPs was confirmed by the peaks at 2926 cm−1 and 2858 cm−1 -1
Wave number, cm
which were ascribed to very intense asymmetric and symmetric
stretching vibrations of C–H bonds of the CH2 groups in the octyl SiO2 SiO2-OTES OTES
substituent [63]. Additionally, the peak at 960 cm−1 which was as-
cribed to Si–O–Si bond, and the disappearance of the peak at Fig. 3. IR spectrum of SiO2, SiO2-OTES, and OTES.

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L.M. Corredor, et al. Fuel 252 (2019) 622–634

Transmittance, %

Transmittance, %
(a) (b)

4000 3200 2800 2200 1600 1000 400 4000 3200 2800 2200 1600 1000 400
-1 -1
Wave number, cm Wave number, cm

SiO2 SiO2-OAA OA SiO2 SiO2-SAA SA

Fig. 4. IR spectrum of (a) SiO2-OAA, and (b) SiO2-SAA.

100 120 7. Hybrid dispersion characterization

90
80 7.1. ζ-potential measurements
80
Heat flow, mW
Weight, %

40 The ζ-potential values of the different NP dispersions are provided

70
60
50
40
Exo up
30
0 200 400 600
o
Temperature, C
SiO2 TGA SiO2-OAA TGA SiO2-SAA TGA
SiO2 DSC SiO2-OAA DSC SiO2-SAA DSC
Fig. 5. TG/DSC profiles of SiO2, SiO2-OTES, SiO2-SAA, and SiO2-OAA.
into two regions, desorption of physisorbed water completed up to
400 °C and dehydroxylation process of adjacent –OH groups between
400 °C and 800 °C [66]. The percentage of weight loss related to each
region was 25.7% and 6.0%, respectively.
A three-step weight loss was identified in the TGA profiles of all
modified NPs. The first step occurred below 200 °C which was attrib-
uted to the evaporation of physically adsorbed water and volatile sol-
vents. The weight loss in this region was 6.34%, 10.99% and 31.83%
for SiO2-SAA, SiO2-OAA and SiO2-OTES NPs, respectively. The second
step was attributed to the thermal decomposition of each modifier
grafted onto the surface of the NPs. For SiO2-OAA, the second step was
observed from 220 °C to 330 °C (Fig. 5, purple line) [67] whereas for
SiO2-SAA the second step was observed from 210 °C to 330 °C (Fig. 5,
blue line) [68] and for SiO2-OTES from 200 °C to 370 °C [23] (Fig. 5,
green line). The weight loss in this region was 11.7%, 13% and 15.5%
for SiO2-OAA, SiO2-SAA and SiO2-OTES NPs, respectively. In the final
step, the weight loss was attributed to the combustion of the degraded
product.
Fig. 6 shows the NPs dispersed in different mixtures of DI water/
propanol (W/A). It was observed that the precipitate of SiO2-SAA NPs
and SiO2-OAA NPs increased as the concentration of DI water in the
mixture increased, while the precipitate of SiO2-OTES NPs reduced.
This test and the water weight losses in the TGA analysis suggests that
the hydrophobicity of modified SiO2 can be ranked as follows: SiO2-
SAA > SiO2-OAA > SiO2-OTES.
in Table 2. Typically, NP dispersions with ζ-potential values lower than
0 −30 mV or larger than +30 mV are stable [69]. SiO2-OAA (−32 mV)
and SiO2-OTES (−29.6 mV) NPs display better stability than SiO2-SAA
-40 (−26.1 mV) NPs in water, despite the borderline zeta potentials, due to
the formation of a larger hydration layer. The hydration layer results
-80 from the hydrogen bonding between the silanol groups on the NPs with
800
the water molecules. This conclusion is supported by the TGA results
which showed that the weight loss associated to water for SiO2-SAA was
only 6.34%, whereas for SiO2-OAA and SiO2-OTES, it was 10.99% and
SiO2-OTES TGA 31.83%, respectively. Examining Table 2, it is concluded that all the
SiO2-OTES DSC hybrid dispersions prepared in this study are stabilized chiefly by steric
repulsion of the adsorbed polymeric chains. The adsorption of HPAM
on the surface occurs via hydrophobic interactions between the
polymer backbone (–CH2–CH2–) and the R-CH3 chain of the modifiers
or by hydrogen bonding between the oxygen or nitrogen from HPAM
and the hydrogen from the SiO2 surface (SiO–H⋯N–H or SiO–-
H⋯O–CNH2) or between the hydrogen from the HPAM and the oxygen
of the SiO2 surface (SiO⋯HNH–CO–C) [70]. The effect of polymer ad-
sorption onto dispersed particles in polymer solutions have been de-
scribed in detail by Kawaguchi [71]. In this study, the effect of pH on
the configuration of the adsorbed polymer molecules on the NP surface
was not considered because the pH values of the hybrids did not change
significantly (between 6.9 and 8.18).
7.2. Cryo-SEM results
Fig. 7 depicts cryo-SEM images of aqueous unmodified and modified
SiO2 dispersions before and after adding HPAM. The size of the un-
modified SiO2 NP aggregates in DI water is larger than those of the
modified SiO2 NPs (see Fig. 7A-D). This can be attributed to the hy-
drogen bonding between the –OH groups on the surface of the un-
modified SiO2 NPs. The size of the aggregates of the unmodified NPs
decreased after the surface was modified with OTES because the re-
pulsive forces between OTES molecules prevent the aggregation of the
NPs (see Fig. 7A (1) and B (1)). Smaller aggregates are also observed for
SiO2-SAA and SiO2-OAA NPs. Their high hydrophobicity leads to the
formation of larger aggregates which precipitated out, despite the ul-
trasonication, and, hence, could not be detected by the cryo-SEM
images (see Fig. 7C (1-2) and D (1-2)). When HPAM was added to the
aqueous dispersions, some polymer chains were adsorbed onto the SiO2
surface through hydrogen bonding or hydrophobic interaction. For the
SiO2-SAA, SiO2-OAA and SiO2-OTES hybrid dispersions, the repulsive
electrostatic forces between coated NP-coated NP and coated NP-

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L.M. Corredor, et al. Fuel 252 (2019) 622–634

Fig. 6. Dispersion stability test of 1.0 wt% (A) SiO2-SAA, (B) SiO2-OAA, and (C) SiO2-OTES in water/propanol (W/A) mixtures.

Table 2 [72]. We believe the role of the depletion attraction forces is minimal
ζ-potential and pH values of aqueous and hybrid dispersions of the modified for the modified NPs, especially since for the modified NP hybrid dis-
and unmodified SiO2 NPs at 20 °C. persions the interaction with the HPAM chains prevented the floccu-
NP type HPAM NP concentration, ζ-Potential @ pH @ lation of the coated NPs, as evident from the different state of aggre-
concentration, ppm wt% 20 °C 20 °C gration of silica NP before and after adding HPAM molecules seen in
Fig. 7, hence minimizing the role of the depletion attractive forces. The
SiO2 4000 1.0 −85.4 7.48
adsorbed polymeric chains positively influenced the dispersivity of the
4000 2.0 −84.5 7.26
4000 3.0 −71.4 7.14 NPs, reducing the size of the aggregates by effective steric repulsion
4000 4.0 −66.3 6.9 (see Fig. 7A-D (3-4)). Some of the large aggregates formed by SiO2-SAA
0 2.0 −15.3 6 and SiO2-OAA NPs were captured in the cryo-SEM images after the
SiO2-OTES 4000 1.0 −82 8.1 addition of HPAM (see Fig. 7C (4) and D (4)).
4000 2.0 −76.7 7.86
4000 3.0 −73.3 7.73
4000 4.0 −63.2 7.69 8. Rheological characterization
0 2.0 −29.6 5.81

SiO2-OAA 4000 1.0 −75.3 8.18 8.1. Linear viscoelastic properties

4000 2.0 −70.8 8.11
4000 3.0 −67.3 8.10 Rheometry provides a distinctive, sophisticated tool to study the
4000 4.0 −64.8 8.0
0 2.0 −32 5.29
network structure of flocculated colloidal gels, yielding significant in-
formation on the nanofiller structural characteristics in a polymer so-
SiO2-SAA 4000 1.0 −68 7.82
lution [24,70]. The linear viscoelastic properties are affected by the
4000 2.0 −63 7.14
4000 3.0 −59.8 6.95 network structure of polymer chains in the polymer solution systems,
4000 4.0 −56.1 6.84 and this network structure can be captured in frequency sweep test
0 2.0 −26.1 4.99 [38,40,73]. The storage modulus (G') and the loss modulus (G'') are the
two main parameters that represent the linear viscoelastic properties. G'
provides information on the rigidity of the network structure, while G″
polymer (both negatively charged) contribute to disperse the NPs into quantifies how readily an applied stress to the structure is relaxed or
the polymer solution and to keep the polymer in an extended config- dissipated [74,75]. Fig. 8 shows G' and G″ of hybrid dispersions of
uration. However, the electrostatic repulsive forces do not play a major different unmodified and modified silica NPs and HPAM under small-
role in the adsorption of the polymer onto the coated NP surface. The amplitude oscillatory shear (strain amplitude γ0 = 0.1%) for an angular
van der Waals forces (hydrogen bonding) between NP-NP and NP- frequency range from 0.1 to 10 rad/s at 35 °C. It should be noted that in
polymer are reduced following modifying the NP surface with OAA, log-log scale, the errors are within the data point markers.
SAA and OTES because the number of –OH groups available on the NP As can be seen in Fig. 8b and c, increasing the content of SiO2-SAA
surface is reduced. In the meantime, the role of the –OH groups in and SiO2-OAA NPs damages the network structure of HPAM molecules
polymer adsorption is not significant. Otherwise, these forces are sig- and decreases the storage modulus of hybrid dispersions, particularly in
nificant in the absence of steric effects, i.e. for unmodified silica NPs the low-frequency region. In other words, SAA-based and OAA-based

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L.M. Corredor, et al.
Fig. 7. Cryo-SEM images of A) unmodified SiO2, B) SiO2-OTES, C) SiO2-OAA, and D) SiO2-SAA NPs dispersed in DI water or 4000 ppm of HPAM solution at low (1–3)
and high magnification (2–4).
hybrid dispersions have a weaker network structure compared to the
HPAM solution. Conversely, incorporating unmodified and SiO2-OTES
NPs improve the storage and loss moduli of HPAM solution, particularly
at low-frequencies (see Fig. 8a and d).
The reason for such differences in the network strength of hybrid
dispersions originates from the surface chemistry of unmodified and
modified silica NPs. Such different behavior of unmodified and mod-
ified silica NPs can be related to their dispersion state in HPAM solution
and the configuration of adsorbed HPAM molecule on the surface of
silica NPs. Firstly, the dispersion of unmodified and modified silica NPs
with and without HPAM molecules was explained in the cryo-SEM
image discussion. Secondly, different configurations of adsorbed
polymer molecules onto the surface of carboxylic acid modified surfaces
(SAA and OAA) and silane modified surface (OTES) are expected to
have a significant effect in addition to the dispersion state [76]. Possible
configurations of adsorbed HPAM molecule on the surface of modified
NPs are depicted in Fig. 9.
We showed that the modified silica NPs can be ranked based on
their hydrophobicity as follows: SiO2-SAA > SiO2-OAA > SiO2-OTES.
For SiO2-OTES NPs, due to the hydrophobicity of the modified chain,
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Fuel 252 (2019) 622–634
hydrophobic interaction between the backbone of HPAM and the hy-
drophobic functional group on SiO2-OTES NPs is the main driving
mechanism to bring HPAM molecules to the vicinity of SiO2-OTES NPs.
Due to large occupied space of silane on the surface SiO2-OTES NPs and
the strength of hydrophobic affinity and electrostatic repulsion between
HPAM molecules and SiO2-OTES NPs, the contact of HPAM molecules
and SiO2-OTES NPs occurs with a minimal number of segments at-
tached to the surface of SiO2-OTES NPs. This phenomenon increases the
probability of creating configuration (A) in Fig. 9 for OTES-hybrid
dispersions. In such configuration, polymer chains are moving and
protruding freely into the aqueous phase with high probability for
bridging between SiO2-OTES NPs and creating a 3D network formation.
Frequency sweep results also confirm that by incorporating OTES NPs,
the G' of hybrid dispersion increases and a stronger network is formed.
Similarly, in SAA-based and OAA-based hybrid dispersions, hydro-
phobic interaction between the backbone of HPAM and the hydro-
phobic functional group of modified silica NPs control the adsorption of
HPAM molecules. However, more hydrophobic affinity of SiO2-SAA and
SiO2-OAA NPs compared to SiO2-OTES NPs may increase the number of
HPAM segments attached to the SAA and OAA silica NPs. As a result,
L.M. Corredor, et al.
Fig. 8. Storage (G' , closed symbols) and loss (G'' , open symbols) moduli of the hybrid dispersions at 0.0, 1.0, 2.0, and 4.0 wt% of (a) unmodified and (b) SiO2-SAA
NPs, (c) SiO2-OAA NPs, and (d) SiO2-OTES modified silica NPs. HPAM = 4000 ppm.
Fig. 9. Possible configuration of HPAM molecules adsorbed at NP/water in-
terface (A) random coil (high molecular weight polymers), (B) flat multiple site
attachments (strong adsorption).
629
Fuel 252 (2019) 622–634
configuration (B) in Fig. 9 is predicted to be more likely in SAA-based
and OAA-based hybrid dispersions. Any standing configuration for SAA-
based and OAA-based hybrid dispersions is not consistent with the
frequency sweep results. If the HPAM molecule can stand on the surface
of SiO2-SAA or SiO2-OAA NPs, by increasing the content of SiO2-SAA or
SiO2-OAA NPs, the probability of polymer bridging increases, and
larger storage modulus should be expected, which is not the case for
SAA-based and OAA-based hybrid dispersions (see storage modulus in
Fig. 8b and 8c). Moreover, due to the unsaturated nature of the SiO2-
OAA NPs, the hydrophobic affinity of SiO2-OAA NPs is less than SiO2-
SAA NPs and as a result, the severity of disruption of HPAM network by
the addition of OAA modified silica NPs is less than the addition of
L.M. Corredor, et al. Fuel 252 (2019) 622–634

SiO2-SAA NPs. solution. In contrast, for OTES-based hybrid dispersions, by increasing

8.2. Nonlinear viscoelastic properties
Due to converging and diverging pores in porous media, hybrid
dispersions may experience large deformation, which can be exten-
sional or shear. Thus, from a practical point of view, the material re-
sponse will likely fall into a nonlinear regime of deformation. In this
work, large shear deformation is studied to characterize the flow be-
havior of the hybrid dispersions. Fig. 10 depicts the G' of various hybrid
dispersions at a constant frequency (=0.5 rad/s) and various strain
amplitudes (1–1000%) (The loss modulus (G″) plot in the strain sweep
test is included in the Supplemental information, Fig. S1). The errors in
modulus for the strain sweep test are within the data point markers. The
plateau storage modulus (modulus in linear viscoelastic (LVR) region)
and the critical strain amplitude (the strain amplitude at which G' starts
decreasing and reaches 90% of its original value) are the two main
parameters which can be extracted from strain sweep test. In LVR, the
applied strain amplitude is not large enough to disrupt the at-rest
structures (i.e. storage modulus is independent of applied strain am-
plitude). However, by further increase in strain amplitude, the non-LVR
is approached (storage modulus changes with applied strain amplitude)
(see Fig. 10).
As expected from the frequency sweep test, by increasing the con-
tent of SiO2-OAA NPs, the plateau G' did not change significantly
compared with HPAM solution (Fig. 10c). In addition, the critical strain
amplitude for the OAA-based hybrid dispersion did not shift sig-
nificantly relative to HPAM solution. However, by increasing the con-
tent of SiO2-SAA NPs (see Fig. 10b), the plateau for G' decreases to
0.8 Pa for HPAM/4.0 wt% of SiO2-SAA NP solution from the plateau G'
for HPAM solution, which is 8 Pa. Moreover, the critical strain ampli-
tude reaches approximately 8% for HPAM/4.0 wt% of SiO2-SAA NP
solution (the critical strain amplitude for HPAM solution is about 60%).
SiO2-SAA NPs aggregates can adsorb HPAM chains and extract them
from the aqueous media and thus prevent them from creating a rigid
network, resulting in lower plateau modulus compared with HPAM
the concentration of SiO2-OTES NPs, the plateau storage modulus in-
creases fivefold to 40 Pa for HPAM/4.0 wt% of SiO2-OTES NP solution
(see Fig. 10d). Overall, the strain sweep results confirm that SiO2-OTES
NPs improve the viscoelastic properties of HPAM solution significantly
in the linear region.
8.3. Intra-cycle shear-thickening behavior
It is desirable to find a clear physical meaning for the measured
storage and loss moduli in the nonlinear region. In the linear viscoe-
lastic region, the output stress signals are simple sinusoidal functions.
However, by increasing the strain amplitude and shifting into the
nonlinear region, shear stress cannot be described simply by sinusoidal
waves. The mathematical details of shear stress (τ) response in the
linear and the nonlinear regions and the stress decomposition method
can be found in our previous works [24,25,77].
When we are in one single cycle of oscillations at a constant strain
amplitude, elastic and viscous local responses of a material at minimum
and maximum instantaneous strains and strain-rates, which are denoted
'
byGM , GL' , ηM' , ηL' , respectively, can be very helpful to characterize the
nonlinear viscoelastic behavior and link the network structure to the
rheological data. It should be noted here that all local nonlinear
properties are compiled directly by the rheometer software (Anton-Paar
Rheoplus/32 V3.62). To interpret local nonlinear properties quantita-
tively, shear-thickening and strain-stiffening ratios were defined as
follows [78].
GL' − GM
'
S= ,
GL' (1)
η' L − η' M
T= .
η' L (2)
Positive S and T represent intra-cycle strain-stiffening and intra-
cycle shear-thickening behaviors, respectively, and negative S and T
indicate intra-cycle strain-softening and intra-cycle shear-thinning

10 2 10 2
(a) (b)

10 1 10 1
G'>Pa]

G'>Pa]

10 0 10 0

G'
HPAM 3630 G'
10 -1 HPAM 3630/1.0 wt%-Unmod-SiO2 10 -1 HPAM 3630
HPAM 3630/1.0 wt%-SiO2-SAA
HPAM 3630/2.0 wt%-Unmod-SiO2
HPAM 3630/2.0 wt%-SiO2-SAA
HPAM 3630/4.0 wt%-Unmod-SiO2
HPAM 3630/4.0 wt%-SiO2-SAA
10 -2 0 1 2 3 10 -2 0 1 2 3
10 10 10 10 10 10 10 10
Ȗ[%] Ȗ[%]
10 2 10 2
(c) (d)

10 1 10 1
G'>Pa]

G'>Pa]

10 0 10 0

G' G'
HPAM 3630 HPAM 3630
10 -1 10 -1 HPAM 3630/1.0 wt%-SiO2-OTES
HPAM 3630/1.0 wt%-SiO2-OAA
HPAM 3630/2.0 wt%-SiO2-OAA HPAM 3630/2.0 wt%-SiO2-OTES
HPAM 3630/4.0 wt%-SiO2-OAA HPAM 3630/4.0 wt%-SiO2-OTES
10 -2 0 1 2 3 10 -2 0 1 2 3
10 10 10 10 10 10 10 10
Ȗ[%] Ȗ[%]

Fig. 10. Oscillatory strain amplitude sweep response of the hybrid dispersions of HPAM and the different silica NPs at a fixed angular frequency (0.5 rad/s).
4000 ppm of HPAM solution with (a) unmodified silica NPs, (b) SiO2-SAA NPs, (c) SiO2-OAA NPs, and (d) SiO2-OTES NPs.

630
L.M. Corredor, et al.
responses, respectively. In this study, only intra-cycle shear-thickening
ratio of the hybrid dispersions are presented in Fig. 11 (the strain-stif-
fening ratios are included in the Supplemental information, Fig. S2). As
can be seen in Fig. 11, for HPAM solution without silica NPs, T value is
approximately zero up to γ ≈ 60%, then T reaches a positive maximum
value at γ ≈ 250% followed by a decreasing trend back to approxi-
mately zero (see black line in Fig. 11a). The positive T reveals the oc-
currence of intra-cycle shear-thickening response. Generally speaking,
in the low-frequency region, the nonlinear viscoelastic behavior is
mainly described using a mechanism controlled by strain-rate-induced
effects [79]. T > 0 could be related to the rate of flow-enhanced for-
mation of network bonds and the rate of bond breakage for HPAM
solution when deformation is applied in a single cycle. When the former
is greater than the latter in one cycle, intra-cycle shear-thickening be-
havior occurs. Dupuis et al. [80] also studied the rheological properties
of solutions of high molecular weight partially hydrolyzed poly-
acrylamide. They suggested that the shear-thickening behavior of such
polymers originates from the formation and destruction of aggregates,
which are related to intra- and inter-molecular interactions. More de-
tails on the shear-thickening behavior can also be found in Hu and
Jaimeson [81], and Bharadwaj et al. [79].
However, by increasing the concentration of SiO2-SAA NPs, the
maximum positive value decreases and shear-thinning (T < 0) beha-
vior arises (see Fig. 11b). For HPAM/4.0 wt% of SiO2-SAA NP, the
transition to nonlinear region starts at lower strain amplitudes
(γ = 10%), and the maximum of T disappears. The same intra-cycle
shear thickening behavior is observed for the addition of other silica
NPs (see Fig. 11a, c, and d). The shear-thickening ratio (T ) decreased as
unmodified and modified silica NP concentration increased. This phe-
nomenon could be attributed to immobilization of polymer chains at
the interface which makes a portion of the chains unavailable for de-
formation-induced structuring in the polymer phase [82–84]. Such
behavior is observed for the whole range of concentration of all hybrid
dispersions.
Surprisingly, introducing the different types of modified and
80
60
40
20
T [%]
0
-20 HPAM 3630
-40 HPAM 3630/1.0 wt%-Unmod-SiO2
HPAM 3630/2.0 wt%-Unmod-SiO2
-60
HPAM 3630/4.0 wt%-Unmod-SiO2
-80
0 1
10 10 10
Ȗ[%]
80
60
40
20
T [%]
0
-20 HPAM 3630
-40 HPAM 3630/1.0 wt%-SiO2-OAA
HPAM 3630/2.0 wt%-SiO2-OAA
-60
HPAM 3630/4.0 wt%-SiO2-OAA
-80 0 1
10 10 10
Ȗ[%]
Fig. 11. Intra-cycle shear-thickening ratio of the hybrid dispersion of HPAM and all silica NPs. 4000 ppm of HPAM solution with (a) unmodified silica NPs, (b) SAA
NPs, (c) OAA NPs, and (d) OTES NPs.
Fuel 252 (2019) 622–634
unmodified silica NPs leads to a similar effect on the behavior of the
hybrid dispersions at higher strain amplitudes, well above the yield
point of all systems (where the strain amplitude is much larger than the
critical strain amplitude). As an example, for HPAM 3630/unmodified
SiO2, the shear-thinning (T < 0) behavior starts at γ0 > 200% (see
Fig. 11a, blue line). By increasing the weight fraction of the different
types of modified and unmodified silica NPs, the value of the strain
amplitude at which T changes sign to negative values, decreases. All
hybrid dispersions exhibit an intra-cycle shear-thinning viscoelastic
behavior (T < 0) at higher strain amplitudes. Such behavior could be
explained in conjunction with the wide-spread bond breakup in the
fumed silica NP flocculated structures, the orientation of the rigid
polymer chains parallel to the flow direction and slippage at the NP-
polymer interface [85–89]. Overall, introducing the different SiO2 NPs
decreases the shear-thickening behavior of the hybrid dispersions, de-
creases the critical strain amplitude, and enhances the shear-thinning
behavior above the yield point of all systems.
8.4. Core flooding results
In the last part, the performance of all hybrid dispersions of HPAM/
NPs for displacement of heavy oil was evaluated. Figs. 12 and 13 show
the pressure difference of sand-pack and the cumulative oil recovery
versus pore volume of the injected fluid at 25 °C, respectively. The
pressure difference drops during secondary water flooding (see WF#2
in Fig. 12) and remains low and constant around 2.5 psi. During the
injection of the HPAM solution and the HPAM/NP dispersions (see PF
in Fig. 12), the pressure difference increased. The pressure differences
observed for 0.5 PV of HPAM/1.0 wt% SiO2-SAA and HPAM/1.0 wt%
SiO2-OAA dispersions were lower than those of the HPAM solution (0.5
PV) due to their lower viscoelastic properties and higher mobility ratio.
The details of viscoelastic property reduction of SiO2-SAA and SiO2-
OAA NPs was explained earlier. In contrast, the higher-pressure dif-
ferences of the HPAM/1.0 wt% SiO2-OTES dispersions can be related to
higher viscoelastic properties, lower mobility ratio, and pore blockage
(a) (b)
HPAM 3630
HPAM 3630/1.0 wt%-SiO2-SAA
HPAM 3630/2.0 wt%-SiO2-SAA
HPAM 3630/4.0 wt%-SiO2-SAA
2 3 0 1 2 3
10 10 10 10 10
Ȗ[%]
(c) (d)
HPAM 3630
HPAM 3630/1.0 wt%-SiO2-OTES
HPAM 3630/2.0 wt%-SiO2-OTES
HPAM 3630/4.0 wt%-SiO2-OTES
2 3 0 1 2 3
10 10 10 10 10
Ȗ[%]
631
L.M. Corredor, et al.
40
WF #2 PF
Pressure (psi)
30
20
10
0 10
0 0.5 1 1.5
Pore Volume
Fig. 12. Pressure drop as a function of pore volume of the injected fluids at
25 °C (black line – HPAM, blue line – HPAM/ 1.0 wt% SiO2-SAA, purple line –
HPAM/ 1.0 wt% SiO2-OAA, red line – HPAM/ 1.0 wt% SiO2, green line –
HPAM/ 1.0 wt% SiO2-OTES). (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
80
WF #2 PF WF #3
60
Oil Recovery (%)
40
20
0 0.5 wt%), which should have smaller aggregates, were injected into the
0 0.5 1 1.5 2 2.5
Pore Volume
Fig. 13. Cumulative oil recovery as a function of pore volume of the injected
fluids at 25 °C (light blue line – water, black line – HPAM, blue line – HPAM/
1.0 wt% SiO2-SAA, purple line – HPAM/ 1.0 wt% SiO2-OAA, red line – HPAM/
1.0 wt% SiO2, green line – HPAM/ 1.0 wt% SiO2-OTES). (For interpretation of
the references to colour in this figure legend, the reader is referred to the web
version of this article.)
of the SiO2-OTES NPs in the sand-pack (to have a better understanding
of viscosity change at different shear rates, the flow curves of all hybrid
dispersions are included in the Supplemental information, Fig. S3). The
pore blockage mechanism of NPs in porous media and its effect on ul-
timate oil recovery will be discussed later.
At the end of the extended water flooding (see WF #3 in Fig. 12),
the pressure differences reached their initial value of ∼2.5 psi for the
HPAM solution and the HPAM/1.0 wt% unmodified SiO2, HPAM/1.0 wt
% SiO2-OAA, and HPAM/1.0 wt% SiO2-OAA dispersions. The higher
pressure drop observed for HPAM/1.0 wt% SiO2-OTES dispersions, at
the end of the extended water flooding, suggest a reduction in the
permeability of the porous medium by virtue of the higher adsorption/
retention of the NPs in the sand-pack [90].
The cumulative oil recovery after water flooding and (0.5 PV)
HPAM flooding was 43.1% and 71.4% OOIP, respectively (Fig. 13). It is
observed that the addition of 1.0 wt% of unmodified SiO2 and SiO2-
OTES NPs to the HPAM solution did not change the performance of the
polymer flooding, while the addition of 1.0 wt% of SiO2-OAA and SiO2-
SAA NPs reduced the cumulative oil recovery from 71.4% OOIP (for 0.5
PV HPAM solution) to 59.3% and 62.6% OOIP, respectively.
The main reason for lower cumulative oil recovery for water
flooding is viscous fingering. Adding polymer molecules increases the
viscosity of the injected fluid and decreases the mobility ratio and
prevents viscous fingering to a certain extent. It is well documented in
the literature that in water-wet systems, water (wetting phase) occupies
the smaller pores and oil (non-wetting phase) mainly resides in the
larger pores [3]. As a result, during water flooding, water tends to enter
smaller pores and bypasses large amount of oil residing in the larger
Fuel 252 (2019) 622–634
30 80
WF #3
WF #2 PF 70
25
Oil Recovery (%)
60
Pressure (psi)
20
50
15 40
30
2 2.5 3 20
5
WF #3 10
0 0
0 0.5 1 1.5 2 2.5 3
Pore Volume
Fig. 14. Cumulative oil recovery and pressure drop as a function of pore vo-
lume of the injected fluids at 25 °C (green line – HPAM/1.0 wt% SiO2-OTES,
light purple line – HPAM/0.5 wt% SiO2-OTES, grey line – HPAM/0.2 wt% SiO2-
71.6%
OTES). (For interpretation of the references to colour in this figure legend, the
71.4%
70.9% reader is referred to the web version of this article.)
62.6%
59.3%
pores. By adding NPs, if they can enter the smaller pores, they can block
these pores and force water to enter the larger pores and displace the
43.1% remaining oil and increase the ultimate oil recovery [91]. Regarding the
pressure difference and the cumulative oil recovery of HPAM/1.0 wt%
SiO2-OTES, it can be concluded that the aggregate size of 1.0 wt% SiO2-
OTES NPs is not sufficiently small to go to the smaller water-wet pores,
block them, and improve oil recovery compared to HPAM solution. To
test this hypothesis, two lower concentrations of OTES NPs (0.2 and
3
sand-pack (Fig. 14). The cumulative oil recovery of the HPAM solution
increased to 75.7% and 73.8% of OOIP upon adding 0.2 and 0.5 wt% of
SiO2-OTES NPs, respectively. Higher recoveries at lower OTES con-
centrations suggest better propagation of the NPs inside the sand-pack
and blockage of water-wet pores.
In general, it can be concluded that the performance of the HPAM/
NPs for EOR processes is mainly related to the size of the NP aggregates
and the interaction of the polymer and the NP in the aqueous solution,
i.e. the network structure of the HPAM/NP dispersion. The NPs (SiO2-
OAA and SiO2-SAA NPs) that negatively affected the viscoelastic
properties and the network structure of the polymer solution yielded
lower oil recovery than that of the HPAM solution and the NPs with
positive effect (SiO2-OTES NPs) on the network structure of HPAM
solution. The SiO2-OTES NPs system exhibited better dispersion, and
was stable in HPAM solution, thus yielding higher oil recovery. It
should be mentioned here that the effects of salinity and temperature
on the viscoelastic properties and heavy oil recovery of the hybrid
dispersions were not assessed in this study.
9. Conclusions
By altering the silanols of the surface of SiO2 NPs, three differently
modified SiO2 NPs were synthesized and characterized using TGA, DSC,
and FTIR. The colloidal stability, dispersion state of the NPs, and the
flow behavior of the aqueous solution of HPAM/different SiO2 NPs
were investigated using ζ-potential, cryo-SEM, and linear and nonlinear
rheology, respectively. Finally, the performance of HPAM/all SiO2 NPs
while displacing heavy oil were evaluated in a linear sand-pack set up.
In the linear viscoelastic region, it was shown that bare SiO2 NPs che-
mically modified with silane (SiO2-OTES NPs) improved the viscoelastic
properties of HPAM solution compared to carboxylic acids modified
NPs (SiO2-SAA and SiO2-OAA). Such improvement originated from
better dispersion state of SiO2-OTES NPs and standing configuration of
HPAM on the surface of SiO2-OTES NPs, which increased the prob-
ability of polymer bridging. However, in the nonlinear region, all silica
NPs decreased the intra-cycle shear-thickening behavior and led to se-
vere intra-cycle shear-thinning after yielding of HPAM/ SiO2 NPs
632
L.M. Corredor, et al.
network. The displacement tests showed that adding either SiO2-SAA
and SiO2-OAA NPs to HPAM solution, both of which had a negative
effect on the HPAM network structure, reduced the oil recovery of the
HPAM solution from 71.4% OOIP to 59.3% and 62.6% OOIP, respec-
tively. In contrast, incorporation of 0.2 wt% SiO2-OTES NPs to HPAM
solution increased the oil recovery to 75.7% OOIP.
Acknowledgement
The authors would like to thank Amitabha Majumdar and Ola Jabar
for their technical assistance. Laura M. Corredor gratefully acknowl-
edges Ecopetrol S.A for the scholarship to pursue her graduate studies.
This research was partially funded by NSERC Discovery Grants
#05503-2015 (US) and 03769-2017 (ZC), NSERC/AIEES/Energi
Simulation IRC in Reservoir Simulation, AITF (iCore) Chair in Reservoir
Modelling, and the Frank and Sarah Meyer Foundation CMG
Collaboration Centre.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2019.04.145.
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