Geosystem Engineering

ISSN: 1226-9328 (Print) 2166-3394 (Online) Journal homepage: https://www.tandfonline.com/loi/tges20

Stable SiO2–TiO2 composite-based nanofluid

of improved rheological behaviour for high-
temperature oilfield applications

Ravi Shankar Kumar & Tushar Sharma

To cite this article: Ravi Shankar Kumar & Tushar Sharma (2020): Stable SiO2–TiO2 composite-
based nanofluid of improved rheological behaviour for high-temperature oilfield applications,
Geosystem Engineering, DOI: 10.1080/12269328.2020.1713909

To link to this article: https://doi.org/10.1080/12269328.2020.1713909

Published online: 16 Jan 2020.

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GEOSYSTEM ENGINEERING
https://doi.org/10.1080/12269328.2020.1713909

RESEARCH ARTICLE

Stable SiO2–TiO2 composite-based nanofluid of improved rheological behaviour

for high-temperature oilfield applications
Ravi Shankar Kumar and Tushar Sharma
Enhanced Oil Recovery Laboratory, Department of Petroleum Engineering, Rajiv Gandhi Institute of Petroleum Technology, Jais, India

ABSTRACT ARTICLE HISTORY

Nanofluid synthesis in pure water is associated with premature settlement resulting in least disper- Received 7 May 2019
sion stability. Therefore, in this study, polyacrylamide (PAM) is used as viscosity enhancer to improve Accepted 30 December 2019
dispersion stability of nanofluid stabilized by composites of silica and titania. Different techniques KEYWORDS
such as dynamic light scattering measurements, electrical conductivity, scanning electron micro- Nanoparticles; nanofluid;
scopy, and rheological studies are used to support the analysis. The use of silica and titania polymer; rheology; stability;
nanoparticles together with PAM has additional advantage over particle agglomeration, and thus, temperature
the dispersion stability improved. Further, nanofluid stabilized by composites of silica and titania was
tested for rheological measurements at 90°C to find nanotechnology applicability in high-tempera-
ture applications. The shear-thinning behaviour of nanofluids at high temperature (90°C) was least
affected by shear deformation and reduced to 0.48 mPa.s at higher shear rate (4200 s−1), while shear
thinning of PAM solution seriously varied with increasing shear deformation and takes the edge of
0.0005 mPa.s at higher shear rate (4200 s−1). In addition, the thermal stability of nanofluids was better
due to slight decrease in viscosity with increasing temperature, which makes them suitable to be
utilized at high-temperature applications in widespread industrial areas including oilfield where the
temperature becomes a major factor.

1. Introduction temperature (20–50°C) on viscosity values of PAM solu-

tions of concentration ranges from 0.2 to 0.5 wt%, and it
Polyacrylamide (PAM) is one of the cost-effective
was found that viscosity of solutions significantly
water-soluble polymers which is abundantly available
reduced with increasing temperature and finally reaches
in oilfield and largely used for water shut applications
to minimum level of 0.26 cp at 50°C. Therefore, it is
(Fatimah, Almohsin, Michael, Bataweel, & Alsharaeh,
important to improve the rheological behaviour of poly-
2019), permeability modifications (Marandi, Salehi, &
mer solutions using a better stabilizer that not only
Moghadam, 2018), oil recovery applications (Sharma,
works as rheology modifier but also shows least tem-
Iglauer, & Sangwai, 2016), and viscosity enhancement
perature dependency.
(Kumar & Sharma, 2018). PAM, being a high-molecu-
Nanofluid is an interdisciplinary nanomaterial which
lar-weight polymer, can provide important modifica-
is synthesized by small-size nanoparticles(NPs) and
tions in rheological behaviour of the base solution in
shows promising results in various applications such
which it is added. Additionally, PAM solutions are
as oil recovery (Zheng, Cheng, Wei, Li, & Zhang,
expected to exhibit the least effect of shear deformation,
2017), exploration (Liu, Jin, & Ding, 2016), fluid loss
and as a result, they can provide relatively better sweep
control (Medhi, Chowdhury, Gupta, & Mazumdar,
efficiency and mobility ratio in oilfield applications than
2019), and altering rock wettability (Rostami, Sharifi,
conventional methods (El-hoshoudy, Desouky, Al-
Aminshahidy, & Fahimpour, 2019). Moreover, the
Sabagh, Betiha, & Mahmoud, 2017). However, the use
enhanced use of NPs in several industrial applications
of PAM is not only limited to normal oilfield conditions
is supported by their superior thermal conductivity
but it is also used for high-temperature applications
(Keyvani, Afrand, Toghraie, & Reiszadeh, 2018) and
where most of the polymer methods fail to perform
heat transfer ability (Moradi, Toghraie, Isfahani, &
and show deformed rheological behaviour (Tapias,
Hosseinian, 2019), where temperature becomes an
Lizcano, & Lopes, 2018). The effect of temperature on
insignificant factor on properties of nanofluids. For
viscosity of PAM solutions is reported in several reports;
example, silica NPs are solid charged particles of size
for example, Yang (1999) studied the effect of increasing

CONTACT Tushar Sharma tusharsharma.ism@gmail.com Enhanced Oil Recovery Laboratory, Department of Petroleum Engineering, Rajiv Gandhi
Institute of Petroleum Technology, Jais, UP, 229304, India
© 2020 The Korean Society of Mineral and Energy Resources Engineers (KSMER)
2 R. S. KUMAR AND T. SHARMA
ranges from 1 to 100 nm which are thermally conduc-
tive and possess the ability to improve the stability and
rheological behaviour of polymer solutions (Sharma,
Kumar, & Sangwai, 2014). However, all NPs in nano-
fluid are expected to agglomerate to minimize the sur-
face energy, resulting in NPs to form large-size clusters
those intend to settle over the period of time (Yang,
Kelkar, Corti, & Franses, 2016). The agglomeration
reduces the overall population of NPs from the suspen-
sion, resulting in nanofluid to show premature settle-
ment (an instability issue) and deformed rheological
properties (Kumar & Sharma, 2018). In nanofluid
synthesis, the temperature is of key importance as it
can significantly affect the stability of dispersed NPs by
providing additional energy to Brownian motion of
NPs. NPs, under enhanced Brownian motion, are sus-
ceptible to undergo random collisions with other NPs,
and as a result, NPs may agglomerate and settle. Thus, a
stable nanofluid may exhibit premature NP settlement
at high temperature and become rheologically unstable
(Zadeh & Toghraie, 2018). The occurrence of agglom-
eration between similar NPs can be controlled by intro-
ducing another NP (of similar charge) that will help to
increase electrostatic repulsion and stabilize the nano-
fluid. The inclusion of TiO2 (as co-stabilizer) in prime
nanofluid can render the effect of particle settlement via
stabilizing the main NPs as suggested by Yang and Hu
(2017). Moreover, TiO2 has mainly three morphologies
which are rutile, anatase, and brookite (Abbasi, 2018).
The rutile and anatase morphologies of TiO2 consist of
tetragonal structure, and it varied along the sharing of
corner edges or corner connections, while brookite has
commonly orthorhombic structure (Abbasi, 2019).
However, rutile morphology has shown a wide area of
interest in various industrial applications including bio-
medical and oil and gas industry. Since TiO2 is a better
heat conductive material and thermally stable, it may
stabilize the nanofluid at high temperature by control-
ling the rate of agglomeration and provide long-term
stability to the nanofluid. Moreover, it is very clear that
NPs in nanofluids have the tendency to show agglom-
erations and further sedimentation in the nanofluid
which leads to instability and make nanofluid a rheolo-
gically deformed fluid. PAM solution (base fluid)
reduced the rate of sedimentation by increasing the
viscosity of nanofluid. At high temperature, PAM fluid
possesses thermal degradation due to chain scission
(Król-Morkisz & Pielichowska, 2019); it leads to the
decomposition of the solution. Further, it destabilizes
the rheological behavior and limits their applicability in
oilfield applications. Thus, the inclusion of thermally
stable NP, viz. TiO2, in silica nanofluid of PAM
increases the thermal stability of base fluid. The novelty
of the study lies in the use of novel nanomaterials of
SiO2–TiO2 those are thermally and rheologically stable
than pure PAM solution, a key factor for the use of
nanomaterials in oilfield schemes where temperature
becomes a limiting factor for PAM solution.
Therefore, in this study, we have reported the synthesis
of a silica nanofluid using the varying concentration of
SiO2 NPs (0.2–0.4 wt%, size ~15 nm) dispersed in base
PAM solution of 1000 ppm. NP TiO2 (size ~20 nm), as a
stabilizer, is included in silica nanofluid, considering its
favourable impact on NP agglomeration and nanofluid
stability. The concentration of TiO2 NP was kept constant
and low, viz. 0.05 wt%, as suggested for TiO2 use in
oilfield schemes (Bayat, Junin, Samsuri, Piroozian, &
Hokmabadi, 2014). The viscosity vs. shear rate measure-
ments was conducted at high temperature (90°C).
2. Experimental work
2.1. Materials
For this study, polymer PAM, with purity >90% and
molecular weight 107 g/mol, was obtained from SNF
Floerger, India, and used as received. Hydrophilic SiO2
(amorphous, purity 99.50%, and size ~15 nm) and hydro-
philic TiO2 (rutile, purity 92.00%, and size ~20 nm) were
used as received from Sisco Research Laboratories (SRL)
Pvt. Ltd, India. Deionized water (DI) of electrical con-
ductivity 0.0054 mS/cm was obtained by Millipore® Elix-
10 water purification apparatus for the preparation of
PAM solutions and nanofluids. A laboratory-grade mag-
netic stirrer (speed ranges from 0 to 1200 rpm) was used
to prepare the PAM solutions, and industrial mixer
(Oster, speed from 6000 to 20,000 rpm) was used to
synthesize the nanofluids.
2.2. Preparation of nanofluid
In this study, the synthesis of nanofluid using SiO2 and
TiO2 NP (as co-stabilizer) is proposed for high-tempera-
ture applications. The scheme of the nanofluid formula-
tion is shown in Figure 1. The nanofluid is prepared in
viscous base fluid of polymer PAM (1000 ppm) as nano-
fluid preparation in water was unsuccessful due to pre-
mature sedimentation of NPs. To prepare nanofluid, first
base fluid of 1000 ppm is prepared by dissolving 1 g of
polymer PAM in DI water at a stirring speed of 400 rpm
for 8 h (Kumar & Sharma, 2018). Next, NP SiO2 of
varying concentration (0.2, 0.3, and 0.4 wt%) was added
to viscous PAM solution, and the resulting milky colloi-
dal solution is regarded as silica nanofluid. PAM was
added as a thickening agent to stabilize the dispersed
silica NPs in a nanofluid. Further, NP TiO2 of 0.05 wt%

Figure 1. Schematic representation of the formulation methodology of stable nanofluid.
was added to silica nanofluid, and the resulting nanofluid
is regarded as nanofluid of SiO2–TiO2 composites. The
concentration of TiO2 was less, viz. 0.05 wt%, as recom-
mended (Bayat et al., 2014) to avoid oilfield problems,
e.g., pore blockage, formation damage, and reduced oil
production. Finally, nanofluids were sonicated for 120–
180 min using digital ultra-sonication bath at a frequency
of 30 Hz to ensure that the nanofluids received homo-
genization. A similar procedure is adopted to prepare
each nanofluid sample as given in Table 1. The compre-
hensive details of the synthesized nanofluids (viz. PST-1,
PST-2, and PST-3) and their nomenclature have been
provided in Table 1.
2.3. Nanofluid characterization
Nanofluids were characterized for size distribution using
dynamic light scattering (DLS)-based instrument Zetasizer
(NanoZS, Malvern® France), which is based on 173° light-
scattering angle to analyse colloidal suspensions. For scanning
electron microscopy (SEM) analysis, a field-emission scanning
electron microscope (FE-SEM, Nova NanoSEM) was used.
Nova NanoSEM is configured with an energy-dispersive X-
Table 1. Compositional details of the formulated nanofluid and
corresponding nomenclature.
S.
No. Base fluid Nanoparticle concentration Nomenclature
1
2
1000 ppm PAM
solution
0.2 wt% SiO2 + 0.05 wt% TiO2
0.3 wt% SiO2 + 0.05 wt% TiO2
PST-1
PST-2
3 0.4 wt% SiO2 + 0.05 wt% TiO2 PST-3
GEOSYSTEM ENGINEERING 3
ray spectroscopy (EDS/EDX) detector that was used to visua-
lize the compositional details of NPs in the nanofluid system.
The rheological measurements for nanofluids were performed
for viscosity vs. shear rate using HPHT rheometer (MCR-52,
Anton Paar, Austria). The rheometer consists of a bob and
cup assembly, and the external shear force was applied
through a spindle attached to magnetic coupling. A varying
shear rate ranges from 0.1 to 1000 s−1 was applied. Digital
ultrasonic cleaner (Labman India, frequency ~40 KHz) was
used to sonicate and homogenize NPs in formulated nano-
fluids. All chemicals, used to formulate the nanofluids, were
weighed using a digital weighing balance (Mettler Toledo,
ME204) with a repeatability of 0.1 mg.
4. Results and discussion
This section first discusses the stability results for nano-
fluids using visual appearance followed by a discussion on
their DLS and electrical conductivity measurements. SEM
analysis is presented to visualize the presence of titania
particles in interstices of silica nanofluid. Finally, rheolo-
gical measurements for viscosity vs. shear rate as a func-
tion of storage period and temperature were discussed.
4.1. Dispersion stability of nanofluids
These measurements were conducted to measure the rate
of sedimentation in nanofluids; nanofluid exhibiting least
NP sedimentation with time is regarded as a stable nano-
fluid (Kumar & Sharma, 2018). Therefore, the prepared
nanofluids were transferred to a transparent vessel and
kept undisturbed to visualize the changes in colour with
4 R. S. KUMAR AND T. SHARMA

time. The formulated nanofluid samples with base fluid
(1000 ppm PAM solution), viz. PST-1 (0.2 wt% SiO2 +
0.05 wt% TiO2), PST-2 (0.3 wt% SiO2 + 0.05 wt% TiO2),
and PST-3 (0.4 wt% SiO2 + 0.05 wt% TiO2), were milky in
appearance at the time of preparation. The nanofluids
progressively exhibited a transition from milky phase to
translucent due to settlement of dispersed NPs. The rate
of sedimentation in nanofluids was measured gravimetri-
cally; settled NPs from the vessels were collected and
cleaned using toluene. It was followed by their drying in
an oven to measure the actual weight of settled NPs out of
total NPs used at the time of preparation. The first sign of
colour change in PST nanofluids was observed after 3
weeks (~21 days) of preparation as shown in Figure 2. As
the gradual settlement occurs in PST nanofluids, samples
were carefully transferred to another transparent vessel
for further analysis. The dispersion stability for PST-1
was observed 35 days, whereas it was 39 days for PST-2
and more than 45 days for PST-3 as given in Table 2
which is in line with our previous study (Kumar &
Sharma, 2018). For the nanofluids, it was observed that
only 8–10% of NPs settled in first 21 days. For PST-1,
more than 80% NPs settled after 35 days, while ~77%
and ~69% NPs settled for PST-2 and PST-3 after 35 days
of preparation, respectively. Saha, Uppaluri, and Tiwari
(2018) also conducted the dispersion stability analysis for
3 wt% silica nanofluid in 5000 ppm Xanthan Gum (XG, a
typical oilfield polymer) over a time period of 10 days,
and they found that nanofluid exhibited better dispersion
stability with insignificant settlement. Therefore, in this
study, the use of PAM as a base fluid reduced the effect of
sedimentation by increasing the viscosity of solution.
Moreover, the main reason for enhancement in disper-
sion stability is attributed to the homogeneous distribu-
tion of silica NPs in nanofluid. The presence of TiO2 may
help to maintain uniform distribution of SiO2 NPs by
creating a surface charge or potential in nanofluid and
reduced the effect of agglomeration. Thus, it can be
inferred that PST-3 nanofluid showed higher dispersion
stability with 0.4 wt% SiO2 and 0.05 wt% TiO2 NPs in the
system.
4.2. DLS measurements for nanofluids
Zeta potential and size distribution for nanofluids were
measured at 25°C just after the sonication to avoid the
possibility of NP aggregation, leading to a change in the
size of NPs. Zeta potential and size distribution for each
nanofluid were measured on the first day of preparation,
and the results are given in Table 1. SiO2 NPs were
smaller in size (~15 nm); however, DLS measurements
showed an increase in NP size for all PST nanofluids,
which indicates that NPs tend to agglomerate due to
Vander Waals forces. On the first day of preparation,

Figure 2. Nanofluid stability analysis using visual appearance on (a) 1st day, (b) 21st day, and (c) 35th day for formulated nanofluid, viz.
PST-1, PST-2, and PST-3.

Table 2. DLS measurements (zeta potential and average size distribution) of nanofluid as a function of sample storage time.
Zeta potential (mV) Size distribution (nm)
Dispersion stability
Nanofluid samples (days) 1st day (%) error 35th day (%) error 1st day (%) error 35th day (%) error
PST-1 35 −39.5 ±1.7 −29.5 ±0.5 302 ±1.5 127 ±0.4
PST-2 39 −42.7 ±0.9 −31.2 ±1.5 328 ±2.0 111 ±0.9
PST-3 49 −45.4 ±2.5 −34.1 ±1.2 399 ±1.5 107 ±0.5

the average NP size of PST-1 and PST-2 was determined
as 302 ± 1.5% and 328 ± 2.0% nm, respectively, while NP
size in PST-3 was determined as 399 ± 1.5% nm (see
Table 2). The occurrence of agglomeration leading to
NP settlement in silica nanofluid is in accordance with
Kumar and Sharma (2018), where the average particle
size was observed 412 nm with 0.5 wt% silica and 0.05
wt% titania in the 1000 ppm of PAM solution; however,
the average size of NPs reduced with time. In addition,
after 35 days of the preparation, the size of remaining
NPs in PST-1 (127 ± 0.4% nm) and PST-2 (111 ± 0.9%
nm) nanofluids was higher than the one with PST-3
(107 ± 0.5% nm) as given in Table 2. Typically, NPs
with higher agglomeration settle faster with time; as a
result, the nanofluid body exhibits NPs of lower size as
shown in Table 2. The reduction in size of the NPs in all
PST nanofluids after the storage period of 35 days indi-
cates that nanofluid with higher size exhibited faster
sedimentation. Hence, most of the NPs of higher sizes
settled and nanofluid left with NPs of lower size (see
Table 2). The reduced average size of NPs showed the
uniform distribution of NPs in the nanofluid due to the
presence of TiO2 and PAM solution.
Zeta potential is inversely proportional to NP stabi-
lity in colloidal suspension; DLS measurements showing
insignificant change in zeta potential value (over a per-
iod of 35 days) of nanofluid illustrate uniform NP dis-
tribution without sedimentation/agglomeration, and
therefore, decreasing zeta potential is a clear indication
of increasing instability in nanofluids. In addition, any
colloidal suspension is called stable if zeta potential lies
in between ±30 mV limits (Kumar & Sharma, 2018). For
nanofluid sample PST-1, zeta potential value was deter-
mined as −39.5 ± 1.7% mV on the first day of prepara-
tion, and it decreases to −29.5 ± 0.5% mV after 35 days
of storage period. It indicates that PST-1 became
unstable after 35 days as zeta potential reaches closer
to the limit of stability. Similarly, for PST-2 and PST-3,
zeta potential values were −42.7 ± 0.9% and
−45.4 ± 2.5% mV, respectively, on the first day of pre-
paration. These values reduced to −31.2 ± 1.5% and
−34.1 ± 1.2 mV after 35 days of storage time as given
in Table 2. Thus, PST-2 and PST-3 were still stable
colloidal suspensions than PST-1. The decrease in zeta
potential indicates more settlements of NPs in the nano-
fluid, resulting in lower dispersion stability in PST-1 as
compared to PST-2 and PST-3. From the results, the
zeta potential of PST-1 is lower than PST-3 for both 1st
and 35th days (storage period). This indicates that tita-
nia composites with SiO2 in PST-3 are less agglomerated
than the ones of PST-1 which is phenomenal and makes
PST-3 a relatively more stable nanofluid than PST-1.
From the literature, it was observed that titania NPs
GEOSYSTEM ENGINEERING 5
possess higher zeta potential as compared to silica NPs
(Kumar & Sharma, 2018). Generally, the presence of
titania in silica nanofluid produces electrostatic poten-
tial which leads to uniform distribution of NPs; thus, the
nanofluid consisted of 0.4 wt% silica and 0.05 wt%
titania (PST-3) showed more stability than PST-2 and
PST-1. Moreover, a stable nanofluid represents the uni-
form distribution of NPs in nanofluid which is never-
theless superior for high-temperature applications. The
more the NPs in suspension, the more they can partici-
pate for thermal stability.
4.3. Electrical conductivity measurements of
nanofluids
The electrical conductivity of nanofluid has a good depen-
dency on NP presence/settlement in suspension, and any
change in electrical conductivity directly indicates the
changes in NP population in bulk phase of nanofluid
(Minea, 2019). Therefore, high electrical conductivity is
the representation of homogeneous nanofluid system
where NPs can easily communicate and show the better
transportation of surface charges, while low conductivity
represents loosen structure that barely has NPs to commu-
nicate conductivity as a large fraction of NPs settled with
time. Thus, the increase in agglomeration significantly
reduces the population of dispersed NPs in nanofluid and
can be easily identified by the electrical conductivity mea-
surements (Minea, 2019). The electrical conductivity mea-
surements for formulated nanofluids were carried out at
room temperature using electrical conductivity meter
(Hanna Instruments, USA, Model HI98129) with uncer-
tainty of ±0.5% to 3.0%. During each measurement, the
used electrode of conductivity meter was prudently cleaned
and dried at ambient temperature. The electrical conduc-
tivity measurements were conducted on fresh nanofluid
samples and samples stored for 35 days to understand the
phenomenon of NP settlement in nanofluids. The electrical
conductivity measurements, as a function of the storage
period, for nanofluid samples, viz. PST-1, PST-2, and PST-
3, are shown in Figure 3. From Figure 3, it was observed
that the electrical conductivity of fresh nanofluids was 288,
292, and 297 µS/cm for PST-1, PST-2, and PST-3, respec-
tively. The electrical conductivity of PST-3 nanofluid was
found higher than that of PST-1 which is in accordance
with zeta potential results of PST-3. It confirms that the
high value of electrical conductivity is the sign of uniform
NP distribution which helped to grant more surface
charges, resulting in achieving higher magnitude of elec-
trical conductivity, consistent with the findings of Zawrah,
Khattab, Girgis, El Daidamony, and Abdel Aziz (2016). In
addition, the high value of electrical conductivity for PST-3
relatively shows uniform NP distribution which is helpful
6 R. S. KUMAR AND T. SHARMA
Figure 3. Electrical conductivity of formulated nanofluids as a function of time at ambient temperature.
to access more surface charges, resulting in higher magni-
tude of electrical conductivity in the system (Zawrah et al.,
2016). After the 25 days of storage, there was an increase in
electrical conductivity, and its value increased to 305, 319,
and 321 µS/cm for PST-1, PST-2, and PST-3, respectively
(Figure 3). The increase in electrical conductivity shows the
aggregation period of NPs in the nanofluid, which indicates
that NPs formed clusters of larger size. Thus, NPs came
closer and communicate easily to participate in electro-
phoresis which is also consistent with the previous study
on electrical conductivity measurements for graphene
oxide NPs (Hadadian, Goharshadi, & Youssefi, 2014).
However, after 35 days of storage, a significant reduction
in electrical conductivity values was observed; electrical
conductivity reduces to 235, 266, and 281 µS/cm for PST-
1, PST-2, and PST-3, respectively. The reduction in elec-
trical conductivity indicates nanofluid consists of a reduced
population of NPs to communicate in the system which
can be easily supported by lower zeta potential value of
PST-1 (Table 2). The electrical conductivity of PST-3 nano-
fluid was measured higher than PST-1 which is in accor-
dance with zeta potential results of PST-3, which is in
agreement with the reported electrical conductivity results
of Minea (2019) where less agglomerated NPs proposed
higher electrical conductivity within nanofluid. However,
the premature agglomeration significantly reduced the sur-
face charge of NPs resulting in surface potential of NPs and
electrical conductivity of nanofluid reduced (Minea, 2019).
Thus, this study on the electrical conductivity of nanofluid
indicates that nanofluid systems are metastable where NPs
are subjected to agglomerate and show changes in electrical
conductivity with time. This study then summarized that
NPs formed clusters of large agglomeration within the
nanofluid, and this was regarded as the main reason for
reduction in electrical conductivity of nanofluid. Moreover,
the reduction of the surface potential of NPs within the
nanofluid showed irregular pathways for electrically con-
ductive NPs, and thus, the electrical conductivity of nano-
fluid reduced.
4.4. SEM/EDS analysis of nanofluids
For nanofluids, SEM/EDS analysis was performed to
visualize the morphological structure of formed clusters
and the presence of NPs in nanofluid, respectively.
From Figure 4(a,b), it was observed that the size of
NPs in the PST samples was greater than the individual
particle size used at the time of preparation of nanofluid.
Therefore, it is clear that the NPs in nanofluid agglom-
erated in the form of clusters of larger size which was
also observed in the size distribution study using DLS
method. Furthermore, the presence of TiO2 NP in the
interstices of SiO2 nanofluid was confirmed by EDS
mapping results for PST-1 in Figure 5. From Figure 5,

Figure 4. FE-SEM image showing morphological structure of agglomerated NPs in the nanofluid (a) PST-1 and (b) PST-3.
it can be seen that TiO2 NPs uniformly distributed and
helped to stabilize SiO2 NPs in a nanofluid. Nanofluids
were synthesized to find their usage in oilfield applica-
tions where pore size of hydrocarbon formations is an
important factor. The smaller size and reduced sedi-
mentation rate allow nanofluids to easily invade the
pore space in the formation and helped to enhance oil
recovery (Sharma et al., 2016). Thus, nanofluid exhibit-
ing smaller NP size will exhibit easy and unblocked
transportation through pore space of formation.
4.5. Rheological analysis of nanofluids
The viscosity measurements for fluid systems were per-
formed using HPHT rheometer (MCR-52, Anton Paar,
Austria) to understand the effect of NP settlement on flow
behaviour. The rheometer consists of a bob and cup
assembly, and the external shear force was applied
GEOSYSTEM ENGINEERING 7
through a spindle attached to magnetic coupling. A vary-
ing shear rate ranges from 0.1 to 1000 s−1 was applied
(Moldoveanu, Ibanescu, Danu, & Minea, 2018). For the
effect of high temperature, viscosity measurements were
conducted at 90°C and compared with the results at 25°C.
The viscosity of 1000 ppm PAM solution and formulated
nanofluids was measured thrice, in order to produce
repeatability and accuracy in the results as presented in
Table 3. Viscosity as a part of rheology is one of the
important parameters to describe the fluid behaviour of
viscous samples such as polymer solutions (Lu et al.,
2015), emulsions (Narukulla, Ojha, & Sharma, 2017;
Sharma et al., 2014), and nanofluids (Chen, Xie, Li, &
Chen, 2018). These measurements were conducted on
freshly prepared nanofluids and nanofluids after 35 days
of preparation to understand the effect of NP settlement
on flow behaviour. For the effect of high temperature,
viscosity measurements were conducted at 90°C and
8 R. S. KUMAR AND T. SHARMA

Figure 5. FE-SEM image showing elemental mapping for SiO2 and TiO2 in PST-1 nanofluid after 35 days of storage period.

compared with the results at 25°C. The viscosity result for on shear deformation which makes them suitable to be
PAM solution is shown in Figure 6(a); the zero-shear utilized for varying shear flow conditions. Thus, as com-
viscosity (at 26.5 s−1) of PAM solution was determined pared to PAM solution, freshly prepared nanofluids were
as 1.42 mPa.s which is in agreement with the literature rheologically stable fluid without showing the sign of
value (Kumar & Sharma, 2018). The inclusion of SiO2 shear-thinning non-Newtonian. Figure 6(b) shows the
and TiO2 in PAM fluid significantly increased the viscos- effect of storage period (35 days) on viscosity of nano-
ity to 2.32 ± 4.5%, 2.41 ± 2.41%, and 2.54 ± 3.0% mPa.s fluids; the viscosity decreased to 1.61 ± 4.0%, 1.99 ± 1.5%,
for PST-1, PST-2, and PST-3, respectively, as shown in and 2.43 ± 2.5% mPa.s for PST-1, PST-2, and PST-3,
Figure 6(a) which is in accordance with our previous respectively. In addition, the flow behaviour of all nano-
study on viscosity determination for silica nanofluid fluids is dominated by shear-thinning non-Newtonian.
(Kumar & Sharma, 2018). The enhancement in the visc- The rate of shear thinning was higher in PST-1 than PST-
osity of polymer solution due to the inclusion of NPs is in 3 nanofluid; as a result, its viscosity reached a minimum
agreement with the reported study (Mahbubul, Saidur, level of 0.2 mPa.s at high shear rates. The rheological
Amalina, Elcioglu, & Okutucu-Ozyurt, 2015). In addi- measurements confirm that PST-3 was rheologically
tion, it is to be noted here that the PAM solution exhib- stable fluid than PST-1 as PST-1 exhibited higher viscos-
ited shear-thinning behaviour; viscosity decreases with ity reduction with increasing shear rate than PST-3
increasing shear rate. However, the flow behaviour of (Figure 6(b)). This indicates that rheological property
nanofluid seems Newtonian as shown by almost plateau (viscosity) of PST-1 is highly dependent on shear condi-
in viscosity variation with the shear rate in Figure 6(a). tions. This might be attributed to the fact that PST-1 after
Therefore, nanofluid flow behaviour is least dependent 35 days hardly left with NPs to absorb energy during
shear deformation, resulting in PST-1 exhibiting higher
shear thinning than PST-3. This can be easily correlated
Table 3. Viscosity results with accuracy at ambient temperature
with shear thinning of PAM solution which is sharp as it
and at high temperature (90°C).
Viscosity (mPa.s) at 25°C Viscosity (mPa.s)
exhibited no NPs to absorb energy during shear deforma-
Samples Day-1 (%) error Day-35 (%) error @ 90° C (%) error
tion, and therefore, PST-1 rheology is slightly stable than
PAM fluid 1.42 ±5.0 0.85 ±3.5 0.65 ±6.0 PAM as it contains some NPs in suspension. This again
PST-1 2.32 ±4.5 1.61 ±4.0 1.25 ±4.0 shows that PST-3 exhibited less agglomeration with time
PST-2 2.41 ±2.5 1.99 ±1.5 2.23 ±2.0
PST-3 2.54 ±3.0 2.43 ±2.5 2.39 ±1.5
which is in line with its zeta potential and electrical
conductivity results. Thus, TiO2 composites with SiO2

Figure 6. Viscosity with shear rate results of formulated nanofluid as a function of storage time on (a) 1st day and (b) 35th day, and (c)
variation of viscosity with shear rate of PAM fluid and nanofluids at 90°C.
provided improved rheological properties in PST-3 than
PST-1 which is of key importance for various applications
where conventional colloidal suspensions face challenges.
The knowledge of rheological properties at high tempera-
ture is of key importance for oil recovery applications.
Therefore, viscosity measurements were performed at 90°C
for all fluid systems and compared to visualize the least effect
of temperature on flow properties of fluid. The effect of high
temperature (90°C) on the viscosity of PAM solution and
nanofluids was investigated, and the results are provided in
Figure 6(c). It was observed that the viscosity of PAM solu-
tion and nanofluids reduced; however, PAM solution exhib-
ited a higher reduction than nanofluids due to thermal
degradation of polymer chains by chain scission. The visc-
osity of PAM solution reduced to 0.65 ± 6.0% mPa.s (at 26.5
s−1) at 90°C, while the viscosity of nanofluids reduced to 1.25
± 4.0%, 2.23 ± 2.0%, and 2.39 ± 1.5% mPa.s for PST-1, PST-
2, and PST-3, respectively, as shown in Figure 6(c). Thus, it is
GEOSYSTEM ENGINEERING 9
clear that the viscosity of fluid systems decreased with
increasing temperature. However, the effect of temperature
was relatively least on nanofluid flow behaviour which might
be due to the uniform dispersion of NPs in nanofluid body,
consistent with the findings of Vallejo, Pérez-Tavernier,
Cabaleiro, Fernández-Seara, and Lugo (2018). Moreover,
the viscosity reduction was less in PST-3 as compared to
PST-2 and PST-1, which is a clear indication of thermal
stability due to the presence of titania NPs within nanofluid
(Raud, Hosterman, Diana, Steinberg, & Will, 2017). The fact
of enhanced thermal stability in NP-based colloidal suspen-
sions is in line with the reported findings in the literature
(Amiri et al., 2015; Cherecheş, Prado, Cherecheş, Minea, &
Lugo, 2019). A similar trend of viscosity reduction was
observed by Zadeh and Toghraie (2018) where viscosity of
silver/ethylene glycol nanofluid was determined for different
volume fraction and temperature (up to 55°C). It was found
that viscosity reduced from 21 mPa.s (25°C) to ~12 mPa.s
10 R. S. KUMAR AND T. SHARMA
(55°C) for 0.5% of volume fraction of nanofluid. Thus, it is
clear that the effect of high temperature was least on nano-
fluid viscosity than PAM solution due to the presence of NPs
in the system. Since TiO2 is a thermally stable material, it
helped silica nanofluid to possess lesser shear deformation
against temperature. However, PST-1 exhibited a higher
reduction in viscosity than PST-2 and PST-3. Since NP
concentration in PST-1 was lower, enough thermal bridging
between PAM and NPs could not be developed, and NPs
exhibited significant Brownian motions, resulting in higher
reduction in viscosity. The inclusion of TiO2 NPs in silica
nanofluid provided hybrid composites of least dependency
on temperature. Agromayor et al. (2016) tested graphene
oxide NPs for thermal and heat transfer applications and
concluded that the use of NPs within nanofluid is a promis-
ing solution for thermal applications where conventional
fluids face challenges. The designed nanofluid with the
hybrid composites of silica and titania in this study is suitable
for several industrial applications including oilfield where the
temperature becomes a major challenge.
5. Conclusions
The thermal stability of nanofluid, prepared by compo-
sites of SiO2–TiO2, is investigated for rheological proper-
ties at 90°C and compared with the ones of simple
aqueous PAM solution (1000 ppm) to find the suitability
of nanofluid in oilfield applications. The study highlights
important fundamental aspects of nanofluid synthesis,
dispersion stability, NP agglomeration, and rheological
properties. SiO2 and TiO2 NPs were smaller in size (~15
and 20 nm, respectively) and remained suspended for
more than a month in the aqueous phase of PAM, while
in water, these NPs settled within a day. The enhanced
dispersion stability in nanofluid was induced by the inter-
action between NPs and PAM entanglements. The
absorption of PAM chains on SiO2–TiO2 composites
resulted in the formation of a steric monolayer around
NPs that provided good strength to the network of dis-
persed NPs. Consequently, higher viscosity is obtained
for nanofluids. In addition, nanofluids exhibited the least
shear thinning than PAM solution; however, a slight
change in shear thinning of nanofluids is attributed to
time-dependent NP agglomeration and settlement which
had an inverse relationship with the concentration of
SiO2 NPs. Furthermore, the thermal stability of nano-
fluids performed well than PAM solution, resulting in
nanofluid viscosity and shear thinning marginally chan-
ged with increasing temperature (90°C). Thus, this study
concludes that nanofluid can be an alternative solution
for oilfield high-temperature applications where a con-
ventional polymer fluid may show challenges.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by the Science and Engineering
Research Board, Department of Science and Technology,
Govt. of India [SB/S3/CE/057/2015].
References
Abbasi, S. (2018). Investigation of the enhancement and opti-
mization of the photocatalytic activity of modified TiO2
nanoparticles with SnO2 nanoparticles using statistical
method. Materials Research Express, 5(6), 066302.
Abbasi, S. (2019). Photocatalytic activity study of coated ana-
tase-rutile titania nanoparticles with nanocrystalline tin
dioxide based on the statistical analysis. Environmental
Monitoring and Assessment, 191(4), 206.
Agromayor, R., Cabaleiro, D., Pardinas, A., Vallejo, J.,
Fernandez-Seara, J., & Lugo, L. (2016). Heat transfer per-
formance of functionalized graphene nanoplatelet aqueous
nanofluids. Materials, 9, 455.
Amiri, A., Sadri, R., Shanbedi, M., Ahmadi, G., Kazi, S. N.,
Chew, B. T., & Zubir, M. N. M. (2015). Synthesis of ethy-
lene glycol-treated graphene nanoplatelets with one-pot,
microwave-assisted functionalization for use as a high per-
formance engine coolant. Energy Conversion and
Management, 101, 767–777.
Bayat, A. E., Junin, R., Samsuri, A., Piroozian, A., &
Hokmabadi, M. (2014). Impact of metal oxide nanoparti-
cles on enhanced oil recovery from limestone media at
several temperatures. Energy & Fuels : an American
Chemical Society Journal, 28(10), 6255–6266.
Chen, X., Xie, X. T., Li, Y., & Chen, S. (2018). Investigation of
the synergistic effect of alumina nanofluids and surfactant
on oil recovery-interfacial tension, emulsion stability and
viscosity reduction of heavy oil. Petroleum Science and
Technology, 36(15), 1131–1136.
Cherecheş, E. I., Prado, J. I., Cherecheş, M., Minea, A. A., &
Lugo, L. (2019). Experimental study on thermophysical
properties of alumina nanoparticle enhanced ionic liquids.
Journal of Molecular Liquids, 291, 111332.
El-hoshoudy, A. N., Desouky, S. E. M., Al-Sabagh, A. M., Betiha,
M. A., & Mahmoud, S. (2017). Evaluation of solution and
rheological properties for hydrophobically associated polyacry-
lamide copolymer as a promised enhanced oil recovery candi-
date. Egyptian Journal of Petroleum, 26(3), 779–785.
Fatimah, A., Almohsin, A., Michael, F. M., Bataweel, M., &
Alsharaeh, E. (2019). Polymer nanocomposites for water
shutoff application – A review. Materials Research Express,
6, 032001.
Hadadian, M., Goharshadi, E. K., & Youssefi, A. (2014).
Electrical conductivity, thermal conductivity, and rheologi-
cal properties of graphene oxide-based nanofluids. Journal
of Nanoparticle Research, 16(12), 2788.
Keyvani, M., Afrand, M., Toghraie, D., & Reiszadeh, M. (2018).
An experimental study on the thermal conductivity of cer-
ium oxide/ethylene glycol nanofluid: Developing a new cor-
relation. Journal of Molecular Liquids, 266, 211–217.

Król-Morkisz, K., & Pielichowska, K. (2019). Thermal decom-
position of polymer nanocomposites with functionalized
nanoparticles: Polymer composites with functionalized
nanoparticles, in Polymer composites with functionalized
nanoparticles : synthesis, properties, and applications,
Elsevier Inc., cop. 2019. ISBN: 978-0-12-814064-2. 430–435
Kumar, R. S., & Sharma, T. (2018). Stability and rheological proper-
ties of nanofluids stabilized by sio2 nanoparticles and SiO2-TiO2
nanocomposites for oilfield applications. Colloids and Surfaces
A: Physicochemical and Engineering Aspects, 539, 171–183.
Liu, H., Jin, X., & Ding, B. (2016). Application of nanotech-
nology in petroleum exploration and development.
Petroleum Exploration and Development, 43(6), 1107–1115.
Lu, X., Jiang, H., Li, J., Zhao, L., Pei, Y., Zhao, Y., . . . Fang, W.
(2015). Polymer thermal degradation in high-temperature
reservoirs. Petroleum Science and Technology, 33(17–18),
1571–1579.
Mahbubul, I. M., Saidur, R., Amalina, M. A., Elcioglu, E. B., &
Okutucu-Ozyurt, T. (2015). Effective ultrasonication pro-
cess for better colloidal dispersion of nanofluid. Ultrasonics
Sonochemistry, 26, 361–369.
Marandi, S. Z., Salehi, M. B., & Moghadam, A. M. (2018). Sand
control: Experimental performance of polyacrylamide hydro-
gels. Journal of Petroleum Science and Engineering, 170, 430–439.
Medhi, S., Chowdhury, S., Gupta, D. K., & Mazumdar, A.
(2019). An investigation on the effects of silica and copper
oxide nanoparticles on rheological and fluid loss property
of drilling fluids. Journal of Petroleum Exploration and
Production Technology, ISSN: 2190: 0566, 1–11.
Minea, A. A. (2019). A review on electrical conductivity of
nanoparticle-enhanced fluids. Nanomaterials, 9, 1592.
Moldoveanu, G. M., Ibanescu, C., Danu, M., & Minea, A. A.
(2018). Viscosity estimation of Al2O3, SiO2 nanofluids and
their hybrid: An experimental study. Journal of Molecular
Liquids, 253, 188–196.
Moradi, A., Toghraie, D., Isfahani, A. H. M., & Hosseinian, A.
(2019). An experimental study on MWCNT–water nano-
fluids flow and transfer in double-pipe heat exchanger
using porous media. Journal of Thermal Analysis and
Calorimetry, 137(5), 1797–1807.
Narukulla, R., Ojha, U., & Sharma, T. (2017). Stable & re-
dispersible polyacryloyl hydrazide–Ag nanocomposite
Pickering emulsions. Soft Matter, 13, 6118–6128.
Raud, R., Hosterman, B., Diana, A., Steinberg, T. A., & Will,
G. (2017). Experimental study of the interactivity, specific
heat, and latent heat of fusion of water based nanofluids.
Applied Thermal Engineering, 117, 164–168.
Rostami, P., Sharifi, M., Aminshahidy, B., & Fahimpour, J.
(2019). Enhanced oil recovery using silica nanoparticles in
GEOSYSTEM ENGINEERING 11
the presence of salts for wettability alteration. Journal of
Dispersion Science and Technology, ISSN : 1532:2351,1–12.
Saha, R., Uppaluri, R. V. S., & Tiwari, P. (2018). Silica nano-
particle assisted polymer flooding of heavy crude oil:
Emulsification, rheology, and wettability alteration charac-
teristics. Industrial & Engineering Chemistry Research, 57
(18), 6364–6376.
Sharma, T., Iglauer, S., & Sangwai, J. S. (2016). Silica nano-
fluids in an oilfield polymer polyacrylamide: Interfacial
properties, wettability alteration, and applications for che-
mical enhanced oil recovery. Industrial and Engineering
Chemistry Research, 55(48), 12387–12397.
Sharma, T., Kumar, G. S., & Sangwai, J. S. (2014). Enhanced
oil recovery using oil-in-water (o/w) emulsion stabilized by
nanoparticle, surfactant and polymer in the presence of
NaCl. Geosystem Engineering, 17(3), 195–205.
Tapias, F. A., Lizcano, J. C., & Lopes, R. B. (2018). Effects of
salts and temperature on rheological and viscoelastic beha-
vior of low molecular weight HPAM solutions. Revista
Fuentes: El reventón energético, 16(1), 19–35.
Vallejo, J. P., Pérez-Tavernier, J., Cabaleiro, D., Fernández-
Seara, J., & Lugo, L. (2018). Potential heat
transfer enhancement of functionalized graphene nano-
platelet dispersions in a propylene glycol-water mixture.
Thermophysical profile. The Journal of Chemical
Thermodynamics, 123, 174–184.
Yang, L., & Hu, Y. (2017). Toward TiO2 nanofluids—Part 1:
Preparation and properties. Nanoscale Research Letters,
12, 417.
Yang, M. H. (1999). Rheological behavior of polyacrylamide
solution. Journal of Polymer Engineering, 19(5), 371–381.
Yang, Y., Kelkar, A. V., Corti, D. S., & Franses, E. I. (2016).
Effect of interparticle interactions on agglomeration and
sedimentation rates of colloidal silica microspheres.
Langmuir, 32(20), 5111–5123.
Zadeh, A. D., & Toghraie, D. (2018). Experimental investiga-
tion for developing a new model for the dynamic viscosity
of silver/ethylene glycol nanofluid at different temperatures
and solid volume fractions. Journal of Thermal Analysis and
Calorimetry, 131(2), 1449–1461.
Zawrah, M. F., Khattab, R. M., Girgis, L. G., El Daidamony,
H., & Abdel Aziz, R. E. (2016). Stability and electrical
conductivity of water-base Al2O3 nanofluids for different
applications. HBRC Journal, 12(3), 227–234.
Zheng, C., Cheng, Y., Wei, Q., Li, X., & Zhang, Z. (2017).
Suspension of surface-modified nano-SiO2 in partially
hydrolyzed aqueous solution of polyacrylamide for
enhanced oil recovery. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 524, 169–177.