Applied Nanoscience

https://doi.org/10.1007/s13204-020-01597-3

ORIGINAL ARTICLE

Improving the thermo‑physical and rheological properties of crude

oil (CO) by the synthesized CuO/SiO2/CaP nanocomposite for drag
reduction through horizontal pipelines
Reza Mansourian1 · Seyedeh Maryam Mousavi1 · Efstathios E. Michaelides2

Received: 30 June 2020 / Accepted: 20 October 2020

© King Abdulaziz City for Science and Technology 2020

Abstract
The thermo-physical properties and rheological behavior of crude oil (CO) have substantial efficacies on transportation, pro-
cessing, and refinery operation. S
­ iO2 (silica)–CaP (calcium phosphate)–CuO (copper oxide) nanocomposite was synthesized
by the sono-co-precipitation technique. In this work, the impact of nanocomposite volume fraction as well as temperature
on the thermo-physical and also rheological characteristics of S ­ iO2–CaP–CuO-based CO nanofluid were evaluated. All
experimental tests were done in the temperatures and nanocomposite concentrations of 25–55 °C and 0.05–0.75 vol.%,
respectively. Also, the drag reduction of the nanofluid in horizontal pipelines was elucidated by the ­SiO2–CaP–CuO-based
CO nanofluid at 25 °C. The highest dynamic viscosity enhancement was found to be about 44.57% for 0.75 vol.% nano-
composite particles. The nanofluids thermal conductivity augmented with nanocomposite volume fraction increment. The
greatest increment in nanofluids thermal conductivity was obtained about 17.26% at 0.75 vol.%. Moreover, four correlations
were expanded for the dynamic viscosity and thermo-physical characteristics of the nanofluids with relative average devia-
tion (RAD) percentage of less than 1%, which depended on temperature and nanocomposite volume concentration. The
empirical relationships indicated a satisfactory compliance with the laboratory data. Additionally, outcomes demonstrated
that the drag reduction of hybrid nanofluid in the horizontal pipeline under fully turbulent flow increased with enhancing the
nanofluid concentration. Drag reduction of the nanofluids in the rough pipelines was higher than that in the smooth pipeline
at the same Reynolds number in the range of 6500–42,000 and different pipe’s diameter (0.5–1 in.). No considerable increase
and/or a reduction in hybrid nanofluid thermal conductivity was found for the recovered nanocomposite in various volume
concentrations. The highest dynamic viscosity reduction after three times recovery treatment was obtained about 0.7% for
0.5 vol.% nanocomposite particles.

Keywords  Volume concentration · SiO2–CaP–CuO · Nanofluids · Nanocomposite · Viscosity · Crude oil · Drag reduction

Abbreviations SDS Sodium dodecyl sulfate

CO Crude oil T Temperature (°C)
Cp Specific heat capacity (kj/kg K) x Vol.% nanofluid
DR Drag reduction φ Volume concentration
EG Ethylene glycol γ Shear rate(s−1)
nf Nanofluid ρ Density (g/cm3)
np Nanoparticle μ Viscosity (Pa s)
k Thermal conductivity (W/m K) τ Shear stress (Pa)

* Efstathios E. Michaelides Introduction

michaelidesefstathiosestathis@gmail.com
1
Department of Chemical and Petroleum Engineering, Shiraz Nowadays, improving heat transfer and enhancing drag
University, Shiraz, Iran reduction of gas and liquid which is transported through
2
Department of Mechanical Engineering, University of Texas pipelines have attracted considerable attention due to saving
at San Antonio, San Antonio, TX 78259, USA energy and reducing friction between the flowing fluid and

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Vol.:(0123456789)

the pipe wall (Pourhoseini et al. 2018; Jafaryar et al. 2018;
Chakraborty et al. 2017; Ghadikolaei et al. 2017). The con-
ventional fluids including crude oil (CO), deionized water,
and ethylene glycol (EG) have so weak heat transfer proper-
ties and also dynamic viscosity (He et al. 2007; Fotukian ad
Nasr Esfahany 2010; Ahmadi Nadooshan et al. 2018; Akh-
gar and Toghraie 2018). Since crude oil (CO) is an impor-
tant source of energy, evaluating how the crude oil flows in
pipelines and investigating their thermal properties are vital
issues for constructing the appropriate industrial equipment
(Li et al. 2018; Yang et al. 2017). Thermal conductivity
as a thermophysical property of the base liquids is a vital
parameter which affects the rate of heat transfer in industrial
systems (Arzanipour and Farahbod 2017). Dispersing solid
particles (micro-particles and or nanoparticles) with greater
thermal conductivity in the conventional fluids can improve
the thermal conductivity of these fluids (Askari et al. 2016).
Nanofluid is a term which was introduced by Choi (2009)
for the first time. Choi created nanofluids by dispersing nan-
oparticles in the base liquids. It has been revealed that the
dispersion of metal, nonmetallic, ceramic, and metal oxide
nanoparticles as well as carbon nanotubes (CNT) into the
base fluids ameliorates the thermo-physical, and rheologi-
cal properties’ offluids (Lee et al. 2010; Phuoc et al. 2010;
Hyun Ko et al. 2007; Lang et al. 2004; Choi 2009; Chen
et al. 2008; Akhgar and Toghraie 2018; Nasajpour Esfa-
hani et al. 2018). Many scholars carried out experimental
studies on the rheological behavior of nanofluids (Kulkarni
et al. 2006; Hamilton and Crosser 1962; Khanafer and Vafai
2011; Mousavi et al. 2016, 2019; Sujith et al. 2019; Abbas
et al. 2019; Hameed et al. 2019; Guimarey et al. 2018;
Chen et al. 2008; Sanukrishna et al. 2018; Kannaiyan et al.
2017; Alirezaie et al. 2017; Karimi-Nazarabad et al. 2016;
Zhang et al. 2006). Toghraie et al. (2016) experimentally
studied the water-based nanofluid dynamic viscosity. Their
experimental outcome results revealed that the F ­ e3O4/water
nanofluid dynamic viscosity decreased considerably with
temperature augmentation. Additionally, the dynamic vis-
cosity was enhanced with the solid nanoparticle volume
fraction augmentation. The maximum dynamic viscosity
enhancement was about 129.7%. Chiam et al. (2016) studied
experimentally the thermal conductivity as well as viscosity
of ­Al2O3/water nanofluids at the various volume ratios of
deionized water (DI)/ethylene glycol (EG). Results dem-
onstrated that the nanofluid mean dynamic viscosity aug-
mented more than 50% for volume ratio of 60% water/40%
EG. The dynamic viscosity of these nanofluids decreased
by reducing the water/EG volume ratio.
The rheological behavior of deionized (DI) water-based
copper oxide nanofluid was experimentally evaluated by
Kulkarni et al. (2006). Prepared nanofluids had the time-
independent pseudo-plastic and the shear-thinning behav-
ior. Saeedinia et  al. (2012) experimentally studied the
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Applied Nanoscience
rheological characteristics and thermal conductivity of cop-
per oxide-based oil nanofluid. They found the nanofluids’
heat capacity reduced with an augmentation in the nanopar-
ticle volume fraction. Also, an augmentation of about 6.2%
in the nanofluid thermal conductivity was reported at 2 wt%.
Saeedinia et  al. (Saeedinia et  al. 2012) studied the
thermo-physical properties of the Cu/gear oil nanofluid. The
Greatest thermal conductivity increment is about 30% at 2
vol.% at 80 °C. The viscosity of nanofluids increased by 71%
at 2 vol.%. Also, the influence of copper oxide nanoparticles
on the viscosity of gear oil was investigated by Kole and Dey
(2013). The rheology behavior of the viscosity of gear oil
altered from Newtonian to non-Newtonian behavior with an
enhancement volume concentration of CuO nanoparticles
(NPs). Mousavi and coworkers evaluated the influence of
MgO/TiO2 and CuO/MgO/TiO2 NPs on the thermophysical
and rheological characteristics of water-based nanofluids.
They found considerable improvement in the properties
of distilled water (Mousavi et al. 2019). Some works were
experimentally performed on the drag reduction by nano-
fluids through pipelines by Nguyen et al. (2013), Chen et al.
(2011), and Sohel Murshed et al. (2009).
Vafaei et al. (2009) evaluated experimentally the tribo-
logical properties of the synthesized alumina/silicate nano-
composite through a horizontal pipeline. Results revealed
that the friction factor using alumina/silicate nanocomposite
through the horizontal pipeline was reduced in comparison
with pure alumina and or silicate nanoparticles.
The rheological behavior of alumina/water nanofluid was
investigated by Murshed et al. (2008). They found that the
friction coefficient reduced about 40–50% as compared to
water.
Yang and Dou (2010) studied the impact of nanoparti-
cles size employing Au nanoparticles of 5 and 20 nm. They
found that the friction factor reduction using Au nanoparti-
cles of 20 nm through a horizontal pipeline was more than
that using Au nanoparticles of 5 nm due to difference in
asperity interaction.
Due to the positive effects of some nanoparticles on
heat transfer and drag reduction, researchers employed
the frequently nanoparticle synthesis procedures includ-
ing ball-milling and chemical vapor deposition. Hu et al.
(2009) synthesized the thermo-chemical procedure to
prepare ­Al2O3-Cu nanocomposite with the aid of Copper
(II) nitrate and aluminum nitrate as hydrate reagent mate-
rials. MWCNT/Fe3O4 nanocomposite was synthesized by
Garbacz et al. (2007) using the co-precipitation technique.
Liu et al. (2010) prepared graphene-wrapped multi-walled
carbon nanotubes employing chemical vapor deposition
(CVD) method with the aid of graphene oxide and ­MmNi3
as precursors. Wet chemical technique was applied by
Gyr and Bühler (2010) to synthesize the silicon/MWCNT
Applied Nanoscience
nanocomposite. Hu et al. (2009) synthesized aluminum–zinc
nanocomposite using the alloying procedure.
Some researchers experimentally investigated the effect
of solid particles on drag reduction recently. Yanuar et al.
(2017) evaluated the influences of nanofluid on drag dec-
rement which flows into pipeline under turbulent regime.
The homogenous suspension of Alumina nanoparticles and
distilled water as base fluid at the concentration of 100,
200, and 300 ppm. Results showed that the greatest drag
reduction (38%) by nanofluid was obtained at the Reyn-
olds number between 4000 and 20,000. In another study,
nanosilica/poly-α-olefin nanocomposite was synthesized
by Dai et al. (2017) and the influence of surface modifica-
tion on the drag decrement was evaluated with the help of
Y-amino propyl triethoxysilane. Experiment results indi-
cated that the percentage of drag reduction reached to 40%
for the best nanocomposite. ShUNP2-10 nanoparticles was
synthesized for the first time by Chunyuan et al. (2013) for
the purpose of drag reduction through microchannels. This
nanocomposite has a considerable effect on the drag reduc-
tion (27%). Pouranfard et al. (2014) evaluated the influence
of silica/water nanofluid on drag decrement in the presence
of surfactant through pipelines. They noticed that the per-
centage of drag reduction in rough tubes was higher than
that in smooth tubes. Moreover, drag reduction enhanced
24% at the nanoparticle concentration of 0.75 vol.%. One
of the research was experimentally carried out on the effect
of ­SiO2 and ­TiO2 nanoparticles dispersed into water on the
drag-reducing in the nanoparticles concentration of 0.5 and
1 wt.%. Using these nanoparticles could increase the drag
reduction 20% and 29% (Karimi Rad et al. 2018).
Nevertheless, such a ­SiO2–CaP–CuO nanocomposite has
not been synthesized yet. This nanocomposite was employed
as a drag-reducing agent due to the tribological properties
and also surface tension reduction property of silica, cal-
cium, phosphate, and copper.
These materials were appropriate for the purpose of this
study. This nanocomposite possibly forms ceramic compos-
ites with metal during friction to increase the anti-wear capa-
bility due to having tribological properties’ effectiveness on
drag reduction. This phenomenon causes friction reduction
between pipe surface and liquid phase, and drag reduction.
Also, the nanotribology studies show that some of nanoparti-
cles, such as nano-SiO2, have unique properties of anti-wear-
ing, friction reduction, and high load capacity in lubrication
and tribology causes lower pressure drop of fluids in pipe
flows (Li et al. 2003; Goto et al. 2004; Radice et al. 2006;
Garbacz et al. 2007; Wu et al. 2007; Sun et al. 2008; Hu
et al. 2009; Ma et al. 2009; Gyr et al. 2010; Liu et al. 2010;
Liou et al. 2012; Manocha et al. 2018). Nanoparticles with
surfatant as modifiers create covalent bonds, which modify
the nanoparticle’s surface properties and build nanoparticles
disperse well and progressively in many organic mediums.
In the current study, some thermal properties including
dynamic viscosity, density, thermal conductivity, and heat
capacity of ­SiO2–CaP–CuO/CO nanofluids were measured at
the volume concentration of 0.05, 0.25, 0.5, and 0.75% under
the temperature ranging from 25 to 55 °C. ­SiO2–CaP–CuO
nanoparticles were synthesized for the first time using the
sono-co-precipitation method. The synthesized nanoparti-
cles have anti-friction properties, high thermal conductivity,
and also low price. Four new correlations were suggested
for forecasting of thermal and rheological characteristics in
terms of temperature and also solid particle volume frac-
tion using Table Curve 3D-software. ­SiO2–CaP–CuO/CO
nanofluids were employed as the drag reduction agent. The
­SiO2–CaP–CuO/CO nanofluids at various Reynolds numbers
(6500–24,000) were injected into the horizontal pipelines,
and the impacts of pipe diameter (0.5″ and 1″) and relative
roughness (ɛ/D, 0% and 2%) of the pipes were elucidated
on the drag reduction. The main target of this research is to
synthesize a drag reduction agent compound for the drag
reduction and improvement of heat transfer characteristics.
Materials and methods
Materials
In this study, the following chemical materials are provided
Distilled water (DW), copper(II) acetate monohy-
drate (Merck, Germany), 99.0–102.0 wt%; calcium chlo-
ride, (Merck, Germany), ≥ 98 wt%; ammonium hydrogen
phosphate (Sigma-Aldrich), ≥ 99.0 wt%; EDTA (ethylene
diamine tetraacetic acid) (Sigma-Aldrich), 99.4 wt%; sodium
dodecyl sulfate (SDS) (Sigma-Aldrich), 98 wt%; silicic acid
(Merck, Germany), 99.9 wt%; ethanol (Merck, Germany),
97 wt% and ­NH4OH (Merck, Germany), 30–32% (ammo-
nium hydroxide solution).
Methods
In this section, the synthesis of S
­ iO2–CaP–CuO/nanocom-
posite, ­SiO2–CaP–CuO/CO nanofluid preparation, stability
of hybrid nanofluids, and characterization of S
­ iO2–CaP–CuO
nanocomposite are described:
Synthesis of ­SiO2–CaP–CuO/nanocomposite
The homogenous ­ S iO 2 –CaP–CuO nanocompos-
ite was synthesized by hydrolysis of the precursors
including(CH 3 COO) 2 Cu + H 2 O, calcium chloride,
ammonium phosphate, ethylene diaminetetraacetic acid
(EDTA), and silicic acid in ethanol and DW solution
in the presence of ­N H 4OH (ammonium hydroxide) as
a pH controller material. DW and ethanol were kept in
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 Applied Nanoscience

an ultrasonic bath at ambient temperature. A specified Table 1  The characteristic of S

­ iO2–CaP–CuO nanocomposite
amount of precursor solution was added while ultra- Test Result Technique
sonicating and stirring by a magnet for 55 min. ­NH4OH
solution was then added about 20 min to boost the polym- Morphology Spherical SEM image
erization (condensation) reaction. Ultra-sonication was Size (nm) 85 SEM image
also continued for 80 min to attain a uniform suspension. Color Black –
Afterwards, the final mixture was aged for 18 h to pre- Specific heat capacity (J/kg k) 515 DSC
cipitate. The prepared black nanocomposite solid pow- Density (g/cm3) 5.8 DCS
der was filtered and washed and eventually dried in the Purity (vol.%) > 99% –
microwave oven at 100 ͦ C for 5 h.

SiO2–CaP–CuO/CO nanofluid preparation Table 2  The characteristic of Iranian crude oil

In this research, sodium dodecyl sulfate (SDS) was
employed as a dispersant. The mentioned dispersant
and ­S iO 2–CaP–CuO nanocomposite were dispersed in
distilled water in the specified concentration range of
0.05–0.75 vol.%, and then, the suspension of solid nanocom-
posite and SDS was magnetically stirred to make a homog-
enous mixture. Next, these suspensions were ultrasonicated
with a power of 150 W by the ultrasonic device to fabricate
well-mixed mixtures.
The volume concentration of nanocomposite was calcu-
lated using Eq. (1) (Nguyen et al. 2013):
[w ] measurement
nanocomposite
𝜌nanocomposite
� × 100 = [
w
] [
wCO
], (1)
nanocomposite
𝜌nanocomposite
+ 𝜌CO
where φ and w stand the volume concentration and the mass
of ­SiO2–CaP–CuO nanocomposite, in sequence.
Stability of hybrid nanofluids
Stability is one of the vital issues that can be effective in the
augmentation of heat transfer and drag reduction with the
help of nanofluids. An unstable nanofluid will have weak
thermophysical and rheological properties owing to the
aggregation of solid particles in the base liquid (Wu et al.
2007). To evaluate the stability of S­ iO2–CaP–CuO/CO nano-
fluids, the Zetasizer apparatus working upon the dynamic
light scattering, laser Doppler micro-electrophoresis, and
static light scattering techniques was used to measure the
zeta potential of the nanofluids. Researchers reported a sta-
ble suspension is a suspension having a great zeta-potential
value (between ± 30 mV and ± 45 mV), while suspensions
with low value of Zeta potential (≤ ± 30 mV) create a rapid
deposition of solid particles (Li et al. 2008).
Characterization of hybrid nanofluids
The properties of the nanocomposite and crude oil were
experimentally measured in Tables 1 and 2.
Property Value Technique
API gravity at 20 °C 31.5 IP-2000
Heat capacity (kJ/kg k) 3.1 DSC
Thermal conductivity (W/m k) 0.11 Transient hot
wire, ASTM D
5334
Density at 20 °C (g/cm3) 0.886 IP-160
Kinematic viscosity at 40 °C, cSt 6.356 IP-71
Thermophysical and rheological properties’
One of the main purposes of this work is to elucidate the
thermal and rheological characteristics of the nanofluid.
There are some methods to measure the nanofluid thermal
conductivity such as transient hot-wire procedure, tempera-
ture oscillation technique, omega-3 method, and cylindri-
cal cell technique. In the current study, this property of
­SiO2–CaP–CuO/CO nanofluid was estimated via a KD2-pro
thermal characteristics analyzer, working upon the transient
hot-wire (THW) procedure with a precision of ± 5% W/m K.
The nanofluid thermal conductivity was measured five times,
and its average value was reported. The nanofluid dynamic
viscosity was estimated using the viscometer device (DV-
II + Pro, Brookfield Company, USA) with an accuracy of
±1.0% . The instrument is composed of a spindle and a water
bath to control temperature. This apparatus measures the
values of dynamic viscosity and also shear stress at the
different shear rates (10–80 s−1). This experimental appa-
ratus was calibrated with the Brookfield viscosity stand-
ard fluids. Also, the density meter device (DMA 4500 M,
Anton Paar Company, Austria) is employed to evaluate the
values of nanofluid density. For confidence, the crude oil
density was measured and also compared with the experi-
mental data (Li et al. 2008), which showed an acceptable
accuracy (5 × 10–5 g/cm3). The nanofluid heat capacity was
measured by a calorimeter (DSC1 STAR, Mettler-Toledo,
United States). The S
­ iO2–CaP–CuO/CO nanofluid-specific

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heat capacity was calculated from experimental heat flow
data points by employing the Mettler Toledo Stare soft-
ware. Standard material which was employed to measure
the specific heat capacity is Sapphire. The Sapphire’s heat
capacity was first measured to confirm the reliability of this
technique. The precision of temperature in DSC1 apparatus
is about ± 0.2 K. This device was calibrated with chemical
materials of aluminum and cyclohexane.
It should be noted that the range of temperature and
solid nanoparticle volume concentration for measuring the
aforementioned thermal characteristic was 15–60 °C and
0.05–0.75 vol.%, respectively.
Drag reduction evaluation
Another important objective of this experimental evalu-
ation is to elucidate the drag reduction by injecting the
­SiO2–CaP–CuO/CO nanofluids through the horizontal pipe-
line (single-phase flow of crude oil).
Drag reduction denotes a flow phenomenon in which
employing additives reduce significantly the friction factor
of a gas and or a liquid. In this study, the drag reduction
was evaluated to improve capacity, decrease the pumping
power, and enhance the mechanical performance employing
the aforementioned nanocomposite. The percentage of drag
reduction was estimated by the following equation:
ΔP − ΔPa
Drag reduction% = × 100, (2)
ΔP
where ΔP is the pressure drop of CO and ΔPa is the pressure
drop of ­SiO2–CaP–CuO/CO nanofluids.
An experimental setup was constructed for measuring the
pressure difference data at the considered nanocomposite
Fig. 1  Schematic flow of the
drag reduction experimental
setup
concentration (Fig. 1). The apparatus test section is a smooth
galvanized iron pipeline with 1 m long and 0.27 cm ID. First,
a crude oil was pumped through this pipeline at the flow
rate range of 200–1400 h−1, and the difference between the
inlet pressure and outlet pressure of pipeline was measured.
Afterwards, ­SiO2–CaP–CuO/CO nanofluids were injected
through the horizontal pipelines, and the pressure difference
values were measured. Because of importance of drag dec-
rement evaluation in turbulent flow of pipelines (Wang and
Bao 2009; Hosseini et al. 2010; Xie et al. 2003a, b; Drzazga
et al. 2013), the authors concentrated on the turbulent regime
in this work. The CO and nanofluid volumetric flow rates
were adjusted by a rotameter with the flow rate range of
0–2000 l h−1.
The pressure drops in axial direction through the pipes
were measured employing a differential pressure transmitter,
(KH3351, Rosemount Corporation, USA), with the accu-
racy of 0.001 mbar. To reduce the entrance and also the exit
effects, the differential pressure taps were placed at 17 cm
from the inlet and outlet of the pipeline. It should be noted
that the nanofluids were injected through the pipelines by
employing a gear pump at the inlet of this pipeline. The
schematic diagram of this setup is demonstrated in Fig. 1. To
confirm the accuracy of these laboratory data points, friction
factors are calculated using Blausius equation and compared
with the experimental data, as depicted in Fig. 2. Friction
factor values are calculated by Eqs. (3) and (4) based on
experimental data and Blausius equation:
2ΔPD
f = , (3)
𝜌u2 L
13

Fig. 2  Comparing experimental data of friction factor with the calcu-
lated data of friction factor using Blausius equation
0.316
f = , (4)
Re0.25
where f, Δp, D, ρ, u, L, and Re denote the friction factor,
pressure drop, pipe diameter, density, velocity, pipe length,
and Reynolds number, respectively. All experiments were
repeated four times.
Results and discussion
Characterization of ­SiO2–CaP–CuO nanocomposite
The characterization of the nanocomposite was elucidated
by SEM, TEM, and EDAX analysis. SEM and TEM images
(Figs. 3, 4) demonstrated that the nanofluid morphology
was somehow spherical, and its mean diameter was approxi-
mately 85 nm.
Fig. 3  TEM image of the S
­ iO2–CaP–CuO nanocomposite
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Fig. 4  SEM image of the S
­ iO2–CaP–CuO nanocomposite
EDAX analysis (Fig. 5) further confirmed the presence
of calcium, phosphate, copper, oxygen, and silica elements
in the nanocomposite. The mass percentages of oxygen,
calcium, copper, phosphate, and silica in the nanocompos-
ite were equal to 19.7, 19.4, 22.2, and 28.4, respectively.
The information about this nanocomposite was acquired by
EDAX analysis, as shown in Table 3.
Stability of hybrid nanofluid
To evaluate the stability of S ­ iO2–CaP–CuO/CO nanoflu-
ids, zeta-potential analyses were used, as shown in Fig. 6.
The nanofluid zeta potential was analyzed at the optimum
ultrasonication time with 0.05, 0.25, 0.5, and 0.75 vol.% of
the nanocomposite under ambient temperature, which had
the mean zeta potential of − 5.3, − 31.8, and − 5.3 mV,
as depicted in Fig. 6a–c. The aforementioned analysis was
performed 1 day after the preparation of the nanofluid with
0.05, 0.25, 0.5, and 0.75 vol. % of the nanocomposite.
Thermophysical and rheological characteristics
evaluation
Measuring the base fluid thermal conductivity is a sig-
nificant factor in evaluation of the fluid heat transfer rate
improvement. There are various models to suggest the nano-
fluids thermal conductivity. Hamilton-Crosser (Kannaiyan
et al. 2017) suggested a model for the property of solid–liq-
uid suspensions (Keff) as follows (Eq. 5):
( )
keff knp + (n − 1)kbf + (n − 1)𝜑 knp − kbf
= ( ) , (5)
kbf knp + (n − 1)kbf − 𝜑 knp − kbf
where Knp and also Kbf are the nanoparticles and base liquid
thermal conductivity, respectively. 𝜑 means the NPs con-
centration. Also, n denoting the experimental shape factor
is as follows:
Applied Nanoscience

Fig. 5  EDAX pattern of the

nanocomposite

Table 3  Calculated Element wt.% also illustrates the comparison among the experimental and
composition of ­SiO2–CaP–CuO the calculated thermal conductivity of ­SiO2–CaP–CuO/CO
nanocomposite by EDAX OK 18.17 nanofluids obtained from the H–C, Maxwell, and the Lu–Lin
analysis
Cu K 35 models. As can be depicted, the aforementioned correlations
Mg K 0.64 do not consider the effective parameters of the increment in
PK 10.73 this property such as particles size, the interfacial layer at the
Si L 10.65 interface of particle–base fluid, and temperature.
Ca L 22.40 To elucidate the heat characteristic and drag decrement,
Na L 0.33 the heat capacity, dynamic viscosity, thermal conductiv-
KL 0.70 ity, and also the density of the nanofluids were laboratory
SL 0.38 measured under the temperatures of 20–50 °C and nanocom-
Nb L 0.40 posite volume concentrations of 0.0–0.75 vol.%. As could
Al L 0.60 be depicted in Fig. 8, the nanofluid thermal conductivity
Totals 100.00 enhances with augmentation in temperature. This is owing
to an increase in solid particle Brownian motion (nano-
composite particles). In fact, temperature increment in the
3 nanofluid causes enhancing the homogeneity of suspension,
n= , (6) which caused the nanofluid thermal conductivity to enhance.
𝜓
Also, since the nanoparticles thermal conductivity is more
where 𝜓 denotes particle sphericity coefficient. The value of than that of crude oil, so the nanofluid thermal conductivity
n is equal to 3 for the spherical particles. increases with rising nanocomposite concentration.
Alirezaie et al. (2017) suggested another correlation to Figure 9 depicts the nanofluid density against tempera-
calculate the nanofluid thermal conductivity for the spherical ture at different nanocomposite volume concentrations. As
solid particles, which is expressed as follows: observed in Fig. 9, the THNFs’ density is more than that of
keff crude oil and it decreases with enhancing temperature.
= 1 + 2.25𝜑 + 2.27𝜑2 . (7) As observed from Figs. 10 and 11, the hybrid nanofluid
kbf
dynamic viscosity reduces with the temperature enhance-
Another correlation for evaluating the nanofluids thermal ment and it significantly increases with an escalation in the
conductivity was proposed by Maxwell (Zhang 2006), which nanoparticles volume concentrations. It is because of the fact
can be expressed as: that if the temperature rises, the Brownian motion of nano-
particles enhances and consequently causes the hybrid nano-
keff knp + 2kbf + 2(knp − kbf )𝜑 fluids dynamic viscosity to decrease. Highest enhancement
= . (8)
kbf knp + 2kbf − (knp − kbf )𝜑 in the mentioned nanofluid dynamic viscosity was about
44.57% at 0.75 vol.% of the nanocomposite concentration.
Thermal conductivity of the S­ iO2–CaP–CuO/CO ternary Determining the nanofluid behavior (Newtonian or non-
hybrid nanofluid was measured at the nanocomposite vol- Newtonian) is one of the most significant effective character-
ume concentration of 0.05, 0.25, 0.5, and 0.75 vol.% under istics on the fluid flow. Figure 12 depicts all aforementioned
the temperatures in the range of 15–60 °C shown in Fig. 7. It nanofluids which have nearly the similar dynamic viscosity

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Fig. 7  Comparing among laboratory data point and classical correla-

tions for measuring nanofluid thermal conductivity

Fig. 8  Influence of temperature on the ternary hybrid nanofluid ther-

mal conductivity at different nanocomposite volume concentrations

Fig. 6  Zeta-potential graph for the ­SiO2–CaP–CuO nanocomposite

dispersed in CO at the nanocomposite concentration of a 0.05, b 0.5,
and c 0.75 vol.%

at different shear rates under the temperatures of 30–50 °C

with the nanocomposite concentration of 0.75 vol.%. It
was found that the rheological behavior of the crude oil
and ­SiO2–CaP–CuO/CO nanofluid is Newtonian owing to
linear variation in the nanofluids shear stress against their
shear rate. Xie et al. (2003a, b) observed a considerable Fig. 9  Influence of temperature on the nanofluids density at different
improvement in thermal transfer rate and drag decrement nanocomposite 10 concentrations

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Applied Nanoscience

Fig. 12  Dynamic viscosity of the crude oil at different shear rates

Fig. 10  Influence of temperature on the dynamic viscosity of S

­ iO2–
CaP–CuO/CO nanofluid at different nanocomposite volume concen-
trations

for Newtonian fluid as compared to non-Newtonian fluid

which are in line with the result obtained from this work.
Over the shear rate value of 8–48 1/s, the nanofluids tends
to a Newtonian behavior. As mainly reported, shear-thinning
effect can be attributed to de-agglomeration of the nano-
composite and/or realignment of the clusters in the direction
of the shearing flow due to the form of primary particles,
resulting in less viscous force. The fact that the hybrid nano-
fluids are mainly treated as Newtonian fluid may be plausible
following the shear rate range investigated.
Figure 13 illustrates the shear stress against the shear rate Fig. 13  Shear stress against shear rate at different nanocomposite vol-
at different solid nanocomposite volume concentrations. As ume concentrations and 303 K
can be depicted, the nanofluids shear stress augmented with
enhancing their shear rate, which is demonstrative of the
nanofluid Newtonian. This can be elucidated because of large specific surface
Figure 14 illustrates the ­SiO2–CaP–CuO/Co nanofluid- area of the nanocomposite, which offers greater contact area
specific heat capacity against temperature at the various with crude oil. Additionally, enhancing the loading of nano-
volume fractions. As can be seen, the heat capacity of CO composite into fixed value will create a phase transformation
and ­SiO2–CaP–CuO/Co nanofluids decrease with rising in the crude oil. Besides, the contact resistance will reduce at
temperature. hybrid nanofluid causing increase the thermal conductivity

Fig. 11  Influence of nanocom-
posite concentration on the
dynamic viscosity of nanofluids
at different temperatures

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 Applied Nanoscience

Fig. 14  Effect of temperature
on the ­SiO2–CaP–CuO/CO
nanofluid heat capacity at dif-
ferent nanocomposite volume
concentrations

of hybrid nanofluid. This results in a lower energy require- The deviation between the experimental results and those
ment for the similar temperature enhancement that decreases obtained from the suggested correlations can be computed
the value of the heat capacity. employing Levenberg–Marquardt algorithm (LMA) as
Four correlations were suggested for calculating K (ther- follows:
mal conductivity), μ (dynamic viscosity), Cp (heat capacity), ∑N
and ρ (density) of ­SiO2–CaP–CuO/CO nanofluid using Table (Mpred,K − Mexp,K )2
LSM = min
K=1
, (13)
Curve 3D-software, as expressed below: N

(9)
( ) ( / ) ( / ) ( / ) ( / )
Knf = 0.73568391 + −9.6816854∕T + 283.69209 T 2 + −4718.8713 T 3 + 43232.493 T 4 + −175511.53 T 5
+ (285.313 × 𝜑) + −159755.35 × 𝜑2 + 41755315 × 𝜑3 − (4.58336511 × 109 × 𝜑4 ,
( ) ( )

𝜌nf = 1.0031583 + (−0.00012513685 × T) + −4.56833755 × 10−6 × T 2 + (4.3613855 × 𝜑) + −15.556613 × 𝜑2 , (10)

( ) ( ( ))

𝜇nf = 1.7366342 + (−0.043695678 × T) + (95.543052 × 𝜑) + 0.00046772016 × T 2 + −29249.903 × 𝜑2

( ) ( )

+ (1.3496487 × T × 𝜑) + −1.6016472 × 10−6 × T 3 + 6832500 × 𝜑3 + −337.97403 × T × 𝜑2 (11)

( ) ( ) ( )

+ −0.011498485 × T 2 × 𝜑 ,
( )

Cp = 1.865605 + 0.000774T + 0.007058∕𝜑 − 0.00036T 2 − 1.2 × 10−5 ∕𝜑2

+ 4.6 × 10−6 T∕𝜑 + 3.15 × 10−6 T 3 + 4.58 × 10−9 ∕𝜑3 (12)
−9 2 −9 2
− 2.4 × 10 T∕𝜑 − 1.8 × 10 T ∕𝜑,

where Cp, T, µ, k, ρ, and φ stand the heat capacity, tempera-
ture, dynamic viscosity, thermal conductivity, density, and
the volume fraction, respectively. Subscript nf means the
nanofluid.
Figures 15, 16, 17 and 18 illustrate the difference between
the obtained results from the suggested correlations and
those experimentally obtained at different volume concen-
trations. As can be seen from the aforementioned figures, the
laboratory measured properties are in excellent conformity
with those predicted from the suggested models.
where MK stands the thermal conductivity, dynamic vis-
cosity, specific heat capacity, and density. Subscripts pred.
and also exp. denote the proposed thermophysical proper-
ties from the proposed models and laboratory properties, in
sequence. N means the total number of data points.
The maximum deviation percentages for the dynamic
viscosity as rheological property, and thermal properties
including thermal conductivity, heat capacity, and den-
sity were found to be about 0.02, 0.02, 0.01, and 0.1%,
respectively.

13
Applied Nanoscience
Fig. 15  Comparing the values obtained from the suggested relation-
ship and laboratory data points of the thermal conductivity of S
­ iO2–
CaP–CuO/CO nanofluid at different nanocomposite volume concen-
trations in a 30 °C and b 50 °C
The effect of S
­ iO2–CaP–CuO nanocomposite recovery on
the dynamic viscosity of nanofluids was also evaluated. The
aim of the nanofluid recovery evaluation was to check are the
recovered nanoparticles suitable economically?
First, the synthesized nanocomposites were dispersed in
the crude oil under the specified sonication time and power
and SDS volume fraction to anticipate the dynamic viscos-
ity of ­SiO2–CaP–CuO/CO nanofluids. This nanocomposite
is afterwards separated from the crude oil using the centri-
fuge device and next dried in a microwave oven at 100 °C.
­SiO2–CaP–CuO nanocomposite recovery operation is per-
formed in three steps, and the dynamic viscosity of ternary
hybrid nanofluid was estimated, as depicted in Fig. 19.
After the recovery operation steps of first and secondary
for the ­SiO2–CaP–CuO/CO nanofluids, the dynamic viscos-
ity of S­ iO2–CaP–CuO/CO nanofluids did not considerably
vary. However, after the third time of recovery operation of
­SiO2–CaP–CuO/CO nanofluids, an increase in the dynamic
viscosity of ­SiO2–CaP–CuO/CO nanofluids was observed.
The most significant reason for this changes is because of the
functional groups variation on the surface of solid nanocom-
posite during the recovery operation of the nanocomposite.
Fig. 16  Comparing the values obtained from the suggested relation-
ship and laboratory data points of the density of S
­ iO2–CaP–CuO/
CO nanofluid at different nanocomposite volume concentrations in a
30 °C and b 50 °C
It was seen we cannot employ recovered nanoparticles
again, because after a while, they lose their original perfor-
mance. Therefore, it is better not to use them again.
Drag reduction evaluation
Figures  20 and 21 demonstrate the percentage of drag
reduction of the nanofluids versus the nanocomposite vol-
ume concentration in the horizontal pipelines. It is revealed
that when the ­SiO2–CaP–CuO/CO ternary hybrid nanofluid
in a low nanocomposite concentration of 0.05 vol.% was
injected into the horizontal pipeline, the percentage of drag
reduction of the nanofluid decreased at the same Re (Reyn-
olds number). Besides, the drag reduction percentage of the
­SiO2–CaP–CuO/CO nanofluid increases with the nanofluid
volume concentration enhancement. However, there exist an
optimum volume concentration, which no more considerable
drag reduction of the S­ iO2–CaP–CuO/CO nanofluid can be
obtained with further increment of concentration. In this
study, the optimum volume concentration was obtained to
be 0.5 vol.% of ­SiO2–CaP–CuO nanocomposite.
13
 Applied Nanoscience

Fig. 17  Comparing the values obtained from the suggested relation-
ship and laboratory data points of the dynamic viscosity of ­SiO2–
CaP–CuO/CO nanofluid at different volume concentrations in a 30 °C
and b 50 °C
Fig. 18  Comparing the values obtained from the suggested relation-
ship and laboratory data points of the heat capacity of S
­ iO2–CaP–
CuO/CO ternary hybrid nanofluid at different nanocomposite volume
concentrations in a 25 °C and b 50 °C

Moreover, the effect of the nanocomposite volume the percentage of drag reduction of the ­SiO2–CaP–CuO/CO
concentration on the nanofluids tribology efficiency was nanofluid in the rough tube is more than that in the smooth
examined in this research. In other words, there were no one in similar Reynolds number, as the magnitude of tur-
adequate nanocomposites for smoothing the surface of hori- bulence in rough tubes is higher than smooth one. After-
zontal pipelines at the nanocomposite volume concentration. wards, the reducing drag phenomenon mechanism by the
However, the amount of nanocomposite smoothing the sur- silica–CaP–CuO nanocomposite in CO is to modify surface
face of horizontal pipeline increases in the nanocomposite
volume fraction increment. To elucidate the effect of hori-
zontal pipeline roughness, the percentage variation of drag
reduction of the nanofluids versus nanocomposite volume
concentrations is demonstrated in Fig. 22 at various degrees
of rough pipe under fully turbulent flow. Results revealed
that by increasing the horizontal pipeline diameter, the per-
centage of drag reduction of the nanofluids enhances. This
is because of enhancing the relative roughness (e/D) with
reducing the horizontal pipeline diameter, and as a conse-
quence, this leads to the greater turbulence and a higher per-
centage of drag reduction. The percentage of drag reduction
of the ­SiO2–CaP–CuO/CO nanofluid through the horizontal
pipelines (smooth and rough pipelines) for the same L/D of
Fig. 19  The effect of ­SiO2–CaP–CuO nanocomposites’ recovery on
pipeline at various Reynolds numbers is compared with one the dynamic viscosity of nanofluids at 50  °C in the nanocomposite
another (see Fig. 22). Experimental results demonstrate that concentration of 0.75 vol.%

13
Applied Nanoscience
Fig. 20  Variations of the percentage of drag reduction of the ­SiO2–
CaP–CuO/CO nanofluid at different volume concentrations for 1 inch
rough pipe diameter
Fig. 21  Comparison of the percentage of drag reduction of the ­SiO2–
CaP–CuO/CO nanofluids at different volume concentrations for vari-
ous horizontal rough pipelines with Re = 11,186
Fig. 22  Comparison of the percentage of the drag reduction of
­SiO2–CaP–CuO/CO nanofluid at different volume concentrations for
smooth and rough horizontal pipelines with the diameter of 0.5 inch
tension, since the ­SiO2–CaP–CuO nanocomposite pos-
sesses an excellent rigidity and this nanocomposite causes
to decrease the friction factor as well as drag factor by dis-
persing the nanocomposites into the crude oil. To compre-
hend the drag reduction mechanism of the ­SiO2–CaP–CuO/
CO nanofluid in microscopic scale (Wu et al. 2007), 10 cm
of this horizontal pipeline was cut in the axial direction to
partition this horizontal tubes by two analogous sections.
The SEM images of the cut internal surface horizontal tube
which get in touch with passing crude oil and or the nano-
fluids are shown in Fig. 23. This figure shows that the extent
of pipe roughness reduces by diffusing the nanocomposites
onto pore surface of horizontal pipe-lines.
These analyses confirm that the mechanism of this phe-
nomena is to deposit the nanocomposite onto the surface of
micro-pores of the horizontal pipeline.
Figure  24 demonstrates a comparison between the
obtained values from the experimental data and results
obtained from Pouranfard et al.’s work (Pouranfard et al.
2014). at Reynolds number of 11,000 in the different diam-
eters for rough pipe. It is obvious that the synthesized nano-
composite could enhance more the drag reduction of nano-
fluids (about 22%) at different concentration as compared to
­SiO2 nanoparticles; This was probably due to more reduction
in surface tension of nanofluids (more surface modification
by the new nanocomposite because of their contact with
pipe surfaces).
Conclusions
In the present work, the influence of temperature and nano-
composite volume fraction on the thermo-physical including
density, thermal conductivity, and CP (heat capacity) and
rheological characteristics of ­SiO2–CaP–CuO/CO nano-
fluid was experimentally evaluated at the nanocomposite
concentrations and also temperatures of 0.05–0.75 vol.%
and 25–55 °C, in sequence. Additionally, several experi-
mental works were carried out on the drag reduction of the
­SiO2–CaP–CuO/CO nanofluid through the horizontal pipe-
lines with different relative roughness and L/D ratio.
Altogether, the following findings were obtained:
Thermal conductivity of the ­SiO2–CaP–CuO/CO nano-
fluid enhanced with rising temperature. Also, the results
demonstrated that the addition of S­ iO2–CaP–CuO nanocom-
posite to the crude oil increased the thermal conductivity of
crude oil. The maximum enhancement was about 17.26%
at 0.75 vol.% of the nanocomposite. The S ­ iO2–CaP–CuO/
CO ternary hybrid nanofluid dynamic viscosity decreased
with temperature enhancement. Also, the dynamic viscosity
augmented with enhancing nanocomposite volume concen-
tration. The highest increment in the dynamic viscosity of
the ­SiO2–CaP–CuO/CO nanofluid is about 44.57% at 0.75
13

Fig. 23  SEM images of the rough horizontal pipeline surface: a after the nanofluid injection and b before the nanofluid injection
Fig. 24  Comparison between present experimental work and Pouran-
fard et al.’s work for the drag reduction of nanofluid at Re = 11,000
vol.% of the nanocomposite. Moreover, these nanofluids
have Newtonian behavior at the aforementioned tempera-
tures and nanocomposite volume concentrations. Adding
­SiO2–CaP–CuO nanocomposite into the crude oil caused
the nanofluid density increment in comparison with the base
liquid and a decrease with rising temperature. The highest
percentage increase was about 5.37% at 0.75 vol.% of the
­SiO2–CaP–CuO nanocomposite. The results of the measured
specific heat capacity indicated a downtrend with enhanc-
ing the S
­ iO2–CaP–CuO nanocomposite volume concentra-
tion. Four relationships have been suggested to forecast the
thermal and rheological characteristics of ceramic–metal
composite-based CO ternary hybrid nanofluids depending
on nanocomposite volume fraction and temperature. Results
obtained from the suggested relationships are in excellent
compromise with the laboratory data points. Percentage of
13
Applied Nanoscience
drag reduction with S­ iO2–CaP–CuO/CO nanofluid enhanced
with the nanocomposite volume concentration increment;
however, there exist an optimum nanocomposite volume
concentration, which no considerable drag reduction can be
observed at the concentration of higher than optimum one.
The mechanism of drag reduction of the ­SiO2–CaP–CuO/CO
nanofluid was the surface modification because of their con-
tact with the surface of horizontal pipeline. The percentage
of drag reduction of the ­SiO2–CaP–CuO/CO nanofluid in a
rough horizontal pipeline was higher than that in a smooth
pipeline because of existence of more turbulence in the
rough horizontal pipeline. Due to the greater turbulence in a
horizontal pipeline with a lower diameter or greater relative
roughness, the drag reduction of the S ­ iO2–CaP–CuO/CO
nanofluid enhanced with increasing the relative roughness
or enhancing the L/D ratio of horizontal pipeline. The SEM
images of the internal surface of pipes after the injection of
nanofluids confirmed that the effect of nanocomposite on
the roughness of the horizontal pipeline leads to a decrease
in drag coefficient in macroscopic scale.
Acknowledgments  The authors appreciatively acknowledge the Shiraz
University for the support to this experimental work. The study was
supported by the Shiraz University and the 111 project (B16038) for
the support.
Funding  Funding was provided by National Drought Research Insti-
tute, Shiraz University and Shiraz University.
Compliance with ethical standards 
Conflict of interest  The author declare that they have no conflicts of
interest.
Ethical approval  This article dose not contain any studies involving
animals performed by any of the authors.
Applied Nanoscience

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