Article

Cite This: Energy Fuels 2019, 33, 9671−9680 pubs.acs.org/EF

Effect of the NiO/SiO2 Nanoparticles-Assisted Ultrasound Cavitation

Process on the Rheological Properties of Heavy Crude Oil: Steady
State Rheometry and Oscillatory Tests
Daniel Montes,† Esteban A. Taborda,† Mario Minale,*,‡ Farid B. Cortés,† and Camilo A. Franco*,†
†
Grupo de Investigación en Fenómenos de Superficie−Michael Polanyi, Facultad de Minas, Universidad Nacional de Colombia,
Sede Medellín 4309000, Colombia
‡
Department of Engineering, University of Campania Luigi Vanvitelli, via Roma 29, 81031 Aversa, Caserta, Campania, Italy
*
S Supporting Information
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ABSTRACT: This manuscript has the primary objective of demonstrating the changes in the rheological behavior of heavy
crude oils (HO) in response to the application of ultrasound cavitation assisted with NiO-functionalized SiO2 nanoparticles
(SiNi1). A HO with an asphaltene mass fraction of 17.0% was used for the tests which were carried out at 25 °C and 1 atm with
a fixed ultrasound frequency and power of 37 kHz and 400 W, respectively. The viscosity measurements were performed on
four different samples: the HO in the absence of nanoparticles and ultrasound irradiation (sample A), the HO alongside
ultrasound irradiation (sample B), the HO with the addition of nanoparticles (sample C), and, finally, the HO in the presence
of the mentioned nanomaterial and ultrasound irradiation (sample D). It was observed that a single treatment, whatever it is,
only slightly changed the original HO rheology, while the cooperative action of ultrasound cavitation and nanoparticles addition
induced several measurable differences with respect to the HO: The viscosity was reduced up to 50−60%, depending on the
applied shear rate; the power per unit of volume dissipated during a hysteresis cycle was decreased of about the 70%; the sample
elasticity was measurably reduced, and accordingly, the relaxation time measurable for the original HO was not detectable
anymore. These findings can be explained by hypothesizing that the original HO viscoelastic microstructure is broken down by
the proposed combined treatments as the asphaltenes may stably adsorb on the nanoparticles and the subsequent size reduction
process of the asphaltene aggregates is enhanced by the ultrasound irradiation.

1. INTRODUCTION
Currently, heavy oil (HO) production and transportation are
significantly increased to compensate for the depletion of light
oil reservoirs.1,2 However, the physicochemical properties of
these fluids, such as high density, high asphaltene content, and
high viscosity, lead to low-efficiency operations with non-cost-
effective results.3
In heavy oils, the high content of asphaltenes and resins
leads to the formation of complex hierarchical microstructures4
that may also arrange to form a viscoelastic network,5 which
results in extra-high oil viscosity, that is an essential parameter
for production and transportation designing.6 Hence, several
investigations are focused on the crude oil dilution for
adjusting its viscosity to pipeline standards.6−9 Nonetheless,
addition of solvents tends to worsen transportation or
production operations. Indeed, the solvent, depending on its
chemical nature, may induce an undesired modification of the
crude oil microstructure that can drive even to the
precipitation of asphaltenes.4
Moreover, the complex heavy crude oil matrix also affects
other HO rheological properties, and often, both thixotropy10
and viscoelasticity11,12 are observed. Viscoelasticity induces to
a fluid a behavior in between an elastic solid, able to recover an
imposed strain when the applied stress is removed, and a
purely viscous fluid, able to dissipate all the energy
accumulated during a deformation. Thixotropy is defined as
“the continuous decrease of viscosity with time when flow is
applied to a sample that has been previously at rest and the
subsequent recovery of viscosity in time when the flow is
discontinued”.13 The transient behavior of a fluid can be
investigated to study thixotropy, and in particular, the
hysteresis technique, introduced by Green and Weltman,14
can be used. It consists in increasing and decreasing the
applied shear rate from zero to a maximum value. When the
stress is plotted vs the shear rate, typically a hysteresis loop is
detected. The loop dimension will depend on the rate at which
the shear rate is varied and on the resting time.15,16 This effect
may be also related to an irreversible microstructure
modification that induces a plastic deformation, usual in
solids,17 which is associated with an energy loss. The study of
the HO thixotropy is essential during the designing of
transport operations to avoid overestimations of the amounts
of diluents and of the temperature necessary to reach pipeline
transportation standards or to avoid possible underestimations
that could affect equipment integrity.18
Mortazavi-Manesh et al.18 studied the thixotropic behavior
of Maya crude oil using hysteresis loop tests concluding that
thixotropy is reduced upon temperature increase. With
dynamic experiments, Wardhaugh et al.12 characterized the
viscoelasticity of waxy crude oils to investigate how it affects
Received: July 12, 2019
Revised: August 27, 2019
Published: September 6, 2019

© 2019 American Chemical Society 9671 DOI: 10.1021/acs.energyfuels.9b02288

Energy Fuels 2019, 33, 9671−9680
Energy & Fuels
Table 1. Investigated Samples
A B C D
heavy oil heavy oil + 2000 mg·L−1 SiNi1 heavy oil + sonication for 90 min
nanoparticles 400 W/37 kHz
the yield point. They found that the 3D internal microstructure
of the investigated oils induces a solid-like behavior with
conventional elastic, creep, and fracture properties. Ghannam
et al.16 evaluated the HO rheological properties with the
addition of light hydrocarbons, concluding that the samples
were shear thinning and showed time dependency related to
thixotropy, which decreases with the addition of light
hydrocarbons. Moreover, Taborda et al.19 studied the HO
internal structure alteration caused by nanoparticles addition
through steady state and dynamic rheological tests. They found
that the addition of nanoparticles significantly reduces the oil
viscosity, yield stress, and elasticity.
In recent years, cavitation has been exploited as a technique
capable of reducing a fluid viscosity.20,21 Rahimi et al.22 studied
the combined effect of ultrasonic irradiation and heating on the
HO viscosity, showing that the viscosity reduction induced by
cavitation increases with temperature. Furthermore, also the
addition of nanoparticles to an HO improves the effect of
cavitation on the viscosity reduction thanks to their high
dispersibility, high surface-area-to-volume-ratios, high asphal-
tenes selectivity, and adsorptive capacity.23−26 Askarian et al.27
employed metal nanoparticles for this purpose, obtaining a
final viscosity reduction of 20% due to the enhancement of the
viscoelastic network disruption. Recently, hybrid nanoparticles
of supported hygroscopic salts (SHS) showed excellent
asphaltene adsorptive capacities,28−32 making them suitable
for enhancing the ultrasound-induced viscosity reduction.
According to the authors, in the literature, the coupled effect
of cavitation and nanoparticles addition on both viscosity and
elasticity of HO has never been investigated. To the best of our
knowledge, only Montes et al.33 showed some preliminary
results on the sole heavy oil viscosity reduction induced by the
use of nanoparticles (NiO-functionalized SiO2, SiNi1) coupled
with ultrasound cavitation. The authors investigated the effect
of both the cavitation time and the nanoparticles concentration
concluding that after 90 min of exposure with 2000 mg·L−1 of
SiNi1 nanoparticles the viscosity of the HO at a shear rate of
10 s−1 was reduced 44%. This result is achieved due to the HO
internal microstructure modification induced by cavitation
coupled to the asphaltenes adsorption on the nanoparticles.
The aim of this paper is assessing the preliminary results of
Montes et al.33 by evaluating the effect of the proposed
combined treatments on the rheological properties of the
heavy oil. The steady state behavior and the dynamic response
of the material are investigated before and after the
functionalized nanoparticles-assisted ultrasound cavitation.
Also, the HO thixotropy is investigated through hysteresis
loop tests. Since rheology is a very sensitive tool to investigate
the microstructure of complex fluids, like the heavy oils,34 it is
expected to understand the microstructure modification
induced by cavitation combined with nanotechnology treat-
ments so that this study might open a broader landscape about
the impacts of nanotechnology in the production and
transportation of heavy oils.
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heavy oil + 2000 mg·L−1 SiNi1 nanoparticles + sonication for 90
min 400 W/37 kHz
2. MATERIALS AND METHODS
2.1. Materials. Nickel oxide nanocrystals functionalized over 7 nm
fumed silica nanoparticles (SiNi1) were synthesized following the
procedure described in a previous study.33 More information about
the characterization of the nanoparticles is reported in previous
papers.29−31 The HO used has a density corresponding to 13°API and
approximately 40% of emulsified water. SARA measurement was
carried out through a microdeasphalting technique coupled with thin
layer chromatography following the IP 469 standard35 and using a
TLC-FID/FPD Iatroscan MK6 (Iatron Laboratories Inc., Tokyo,
Japan). The characterization results showed that mass fractions of
saturates, aromatics, resins, and asphaltenes are 18.2%, 23.1%, 41.7%,
and 17.0%, respectively.
Four different samples are investigated: (A) HO, (B) HO with
nanoparticles, (C) sonicated HO, and (D) HO with nanoparticles
subsequently sonicated (Table 1).
2.2. Methods. 2.2.1. Asphaltenes Characterization and
Aggregates Size Measurements. The asphaltenes were characterized
by their chemical composition, and aggregation kinetics were also
measured for confirming the existence of the viscoelastic network.
First, the asphaltenes were extracted from the crude oil under
investigation following the method described in previous works.24,32
Concisely, a certain HO volume was diluted with n-heptane in a 40:1
crude oil/diluent ratio. The mixture was sonicated for 2 h and
subsequently stirred for 20 h at 300 rpm; then it was filtered and
diluted again in a 4:1 ratio with n-heptane. The suspension was
centrifuged for 30 min at 4500 rpm for obtaining the asphaltenes,
which were washed with n-heptane several times until no impurities
were observed in the residue.
The asphaltenes chemical composition was characterized through
X-ray photoelectron spectroscopy (XPS) with a PHOIBOS 150 1D-
DLD (SPECS GmbH, Berlin, Germany) photoelectronic X-ray
spectrometer (NAP-XPS) analyzer using monochromatic light of Al
Kα (1486.7 Ev, 13 kV, 100 W) with 100 and 30 eV energy steps for
general and high-resolution spectrum; the steps for general and high-
resolution spectra were 1 and 0.1 eV respectively. Moreover, the
asphaltenes mean aggregates size was measured through the dynamic
light scattering technique (DLS) using a NanoPlus-3 (Micromeritics,
GA, USA). Briefly, n-heptane/toluene (Heptol) model solutions were
prepared with 50 vol % of toluene and 1000 mg·L−1 of asphaltenes,
the mixture was stirred at 300 rpm for the entire duration of the
experiments, and aliquots were taken for carrying out the measure-
ments. The same procedure was applied consequently for Heptol
model solutions at the same conditions of sample D: first, the SiNi1
nanoparticles were added to the solutions, and then the obtained
suspensions were sonicated for 90 min before measuring asphaltenes
aggregation.
2.2.2. Samples Preparation. The colloidal suspensions made of
HO and 2000 mg·L−1 of SiNi1 nanoparticles were prepared by hand
stirring for 15 min at 30 °C in order to facilitate mixing homogeneity
due to the sample high viscosity, which made unfeasible the use of
other mechanical methods of mixing.
Ultrasound cavitation was applied for 90 min to the pure HO
(sample C) and to the colloidal suspension discussed above (sample
D). An Elmasonic E60H (Elma Schmidbauer GmbH, Singen,
Germany) sonicator with a power of 400 W and frequency of 37
kHz was used, and the samples were monitored to avoid the
temperature increase induced by ultrasound exposure.
All of the samples were left at rest for 10 min before carrying out
any further tests.
2.2.3. Rheological Measurements. Prior to any rheological test,
before loading, the samples were preconditioned by hand mixing for 5
min to start from a microstructure which resembles the one
DOI: 10.1021/acs.energyfuels.9b02288
Energy Fuels 2019, 33, 9671−9680
Energy & Fuels
encountered in real field applications more than that obtained at the
end of a preconditioning steady simple shear flow, as typically done in
rheometry.
First, a flow curve is obtained by running a shear rate ramp soon
after having loaded the sample in the rheometer. The shear rate was
increased from ∼3 to ∼100 s−1 in 2 min to limit oil light tense
evaporation and to obtain a flow curve characterization in a very short
time, as typically required in control operations in real field
applications.
To compare the different samples, the degree of viscosity reduction
(DVR) is estimated. It is defined as
ij η − η yz
DVR = jjjj HO treat z
zz × 100
j zz
k {
η reproducible; the uncertainties are presented as error bars, and it is
HO (1)
where ηHO and ηtreat are the viscosities of the heavy oil (sample A) and
of the sample after a specific treatment (samples B−D),
respectively.36,37 The viscosities in eq 1 are measured at three
characteristic shear rates during the increasing shear rate ramp.
Hysteresis loop tests were performed to investigate the material
thixotropy on freshly loaded samples. The shear rate was first
increased from ∼3 to ∼100 s−1 in 2 min, as in the flow curve
determination, and then it was decreased from ∼100 to ∼3 s−1 always
in 2 min. In the increasing shear rate ramp, the sample viscosity
change can be associated with the internal microstructure breakdown,
while in the decreasing shear rate ramp, a microstructure buildup can
occur.15,38−40 Each whole experiment lasted about only 4 min.
To characterize the sample hysteresis the area enclosed by the loop
(WL) in a stress vs shear rate plot was evaluated.13 WL is the power
per unit of volume dissipated by the sample in the loop test
γmin
̇ 3.1. Asphaltenes Chemical Composition Character-
WL = ∫γ ̇ (σBD − σBU)dγ ̇
(1a)
min
where σBD and σBU are the shear stresses in the increasing and
decreasing shear rate ramp, respectively. γ̇min and γ̇max are the
minimum and maximum shear rate in the hysteresis loop test. The
thixotropy index is also estimated. It is defined as the normalized area
enclosed by the loop in a viscosity vs shear rate plot
i BD − BU yz
thixotrophy index = jjj
zz × 100
k BD {
γ̇
∫γ ̇ min (ηBD − ηBU)dγ ̇
min
= × 100
γ̇
∫γ ̇ min ηBD dγ ̇
min (2)
where BD and BU represent the areas under the breakdown and
build-up curves, respectively, and ηBD and ηBU the viscosities during
the increasing and decreasing shear rate ramp, respectively.41
Finally, the viscoelasticity of the samples was characterized by
dynamic experiments run on fresh samples. A frequency sweep test,
from 0.63 to 250 rad/s, at a constant strain of 3% was performed.
Amplitude sweep tests allowed one to verify that with the chosen
applied strain (3%) the samples are in the linear regime,33 and the
torque of the rheometer is significantly higher than the lower limit of
the instrument.42,43
All of the rheological measurements were carried out using a
Kinexus Pro+ (Malvern, UK) rheometer equipped with a Peltier cell
to control the temperature with a precision of 1 ×10−2 °C. With
multiphase fluids wall slip44 may occur, and to prevent or limit it a
serrated parallel plate−plate geometry with a diameter of 20 mm is
used. It is equipped with a solvent trap to limit light tense
evaporation, and a fixed gap of 0.3 mm is used for all of the
experiments. Such a small gap was chosen to have the possibility to
exploit high shear rates. We checked the instrument alignment by
measuring the viscosity at different gaps with the serrated plates.45 We
found that the shear rate is independent of the gap for gaps larger than
0.5 mm, while it decreases for lower gaps. The observed behavior is
due to an unavoidable intrinsic misalignment of the instrument and to
a residual wall slip induced by the flow through the geometry
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roughness.46 For gaps below 0.5 mm, the viscosity will be
consequently underestimated and the data might be postprocessed
to correct the experimental values.46,47 However, the residual wall slip
will affect all of the investigated samples in the same way,46 and
consequently, the viscosity will be identically underestimated. Since
the goal of the paper is only to compare the behavior of different
samples, as long as the data are taken at the same gap, the comparison
consistency will not be affected by the wall slip. Thus, for the sake of
simplicity, we will report in the following the data as they are
measured without a postprocessing.
All tests were run at 25 °C and 1 atm. All experiments were carried
out by triplicate, so to ensure that the initial conditions obtained with
the manual mixing followed by the sample loading are actually
worth mentioning that a maximum 3% error is recorded among the
different replicates in all of the rheological tests that we run. This
small error demonstrates the accuracy of the sample preparation and
of the measurement procedure as well as it guarantees the tests
repeatability.
3. RESULTS AND DISCUSSION
The results reported in this study are mainly divided into four
sections: (I) asphaltenes chemical composition character-
ization and aggregation tests, (II) evaluation of the viscosity
reduction due to addition of nanoparticles, ultrasound
cavitation, and combination of the two, (III) preliminary
investigation of the thixotropy of the samples with a single
hysteresis loop experiment, and (IV) assessment of the
treatment effects by dynamical mechanical experiments.
ization and Aggregation Tests. It has been mentioned
throughout this manuscript that the HO microstructure is
formed by the crude oil heavy fractions such as asphaltenes and
resins.48 In particular, the asphaltenes by means of their
chemical structure including heteroatoms (oxygen, nitrogen
sulfur)49,50 have a self-association trend fomented by different
mechanisms such as van der Waals forces, H-bonding, and
π−π stacking interactions,51 leading to aggregation of these
molecules, which causes formation of clusters.52
It is well known that in light crude oils this behavior prompts
the asphaltenes precipitation/deposition at certain pressure
conditions. However, in the HO cases, its microstructure is
usually configured in a viscoelastic network.49 The viscoelastic
network existence is driven by two particularly important
factors, a high amount of resins which stabilize the asphaltenes
in the oil matrix, and the asphaltenes content that must be
higher than a mass fraction of 5%.53,54 It can be said from the
asphaltenes content in the evaluated HO that the existence of a
viscoelastic network is more than possible. Nevertheless,
detailed analyses were carried out for obtaining some more
insights over this matter.
In Table S1 of the Supporting Information the chemical
composition of the asphaltenes characterized through the XPS
technique can be observed. The presence of the mentioned
heteroatoms could be an indicator of asphaltenes−asphaltenes
interaction forces.51 Hence, the asphaltenes clusters formation
was studied through aggregation kinetics and are shown in
Figure S1 of the Supporting Information, where an initial
aggregates size growth and a reduction until reaching a
stabilized system after 230 min can be observed. This
phenomenon is explained by the effect of the mixture shearing
in the asphaltenes interactions and clusters configuration,
which is a similar behavior of that observed in the HO
microstructure breakdown after subjecting the fluid to
shearing.
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Energy Fuels 2019, 33, 9671−9680
Energy & Fuels Article

Figure 1. Viscosity vs shear rate of the four samples of Table 1 as measured during the increasing shear rate ramp (BD). (A) Heavy oil (HO), (B)
HO with nanoparticles, (C) sonicated HO, and (D) HO with the addition nanoparticles and sonicated. Error bars are ± the standard deviation of
three sets of data. Lines are the predictions of Cross equation, eq 3, obtained with the best-fit parameters of Table 2. Gray regions highlight the data
taken to evaluate the degree of viscosity reduction (DVR).

Table 2. Best-Fit Parameters of the Cross Equation, Eq 3a

R2 η0 [Pa·s] η∞ [Pa·s] Α [s] m
sample A 0.999986 131.5 ± 5.5 26.4 ± 2.2 0.061 ± 0.004 1.29 ± 0.12
sample B 0.999996 113.5 ± 1.9 32.1 ± 0.6 0.067 ± 0.002 1.57 ± 0.06
sample C 0.999997 102.9 ± 1.4 30.7 ± 0.4 0.063 ± 0.002 1.67 ± 0.06
sample D 0.999931 70.4 ± 3.9 0 0.054 ± 0.007 0.96 ± 0.04
a
Uncertainties are the standard error of the estimated parameter, and R2 is the regression coefficient of determination.

Similar results were obtained previously,37 corroborating the
hypothesis that the HO microstructure is formed by
asphaltenes clusters configured into a viscoelastic network.
On the other hand, in Figure S1 the asphaltenes aggregation
kinetics in the presence of nanoparticles and ultrasound
irradiation is also seen. It is observed that both mechanisms
have an important effect on the formation of the clusters as
these have a lower size and a faster stabilization in comparison
with the system without treatment.
From these results it can be deduced that application of
ultrasound alongside nanoparticles would have an important
effect over HO microstructure. In this sense, this phenomenon
was studied by rheological tests for identifying changes in the
fluid rheological properties.
3.2. Viscosity Reduction Evaluation. Figure 1 shows the
viscosity of the four investigated samples (Table 1) vs the
shear rate as measured during the breakdown (BD) ramp, i.e.,
while increasing the shear rate. All the samples show a shear
thinning behavior, where the viscosity decreases with the shear
rate. This is probably due to a shear-induced microstructure
reorganization, more than to a purely viscoelastic effect. The
viscosities of the four samples seem to tend to a zero-shear
plateau as the shear rate is decreased, though the plateau value
cannot be clearly estimated from the data at hand. A high shear
plateau seems to be approached by samples A, B, and C but
not by sample D. Thus, from a practical and engineering point
of view, the data can be interpolated with the Cross model,35
eq 3, which accounts for both a zero-shear and a high-shear
9674
plateau, moreover, in previous studies involving nanoparticles-
heavy-oil systems it nicely interpolated the experimental data37
η − η∞
η = η∞ + 0
1 + (αγ )̇ m (3)
where η is the viscosity, α a characteristic relaxation time above
which the system shows a shear thinning behavior, γ̇ the shear
rate, m a constant, η0 the zero shear viscosity, and η∞ the
viscosity plateau at high shear rates. The predictions of the
Cross equation, eq 3, are also shown in Figure 1 as solid gray
lines passing through the data. The best-fit parameters are
reported in Table 2 for the four samples, together with the
coefficient of determination, R2. Notice that for sample D we
imposed η∞ = 0, since the data do not show even only the
trend toward a faraway plateau at high shear rates.
Data in Figure 1 clearly show that the sole addition of
nanoparticles and the sole sonication are able to similarly
decrease the HO viscosity without however qualitatively
changing the rheological behavior of the treated samples
with respect to the native HO. Indeed, a tendency toward both
the zero-shear and the high-shear plateau can be guessed from
the data of samples A, B, and C, and their shear thinning
behavior is very similar, with the coefficient m (Table 2) of the
Cross equation being almost the same. Conversely, when both
functionalized nanoparticles addition and ultrasound cavitation
treatment are applied to the HO a significant rheological
difference is observed: First, the viscosity is more than halved
at each shear rate; the tendency toward a high-shear plateau is
DOI: 10.1021/acs.energyfuels.9b02288
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Energy & Fuels
Figure 2. Viscosity (histogram) and DVR (line−symbol plot) calculated at three different shear rates of the four samples of Table 1: (A) heavy oil
(HO), (B) HO with nanoparticles, (C) sonicated HO, and (D) HO with addition of nanoparticles and sonicated. Error bars are the standard
deviation of three sets of data.
not observable anymore; last but not least, the shear thinning
behavior is changed and a terminal behavior with power law
index n = 0.04 (eq 4) can be identified
η = kγ ṅ − 1 (4)
where k is the so-called consistency index. Such a pronounced
shear thinning resembles very much that of suspensions.55
Notice that by comparing eq 4, first proposed by the Ostwald−
de Waele56−58 and valid for power law fluids,59,60 with eq 3
with η∞ = 0 it is readily obtained that n = 1 − m and k = η0α−m.
To better quantify the viscosity reduction induced by each
treatment and by the combination of the two, the viscosity
reduction index, DVR, eq 1, is calculated at the three shear
rates highlighted with the gray shadows in Figure 1. The lowest
value, 3.7 s−1, is in the region where the trend toward the zero-
shear plateau can be observed, the highest value, 70.3 s−1, is in
the region where samples A, B, and C are approaching the
high-shear plateau, and finally the intermediate value, 19.7 s−1,
is very close to the value of 20 s−1 at which the viscosity is
conventionally measured to characterize the fluid rheology in
pipeline transportation.8 Figure 2 shows the viscosities and
DVR of the four samples.
It can be seen that by adding the functionalized nano-
particles to the HO (sample B) a viscosity reduction of about
11% is achieved at the two lowest shear rates and a significantly
smaller reduction of 2.7% at the highest shear rate. This can be
attributed to the high asphaltenes selectivity and adsorption
capability of the used nanoparticles23,24 that were both
enhanced by assembling active sites of nickel oxide over the
support surface.32,61,62 According to several studies the
adsorption phenomenon is identified as a potential first
mechanism of HO viscosity reduction,19,37,63 as it can modify
the internal fluid microstructure,19 disrupting the asphaltene
viscoelastic network or reducing the dimensions of the
asphaltene macroclusters,4 which are the primary causes of
the high viscosity of heavy oils.
Similarly, the application of ultrasound cavitation to the
heavy oil (sample C) induces a viscosity reduction of about
18% at γ̇ = 3.7 s−l, 16% at 19.7 s−1, and 8.3% at 70.3 s−1. This
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can be mainly due to the ultrasound-induced weakening of the
asphaltenes−asphaltenes interactions,22 causing a size reduc-
tion of their aggregates.64
For the employed nanoparticles concentration and ultra-
sound irradiation time conditions, it is observed that the sole
ultrasound cavitation seems to be more effective than the sole
addition of nanoparticles, which is in accordance with the
results obtained in a previous study.33 Nevertheless, it is worth
mentioning that in these preceding results it was obtained that
a dosage of 1000 mg·L−1 of nanoparticles had a better
performance in viscosity reduction than the sole ultrasound
irradiation, while by using 2000 mg·L−1 of SiNi1 with 90 min
of ultrasound irradiation the process is enhanced due to a
better synergy between both mechanisms.
Remarkably, the viscosity reduction measured at the highest
shear rate in both cases, the sole nanoparticles addition and the
sole ultrasound irradiation, is significantly smaller than those
measured at smaller shear rates. This is due to the fact that the
high-shear rate plateau of the HO seems to be practically
unaffected by the single treatment, see Figure 1 and Table 2.
The dispersing action exerted by the flow results thus
comparable to those induced either by the nanoparticles or
by the ultrasound cavitation. The two treatments actually
promote the asphaltene macroclusters dispersion or the
asphaltene network disruption, obtained mechanically by the
flow, to lower shear rates.
Finally, the combination of the two treatments, i.e., the
application of ultrasound cavitation in the presence of the
functionalized nanoparticles, significantly enhances the vis-
cosity reduction at any shear rate obtaining a DVR of 50% at
3.7 s−1, 53% at 19.7 s−1, and 62.5% at 20.3 s−1. As discussed
above, the rheology is significantly modified as the high-shear
plateau is not observable anymore, and this leads to the very
significant viscosity reduction gained at the highest shear rate.
This can be explained considering that a much finer
microstructure reorganization is induced by the coupled
treatments and that the obtained fine microstructure is more
stable than that of samples B and C.
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Energy & Fuels
Figure 3. Hysteresis loop tests: (a) viscosity vs shear rate; (b) shear stress vs shear rate. Sample A: Heavy oil (HO). Sample D: HO with the
addition of nanoparticles and sonication. Full symbols refer to the increasing shear rate ramps or breakdown (BD) curves and hollow symbols to
the decreasing shear rate ones or build-up (BU) curves. BD viscosity curves are the same in Figure 1. Error bars are ± the standard deviations of
three sets of data.
Although the synergistic effects of the two treatments are
now proven, further investigation of the rheological changes
induced by the treatments to assess the mobility and the flow
capacity improvements of the crude oil and to understand the
mechanisms underneath these improvements is needed. In the
following, for the sake of brevity, we will focus only on samples
A and D, which show the most relevant rheological differences.
3.3. Hysteresis Loop Tests. Crude oils can often show a
thixotropic behavior, and a fast way to investigate it is to run
hysteresis loop tests.10,18 The hysteresis loop may highlight the
difference between the dynamics of the material internal
microstructure breakdown and the build-up in response to an
imposed increasing shear rate and a decreasing one,
respectively.15,38
Results are shown in Figure 3, where the hysteresis loop
areas are shadowed. In Figure 3a the viscosity of the BD and
BU curves are shown for both samples A and D, while in
Figure 3b the stress vs shear rate is plotted. In the last case, the
shadowed area represents WL (eq 1a), i.e., the power per unit
of volume dissipated by the sample in the loop test. It is clear
that WL of HO is much larger than that of sample D. To
quantify the observed difference, WL is calculated by first
smoothing the data with a cubic spline and then by numerically
evaluating the integrals. The results are summarized in Table 3,
Table 3. Hysteresis Loop Parameters of the Untreated
Heavy Oil (Sample A) and of the Heavy Oil with the
Addition of Nanoparticles and after Sonication (Sample D)a
WL [Pa s−1] thixotropy index [%]
sample A 2.9 × 105 28.3
sample D 8.3 × 104 15.8
a
WL is the dissipated power per unit of volume; thixotropy index is
defined in eq 2.
and it is found that the dissipated power per unit volume by
sample D amounts to about only the 29% of that dissipated by
sample A. Also, the thixotropy index, eq 2, is calculated by
numerically evaluating the viscosity integrals after having
smoothed the data with a cubic spline, and the results are
shown in Table 3.
The large difference between both WL and the thixotropy
index of the two samples suggests that the original heavy oil
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shows a thixotropy behavior more pronounced than that of the
same oil once treated with both the addition of nanoparticles
and ultrasound cavitation. Moreover, it can be noticed that the
first points of the BU curve of sample A (at the largest shear
rates) are slightly larger than the last points of the BD curve,
because once at rest the microstructure starts to rebuildup, as it
always happens in a thixotropic material. The same is not
observed for sample D. Besides this, it is worthwhile noticing
that the BU viscosity curve of sample A shows essentially a
Newtonian behavior. This can be explained assuming that the
flow breaks down the oil microstructure that is not
reconstituted in the BU curve while rapidly decreasing, in
only 2 min, the shear rate from 100 to 3 s−1. If the
microstructure remains unaltered during the BU curve,
accordingly the viscosity does not vary with the shear rate.
Conversely, in sample D the HO original microstructure was
already broken down by the synergistic action of asphaltene
adsorption on the nanoparticles and ultrasound cavitation, and
thus, the initial configuration is characterized by a more
dispersed system. It is probable that the shear thinning
behavior, in this case, is not due to a further breakdown of the
microstructure but by a geometrical reorganization of it, which
is reverted when the shear rate is decreased in the BU curve.
3.4. Viscoelastic Moduli. To further investigate if the
different rheological behavior of samples A and D is due to a
change of microstructure, the dynamic moduli of the two
samples are measured. The elastic modulus G′, also known as
the storage modulus, is the modulus of the stress component in
phase with the strain, while the viscous modulus G′′, also
known as loss modulus, is the modulus of the stress
component in phase with the shear rate. Hence, G′ accounts
for the elastic response of the material and thus for the elastic
energy stored during the deformation, while G′′ accounts for
the viscous, plastic, response of the fluid and thus for the
energy dissipated during the deformation.
In Figure 4 G′ and G′′ are plotted vs the imposed frequency.
A clear fluid behavior, where G′′ is significantly larger than G′,
is exhibited by both samples, though the low-frequency limit of
linear viscoelasticity, where G′′ is proportional to the
frequency and G′ to the frequency to the power of two, is
not reached in the investigated frequencies. The loss moduli of
the two samples almost coincide, while small differences are
observable in G′ moduli where that of sample D is slightly
DOI: 10.1021/acs.energyfuels.9b02288
Energy Fuels 2019, 33, 9671−9680
Energy & Fuels
Figure 4. G′ (full symbols) and G′′ (hollow symbols) vs frequency.
Circles are for sample A: Heavy oil (HO). Diamonds for Sample D:
HO with addition of nanoparticles and sonicated.
smaller than that of sample A at any frequency. This suggests
that the differences between the two samples are mainly related
to their different elasticity, more than to their different viscous
behavior.
To better highlight the differences between the two samples,
in Figure 5 both the complex viscosity (Figure 5a) and the
Figure 5. (A) Complex viscosity vs frequency and (B) phase angle vs
frequency of sample A (full symbols) and sample D (hollow symbols).
phase angle (Figure 5b) are plotted vs the frequency. These
data can be calculated from the moduli: In materials like
polymer melts or polymer solution, the complex viscosity can
be directly compared to the viscosity while the phase angle
highlights the relative contribution of the elastic behavior with
respect to the viscous one, being 90° for purely viscous
materials and 0° for purely elastic ones.65
The complex viscosity of the two samples is comparable, and
measurable differences are observed at low frequencies, which
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correspond to low shear rates, in the region approaching the
zero-shear plateau. In this region sample D appears to be less
viscous than sample A, in agreement with the viscosity data
discussed in section 3.1.
The phase angles of the two samples are measurably
different, and that of sample A is always smaller than that of
sample D, confirming that the latter sample is less elastic than
the former one. The phase angles are always larger than 45°
because G′′ is always larger than G′ and, as discussed above,
the materials exhibit a fluid behavior.
3.5. Relaxation Spectra. A viscoelastic fluid has a
behavior in between that of a purely viscous fluid and a purely
elastic material; this implies that this material can dissipate part
of the energy stored during the deformation with different
relaxation mechanisms, each of them with a characteristic
relaxation time. Thus, to better analyze the different elasticity
of the two samples, their relaxation spectra are here calculated.
The relaxation spectrum allows identifying the characteristic
relaxation times of the sample if the last ones lie within the
investigated frequencies.
The relaxation spectra are calculated from the elastic
modulus, G′, of Figure 4 with the approximated equation, eq
5, of second order proposed by Tschoegl66 and also from the
loss modulus G′′ with the approximated equation, eq 6, of the
second order of Schwarzl and Staverman66
1 2
H(t ) = dG′/d ln ω − d G′/d(lnω)2 |1/ ω= t / 2
2 (5)
H(t ) = (2/π )[G″ − d2G″/d(ln ω)2 ]1/ ω= t (6)
where H(t) is the relaxation spectrum, ω is the frequency (rad
s−1), and t is the time (s). To calculate the spectra from the
moduli, data of Figure 4 are first smoothed with a third-order
Bezier polynomial, so to get rid of false results that may come
from the scatter of the data, and eqs 5 and 6 are then applied.
The results are shown in Figure 6, where solid lines refer to
sample A and dashed ones to sample D. Moreover, black lines
are for the spectra calculated from G′, eq 5, and red lines are
Figure 6. Relaxation spectra vs time estimated from the elastic
modulus G′ (black lines) and from the loss modulus G′′ (red lines) of
Figure 4. Spectra of the untreated HO, sample A, are plotted as solid
lines, while those of the HO in the presence of 2000 mg·L−1 of SiNi1
after 90 min of ultrasound cavitation, sample D, are plotted as dashed
lines.
DOI: 10.1021/acs.energyfuels.9b02288
Energy Fuels 2019, 33, 9671−9680
Energy & Fuels
used for the spectra calculated from G′′, eq 6. The
characteristic relaxation times are identified as the abscissas
of the relative maxima of the spectra. Sample A shows a single
relaxation time equal to 1 × 10−2 s if estimated from the
spectrum calculated from G′ (black solid line) and equal to 8 ×
10−3 s if estimated from the spectrum calculated from G′′ (red
solid line). Conversely, both relaxation spectra of sample D are
monotonous, and thus, no relaxation time is identifiable. This
implies that if a relaxation time of sample D exists, it must lie
outside the time range here exploited with the dynamic
moduli, and thus, it must be shorter than 4 × 10−3 s.
The relaxation spectrum is a material function; thus, in
principle, that calculated with eq 5 should coincide with that
calculated with eq 6. This seldom happens because of two
reasons; first, the two equations are approximated; second, the
data are affected by an unavoidable experimental error that
propagates into the calculated spectra. However, the results
that we obtained are quite robust because the relaxation times
of sample A estimated with the two different procedures are in
acceptable agreement, and both relaxation spectra calculated
for sample D are monotonous.
The existence of a relaxation time is in accordance with the
existence of a 3D microstructure formed by the aggregates of
asphaltenes that causes the viscoelastic behavior of the HO,
which then shows a more pronounced elasticity and a larger
viscosity with respect to the treated sample D. Sample D, in
agreement, shows the absence of a relaxation time, at least in
the time range corresponding to the frequencies at which the
experiments were carried out. This suggests that the original
viscoelastic 3D network of the HO is disrupted by addition of
the functionalized nanoparticles coupled to the ultrasound
cavitation.
These results agree with those reported by several authors in
the literature, e.g., Dickinson et al.,67 Soo and Woo,68 and
Behzadfar et al.42 found that bitumens and heavy oils have
characteristic relaxation times associated to the presence of a
3D internal microstructure.
4. CONCLUSIONS
A novel process involving ultrasound cavitation assisted by
nickel oxide nanoparticles functionalized over nanoparticulated
silica support was applied to increase the heavy oil mobility at
reservoir conditions and/or to improve the heavy oil flow
capacity at surface and transportation conditions. The adopted
method led to a viscosity reduction ranging from 50% to more
than 63% by increasing the applied shear rate. We proved that
the sole addition of nanoparticles or ultrasound cavitation
irradiation is not capable of modifying the HO rheology
significantly. A small viscosity reduction is achieved in both
cases, while the combination of the two treatments not only
reduces the viscosity much more than every single treatment
but also modifies qualitatively the HO flow curve. Indeed, the
high shear plateau, which starts to be approached by the HO
for shear rates larger than 70 s−1, disappears for sample D,
where the nanoparticles are added to the HO, and the obtained
suspension is subsequently irradiated. Moreover, the response
of the two samples to a hysteresis loop test is also significantly
different as the HO has a power per unit volume dissipated
during the test 3.5 times larger than that of sample D. This last
result indicates that the original HO microstructure once
broken down by the flow needs a long time to rebuildup;
conversely, the microstructure of sample D is so dispersed that
either it cannot be broken down by the flow or it is able to
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reconstitute itself very quickly. Furthermore, the dynamic data
in the linear regime show that sample D is less elastic than the
HO, and this is corroborated by the estimates of their
relaxation spectra that highlight the existence of a relaxation
time only for the HO, sample A. This last result implies that
the microstructure of HO is either a viscoelastic network of
asphaltenes or it is made of large asphaltenes clusters that can
elastically deform; conversely, sample D is probably a
suspension-like one.
The combined treatments consisting of the addition of
nanoparticles with the subsequent ultrasound cavitation of the
resulting suspension is then able to break the original HO
microstructure. We hypothesize that the asphaltenes stably
adsorb on the nanoparticles and that the size reduction of the
asphaltenes is clearly enhanced by the ultrasound irradiation.
Although further studies are needed to better investigate the
mechanisms involving the heavy oil microstructure modifica-
tion, this paper not only proves the suitability of the
application of this technology to increase the HO flow
capacity but also demonstrates its enhanced performance by
possibly providing a better and more efficient HO production
and transportation design.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.energy-
fuels.9b02288.
Chemical composition characterized through the XPS
technique for the asphaltenes obtained from the
evaluated crude oil; mean aggregate size measured
through the dynamic light scattering (DLS) technique at
298 K using a heptol 50 solution with the asphaltenes
obtained from the evaluated crude oil (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: mario.minale@unicampania.it.
*E-mail: caafrancoar@unal.edu.co.
ORCID
Mario Minale: 0000-0002-7756-3536
Farid B. Cortés: 0000-0003-1207-3859
Camilo A. Franco: 0000-0002-6886-8338
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge COLCIENCIAS and Agencia
Nacional de Hidrocarburos (ANH-Colombia) for their
support provided in Agreement 272 of 2017. We also
recognize the Universidad Nacional de Colombia for logistical
and financial support.
■
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9680 DOI: 10.1021/acs.energyfuels.9b02288

Energy Fuels 2019, 33, 9671−9680