European Polymer Journal 109 (2018) 265–276

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Oil-in-water nanoemulsion stabilized by polymeric surfactant: T

Characterization and properties evaluation for enhanced oil recovery
⁎
Narendra Kumar, Ajay Mandal
Department of Petroleum Engineering, Indian Institute of Technology (Indian School of Mines), Dhanbad 826 004, India

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

Keywords: Nanoemulsions are kinetically stable colloidal dispersion of oil and aqueous phase with droplet size < 200 nm,
Nanoemulsions usually stabilized by a surfactant. In the present study an attempt has been made to formulate a novel type of
Polymeric surfactant nanoemulsion stabilized by a synthesized polymeric surfactant (polymethyl ester sulfonate, PMES), which has
Viscosity and viscoelastic properties dual properties of reducing interfacial tension (IFT) and enhancement of viscosity. The droplet size of less than
Maxwell model
200 nm of the dispersed oil phase in the formulated nanoemulsion, measured by dynamic light scattering (DLS)
Enhanced oil recovery
analysis and zeta potential values (ζ) of less than −30 mV, indicate its high kinetic stability. Stable viscosity
values with shear thinning and shear thickening nature in wide temperature (30–70 °C) range denoted enhanced
thermal stability with improved mobility and displacement efficiency of nanoemulsions. The stability and
viscosity of the nanoemulsion is further improved by incorporation of silica nanoparticles (NPs). Cryo-TEM
micrographs unveil the stabilizing mechanism, interaction of oil droplets with polymer branching of PMES
surfactant and silica NPs. Viscoelastic behavior investigated by Oscillatory method shows that the dynamic
moduli, storage (G′) and loss (G″) of nanoemulsions follow the Maxwell model for viscoelastic materials. Specific
frequency (SF) or cross over point of G′ and G″ denote the transition between viscous and elastic phases. A shift
in SF position by variation in salinity, temperature and NPs concentration change the viscoelastic property of
nanoemulsions.

1. Introduction
The perpetual decline in oil production has raised a need to improve
the oil recovery by development of new technologies to recover the un-
swept areas of the reservoir. Enhanced oil recovery (EOR) technique
comprising approaches of thermal, miscible-immiscible, chemical re-
covery, etc. have been used for decades by oil and gas industries [1].
Chemical EOR methods, using slugs of chemical blends (alkali, surfac-
tants and polymers) have widely been excised for their widespread
mechanisms of wettability alteration, interfacial tension reduction and
improvement of mobility ratio in enhanced oil recovery [2,3]. Typi-
cally, chemical slug contains surfactant which has great ability to re-
duce interfacial tension between oil and water alone (surfactant
flooding) or water soluble polymer that simultaneously improves the
mobility ratio (surfactant-polymer or SP flooding) or in combination
with inorganic bases (alkali-surfactant-polymer or ASP flooding). The
loss of expensive surfactant by adsorption on rock surfaces, shear de-
gradation of conventional polymer like partially hydrolysed poly-
acrylamide (HPAM) and the uncertainty of the in-situ emulsification in
presence of surfactant and alkali with expensive project cost and
volatilities in oil prices make the conventional chemical EOR process
un-economical [4,5]. Implementation of emulsion stabilized by che-
micals (emulsifiers, polymers) in EOR has earlier been reported [6,7].
Three basic mechanisms are followed by emulsions during oil recovery:
reduction of interfacial tension, wettability alteration of rocks and
miscibility of trapped crude oil with the injected emulsions [8,9]. The
poor emulsion stability because of coalescence of the dispersed phase
has hindered its use in EOR. Therefore development of an improved and
robust EOR technique is required to revolutionize the present oil pro-
duction scenario. Nanotechnology approach in emulsions i.e. nanoe-
mulsions with higher kinetic stability may be a revolution in EOR if
addressed properly. An emulsion with droplet size less than 200 nm are
known as nanoemulsion [10]. Nanoemulsions stabilized by surfactants
and polymers may lead to phase separation as discussed above. Appli-
cation of polymeric surfactant may be novel approach to eliminate the
problems of surfactants and polymers. A surfactant having both hy-
drophilic and polymeric adsorbed hydrophobic parts with character-
istics of both polymer and surfactant is known as polymeric surfactant.
A polymeric surfactant synchronizes the high viscous property of a
polymer with interfacial tension reduction ability like a surfactant [11].

⁎
Corresponding author.
E-mail address: ajay@iitism.ac.in (A. Mandal).

https://doi.org/10.1016/j.eurpolymj.2018.09.058
Received 8 August 2018; Received in revised form 25 September 2018; Accepted 28 September 2018
Available online 29 September 2018
0014-3057/ © 2018 Elsevier Ltd. All rights reserved.
N. Kumar, A. Mandal
The application of polymeric surfactant in coating industry and petro-
leum sector as an EOR agent has been reported by a number of re-
searchers [12–14] but its application in emulsions as an EOR agent are
limited. Use of polymeric surfactant in nanoemulsions represents a fa-
vorable option because of occurrence of low interfacial tension and
viscosity enhancement at the same time with positive effect on capillary
number (NC). The introduction of hydrophobic group in a polymeric
surfactant mainly alters the rheology of the solution (thickening of
solutions) [15]. Polymeric surfactant being a single entity does not
undergo phase separation as reported for surfactant-polymer mixture
during the flow stream [16].
Nanoemulsions can be formulated by two methods: high energy
method (ultrasonication) [17] and low energy method (chemical po-
tential of components) [18]. Ease in formation with less preparation
time and small droplet size provide an advantage of high energy
method over low energy method. The continuous Brownian motion of
nano-size droplets with slow coalescence rate increases the kinetic
stability of nanoemulsions with improvement in the mobility ratio and
penetration through the gravel pores of the reservoir [19]. Investigation
of droplet size by dynamic light scattering (DLS) is crucial for the de-
termination of stability and interfacial behavior of nanoemulsions, be-
cause the stability is strongly affected by the amount of surfactant used
[20]. The increase in surface area of contact by small droplet size helps
in interfacial tension reduction because of adsorbed surfactant at the
oil-water interface [21]. The surfactant adsorbed at the surface of oil
droplets forms a coating that prevents their coalescence [22]. The
surfactant adsorption at the oil-water interface might involve several
mechanisms like electrostatic interactions, steric hindrance, van der
Waals interaction, covalent bonding and hydrogen bonding, etc. [23].
The structural or morphological representation of nanoemulsion dro-
plet size, shape, distribution of droplet in continuous phase, interaction
with NPs and the network or branching formed by polymers can be
efficiently investigated by cryogenic transmission electron microscopy
(Cryo-TEM) [24]. Efficacy of EOR depends upon the injected rate and
viscosity of the injected fluid [25]. The hydrophobic or polymer part of
polymeric surfactant in nanoemulsion improves the mobility ratio of
the displacing fluid due to enhanced viscosity which in turn increases
the areal and sweep efficiency [26]. A pseudo plastic/shear thinning
and dilatant/shear thickening characteristics is beneficial in enhanced
oil recovery of the injected fluid or nanoemulsions as it improves its
injectivity with better mobility control at high shear rate [27]. The
injection of polymeric surfactant stabilized nanoemulsion improves the
flow behavior with improvement in the macroscopic sweep efficiency
and reduction in permeability of high permeable zones [28]. A fluid
showing both the properties of viscous and elastic nature is termed as
viscoelastic fluid. The information about viscoelastic nature of injecting
fluid is important for its application in oil recovery. Viscoelastic be-
havior study provides knowledge about dynamic moduli i.e. storage/
elastic modulus (G′) and loss/viscous modulus (G″) with effect of
varying parameters such as temperature, surfactant concentration,
salinity and NPs concentration [29]. A vast segment of experimental
and theoretical study on viscoelastic behavior is dedicated to emulsion
systems [30]. Several articles published on influence of NPs con-
centration on the stability, viscosity and viscoelastic behavior of na-
noemulsions suggest an increase in nanoemulsion stability with en-
hanced rheological properties [31]. Incorporation of hydrophilic silica
nanoparticles (NPs) enhances the stability of nanoemulsions with in-
crease in viscosity because of the distortion generated in the stream line
flow due to the hydrodynamic motion of particles, particle-liquid in-
teractions or interaction of particle with network structure of the hy-
drophobic part of polymeric surfactant. NPs property to travel long
distances without retention and easy passage through porous media
owing to its small size is an advantage for EOR [3]. The objective of
present work is to investigate the behavior of a new formulated EOR
agent (nanoemulsion stabilized by a polymeric surfactant) that elim-
inates the drawbacks of surfactant-polymer system. Light mineral oil,
266
European Polymer Journal 109 (2018) 265–276
anionic polymeric surfactant (PMES) and deionized water were used to
prepare the nanoemulsion. PMES was chosen for nanoemulsion for-
mation because of its biodegradability and environment friendly nature
with high adsorption ability at oil-water interface. Synthesized nanoe-
mulsion was characterized by their droplet size, zeta potential, mor-
phology study and rheological behavior study at varying parameter of
PMES and NPs concentration, salinity and temperature for evaluation of
nanoemulsion efficiency in enhanced oil recovery.
2. Methodology
2.1. Materials
Jatropha oil for the synthesis of PMES was procured from Bulk agro
private limited, India. Light mineral oil (98% pure) having density of
0.85 g/mL at 25 °C and viscosity of 25.5 mPa-s at 30 °C was obtained
from Nice Chemicals, India. Silica, SiO2 nanoparticles (NPs) and
Sodium Chloride (NaCl) was purchased from SRL chemicals. Analytical
grade reagents were used as procured without any further purification.
Carbon coated copper grid of 200 mesh size was provided by SPI sup-
plies. Solution preparations were done in de-ionized water (Millipore,
Molshein, France).
2.2. Synthesis and characterization of PMES
Anionic polymeric-surfactant was synthesized in two steps. Firstly,
sodium methyl ester sulfonate (MES) an anionic surfactant was syn-
thesized by sulfonation from Jatropha oil [32]. Secondly, polymeric
surfactant (polymethyl ester sulfonate, PMES) was synthesized from
MES by free radical polymerization technique with acrylamide as
monomer unit using potassium metabisulphite as initiator by redox
couple method. A simplified molecular structure of polymethyl ester
sulfonate with molecular weight around 2.24 × 106 g/mol is shown in
Fig. 1. The detailed explanation of synthesis process and characteriza-
tion (by FTIR, 1H NMR, FE-SEM, EDX, TGA and molecular weight) is
discussed in our previous work [33].
2.3. Interfacial tension study
The interfacial tension (IFT) between aqueous PMES surfactant so-
lutions at different concentrations and mineral oil (density 0.85 g/ml;
viscosity = 25.5 mPa-s) was measured by spinning drop SVT 20 tensi-
ometer (Dataphysics, Germany) at 30 °C. PMES surfactant solutions
were filled in a glass tube that was loaded inside the tensiometer and
rotated at 4000 rpm followed by mineral oil (2 µL) injection into the
glass tube. Henceforth IFT values were recorded. Eq. (1) was used by
the instrument to obtain the IFT
ω2R3Δ
σ=
4 (1)
where σ is the interfacial tension, ω is the rotational speed of the glass
tube, R is the radius of the oil droplet, Δ is the density difference
between polymeric surfactant solution and mineral oil.
O
A + (n+1) R
OCH3 A R R- C(SO 3Na)COOCH3
n
S
C(SO3Na)COOCH3
O O
ONa
methyl ester sulfonate (MES)
Fig. 1. Molecular structure of polymethyl ester sulfonate. A = free radical ac-
rylamide; R = linear alkyl chain of jatropha oil fatty acid.
N. Kumar, A. Mandal
Fig. 2. Formed nanoemulsion sample from mineral oil and aqueous PMES surfactant solution by Ultrasonication process at 60 W and 26 kHz.
2.4. Nanoemulsion formulation
Ultrasonication process, a high energy method was used for the
preparation of nanoemulsion at varying PMES concentrations. Firstly, a
coarse emulsion was prepared by stirring at 1000 rpm with the help of
magnetic stirrer using 10 wt% light mineral oil and 90 wt% aqueous
PMES surfactant solutions (0.5, 1.0, 1.5 and 2.0 wt% PMES in Di-io-
nized water) in 50 ml glass beaker. Considering the loss of surfactant by
adsorption on rock surfaces and accumulation at oil-water interface,
PMES surfactant concentration was taken higher than critical micelle
concentration. Secondly, the formed coarse emulsions were sonicated
with the help of handheld Ultrasonic Homogenizer UP200Ht (200 W,
26 kHz) for 1 h to obtain nanoemulsion. Fig. 2 shows the picture of
prepared nanoemulsion (a single continuous phase) by ultrasonication
of mineral oil and aqueous PMES surfactant solution. The formation
process decides the stability and droplet size of nanoemulsions.
2.5. Droplet size and surface charge
The average nanoemulsion droplet size was analyzed using dynamic
light scattering (DLS) technology with the help of Zetasizer, Nano- S90
(Malvern Instruments Ltd., U.K.) instrument. The instrument used a
scattering angle of 90° and 21 CFR part 11 software. Dilution in the
ratio 1:100 (prepared emulsion: Di-ionized water) was done prior
testing to ensure the Brownian motion of the droplets. Absorbance
value and refractive index (RI) required in DLS analysis were de-
termined using UV-1800 UV–vis spectrophotometer, Shimadzu, Japan
and Refracto 30PX/30GS (a portable refractometer) respectively. RI
value of 1.33 for water and 1.44 for emulsion was used in the analysis.
Surface charge of emulsion droplet is accounted by zeta potential
measurements. Zeta potential value was determined by Zeta-Meter
system 4.0 using micro electrophoresis technique. The velocity and
direction with which droplets of nanoemulsion sample placed in the
electrophoresis cell move on application of an electric field provides the
zeta potential value and surface charge (positive/negative). To de-
termine the effect of nanoparticles on droplet size and surface charge
silica NPs was added to the prepared nanoemulsions. DLS and Zeta
267
European Polymer Journal 109 (2018) 265–276
potential analysis account for the stability of nanoemulsions. All the
measurements were accomplished at 30° ± 0.1 °C.
2.6. Cryo-TEM micrographs
The morphology of the prepared nanoemulsion droplets in their
original state was studied by cryogenic transmission electron micro-
scopy (Cryo-TEM) with the help of JEOL JEM- 2100F, a computer
controlled high resolution electron microscope that operates at
120–200 kV acceleration voltages. A controlled environment vitrifica-
tion system (CEVS) was used for sample preparation and preservation
of the original structure of the fluid. Micrographs captured by the
transmitted electron from the sample reveal the inner structure of the
emulsion droplets. A detailed explanation of sample preparation and
working of Cryo-TEM is discussed in our previous work [34].
2.7. Rheological behavior study
Rheological characteristic study provides information about the
behavior of the fluid, that is shear thinning or shear thickening nature.
Viscosity of formulated nanoemulsion from PMES surfactant was
measured using Bohlin Gemini 2 rheometer, Germany with cup and bob
geometry maintaining a gap of 0.5 µm. Nanoemulsion sample was
placed in the cup and the shear rate applied by gradual rotation of the
bob measured the torque required for the calculation of shear stress.
The viscosity of the nanoemulsion was measured against shear rate in
the range 0–500 s−1. The viscosity curves were analyzed using math-
ematical models such as Power law (Ostwald de Waele) and Bingham
plastic model. The value of flow behavior index (n) defines the nature
of the fluids. If n < 1 → Pseudoplastic, n = 1 → Newtonian fluid and
n > 1 → Dilatant fluid.
2.7.1. Pseudo plastic nature
The nanoemulsion samples showed shear thinning nature (n < 1)
with no yield stress (τo). The pseudo plastic behavior is described by
following Eq. (2)
τ = k ∗γ̇n (2)
N. Kumar, A. Mandal
30 30oC
25
20
IFT (mN/m)
15
10
5
0 cmc
0.0 0.2 0.4 0.6 0.8 1.0 1.2
PMES concentration (wt.%)
Fig. 3a. Change in IFT with varying PMES surfactant concentration at 30 °C.
where τ is the shear stress, k is the consistency index, n is flow behavior
index and γ̇ is shear rate (du/dy). Value of n and k were calculated
taking log on both side of Eq. (2) and plotting log τ versus log γ̇ . The
apparent or effective viscosity ( μ ) along with n and k values can be
determined by fitting the experimental data to following Eq. (3)
μ = k ∗γ̇n − 1
Though power law model is only a good description of fluid beha-
vior across a shear rate range upto which coefficients are fitted but due
to its simplicity with more versatile than Bingham plastic model it is
widely practiced. However power law model showed poor results at
high shear rate.
2.7.2. Viscoelastic property determination
Viscoelastic property study provides information about the elastic
and viscous nature of fluids and involves determination of real or sto-
rage or elastic modulus (G’) and imaginary or loss or viscous modulus
(G”) as a function of angular frequency (ω). Viscoelastic fluid is a fluid
that shows partial viscous and partial elastic nature under varying
strain. First oscillation strain sweep test was performed with cup and
bob arrangement to estimate the target strain (in the range 0.1–100%)
for a fixed ω value (ω = 1 rad/s). ω = 2πn , where n is frequency in Hz.
The moduli (G’& G”) were determined as a function of strain amplitude.
Estimation of target strain was followed by performance of frequency
sweep test at the fixed strain value with a varying angular frequency
(0.1–100 rad/s). Finally, G’& G” moduli curves were plotted against
angular frequency. If G’ > G” fluid behaves as solid or gel and for
G’ < G” fluid acts as liquid or viscous in nature. For the determination
of sinusoidal stress (τ0 ) in dynamic oscillatory test a sinusoidally
varying strain (γ0 ) with a known amplitude is applied to the sample and
a shifting of phase between stress and strain sinewaves take place by an
angle δ in viscoelastic fluid systems. The value of δ varies between 0°
and 90° (0 < δ > 90°) for a viscoelastic fluid system. A perfectly elastic
solid and perfectly viscous liquid corresponds to δ = 0° and 90° re-
spectively. With known values ofτ0 , γ0 and δ viscoelastic parameters G’,
G” and G* (complex modulus) can be evaluated. A complex modulus or
dynamic modulus is the ratio of sinusoidal stress to sinusoidal
τ
strain, |G∗| = γ0 . A vector analysis of complex modulus provides storage
0
(G’) and loss (G”) moduli, Eq. (4). G’ denotes the part of stress energy
temporarily stored during shear process and G” indicates the energy
required to initiate the flow.
Storage modulus−G'=|G∗|∗cosδ; Loss modulus−G'' = |G∗|∗sinδ
The real or in phase viscosity (μ′) and imaginary viscosity (μ″)
components of viscosity can also be extracted from the preceding
analysis by simple Eq. (5)-
European Polymer Journal 109 (2018) 265–276
G'' '' G'
μ '= ;μ =
ω ω (5)
The in-phase viscosity is also known as dynamic viscosity.
2.7.3. Maxwell fitting
A Maxwell fluid or Maxwell material is a viscoelastic material
having both the properties of elasticity and viscosity. The components
of complex dynamic modulus of the formed nanoemulsion acting as
Maxwell fluid when fitted to Maxwell model for viscoelastic materials is
given as per Eq. (6)
ω2τ 2G0 ωτG0
G ' (ω) = ; G''(ω) =
1 + ω2τ 2 1 + ω2τ 2 (6)
where τ denotes the specific relaxation time (τ =
μ
)
and G0 is the
Go
steady state value of G’ and G” generally occurs in high frequency re-
gion.
3. Results and discussion
3.1. IFT behavior of PMES surfactant
Conventionally polymers have no effect on IFT values but some-
times they increase the IFT value when mixed in the solutions. Earlier
(3) studies reported a reduction in IFT values in the range 2–7 mN/m by the
use of polymeric surfactants [35]. The reduction in IFT values are not in
the ultra-low IFT value range as compared to conventional surfactants
because of the combined effect of high molecular mass and macro-
molecular entanglement of the polymeric surfactants. The IFT value
was measured by spinning drop tensiometer at 30 °C between PMES
surfactant solution and mineral oil. Fig. 3a shows the change in IFT
values with varying PMES surfactant concentration. The synthesized
PMES surfactant showed good results compared to the earlier reported
studies for IFT reduction. The IFT values reduce from 26.52 mN/m at
0.0 wt% to 1.7 mN/m at 0.6 wt% of PMES surfactant concentration.
Initially, a reduction in IFT value was observed with increase in PMES
surfactant concentration till it reached the lowest IFT value. The con-
centration after which IFT values tends to be almost constant with no
further reduction is known as critical micelle concentration (cmc).
Formation of micelles starts in the bulk solution with further addition of
PMES surfactant after cmc. The interfacial property for synthesized
PMES surfactant is controlled by hydrophobic and hydrophilic parts.
The hydrophobic chain tends to attach with crude oil and the hydro-
philic head group gets adsorbed at oil-water interface which helps in
IFT reduction [36]. The low IFT value of PMES surfactant indicates
better oil recovery. The salinity of formation water in the reservoir
plays an important role in the extraction of residual oil during EOR
process by IFT reduction. The salinity effect on the IFT values of op-
timal PMES surfactant concentration of 0.6 wt% is shown in Fig. 3b.
With an increase in salt concentration from 0.0 wt% to 3.5 wt%, IFT
values initially decrease and obtain minimum value of 0.91 mN/m at
2.5 wt%. Salt concentration corresponding to minimum IFT (IFTmin) is
known as optimal salinity (2.5 wt% NaCl). The natural tendency of
surfactants to get adsorbed at the interface in the presence of salt en-
hances the IFT reduction [37]. Further salt addition in the solution after
optimal salinity increases the IFT. The drop and rise in IFT values of
PMES surfactant solution in presence of salt is controlled by numerous
parameters such as hydrophobic and hydrophilic part of PMES surfac-
tant, mineral oil properties. The mechanism behind this peculiar be-
havior of PMES may be due to presence of polar components of PMES
that has substantial impact on IFT alteration at oil-water interface in
presence of salt. The attraction of Na+ and negative charge leads to
(4) decrease in PMES solubility in water with rise in IFT values. Another
theory of IFT reduction at low salinity may be because of the existence
of oil-in-water (O/W) micro-emulsion phase with excess oil, whereas
increase in IFT at high salinity above optimal salinity is due to presence
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N. Kumar, A. Mandal European Polymer Journal 109 (2018) 265–276

4.0 flocculation, creaming, etc. [40]. Fig. 4(a) shows the volume % vs.
30oC
average droplet size of nanoemulsion with PMES surfactant con-
3.5 centration. As observed, a shift towards left in droplet size profile dis-
tribution denote a decrease in the average droplet size of nanoemulsion
3.0
signifying an increased tendency to oil droplets breakdown. The sta-
tistical analysis of droplet size distribution of nanoemulsions was per-
IFT (mN/m)

2.5
formed by log-normal probability distribution function as it best re-
presents formation process (ultrasonication process). The statistical
2.0
analysis is important as it shows the oil droplets dispersion in con-
1.5
tinuous phase. A good fitting was showed by the prepared nanoemul-
sions with 0.979, 0.962, 0.974 and 0.937 values of adjusted coefficient
1.0 of determination (R2). To analyze the concentration effect of silica NPs
on nanoemulsion property, silica NPs was varied in nanoemulsion
0.5 sample with 1.5 wt% PMES surfactant. As may be seen from Table 1, a
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
drop in droplet size of nanoemulsion sample is observed on addition of
salinity (wt.%) NPs. A decrease in average droplet size by incorporation of NPs is due
Fig. 3b. Variation of IFT with increase in salinity at CMC of 0.6 wt% of PMES to formation of a robust layer of nanoparticles over the droplets that
surfactant solution. increase the interfacial area with lowering of IFT and reduction of co-
hesive forces, thereby hindering their coalescence and subsequent de-
crease in droplet size. The average droplet size decreased from
of water-in-oil (W/O) micro-emulsion with excess water [38].
101.85 nm to 72.17 nm when silica NPs concentration increased from
0.1 wt% to 0.5 wt%. An enhanced stability of nanoemulsion is showed
3.2. Effects of PMES surfactant and silica NPs concentration on by NPs inclusion by further drop in droplet size which increase their
nanoemulsion stability Brownian motion, hence improved kinetic stability. An increase in
droplet size was observed with further addition of NPs (90.56 nm at
The dispersed oil droplets size distribution in continuous aqueous 1.0 wt%) indicating the saturation limit of nanoparticles. This may be
phase of PMES surfactant based nanoemulsion is a result of complex due to aggregation of silica NPs. The volume % vs. average droplet size
collaborations between tailor made surfactant and polymeric chains. of nanoemulsion with varying silica NPs concentration is shown in
The interactions of components concurrently contribute to droplet Fig. 4(b). Similar behavior was observed as before, a shift towards left
breakdown and re-coalescence during the emulsification process that in droplet size profile distribution indicating a decrease in the average
effects the distribution of dispersed oil droplets. The shear applied at droplet size. But with an exception for sample with 1.0 wt% silica NPs
the interface of oil and water controls the occurrence of both the phe- in which the shift in profile distribution was towards right denoting an
nomenons. A stable nanoemulsion is formed when the applied shear increase in the droplet size. With 0.902, 0.927, 0.908 and 0.891Values
stress overcomes the Laplace pressure i.e., breakdown process dom- of R2 for silica NPs incorporated nanoemulsion sample denote negli-
inates the re-coalescence [39]. A conventional surfactant based na- gible impact of silica NPs in formation process. The effect of PMES
noemulsion is stabilized basically by the electrostatic repulsion between surfactant and silica NPs concentration on zeta potential was also
the surfactant molecules adsorbed on oil droplets that decrease the IFT analyzed. An increase in zeta potential values were observed denoting
with a rise in interfacial area which indicate an improved breakdown an enhanced nanoemulsion stability. Fig. 5(a, b) shows the change zeta
rate of oil droplets and increase in stability. But a polymeric surfactant potential values with variation in PMES surfactant and silica NPs con-
nanoemulsion is stabilized by two phenomenons- first, the repulsive centration. The increase in zeta potential values for silica NPs loaded
forces acting between the adsorbed surfactant molecules leading to PMES surfactant based nanoemulsion sample was greater than nanoe-
reduction in IFT and second, the steric hindrance caused by the poly- mulsion samples stabilized only by PMES surfactant denoting better
meric chains or the 3-dimensional network structure. The droplet size stabilization of nanoemulsion with NPs inclusion due to the synergetic
measured by Dynamic light scattering (DLS) technique confirms the effect of silica NPs and PMES surfactant molecules. This observation
formation of nanoemulsion. With increase in PMES concentration from (enhanced stability) can also be verified with drop in droplet size for
0.5 wt% to 2.0 wt% the average droplet size decreased from 161.13 nm silica NPs loaded nanoemulsion sample from the DLS data.
to 94.95 nm. Table 1 presents the average droplet size of the nanoe-
mulsion samples with varying PMES surfactant and silica NPs con- 3.3. Cryo-TEM analysis of formulated nanoemulsion
centrations. The decrease in droplet size is because of the increase in
interfacial area with rise in PMES surfactant concentration causing a The morphological structure analysis of the nanoemulsion droplets
reduction in IFT. The nano-size droplets enhance the emulsion stability was done by cryo-TEM imaging. A direct analysis of nanoemulsion
over long period of time as smaller the droplet size more kinetically droplets with information about its internal structure in its natural state
stable the emulsion is with increase in emulsion life because of the is provided by cryo-TEM. The nanoemulsion sample in its frozen-hy-
continuous Brownian motion of the nano-size droplets that dominate drated state display a clear dispersion of nano-scale emulsion droplets
the gravitational forces which cause destabilization of emulsion due to in continuous medium [41]. Fig. 6(a) presents the cryo-TEM micro-
graph of nanoemulsion sample prepared from PMES surfactant. The
Table 1 uniform dispersion of nano-size oil droplets (black spots) in continuous
Effect of PMES surfactant and silica NPs concentration on the average droplet aqueous medium (white background) is clearly visible. It is observable
diameter of nanoemulsion. that each emulsion droplet is separated from the adjacent droplet de-
PMES (wt Average Droplet Silica NPS Average Droplet diameter
noting a surfactant coating over the oil droplet which prevents their
%) diameter (nm) (wt%) (nm) coalescence. The network structure or branching attached to oil dro-
plets, as seen in red square also prevents their coalescence by steric
0.5 161.13 ± 0.54 0.1 101.85 ± 0.31 hindrance and confirms the presence of polymeric part in PMES sur-
1.0 123.74 ± 0.73 0.3 93.03 ± 0.27
factant. Fig. 6(b) shows the accumulation of silica NPs (tiny shiny
1.5 107.51 ± 0.55 0.5 72.17 ± 0.57
2.0 94.95 ± 0.81 1.0 90.56 ± 0.71 particles) on nanoemulsion droplets along with the polymeric branched
structure. The adsorption of NPs over the oil droplets forms a barrier

269
N. Kumar, A. Mandal European Polymer Journal 109 (2018) 265–276

(a) wt.% of PMES 25 (a) wt.% of Silia NPs

0.1 wt. %
25 0.5 wt. %
0.3 wt. %
1.0 wt. %
0.5 wt. %
1.5 wt. %
20 1.0 wt. %
2.0 wt. %
20

volume (%)
15
15
volume (%)

10
10

5 5

0 0
0 50 100 150 200 250 300 0 20 40 60 80 100 120 140
droplet size (nm) droplet size (nm)

Fig. 4. Droplet size variation of prepared nanoemulsion samples at (a) varying PMES and (b) Silica NPs nanoemulsions at 30 °C.

around them which prevents their aggregation with other oil drops, as
discussed in DLS study [42]. Thus the cryo-TEM micrographs of PMES
surfactant based nanoemulsion clearly describe the two stabilizing
mechanisms. First, the formation of surfactant coating over the oil
droplets that prevents their coalescence by the repulsive forces acting
between the adsorbed surfactant molecules and Second, the steric
hindrance caused by the polymeric chains or the 3-dimensional net-
work structure of PMES surfactant attached to oil droplets. The in-
corporation of silica NPs having synergetic effect on the stabilization
mechanism enhance nanoemulsion stability with decrease in droplet
size, Fig. 6(b).
3.4. Viscosity analysis of formed nanoemulsions
3.4.1. Influence of PMES concentration and temperature
Surfactant and polymer play a crucial role in chemical EOR process
by reduction of interfacial tension and improvement of displacing fluid
mobility. However the combined effect is very uncertain when surfac-
tant and polymer are injected simultaneously due to undesired phase
separation. The most used conventional polymer partially hydrolyzed
polyacrylamide (HPAM) undergoes mechanical degradation at higher
shear rates. So, these uncertainties can be eliminated by the application
of polymeric surfactants in EOR processes. Fig. 7(a–c) shows the var-
iation of apparent viscosity with shear for PMES surfactant based na-
noemulsions at varying PMES concentrations and temperatures (30 °C,
50 °C and 70 °C). A drop in viscosity is observed, i.e shear thinning or
pseudo-plastic behavior with increase in shear rate up to 100 s−1 and
with further increase in shear rate nanoemulsion showed an increase in
viscosity, exhibiting shear thickening or dilatant behavior. The shear
thinning behavior at low shear rate can be due to the minimal inter-
action of the emulsion droplets with larger polymeric part. The
streamline arrangement of the emulsion droplets and their disen-
tanglement with rise in shear rate can also lead to such a behavior. At
high shear rates the dominance of polymeric part associated with PMES
surfactant leads to the thickening of the nanoemulsion and rise in
viscosity. Different studies have been proposed for the dilatant behavior
at high shear rates such ODT (order disorder theory), jamming transi-
tion theory and hydrodynamic lubrication theory. As per ODT theory
the emulsion droplets undergo a transformation from ordered to dis-
ordered state with application of shear rate. The disordered condition of
the emulsion droplets leads to increase in their randomness and faster
coalescence of the emulsion droplets that causes thickening of the

-20
(a) PMES (b) silica NPs

-30
zeta potential (mV)
zeta potential (mV)

-25

-35

-30

-40

0.5 1.0 1.5 2.0 0.0 0.2 0.4 0.6 0.8 1.0
PMES (wt%) silica NPs (wt%)
Fig. 5. Effect of (a) PMES and (b) Silica NPs on zeta potential (mV) of PMES based nanoemulsions at 30 °C.

270
N. Kumar, A. Mandal European Polymer Journal 109 (2018) 265–276

Fig. 6. Cryo-TEM micrograph of nanoemulsion formed from PMES (a) without and (b) with silica NPs. The network structure of PMES and its interaction with oil
droplets can be depicted from the micrographs.

40
(a) 0.5 wt. % (b) 0.5 wt. %
28
1.0 wt. % 1.0 wt. %
35 1.5 wt. %
1.5 wt. %
2.0 wt. % 24 2.0 wt. %
30
20
viscosity (mPa-s)
viscosity (mPa-s)

25
16
20

12
15

8
10

4
5

0 0
1 10 100
1 10 100
shear rate (1/s) shear rate (1/s)

(c) 0.5 wt. %

20 1.0 wt. %
1.5 wt. %
2.0 wt. %
16
viscosity (mPa-s)

12

0
1 10 100
shear rate (1/s)
Fig. 7. Apparent viscosity curves for PMES based nanoemulsions at (a) 30 °C (b) 50 °C and (c) 70 °C temperature. A pseudo-plastic behavior with dilatant nature at
high shear rate is observed.

emulsions [43]. According to jamming transition theory dilatant be-
havior at high shear rate is due to increase in frictional contact of the
emulsion droplets [44]. Hydrodynamic lubrication theory states that
when shear rate surpasses the critical value, formation of hydro-clusters
occurs in suspensions that causes an increase in viscosity [45]. The
shear thickening nature at high shear rates is beneficial during injection
of the displacing fluid (nanoemulsion slug) at high injection pressures.
The mobility ratio of the nanoemulsion at high injection rate can be
highly controlled due to high viscosity and the channeling of injected
fluid may also be reduced. It may be seen in Fig. 7(a–c) that, an increase
in viscosity was observed from 19 to 35 mPa-s when PMES surfactant
concentration rose from 0.5 to 2.0 wt% at 30 °C. The rise in viscosity is

271
N. Kumar, A. Mandal European Polymer Journal 109 (2018) 265–276

due to surge in the effective fractional volume of PMES surfactant Table 2

which forms a double layer around the nanoemulsion droplets [46]. Estimation of Arrhenius parameters for nanoemulsion samples.
Another reason for increase of viscosity can be due to increase in Arrhenius parameters Shear rate = 100 1/sec
branching or the network structure of polymer that increases with in-
crease in PMES concentration. A rise in PMES surfactant concentration 0.5 wt% 1.0 wt% 1.5 wt% 2.0 wt%
causes an increase in molecular weight (or increase in monomer units)
Activation energy, Ea (KJ/mole) 10.34844 11.97964 13.72392 13.90433
which in turn increases their entanglement and intermolecular inter- Adj. R-Square (R2) 0.9912 0.9882 0.9952 0.9924
actions of the polymer chains/network structure with oil droplets of the
nanoemulsions.
A drop in viscosity of the prepared nanoemulsions with increase in viscosity.
temperature are shown in Fig. 7(a–c). The effect of temperature on Since PMES surfactant based nanoemulsion showed a drop in visc-
viscosity can be explained by Arrhenius Eq. (7) osity in low shear rate region and a rise in viscosity at high shear rate
Ea region, therefore the flow behavior estimation by power law model
μ (T ) = Ae RT (7) parameters calculation as per Eq. (3) can only be done in low shear rate
region (0–100 s−1). Table 3 presents the values for flow behavior index
where μ – the apparent viscosity in mPa-s of prepared nanoemulsions, A
(n) and consistency index (k) for the prepared nanoemulsion samples at
– a constant, Ea – the activation energy (kJ/mole), R – universal gas
different PMES surfactant concentrations and temperatures (30 °C,
constant (8.314 J/mol-K) and T – absolute temperature (K). As per
50 °C and 70 °C). As seen from the Table 3 that the value of n for each
Arrhenius relation viscosity has an inverse relationship with tempera-
nanoemulsion sample is less than 1 (n < 1), i.e. formulated nanoe-
ture [47]. The synthesized PMES surfactant used for nanoemulsion
mulsions show Non-Newtonian behavior or shear thinning behavior
preparation is greatly influenced with increase in temperature due to its
[51]. An increase in value of n is observed with rise in PMES con-
anionic nature. At high temperature the non-polar tail of PMES gets
centration denoting an enhancement in shear thinning nature of the
destroyed which leads to decrease in viscosity because of unfavorable
nanoemulsions at low shear rates. The drop in viscosity may be en-
micellization [48]. Viscosity decreased from 19 mPa-s at 30 °C to
dorsed due to the emulsion droplets alignment along the flow stream-
10 mPa-s at 70 °C for 0.5 wt% of PMES based nanoemulsion. Viscosity
line and detachment of the droplets with increase of shear rate [52].
reduction can also be attributed to collapse of the polymeric network
Enhancement in pseudo-plastic nature of nanoemulsions improves the
structure of PMES surfactant at high temperature [49]. Another reason
flow ability, hence the injectivity during EOR process [53]. Similar
for decrease in viscosity with rise in temperature may be due to the
behavior is observed for consistency index. An enhancement in visc-
enhanced thermal energy that causes an increase in the vibration of oil
osity is observed with increase of PMES surfactant concentration as
droplets. Enhancement in the vibration leads to reduction in the in-
indicated by rise in value of k. With rise in temperature a drop in value
termolecular interactions with breakage of the polymer branch, oil
of n and k is observed denoting an improvement in shear thinning be-
droplets move faster in Brownian motion in the continuous medium
havior and decrease in viscosity. Thus, denoting an improved rheolo-
which makes nanoemulsions easily flowable [35]. The loose packing of
gical property of the nanoemulsions.
the PMES surfactant molecules with oil droplet s may also contribute in
viscosity reduction by creating more space that allows the surfactant
molecules to slip through each other. Even though, viscosity decreased
3.4.2. Effect of salt concentration on viscosity
with rise in temperature but still the viscosity of nanoemulsions are
The viscosity of the prepared PMES based nanoemulsions may be
more than the conventional surfactant solutions. Fig. 8 presents the plot
affected by the salt present in the reservoir water during EOR process.
of viscosity (ln μ ) and the inverse of temperature (1/T) of the for-
Thus effect of salinity on the viscosity was carried out. Fig. 9 shows the
mulated PMES based nanoemulsion samples using Eq. (7). The graph of
plot of viscosity versus temperature at different salinity for nanoemul-
viscosity dependence on temperature at 100 s−1 with a slope of Ea/R is
sion sample with 1.5 wt% PMES surfactant at shear rate between 15 s−1
almost a straight line. Table 2 presents the calculated values of acti-
(in-situ reservoir condition during EOR). Salt (NaCl) concentration was
vation energies of nanoemulsion samples with fitting parameter (R2).
varied from 0.25 to 1.00 wt%. A sudden drop in viscosity is observed
The activation energy (Ea) increased with increase in PMES con-
from 20.30 mPa-s at 0.00 wt% NaCl to 12.32 mPa-s at 0.25 wt% NaCl at
centration indicating a greater impact of temperature on viscosity [50].
30 °C. With further increase in NaCl concentration from 0.25 wt% to
When fitted the R2 values for nanoemulsions samples reveal a good
1.00 wt% viscosity further decreased from 12.32 mPa-s to 4.89 mPa-s at
agreement with Arrhenius Eq. (7). Thus, the viscous flow activation
30 °C. The influence of salt on viscosity depends not on ionic species
energy decreases with rise in temperature hence a drop in apparent
nature but on the strength of the ion. Electrolyte addition to polymeric
2.0 surfactant (PMES) causes collapse of electrical double layer and loss of
0.5 wt. % 1.0 wt. % polymeric structure (network or branching) which results in decrease of
1.5 wt. % 2.0 wt. %
viscosity. ‘Salting out’ effect by salt addition to PMES based nanoe-
1.5 mulsions may be the reason for decrease of viscosity as it weakens the
polymeric structure and their inter-molecular interactions [54]. Intra-
macro ion electrostatic repulsion, the polymer backbone may also be
affected by salt addition that causes reduction of polymer molecules
1.0
sizes that leads to their less interaction and drop in viscosity [55]. The
ln

influence of temperature on viscosity was much more as compared to

salt addition. Viscosity decreased from 12.32 mPa-s at 30 °C to
0.5
5.91 mPa-s at 70 °C for nanoemulsion sample with 0.25 wt% NaCl. Even
though there was a drop in viscosity values with salinity and tem-
perature but the viscosity values were far more than surfactant solution
0.0
0.0029 0.0030 0.0031 0.0032 0.0033 or conventional emulsions suggesting a stable nanoemulsion formation,
-1
Temperature, 1/T (K ) as high viscosity is a main factor of emulsion stability as it inhibits
coalescence of oil droplets [56]. Thus, from above results salt addition
Fig. 8. Change of ln μ with inverse of temperature for nanoemulsion samples at leads to reduction in viscosity and it is effected by rise in temperature.
different wt% of PMES at 100 s−1 shear rate.

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N. Kumar, A. Mandal European Polymer Journal 109 (2018) 265–276

Table 3
Rheological parameters determination for PMES surfactant based nanoemulsion.
Temp (°C) 0.50 wt% 1.00 wt% 1.50 wt% 2.00 wt%

n n n
n k (Pa s ) n k (Pa s ) n k (Pa s ) n k (Pa sn)

30 0.747 0.013 0.776 0.019 0.783 0.026 0.811 0.028

50 0.741 0.012 0.769 0.017 0.773 0.025 0.781 0.034
70 0.734 0.007 0.755 0.008 0.760 0.011 0.779 0.013

0.00 wt.% NaCl structure is formed when these suspended polymer molecules get at-
20 0.25 wt.% NaCl
tached to silica NPs surface [58]. The flocculated structure doesn’t ea-
0.50 wt.% NaCl
0.75 wt.% NaCl sily breaks and remains stable at high shear rate that leads to an in-
1.00 wt.% NaCl
Viscosity (mPa-s)

crease in viscosity of the nanoemulsion.

10 3.5. Viscoelasticity

Dynamic moduli (G′ and G″) were determined by oscillatory ex-

0
30 50
Temperature ( C)
o ulus (G’) and loss or viscous modulus (G”) oscillatory measurement was
Fig. 9. Apparent viscosity curves for 1.5 wt% PMES based nanoemulsion with
varying NaCl concentration at 30 °C, 50 °C and 70 °C temperatures.
3.4.3. Effect of silica nanoparticles on viscosity
Recently petroleum industries have started using nanoparticles to
improve the rheological properties of the slugs used during EOR pro-
cess. In view of that, effect of nanoparticles on the viscosity of PMES
surfactant based nanoemulsion (0.5 wt% PMES) was studied at 30 °C.
Fig. 10 shows the variation of viscosity with varying SiO2 NPs con-
centration (0.30–1.00 wt%). Inclusion of NPs to nanoemulsion sample
increased the viscosity with display of similar fluid behavior as dis-
cussed before (shear thinning and shear thickening). Viscosity value
increase from 19 mPa-s at 0.00 wt% silica NPs to 28 mPa-s at 1.00 wt%
silica NPs. The silica NPs added to the nanoemulsion gets adsorbed on
the polymeric chains of PMES and act as a cross linker between them,
which results in the formation of micellar aggregates that causes visc-
osity to increase [57]. The phenomenon of silica NPs adsorption could
be explained by flocculated structure formation of silica NPs and PMES
surfactant in the nanoemulsion. The silica NPs surface and polymer
chain remain in direct contact during the adsorption process with rest
of the polymer molecule suspended in the continuous medium away
from NPs surface. A three dimensional network structure or flocculated
periment conducted on nanoemulsion sample with 1.5 wt% of PMES
surfactant. Under deformation of fluid both elastic and viscous behavior
is necessary for determination of dynamic modulus. For the in-
dependent behavior of complex modulus (G*), storage or elastic mod-
70
carried out in linear viscoelastic region. The variation of dynamic
moduli for nanoemulsion sample as a function of angular frequency at
30 °C and 70 °C is shown in Fig. 11. The viscoelastic property of na-
noemulsion extremely relies on PMES surfactant concentration. As de-
picted from (Fig. 11) both G’ and G” increase with increase in angular
frequency suggesting prepared nanoemulsion bear viscoelastic beha-
vior. The dominance of viscous behavior of nanoemulsion (G’ < G”) in
low angular frequency region recommends the build-up of network
structure which is responsible for degradation of elastic nature. Both
elastic and viscous moduli intersect each other at a point after certain
increase of angular frequency. The intersection point is known as cross
over point or specific frequency (SF). With increase in temperature
(30–70 °C) SF moved downwards and shifted towards right i.e. at larger
frequency value; indicating an increase in dominance of viscous mod-
ulus or viscous nature of nanoemulsions. This shift or reduction in
dynamic moduli with frequency is due to the same reason as viscosity
reduces. With temperature the mobility of PMES surfactant molecules
increase that causes a reduction in relaxation time, hence makes na-
noemulsions more flowable [59]. A transition takes place at SF and
G’ > G” denoting the dominance of elastic behavior over viscous be-
havior. For frequency lower to SF, G″ controls the fluid behavior and for
frequency higher to SF G′ guided the fluid behavior. Therefore, in high-
frequency region after SF solid-like or elastic nature of nanoemulsion is
depicted with G″ values becoming almost constant demonstrating

30 o
0.0 wt. % G' G'' at 30 C
0.3 wt. % o
G' G'' at 70 C
0.5 wt. % 10
Dynamic moduli G', G'' (Pa)

25
1.0 wt. %
viscosity (mPa-s)

20
1
15

10
0.1

0 0.01
1 10 100 1E-3 0.01 0.1 1 10 100
shear rate (1/s) Angular frequency (rad/sec)
Fig. 10. Apparent viscosity curves at 30 °C with different silica NPs con- Fig. 11. Viscoelastic curves (G’ and G”) of nanoemulsion sample with 1.5 wt%
centrations for nanoemulsion sample with 0.5 wt% PMES. of PMES at 30 °C and 70 °C temperatures.

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N. Kumar, A. Mandal European Polymer Journal 109 (2018) 265–276

100 100
(a) (b)
Dynamic moduli G", G' (Pa) 10

10 1

Dynamic modulus (Pa)

0.1

1 0.01

1E-3

0.1 G' G" 0.00 wt.% NaCl

1E-4 G' G'' 0.00 wt. % of NaCl

G' G" 0.25 wt.% NaCl G' G'' 0.25 wt. % of NaCl

G' G" 0.50 wt.% NaCl 1E-5 G' G'' 0.50 wt. % of NaCl

G' G" 0.75 wt.% NaCl G' G'' 0.75 wt. % of NaCl

G' G" 1.00 wt.% NaCl G' G'' 1.00 wt. % of NaCl
0.01 1E-6
1E-3 0.01 0.1 1 10 100 1E-4 1E-3 0.01 0.1 1 10 100
Angular frequancy (rad/sec) Angular frequency (rad/sec)

Fig. 12. Influence of salinity on the viscoelastic (G’ and G”) property of nanoemulsion sample with 1.5 wt% of PMES at (a) 30 °C and (b) 70 °C.

Nanoemulsion formed from polymeric surfactant of viscoelastic char-

acteristic play an important role in enhanced oil recovery as they im-
100
prove the microscopic sweep efficiency [61]. The improvements in
Dynamic moduli G", G' (Pa)

microscopic sweep efficiency by nanoemulsion slug injection during

flooding could be endorsed to the unique characteristic of PMES sur-
10
factant. Earlier reports suggest polymers with viscoelastic property are
very efficient in displacing residual oil of different type without appli-
cation of high pressure gradient. Therefore, the formulated PMES based
1
nanoemulsion exhibits both viscous and elastic nature which is im-
G' G" 0.0wt% SiO2
portant for EOR application.
G' G" 0.1 wt% SiO2
0.1 G' G" 0.3 wt% SiO2
G' G" 0.5 wt% SiO2
3.6. Maxwell fitting
G' G" 1.0 wt% SiO2
0.01 The dynamic viscoelastic parameter (G’) for nanoemulsion sample
1E-3 0.01 0.1 1 10 100 with 1.5 wt% of PMES surfactant at varying salinity was fitted to
Angular frequancy (rad/sec) Maxwell’s mechanical model for viscoelastic material using Eq. (6).
Table 4 presents the fitting parameter, adjusted coefficient of de-
Fig. 13. Effect of silica NPs concentration on the viscoelastic (G’ and G”)
termination (R2) at 30 °C and 70 °C for nanoemulsion sample with dif-
property of nanoemulsion sample with 1.5 wt% of PMES at 30 °C.
ferent NaCl concentration. As seen from Table 4, with increase in NaCl
concentration an improvement in R2 values is observed indicating a
better injectivity of nanoemulsions. The effect of salt addition on the good agreement between experimental data and Maxwell model for the
viscoelastic property of prepared nanoemulsion was carried out with formulated nanoemulsions over the frequency range. With increase in
varying salt concentrations (0.25–1.00 wt% NaCl). Fig. 12(a, b) present salinity the disentanglement of the polymeric chain accelerates that
the plot for variation of G’ and G” with angular frequency at different reduces the deviations of G’ and a good fit is obtained with Maxwell
salinity. A decrease in G’ and G” is seen with increase in salinity. The model. With R2 value 0.990 and standard deviation of 0.323 for 0.75 wt
diminishing viscoelastic nature of nanoemulsion caused by salt addition % NaCl concentration at 30 °C denote a good fit of G’ to Maxwell model
may be due to breakdown of network structure or polymer branching suggesting the polymer chains act like random coils, which is the basic
because of the shielding effect of Na+ ion in polar group of PMES
surfactant which results in reduction of electrostatic double layer [60]. Table 4
The influence of temperature on nanoemulsion with salt addition as Maxwell’s fitting parameters: (R2) and standard deviation (SD) at 30 °C and
seen from Fig. 12(a, b) is similar to previous result for nanoemulsion 70 °C for nanoemulsion sample with different NaCl concentrations.
without salt. Both G’ and G” shift downwards with cross over point
Temperature (°C) NaCl (wt%) (R2) Standard deviation (SD)
displaced to lower frequency when temperature increased from 30 °C to
70 °C. Influence of silica NPs on viscoelastic property of PMES based 30 0.00 0.984 0.695
nanoemulsion sample is presented in Fig. 13 at 30 °C. At low frequency 0.25 0.991 0.513
0.50 0.990 0.511
G’ is less than G” (G” > G’) indicating viscous behavior and at high
0.75 0.990 0.323
frequency G’ is more than G” (G’ > G”) denoting elastic nature. With 1.00 0.988 0.297
increase in silica NPs concentration from 0.1 to 1.0 wt% both moduli
70 0.00 0.771 3.172
(G’ and G”) increase with SF moving downwards and shifting towards 0.25 0.530 3.211
right. A shift towards right or increase in angular frequency increases 0.50 0.979 0.306
the viscous regime. Therefore, addition of silica NPs to PMES based 0.75 0.986 0.139
nanoemulsion leads to an increase in frequency for viscous region. 1.00 0.995 0.088

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N. Kumar, A. Mandal European Polymer Journal 109 (2018) 265–276

100
100
(a) (b)
10

10 1
Dynamic moduli G", G' (Pa)

0.1

Dynamic moduli (Pa)

1 0.01

1E-3

0.1 1E-4

1E-5
G' G" 0.75 wt. % NaCl G' G'' 1.00 wt. % of NaCl
fit of G' fit of G'
0.01 1E-6
1E-3 0.01 0.1 1 10 100 1E-4 1E-3 0.01 0.1 1 10 100
Angular frequancy (rad/sec) Angular frequency (rad/sec)

Fig. 14. Maxwell model fit for G’ as a function of angular frequency for 1.5 wt% of PMES nanoemulsion sample with (a) 0.075 wt% NaCl at 30 °C and (b) 1.00 wt%
NaCl at 70 °C.

assumption for the application of Maxwell equation [59]. The fitting
plot of Maxwell model with experimental data for 0.75 wt% NaCl is
shown in Fig. 14(a). The solid lines in the plot represent the fitting data
for Maxwell equation. With further increase in temperature from 30 °C
to 70 °C, at low salinity PMES surfactant based nanoemulsion sample
show a wide deviation from the ideal Maxwell model (low R2 values
with high standard deviation is observed in Table 4. The deviation may
be due to increase in aggregation of PMES molecules at high tem-
perature. With further increase in NaCl concentration an improvement
in R2 values is seen and a downward shift of the cross over point occurs
due to the unfavorable growth of micelles in polymeric surfactant
which reduces the relaxation time. At high salinity (1.00 wt% NaCl),
the micelle starts to reduce and polymer chains begins to behave as
random coils as in the case for 30 °C and a good Maxwell model fit is
obtained (R2 = 0.995). Fig. 14(b) presents the Maxwell model fit for
1.00 wt% NaCl nanoemulsion sample at 70 °C. For a strong fit of Max-
well model as illustrated by Goodwin, the emulsion should be free from
aggregation and polymer chains must behave as random-coils [62].
structure breakdown that causes a reduction in viscoelastic property of
nanoemulsion. An increase in temperature moves SF downwards with a
shift towards right denoting an increase in dominance of viscous nature
of nanoemulsions which makes them more flowable. Inclusion of silica
NPs enhances the viscoelastic property of nanoemulsion with an in-
crease in G’ and G” values leading to a rise in viscous region on angular
frequency plot. A good fit of experimental data to Maxwell model
suggest excellent viscoelastic behavior of PMES surfactant based na-
noemulsions. The unique physicochemical behavior of the nanoemul-
sions are highly encouraging for their application in enhanced oil re-
covery.
Acknowledgement
Authors gratefully acknowledge Central Research Facility (CRF) for
laboratory facilities and Department of Petroleum Engineering, Indian
Institute of Technology (Indian School of Mines), Dhanbad, India for
the financial assistance.

Appendix A. Supplementary material

4. Conclusion
A novel synthesized polymeric surfactant was used for preparation
of oil-water nanoemulsions by ultrasonication method. The formulated
nanoemulsions with sizes of the dispersed oil droplets less than 200 nm,
show long-term kinetic stability. Enhancement of nanoemulsion stabi-
lity was observed by incorporation of silica NPs with zeta potential
values above −30 mV. Analysis of cryo-TEM micrographs unveils the
stabilization mechanism of nanoemulsions by interaction of oil droplets
with NPs and the network structure of PMES surfactant. Exceptional
viscosity values with both pseudo-plastic and dilatant behavior with
increase of shear rate under varying PMES concentration, salinity and
temperature suggests improvement in mobility control of the nanoe-
mulsions with enhancement in displacement efficiency during nanoe-
mulsion injection in enhanced oil recovery. An inclusive study for the
effect of temperature and salinity on viscosity was completed for the
compatibility and stability analysis of the prepared nanoemulsion at
reservoir conditions. Viscoelastic property measurement of PMES sur-
factant based nanoemulsions by oscillatory method showed the dom-
inance of viscous behavior before SF in low frequency region but after
SF in high frequency region elastic behavior is the guiding factor.
Increase in salinity leads to decrease of G’ and G” because of network
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.eurpolymj.2018.09.058.
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