DOI: 10.1002/ente.

201600036

Nanostructured Particles for Controlled Polymer Release

in Enhanced Oil Recovery
Yousef Tamsilian,[a] Ahmad Ramazani S. A.,*[a] Masoom Shaban,[a] Shahab Ayatollahi,[a]
Jose C. de la Cal,[b] James J. Sheng,[c] and Radmila Tomovska*[b, d]
With the decline in oil discoveries over recent decades, it is
believed that enhanced oil recovery (EOR) technologies will
play a key role to meet energy demand in the coming years.
Polymer flooding is used commonly worldwide as an EOR
process. In this work, we propose the synthesis of protected
polyacrylamide (PAM) nanoparticles (PPNs) with a hydrophobic polystyrene (PSt) shell by one-pot two-step inverse
emulsion polymerization, in which the PSt shell was created
by surface polymerization. The shell protects the active PAM
chains from premature degradation caused by the harsh environment in the reservoirs, controls the release of the chains
as rheological modifiers, and additionally, it provides the
chains with prolonged stability. The time-dependent release

of the PPNs promotes the effectiveness of the PPNs as viscosity modifiers, as the maximum viscosity enhancement is
achieved at longer residence times in the reservoirs. This can
be up to 30 days, and the released polymer maintained its activity. Under conditions of high salinity (total dissolved
solids = 178 082 mg L@1), temperatures up to 90 8C, and shear
rates up to 1000 s@1, PPNs have shown superior properties,
such as elastic modulus, shear rate behavior, viscosity loss,
and sand adsorption over PAM, whereas the areal sweep efficiency of PPNs is similar to that of PAM and higher than
that of conventional water flooding. All of this makes PPNs
promising candidates for polymer-enhanced oil recovery.

Introduction
As alternative energy sources have not yet achieved the necessary level to meet the worldQs energy demand, it has
become increasingly important to find an efficient way to enhance the recovery of the oil that remains in oil reservoirs.
Water flooding is one of the methods used most widely for
oil recovery; however, its sweep efficiency is not very high
because of water channeling phenomena. As a first alternative, polymer flooding has been used to overcome the poor
efficiency of water flooding and, because of the increased
viscosity of the aqueous phase,[1, 2] polymer flooding yields
a considerably enhanced oil recovery (EOR).[3, 4] Aqueous
solutions of high-molecular-weight polyacrylamide (PAM)
and its partially hydrolyzed form (HPAM; > 1 X 106 g mol@1)
as thickening agents are the most widely used displacing
fluids to modify the mobility ratio of water to oil because of
the viscosity enhancement of the injected water.[5] This viscosity enhancement results from the high molecular weights
of the polymers and repulsion between the negative charges
along the polymer chains that causes their expansion and increases their hydrodynamic volume in water solution. Therefore, these solutions can push oil to the production wells
before the water channeling phenomenon occurs in the underground reservoirs.[6] However, there are many limitations
of the use of PAM and HPAM in conventional polymer
flooding processes, such as the chemical, thermal, mechanical, shearing, and biological degradation of polymer chains
during the EOR process.[7, 8] The most important polymer
degradation seems to be the chemical one. As there are different types of salts in formation water in oil reservoirs, the
Energy Technol. 2016, 4, 1035 1046

iondipole interaction between the salt cations and the

oxygen atoms of PAM leads to the chemical degradation of
polymer chains and a decrease of the polymer solution viscosity.[9, 10] The interactions of the cations (calcium or magnesium) present in the reservoir brine with the polymer result
in a phase change and precipitation of the polymer chains
(cation shielding effect). Additionally, there is significant
shearing and heating in the near-wellbore and through the
reservoir that may damage the polymer chains.[11] Mechanical
degradation of acrylamide-based polymers caused by flow
[a] Y. Tamsilian, Prof. A. R. S. A., M. Shaban, Prof. S. Ayatollahi
Institute for Nanoscience and Nanotechnology (INST)
Sharif University of Technology
Azadi Ave., Tehran (Iran)
E-mail: ramazani@sharif.edu
[b] Prof. J. C. de la Cal, Dr. R. Tomovska
POLYMAT and Departamento de Qu&mica Aplicada
Facultad de Ciencias Qu&micas
University of the Basque Country UPV/EHU,
Avda. Tolosa 72 Donostia-San Sebasti#n 20018 (Spain)
E-mail: radmila.tomovska@ehu.es
[c] Prof. J. J. Sheng
Bob. L. Herd Department of Petroleum Engineering
Texas Tech University
Box 43111 Lubbock, TX 79409-3111 (USA)
[d] Dr. R. Tomovska
Ikerbascue, Basque Foundation for Science
Maria Diaz de Haro 3, Bilbao 48013 (Spain)
Supporting information and the ORCID identification number(s) for the
author(s) of this article can be found under http://dx.doi.org/10.1002/
ente.201600036.

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1035

through pumps, chokes, and valves has been reported recently.[12, 13] All these effects cause a decrease in the PAM and
HPAM viscosity-enhancement function.
To improve the corresponding polymer solution properties
and to increase the EOR performance, numerous studies associated with attempts to alter the chemical structure of
PAM for polymer flooding process have been undertaken.[1418] These attempts are summarized as a replacement of
acrylamide (AM) moieties with more resistant non-ionic
monomers (for example N-vinyl pyrrolidone; NVP)[14] or
more resistant anionic monomers (e.g., 2-acrylamido-2-methylpropane sulfonic acid; AMPS)[15] that suppress cation
shielding and the precipitation of acrylate moieties in the
polymer chains; the synthesis of comb-polymers to create
steric hindrance between polymer chains and prevent the full
collapse of the hydrodynamic radius (e.g., a polypropylene-gpolyethylene comb-type copolymer);[16] the synthesis of hydrophobically associated polymers for intermolecular association and subsequent viscosity enhancement;[17] and the copolymerization of AM monomers with a thermo-sensitive comonomer to increase the viscosity of the aqueous solution at
high temperatures and salinities.[18] Clearly, the reported efforts are focused on the development of new chemical structures of polymers for EOR applications. On one hand, this
results in the development of complicated synthesis procedures that are difficult to scale up and, on the other hand,
the good performance of the PAM structures already used
widely in polymer flooding on a commercial level can hardly
be overcome.
In this work, we report on a diverse approach that allows
us to take advantage of the good performance of PAM in
flooding processes and simultaneously to overcome the main
drawback of limited stability toward the harsh environment
in the reservoirs. A new method to synthesize coreshell-protected PAM nanostructures (PPNs) by superficial copolymerization with styrene has been developed based on already patented preliminary efforts.[19, 20] Following this procedure,
a polystyrene-rich copolymer forms a protective nanolayer
shell around the PAM chains. This new synthetic method has
been applied to obtain PPNs with different copolymer shell
thicknesses. The stability against degradation and the performance of the nanostructures as a flooding medium in
EOR process were investigated in a simulated harsh environment (high temperature, salinity, and shearing). The efficiency of the coreshell nanostructures was compared to that of
the unprotected PAM polymer.
The advantages of these structures as a medium for polymer flooding are clear. On one hand, the hydrophobic shell
protects the PAM active polymer chains from premature
degradation during the injection and flow processes until
they reach the target. After the contact with oil phase that
dissolves the polystyrene (PSt) shell, a triggered release of
PAM chains, which act as rheological modifiers, occurs. Finally, as PPNs are water insoluble, their aqueous dispersions
are injected into the reservoirs with a significantly lower viscosity (close to the viscosity of water) than the polymer solution used commonly as a flooding medium. This allows the
Energy Technol. 2016, 4, 1035 1046

use of water-flooding equipment for their injection into reservoirs, which ensures a much lower cost than that of traditional polymer flooding.

Results and Discussion

Characterization of the synthesized PPNs
Inverse emulsion polymerization performed in cyclohexane
was used for the two-step synthesis of the coreshell nanostructures. In the first step, AM aqueous solution was dispersed in cyclohexane by using Span20/Span80 emulsifier
and polymerized with ammonium persulfate (APS) initiator
to reach an approximate conversion of 92 %, measured by
using 1H NMR spectroscopy. In the second step, styrene monomer and the aqueous solution of the APS initiator were
added simultaneously to the preheated system (60 8C) to
form the hydrophobic shell. The presence of AM monomer
was expected to induce copolymerization. Under such conditions, APS aqueous droplets are expected to coalesce with
the large hydrophilic PAM particles, and polymerization will
likely continue at the particlecyclohexane interface by the
addition of styrene units to the growing PAM chains. The hydrophobic shell is formed around the PAM particles by further interface polymerization. The high water solubility of
APS ensures preferable contact with PAM particles over styrene homopolymerization in cyclohexane. The polystyrene
chains not copolymerized with PAM (homopolymer) remained dissolved in cyclohexane or were adsorbed at the
particle surface. Homopolymerized polystyrene chains were
eliminated during the recovery and purification of the PPNs.
No presence of residual monomers was found by 1H NMR
spectroscopy of the final PPNs dispersion, which indicates
full monomer conversion.
A representative 1H NMR spectrum of the prepared PPNs
is shown in Figure 1. In this spectrum, two regions can be distinguished clearly. The first one (d = 12 ppm) and the
second one (d = 78 ppm) were assigned to the characteristic
peaks of PAM (from the vinyl group) and polystyrene (aromatic group), respectively. This confirms the presence of
PAM and polystyrene in the PPNs, which demonstrates that
the copolymerization proceeded successfully as homopolymerized polystyrene chains were removed thoroughly.
The average particle diameters and particle size distributions measured by using dynamic light scattering (DLS) of
PAM, LT-PPN (prepared with a low amount of styrene and
considered to have a low shell thickness), and HT-PPN (prepared with a high amount of styrene and considered to have
a high shell thickness) are shown in Figure 2. Both PPNs
have a quite similar average particle size with broader size
distributions and a slightly larger size than the PAM nanoparticles (53 nm). If we bear in mind that the average pore
size in porous media in the reservoirs is in the range of 0.5
50 mm and that the synthesized particles should normally be
approximately one order of magnitude lower to prevent
plugging and to spread out through the porous media, it is
clear that these PPNs are well suited for EOR application.[3]

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Figure 1. 1H NMR spectrum of PPNs.

Figure 2. Particle size distribution of a) LT-PPN, b) HT-PPN, and c) PAM samples (measured by DLS).

We fitted the small-angle X-ray (SAXS) results with the

equivalent hard sphere radius model developed by Chu
et al.[21] for coreshell structures to determine the size of the
core and shells. The observed SAXS profiles of LT-PPN and
HT-PPN and the detailed determination method are presented in the Supporting Information. From these results, the
core diameter and the shell thickness were determined
(Table 1). The core diameters of both PPN structures are
very similar, whereas the shell thickness of HT-PPN is more
than double of that of LT-PPN, as expected (Table 1).

Table 1. Core diameter and shell thickness of LT-PPN and HT-PPN.

Sample

dDLS [nm]

dcore [nm]

Thshell [nm]

dcore/dout

LT-PPN
HT-PPN

72.5
78.4

61.4 : 1
61.6 : 1

10.83 : 1
23.95 : 1

0.85 : 0.5
0.72 : 0.5

0.0027
0.0065

dDLS : the hydrodynamic diameter measured by DLS; dcore : the diameter of

the core section; Thshell : the thickness of the shell section; dcore/dout : core
diameter/outer diameter; p: standard deviation

The differential scanning calorimetry (DSC) results and

glass transition temperature (Tg) of the PPNs sample are
shown in Figure 3. It was determined that the Tg of neat
polystyrene occurs in the range of 98.9104.4 8C, whereas
that of neat PAM is at around 206 8C. In the hybrid PPNs,
two peaks appear (at 113 and 195.5 8C), which reveals two
Energy Technol. 2016, 4, 1035 1046

Figure 3. DSC curve of PPNs.

separate phases that come from the constituents. Strong interactions between the two polymers are clear from the
slight shifts of the Tg values noted for the PPNs with respect
to the neat polymers and by the constricted glass transition
regions.

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Table 2. Viscosity variation of PPN samples dissolved in pure water.

Time interval [day]

1
10
20
30

Kinematic viscosity [mm2 s@1]

30 8C
LT-PPN0.2
LT-PPN0.3

HT-PPN0.2

HT-PPN0.3

60 8C
LT-PPN0.2

LT-PPN0.3

HT-PPN0.2

HT-PPN0.3

1.01
1.00
0.98
1.02

1.00
1.03
0.99
1.05

1.09
1.06
1.01
1.01

0.85
0.79
0.83
0.81

0.89
0.78
0.89
0.80

0.84
0.84
0.81
0.80

0.90
0.77
0.84
0.87

1.11
1.07
1.08
1.09

Release and stability behavior of PPNs

Four different PPN samples dispersed in water were investigated: LT-PPN0.2, LT-PPN0.3, HT-PPN0.2 and HT-PPN0.3
(where the number denote the concentration of PPN in
aqueous dispersions, wt %). To determine the physical stability of PPNs in water, the kinematic viscosity of their aqueous
dispersions was followed over 30 days at 30 and 60 8C, and
the results are presented in Table 2. These dispersions have
viscosities of around 1 mm2 s@1, slightly higher than the viscosity of pure water (0.8 and 0.475 mm2 s@1 at 30 and 60 8C,
respectively)[22] and much lower than that of 0.2 wt % PAM
aqueous solution (18 mm2 s@1). These values were constant
with time at the investigated temperatures. This reveals that
no release of the PAM in pure water happened, which confirms that the PAM chains are really encapsulated within the
protective hydrophobic polystyrene shell that is completely
stable in water. This means that use of these low-viscosity
dispersions of highly stable PPNs may be highly advantageous compared to that of high-viscosity PAM solutions in
polymer flooding.
To determine the release behavior of the PPNs, xylene was
employed as a degassed synthetic oil phase to dissolve the
hydrophobic nanolayer and release the poly(acrylamide-costyrene) [Poly(AM-co-St)] chains (dissolution test). The
time-dependent release behavior of the PPNs samples is
shown in Figure 4 as an augmentation of the solution viscosity by the released Poly(AM-co-St) chains, calculated from
the viscosity of the neat PAM solution with the same concentration. The increase of the viscosity of the aqueous phase is
proportional to the amount of released Poly(AM-co-St)

Figure 4. Release of the PPNs samples over time at 25 8C.

Energy Technol. 2016, 4, 1035 1046

chains. It is clear that the Poly(AM-co-St) chains were released in 1518 h, which depends on the shell thickness and
concentration (Figure 4). The samples with thicker shells released & 10 % less, whereas more concentrated dispersions
released a slightly higher amount of Poly(AM-co-St). Notably, the maximum release of the Poly(AM-co-St) chains was
below 100 % at room temperature, likely because of the incomplete removal of the polystyrene shell. On one hand,
these results indicate that by controlling the shell thickness
and the PPNs content, the release time can be set carefully
according to the necessity and depth of different reservoirs.
However, this behavior allows the introduction of PPNs dispersions into the deeper areas of reservoirs, in which the release of Poly(AM-co-St) allows the water-pushing phase to
become more viscous to displace the remaining oil.
The dissolution test was performed at 30, 60, and 90 8C
using synthetic seawater with total dissolved solids (TDS) of
178,082 mg L@1 (Table S1) to study the effect of temperature
on the release of the Poly(AM-co-St) chains (Figure 5).
The results, presented in Figure 5 as the change in the kinematic viscosity with time at different temperatures, reveal
that PPNs release Poly(AM-co-St) in three different behavior regions: 1) at the initial release time (ti), the coreshell
dispersion had a low viscosity (nmin); 2) at an increased exposure time, the viscosity was enhanced because of polystyrene
dissolution in the oil phase, which reached the maximum
value (nmax) at the critical time (tmax); and 3) after the
Poly(AM-co-St) discharge was complete, the viscosity
became stable. This means that the release of the Poly(AMco-St) chains starts after contact with the oil phase, which is
necessary to dissolve the shell, and reaches its maximum
values after certain period of time, tmax. This critical time depends on temperature, shell thickness, and PPNs concentration in the dispersion. The influence of the PPNs shell thickness is evidenced by a comparison of Figure 5 a and b. nmax
and the release slope between nmin and nmax decrease with increased shell thickness at a constant temperature and concentration, which indicates a decrease of the rate of
Poly(AM-co-St) release because of the increase of polystyrene dissolution resistance to the oil phase. A comparison of
Figure 5 a and c for low shell thickness and Figure 5 b and d
for high shell thickness shows that the effect of increased
PPN concentration is clear: it induced an increase of nmax
and the slope because of the increased number of active
polymer chains. Finally, the temperature increase induced
a higher rate of Poly(AM-co-St) release and a higher nmax

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1038

Figure 5. Time-dependent kinematic viscosity of a) LT-PPN0.2, b) HT-PPN0.2, c) LT-PPN0.3, and d) HT-PPN0.3 at 30, 60, and 90 8C (TDS = 178 082 mg L@1).

was achieved, attributed to improved polystyrene dissolution

in the oil phase and an improved diffusion of Poly(AM-coSt) chains. This viscosity increase at higher temperatures may
also be the effect of copolymer structure. It has been observed previously that the presence of hydrophobic moieties
in HPAM chains induced their self-assembly at increased
temperature,[23, 24] which likely enhances macroscopic viscosity.
The PAM aqueous solution maintained a high viscosity for
30 days at 30 and 60 8C (18.43 and 17.54 mm2 s@1, respectively), however this value decreased significantly at 90 8C
(9.65 mm2 s@1), likely because of the ionic bridge that ultimately resulted in precipitation because divalent cations
have a much stronger effect than monovalent cations.[7, 8, 2528]
The higher stability of the released Poly(AM-co-St) is because of the PSt chains that likely improve the thermal stability of the PAM chains.[29]
To determine the thermal stability of the released
Poly(AM-co-St) after complete release, the viscosity of their
solutions was followed at different times (1, 15, and 30 days)
Energy Technol. 2016, 4, 1035 1046

and different temperatures (30, 60, and 90 8C) in the simulated seawater (TDS = 178 082 mg L@1), and the results are pre-

Table 3. Thermal stability of the PPN samples determined by viscosity

loss after complete Poly(AM-co-St) release at different times and temperatures (TDS = 178 082 mg L@1).

Sample

LT-PPN0.2

HT-PPN0.2

LT-PPN0.3

HT-PPN0.3

Residence time [day]

Kinematic viscosity [mm2 s@1]

30 8C
60 8C
90 8C

1
15
30
1
15
30
1
15
30
1
15
30

15.00
14.90
14.92
13.74
13.70
13.71
15.98
15.92
15.92
13.98
13.99
13.97

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15.40
15.38
15.32
14.54
14.50
14.31
16.10
15.98
15.81
15.00
14.76
14.23

16.20
15.76
14.89
14.64
14.23
14.01
17.75
16.54
15.14
16.04
15.87
15.32

1039

sented in Table 3. A minor viscosity reduction was noticed,

particularly at a higher temperature (90 8C) and after
a longer time (30 days). Until the target was reached, the
active polymer chains injected in the reservoirs in the form
of PPN dispersions are protected from the various processes
of degradation common for unprotected PAM chains.[2932]
After contact with the oil, PPNs start to release the active
Poly(AM-co-St) polymer that maintains its activity as a viscosity enhancer for at least 30 days at 90 8C after complete
release. In this period, released Poly(AM-co-St) pushes the
oil toward the production wells.
As there is a significant shear rate in the oil reservoirs
(except near the wellbore), it is important to obtain a polymer with as high a mechanical resistance as possible, which is
another way to prolong the viscosity-enhancing characteristics of the polymer for EOR application. To determine the
mechanical resistance, the PPN dispersions and PAM solutions were exposed to mechanical mixing in the range of
5002500 rpm at constant temperature (no contact with the
oil phase) for one week in synthetic seawater at 90 8C,
TDS = 178 082 mg L@1 and CPAM = 0.2 wt %, and the viscosity
loss was measured (Figure 6). Of the PPN samples, LT-

Figure 6. Viscosity loss of PPNs dispersions after mechanical mixing for one
week at different speeds in synthetic seawater (TDS = 178,082 mg L@1) at
90 8C; inset: Viscosity loss of PAM solution (CPAM = 0.2 wt %).

PPN0.2 has the maximum viscosity loss ( & 2.37 % at the

maximum mechanical mixing of 2500 rpm) attributed to
a low shell resistance and the disruption of the network.
However, the PAM sample underwent a much higher viscosity reduction (14.50 %, inset of Figure 6) with increased mechanical mixing because of the direct degradation of the unprotected chains. It seems that the polystyrene shell improved the stability of PAM chains against mechanical degradation.
The adsorption of polymers on sand surfaces can change
the flow properties of the porous media and reduce the
water permeability; thus, it is preferable to reduce or even
eliminate this possibility. To check the adsorption of PPNs
Energy Technol. 2016, 4, 1035 1046

and compare it with that of PAM, static adsorption tests in

brine solutions at 30, 60, and 90 8C on sandstone were performed. The comparative adsorption behavior of PPN and
PAM samples as a function of temperature is shown in
Table 4. The PPN samples were significantly less adsorbed
on silicate formations at all temperatures because of the decreased compatibility of the highly hydrophobic polystyrene
shell of the PPNs with the hydrophilic sand surface. The adsorption increased with temperature and polymer concentration because of the augmentation of the probability of interactions between the sand and polymer.

Table 4. Adsorption of PPN and PAM on sandstone at 30, 60, and 90 8C

(TDS = 178 082 mg L@1, CPAM = 0.2 wt %).

T [8C]

Adsorption [mg g@1]

LT-PPN0.2
HT-PPN0.2

LT-PPN0.3

HT-PPN0.3

PAM

30
60
90

0.24
0.26
0.27

0.32
0.43
0.64

0.37
0.50
0.69

0.9
1.1
1.7

0.27
0.30
0.33

According to the presented characterization, the LTPPN0.3 sample could be a good choice for the EOR process.
It seems that the high polymer concentration and low shell
thickness of LT-PPN0.3 leads to a fast response, maximum
viscosity enhancement and thermal stability, and very good
mechanical stability. To confirm that LT-PPN0.3 has an improved performance with respect to PAM, the elastic modulus and comparative steady-shear rheological behavior of LTPPN0.3 were determined.
The viscoelastic properties of the polymer used in the
flooding process influence the macroscopic and microscopic
sweep efficiency and oil recovery strongly. That is, under
high shear-rate conditions, the water-soluble high-molecularweight polymers have a shear-thinning viscosity reduction
because of the uncoiled and disentangled chains that are
aligned and elongated in the fluid-flow shear field. This
effect is decreased for polymers with a higher elastic modulus G that are more effective to displace residual oil in the
core with a pore configuration and important capillary forces
because of a higher flow resistance (pressure drop) through
porous media.[30, 31]
The variation of elastic and loss moduli as a function of
temperature for released Poly(AM-co-St) from LT-PPN0.3
and for PAM solutions is shown in Figure 7. The loss modulus (G) of the LT-PPN0.3 solution remains unchanged,
whereas the elastic modulus (G) increases with increasing
temperature to result in a higher difference at higher temperatures, which indicates that elastic behavior predominates in
the entire investigated temperature range. If we compare the
viscoelasticity of LT-PPN0.3 with that of unprotected PAM,
LT-PPN0.3 presents a highly superior behavior to unprotected PAM, for which G and G decrease with increasing temperature.
The comparative steady-shear rheological results of PAM
aqueous solutions and Poly(AM-co-St) released from LT-

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Oil displacement test for PPNs (flooding experiments)

Figure 7. Effect of heat treatment on the loss and elastic moduli of LT-PPN0.3
(TDS = 178 082 mg L@1, CPAM = 0.2 wt %).

The performance of LT-PPN0.3 in the flooding process was

tested and compared to that of water and PAM. Notably, the
comparison is not straightforward, as a slight modification in
the flooding procedure was introduced in the case of LTPPNs. That is, in the case of water and PAM aqueous solution flooding, the process was performed as usual with the
continuous introduction of 1 pore volume (PV) of the flooding fluid into the reservoir at a constant flow rate of
0.0008 mL min@1 and the displaced fluid was measured. As
the PPN dispersion needs to come into contact with the oil
phase to start to release the active polymer and needs at
least 17 h to release the Poly(AM-co-St) chains, the flooding
experiment with LT-PPN0.3 was changed. Although the
same amount of displacing fluid (1 PV) was used, it was introduced in discontinuous manner: after each 0.1 PV of PPN
dispersion was purged, it was left for 24 h to release. The distribution of the oil at the breakthrough time for the three
flooding types investigated (water, PAM, and PPNs) is
shown in Figure 9. In water flooding (Figure 9 b), water
makes some channels through the oil to reach the wells; nevertheless, in both polymer flooding processes, the solutions
push the oil to production wells with a thick frontier (Figure 10 c and e). The oil recovery results are presented in
Table 5. Clearly, the use of PPNs instead of PAM slightly in-

Table 5. Oil recovery obtained in flooding experiments with 1 mL water,

PAM solution (0.2 wt %) and PPNs dispersions (0.2 and 0.3 wt %).

Figure 8. Steady-shear rheology of PAM and LT-PPN0.3 in synthetic seawater

at 90 8C (TDS = 178 082 mg L@1, CPAM = 0.2 wt %).

PPN0.3 dispersions are presented in Figure 8. In the whole

shear rate region, the viscosity of the LT-PPN0.3 dispersion
is more than one order of magnitude higher than that of the
PAM solution. The behavior of LT-PPN0.3 shows only two
regions, Newtonian at low shear rates and shear-thinning at
high shear rates, whereas the PAM solution has three flow
regimes (first Newtonian, shear-thinning, and second Newtonian). The decrease in the viscosity of LT-PPN0.3 at a high
shear rate may be ascribed to the disruption of the physical
association between the hydrophobic polystyrene chains.
These results clearly show the improved shear-thinning behavior of LT-PPN0.3 with respect to PAM in the harsh environment, which is favorable for the penetration of the polymer solution into a near-wellbore with a high shear rate and
is also helpful to go deep into oil reservoirs with high viscosity and, subsequently, improved sweep efficiency and mobility
control.[32]

Energy Technol. 2016, 4, 1035 1046

Flooding medium

Oil recovery [OOIP %]

water
PAM
LT-PPN0.2
HT-PPN0.2
LT-PPN0.3
HT-PPN0.3

40
60
60
65
68
72

creases the oil recovery efficiency of the flooding process.

However, in the case of PPNs, the same effect was achieved
with a lower amount of active PAM polymer, as PPNs contain polystyrene as well (12 wt % for LT-PPNs, and 37 wt %
for HT-PPNs).
The interfacial tension (IFT), contact angle, and oil recovery of brine, PAM, and PPN solutions from carbonate, fracture carbonate, and sandstone core plugs are shown in
Figure 10. An average of 6.9 % incremental oil recovery by
PPN flooding was obtained (Figure 10 b), whereas the average incremental oil recovery of PAM was 5.95 % (Figure 10 c). The experimental results show that both the polymer flooding processes have a comparable oil recovery
factor, and the incremental oil recovery was higher in the
case of Poly(AM-co-St) released from LT-PPN0.3 as a result
of the higher stability and the lower IFT of the oilnanofluid
interface and lower oil contact angle. It has been reported
previously that the nanofluid will spread along the solid surface and decrease the IFT and contact angle.[33]

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Figure 9. The distribution of the oil at beginning and breakthrough time; a) Saturated micromodel for water and PAM flooding; b) Breakthrough time for water
flooding; c) Breakthrough time for PAM flooding; d) Saturated micromodel for LT-PPN0.3 flooding, after the injection of 0.1 PV, leaving for 24 h and the injection of another 0.1 PV; and e) Breakthrough time for LT-PPN0.3 flooding; T = 30 8C, flow rate = 0.0008 mL min@1 (residence time = 1250 min),
TDS = 178 082 mg L@1, CPAM = 0.2 wt %.

The PPNs flooding process is presented schematically in

Figure 11. The coreshell PPNs aqueous dispersions are injected into the reservoir through the injection well at time 0
(point 0). The dispersions are pumped to reach the target
point 1, the oil phase, for which a time t1 is necessary that depends on the characteristics of the reservoir. At that point,
the flow of the PPNs dispersions should be stopped to allow
the release of the Poly(AM-co-St) chains and the increase of
the viscosity of the pushing fluid. The release period could
be controlled by the characteristics of the protecting shell
(the thickness and the solubility characteristics of the hydrophobic copolymer), which in this study was & 17 h. After
that, the displacing high-viscosity fluid is pushed forward
toward the production well (point 2), at which, because of
the change in mobility ratios between the two phases, it
should enhance the recovery of the oil from the reservoirs.
As the Poly(AM-co-St) chains are thermally and mechanically stable, one would expect prolonged and improved performance, which was not observed in the performance characterization under laboratory conditions. The simulation of
the reservoir conditions in the lab can be very tricky because
of the big difference in the size and pore networks and may
be the main reason why the expected improvement in performance was not demonstrated despite the important improvement of the characteristics of the PPNs.
Energy Technol. 2016, 4, 1035 1046

Conclusions
Protected polyacrylamide nanostructures (PPNs) were synthesized by two-step, one-pot inverse emulsion polymerization of an aqueous acrylamide solution, dispersed in cyclohexane, onto which polystyrene was copolymerized to form
a protective hydrophobic shell. After contact with the oil
phase in a reservoir, the protective shell will dissolve slowly
to allow controlled release of active poly(acrylamide-co-styrene) (Poly(AM-co-St)) polymer that causes an increase of
the viscosity of the aqueous dispersion to displace the remaining oil in the reservoir. Analysis of the chemical composition and particle size distribution measurements confirmed
the coreshell morphology, which had an average core size
of 61 nm and two shell sizes of 11 and 24 nm.
The protected polyacrylamide (PAM) nanostructures show
a time-dependent release behavior that, after contact with
the remaining oil in the deeper areas of reservoirs, results in
penetration of the polymer and increased viscosity of the
water-displacing phase. The viscosity variation of Poly(AMco-St) as an active polymer released from the PPNs shows
three regions: 1) at a short residence time, the PPNs present
a low viscosity similar to kinematic viscosity of displacing
water, 2) an increase of the residence time leads to viscosity
enhancement, and 3) after the critical residence time, stable

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Figure 10. a) IFT and contact angle measurement for crude oil against polymer/brine; b) Oil recovery of LT-PPN0.3 and c) oil recovery of PAM solutions versus
the injected volume of displacing fluid in carbonate, fracture carbonate, and sandstone core plugs, T = 30 8C, TDS = 178 082 mg L@1, CPAM = 0.2 wt %.

Figure 11. Schematic representation of PPNs polymer flooding process.

Energy Technol. 2016, 4, 1035 1046

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viscosity values are achieved. As a result of the low viscosity

of the coreshell dispersions during the initial injection process, the equipment and process costs will be the same as
those of water flooding, which are much lower than those of
traditional polymer flooding. However, the maximum value
of the effective viscosity of the PPNs dispersions is higher
than that of the unprotected PAM solution. The variation of
the elastic and loss moduli as a function of temperature for
PPN dispersions and PAM solutions indicates that PPNs
present a superior elasticity and result in a higher flow resistance through a porous medium, which improves the macroscopic and microscopic sweep efficiency and oil recovery.
The comparative steady-shear rheological results exhibit two
clear differences for PAM and PPN: 1) the viscosity of the
PPN dispersion is higher than that of the PAM solution
during the induced shear rate range and 2) the PPN dispersion shows shear-thinning behavior at a high shear rate with
the viscosity remaining reasonably high, which is favorable
for the penetration of the polymer solution into the nearwellbore. Furthermore, PPNs present a superior behavior to
PAM in a simulated harsh environment: a low maximum viscosity loss in synthetic seawater under mechanical mixing
(2.37 % for PPNs and 14.50 % for PAM). The PPN samples
adsorb poorly on silicate formations at all investigated temperatures likely because of the hydrophobic nature of the
shell. Core and glass micromodel flooding experiments revealed that both flooding processes by PAM solutions and
PPN dispersions have generally comparable macroscopic
areal sweep efficiency and recovery that is, moreover, achieved at a lower polymer content in the case of PPNs.
Therefore, if we take this into consideration, along with
the advantages of PPN during polymer flooding, this study
reveals that PPNs are good candidates for use in the polymer-enhanced oil recovery process.

Abbreviations
AMPS: 2-acrylamid-2-methylpropane sulfonate; AM: acrylamide; APS: ammonium persulfate; DLS: dynamic light
scattering; DSC: differential scanning calorimetry; EOR: enhanced oil recovery; HLB: hydrophiliclipophilic balance;
HPAM: partially hydrolyzed polyacrylamide; LT-PPN: protected polyacrylamide with low shell thickness; HT-PPN:
protected polyacrylamide with high shell thicknesses; NVP:
N-vinyl pyrrolidone; PAM: polyacrylamide; Poly(AM-co-St):
polyacrylamide-co-polystyrene; PPN: protected polyacrylamide nanostructure; SANS: small-angle neutron scattering;
SAXS: small-angle X-ray scattering; TDS: total dissolved
solids.

Energy Technol. 2016, 4, 1035 1046

Experimental Section
Materials
Acrylamide (AM, + 99.0 %), ammonium persulfate (APS,
+ 99.9 %), xylene (+ 99.5 %), toluene (+ 99.0 %), ethanol (+
99.0 %), and cyclohexane (+ 99.9 %) were used as received from
SigmaAldrich Company. A mixture of sorbitan monolaurate
Span20 and monooleate Span80 emulsifiers (Merck Co.), with
a hydrophiliclipophilic balance (HLB) of 8.6 and 4.3, respectively, was used without further purification. Styrene monomer
(+ 99.9 %, Merck Co.) was treated with 1 m NaOH aqueous solution to remove the inhibitor and was distilled under reduced
pressure under a N2 atmosphere before polymerization. Doubledistilled water used for the preparation of emulsion was deprived
of oxygen by heating to boiling point and cooling under a stream
of nitrogen.

Synthesis and polymerization

The synthesis comprised two steps: 1) the synthesis of high-molecular-weight PAM nanoparticles by inverse emulsion polymerization and 2) their encapsulation by a copolymerized polystyrene
nanolayer coating as a hydrophobic protective shell. The first
step involves inverse emulsion polymerization of an aqueous solution of AM (49 g, 23 wt % AM solution) dispersed in the cyclohexane oil phase (163 g, 76 wt %) and stabilized by Span20/
Span80 (1 wt %, HLB = 6.5) at 60 8C for 120 min, initiated by
0.02 % weight based on monomer (wbm) of APS. After 120 min,
when approximately 92 % AM conversion was achieved, styrene
monomer was added together with APS (0.01 %wbm) into the
inverse emulsion and polymerized in situ at 60 8C for 180 min to
encapsulate the PAM nanoparticles. Two different amounts of
styrene monomer (1.8 and 9 g) were added in the second step to
produce two different shell thicknesses: low (LT-PPN) and high
(HT-PPN) shell thicknesses.
The PPNs were precipitated with an excess amount of acetone
(1:6), dried by using a freeze dryer (Model: FD-10; Pishtaz Engineering Co.) at @50 8C for 48 h, after which they were washed
with acetone and ethanol to remove the polystyrene homopolymer, surfactants and unreacted monomers. During this procedure
the homopolymer polystyrene chains were removed as they are
soluble in acetone. In the next experiments, aqueous dispersions
of LT-PPN and HT-PPN were prepared at two polymer concentrations: 0.2 and 0.3 wt %. The experimental procedures are explained in detail in the Supporting Information, and the polymerization set-up is presented in Figure S1.

Characterization of the synthesized PPNs

To determine the monomer conversion and chemical composition of the PPNs, 1H NMR spectroscopy (250 MHz Bruker spectrometer in CDCl3 solvent) was used to follow the decrease of
the monomer peaks centered in the range of d = 5.26.7 ppm
characteristic of the vinyl group.
The particle size and their distributions were measured by using
Malvern ZetasizerQs Nano Series dynamic light scattering (DLS).
The samples were prepared by injecting one drop of the final dispersion into a 10 wt % solution of Span80/Span20 in cyclohexane
under vigorous mixing (10 000 rpm). This instrument included
a laser as the light source with a wavelength of 633 nm and a scattering angle of 908 at 25 8C.

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To determine the size of the core and of the shell of the PPNs,
a combination of the equivalent hard sphere radius method provided by Chu et al.[21] and the results of SAXS experiments (performed by using an Anton PaarSAXSess mc2 Small- & Wideangle X-ray scattering system) was used. Details of how the size
of the core and the size of the shell of the PPN nanostructures
were determined are given in Figures S2 and S3.
DSC (TGA/DSC 3 + , Thermogravimetric Analyzer with a small
furnace, METTLER TOLEDO Co.) was performed on samples
of approximately 510 mg placed in closed Al pans. The analyses
were performed under a N2 flow of 20 mL min@1 at a heating rate
of 10 8C min@1 from 50 to 220 8C. Two scans were obtained for
each sample and the data were analyzed using the second-scan
curve. The Tg of the materials was obtained from the first derivative of the DSC curves.
The molecular weight of PAM nanoparticles before copolymerization with the PSt was calculated using the MarkHouwink
equation [Eq. (1)]:

hAIntr

mL
g
6:31 > 10@3 ? Mw0:8

g
mol

in which [h]Intr is the intrinsic viscosity, determined from the intercept value of a linear regression of the relationship between
the reduced viscosity and polymer concentration.[34] The viscosity
of each of the polymer solutions at different concentrations was
measured three times by using an Ubbelohde capillary viscometer (constant factor = 0.01024 mm2 s@2). Details of the procedure
are presented in the Supporting Information. The molecular
weight of the polymer nanoparticles was determined to be
& 7 000 000 Da.

Characterization of PPNs dispersions

Four different PPN samples were investigated to determine their
release behavior and stability: two different shell thicknesses
(low and high thickness) and two different concentrations of
PPNs in the dispersions (0.2 and 0.3 wt %) were labeled as LTPPN0.2, LT-PPN0.3, HT-PPN0.2 and HT-PPN0.3.
To investigate the kinematic viscosity variation, PPN samples
were dispersed in water and kept for one month at 30 and 60 8C.
A sample of 10 mL of the dispersion was removed from the solution at various time intervals. Then, the viscosity of the dispersions was determined by using the Ubbelohde capillary viscometry method (viscometer constant = 0.01024 mm2 s@2).
Dissolution tests were performed using xylene as a degassed synthetic oil phase to dissolve the PPN hydrophobic nanolayer by
mixing 100 mL xylene with 100 mL PPN aqueous dispersion,
after which the samples were extracted from the aqueous phase,
near to the interface, at different time intervals (125 h) and
their kinematic viscosity was measured by using the Ubbelohde
capillary viscometry method. The set-up for these measurements
is presented in Figure S5. To determine the release behavior of
the PPNs dispersions in contact with the oil phase in the reservoirs, the dissolution test was performed at 25 8C. It was assumed
that the augmentation of the kinematic viscosity is proportional
to the released amount of Poly(AM-co-St) and the proportion
released was calculated based on the viscosity of bare PAM solution with the same polymer concentration. To determine the stability of the PPNs dispersions against temperature and salinity,
the dissolution test was performed at different temperatures (30,
Energy Technol. 2016, 4, 1035 1046

60, and 90 8C) in synthetic seawater, which was prepared by

adding inorganic salts to deionized water (Table S1). The TDS of
the synthetic seawater was 178 082 mg L@1.
The mechanical resistance of PPN dispersions and PAM solutions (without contact with oil) in the synthetic seawater was investigated under mechanical mixing at different speeds at 90 8C.
Samples were withdrawn after one week, and the viscosity of the
dispersions was measured by using the Ubbelohde viscometry
method, from which the viscosity loss was calculated.
The comparative steady- and dynamic-shear rheological of PAM
and PPNs were measured by using a MCR 301 Physica (Anton
Paar) rheometer equipped with cone and plate geometry.
To determine the resistance of the PPN dispersions to adsorption
on a sand surface, static adsorption tests were performed in brine
solutions at 30, 60, and 90 8C. PPN dispersion and PAM solution
(10 mL) were added to sandstone (10 g, quartz 56.5 wt %, calcite
28 wt %, clay 7.4 wt %, others 8.1 wt %) in glass vials, homogenized by hand-shaking for 5 min and left to equilibrate for 24 h.
The mixture was filtered through a 2.5 mm filter, and the amount
of polymer retained by the sand was determined by UV/Vis
spectroscopy (Shimadzu, UV-3600 Plus spectrophotometer, maximum resolution: 0.1 nm, wavelength range of 1853300 nm). It
was assumed that the polymer retained by the sand was absorbed
at the sand surface.

Characterization of PPNs performance

In this study, three flooding processes were investigated: water
flooding, PAM flooding, and PPN flooding at 1 bar and 30 8C.
Details of the flooding experimental procedures, the equipment
used and the characteristics of the materials used (crude oil and
porous micromodel) are given in the Supporting Information.
Briefly, a transparent glass micromodel set-up was used to investigate the PPN performance during polymer flooding. The set-up
included a pore network micromodel, a cleaning system,
a Quizix5000 pump and an optical data acquisition system (24
mega-pixel digital camera). The micromodel was made of a 2 D
pore structure etched onto the surface of a flat glass plate, which
was originally wet with water, that was covered by another glass
plate to create the pore network between the two plates.[35] After
the glass micromodel was thoroughly prepared for the experiments (details can be found in the Supporting Information), it
was saturated with crude oil and 1 PV displacing fluid (i.e.,
water, PAM or PPNs) was injected from the inlet port into the
micromodel with an injection flow rate of 0.0008 mL min@1. This
injection flow rate was selected as an optimum value in terms of
oil recovery, experiment duration, and non-Darcy effect[36] to
control the injection flow rate of fluids. Consequently, the oil recovery was recorded as the percentage of the initial original oil
in place (OOIP) during the displacement stages by image processing of the captured photos. Notably, in the case of PPNs dispersions, after the injection of 0.1 PV they were left 24 h to have
sufficient time to release the Poly(AM-co-St) chains before they
were pushed forward with another 0.1 PV of original dispersions
and left another 24 h to release. This was continued until 1 PV of
the dispersion was introduced into the micromodel. Thus, if the
performance of PPNs with PAM is compared, this difference in
measurements should be taken into account.
Oil recovery in the core plugs was determined using three different core plugs with different PV values (carbonate with
30.10 %PV, fracture carbonate 28.76 %PV, and sandstone

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24.23 %PV) with a range of permeability from 20 to 55 mD (low

to medium permeability). The preparation of the core plugs and
their petrophysical characteristics are detailed in the Supporting
Information. The core plugs were saturated with brine (TDS =
178 082 mg L@1; Table S1) by using a vacuum container at 0.1 bar,
after which degassed crude oil was injected at rates from
0.01 mL min@1 for 2 PV until no more brine was produced. Oil in
place was calculated from the volume of outlet brine and dead
volume. Brine was then injected as a secondary recovery process
(first imbibition process) at a constant rate of 0.25 mL min@1 for
nearly 1.21.4 %PV until no more oil was produced, which thereby established residual oil saturation. Then, a third injection followed at a constant rate of 0.05 mL min@1 of polymer (PPNs or
PAM) for 1.6 %PV as a tertiary recovery step. To displace the
polymer solutions, post-brine flooding was performed at a constant rate of 0.25 mL min@1. The total amount of recovered oil
was determined by the ratio of measured recovered oil to total
oil in place. Again, if PPNs were introduced, the process was performed in discontinuous mode, and the PPNs were left for 24 h
to release the active Poly(AM-co-St) chains.
The IFT between the crude oil and brine/polymer aqueous phase
was measured by using a spinning-drop tensiometer under ambient conditions [Eq. (2)]. The drop volume and rotation speed
were in range of 23 mL and 45005500 rpm, respectively.

D1::Dm 3
0 /
L
8n3 :C: D

in which s is the interfacial tension [dyn cm@1], D1 is the density

difference [g cm@3], is rotational rate of the cylinder [s@1], Dm
is the measured drop diameter [cm], n is the refractive index of
the heavy fluid, D is the true diameter of the drop (D = Dm/n), C
is the correction factor and L/D is the aspect ratio of the drop
length to its diameter. The average refractive index for brine,
PAM (cp = 0.2 wt %) and LT-PPN0.3 was 1.338, 1.452, and 1.495,
respectively, by using a refractometer (Mettler Toledo).
The contact angle, q, between crude oil and the brine/polymer
aqueous phase was measured on a sandstone slice by using a Goniometry KSV CAM instrument at RT [Eq. (3)].

ss s sl sl cosq

in which s describes the interfacial tension components of the

phase, indices s and l denote solid and liquid phases, ssl represents the interfacial tension between the two phases, and q is the
contact angle that corresponds to the angle between sl and ssl.

The authors are grateful to the support from National Iranian

South Oil Company (NISOC).

Keywords: enhanced oil recovery oilwater interface

nanoparticles polyacrylamide polymers

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Received: January 18, 2016

Revised: February 23, 2016
Published online on May 3, 2016

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