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Journal of the Taiwan Institute of Chemical Engineers

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Star-like hydrophobically associative polyacrylamide for enhanced oil

recovery: Comprehensive properties in harsh reservoir conditions
Rui Liu a,b,∗, Wanfen Pu a,∗∗, James J. Sheng a,b, Daijun Du a
a
State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, People’s Republic of China
b
BoL L. Herd Department of Petroleum Engineering, Texas Tech University, P. O. BOX 43111, Lubbock, TX 79409, USA

a r t i c l e i n f o a b s t r a c t

Article history: This work fabricated a novel star-like hydrophobically associative polyacrylamide called SHPAM used in
Received 21 June 2017 enhanced oil recovery (EOR) processes in harsh reservoir conditions. SHPAM composed of a core of nano-
Revised 24 August 2017
silica and a layer of amphiphilic-polymeric chains was synthesized via a facile water free radical polymer-
Accepted 26 August 2017
ization. It was systematically characterized using TEM, SEM, IR, 1 H NMR and DLS. Measurements from
Available online xxx
solubility, thickening efficiency, long-term stability and rheological performance indicated that the three-
Keywords: dimensional microstructure and intermolecular associations provided SHPAM solution with fantastically
Nano-silica particles comprehensive properties, outperforming hydrophobically associative polyacrylamide. The evidence from
Star-like hydrophobically associative rectangle cores in a serial model experiments implied that SHPAM was well compatible with permeable
polyacrylamide cores and it had desirable injectivity with sustainable mobility control in porous media. Moreover, core
Comprehensive properties flooding tests revealed that after extensive water flooding, SHPAM with the concentration of 1500 mg/L
Polymer flooding
increased the oil recovery factor by 20% in sandstone cores. This study showed the robust potential of
Harsh reservoir conditions
SHPAM as a polymer flooding candidate in high temperature and high salinity reservoirs where harsh
conditions associated with lack of fresh water constrain the applications of conventional polymers.
© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Abbreviations MeDiC8 AM 2-methyl-N, N-dioctyl-acrylamide

NPs nano-silica particles
1H NMR nuclear magnetic resonance spectroscopy PAMAM hyperbranched polyamidoamine
AA acrylic acid SDS sodium dodecyl sulfonate
AIBA 2, 2 -azobis (2-amidinopropane) dihydrochloride SEM scanning electron microscopy
AM acrylamide SHPAM star-like hydrophobically associative polyacrylamide
APTES 3-aminopropyltriethoxysilane TEM transmission electronic microscopy
DLS dynamic laser light scattering TEOS tetraethoxysilane
DMSO dimethylsulfoxide
EDA ethylenediamine
EOR enhanced oil recovery 1. Introduction
FNPs functionalized PAMAM-anchored NPs
G2.0 generation two Only a small fraction of original oil in place (OOIP) is extracted
HAPAM hydrophobically associative polyacrylamide from subterranean formations by natural depletion. For the ma-
HPAM partially hydrolyzed polyacrylamide jority of conventional oil reservoirs worldwide, water is injected
IR infrared spectroscopy from the wells to displace residual oil after the initial exploitation,
MA methyl acrylate which is named water flooding. Nevertheless, nearly 70% of the
MAH maleic anhydride OOIP is still trapped in geological formations even the extensive
water flooding was implemented because the unfavorable mobil-
ity of water over crude oil in reservoir conditions results in water
directly bypassing oil [1–3]. Therefore, it is necessary to have en-
∗
Corresponding author at: State Key Laboratory of Oil and Gas Reservoir Geol-
hanced oil recovery (EOR) processes. Numerous laboratory studies
ogy and Exploitation, Southwest Petroleum University, Chengdu 610500, People’s
Republic of China. and field applications have indicated that polymer-based process
∗∗
Corresponding author. is a fairly effective EOR technique, because it fulfills three unique
E-mail addresses: breakthroughliu@163.com (R. Liu), pwf58@163.com (W. Pu). mechanisms: mobility ratio control [4], selectively reducing perme-

http://dx.doi.org/10.1016/j.jtice.2017.08.043
1876-1070/© 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: R. Liu et al., Star-like hydrophobically associative polyacrylamide for enhanced oil recov-
ery: Comprehensive properties in harsh reservoir conditions, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.043
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2 R. Liu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–11

tures were similar to three-dimensional spheres [20]. Such water

Nomenclature soluble star-like polymers can be engineered to controllable prop-
erties via manipulating NPs size and polymeric monomers in com-
[ƞ] intrinsic viscosity number (mL/g) bination. They may expand the application of polymer flooding, es-
c mass concentration (mg/L) pecially, in hostile reservoirs where fresh water resource is usually
c∗ critical overlapping concentration (mg/L) insufficient and polymer flooding systems directly prepared with
CAC critical associative concentration (mg/L) formation water are thus urgently demanded. In addition, crucial
Et cumulative oil recovery (%) work on comprehensive properties of polymer flooding systems in-
Ew initial water flooding oil recovery (%) cluding viscosification, rheology, viscoelasticity, long-term stability,
fr resistance factor, dimensionless injectivity and oil recovery efficiency at reservoir scale is indis-
frr residual resistance factor, dimensionless pensable because the geological formation, temperature and salin-
G storage moduli (Pa) ity vary from a reservoir to another.
G loss moduli (Pa) This study aimed to offer a novel star-like associative polyacry-
G0 plateau storage moduli (Pa) lamide (SHPAM) consisting of nano-silica as the core and a layer
Gc crossed moduli (Pa) of amphiphilic polymeric-chains as the shell for polymer flood-
k permeability (mD) ing in harsh reservoir conditions. Firstly, functionalized genera-
Mw molecular weight (g/mol) tion two hyperbranched polyamidoamine (G2.0 PAMAM)-anchored
NA Avogadro number, 6.02 × 1023 NPs (FNPs) were synthesized. Meanwhile, a novel hydrophobic
OOIP original oil in place (t) monomer named 2-methyl-N,N-dioctyl-acrylamide (MeDiC8 AM)
Rg gyration radius (nm) was self-prepared. Secondly, on the basis of FNPs and MeDiC8 AM,
Sio initial oil saturation (%) SHPAM was synthesized via a mild water free radical polymer-
t flow time of polymer solutions or brine (s) ization. Thirdly, SHPAM was characterized by combining transmis-
P pressure differential (MPa) sion electronic microscopy (TEM), scanning electron microscopy
η0 zero shear viscosity (Pa·s) (SEM), infrared spectroscopy (IR), nuclear magnetic resonance
ηr relative viscosity, dimensionless spectroscopy (1 H NMR) and wide angle dynamic laser light scat-
ηsp specific viscosity, dimensionless tering (DLS). Finally, the mechanisms contributed to the compre-
λ relaxation time (s) hensive properties of SHPAM were investigated by implementing
φ porosity (%) static analysis, rheological measurement and core displacement ex-
ω angular frequency (rad/s) periments.

ability of water channels [5], and viscoelastic flow in porous media
[6].
One of the most commercial water-soluble polymers used in
polymer flooding process is partially hydrolyzed polyacrylamide
(HPAM). HPAM consists of a large proportion of intermediate hy-
drophilic amide groups and the remaining of superior hydrophilic
carboxyl groups [7]. Both amide groups and carboxyl groups are
linearly introduced onto the backbone of polymeric chains, provid-
ing HPAM with favorable solubility and desirable viscosification in
fresh water and low salinity formation water. Most recently, oil-
field applications have seen polymer flooding move into new fields
where everlasting properties and high cost performance in harsh
reservoir conditions are paramount requirements [8,9]. However,
the very limited thickening efficiency and poor long term-stability
of HPAM in hash reservoir conditions hinder its wider application.
It is due to the extreme deformation of the linear flexible chains at
elevated temperature as well as the shielding electrostatic repul-
sion of carboxyl groups in the presence of high strength cations.
The literature information shows that hydrophobically associa-
tive polyacrylamide (HAPAM) in which HPAM is modified by in-
troducing a small proportion of hydrophobic pendants onto the
backbone can somehow improve the stability of polymeric chains
[10–14]. Above the critical associative concentration (CAC), inter-
molecular associations between neighboring polymeric chains con-
struct a dynamic physical network, bestowing HAPAM versatile ap-
plications [15,16]. However, pilot tests have indicated that HAPAM
takes much more time to dissolve completely in water than HPAM
at the equivalent concentration [6,17]. On the other hand, a “mi-
nority of polymeric species” caused by the strong intermolecular
associations of hydrophobic pendants may impair the injectivity of
HAPAM in porous media [18,19]. Therefore, both the nature and the
component of hydrophobic moieties of HAPAM need to be deliber-
ately designed to meet its solubility and injectivity.
In a previous study, we have initiated polymeric chains hybrid
nano-silica particles (NPs) as EOR chemicals because their struc-
2. Experimental sections
2.1. Materials
Tetraethoxysilane (TEOS, 99.0%), 3-aminopropyltriethoxysilane
(APTES, 99.0%), Di-N-octylamine (97.0%) and methacryloyl chloride
(98.0%) were purchased from Aldrich. Absolute ethanol (>99.0%),
concentrated ammonia (35.0%) in water, dimethylsulfoxide (DMSO,
>99.0%) and methyl acrylate (MA, >98.0%), ethylenediamine (EDA,
>97.0%), maleic anhydride (MAH, >97.0%), acrylic acid (AA, 98.0%)
and sodium dodecyl sulfonate (SDS, 98%) were purchased from
Chengdu Kelong Chemical Reagent Co., Ltd (China). 2, 2 -azobis (2-
amidinopropane) dihydrochloride (AIBA, >97.0%) were purchased
from Alfa-Aesar. These chemicals were used as received. Acry-
lamide (AM, 95.0%) was purchased from Chengdu KeLong Chem-
ical Reagent Co., Ltd, which was recrystallized prior to use. HPAM
was purchased from SNF Floerger Group (France) with molecular
weight (Mw ) of 1.86 × 107 g/mol and hydrolysis degree of 30.3%.
All the supplementary solvents and chemical reagents were of
reagent grade, which were purchased from Aladdin and used with-
out purification. Millipore distilled water with an electrical resis-
tance of 18.0 M was used. Crude oil and formation water were
obtained from a certain block in Karamy Oilfield (China). The vis-
cosity and density of crude oil at the reservoir temperature of
82.3 °C were 5.13 mPa·s and 0.852 g/cm, respectively. The SARA
fractions of the crude oil were as follows: saturated hydrocar-
bon 73.13%, aromatic hydrocarbon 16.34%, resin 10.03% and as-
phaltene 0.5%. The paraffin content was around 8.3%. The natu-
ral formation water was not directly used because it contains a
small amount of undissolved particles, such as clay and physi-
cal impurities. Therefore, the formation water used in this study
was synthetic brine whose total salinity and inorganic composition
were consistent with the natural formation water. The total salin-
ity of formation water was 39,931.6 mg/L and the inorganic com-
position was K+ + Na+ = 12,152.2 mg/L, Ca2+ + Mg2+ = 203.6 mg/L,
Cl− + HCO3 − = 12,835.9 mg/L, CO3 2- + SO4 2− = 14,739.9 mg/L. Cores

Please cite this article as: R. Liu et al., Star-like hydrophobically associative polyacrylamide for enhanced oil recov-
ery: Comprehensive properties in harsh reservoir conditions, Journal of the Taiwan Institute of Chemical Engineers (2017),
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Scheme 1. Synthetic procedure to synthesize (a) MeDiC8 AM, and SHPAM based on (b) FNPs.

used in the core displacement experiments were artificial rectan-
gle sandstone cores which were consolidated cuboids with slightly
heterogeneous.
2.2. Synthesis of MeDiC8 AM and FNPs
of SHPAM was depicted in Scheme 1c. As a reference, one type
of HAPAM with the twin-tailed octyl chains as hydrophobic moi-
eties based on AM, AA and MeDiC8 AM was synthesized under the
identical monomers feed and following the procedure mentioned
above.

2.4. Polymer solution preparation

The hydrophobic monomer MeDiC8 AM was self-prepared by
employing one-pot method (Scheme 1a). NPs were synthesized in
advance by the improvement of StÖber method [21]. Afterward,
FNPs were synthesized (Scheme 1b) by MAH functionalizing G2.0
PAMAM-anchored NPs [22]. The detailed procedure is available in
Supplementary material.
2.3. Synthesis of SHPAM
Typically, 1.2 g of SDS was dissolved in 50 mL of deionized wa-
ter and then 0.15 g of MeDiC8 AM was dissolved in the SDS micel-
lar solution. 8.5 g of AM, 2.5 g of AA, 0.1 g of FNPs and 0.06 g of
AIBA were added into the mixture followed by adding some vol-
ume of deionized water to obtain 15.6% mass concentration of to-
tal monomers. SHPAM was synthesized and then purified accord-
ing the procedure in the literature [20]. The chemical structure
Polymer stock solutions with the concentration of 50 0 0 mg/L
were prepared by dissolving a known amount of polymer pow-
ders into formation water unless otherwise specified. While adding
polymer powders, the formation water was slowly stirred to avoid
any fisheye. After 2 h of stirring, the solutions were treated by
some amount of thiourea as a preservative and then remained still
for 48 h at an ambient environment to remove air bubbles. The so-
lutions were subsequently filtered with 3.0 μm of nucleopore mem-
brane to remove undissolved particles. Finally, the stock solutions
were diluted to a certain polymer concentration for use.
2.5. Characterizations and measurements
TEM measurements were performed on a Hitachi H-9500 elec-
tron microscope with a point resolution of 1.8 Å operated at an

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ery: Comprehensive properties in harsh reservoir conditions, Journal of the Taiwan Institute of Chemical Engineers (2017),
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Fig. 1. The schematic diagram of the two serial rectangle cores model set-up.

Table 1
Physical parameters of rectangle sandstone cores.

Core no. Length (cm) Wide (cm) Height (cm) k (mD) φ (%) Sio (%)

1# 30.02 4.49 4.51 245.9 20.6 /

2# 30.05 4.50 4.46 302.6 21.3 /
3# 29.87 4.48 4.43 345.8 22.6 /
4# 29.93 4.50 4.47 389.2 23.7 /
5# 29.89 4.47 4.50 213.6 20.9 73.2
6# 30.07 4.43 4.49 267.9 19.7 74.2
7# 30.04 4.42 4.50 403.5 22.4 75.6
8# 29.98 4.48 4.52 292.6 20.2 71.8

accelerating voltage of 300 kV. The morphologies of samples were
characterized by SEM (Quanta 450) at an operating voltage of
20 kV. The IR spectrum was carried out using a WQF-520 spec-
trometer on KBr pellet. The 1 H NMR spectrum was measured on a
Bruker DPX-400 spectrometer at 400 MHz, using deuterated water
(D2 O, 99.0%) as solvent. The intrinsic viscosity number (ƞ) of sam-
ples prepared by 1.0 M NaCl solution was measured by an Ubbe-
lohde capillary viscometer at 25 °C. The hydrodynamic diameters
of samples were measured using a BI-200SM DLS instrument. The
apparent viscosity of samples was measured by a Brookfield DV-Ш
rheometer at the shear rate of 10 s−1 which is similar to the ac-
tual shear rate of fluids in deep porous media of the target forma-
tion in Karamy Oilfield. The rheological experiments were carried
out on a Physical MCR 302 (Anton Paar) rheometer. Measurements
were then performed in a shear model using a double slit geome-
try system (DG 26.7). Frequency oscillatory sweep in the range of
0.01 to 100 Hz was applied. A strain of 0.6% struck a good balance
between torque sensitivity and response in the linear viscoelastic
regime for the samples. The storage moduli (G ) and loss moduli
(G ) were then measured. The long-term stability of polymer solu-
tions in anaerobic condition at 82.3 °C was measured.
2.6. Flow behavior of SHPAM solution in porous media and core
flooding tests for EOR
The parameters of rectangle sandstone cores, including size,
porosity (φ ), permeability (k) and initial oil saturation (Sio )
were measured according to the method in previous study [20].
Core displacement experiments using rectangle sandstone cores
(30 cm × 4.5 cm × 4.5 cm) in a serial cores model (Fig. 1), were car-
ried out to simulate the flow behavior of SHPAM solution in porous
media, such as pressure differential (P), resistance factor (fr ) and
residual resistance factor (frr ). Moreover, parallel core flooding tests
were conducted to quantify EOR efficiency of SHPAM in harsh
reservoir conditions. Formation water was first flooded through the
oil saturated cores until the water cut from the outlet of the cores
was higher than 98%. Subsequently, 0.3 pore volume of polymer
solution prepared by formation water was flooded. Finally, the ex-
tensive chase water was flooded until no additional oil was pro-
duced. The flow rate over the whole procedure was 0.5 mL/min.
The EOR factor was determined from the data of cumulative oil re-
covery (Et ) and initial water flooding oil recovery (Ew ). The physical
parameters of rectangle sandstone cores were listed in Table 1.
3. Results and discussion
3.1. Synthesis and characterization of SHPAM and HAPAM
Scheme 1a illustrated the routine to prepare the twin-tailed hy-
drophobic monomer (MeDiC8 AM). The IR spectrum from Fig. 2a in-
dicated that the characteristic adsorption band at 3450 cm−1 was
assigned to –NH– stretching vibration of –CONH, 2925 cm−1 was
attributed to –C–H and –C = C– stretching vibration, 1670 cm−1
was attributed to –C = O stretching vibration, 1461 cm−1 was at-
tributed to –C–H and –N–H bending vibration; meanwhile, the two
bands at 1370 and 1320 cm−1 were assigned to the asymmetric vi-
bration of three methyl groups (–CH3 ).
The TEM image as depicted in Fig. 3a demonstrated that NPs
had a uniform size distribution with a diameter of 25 nm. Due
to large amount of hydroxyl groups onto NPs surfaces, APTES-
immobilized NPs were carried out to prepare amine groups ter-
minated NPs. By successively repeating the Michael addition reac-
tion of MA and amidation reaction of EDA, G2.0 PAMAM-anchored
NPs were prepared. Maleic acid groups terminated G2.0 PAMAM-
anchored NPs (FNPs) were then synthesized by ring opening re-
action of MAH with amine groups of G2.0 PAMAM-anchored NPs
using DMSO as solvent. The TEM image as shown in Fig. 3b im-
plied that FNPs distributed uniformly with an average diameter
of 30 nm. The evidence from IR spectrum as shown in Fig. 2a in-
dicated that besides the characteristic bands at 1637 cm−1 for –
C = O stretching vibration and at 1100 cm−1 for –Si–O– stretch-
ing vibration, the very strong absorptions at 3430 cm−1 was as-
signed to synergistic stretching vibration for –NH2 of –CONH2 and
for –N–H of PAMAM. Meanwhile, the 1 H NMR spectrum as shown

Please cite this article as: R. Liu et al., Star-like hydrophobically associative polyacrylamide for enhanced oil recov-
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(a) NPs
(b)
FNPs
HAPAM
720
2925
1302.6
1541

1670

MeDiC8AM 3438
SHPAM 1118

1049
1449
1665
3421

3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500
-1 -1
Wavenumbers（cm ） Wavenumbers (cm )

(d)

e
b1, c3
g, b2
D2O c1, c2, c4
CH3OH a, h

Fig. 2. IR spectra of (a) monomers and (b) polymers, and 1 H NMR spectra of (c) FNPs and (d) SHPAM.

Fig. 3. TEM images of (a) NPs and (b) FNPs in the dry state, SEM image of (c) HPAM, (d) mimic three-dimensional structure of SHPAM, and SEM images of (e) HAPAM and
(f) SHPAM (polymer concentration of 1500 mg/L that was prepared with deionized water).

Please cite this article as: R. Liu et al., Star-like hydrophobically associative polyacrylamide for enhanced oil recov-
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Fig. 4. (a) ηsp /c and ln ηr /c as a function of polymer concentration at 1.0 M NaCl solutions and (b) hydrodynamic diameter distribution of SHPAM and HAPAM samples
(polymer concentration of 50 mg/L) (25 °C).
in Fig. 2c indicated that the triplet peak at 0.6 ppm was ascribed
to the protons attached to –Si–CH2 –; the quintet at 1.65 ppm was
due to the protons attached to –CH2 –; the triplet at 2.9 ppm was
assigned to the protons connected with –CH2 –NH–; the peak at
6.2 ppm was ascribed to the protons connected with –CH = CH–.
Scheme 1c illustrated the routine to synthesize SHPAM based on
FNPs and MeDiC8 AM. As a reference, HAPAM based on MeDiC8 AM
was synthesized under the monomers concentration and synthetic
procedure identical to that for SHPAM. As for IR spectrum of SH-
PAM (Fig. 2b), besides the characteristic band of HAPAM that 3340
cm−1 was for the –N–H stretching vibration of –CONH2 , 2925 cm−1
for the asymmetric stretching vibration of –CH3 , 1670 cm−1 for –
C = O stretching vibration, 1540 cm−1 for –C–H and –N–H bending
vibration; 1049 cm−1 was assigned to –Si–O– stretching and 800
cm−1 was attributed to –Si–O–Si– bending vibration.
Meanwhile, the evidence from 1 H NMR spectrum of SHPAM as
shown in Fig. 2d confirmed that the peak at 0.78 ppm was at-
tributed to the –Si–CH2 – and –CH3 connected to the twin-tailed
alkyl chain; the peak at 1.20 ppm was assigned to the –CH2 – of the
twin-tailed alkyl chain and the –CH3 connected to the backbone of
polymeric chain; the peak at 1.62 ppm was assigned to the –CH2 –
of the backbone from polymeric chain; the peak at 2.16 ppm was
attributed to the –CH– of the backbone from polymeric chain and
the peak at 2.25 ppm was assigned to the –CH2 – connected to the
nitrogen.
3.2. Internal parameters of SHPAM and HAPAM
The Mw for SHPAM and HAPAM can be calculated from (η) and
gyration radius (Rg ) by utilizing the Rubinstein equation [23]:
Mw = 4.2R3g NA /[η], [η] ≈ 1/c∗
Here, NA is Avogadro number, and c∗ is the critical overlap-
ping concentration that distinguishes the dilute regime from the
semidilute regime of polymer solution. [η] and Rg can be deter-
mined by Ubbelohde capillary viscometer measurement and DLS
analysis, respectively. To obtain [η], relative viscosity (ηr ) and spe-
cific viscosity (ηsp ) of samples prepared with 1.0 M NaCl solution
were measured using the flow time of 1.0 M NaCl solution in an
Ubbelohde capillary viscometer as a reference.
ηr = t/t0
ηsp = ηr − 1
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Here, t is the flow time of polymer solutions, s; t0 is the flow
time of the 1.0 M NaCl solution, s. [η] was calculated by plotting
ηsp /c and ln ηr /c of polymer solutions against concentration and
extrapolating to infinite dilution and taking the intercept. If the in-
tercept is not the same point, [η] is equal to the average of the
intercept.
From the ηsp /c and ln ηr /c plots of SHPAM and HAPAM solu-
tions as shown in Fig. 4a, [η] was then 1699.3 mL/g for SHPAM
and 2034.4 mL/g for HAPAM, respectively. In addition, from the hy-
drodynamic diameter distribution of samples as shown in Fig. 4b,
Rg assumed median hydrodynamic radius, was 193 nm for SH-
PAM and 216 nm for HAPAM, respectively. According to the Eq. (1),
Mw was 1.07 × 107 g/mol with c∗ of 588 mg/L for SHPAM, and
1.25 × 107 g/mol with c∗ of 492 mg/L for HAPAM, respectively.
According to the reputation theory [23], CAC is in the semidilute
regime because the intermolecular interactions of polymeric chains
are limited to the tube. Near the CAC, the plateau storage moduli
(G0 ) behaves following the equation [24]:
G0 ∝ (c − CAC )α (4)
Typically, G as a function of angular frequency (ω) for SHPAM
solutions is shown in Fig. 5a, and then the data of lg G0 as a func-
tion of lg c was calculated as shown in Fig. 5b. It was G0 ∝c6.83 for
SHPAM. By tuning CAC to minimize the error in the slop of lg G0
over lg (c−CAC), it was then G0 ∝(c − CAC)0.835 , and thus, CAC was
1080 mg/L for SHPAM. From the data of lg G0 as a function of lg c
for HAPAM as shown in Fig. 5c, CAC was 920 mg/L for HAPAM.
3.3. Comprehensive properties
The solubility in the primary solvent like fresh water and the
(1) second solvent like brine is a mandatory criteria of a polymer for
chemical EOR process [7]. The dissolution behavior of SHPAM, HA-
PAM and HPAM in formation water was studied by measuring their
apparent viscosity as a function of dissolving time (Fig. 6).
The apparent viscosity was low at the beginning of dissolving
stage, and increased with the increase in dissolving time, and fi-
nally reached a constant when polymer powders were completely
dissolved. The dissolving time for HPAM was around 90 min, in-
dicating the linear hydrophilic structure of HPAM had a desirable
solubility in high salinity formation water. It was noteworthy that
(2) hydrophobic microdomains constructed by the twin-tailed alkyl
chains hindered the diffusion rate of water molecules from the
bulk solvent to HAPAM powders, and thus the dissolving time for
(3) HAPAM was almost twice that for HPAM. However, the dissolving
hydrophobically associative polyacrylamide for enhanced oil recov-
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Fig. 5. (a) G as a function of ω for SHPAM solutions, and lg G0 as a function of lg c for (b) SHPAM and (c) HAPAM.

Viscosification is one of the most significant properties for poly-

Fig. 6. Curves of apparent viscosity for polymers solutions as a function of dissolv-
ing time (polymer concentration of 1500 mg/L, 25 °C.
time for SHPAM was around 120 min which was much less than
HAPAM, even though its hydrophobic pendants were almost iden-
tical to HAPAM. It indicated that the smaller Mw of each polymeric
chain of SHPAM provided SHPAM powders with desirable solubility
in brine.
mers employed in the enhancement of viscosity of displacement
fluids [8]. The thickening efficiency of polymers solutions prepared
with formation water at 25 °C is shown in Fig. 7a. HPAM had
a limited thickening efficiency despite its highest Mw compared
with those of SHPAM and HAPAM. It could be interpreted that
the viscosification of HPAM significantly depended on the electro-
static repulsion of carboxyl groups which, however, was severely
screened by high strength cationic ions. The effect of cationic ions
on the viscosity of hydrophobically associative polymers could be
explained from two sides. One was due to the shielding effect of
cationic ions, the electrostatic repulsion between neighboring poly-
meric chains was weakened. It resulted in the compressed poly-
meric coils, accompanying with the decrease in solution viscos-
ity. The other was due to the increase in polarity with the in-
crease in salinity of solvent, which facilitated the formation of hy-
drophobic microdomains of polymer solution. Therefore, HAPAM
solution had better thickening efficiency than HPAM at the equiv-
alent concentration. The most excellent viscosification for SHPAM
originated from the nano-silica core and multiple associative poly-
meric chains which provided SHPAM with the toughest morphol-
ogy and strongest intermolecular associations. Moreover, the thick-
ening efficiency of polymers solutions prepared by formation wa-
ter at 82.3 °C was measured (Fig. 7b). The evidence confirmed that
the rigid nano-silica and the multiple polymeric chains with twin-
tailed hydrophobic moieties endowed SHPAM desirable viscosifica-
tion in harsh conditions.

Please cite this article as: R. Liu et al., Star-like hydrophobically associative polyacrylamide for enhanced oil recov-
ery: Comprehensive properties in harsh reservoir conditions, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.043
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8 R. Liu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–11

Fig. 7. Apparent viscosity of polymers solutions as a function of concentration at (a) 25 °C and (b) 82.3 °C (shear rate of 10 s−1 ); and apparent viscosity of polymers solutions
prepared with (c) formation water and (d) three times salinity formation water as a function of aging time at 82.3 °C (these aging polymers solutions were first cooled and
then their apparent viscosity was measured at 25 °C, polymer concentration of 1750 mg/L, shear rate of 10 s−1 ).

The long-term stability of polymers solutions with the concen-
tration of 1750 mg/L in harsh conditions was studied. The appar-
ent viscosity curves of polymers solutions as a function of aging
time are shown in Fig. 7c. The apparent viscosity of HPAM solu-
tion sharply decreased at the initial aging period of 30 days, sug-
gesting that the linear polymeric chains underwent severe degra-
dation. After 120 days of aging, the apparent viscosity of HPAM
solution was only 9.3 mPa·s with viscosity retention less than 25%.
The high salinity formation of water together with the reservoir
temperature of 82.3 °C hindered HPAM flooding at an acceptable
concentration regime. The apparent viscosity of SHPAM and HA-
PAM samples slightly decreased at the initial aging period, and
then kept plateau with the increase in aging time. After 120 days
of aging, the apparent viscosity was 80.3 mPa·s with viscosity re-
tention of 65.2% for SHPAM and 57.6 mPa·s with viscosity retention
of 59.1% for HAPAM, respectively. In addition, the long-term stabil-
ity of polymers solutions with the concentration of 1750 mg/L pre-
pared with three times salinity formation water (total salinity of
119,795.1 mg/L) at 82.3 °C was conducted (Fig. 7d). The apparent
viscosity of fresh solutions was 76.3 mPa·s for SHPAM, 46.4 mPa·s
for HAPAM and 19.5 mPa·s for HPAM, respectively. After 120 days
of aging, the apparent viscosity was 42.6 mPa·s with viscosity re-
tention of 55.8% for SHPAM, 21.8 mPa·s with viscosity retention of
46.9% for HAPAM, and 7.6 mPa·s with viscosity retention of 38.9%
for HPAM, respectively. The data from long-term stability experi-
ments indicated that SHPAM could endure high strength salinity
with a variable concentration in harsh reservoirs.
The structure of porous media could be seen as variation of
openings and confined throats where polymer coils must navigate
[9,20], in the terms of deformation or smaller clusters. The rheo-
logical property of polymer solution makes polymer coils propa-
gate through the variable porous media without severe degrada-
tion. The viscosity curves of polymers solutions as a function of
shear rate at 82.3 °C are shown in Fig. 8a. The viscosity of HPAM
was limited despite the highest concentration of 20 0 0 mg/L used. It
was interesting to figure out the star-like microstructure and mul-
tiple polymeric chains with hydrophobic pendants guaranteed SH-
PAM temporal behavior in multiscale. SHPAM solution displayed
shearing thickening over the shear rate higher than 10 0 0 s−1 in
comparison to that for HAPAM and HPAM. Even if SPHAM concen-
tration was decreased by 250 mg/L, the viscosity of SHPAM solution
was higher than HAPAM over the whole shear rate region.
The curves of G and G as a function of angular frequency (ω)
from oscillatory experiment were measured (Fig. 8b). The lg G and
lgG displayed approximately linear relation to lg ω. At a certain
ω, G equal to G was defined as crossed moduli (Gc ). The relax-
ation time (λ) corresponding to the Gc quantified the disentangle-
ment time or disassociated time of polymers which limited outside
the tube based on the Sticky–Rouse model [25]. Moreover, the zero
shear viscosity (η0 ) of polymer solution could be scaled by corre-
lating Gc and λ from the following equations:
η0 = 2 G c λ (5)
2π /λ = ω (6)
The viscoelastic parameters of polymers solutions with the con-
centration of 20 0 0 mg/L were calculated. The Gc and λ were then

Please cite this article as: R. Liu et al., Star-like hydrophobically associative polyacrylamide for enhanced oil recov-
ery: Comprehensive properties in harsh reservoir conditions, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.043
JID: JTICE
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R. Liu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–11
Fig. 8. (a) Viscosity as a function of shear rate for polymers solutions prepared with formation water at 82.3 °C, and (b) G’ and G as a function of ω for polymers solutions
prepared by formation water at 25 °C (polymer concentration of 20 0 0 mg/L).
0.15 Pa and 0.41 s for HPAM, 0.082 Pa and 12.2 s for HAPAM, and
0.085 Pa and 42.4 s for SHPAM, respectively. It was noteworthy that
the η0 for SHPAM solution was 7.2 Pa·s which was 3.6 times to
that for HAPAM and 60 times to that for HPAM, respectively.
The morphologies of polymers solutions from SEM images ver-
ified their comprehensive properties in harsh conditions. The mi-
crostructure of HPAM (Fig. 3c) was irregular and rough due to the
disordered entanglement of hydrophilic chains, whereas the inter-
molecular associations together with the entanglement of HAPAM
constructed a more regular microstructure (Fig. 3e). Noticeably, the
star-like microstructure with nano-silica as the core and hydropho-
bic polymeric chains as the shell contributed to the most regular
morphology of SHPAM (Fig. 3f). Such three- dimensional morphol-
ogy provided SHPAM with robust aforesaid comprehensive proper-
ties in harsh reservoir conditions.
3.4. Flow behavior of SHPAM solution in porous media
The pressure differential profiles (P1 and P2 ) of SHPAM so-
lution in two serial rectangle sandstone cores with permeability
ranging 20 0–40 0 mD are shown in Fig. 9a–b. SHPAM solution was
designed to flow through a lower permeability core followed by a
higher permeability core. In the case of the first core, P1 gradu-
ally increased with the increase in SHPAM slug and then kept sta-
ble. It was noteworthy that the pressure differential profile (P2 )
of the second core was hysteretic to P1 of the first core, demon-
strating the temporal and spatial flow behavior of SHPAM solution
in porous media. P2 reached stable after SHPAM solution was
breakthrough from the outlet of the second core.
The evidence from P1 and P2 curves indicated that SH-
PAM could navigate through porous media in depth without caus-
ing any face plugging or internal filterable cake. Moreover, SHPAM
was well compatible with permeable cores because SHPAM solu-
tion with the concentration of 1500 mg/L had benign injectivity in
variable permeability ratio of cores. The chase water was subse-
quently flooded after the pressure differential of two serial cores
reached equilibrium. P2 was also in hysteresis, indicating the sta-
ble frontier and the persistent mobility control of SHPAM solution
in porous media. On one hand, the mobility control capability of
SHPAM over formation water at 82.3 °C was quantified by fr , which
was 43.2 for core 1#, 39.5 for core 2#, 46.7 for core 3# and 50.6
for 4#, respectively. On the other hand, the reduced degree of per-
meability due to the irreversible adsorption and hydrodynamic re-
tention of SHPAM in dominant pores and throats was quantified
by frr , which was 9.8 for core 1#, 12.7 for core 2#, 14.3 for core
Please cite this article as: R. Liu et al., Star-like
ery: Comprehensive properties in harsh reservoir conditions, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.043
[m5G;September 7, 2017;0:1]
9
3# and 10.7 for 4#, respectively. The results revealed that SHPAM
solution with the acceptable concentration could build expected fr
and frr in hash reservoir conditions.
3.5. Polymer flooding for EOR
Polymers solutions employed in the EOR process were aged
for 60 days at 82.3 °C. The pressure differential histories, water
cut and cumulative oil recovery curves as a function of injected
pore volume of formation water or polymers solutions for rect-
angle cores are shown in Fig. 9c–f. The initial water flooding had
the oil recovery of Ew ranging 64–67%. As for HPAM solution with
the concentration of 20 0 0 mg/L, the incremental oil recovery factor
was 9.2%, indicating that HPAM had limited EOR efficiency in harsh
conditions despite the high concentration was employed (Fig. 9c).
As for HAPAM solution with the concentration of 1750 mg/L, the
incremental oil recovery factor was 12.5% with Et of 79.3% (Fig. 9d).
HAPAM concentration was lower than that of HPAM, whereas HA-
PAM had higher EOR efficiency, implying that the intermolecular
interactions of polymeric chains provided HAPAM with higher mo-
bility control ability. The highest incremental oil recovery factor
of 20% with Et of 86% for core 7# was achieved by SHPAM so-
lution at the concentration of 1500 mg/L (Fig. 9e). Moreover, SH-
PAM was compatible with permeability because the correspond-
ing EOR efficiency with Et of 85% for higher permeability core 8#
was achieved by employing the identical concentration and pore
volume (Fig. 9f). The evidence from EOR tests confirmed that be-
sides the hydrophobically intermolecular interactions of polymeric
chains, star-like morphology of SHPAM contributed to its desirable
and stable mobility control ability. As a result, the expecting EOR
efficiency was achieved in harsh reservoir conditions.
3.6. Brief analysis of prospects
Recently, the need for exploiting more unconventional oil reser-
voirs for crude recovery significantly increased the number of ma-
ture reservoirs which could be targeted for polymer flooding as an
EOR technology [26]. Development of more efficient polymers, re-
garding their prominent comprehensive properties in harsh reser-
voirs, from design in laboratory to manufacture in petroleum in-
dustry is a crucial mission. Besides the addition of a small amount
of functionalized nano-silica particles, SHPAM is prepared using
AM, AA and the hydrophobic monomer (MeDiC8 AM) via a facile
free radical polymerization whose manufacturing procedure is sim-
ilar to HAPAM. The feasible raw materials for synthesizing FNPs
hydrophobically associative polyacrylamide for enhanced oil recov-
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10 R. Liu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–11

Fig. 9. (a and b) Pressure differential profiles of SHPAM solution with the concentration of 1500 mg/L prepared with formation of water in two serial sandstone cores at
82.3 °C; and (c)–(f) pressure differential histories, water cut and cumulative oil recovery curves as a function of injected pore volume of formation water or polymers
solutions at 82.3 °C.

may result in a slightly higher manufacturing cost compared to
HAPAM. The comprehensive properties of SHPAM discussed above,
however, are noticeable in harsh conditions even when lower con-
centration was used in comparison to that for HAPAM. SHPAM
may have promising applications in mature reservoirs for EOR pur-
poses. Further development of SHPAM products is in progress in
our group.
4. Conclusions
SHPAM consisting of nano-silica as the core and a layer of
amphiphilic-polymeric chains as the shell was synthesized and
its comprehensive properties were measured to elucidate its un-
derlying applications in hostile reservoirs. TEM, SEM, IR and 1 H
NMR analysis proved that the notion and method of preparing SH-
PAM was fairly practicable. Despite relatively high Mw , the smaller
molecular weight of each polymeric chain provided SHPAM with
desirable solubility in high salinity brine. The star-like morphol-
ogy associated with the intermolecular associations of neighboring
polymeric chains made SHPAM have superior thickening efficiency
and long-term stability. SHPAM displayed shear thickening behav-
ior in multiscale compared to the monotonous shear thinning of
HAPAM and HPAM over the shear rate regime. In addition, the
η0 of SHPAM solution with the concentration of 20 0 0 mg/L was
3.6 times to that for HAPAM and 60 times that for HPAM at the
equivalent concentration. SHPAM was well compatible with per-
meable cores and had sustainable mobility control in depth. After
the extensive water flooding, EOR efficiency was increased by 20%
for 0.3 pore volume of SHPAM at an acceptable concentration of
1500 mg/L. Based on the work of this paper, SHPAM may have ro-
bust applications in chemical EOR processes in high temperature
and high salinity reservoirs.
Acknowledgments
We are grateful to Chinese Postdoctoral Science Foundation
(2017M612994), and the Scientific and technological Supporting
Program (2016FZ0114) by Science & Technology Department of

Please cite this article as: R. Liu et al., Star-like hydrophobically associative polyacrylamide for enhanced oil recov-
ery: Comprehensive properties in harsh reservoir conditions, Journal of the Taiwan Institute of Chemical Engineers (2017),
http://dx.doi.org/10.1016/j.jtice.2017.08.043
JID: JTICE
ARTICLE IN PRESS
R. Liu et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2017) 1–11
Sichuan Province for financial support of this work. The authors
appreciate reviewers for their constructive comments.
Supplementary materials
Detailed information of parameters of rectangle cores and the
procedure for synthesis of FNPs and MeDiC8 AM are available in
Supplementary material.
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.jtice.2017.08.043.
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