Petroleum Science and Technology

ISSN: 1091-6466 (Print) 1532-2459 (Online) Journal homepage: http://www.tandfonline.com/loi/lpet20

Studies on behavior of suspension of silica

nanoparticle in aqueous polyacrylamide solution
for application in enhanced oil recovery

Neetish Kumar Maurya & Ajay Mandal

To cite this article: Neetish Kumar Maurya & Ajay Mandal (2016) Studies on behavior
of suspension of silica nanoparticle in aqueous polyacrylamide solution for application
in enhanced oil recovery, Petroleum Science and Technology, 34:5, 429-436, DOI:
10.1080/10916466.2016.1145693

To link to this article: http://dx.doi.org/10.1080/10916466.2016.1145693

Published online: 06 Apr 2016.

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 PETROLEUM SCIENCE AND TECHNOLOGY
, VOL. , NO. , –
http://dx.doi.org/./..

Studies on behavior of suspension of silica nanoparticle in aqueous

polyacrylamide solution for application in enhanced oil recovery
Neetish Kumar Maurya and Ajay Mandal
Department of Petroleum Engineering, Indian School of Mines, Dhanbad, India

ABSTRACT KEYWORDS
The use of nanoparticle/polymer suspension for high-temperature and high- Rheology; silica nanoparticle;
saline reservoir was investigated by measuring rheological properties and polyacrylamide; suspension;
characterizing the interaction between polymer and nanoparticle. Polyacry- enhanced oil recovery
lamide (PAM) and silica nanoparticle were used in this study. The result indi-
Downloaded by [Universite Laval] at 02:29 11 April 2016

cates that silica/PAM suspension have higher viscosity and viscosity retention
was improved in the presence of salt and at high temperature as compared to
simple PAM solution. Improved performance was attributed to the formation
of complex macromolecular structure. PAM gets adsorbed on the surface of sil-
ica due to hydrogen bonding and the silica particle act as physical cross-linker
between polymeric chains, resulting in improvement of viscosity.

1. Introduction
Polymers such as polyacrylamide (PAM) and its derivatives such as partially hydrolyzed polyacrylamides
(HPAM) have been widely used in different enhanced oil recovery (EOR) applications (Abidin et al.,
2012; Afolabi, 2015) as a mobility improver. However these polymers are sensitive to high temperature
and inorganic salt, which leads to decrease in viscosity in such conditions, and thus reduced oil recovery
(Levitt and Pope, 2008; Zhang et al., 2006). In aqueous solutions, the amide groups present in polymer
molecule immediately hydrolyzed into carboxylic group, which reacts with the ions presents in solution
and as a result, the viscosity is decreased. In severe condition, it even leads to precipitation (Muller, 1981;
Abu-Sharkh, 2002). The precipitation will lead to loss in mobility control and might even block the small
pore network inside reservoir thus decreasing the permeability. At high temperature, the precipitation
problem is much severe. This possesses some difficulties for such polymer to be used in high-temperature
environment in reservoir where hard brines are present.
Hybrid/suspension and grafted nanoparticles with polymer have been shown to provide better rheo-
logical performance at laboratory scale (Zhu et al., 2014; Yousefvand and Jafari, 2015). An interesting
quality of polymers is to encourage bridging induced flocculation of nanoparticles present in water,
which leads to improved rheological property (Otsubo et al., 1984; Kamibayashi et al., 2005). Also,
the particle polymer interaction can lead to better salt and temperature tolerance for polymer solution
(Zaman et al., 2002; Aalaie, 2012). When a combination of polyacrylic acid (PAA) and polyethylene
(PEO) were added in silica suspension, the polymer was adsorbed on the surface of silica particle, lead-
ing to a structured formation which resulted in improved viscosity of suspension (Whitby et al., 2003).
When a silica nanoparticle was added in xanthan gum (XG) and locust bean gum (LBG) biopolymer and
their combined gel (LX), it was found that it alters the properties of biopolymer solutions and gels and
increases viscosity and elasticity in xanthan gum solutions (Kennedy at al., 2014).

CONTACT Ajay Mandal mandal_ajay@hotmail.com Department of Petroleum Engineering, Indian School of Mines, Dhanbad,
India-.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.
©  Taylor & Francis Group, LLC
 430 N. K. MAURYA AND A. MANDAL.

The aim of the present study is to find out the effect of including a silica nanoparticle with commonly
used oil field polymer polyacrylamide. Rheological experiments were performed on silica/PAM suspen-
sion in water and effect of salt and temperature were investigated. The results were compared with those
of pure PAM solution at different silica/polymer concentrations, shear rates, salt concentrations, and
temperatures.

2. Experimental
Polyacrylamide with average molecular weight of 5×106 to 6×106 g/mol−1 was procured from Sigma-
Aldrich. SiO2 nanoparticle, size range of 20–30 nm and molecular weight 60.08 was purchased from
Sisco-Research Laboratories. Sodium chloride was used for preparation of brine.

2.1. Sample preparation

At first PAM solution was prepared by addition of PAM to deionized water while gently stirring on a
magnetic stirrer for 10–12 h. NaCl salt was added to obtain the desired salinity. Suspension of Silica
nanoparticle was created by adding powder of silica in water and agitating it in an ultrasonic homoge-
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nizer for 15 min. The silica/PAM suspension was created by mixing equal volumes of PAM solution and
silica suspension at desired temperature. The silica/PAM suspension was then gently stirred on mag-
netic stirrer for 24–30 h and then left for 10 h to let it equilibrate before doing any further studies. After
preparation, FTIR of PAM solution and silica/PAM suspension were first analyzed using Perkin Elmer
Spectrum 2 spectrophotometer.

2.2. Rheological studies

Rheological studies were performed using a Bohlin Gemini Rheometer (Malvern Instruments, England).
Rheological measurements were taken under both steady and oscillatory shear to calculate both steady
and dynamic properties. Under steady shear, the flow curves were recorded at shear rates between 1–100
sec−1 . For oscillatory shear, at first, stress-sweep measurement was performed to find out the linear vis-
coelastic region. Thereafter all the dynamic frequency behaviors of sample were taken in this viscoelastic
region.

3. Results and discussion

3.1. FT-IR spectroscopy

To investigate, the interaction between silica and PAM, FT-IR spectroscopy was performed for PAM
solution and silica/PAM suspension and the result is presented in Figure 1. The peaks in the wavenum-
ber range from 900 to 4000 cm−1 are almost identical for both the system. Both systems confirm strong
stretching vibration peaks approximately around 3400 cm−1 and 1660 cm−1 indicating the presence of
amino group and carbonyl group of polyacrylamide. In FT-IR spectra of silica/PAM a new peak appears
at 1106.8 cm−1 , which is due to presence of the Si–O–Si asymmetric band stretching vibration. It can also
be noted that in FT-IR spectra of silica/PAM suspension, the peak around 3340 cm−1 becomes broader.
This indicates the formation of hydrogen bonds between the amide groups and the silanol functions of
the silica particles (Kennedy et al., 2014), suggesting a strong interaction between polymer and nanopar-
ticles in silica/PAM suspension.

3.2. Rheological behavior of PAM solution and PAM/silica suspension in water

The effect shear rate on the viscosity of PAM/Silica suspensions were studied. The results are plotted
in Figures 2a and 2b for two different PAM concentrations of 2500 and 5000 ppm with varying silica
concentration from 2000 to 10000 ppm. Results indicate that the addition of silica nanoparticles in PAM
 PETROLEUM SCIENCE AND TECHNOLOGY 431
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Figure . Comparison of FT-IR spectra of  ppm PAM solution and  ppm silica/ PAM suspension.

Figure . Effect of silica nanoparticle concentration on rheological behavior of silica/PAM suspension with PAM concentration of (a)
 ppm and (b)  ppm. (c) Relative increase in viscosity of silica/PAM suspension with increase in concentration of silica nanoparticle
for two fixed PAM concentration of  and  ppm respectively measured at fix shear rate of  sec− .
 432 N. K. MAURYA AND A. MANDAL.
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Figure . (a) Mechanism of irreversible bridging of silica particles through adsorption of PAM on silica surface. (b) Effect of polymer
concentration on degree of bridging of silica particle in silica/PAM suspension.

solution leads to an increase in the viscosity. Across all polymer concentration, silica/PAM suspension
has higher viscosity than PAM solution. Also, the silica/PAM suspensions depict a non-Newtonian, shear
thinning behavior (i.e., the viscosity continuously decreased with increasing shear rate). This behavior
is same as of reported polymer/particle suspension (Choi et al., 1999).
The incremental viscosity and shear thinning behavior of silica/PAM suspension can be attributed to
strong interaction between PAM and silica particles in water. As discussed in FT-IR spectroscopy there
are strong interactions between PAM and silica due to formation of hydrogen bonds. The formation of
hydrogen bond leads to adsorption of PAM macromolecules at the surface of silica nanoparticle (Lafuma
et al., 1991). So the polymer chain is now physically bound at the surface of silica particles. As a result of
this, the silica particle acts as physical cross-linker between different polymeric chains. This phenomenon
can be best explained by formation of flocculated structure containing silica and PAM and the process
is modeled in Figure 3a. During adsorption, a polymer chain need not to be attached only to a single
particle surface. In fact, it can be adsorbed to more than one particle at a time and also a number of
polymeric chains can be adsorbed on the surface of particle and it is usually irreversible (Otsubo et al.,
1984). Upon adsorption, only a portion of polymeric chain is in direct contact of silica surface at single or
several point, while the rest (tail) extend away from the surface into the solution. These tails get adsorbed
onto one or different silica particle when it comes into contact surface of silica. This results in flocculation
 PETROLEUM SCIENCE AND TECHNOLOGY 433

Figure . (a) Effect of increasing NaCl concentration on viscosity of  ppm silica/ PAM suspension. (b) Relative decrease in vis-
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cosity of  ppm PAM solution and  ppm silica/ PAM suspension with increasing concentration of NaCl measured at fix shear
rate of  sec− .

of silica particle and a micelle type, and three-dimensional network of flocs is developed (Zaman et al.,
2002). Because of the irreversible adsorption of polymer, the resultant macromolecular structure is not
easily broken and stable, and it leads to increase in viscosity of the suspension. The bridges between these
silica particles and PAM are not broken in a quiescent state, but progressively weakens in shear fields,
thus the flow of flocculated suspensions is shear-thinning (Kamibayashi et al., 2005). Polymer adsorption
is irreversible because polymeric chains may attach to the surface at several points but may not be able
to desorb simultaneously from all sites. Also, a number of polymeric chains are attached to the surface
at different points at any time. The free energy responsible for each hydrogen bond is very low but the
total free energy for a single macromolecule is very large; thus, adsorption is irreversible process (Lafuma
et al., 19990).
Relative increase in viscosity with increase in concentration of silica nanoparticles has been reported
in Figure 2c for two fixed polymer concentrations of 2500 and 5000 ppm, respectively. It can be seen
that at lower concentrations of polymer the silica/PAM suspension has high viscosity. The reason for
this can be explained as follow and have been modeled in Figure 3b. The change in viscosity of suspen-
sion can be accredited to two things. First, a decrease in viscosity of solution due to polymer adsorption
will reduce the polymer concentration. Second, an increase in viscosity due to formation of flocculation
induced micelle type three-dimensional network. When the polymer concentration is less, the increase
in viscosity due to formation of three-dimensional network of flocs is greater than decrease in viscosity
due to adsorption. Because at low polymer concentration there will not be sufficient polymer to cover
the complete particle surface and hence it will promote the bridging of the polymer with a number of
silica nanoparticles and a strong network will be developed (Figure 3b, iii). However, at very low con-
centration of polymer the viscosity of suspension will decrease. As degree of irreversible bridging will be
very less (Figure 3b, i) and the decrease in viscosity due to polymer adsorption will dominate (Nabzar
et al., 1988; Saito et al., 2008). Thus, there will also exist a critical saturation where viscosity will start to
decline. At intermediate and high concentrations of polymer, the degree of cross bridging through poly-
mer adsorption on particle will be intermediate as a sufficient number of polymeric chain in the solution
will be present for surface coverage of particle. (Figure 3b, ii).

3.3. Effect of salt concentration on viscosity of PAM and PAM/silica suspension in water
The studies on effect of salt on the viscosity of particle/polymer suspension are meager and this aspect
has been investigated in detail. The data obtained from the result have been reported in Figures 4a and
4b. From Figure 4a it can be seen that viscosity of silica/PAM suspension decreases upon the addition of
 434 N. K. MAURYA AND A. MANDAL.

Figure . (a) Viscosity of silica ( ppm)/PAM ( ppm) suspension in water as a function of shear rate for three different temperature
of , , and °. (b) Viscosity plotted as a function of temperature for  ppm PAM solution and silica ( ppm)/PAM ( ppm)
suspension in pure water measured at a shear rate of  sec− .
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salt in suspension. The behavior is same as of a simple PAM solution. However from Figure 4b it can be
seen that the decrease in viscosity in case of silica/PAM suspension is less than that in case of PAM solu-
tion. In presence of water, the hydrolysis of amide group of PAM chain leads to formation of carboxylic
group and due to its negative charge the amount of negative charge on the polymer chain increases.
The repulsion between negative charges of carboxylic group leads to stretching of PAM molecules in its
macromolecules structure. Thus, PAM macromolecules have high hydrodynamic radius and have higher
viscosity. But once the salt such as NaCl is added, the negative charge on the carboxylic group is neu-
tralized and repulsion between molecules decreases. So the hydrodynamic radius PAM macromolecules
decrease, which leads to lower viscosity. In silica/PAM suspension there will be two forces at work. First,
the bridging induced flocculation of particle will try to increase the viscosity and on the other hand neu-
tralization of negative charge will try to decrease the viscosity. The overall viscosity will be higher than
PAM solution due to dominating bridging induced flocculation of particle. At higher concentrations of
silica particles, when almost all of the polymeric chain are adsorbed on the silica surface, the effect of
salt on the viscosity will be very low and the silica/PAM mixture will have much higher viscosity to that
those of PAM solution.

3.4. Effect of temperature on viscosity of PAM solution and PAM/silica suspension

The loss of viscosity of PAM and its derivative at elevated temperature is one of the drawbacks for its
use in high pressure-high temperature environment. The effect of temperature on PAM and silica/PAM
suspension in water has been studied and results are presented in Figures 5a and 5b. The results indicate
that the viscosity of both PAM solution and silica/PAM suspension is strongly dependent on temperature
and for both systems, the viscosity is decreased as the temperature increased. These results are at par with
the reported behavior of commonly used water-soluble polymer solution. But as shown in Figure 5b, the
viscosity of silica/PAM suspension is at least 1.5 times higher than that of PAM solution at all tempera-
ture. For PAM at higher temperature the mobility of molecules is increased, which in turn decreases the
intermolecular interaction in polymer macromolecules and the probability of their coiling, which in turn
decreases the viscosity of the solution. For silica/PAM suspensions as discussed above adsorption of poly-
mer on silica surface leads to formation of micelle type three-dimensional network of flocs, which leads
to increase in viscosity. Even at higher temperature, the strong interaction between polymeric chains and
silica still exists which leads to improved thermal stability of silica/PAM suspension. Thus even at ele-
vated temperature stable structure leads to a higher viscosity than that of simple PAM solution. At higher
temperature the decrease in viscosity of silica/PAM suspension mainly due to decrease in adsorption of
polyacrylamide at silica surface at higher temperature (Wisniewska et al., 2012). At higher temperature,
 PETROLEUM SCIENCE AND TECHNOLOGY 435
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Figure . (a) Storage (G ) and loss modulus (G ) of  ppm PAM solution as function of angular frequency under a controlled strain of
γ  = %. (b) Storage (G ) and loss modulus (G ) of  ppm PAM/ ppm silica suspension function of angular frequency under a
controlled strain of γ  = %. (c) Comparative graphs of Storage (G ) and loss modulus (G ) for PAM and PAM/silica suspension under a
controlled strain of γ  = %.

the hydrogen bonds that have been formed between PAM and silica become weak. This leads to weak-
ening of network structure and decrease in viscosity of silica/PAM suspension. However, the viscosity is
still higher than that of PAM suspension.

3.5. Dynamic rheology studies of PAM and PAM/silica suspension

Under the influence of a constant oscillatory strain (i.e., γ 0 = 10%), the response of PAM and PAM/silica
suspension to different angular frequency was studied and both the storage modulus (G ), loss modulus
(G ) were measured. Figures 6a and 6b is the plot of modulus (G ), loss modulus (G ) as a function on
increasing angular frequency for PAM and PAM/silica suspension respectively and in Figure 6c is the
comparative viscoelastic response of both the system is presented. The storage modulus (G ) is used to
estimate the elastic behavior of the materials. On the other hand, the loss modulus (G ) is the character-
istic of the viscous behaviors. When the value of G is higher than G , it represents that the suspension
exhibits liquid-like behaviors. Vice versa when elastic component is higher than the viscous component
and the systems display viscoelastic gel-like behaviors. For both systems, the values of G and G increased
with the increasing frequency. For PAM/silica suspension the value of G is higher than that of simple
PAM solution. There is very little change in the value of G upon addition of silica nanoparticles. These
results show that due to addition of silica nanoparticles, which leads to interaction of PAM and silica
 436 N. K. MAURYA AND A. MANDAL.

and the formation of complex network structure takes place by the adsorption of polymeric chain on
the silica surface. This enhances the elasticity of polymeric suspension and so elasticity of suspension is
more as compared to pure polymeric solution. The results are in tandem with the earlier reported result
for particle suspension in polymer (Kennedy et al., 2014; Zhu et al., 2014).

4. Conclusion
The performance of silica/PAM suspension in terms of rheological properties was investigated for EOR
application. In laboratory experiments, the effects of nanoparticle concentration, polymer concentra-
tion, temperature, and salinity on the rheological properties of the silica/PAM suspensions were studied.
With the introduction of nanoparticle in the PAM solution, a complex micelle type three-dimensional
network structure was formed by irreversible bridging of polymeric chain with nanoparticle. The adsorp-
tion of polymeric chain on silica nanoparticle surface was attributed to formation of hydrogen bonds.
Such interaction leads to a remarkable increase in apparent viscosity of suspension as compared with
viscosity of PAM solution at all condition. Addition of silica nanoparticles also leads to improved salt
tolerance and low long-term thermal degradation of suspension. The increase in concentration of sil-
ica found to strengthen the network structure of polymeric solution and thus lead to improvement in
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apparent viscosity and other properties. The obtained result shows a promising prospect for silica/PAM
suspension for potential application in EOR operations due to its stability at higher temperature and high
salinity.

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