SPE 113620

Mechanistic Interpretation and Utilization of Viscoelastic Behavior of

Polymer Solutions for Improved Polymer-Flood Efficiency
Mojdeh Delshad, SPE, Do Hoon Kim, Oluwaseun A. Magbagbeola, SPE, Chun Huh, SPE, Gary A. Pope, SPE,
and Farhad Tarahhom, SPE, The University of Texas at Austin
Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE/DOE Improved Oil Recovery Symposium held in Tulsa, Oklahoma, U.S.A., 1923April2008.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
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Abstract
There are increasing laboratory and field evidences that the viscoelastic characteristics of polymer solutions help improve
polymer-flood efficiency. Extensive rheological measurements and laboratory corefloods with partially hydrolyzed
polyacrylamide polymers with very high molecular weight were carried out to delineate the role of their viscoelastic behavior
in improving oil recovery from polymer flood. Different polymer solutions elastic contribution is modeled in the polymers
apparent viscosity in porous media, which is implemented in UTCHEM simulator for quantification of improved reservoir
sweep.
As the application range of polymer flood is extended to recover more viscous oils with use of polymers at high
concentrations and with very high molecular weights, a mechanistic understanding of polymer rheology in porous media and
accurate numerical modeling are essential for successful field implementation of polymer flood.
Oscillatory and shear viscosity measurements and polymer flow coreflood experiments were carried out for different
shear rates (and flow velocities and permeabilities in core), polymer concentrations, and molecular weights. The polymers
shear-thickening characteristic was correlated with the Deborah number via its molecular relaxation time, which is in turn
determined from the rheological data. An apparent viscosity model that accounts for both shear-thinning and shear-
thickening behavior of polymer in porous media was developed, which fit the laboratory data well. The model was then
implemented in a compositional chemical flooding simulator and successfully history-matched published coreflood oil
recovery experiment.
Through systematic rheological measurements and corefloods, and their use in the apparent viscosity model for
simulation, the elastic contribution of different polymers in improving polymer-flood efficiency is quantified. Specifically, a
polymer solutions shear-thickening behavior is characterized in terms of the molecular relaxation time determined from bulk
rheology measurements.

Introduction
For a majority of oil reservoirs, large amounts of oil are still left unrecovered even after extensive waterflooding, due to
reservoir heterogeneity. Once water channels are formed through high-permeability zones, the water subsequently injected
simply bypasses the oil stranded in the low-permeability zones. To recover the bypassed oil, a low-concentration polymer
solution that viscosifies water is injected to improve the reservoir sweep efficiency. An extensive research has been carried
out for more than 50 years to develop and refine the polymer flooding process (see e.g., Sorbie, 1991). Polymer flooding is
now considered to be a technically and commercially proven improved oil recovery process, especially since its large-scale
application at Daqing field in northern China where about 300,000 barrels of incremental oil per day is attributed to polymer
flooding (Wang et al., 2001). Like applications elsewhere, a partially hydrolyzed polyacrylamide (HPAM) is employed,
which is available at low cost worldwide.
A key characteristics of polymers used for polymer flooding is that they are shear-thinning, i.e., the polymer solution
viscosity decreases with shear rate, and consequently its apparent viscosity in reservoir rock decreases in general with flow
velocity. This is a desirable property, because the polymer solution can be injected at the well where the flow velocity is
high, without too much pressure drop. This property is at the same time a weakness in displacing the bypassed oil from deep
in the reservoir, because the flow velocity in the high-permeability zone would be higher than that in the low-permeability
zone, and accordingly, the polymer solution viscosity in the high-permeability zone could be lower than that in the low-
permeability zone. Therefore, the objective of sending more of the injected fluid to the low-permeability zone may not be
2 SPE 113620
fully realized. A simple analysis elaborating this point has been made by Jones (1980). It shows that, except for the near
wellbore, the presence of a shear-thickening fluid for the bulk of the reservoir volume is more effective in displacing the
bypassed oil from the low-permeability zone. The apparent viscosity of polymer solution in the high-permeability zones
could then become high, fulfilling the objective of improving the sweep efficiency. Ideal characteristics for the polymer
solution therefore will be that its viscosity is low near the injection wellbore, but otherwise it is shear-thickening with a high
viscosity.

The Shear-Thickening Behavior of HPAM. One important characteristics of a HPAM solution flowing in porous media is
that, while it is shear-thinning at low-to-intermediate flow velocity (or effective shear rate), beyond a certain flow velocity, it
becomes highly shear-thickening (see, e.g., Maerker, 1984). The main reason for the high apparent viscosity is that, as the
polymer molecules flow through series of pore bodies and pore throats in reservoir rock, the flow field elongation and
contraction occurs. If the flow velocity is too high, the polymer molecules do not have sufficient relaxation time to stretch
and re-coil, adjusting to the flow. The resultant elastic strain causes its apparent high viscosity. HPAM with a higher
molecular weight (MW) exhibits a more shear-thickening behavior than a lower-MW one, at a given flow velocity. This
point is further elaborated later.
One interesting development with the Daqing polymer flood mentioned above is worth to note here. The Daqing
researchers observed in the laboratory coreflood experiments that the viscoelasticity of HPAM solution helps to displace even
the residual oil left after extensive waterflood, and they are moving towards employing very high molecular weight HPAM
(> 15 million) which shows more prominent elastic behavior (Wang et al., 2001). While it is generally believed that polymer
flooding cannot displace the waterflood residual oil saturation, there are evidences that, when a polymerflood is carried out
without waterflood, its residual oil saturation can be lower than the waterflood residual oil saturation (see Huh and Pope,
2008 for literature review). A possible mechanism for the reduction in the residual oil saturation from the secondary
polymerflood is discussed in Huh and Pope (2008). Another possible explanation for the added improvement in oil recovery
is that the polymers shear-thickening behavior helped to displace the still mobile but hard-to-displace oil near the residual oil
condition faster, or displace the bypassed oil in small-scale heterogeneities more effectively.
Based on the earlier literature evidences and Chinese observations, it appears that the shear-thickening characteristics of
polymer solution, combined with its viscosifying ability, can have impact on improving the sweep of the oil bypassed due to
reservoir heterogeneity. The potential benefit of the shear-thickening in improving sweep efficiency, in fact, had been
recognized earlier (e.g., Jones, 1980). A critical question that still needs to be resolved is the high pressure drop and the
potential mechanical degradation at the injection well, when the polymer is shear-thickening. A number of researchers earlier
attempted to develop polymers that are shear-thickening at moderate flow velocities, but shear-thinning at high flow
velocities (Maerker and Sinton, 1984). These polymers, known as bi-functional or associative polymers, are quite expensive
to manufacture and difficult to control their behavior in the reservoir. It is also difficult to adjust their molecular structure to
fit the different flow velocity and salinity requirements for different reservoirs.
With relatively low molecular weight HPAMs that have been employed for IOR earlier, the shear-thickening behavior
usually does not develop in the range of flow velocities in the reservoir. Therefore, a shear-thinning rheology model, such as
the Carreau model as described below, is employed. With the use of HPAM with molecular weight greater than 20 million,
the shear-thickening behavior could be important, and a reliable rheological correlation that accounts for both shear-thinning
and shear-thickening behavior needs to be developed. Recognizing its importance, a number of researchers attempted to
model the shear-thickening behavior in terms of the polymer molecular parameters and the fluid flow conditions in porous
media (Hirasaki and Pope, 1974; Haas and Durst, 1981; Heemskerk et al., 1984; Masuda et al., 1992; Ranjbar et al., 1992;
Han et al., 1995). The main objective of this work is to develop such a correlation for the entire range of flow velocity,
without actually measuring the apparent viscosity of polymer solution flowing in a reservoir rock, but from the rheometric
measurements of viscosity.

Rheological Model for HPAM Solution
An apparent viscosity model that covers the full spectrum of Newtonian, shear-thinning and shear-thickening behaviors in
reservoir rock is proposed here. It is a composite of the Carreau model and an empirical model that correlates the shear-
thickening viscosity trend with the Deborah number, a ratio of polymer molecules relaxation time to its average residence
time between pore body and pore throat. A key feature of this model is that the apparent viscosity can be correlated with the
full range of Darcy velocity, via the effective shear rate. An important advantage of the model is that the apparent viscosity
correlation for different polymers and different rocks could be obtained based on the rheometric measurements of polymer
solution viscosity and some limited coreflood data. Deborah number was obtained from the rheometric measurements and
the Rouse model (Bird, 1977) for relaxation time.

Apparent Viscosity Model for Full Velocity Range. In developing a comprehensive model for apparent viscosity, we
assume that its dependence on Darcy velocity (or effective shear rate) consists of two parts: shear-viscosity-dominant part,

sh
, and elongational-viscosity-dominant part,
el
:

sh el
= + (1)
SPE 113620 3
A composite apparent viscosity model is then proposed in which the shear-viscosity-dominant part is represented by the
Carreau equation, shown below, and the elongational-viscosity-dominant part is represented in terms of the Deborah number,
as was modeled by Hirasaki and Pope (1974) and others.

Apparent Viscosity for the Shear-Thinning Regime. For polymers that show shear-thinning behavior, a widely employed
rheological model for such solutions is the Carreau model (Cannella et al., 1988):

(n 1) /
0
sh p eff
( ) 1 ( )

= +


(2)
where
sh
is the apparent shear viscosity in porous media;
0
p
and

are the limiting Newtonian viscosities at the low and

high shear limits, respectively;
eff
is the effective shear rate (Eq. 3); and n are polymer-specific empirical constants; and
is generally taken to be 2. For intermediate shear rates, the Carreau equation shows a power-law relation.
The above expression, originally for viscometer-measured viscosity, can be converted to the apparent viscosity of
polymer solution flowing in porous media, by replacing the shear rate with the following effective shear rate expression
applicable for a permeable rock:

n /(n 1)
w
eff
rw w
u 3n 1
C
4n kk S

+
=




(3)
where u
w
is Darcy velocity of the polymer-containing water phase; k is permeability; k
rw
is the water relative permeability; S
w

is water saturation; and is porosity. Cannella et al. (1988) reported that C = 6.0 in the above equation fits a wide variety of
coreflood data well. However, in general C is a function of permeability and porosity. Wreath et al. (1990) made a
comprehensive review on different expression for the effective shear rate, including the above.

Apparent Viscosity for the Shear-Thickening Regime. As the polymer molecules flow through series of pore bodies and
pore throats in reservoir rock, the flow field elongation and contraction occurs. Accordingly, the polymer molecules
repeatedly stretch and re-coil to adjust to the flow field. If the flow velocity is too high, the polymer molecules do not have
sufficient relaxation time to stretch and re-coil, adjusting to the flow. The resultant elastic strain causes its apparent high
viscosity, represented as shear-thickening behavior.
In order to account for the shear-thickening behavior, we therefore assume, as others, that
el
is an empirical function of
Deborah number, N
Deb
. The Deborah number, which is a ratio of the relaxation time for a polymer molecule (
r
) to the
characteristic period for elongation and contraction as the fluid flows through a series of pore throats and pore bodies (
E
), is
shown to characterize the polymers elastic strain (Bird et al. 1977).
Hirasaki and Pope (1974) proposed a model of the form

el sh Deb
/[1 N ] = (4)
Masuda et al. (1992) proposed
( )
c
m
el sh c Deb
C N = (5)
where C
c
and m
c
are empirical constants. We propose here another model that is not scaled by
sh
:
( )
( )
2
n 1
el max 2 Deb
1 exp N

=


(6)
where
max
,
2
and n
2
are empirical constants. One notable distinction between the earlier models (Eqs. 4 and 5) and the
proposed model (Eq. 6) is that, while the
el
values from the earlier models could increase indefinitely as N
Deb
increases, the
proposed model provides the plateau value of
max
.
In the above equations, the Deborah number may be defined as

r
Deb r eff
E
N

=

(7)
assuming, as Masuda et al. (1992) did, the inverse of the effective shear rate Eq. 3 is a good approximation for the average
residence time,
E
. Hirasaki and Pope (1974), Durst et al. (1981) and Haas and Durst (1981) approximated the average
residence time with the inverse of the rate of flow elongation and contraction in the reservoir rock, :
4 SPE 113620

w
E w rw w
u 1 v
d (1 S ) 150kk / S
= = =

(8)
where v is the interstitial velocity, and the latter expression of Eq. 8 being obtained with use of Kozeny-Carman equation for
d, the average pore size. Note that the effective shear rate, Eq. 3, and Eq. 8 have the same dependence on the key parameters,
u
w
, k, and k
rw
, but the coefficient values will be different.
The apparent viscosity expression that covers the entire range of Darcy velocity is, by combining Eqs. 1, 2, and 6:
( )
( )
2
(n 1) /
n 1 0
p eff max 2 r eff
( ) 1 ( ) 1 exp





= + + +



(9)
Several models have been proposed to predict the polymer molecules relaxation time as briefly reviewed below.

Models for Polymer Molecules Relaxation Time. The relaxation time models can be broadly divided into two: (i) those
that rely entirely on empirical measurements; and (ii) those that are based on the theoretical consideration of dynamics of
polymer molecules in solution. Two widely employed models are described below, and other models are briefly discussed in
the Appendix.
The relative magnitude of viscous and elastic components of transient viscosity of a polymer solution is commonly
obtained by performing a dynamic frequency sweep test with a rheometer. From the stress response to the oscillatory strain,
the complex solution viscosity,
*
V E
i = , is obtained where
E
G / = and
V
G / = are, respectively, its
imaginary and real parts. Here, is angular frequency in rad/s; G' is storage modulus, representing elastic component of
viscoelasticity of polymer solution; and G" is loss modulus, representing its viscous component.

The G' and G" Cross-Over Point Model. Since G' and G" represent the elastic and viscous components of
viscoelasticity, it has been suggested that the inverse of the frequency at which G' and G" intersects is the characteristic
relaxation time of the polymer solution (Volpert et al., 1998; Castelletto et al., 2004). This intersection has also been
described as an indication of the onset of a phenomenon called entanglement coupling. This is a phenomenon whereby there
is a strong coupling of neighboring molecules to molecular motion along the chain.

Rouse Model. The data from the dynamic frequency sweep test (G' and G" versus frequency) is usually fitted with this
model in order to obtain a spectrum of relaxation times. The model is given as:

( )
2 2
N
p p
2 2
p 1 p
c RT
G
M
1
=

=
+

(10)

( )
N
p p
2 2
p 1 p
c RT
G
M
1
=

=
+

(11)
where c
p
is polymer concentration in g/cc; and
p
is relaxation times in s. The polymer molecule is represented as a chain of
N beads connected together using N 1 elastic springs, and the longest of the spectrum of relaxation times obtained is used
for the flow data through cores (Heemskerk et al., 1984). Note that, unlike other models in the Appendix, it accounts for the
effects of polymer concentration.

Experimental Results and Model Validation
A relaxation time model that best characterizes the available rheometry data is first sought. Employing polymer flow
coreflood data, the validity of the proposed apparent viscosity model (Eq. 9) is then tested.

Testing of Relaxation Time Models with Rheometer Data. The above models were tested with several oscillatory
viscosity data obtained by Yuan (1981) and the present work. The ARES LS-1 Rheometer from TA Instruments was used to
measure the bulk viscosity and oscillatory/dynamic properties such as the storage and loss modulus of the polymer solution.
It is a mechanical spectrometer that operates by measuring the resulting torque generated by a sample in which a dynamic or
steady strain deformation has been applied. The motor applies the strain while the torque is measured by the transducer. The
ARES includes a dynamic frequency range of six decades. Powdered Flopaam 3630S and Flopaam 3330S from SNF
Floerger; see Table 1 were used in these experiments. Stainless steel filter press apparatus with rubber O-rings was used.
The filters were manufactured by Millipore. The fluid to be filtered was put in a stainless steel reservoir with filter press
connected onto the top with Swagelok fittings. The fluid is pressurized and forced through the filter using Argon gas.
SPE 113620 5
Polymer solutions were filtered at 15 psi using 1.2 m filter paper. The brine solution, referred to Brine A, contained 20,000
ppm total dissolved solids comprising of 15400 ppm Na
+
, 2540 ppm Ca
++
, and 2100 Mg
++
.
Figure 1 shows the storage and loss modulus (G', G") obtained from a dynamic frequency sweep test made with 1500
ppm Flopaam 3630S. The G'-G" cross-over point for the polymer solution is obtained at the angular frequency of = 17.61
rad/s, which gives the relaxation time of
r
= 0.0568 s. The data in Fig. 1 were also employed to test the classical Rouse
model. A three-parameter regression fit of the experimental data to Eqs. 10 and 11 (
p
with p = 1 to 3) was made as shown in
Fig. 2. The relaxation times obtained were:
1
,
2
,
3
= 0.0859, 0.0002, 0.0090 s, respectively. The longest relaxation time,

1
, may be used in computing the Deborah number. The reasonable closeness of the values from the G'-G" cross-over point
model and the classical Rouse model (0.0568 vs. 0.0859) gives us some confidence in using them for the Deborah number
calculation.
Figures 3 and 4 show similar analysis for lower concentration of 500 ppm Flopaam 3360S and 1500 ppm Flopaam
3330S in the same brine composition. The polymer properties and the calculated relaxation times using Rouse model are
given in Table 1. Higher MW and/or higher concentration polymer solution showed larger relaxation time as expected.
Furthermore, the relaxation time of the higher MW polymer (Flopaam 3630S) at 500 ppm was still larger than that of lower
MW polymer (Flopaam 3330S) at 1500 ppm in the same solvent. This indicates that MW has a more dominant effect than
concentration in the range of our experiment.

Apparent Viscosity Model Validation with Coreflood Results. The coreflood was set-up in a horizontal configuration in a
stainless steel core holder. About 1000 psi confining pressure is applied on the core holder in order to effectively hold the
core in place during the experiments. Several transducers were used for more accuarte pressure drop measurements.
Transducers were connected to the core holder such that the pressure differences measured were those between the inlet to
middle sections, middle to outlet, and across the whole core. A 1" diameter by 8" length Berea sandstone core was used. The
apparent viscosity was calculated as

brine
app
k A P
q L

= (12)
where A is the cross-sectional area of core, q is the flow rate, P is pressure drop, and L is the length of core.
The proposed viscoelastic viscosity model was first tested against published data of Yuan (1981) for 1000 ppm Pusher
700 polymer in both 1% NaCl and 0.1% NaCl solutions. Figures 5 and 6 give a good match of apparent viscosity for the
entire range of shear rates. The onset of shear thickening behavior was at about 20 s
-1
for low salinity and on the order of 100
s
-1
for high salinity polymer solution. Figure 7 shows an excellent match of our measurements for single-phase flow of 1500
ppm Flopaam 3630S solution in a Berea core with the viscoelastic model. The shear thickening behavior for 1500 ppm
Flopaam 3630S in high salinity brine A started at effective shear rate of about 20 s
-1
.
The results indicate that the viscoelastic model proposed can predict the single-phase flow behavior of polymer solutions
for different HPAM polymers, polymer concentrations, and molecular weight over a wide range of shear rates.

Implementation and Validation of Viscosity Model in UTCHEM. UTCHEM is the University of Texas Chemical
flooding simulator (Delshad et al., 1996; Delshad et al., 2002). The non-Newtonian polymer solution viscosity in UTCHEM
as a function of effective shear rate is modeled by Meter's equation:

1
2
0
p w
app w
P 1
eff
1

= +

&
&
(13)
where
1 2
& is the shear rate at which viscosity is the average of
0
p
and

w
and P

is an empirical coefficient. Effective
shear rate is calculated using Eq. 3 and a value of 0.48 for n. The shear thinning plateau viscosity (
0
p
) is computed as a
function of polymer (C
p
) and an effective salinity (C
SEP
) as follows.

( )
p
S
0 2 3
p w p1 p p2 p p3 p
SEP
1 A C A C A C C

= + + +


(14)
where A
P1
, A
P2
, A
P3
, and S
P
are constant model input parameters. The effective salinity for polymer (C
SEP
) taking into
account both anion and divalent cation concentrations is defined as

( )
51 P 61
SEP
11
C 1 C
C
C
+
= (15)
6 SPE 113620
where C
51
is the total anion concentration in water (Eq/l), C
61
is total divalent cation concentration in water (Eq/l), C
11
is
aqueous phase water concentration (volume fraction), and
p
is a constant input model parameter.
The implementation of the viscoelastic model in UTCHEM follows Eq. 9 assuming =2 and the high shear viscosity
(

) approaches the water viscosity (
w
).
( )
( )
2
(n 1) / 2
n 1 0 2
app w p w eff max 2 r eff
( ) 1 ( ) 1 exp

= + + +



(16)
Similar to the shear thinning plateau viscosity, the shear thickening plateau viscosity (
max
) is computed as a function of
polymer (C
p
) and effective salinity (C
SEP
) as follows.

( )
p
S
2
max w p11 p p22 p
SEP
1 A C A C C

= + +


(17)
where A
P11
and A
P22
are model input parameters.
Table 2 summarizes the fitting model parameters of Eq. 16 using several polymer data sets.

UTCHEM Coreflood History Match. The viscoelastic model, its extension to two-phase flow of oil and water, and its
implementation in UTCHEM was validated using polymerflood oil recovery experiment performed by Masuda et al. (1992).
Masuda et al. measured the rheological behavior of a 200 ppm HPAM polymer solution in a glass bead pack as shown in
Fig. 8 along with the bulk viscosity measured in a capillary viscometer. We successfully matched their results with the
viscoelastic model as given in Fig. 8. The shear thickening regime started at the effective shear rate of 2 s
-1
.
Masuda et al. (1992) performed 1D polymerflood oil recovery experiment in a glass bead pack (Core G-7) and measured
oil recovery, pressure drop, and oil cut. We successfully matched the coreflood results using modified UTCHEM as shown
in Figs. 9 through 11. Table 3 gives the core and fluid properties used in the simulation.
Another simulation was performed where we used the original shear thinning viscosity model in UTCHEM (Eq. 13). The
results indicated that the pressure drop, oil cut, and oil recovery can be predicted much closer to the coreflood results by the
viscoelastic model than the shear-thinning model (Figs. 9 through 11). Our findings were consistent with those of Masuda et
al. where the shear thickening behavior of the large molecular size polymer in high velocity floods may have a role in
improving oil recovery.

Summary and Conclusions
Oscillatory and shear viscosity measurements and polymer flow coreflood experiments were carried out for different
shear rates, polymer concentrations, and molecular weights, and were successfully employed to develop a new
apparent viscosity model for polymer solutions flowing in porous media.
The polymers shear-thickening characteristic was correlated with the Deborah number via its molecular relaxation
time, which is in turn determined from the rheological data.
The storage and loss modulus (G', G") were obtained from a dynamic frequency sweep test. The relaxation time
corresponding to the G'-G" cross-over point was very close to that obtained from the classical Rouse model and can
be employed to calculate the Deborah number.
An apparent viscosity model that accounts for both shear-thinning and shear-thickening behavior of polymer in
porous media was developed and was tested by history matching polymer coreflood results.
The viscoelastic model successfully fit the apparent viscosity over a wide range of Darcy velocity for several
polymer solutions.
The viscoelastic model was implemented in UTCHEM and successfully history-matched published oil recovery
polymerflood laboratory results.

Acknowlegements
The authors would like to acknowledge the financial support of 18 companies who participate in the Chemical EOR
Industrial Associates Project in the Center for Petroleum and Geosystems Engineering (CPGE)
(http://www.cpge.utexas.edu/ceor/) at The University of Texas at Austin.

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moduli during shear thickening of a polymer solution", J. Rheol., 47(4), 1041-1050, Jul/Aug 2003.
Ranjbar, M., Rupp, J., Pusch, G., and Meyn, R., "Quantification and Optimization of Viscoelastic Effects of Polymer
Solutions for Enhanced Oil Recovery", SPE/DOE 24154 presented at SPE/DOE 8th Symp. Enhanced Oil Recovery,
Tulsa, OK, Apr. 22-24, 1992.
Sorbie, K. S., Polymer-Improved Oil Recovery, Blackie, Glasgow and London, 1991.
Southwick, J. G., and Manke, C. W., Molecular Degradation, Injectivity, and Elastic Properties of Polymer Solutions, SPE
Res. Eng., 1193-1201, Nov. 1988.
Thurston, G. B., "Characterization of Polymer solutions in flow through porous media", Intl. Congress on Rheology, Mexico,
1984.
Thurston, G. B., and Pope, G. A., Viscoelastic Properties and Rheology of Fluids in EOR, unpublished report, Univ. Texas
at Austin, 1981.
Volpert, E, Selb, J., and Candau, F, "Associating behavior of Polyacrylamide hydrophobically modified with
dihexylacrylamide" Polymer , 39, 1025-1033, 1998.
Wang, D., Xia, H., Liu, Z., and Yang, Q., "Study of the Mechanism of Polymer Solution with Visco-Elastic Behavior
Increasing Microscopic Oil Displacement Efficiency and the Forming of Steady Oil Thread Flow Channel", SPE
68723 presented at SPE Asia Pacific Oil Gas Conf., Jakarta, Indonesia, Apr. 17-19, 2001.
Wreath, D., Pope, G. A., and Sepehrnoori, K., "Dependence of Polymer Apparent Viscosity on the Permeable Media and
Flow Conditions", In Situ, 14(3), 263-284, 1990.
Xia, H., Wang, D., Wu, J., and Kong, F., "Elasticity of HPAM Solutions Increases Displacement Efficiency under Mixed
Wettability Conditions", SPE 88456 presented at SPE Asia Pacific Oil Gas Conf., Perth, Australia, Oct. 18-20, 2004.
Yuan, M., "A rheological study of polymer and microemulsion in porous media", MS Thesis, University of Texas at Austin,
May 1981.

Appendix: Other Models for Polymer Molecules Relaxation Time
Bead-Spring Model with no Interaction Among Beads. This model has been derived using the Rouse theory for relaxation
processes and is given as:
8 SPE 113620

[ ]
s
p
2 2
6 M
p RT

=

(A1)
where [ ] = intrinsic viscosity;
s
= solvent viscosity; M = molecular weight of polymer; RT = gas constant and absolute
temperature; and p is the number of chain elements in the bead-spring model of a polymer molecule, which is connected
end-to-end by N beads. The intrinsic viscosity, which is a measure of the size of a polymer molecule in solution, is defined
by

p
o s
c 0
s p
( )
[ ] lim
c

(A2)
where
o
is the limiting Newtonian viscosity at low shear limit, and c
p
is polymer concentration.

The Non-Linear Elastic Dumbbell Model. This model combines the elastic nature of polymer molecules (represented as
dumbbells) and the viscous properties of the solvent. According to Haas and Durst (1982), the largest Zimm relaxation time
is given as:

[ ]
s
z
M
0.42
RT

= (A3)
The Zimm theory is a modification of the bead-spring chain model in which the motion of the beads is strongly influenced by
the viscous drag of other beads of the chain.

The Rod-Climbing Height Model. The relaxation time is estimated using data obtained from rod-climbing experiments.
Results from the experiments combined with coefficients of a second order fluid model is correlated with the first normal
stress difference coefficient. This leads to a relaxation time definition given as:

s

(A4)
where = rod-climbing constant; and
s
= solution viscosity. Other relevant relationships for this model available in
literature are (Munoz et al., 2003):

1
2
N
4
=
&
(A5)
( )
0.7
2
1
0
N 2G 1 G G

= +


(A6)
where N
1
is the first normal stress difference (Pa); and & is shear rate. The major limitation in applying this model is the
difficulty in measuring the first normal stress difference of dilute polymer solutions. First normal stress measurements are
more practical with polymer melts.

Relaxation Time at a Fixed Frequency. According to Thurston (1984), at a particular frequency of flow excitation, an
effective relaxation time can be calculated. This relaxation time is based on the imaginary and real parts of the complex
viscosity of the polymer solution:

E
V

(A7)



SPE 113620 9
Table 1Comparison of Polymers Relaxation Time at T = 298 K
Polymer Flopaam 3630S Flopaam 3630S Flopaam 3330S
Polymer conc., ppm 1500 500 1500
Solvent Brine A
*
Brine A
*
Brine A
*

M, g/mol 20x106 20x106 8x106
Degree of hydrolysis, % 30 30 30
r
, s (Rouse Model) 0.086 0.058 0.035
*
Brine A contains 20,000 ppm TDS comprising of 15,400 ppm Na
+
, 2540 ppm Ca
++
, and 2100 ppm Mg
++
.


Table 2Fitting Parameters for the Viscoelastic Model
Yuan, 1980 Yuan, 1980 Masuda et al.,1992 This work
Polymer Pusher 700 Pusher 700 HPAM Flopaam 3630S
Polymer conc., ppm 1000 1000 200 1500
Molecular weight, g/mol 5x10
6
5x10
6
15x10
6
20x10
6

Solvent 1% NaCl 0.1% NaCl Not known Brine A
, s 0.057 0.158 1.088 0.221
n
1
0.75 0.59 0.746 0.755
n
2
2.54 1.71 2.6 2.15
2 r
, s 0.0005 0.0009 0.007 0.0005
0
, cp
8 36 8.5 13.7
max
, cp 40 40 20 108


Table 3Simulation Input for 1-D Coreflood
Core length, cm 46.9
Core diameter, cm 2.83
Porosity 0.372
Permeability, D 27.25
Initial water saturation 0.101
Residual oil saturation to water 0.136
Polymer conc., ppm 200
Oil viscosity, cp 25
Water Viscosity, cp 0.9
Injection rate, m/s 60.6 (0.116 ft
3
/d)


10 SPE 113620
0.0001
0.001
0.01
0.1
1
10
0.01 0.1 1 10 100 1000
(rad/s)
G
'

&

G
"

(
d
y
n
e
s
/
c
m
2
)
G"
G'

Fig. 1Dynamic frequency sweep test fro 1500 ppm Flopaam 3630S in Brine A.
0.0001
0.001
0.01
0.1
1
10
0.01 0.1 1 10 100 1000
(rad/s)
G
'

&

G
"

(
d
y
n
e
s
/
c
m
2
)
G"
G'
Points: Measured
Curves: Rouse Model

Fig. 2Rouse model fit to dynamic frequency sweep test data of 1500 ppm Flopaam 3630S in Brine A.

SPE 113620 11
0.0001
0.001
0.01
0.1
1
10
0.01 0.1 1 10 100 1000
(rad/s)
G
'

&

G
"

(
d
y
n
e
s
/
c
m
2
)
G"
G'
Points: Measured
Curves: Rouse Model

Fig. 3Rouse model fit to Dynamic frequency sweep test data for 500ppm Flopaam 3630S in Brine A.

0.0001
0.001
0.01
0.1
1
10
0.01 0.1 1 10 100 1000
(rad/s)
G
'

&

G
"

(
d
y
n
e
s
/
c
m
2
)
G"
G'
Points: Measured
Curves: Rouse Model

Fig. 4Rouse model fit to Dynamic frequency sweep test data for 1500ppm Flopaam 3330S in Brine A.
12 SPE 113620

1
10
100
1 10 100 1000 10000
Shear Rate (s
-1
)
V
i
s
c
o
s
i
t
y

(
c
p
)
Shear Thinning Model
Viscoelastic Model
Measured Bulk Viscosity
Measured Apparent Viscosity

Fig. 5Viscoelastic model fit to1000 ppm Pusher 700 in 1% NaCl (data from Yuan, 1981).
1
10
100
1 10 100 1000 10000
Shear Rate (s
-1
)
V
i
s
c
o
s
i
t
y

(
c
p
)
Shear Thinning Model
Viscoelastic Model
Measured Bulk Viscosity
Measured Apparent Viscosity

Fig. 6Viscoelastic model fit to 1000 ppm Pusher 700 in 0.1% NaCl (data from Yuan, 1981).
SPE 113620 13
1
10
100
0.1 1 10 100 1000 10000
Shear Rate (s
-1
)
V
i
s
c
o
s
i
t
y

(
c
p
)
Shear Thinning Model
Viscoleastic Model
Measured Bulk Viscosity
Measured Apparent Viscosity

Fig. 7Viscoelastic model fit to 1500 ppm Flopaam 3630S in Brine A.
1
10
100
0.1 1 10 100 1000
Shear Rate (s
-1
)
V
i
s
c
o
s
i
t
y

(
c
p
)
Shear Thinning Model
Viscoelastic Model
Measured Bulk Viscosity
Measured Apparent Viscosity

Fig. 8Viscoelastic model fit to 200 ppm HPAM (Data of Masuda et al., 1992).
14 SPE 113620
0.0
0.2
0.4
0.6
0.8
1.0
0 1 2 3 4 5 6 7 8 9
Pore Volumes

R
e
c
o
v
e
r
y

E
f
f
i
c
i
e
n
c
y
UTCHEM-Viscoelastic Model
Coreflood Data (Masuda et al., 1992)
UTCHEM-Shear Thinning Model

Fig. 9Comparison of simulated oil recovery efficiency with data from Fig. 6 of Masuda et al., 1992.
0.0
0.2
0.4
0.6
0.8
1.0
0 1 2 3 4 5 6 7 8 9
Pore Volumes
F
r
a
c
t
i
o
n
a
l

F
l
o
w

o
f

O
i
l

a
t

O
u
t
l
e
t
UTCHEM-Viscoelastic Model
Coreflood Data (Masuda et al., 1992)
UTCHEM-Shear Thinning Model

Fig. 10Comparison of simulated oil cut with data from Fig. 7 of Masuda et al., 1992.
SPE 113620 15
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9
Pore Volumes
P
r
e
s
s
u
r
e

D
r
o
p


(
k
P
a
)
UTCHEM-Viscoelastic Model
Coreflood Data-Masuda et al., 1992
UTCHEM-Shear Thinning Model

Fig. 11Comparison of simulated pressure drop with data of Fig. 8 from Masuda et al., 1992.