SPE 93254
Rheology and Transport in Porous Media of New Water Shutoff/Conformance Control
Microgels
D. Rousseau, G. Chauveteau, M. Renard, R. Tabary, and A. Zaitoun, Institut Français du Pétrole;
P. Mallo and O. Braun, Seppic; and A. Omari, LMDA-ISTAB, Bordeaux U.
Copyright 2005, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2005 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 2 – 4 February 2005.
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Abstract
The performances of new microgels specifically designed for
water shutoff and conformance control were extensively
investigated at laboratory scale. These microgels are
preformed, stable, fully water soluble, size controlled with a
narrow size distribution, and non-toxic. They reduce water
permeability by forming adsorbed layers soft enough to be
very easily collapsed by oil-water capillary pressure, so that
oil permeability is not significantly affected. Since the
manufacturing process of these new microgels make possible
to vary chemical composition, size and crosslink density, they
can be designed as desired to meet the requirements of a given
field application. The laboratory results reported in this paper
concerns mainly three microgel samples having significantly
different crosslink densities. We describe the relevant
laboratory methods used to determine main microgel
characteristics. The microgels have remarkable mechanical,
chemical and thermal stability. Their behavior in porous media
have been investigated extensively, showing that: 1) their
propagation distance is only limited by the volume injected, 2)
their injectivity is facilitated by a shear-thinning behavior and
3) water permeability reduction can be achieved as desired by
controlling the thickness of adsorbed layer. Thus, this new
microgels, now available at industrial scale, look as very
promising tools, not only for water shutoff but also for
conformance control in heterogeneous reservoirs.
Introduction
Background
In a global context of growing energy needs with a perspective
of depletion of oil and gas resources, extending the life of
hydrocarbon reservoirs is a real challenge for the decades to
come. In that situation, as well as for environmental reasons,
reducing significantly water production and improving oil
recovery efficiency is an important goal for oil industry. Thus
the development of more reliable techniques using "green"
products for water-shutoff, conformance, and mobility control
is of crucial interest.
Among the methods available to reduce water production [1],
injecting a gelling system composed of a polymer and a
crosslinker has been widely used [2-5]. In this process, the gel
is formed in-situ. Since gelling properties have been found to
depend on many factors [6-11], the gelling time, the final gel
strength and also the depth of the gel penetration is quite
difficult to predict. This difficulty results from the
uncertainties concerning different factors: shear stresses both
in surface facilities and in near-wellbore area and also
physico-chemical environment around the well (pH, salinity
and temperature). Moreover, both polymer and/or crosslinker
adsorption in the near-wellbore region and dilution by
dispersion during the placement can affect the effectiveness of
the treatment.
To overcome these severe drawbacks, different authors have
recently proposed new methods, aimed at improving the
process by injecting preformed gels particles or dilute gelling
systems. Bai et al. method [12,13] consists in drying, crushing
and sieving polymeric gels prior to injecting them. Mack et al.
[14,15] method consists in obtaining "colloidal dispersion
gels" (CDG) by crosslinking low concentration polymer
solutions with low amounts of chromium acetate or aluminium
citrate. This process slows down the gelation kinetics, so that,
on a well injection time scale, those systems only form
separate gel bundles, thus making possible to enter the matrix
rock. However, the in-depth propagation of these two of gels
remains questionable. In 1999, Chauveteau et al. introduced
[16] a completely new concept which consists of injecting
fully water soluble, non-toxic, soft, stable and size-controlled
microgels into the reservoir. A first type of microgels, using an
environmentally friendly zirconium crosslinker, has been
extensively studied in the past years, regarding both the
understanding of gelation mechanisms and the transport
properties in porous media [16-23]. More recently, a second
type of microgels, which are covalently crosslinked, was
introduced [24]. These microgels, now available at industrial
scale, have been shown to have very attractive properties for
both water shutoff and conformance control operations.
2 SPE 93254
Scope of paper
The purpose of the present paper is to complete and extend our
previous investigation [24] to new samples of covalently
crosslinked microgels having different chemistry and crosslink
density. Among all the samples possibly manufactured, three
were selected for a detailed investigation, including the sample
studied in [24]. In a first section, materials and methods are
described. Then, the main results are presented and discussed,
beginning with characteristics of these microgels in solution,
and solution rheology, continuing with their stability under
mechanical, thermal or chemical stresses, and finishing with
their transport properties in porous media, showing their easy
in-depth propagation at long distances, and the possibility of
achieving the desired permeability control.
Experimental
Materials
The new microgels presented in this study are colloidal
particles of acrylamide-based polymeric gels with neutral
organic covalent crosslinkers. Such compounds are 100% non-
toxic. Properties of these microgels depend on their
manufacturing conditions, on polymer chains chemistry and
on crosslink density. In our last publication [24] only one
microgel sample was studied. Now, a broad range of microgel
types is available. This study is mainly focused on three
microgel samples having different crosslink densities, we refer
to as high (A), medium (B) and low (C) crosslink density.
Sample A is the same as the one studied in Ref. [24]. In order
to show the differences between microgels and linear
polymers, experiments have also been performed with a high
molecular weight linear polymer we refer to as sample D,
having very similar chemical composition than the microgels.
Microgel solvent was a brine we refer to as "standard brine"
composed of 20 g/L NaCl and of 0.4 g/L NaN3 (used as
bactericide and as stabilizer to prevent free-radical
degradation) in distilled water. This brine was filtered through
0.22 µm MilliporeTM cellulose membrane to remove any fine
particle in suspension. Before injection into the cores, the
brine was degassed under vacuum and kept under helium cap
to prevent bubble formation in the porous medium during core
flow tests. It shall be emphasized that microgel solutions were
not filtered prior to their injection into the cores. The oil was a
mineral oil (Marcol™) having a viscosity of 8.3 mPa.s at 30°C
(2.9 mPa.s at 70°C), and a density of 0.822 g/cm3 (at 30°C).
Methods and techniques
Determination of size in solution
Microgels size in solution was estimated independently by
both static and dynamic light scattering techniques.
The Static Light Scattering technique used is able to determine
the size of particles dispersed in a liquid provided that their
effective internal refraction index and particle size are high
enough. This technique is based on direct measurements of the
scattered intensity at different angles. The intensity
distribution is analyzed according to Mie theory. The
experiments were performed using a Horiba LA-900 Particle
Size Distribution Analyzer. This apparatus is equipped with
two light sources, a He-Ne laser (wavelength λ = 632.8 nm)
and a blue and red monochromed tungsten lamp with a set of
photodiode detectors which allows to measure at once the
intensity of forward scattered light (at small and wide angle)
and of back scattered light. Size determination is then possible
over a wide range, from 0.04 to 1000 µm. All experiments
were carried out at ambient temperature (20 to 25°C).
The Dynamic Light Scattering technique used, also called
Photon Correlation Spectroscopy (PCS), determines the
hydrodynamic radius Rh of the dispersed particles. This
technique is based on the fact that the Brownian motion of
colloidal particles causes the light scattered from a dispersion
to fluctuate with time [25]. Measurements of the light
scattered versus time are performed at a given scattering
vector q = (4nπ / λ ) sin(θ / 2) , θ being the scattering angle, λ
the wavelength and n the solvent refractive index. A correlator
is used to obtain the autocorrelation function G(τ) of the
fluctuating intensity. For a dilute suspension, this function is
directly related to the position of the individual particles. If
their size distribution is narrow, G(τ) shows an exponential
decay parameterized by a decay rate Γ ; for polydisperse
and/or multimodal suspensions, the distribution of Γ values is
computed from G(τ) with numerical algorithms. For qRh < 1
or qR h ~ 1 (low angles), each Γ value is proportional to the
translation diffusion coefficient D0 of particles of a given size.
Their hydrodynamic radius Rh is then given by the Stokes-
Einstein equation:
Rh = k BT / 6πη 0 D0 (1)
where kB, T , η0 are Boltzmann constant, absolute temperature
and solvent viscosity respectively. It should be noted that for
qR h > 1 (wide angles), internal respiration modes affect the
determination of Γ which is no longer proportional to the
translation diffusion coefficient: as a consequence, the size is
underestimated. The experiments were performed using a
Coulter® N4 PlusTM 3000 with an 80-channel multi-τ
correlator in combination with a 10 mW He-Ne laser
(wavelength λ=632.8 nm). Temperature was kept constant at
20°C. Measurements were performed at 3 angles of
observation θ (15.7°, 23° and 30.1°), corresponding to
scattering vector values ranging from 3.6×10-3 to 6.9×10-2 nm-1
(n=1.33 for the brine used). Γ distributions were calculated
with a Contin routine. The analyzed solutions were highly
diluted to prevent multiple scattering and interaction effects.
Viscosity measurements
A low-shear viscometer (LS30 from Contraves) having a
Couette geometry (0.5 mm gap) was used to measure the
viscosity at various shear rates (from 0.1 s-1 to 70 s-1) of both
microgel solutions and solvent and thus to determine
accurately the relative viscosity, i.e. the solution-to-solvent
viscosity ratio. A few viscosity measurements were performed
at high shear rate (above 100 s-1) with an MCR300 rheometer
from Physica-Anton-Paar fitted with a Mooney-Ewart
geometry (coaxial cylinders with cone and plate at the bottom)
with 0.6 mm gap, used in rotational mode. For all viscosity
measurements, temperature was kept constant at 30°C.
Newtonian relative viscosities (ηro) of the solutions were
deduced from plots of relative viscosities versus shear rates.
Then the values of both intrinsic viscosity [η] and Huggins
SPE 93254
constant KH of the colloids in suspensions were derived from
plots of the newtonian specific reduced viscosity
η spr = (η ro − 1) / C versus microgel concentration C,
according to the Huggins equation [25,26]:
η spr = [η ] + K H [η ]2 C (2)
The parameters [η] and KH characterize respectively the
internal density of the colloids and their interactions in
solution. [η] is linked to the colloids density ρ, i.e. their mass
to effective hydrodynamic volume ratio, by [η ]ρ = 5 / 2 .
Consequently, the effective volume fraction Φ of the colloids
in solution is given by φ = 2C[η ] / 5 . The critical value of this
parameter is Φ≈0.63, i.e. the effective volume fraction for
which the viscosity of hard spheres dispersions become
infinite [25]. For inter-penetrable polymeric colloids, Φ is an
overlap parameter and thus can have values above unity. For a
neutral flexible polymer, KH increases from 0.3 in a good
solvent, i.e. with a segment-segment net repulsion at very
short distances, up to a value of 0.5 in a theta solvent. More
generally, for objects showing low internal permeability even
in good solvent conditions, KH value is expected to increase as
internal permeability decrease, reaching values as high as 1
when these permeability drops to zero [25]. KH values higher
than 1 indicate the presence of attractive interactions between
colloids. When the colloid size is smaller than the
hydrodynamic pore throat size, the transport in porous media
is expected to be easy as long as the value of KH indicates that
microgels are strictly repulsive, since in this case the
formation of multiple adsorbed layers is prevented. By
contrast, when microgels are manufactured to be partly
attractive, a multilayer adsorption can occur, resulting in a
complete plugging when the adsorbed layer thickness reaches
pore throat hydrodynamic radius. Such a property gives the
possibility of completely plugging a water-producing layer, if
desired [19].
Linear viscoelastic properties
Dynamic shear rheology experiments were performed with a
MCR300 rheometer from Anton-Paar-Physica in controlled
rate (CR) conditions. Although this apparatus is designed for
working under controlled stress (CS) conditions, CR
experiments can also be performed by mean of an electronic
management of the force applied to the rotor. For the tests
reported in this paper, the MCR300 was equipped with a
75mm cone/plate geometry of 1° angle, ensuring a constant
shear rate all over the sample. Linearity tests have been carried
out before all shear modulus measurements. Thus, depending
on the samples, the fixed strain rate applied during the
frequency sweeps ranged from 1% (high concentrations) to
10% (low concentrations). In order to check for evaporation
effects during the measuring time, the frequency sweeps were
systematically repeated. However, evaporation appeared as a
factor limiting duration of the test, and consequently the low-
frequency limit. Moreover, a high-frequency limit appears
from the mechanical resonance of the measuring system.
Consequently, dynamic shear modulus measurements were
possible only for frequencies ranging from 0.01 Hz (at least)
to about 5 Hz. Temperature was kept constant at 30°C
throughout all experiments.
3
Mechanical, thermal and chemical stability
Mechanical, thermal and chemical stability tests were carried
out by measuring dimensionless viscosity respectively before
and after application of very high shear rates, before and after
aging at high temperature, and with or without H2S present in
the solution. Very high shear rates (around 15000 s-1) were
obtained with a mixing device (Ultra-Turrax®, from IKA
Labortechnik). Aging effects were tested at 120°C and 150°C
on durations ranging from 1 to 90 days. The glass bottles used
for thermal stability tests were sealed under vacuum to
minimize the oxygen content and consequently the
degradation due to the presence of oxygen, which creates free
radicals in presence of impurities [26]. However, no special
effort was made for a complete oxygen elimination, thus being
representative of most field test conditions. Regarding the
chemical stability tests, concentrated microgels and polymer
solutions were dissolved in aerated conditions, respectively in
a high salinity oilfield production water containing volatile
hydrogen sulfide (H2S), and in the same brine from which H2S
had been previously removed by evaporation under
mechanical stirring. H2S, which forms free radicals when
reacting with dissolved oxygen, is well known to be
responsible of polymer degradation [26,27]. Comparative
viscosity measurements were then performed on the solutions
in the brines with or without H2S.
All viscosity measurements were carried out at 30°C in the
Newtonian regime with the LS30 viscometer.
Transport in porous media
Model granular packs
To evaluate the in-depth propagation of a polymer solution or
a colloidal dispersion as well as the adsorption properties of
the polymer molecules or colloids (hydrodynamic thickness of
adsorbed layer and adsorption density), the solution was
injected in a model porous medium having well-known and
reproducible pore structure and surface properties. Silicon
carbide (SiC) particles packs are such model porous media
[28-30]. The granular media in our experiments were 80 µm
SiC particles packs, leading to porosities ϕ = 41±1% and
2
absolute permeabilities k = 3.1±0.1 µm . As shown in Fig. 14,
the pack holder used was equipped with 5 pressure taps
enabling to measure pressure drops in different sections:
section 1, upstream; section 2 downstream; section 3, total
length. The presence of these five pressure taps allows to
detect any entrance plugging by recording the values of both
permeability and mobility reductions simultaneously on the
three sections. Brine or unfiltered microgel solutions were
injected in the porous medium by two Labotron® pumps, (flow
rates from 0.1 to 1000 cm3/h). Downstream the porous
medium, the set-up was equipped with a calibrated capillary
and an on-line spectrophotometer, in order to measure the
polymer or microgel concentration in the effluents, and with
an on-line pH-meter. In order to measure reference
concentration and pH of the injected solutions, a bypass of the
porous medium was also possible. Both the porous medium
and the capillary were immersed in a thermo-regulated bath
adjusted at T=30°C. The procedure was as follows: 1)
preliminary injection of several pore volumes of brine at 2
cm3/h; 2) brine injection at various flow rates and
4 SPE 93254
determination of the absolute permeability k; 3) microgel
injection at 2 cm3/h corresponding to low shear rates (around
10 s-1) while recording the pressure drops; 4) brine injection at
2 cm3/h to remove the non-adsorbed polymers/microgels; 5)
brine injection at various flow rates while recording the
pressure drops. Mobility and permeability reduction, Rm and
Rk, are then defined as the ratios of pressure drops during and
after microgel injection respectively, to pressure drops before
microgel injection.
Natural sandstone
Core flood experiments were also performed with Berea
sandstone cores. The experiment reported here was carried out
in two-phase flow conditions (water and oil). It aimed at
evaluating the performances of microgels as Disproportionate
Permeability Reducers (DPR). The plug was cored in a
direction parallel to the bedding plane and in the presence of
salt water (30 g/L NaCl) to prevent clay swelling. Then, it was
immersed in methylic alcohol to extract water and dried in an
oven at low temperature (60°C) to prevent possible clay
alteration. The core was placed in a Viton sleeve and then in a
Hassler cell. A nitrogen confining pressure of 3 MPa was
maintained on the sleeves for lateral tightness.
The procedure was as follows: 1) preliminary injection of
several pore volumes of brine; 2) brine injection at various
flow rates to determine the absolute permeability k; 3) several
oil and brine injection cycles for preconditioning the core and
thus checking the reproducibility of end-point relative
permeabilities kro and krw; 4) microgel injection at 4 cm3/h at
residual oil saturation and determination of Rm; 5) brine
injection at 4 cm3/h to remove the non-adsorbed microgels; 6)
brine injection at various flow rates and determination of Rk;
7) oil injection to evaluate the effect of adsorbed microgels on
oil relative permeability. This experiment was carried out on a
2
core with an absolute permeability k=0.302 µm for a porosity
ϕ=21.5% and, at residual oil saturation, a water permeability
kw=0.020 µm2 for a porosity ϕw=11.8%.
Results and discussion
1. Characteristics of microgels in solution
1.1. Size in solution
Figs. 1 and 2 show examples of size distributions obtained by
static and dynamic light scattering respectively. Results
concern the high crosslink density microgel (sample A) and
the linear polymer (sample D). In the static light scattering
experiment, an average diameter D≈2.3µm is found for the
microgel, while it is not possible to measure a size for the
polymer. In the PCS experiment, average hydrodynamic
diameters Dh≈2µm and Dh≈0.4µm are found for the microgel
and the polymer respectively. Such a value for the
hydrodynamic size of a polymer is expected since it is known
that linear polymers cannot be bigger than 0.6 µm when
dissolved in our standard brine [26]. The fact that
hydrodynamic diameters are slightly smaller than direct
particle sizes is expected and is well known for linear
polymers [26]. Moreover, it is worth indicating that direct
microscopy observations also lead to microgels size around 2
µm, with very low polydispersity and, within the accuracy of
the technique, spherical shapes [31]. Finally, the results of the
size measurements indicate that: 1) microgels particles are
significantly larger than linear polymers; 2) their size
distribution is monomodal and narrow, as expected from their
manufacturing process, although they were not pre-filtered. As
shown by the experiments in model porous media (see below
section 3), the size of microgels when adsorbed depends on
both their crosslink density and the concentration of the
solution from which they have been injected.
1.2. Internal density and mutual interactions
The variations of microgel specific reduced viscosity are
plotted at zero shear rate limit versus concentration in Fig. 3.
According to Huggins equation (Eq. 2), the extrapolation at
zero concentration gives the intrinsic viscosity of the
microgels in solution : [η] = 428 cm3/g for the high crosslink
density microgel (highest internal density), [η] = 719 cm3/g
for the medium crosslink density microgel (intermediate
internal density) and [η] = 884 cm3/g for the low crosslink
density microgel (lowest internal density). All these intrinsic
viscosity values are significantly lower than the ones of
corresponding linear polymers ([η] = 2840 cm3/g for sample
D). However, even the microgel having the higher internal
density (higher crosslink density) remain soft enough to be
easily collapsed by capillary pressure, as demonstrated by
their excellent DPR properties (see below section 4.3).
The Huggins constants derived from the slope of the curves of
Fig. 3 are never higher than unity and thus suggest an absence
of attractive interactions between the colloids. This
observation is confirmed by the good propagation of the
microgels in porous media (see below section 4). The Huggins
constants values increase with the internal density of the
samples: KH ≈ 0.4, 0.6 and 1.0 respectively for the low,
medium and high crosslink density microgels. Note that KH is
slightly smaller than 0.4 for the linear polymer (sample D).
2. Rheology of microgel solutions
2.1. Shear viscosity
To illustrate the broad range of currently available microgels,
relative viscosity measurements have been performed on
various microgels differing by their crosslink density
(manufactured with two types of crosslinker we refer to as
type I and type II). Results shown in Fig. 4, obtained at a fixed
concentration C=6g/L, give relative viscosities spread out on
more than one decade, from ηr~3 to ηr~30, showing that
microgels internal density can be adjusted as desired.
More detailed results of viscosity tests performed on the high
and the medium crosslink density microgel are shown on Fig.
5 and Fig. 6 respectively for different effective volume
fractions Φ. As expected for soft microgels, a small decrease
in viscosity is observed only at the highest shear rates, and a
plateau is clearly observed at low shear rates, i.e. in the
newtonian regime where microgel conformation is unaffected
by shear stresses.
Fig. 7 shows newtonian relative viscosities as a function of the
effective volume fraction for the linear polymer solutions
(sample D) and for the medium and the high crosslink density
microgels (sample B and A). The Krieger curve for
dispersions of hard spheres [25] is also plotted. The curves
show that the smaller the intrinsic viscosity, the closer from
hard spheres the behavior of microgels is. Such a graph clearly
SPE 93254
confirms that microgels are more rigid and/or less penetrable
than linear polymers.
Fig. 8 shows the shear rate dependence of the relative
viscosity for Φ=0.34 solutions (low concentration) of the
linear polymer (sample D) and the high crosslink density
microgel (sample A). For each sample, plotted values are
evolutions of the measured viscosity at a given shear rate
relative to their newtonian value. Experimental data have been
fitted with Carreau model curves [26,32]. The decrease in
relative viscosity as shear rate increases is more significant for
the polymer than for the microgel. This observation indicates
that the deformability of the microgel is lower than of the
polymer. Such a result is obviously a consequence of the
crosslinked structure of the microgel, and is in good agreement
with the conclusions of mechanical resistance tests (see below
section 3.1).
2.2. Dynamic shear rheology
Figs. 9 and 10 give the results of complex shear moduli
measurements (G', storage modulus and G'', loss modulus) as a
function of the frequency f, performed for different
concentrations of, respectively, high and low crosslink density
microgel solutions. The shear moduli of the two microgels
vary differently with effective volume fraction. Both microgel
solutions behave roughly like liquids (G''~ω, G'~ ω2, ω=2πf)
in dilute or weakly concentrated solutions. When
concentration increases, low crosslink density microgels
moduli keep indicating a liquid with increasing viscosity while
high crosslink density microgel moduli are reminiscent of a
sol-gel transition [33,34]. Indeed, on Fig. 9, despite the low-
frequency limit of the experiment, a transition to a "plateau-
like" response for G' is clearly observed, while the G''~ ω
domain is only observed for the lowest concentration,
indicating that this domain is shifted to lower frequencies for
the other concentrations, and therefore that the viscosity is
diverging. Obviously, the pseudo-gel obtained by
concentrating high crosslink density microgel particles is not a
true macroscopic polymeric gel, since the interactions between
particles cannot be of the same kind as the intra-particles
covalent bonds. Moreover, the KH value and the good
propagation in porous media seem to exclude any possible
weak attractive interaction between particles. Sol-gel
transition could then originate from purely steric effects.
Finally, these dynamic shear rheology results illustrate again
the high variability of the physico-chemical properties of the
available microgels.
3. Robustness of microgels
3.1. Mechanical stability test
Fig. 11 shows results of mechanical stability tests carried out
on high, medium and low crosslink density microgels (sample
A, B and C), and the linear polymer (sample D). Very high
shear rates (around 15000 s-1) were applied on the different
solutions for different durations (total time ths) and then the
viscosities were measured. Viscosities are plotted as specific
reduced viscosities (ηspr) in order to check for the possible
alterations of microgel and polymer structures. The
concentration of all solutions was C=1g/L. After only one
minute of high shear treatment, ηspr for the linear polymer
solution is only 20% of its original value whereas the viscosity
5
of the microgel solutions remains practically constant
(between ±10% of their original values) after 16 minutes. The
slight increase in ηspr for the medium crosslink density
microgel can be interpreted by a swelling after the breaking of
a few bounds by shear forces. These results clearly
demonstrate the excellent mechanical stability of these
microgels.
3.2. Chemical stability test
Chemical stability tests were carried out on high crosslink
density microgel solutions having newtonian viscosity of
η0~20cP and on a linear polymer solution of similar viscosity
(η0~16cP). Fig. 12 shows that, after two days, the viscosity of
microgels in brine containing H2S is roughly the same as
without H2S, while the viscosity of the linear polymer solution
drops down to about 45% of its value without H2S. This result
clearly shows the very good chemical stability of crosslinked
polymer species as compared to linear polymers.
3.3. Thermal stability test
The long-term stability was checked at temperatures of 120
and 150°C over a period of three months (Fig. 13). At both
temperatures, viscosity and thus the size of the microgels
increases and then decreases to reach a stabilized value. The
size increase is due to the well-known hydrolysis of
acrylamide groups. The decrease with aging time which is
clearly observed at 150°C is likely due to free-radical
degradation. The confirmation that this good stability of
microgels is due to their crosslinked character is evidenced by
the strong drop in viscosity observed (Fig. 13) after only 1 day
for a linear polymer (HSPAM) having the same chemical
composition.
4. Transport in porous media
Two types of transport characteristics are important for water
shutoff and conformance control operations 1) the ability of
microgels to be transported at large distances from the well-
bore, a property often referred to as in-depth propagation and
2) the microgel adsorption density which controls, together
with microgel concentration, the frontal velocity compared to
that of a non-adsorbing fluid.
4.1. In-depth propagation
Previous results concerning the propagation of the high
crosslink density microgel in model porous media have
already been presented [24]. In this paper is reported in details
the propagation of a dilute solution (Φ=0.12, C=400 mg/L) of
medium crosslink density microgel in a SiC pack. Fig. 15
shows the variation in mobility reduction (Rm) as a function of
the number of pore volumes (PV) of solution injected on the
first internal part of the pack (section BC, upstream), on the
second part (section CD, downstream) and also on the total
length (section AE). Since the pore volume of the SiC packs
used is about of 7.5-8 cm3, injection of one PV at 2cm3/h takes
about 4 hours. For all sections, Rm increases almost linearly in
a first step with a certain delay due to adsorption and then
level off at a plateau value, which is practically the same
whatever the distance from the inlet is (the slightly higher Rm
value for the downstream section comes from a lower initial
permeability of this section). Fig. 15 also shows the evolution
of the effluent concentration relatively to the concentration of
the injected solution. A stabilization of effluent concentration
6 SPE 93254
at 100% of the inlet value is observed after about 5 PV
injected. After injection of the microgel solution, non adsorbed
particles were displaced by brine. It is observed that, as
effluent concentration reaches 0%, the pressure drops in the
different sections of the pack remain higher than before
microgel injection. This indicates a reduction in the water
permeability of the porous medium. This effect originates
from microgels adsorption which create a layer of extremely
low permeability. After measuring of Rk at different flow
rates, a second injection of the same microgel solution in the
same pack was performed. Results shown in Fig. 16 indicate
that: 1) the Rm values are perfectly constant from 1 PV to 17
PV and remain the same on the three sections, 2) effluent
concentration is stable and equal to 100%, 3) Rk after
complete displacement of microgels by brine has the same
value as after the first microgel injection. This highlights the
fact that the amount of microgel adsorbed on the pore surface
remains constant whatever the number of pore volumes
injected is. More generally, the results of the two injections of
unfiltered microgel solutions clearly show a complete absence
of plugging and a very easy in-depth propagation of the
microgels through the porous medium.
4.2. Water permeability control by adsorption
As pointed out previously, controlling permeability by
adsorption of microgels onto rock pore surfaces allow to
control the permeability to water inside the reservoir
everywhere the microgels have been placed without affecting
oil permeability [24]. That is the reason why microgel
adsorption properties have been investigated in details. The
main results are reported below.
Thickness of adsorbed layer
The measurements of Rk in model granular pack at different
flow rates lead to an estimation of the pore throat size
reduction, and thus of the thickness of adsorbed layer, as a
function of the shear rate. The hydrodynamic thickness of
adsorbed layers εh were calculated with [26]:
ε h = rh (1 − Rk −1 / 4 ) (3)
where rh = 1.15(8k / φ )1 / 2 is the pore throat radius. The values
of adsorbed layer thickness derived from Eq. 3 are plotted in
Fig.17 versus the wall shear rate γ which can be estimated for
porous media flows by:
γ = 2.5 × 4v / rh (4)
where υ is the interstitial mean velocity and 2.5 a factor which
has been previously determined for such sharp-edged granular
packs [26]. As expected from the stable and identical values of
Rm during the microgels injection, εh values are the same for
the three sections of the pack, and do not depend on the
number of PV injected. Due to the deformation of the
microgels when adsorbing on the solid surface, the
hydrodynamic thickness of the adsorbed microgel layer is
significantly smaller (εh=0.8µm) than the hydrodynamic size
of the microgels in solution determined by light scattering
(around 2 µm). This observation is compatible with our
previous results [24], which indicate that less deformable
microgels, namely high crosslink density microgels, create
adsorbed layer thicknesses (εh≈1.7 µm) that are closer to their
size in solution (Dh≈2 µm).
Adsorption density
Adsorption density, which is defined as the adsorbed amount
per unit area of pore surface, can be determined only from
grain packs having a well-know specific surface area. (for SiC
80µm, S =0.049 m2/g [35]). Adsorption density was derived
from both the variations of Rm in the different sections and the
recording of the effluent concentration as a function of pore
volumes injected. The two methods gave approximately the
same value for adsorption density, i.e. Γ=780 µg/m2. This
value is significantly lower than what can be calculated by
assuming that an homogeneous layer of thickness εh=0.8µm
and an internal density identical to that of the microgels in
dilute solution is formed (Γth=2800 µg/m2). Such an
observation is consistent with the hypothesis of a random
sequential adsorption of unpenetrable microgels onto
accessible surface [36,37]. This results suggests that free
adsorption sites remain available for an eventual forced over-
adsorption of microgels as previously found for polymers [38].
A complete interpretation of those results would require
additional investigations which are now in progress.
Rheological behavior of adsorbed layer
In Fig. 18 are plotted the εh values versus shear rate obtained
after injection of dilute solutions of high crosslink density
microgels (from [24]), medium crosslink density microgels
(experiment described above) and an acrylamide linear
polymer comparable to sample D. Since the εh values are
identical on the three sections of the pack, we plotted only the
results from the upstream (BC) section. Moreover, all
adsorbed layer thicknesses do not depend on the number of PV
injected. Results indicate that: 1) εh increases with crosslink
density for microgels having similar size in solution, 2) εh
increases with shear rate (shear thickening) for linear polymer,
whereas it remains constant or slightly decreases (shear
thinning) for microgels. Concerning the polymer, the second
observation is characteristic of its sensitivity to elongational
forces located behind the grains [26]. The absence of shear
thickening behavior for microgels comes from their
crosslinked structure which prevents significant elongational
deformations. It should be noted that shear-thinning behavior
has already been observed with less structured microgels [20].
Methods for controlling adsorbed layer thickness
At least three methods can be used to control the thickness of
adsorbed layer. The first one consists of injecting microgels of
different sizes. The second one consists of increasing
concentration above critical overlap value. The third one
consists of injecting the microgels at a velocity higher than a
critical value. These two last methods have already been
investigated in the case of linear polymers [26] and significant
increases in adsorbed layer thickness with concentration have
been observed.
The second method is expected to be valid even for
unpenetrable but deformable polymer species. In this case,
concentration reduces the size of the colloid is reduced in
solution and thus the number of adsorbed particles increases
leading to higher layers thicknesses. In order to test this
method for microgels, we performed injections of high
crosslink density microgel (sample A) in different 80 µm SiC
SPE 93254
packs having similar characteristics. Concentration of
injection (Cinj) were 0.4g/L (Φ=0.07), 1g/L (Φ=0.17), 3g/L
(Φ=0.51) and 6g/L (Φ=1.03). Main results are shown in Figs.
19 and 20. Three clear observations can be made: 1) the
adsorbed layer behave as a shear thinning material whatever
Cinj is; 2) in diluted conditions regime, the thickness of
adsorbed layer does not vary significantly with Cinj; 3) the
thickness of adsorbed layer increase very significantly with
Cinj from low concentration regime to semi-dilutes regime
whatever the shear rate (at γ = 10 s-1, εh increases from 1.7 µm
at 0.4g/L up to nearly 4 µm at 6g/L).
The third method, we refer to as flow-inducted adsorption,
concerns only inter-penetrable species. This flow-inducted
adsorption is caused by hydrodynamic forces which, when
shear rates are high enough, become non-negligible compared
to thermal diffusion forces, and thus increases the number of
adsorbed microgels and consequently the adsorbed layer
thickness. Investigations concerning this last method for
controlling permeability are currently in progress and will be
described in details in a forthcoming paper.
4.3. Water and oil permeability control by adsorption
The currently used method to achieve disproportionate
permeability reduction consists in injecting a polymer solution
together with a crosslinker to get a weak gel, waiting for the
gel to be formed where the mixture have been placed, and then
putting back the well in production, thus causing a breakdown
of the gel in the highest permeability layers. As a
consequence, water permeability is selectively reduced where
gel has been broken, but large zones of the reservoir likely
remain plugged by the gel and oil production is certainly
reduced. The method we propose consists of injecting soft
fully water soluble microgels in the reservoir which adsorb
everywhere they have been placed without any complete local
pore plugging.
Results presented in this section are taken from [24], except
for what concerns centrifugation results, which are new data.
The high crosslink density microgel injection was conducted
at Sw=1-Sor for a concentration C=3000 mg/L. DPR
properties can be quantified by comparing the relative
permeability curves before and after adsorption of microgels.
These curves, which are shown in Fig. 21, have been derived
from the displacement cycles related in the above section
describing the experimental methods. It is observed that water
permeability is strongly reduced whatever the saturation is (by
a factor around 20 at Sw=0.529). Note that the water relative
permeability values obtained at higher saturation were
measured after some oil displacement, so that water phase is
likely discontinuous. As a consequence, they cannot be
interpreted as “true” relative permeability. By contrast, oil
permeability curve seems to be unchanged. However, it was
observed that the minimum water saturation (Swi) reached in
presence of adsorbed microgel remains substantially larger
than that found in their absence. This observation was
attributed to a kinetic effect, namely the strong reduction in
water permeability caused by the presence of adsorbed
microgel. Under these conditions, oil injection should have
been much longer. This interpretation has been confirmed by
centrifugation experiments which show clearly that both Swi
and the corresponding kro were strictly independent of the
7
presence of microgels. In addition, kro value is as high as the
absolute permeability (kro very close to 1). These results
confirm that microgels are excellent DPR products.
Conclusions
1. New microgels, specifically designed for water shutoff and
conformance control, having various crosslink density, and
chemical composition, which are now available at industrial
scale, have been tested at the lab scale.
2. Their characteristics in solution (size, polydispersity and
internal density, shear viscosity and viscoelasticity) can be
reliably determined by using relevant techniques described in
this paper.
3. The in-depth propagation at long distances is very good and
only limited by the injected volume even for unfiltered
solutions.
4. These microgels, when adsorbed, reduce water permeability
by forming thick adsorbed layers which are soft enough to be
collapsed on pore walls by capillary forces in the presence of
oil so that oil permeability remains unaffected.
5. A control of adorbed layer thickness and thus of water
permeability can be achieved by different methods: microgel
size selection, increasing concentration of injection and flow-
induced over-adsorption (in progress).
6. Microgels solutions behave in porous media as shear
thinning fluids, thus facilitating their injectivity in field
operations.
7. Mechanical, chemical and thermal stability of these
microgels were found to be excellent due to their crosslinked
structure.
Due to the remarkable ability of these microgels to control the
permeability at long distances without any plugging tendency,
they appear to be good candidates, not only for water shutoff
operations but also for conformance control of heterogeneous
reservoir. Moreover, such microgels could also be used as
mobility control fluids when reservoir conditions are to severe
to used linear polymers.
Acknowledgment
The authors wish to thank IFP and SEPPIC for permission to
publish these results.
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 SPE 93254 9

100

30 high crosslink density microgel high crosslink density microgel

Statistical frequency (%)

Statistical frequency (%)

(sample A) 80 (sample A)

60
20

linear polymer
40 (sample D)

10
20

0 0
0.1 1 10 0.01 0.1 1 10
Particle diameter, D (µm) Particle hydrodynamic diameter, Dh (µm)

Fig. 1 - Size determination of a dilute solution (C=0.6g/L) of high Fig. 2 - Hydrodynamic size determination of dilute solutions
crosslink density microgels by static light scattering. (0.2g/L) of high crosslink density microgels and linear
polymers (sample D) by dynamic light scattering (PCS).

2000 100
medium crosslink density microgel :
crosslinker type II
[η] = 719 cm3/g ; KH = 0.6
Relative viscosity, ηr @ C=6g/L
Specific reduced viscosity,

low crosslink density microgel :

1500 [η] = 884cm3/g ; KH = 0.4
ηspr (cm /g)
3

1000 10

500
crosslinker type I
high crosslink density microgel :
[η] = 428 cm3/g ; KH = 1

0 1
0 0.0005 0.001 0.0015 0.002 0.01 0.1 1 10 100 1000
Microgel concentration, C (g/cm )
3
Shear rate, γ.(s-1)

Fig. 3 - Determination of intrinsic viscosities and Huggins Fig. 4 - Relative viscosity measurements of solutions of microgels
constants for high, medium and low crosslink density made with crosslinker of types I and II at various
microgels dissolved in standard brine at T=30°C. concentrations. Solutions are dissolved in "standard
brine" at C=6g/L, measurements are performed at T=30°C.

100 100

Φ=1.03 (6g/L) Φ=0.68 (4g/L) Φ=0.86 (3g/L)

Φ=1.73 (6g/L)
Relative viscosity, ηr
Relative viscosity, ηr

Φ=0.34 (2g/L) Φ=0.58 (2g/L)

Φ=0.26 (1.5g/L) Φ=0.43 (1.5g/L)

10 10

Φ=0.29 (1g/L)

Φ=0.17 (1g/L)

Φ=0.23 (0.8g/L)
Φ=0.13 (0.75g/L)
Φ=0.09 (0.5g/L) Φ=0.14 (0.5g/L)

1 1
0.1 1 10 100 1000 0.1 1 10 100 1000
Shear rate, γ. (s-1) Shear rate, γ. (s-1)

Fig. 5 - Effective volume fraction (concentration) dependence of Fig. 6 - Effective volume fraction (concentration) dependence of
relative viscosity of the high crosslink density microgel in relative viscosity of the medium crosslink density microgel
"standard brine" solutions at T=30°C. in "standard brine" solutions, at T=30°C.
 10 SPE 93254

10000
hard spheres
0
microgel Φ=0.34 (C=2g/L)
medium crosslink
Relative viscosity, ηr

1000 density microgel -0.02

Log10 (ηr/ηro)
high crosslink density -0.04
100 microgel

-0.06
polymer Φ=0.34 (C=0.3g/L)
10
-0.08
linear polymer

1 -0.1
0.01 0.1 1 10 1 10 100 1000
Effective volume fraction, Φ = 2C[η]/5 Shear rate, γ. (s-1)

Fig. 7 - Variations of zero shear relative viscosity with effective Fig. 8 - Evolution of the measured viscosity at a given shear rate
volume fraction showing a microgels behavior (ηr) relatively to the newtonian value (ηro) for diluted
intermediate between hard spheres and linear polymers solutions of high crosslink density microgel and linear
(solutions in "standard brine", T=30°C). polymer (sample D) ; solutions in "standard brine", T=30°C.

10 10 10 10
G' Φ=3.42 G'' G' G''
Φ=7.04 Φ=7.04
Shear modulus, G' & G" (Pa)

Shear modulus, G' & G" (Pa)

(20g/L)
(20g/L) (20g/L)

1 Φ=5.63 Φ=5.63
Φ=3.42 (16g/L) (16g/L)
1 1 1
(20g/L)
Φ=4.22
Φ=2.74 (12g/L)
(16g/L) 0.1 Φ=4.22
Φ=2.74 (12g/L)
(16g/L)
Φ=2.05
0.1 0.1 0.1
(12g/L) Φ=2.05
Φ=2.82 Φ=2.82
(12g/L) 0.01 (8g/L) (8g/L)

Φ=1.37 Φ=0.68 Φ=1.41

Φ=1.37 (4g/L)
(8g/L) (4g/L) Φ=1.41 (4g/L)
(8g/L) Φ=0.68 (4g/L)
0.01 0.01 0.001 0.01
0.01 0.1 1 10 0.01 0.1 1 10
10 0.01 0.1 1 10 0.01 0.1 1 10
1
Frequency, f (Hz) Frequency, f (Hz) Frequency, f (Hz) Frequency, f (Hz)

Fig. 9 - Effective volume fraction (concentration) dependence of Fig. 10 - Effective volume fraction (concentration) dependence of
the dynamic shear moduli of high crosslink density the dynamic shear moduli of low crosslink density
microgels (solutions in "standard brine", T=30°C). microgels (solutions in "standard brine", T=30°C).

medium crosslink 150

Newtonian viscosity relative evolution (%)

high crosslink density microgels,

140 density microgel high crosslink linear polymer, η0initial~16cP
η0initial~20cP
Specific reduced viscosity (ηspr)

density microgel

120 125
relative evolution (%)

100
100

80
75
60
low crosslink
density microgel
40 50

20
25
polymer
0
0 2 4 6 8 10 12 14 16 0
High shear treatment duration, ths (min) production brine without H2S production brine with H2S (after 2 days)
Fig. 11 - Specific reduced viscosity evolution with high shear
treatment duration for high, medium and low crosslink Fig. 12 - Newtonian viscosity evolution after 2 days of high
density microgels as well as linear polymer (sample D); crosslink density microgels and linear polymers.
solutions in "standard brine", T=30°C. Solutions in an oilfield production brine with or without
H2S, T=30°C.
 SPE 93254 11

Microgels 120°C (C=3 g/L, ηo=5.3 cP)

400 Microgels 150°C
HSPAM 120°C (C=4 g/L, ηo=6.9 cP)
350 HSPAM 150°C
300
300 293 288
Viscosity Evolution (%)

256 260 ∆P
TOTAL LENGTH ∆P
250
MICROGEL CALIBRATED spectro
211 SOLUTION PUMP CAPILARY
200 ∆P ∆P
165 UPSTREAM DOWNSTREAM
160 pH
150
103 BRINE
100 81 80 PUMP

48
50 27
0 0 00 0 Porous medium
00
(reference)
0 t0 1 3 7 17 30 90
-50
Time (days) BYPASS T=30°C
-100 -85

Fig. 13 - Thermal stability of a linear polymer (HSPAM) and high Fig. 14 - Experimental set-up for transport in porous media
crosslink density microgels. experiments performed in SiC granular packs.

2.5 2.5
100 100
Effluent concentration (%)

Effluent concentration (%)

CD
Mobility reduction, Rm

Mobility reduction, Rm

80 80
2 2
BC
60 60
AE
BC
A B C D E A B C D E
AE 40 40
1.5 1.5

20 20
CD

1 0 1 0
0 1 2 3 4 5 6 0 5 10 15 20
Pore volumes injected, PV Pore volumes injected, PV

Fig. 15 - Transport of medium crosslink density microgels in SiC Fig. 16 - Transport of medium crosslink density microgels in SiC
granular pack, first injection. granular pack, second injection.

1.4 10
A B C D E A B C D E
Adsorbed layer thickness, εh (µm)

Adsorbed layer thickness, εh (µm)

CD ( )
1.2
AE ( )

1
High crosslink density
microgel
0.8
1
Medium crosslink
0.6 density microgel

BC ( )
0.4
Linear polymer
0.2

0 0.1
1 10 100 1000 1 10 100 1000
Shear rate, γ (s ) . -1
Shear rate, γ. (s-1)

Fig. 17 - Rheology of adsorbed layer of medium crosslink density Fig. 18 - Rheological behavior of adsorbed layer of high and
microgels in SiC model granular pack. Thickness of medium crosslink density microgels and linear polymer in
adsorbed layer (εh) does not depend on the distance from SiC granular packs. Adsorbed microgels are shear
inlet. thinning while linear polymers are shear thickening.
 12 SPE 93254

10 10
A B C D E A B C D E

Adsorbed layer thickness, εh (µm)

Adsorbed layer thickness, εh (µm)

Cinj = 6000 mg/L

Cinj = 3000 mg/L

Cinj = 1000 mg/L

Cinj = 400 mg/L

1 1
1 10 100 1000 0 1000 2000 3000 4000 5000 6000 7000
Shear rate, γ. (s-1) Injection concentration, Cinj (mg/L)

Fig. 19 - Rheology of the adsorbed layer of high crosslink density Fig. 20 - Adsorbed layer thickness εh versus injection
microgels in SiC model granular packs for different concentration Cinj taken at 10s-1 of high crosslink density
concentration of injected solution (Cinj). microgels in SiC model granular packs.

1 0.1
Relative permeability to water krw

before microgel adsorption

kro=0.98
Relative permeability to oil kro

0.9 after microgel adsorption 0.09

end point from kro=0.84
0.8 centrifugation end point from 0.08
displacement
0.7 krw=0.065 0.07
0.6 kro=0.60
0.06
0.5 0.05
0.4 0.04
0.3 0.03
0.2 0.02
krw=0.008
0.1 0.01
0 0
0.2 0.3 0.4 0.5 0.6 0.7
0.2 0.33 0.35 0.550
Water saturation Sw

Fig. 21 - Relative permeability curves before and after microgel

adsorption of high crosslink density microgel in a Berea
core initially placed at residual oil saturation.