SPE 86548
Characterization of Crosslinked Gel Kinetics and Gel Strength Using NMR
Laura Romero-Zeron1, F. Manalo1,2 SPE and A. Kantzas1, 2,SPE, 1. Canada Research Chair in Energy and Imaging
Department of Chemical and Petroleum Engineering, University of Calgary. 2.Tomographic Imaging and
Porous Media Laboratory
Copyright 2004, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Symposium and Exhibition
on Formation Damage Control held in Lafayette, Louisiana, U.S.A., 18–20 February 2004.
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Abstract
Highly crosslinked gels are used in high-permeability
reservoirs to achieve good fluid-loss control during well
completion and workover operations. Crosslinked gels are also
commonly used for shutting off unwanted gas and/or water
influx into production wells, and for improving the
conformance of the near wellbore injection profile in naturally
fractured or in high-permeability reservoirs. In all such
applications, the appropriate design of the gel treatment is
critical to ensure an efficient gel placement. One important
variable of the gel application design is the rheology of the gel
system for establishing the crosslinking kinetics and the gel
strength after gelation is complete.
Rheology of gels and gelation rates are commonly determined
by rheological methods or in a qualitative mode through bottle
testing using a well-known gel strength code (i.e., the
Sydansk’s Code). The rheological measurements can be both
time consuming and expensive, while bottle testing can lead to
an inconsistent gel description as a result of the subjective
nature of the gel strength code. This paper describes the use of
low field nuclear magnetic resonance (NMR0 to monitor
gelation rates and to characterize gel strength. This technique
provides fast and accurate gel strength characterization and
gelation monitoring. Through calibration with polymer
concentration, crosslinker concentration, aging of gels, and the
effect of brine, it is possible to predict NMR parameters. This
then allows for a standardized method for the rheological
categorization of gels.
The results of this work present the correlation between the
NMR spectra, rheological measurements, and the qualitative
codification of gel strength.
Introduction
Gels are swollen polymer networks possessing both the
cohesive properties of solids and the diffusive transport
properties of liquids. If some of the bonds holding the gel
network together can “make-and-break”, the gel is called
reversible. If the bonds do not dissociate, the gel is called
permanent. A permanent gel tends to carry the history of its
formation in its structure, and it is best described as a cross-
linked system of clusters. Clusters range from small, starlike
molecules to large heavily cross-linked, and fairly
concentrated microgel cores 1.
Water-based gels are obtained by crosslinking linear flexible
water soluble polymers using transition metal ions. These gels
are highly elastic with a water content (98% to 99%) trapped
in the three-dimensional polymer structure of the gel 2. Water-
based gels exhibit a wide range of static and dynamic physical
properties that make them suitable for numerous applications
in the oil and gas industry 3, such as plugging off lost
circulation zones during drilling operations, hydraulic
fracturing for stimulating the production of oil and gas
formations, controlling excessive water and gas production
problems, and plugging depleted wells at the end of the
economic life 4,5.
Currently, the most widely used polymer gel-forming
compositions employ either a partly-hydrolyzed
polyacrylamide (HPAm) or an acrylamide co-polymer and a
chromium ion [Cr(III)] crosslinker 6. This network system has
been studied extensively both in the laboratory and in the
field. Achieving reliable performance of this hydrophilic gel
system requires a good understanding of the physical chemical
properties, the viscoelastic behavior of gels, as well as the
interrelation of these two aspects 3. Previous research studies
have addressed primarily the establishment of gelation kinetics
3,4,7-12
and the evaluation of the rheological behavior and
mechanical properties of a given gel system 13-18.
These products are usually mixed in surface facilities, then
pumped downhole through coiled tubing and injected into the
formation over a depth of several feet. For the operators,
gelation time and gel consistency after gel shut-in are the two
most important parameters to control. The gelation time,
which corresponds to a sudden rise in the viscosity, must be
long enough to allow for placement of a sufficient gel
volume16 before gelation starts: early network formation is
undesired 3. Consequently, the rate at which this 3D gel is
formed determines how far the solution can be pushed into the
rock formation away from the injection well before gelation
occurs 7. Gel consistency is related to the maximum pressure
drop the gel can sustain within the porous media 16.
The gelation reaction of polyacrylamide/Cr(III) gels, the
2 SPE 86548
determination of gel point and the mechanical properties
characterization of this polymer network have been commonly
studied by visual observation through bottle testing using a
strength code table 9, through the evaluation of yield stress or
by rheological monitoring of gelation. However, to the best of
our knowledge no one has monitored the formation of these
gel systems and has determined gel point and gel viscosity
using low field NMR. The main advantage of using low field
NMR is that allows a simple, accurate and fast determination
of fluid physical properties such as viscosity. Furthermore, it
is a non-destructive technique that makes possible the
characterization of polymer gels without disruption of the
network structure 19. Finally, it offers the possibility of
downhole evaluation of gelation under certain
well completions.
The hypothesis presented in this paper, and proven by
experimental results, is that monitoring gel formation using
low field NMR enables the determination of gel point (the
point at which cross-linking begins20), and gel viscosity.
In the present work we studied the crosslinking of an aqueous
HPAm/Cr(III)-acetate gel through visual observation (bottle
testing), rheological monitoring, and low field NMR
relaxation. The viscometric behavior of the gel system is
determined as a function of polymer concetration and salinity
of the aqueous solution. In this paper, we present first a brief
literature review of the gelation kinetics, basics on the
dynamic rheology characterization, and low field NMR
theory. In the second part of this paper, we outline the
experimental details and present the processed experimental
data. Finally, we present the interpretation and discussion of
the experimental results.
Literature Review
Gelation Mechanism. The kinetics of the chromium (III)
acetate-polyacrylamide reaction are not well known yet 4,7,21,22.
Therefore the nature of the crosslinks of partially hydrolyzed
polyacrylamide (HPAm) with chromium (III) is still a matter
of debate. As was demonstrated by Sydansk 9 Cr(III)
crosslinking of acrylamide polymers occurs through the
polymer’s pendent hydrolyzed carboxylate groups (Fig. 1).
The crosslinking reaction of HPAm/Cr(III) depends on the
Cr(III) ion source because of the differences in structural
features. Each chromium ion species should react differently
with HPAm and form gels at different gelation rates with
different properties 8. The crosslinking agent is a coordinate-
covalent-bonded Cr(III)-carboxylate complex, often
oligomeric in Cr(III). Acetate is the preferred carboxylate
complex 23. In this complex the chromium anion is a trimer.
The work of Tackett 10 provided information about chromium
acetate structures in aqueous solutions. Thus, depending on
the pH of the aqueous solution, there is an equilibrium
between trimeric cycle and trimeric linear chromium acetate
species as is shown in Fig. 2. During the gelation reaction,
intermolecular crosslinking occurs through Cr(III)-carboxylate
complexes involving coordinate-covalent bonding by the
Cr(III) complex with two carboxylate functional groups on
two different acrylamide polymer molecules 23 as is shown in
Fig. 3. This reaction mechanism enables formation of gels at
pH of 9 where chromium would normally precipitate as
colloidal chromium hydroxide2. The work of Nijenhuis 21
presents a detailed approach on the crosslinking kinetics for
the system Cr(III)-Polyacrylamide. Gelation time for
HPAm/Cr(III) reaction is a strong function of temperature.
Therefore, it follows the Arrhenius equation. The effect of
temperature on gelation kinetics for the system HPAm/Cr(III)
has been widely studied in laboratory, details of those studies
are given elsewhere 6,12,16,23-28.
Another important variable that has a complex influence on
the rate of gelation is the pH of the polymer solution.
Therefore, many gel compositions perform well only in a
specific range of pH, and after the gel mixture is injected in
the formation, the reservoir rock will tend to impose its own
pH on the injected solutions12. Thus enormous amount of
work has been devoted on this matter 3,9,11,29,30.
Gel formation also shows strong dependence on the
maturation time. It indicates that crosslinking processes are
very slow 3. Lockhart 11 demonstrated that network formation
in HPAm/Cr(III) solution can last more that half a year. As
other researchers indicated 31, the process of gelation starts
very slowly, sweeps through a maximum of activity, and when
the gel is “set” the process continues, tapering off into a final
hardening or setting process, which probably continues for a
long time. The time at which the gel is “set” is known as gel
point. At this point the solution just transforms into a gel 3, or
the cross-linking reaction begins20. Several methods are
presented in the literature for the determination of gel point 18.
Since the complexation between Cr(III) and HPAm follows
the Arrhenius equation and knowing gel time from
experimental data, we can make use of the Hurd and Letteron
model 31, 32 to calculate the activation energy of the first step of
crosslinking reaction, when the solution is just transformed
into the gel state. The Hurd and Letteron model 31 is
represented as follows:
R∂ (ln( geltime))
Ea =
∂1 ( )
T
(1)
Where Ea is an apparent activation energy that reflects the
energy involved in the crosslinking reaction16, R is the gas
constant (8.314 J/ (K mole)) and T is the absolute temperature
(K). In this work, the gel time has been measured at 30 oC, and
at different polymer concentrations, crosslinker
concentrations, and solution salinities. The apparent activation
energy of the crosslinking reaction measures the sensitivity of
the gelation kinetics to temperature 16. However, in this paper
we use the apparent activation energy as an additional tool to
evaluate the effect of polymer concentration, crosslinker
concentration, and salinity on the crosslinking reaction. In this
way our results can be compared with previous work.
Gel Syneresis. HPAm/Cr(III) gel systems normally undergo
chemical modifications with time. One of these chemical
instabilities is known as syneresis. Syneresis causes shrinkage
in gel volume and consequently water is expelled from the gel
structure 2. Depending on the composition, a syneresed gel
may occupy as little as 5% of the initial solution volume 6. As
Gales 33 explains, syneresis usually occurs in a gel prepared
from a relatively dilute polymer solution, which has a
relatively low mixing potential compared to a gel with higher
polymer concentration. When the gel is first formed (at the gel
point) the crosslinking density is usually low so that the elastic
potential is still smaller than the mixing potential.
SPE 86548
Crosslinking of network chains continues after the gel point,
giving the network a tighter structure. The continuous
crosslinking leads to an increased crosslinking density, hence
increased elastic potential. After the gel has been aged for a
certain period of time, the elastic potential may exceed the
mixing potential. When the elastic potential is greater than the
mixing potential, the gel shrinks to balance the difference
between the two potentials.
Syneresis is strongly influenced by crosslinker concentration,
brine salinity, pH, and temperature 2,6. In this paper, we
monitor the beginning and the progression of syneresis for our
gel system as a function of time, using low field NMR and by
direct observation through bottle testing.
Rheology of Crosslinked Polyacrylamide Gels. The
viscoelastic properties of polyacrylamide gels and gel strength
are usually evaluated through dynamic oscillatory
measurements 24. Since the material is subjected to only small
sinusoidal shear deformations, there is no disruption of the
network structure 7,34. The general method is to monitor the
gelation process with a dynamic rheometer that allows the
determination of the elastic and viscous responses under low
frequency oscillating shear deformation as a function of time
(Fig. 4). In Fig. 4, G* or complex modulus represents the total
resistance of the gel against the maximum applied strain. G’ or
storage modulus represents the elastic response, which
quantifies the ability of the material to store elastic energy that
can eventually be recovered. G’’ is the loss modulus, which
quantifies the amount of mechanical energy that is
transformed into heat (i.e., energy lost) due to viscous force
14,17
. The relation between the storage and viscous component
is represented by the shift angle (δ) where tan (δ) = G’’/ G’.
More details on basic rheological concepts can be found
elsewhere 15,16. Dynamic rheology is the most recommended
method for characterizing gel strength in contrast to highly
qualitative methods such as the visual consistence, which uses
alpha or numerical codification for assigning gel-strength 14, as
for example the Sydansk gel-strength code 9 shown in Table 1.
In this experimental work, we used the parallel-plate geometry
for the dynamic oscillatory measurements, since previous
studies 14,35 have demonstrated that this geometry offers better
reproducibility of the complex viscosity measurements for
gels. Earlier research 16 has demonstrated that shear strongly
affects the gelation process. So, in order to avoid gel structure
damage during the experiment, low strain (40%) and low
frequency (1 Hz) were used in this work.
Gelation Time Determination. As mentioned before,
gelation time is a fundamental parameter in oil field
applications that requires the injection of a polymer /
crosslinker mixture in a rock formation. The gel point will
determine how deep into the formation the gel can be placed.
The gel point can be determined from dynamic viscoelastic
data following the Tung and Dynes method 36, who
demonstrated that the gel times of many thermosetting resins
coincide with the crossover points of the dynamic storage (G’)
modulus and loss (G’’) modulus measured during isothermal
setting. The correlation between the crossover points and the
gel points was remarkable, suggesting that the loss tangent
(G’’/G’ = tan (δ)) is nearly unity at the gel point (Fig. 5a).
Suematsu 36 provides a more detailed explanation of Tung and
Dynes method. However, it has been demonstrated that for
3
some systems the G’ – G” crossover depends on the specific
choice of frequency 34. Another method that has been recently
suggested using dynamic viscoelastic data is the determination
of the intersection of tanδ at several frequencies as a function
of time (Fig. 5b). This method seems to be very effective
because tanδ is independent of frequency 34.
NMR Basics. Low field NMR detects the response of
hydrogen protons in magnetic fields. Hydrogen protons have a
property known as spin, which causes the protons to act as
small bar magnets. In the presence of an external magnetic
field, the protons will therefore tend to line up either parallel
or anti-parallel to the external field lines. A pulse sequence is
then applied to the protons, giving them energy and causing
them to tip onto another plane, called the transverse plane. As
the excited protons in the transverse plane give off energy,
they return to their equilibrium direction and the signal in the
transverse plane decays. A low field NMR experiment
measures two properties: the strength of the signal, and a
characteristic relaxation time. This characteristic time could
either be the time for the signal to return to its equilibrium
value in the direction of the external field lines (T1) or the time
for the signal to disappear in the transverse plane (T2) 37. Three
types of relaxation exist in fluids: bulk relaxation, surface
relaxation, and diffusion in a magnetic field gradient. Only
bulk fluids are measured in this work, so there is no effect of
surface relaxation. In the laboratory, the fluid sample is placed
in a homogeneous magnetic field, so there is also negligible
accelerated relaxation due to diffusion in a magnetic field
gradient. This means that the measured transverse relaxation is
due only to bulk relaxation 38. Bulk relaxation is a fluid
property, and is a measure of how easily the protons give off
energy to one another. Bulk relaxation can be expressed in the
following form 38:
∝η
1 (2)
T2 B T
Where η is viscosity, 1 is the rate of bulk relaxation (s-1),
T2 B
and T is absolute temperature. Bulk relaxation rate for the
component is inversely related to the viscosity of the
substance, therefore components with higher viscosity will
relax faster than components with lower viscosity. Substances
with higher viscosity have molecules that cannot move by one
another as easily as substances with lower viscosity. This lack
of mobility in higher viscosity components leads to more
frequent exchange of energy between protons of these
components, allowing energy to be dissipated more rapidly. In
this way, low field NMR measurements reproduce
microscopically the occurrence observed macroscopically in
viscosity measurements 37.
The strength of the magnetic signal is directly proportional to
the number of hydrogen protons present, which can be
correlated to the amount of fluid present. Thus, the parameter
Amplitude Index (AI) has been defined to relate NMR
amplitude to a corresponding mass of fluid:
At
AI = (3)
mass
Where AI is amplitude index, At is total NMR amplitude of
the sample, and mass is mass of the sample 37. Using
4 SPE 86548
experimental values of T2 obtained from the NMR monitoring
of the crosslinking process will enable the determination of the
overall reaction order and rate for the polymer gel
under evaluation 39.
Materials and Experimental Procedures
Materials
Brine. Some of the tests were carried out with synthetic brine
having a total dissolved solids content (TDS) of 2 wt %. The
composition of the synthetic brine is presented in Table 2.
Polymer. The polymer used in this study is Alcoflood 935,
supplied by Ciba Specialty Canada Inc. Alcoflood 935 is an
anionic acrylamide copolymer. Some physical properties of
this acrylamide are presented in Table 3.
Crosslinker. The crosslinker used for gel formulation was
chromium acetate solution 50% active in water, supplied by
McGean-Rohco, Inc. Chromium acetate is highly water-
soluble and readily mixes with acrylamide polymer solutions.
Experimental Procedures.
Bottle testing. Bottle testing was one of the experimental
methods used to evaluate the gelation process over an
extensive range of crosslinker concentrations, polymer
concentrations and water salinity. Gelation rate and gel
strength were determined as a function of time through bottle
testing using the Sydansk’s gel-strength code 9 shown in Table
1. Bottle testing was conducted at room temperature using
wide-mouth glass bottles (25ml). The bottles were filled with
12.5 ml of polymer solution and the crosslinking process was
monitored as a function of time starting from the point of
Cr(III) addition to the polymer solution. The bottles were
periodically inverted to check the gel flow behavior under the
influence of gravity and a gel-strength code was assigned as
defined in Table 1. This experimental procedure allowed the
evaluation of the long-term crosslinking process without
disrupting the gel network.
NMR measurements. NMR measurements were carried out
using a Corespec 1,000TM relaxometer at a frequency of 1MHz
and two temperatures 25oC and 30oC. The relaxometer
parameters were set as follows, number of trains = 4, PTD
(ms) =5000, gain = 4, TE (ms) =0.3, number of echoes =5000.
The crosslinking process was monitored at different polymer
concentrations, crosslinker concentrations, and salinities using
two different experimental sets of NMR measurements. In the
first set of experiments, the gel sample (right after mixing the
polymer and the crosslinker) is placed in the NMR tool. An
NMR spectrum was taken each 5 minutes during the first 4 to
5 hours in order to follow very closely the first step of the
crosslinking reaction. These experiments were conducted at
30oC. The second set of experiments, consisted of placing the
gel sample at the beginning of the crosslinking reaction in the
NMR machine. Then, an NMR spectrum was taken each 5
hours during the first two days of gelation reaction. Then, after
the third day of gelation a NMR spectrum was taken daily
during 2 months. These sets of experiments were performed at
25oC. The objective was the long-term evaluation of the
gelation process under different gel compositions.
Rheological measurements. The crosslinking process was
monitored through dynamic rheometry as a function of time,
polymer concentration and salinity of the polymer solution. In
this work the dynamic rheological measurements were
performed using a Rheometric Scientific rheometer model
ARES with 50 mm diameter parallel plates geometry, 1.0 mm
gap, at a frequency of 1 Hz, 40 % strain, and 30oC. The gel
samples were placed onto the plate right after mixing the gel
system or after certain gel aging time and then subjected to a
steady shearing: low strain and low frequency.
Results and Discussion
Bottle testing. The crosslinking process was qualitatively
monitored through visual observation using bottle testing.
Sydansk’s gel-strength code (Table 1) was used for assigning
gel strength. In this section, the experimental observations
obtained from bottle testing are presented and discussed.
Effect of Polymer concentration. Table 4 shows the effect of
polymer concentration on gelation rate and gel strength. These
observations were carried out keeping constant the weight
ratio polymer-to-crosslinker (HPAm:Cr(III)) at 40:1 and 25oC.
Bottle testing results in Table 4 indicate that gelation rate and
gel strength increase with increasing polymer concentration.
Influence of Crosslinker concentration. Bottle testing results
on the effect of crosslinker concentration on gelation rate and
gel strength are shown in Table 5. This experimentation was
performed at room temperature, keeping constant the
concentration of polymer at 1 wt%. As can be seen in Table 5,
gelation rate and gel strength increase with decreasing the
polymer-to-crosslinker weight ratios.
Effect of Salinity. The effect of salinity of polymer solution
on gelation rate and gel strength is presented in Table 6. In this
set of experiments the weight ratio polymer-to-crosslinker
(HPAAm:Cr(III)) was kept constant at 40:1, changing
polymer concentrations and salinity of the polymer solution.
The tests were performed at 25oC. For the gels in Table 6,
gelation rate and gel strength increase with salinity. These
results are counter-intuitive since higher gelation rate and
higher gel strength are expected in salt-free solutions. In salt-
free solutions polymer molecule coil expansion prevails and
higher association degree predominates between polymer
molecules 40, therefore promoting crosslinking. Most likely,
the experimental observations through bottle testing were
dampened by the initial high viscosities of the polymer
solutions in distilled water, making it difficult to differentiate
the evolution of the gel viscosity with time. The experimental
results from Table 6 demonstrate the subjectivity and
inaccuracy of the bottle testing technique for the analysis and
characterization of the HPAm/Cr(III) gelation process and
gel strength.
Low field NMR measurements. The formation of
polyacrylamide/chromium acetate gel was followed using low
field NMR. Since bulk relaxation rate for the gel sample is
inversely related to the gel viscosity, the reaction time
dependence of the bulk relaxation rate has been used to
analyze the gel-network development. The effects of changing
polymer, Cr(III) concentration and salinity of the polymer
solution have been studied. Additionally, estimation of gel
points for different gel compositions and the overall order of
the crosslinking reaction have been attempted.
Effect of Polymer Concentration. Fig. 6 illustrates the effect
of polymer concentration on bulk relaxation rate. The three
SPE 86548
curves in Fig. 6 represent the crosslinking process of
polyacrylamide gels with equal polymer/chromium(III) ratios
(40:1) at different polymer concentrations in synthetic brine.
As the polymer concentration in the gel increased from 0.5%
to 1.5%, bulked relaxation rate increased, which is directly
proportional to the gelation rate and viscosity of the gels.
Effect of Cr (III) concentration. Fig. 7 shows the effect of
crosslinker concentration on bulk relaxation for a Cr(III)-
acetate-HPAm gel that contained 1.0 % HPAm. The results
depicted in Fig. 7 show that bulk relaxation rate increases
when decreasing the polyacrylamide-to-chromium acetate
ratio (or increasing chromium acetate concentration in the
gel). This effect is more pronounced for higher concentrations
of chromium acetate.
Effect of salinity of polymer solution. The effect of brine
salinity on gelation kinetics is illustrated in Fig. 8. In these
experiments the polymer to crosslinker ratio was fixed at 40:1.
Polymer concentration was changed from 0.5 to 1.5%, and
polymer solutions were prepared in distilled water (DIW) and
synthetic brine. As may be observed in Fig. 8, shifting from
distilled water to synthetic brine decreases bulk relaxation
rate, and therefore delays gelation rate. As was mention
before, these results were expected, since HPAm
macromolecule has a structural flexibility that makes it very
sensitive to the ionic environment. Cations have screening
effects on the electrostatic repulsions between charges
monomers 41, which leads to molecules shrinking and a lower
level of interpenetration between chains 16.
Syneresis. As already pointed out in the literature review
section, HPAm/Cr(III) gel systems undergo chemical
modifications with time, specifically syneresis. In the
laboratory, we monitored the beginning and the progression of
syneresis as a function of time for a gel formulated with very
high chromium acetate concentration (16.7 w%). These
experiments were performed at 25oC, during 578 hours, and 1
wt% of polymer concentration in brine. Fig. 9 represents bulk
relaxation rate versus time for two gel formulations. The lower
curve represents a stable gel formulated using a polymer-to-
crosslinker ratio of 40:1. This gel, after 150 hours of
polymer/Cr(III) mixing shows a constant bulk relaxation rate
during the experimentation period. The upper curve shows the
behavior of bulk relaxation rate versus time for a gel
formulated with very high crosslinker concentration (5:1
polymer-to-crosslinker ratio). High crosslinker concentrations
trigger syneresis. Fig. 9 shows that after 120 hours of gel
mixing, bulk relaxation rate decreases progressively with time.
This change in bulk relaxation rate indicates the beginning of
syneresis. Lower values of bulk relaxation rate are related to
the appearance of two phases: shrinked gel and free water. At
this point bulk relaxation rate is proportional to an average
viscosity of the mixture (gel and free water), which is lower
than the gel viscosity per se. This behavior may be better
observed if we look at Fig. 10, which illustrates normalized
amplitude and reaction time as a function of relaxation time
(T2) for the gel under evaluation. In Fig. 10 the dashed curves
with open symbols represent the amplitude baselines of
standard solutions of 16.7 % (5:1 polymer-to-crosslinker ratio)
of chromium acetate in brine and 1% polymer solution in
brine. The thick darkest curve represents the gel just after
polymer and Cr(III) acetate mixing. Departing from the
5
locations of the standard baselines and fresh gel curves in Fig.
10, it is possible to observe the chemical modifications that the
gel endures with time. After four days of crosslinking reaction,
the square symbols curve in Fig.10 shows displacement of the
NMR gel amplitude peak to the left. This indicates the
formation of a viscous gel network, since the signal shifts
toward lower bulk relaxation rates, as it is expected. Later on,
after 9 days of gelation, the gel sample displays two amplitude
peaks. One peak located to the left toward lower relaxation
times and the other peak located to the right of the plot, as the
diamond curve illustrates. At this time, the gel presents
syneresis and two well-defined phases are evident from the
NMR spectra: a solid network structure and an aqueous
solution. The progression of syneresis after 24 days of gelation
is also shown in Fig. 10.
Gel Point. Before the crosslinking polymer has reached its gel
point it consists of a distribution of finite clusters. It is called a
‘sol’ since it is soluble in good solvents. Beyond the gel point,
the polymer is called a ‘gel’. The gel is an infinitely large
macromolecule, which only can swell but not dissolve in a
solvent, even if low molecular weight molecules (sol fraction)
are still extractable from the gel. The gel point is reached
when the largest molecular or supermolecular cluster
approaches infinity 34. In oil field applications, the
determination of the liquid-solid transition of gel systems is
fundamental. Oil field applications require the injection of a
polymer/crosslinker mixture in the reservoir. In these cases,
gel point determines the injection period and the penetration of
the gel into the rock formation. Therefore, gel point constitutes
an essential parameter for designing a field application. In this
experimental work, we evaluated the liquid-solid transition
using low field NMR. These experiments were conducted at
30oC, with a polymer-to-crosslinker ratio of 40:1. Polymer
solution concentrations varied from 0.5 % to 1.5%, and
solutions were prepared in synthetic brine and distilled water.
NMR spectra were taken approximately each five minutes
since the beginning of the crosslinking reaction (just after
mixing polymer and chromium acetate) during the evaluation
period. Fig. 11 presents the bulk relaxation rate versus reaction
time for gels prepared with different concentrations of
polymer solutions in distilled water. The liquid solid transition
for these systems can be determined as the interception point
of the straight lines, which represent two well defined rates of
change of bulk relaxation rate with reaction time.
Approximated gel points or in this case gel point times are
given in Fig. 11, which fluctuates between 58 minutes to 65
minutes. As was expected, higher polymer concentrations
render lower gel point times. The liquid solid-transitions for
gels prepared using synthetic brine are presented in Fig. 12.
Again, NMR spectra show a very well defined change in bulk
relaxation rate versus reaction time, which corresponds to a
sudden rise in the viscosity of the gels. In this case, the gel
point times vary between 65 minutes to 110 minutes. Higher
gel point times than the gels prepared in distilled water were
expected due to the salinity influence on the crosslinking
process. The detection of the liquid-solid transition using low
field NMR is advantageous, because this is an unbiased and
non-intrusive technique. Therefore, it does not intervene or
disrupt in any way the crosslinking reaction. So, the values of
gel point times determined using this technique should be
6 SPE 86548
reliable. However, additional work is required to establish the
relation between gels bulk relaxation rate and the liquid-solid
transition under different experimental conditions, such as
high temperatures.
Crosslinking kinetics. As mentioned earlier, the continuing
buildup of the polymer network is reflected in the bulk
relaxation rate curves. Accordingly, the crosslinking rate of
the polyacrylamide/Cr(III) acetate gels under evaluation are
related to the rate of change of bulk relaxation rate with
respect to time. Microscopically, bulk relaxation rate
represents the rate at which Cr(III) acetate is bonded to the
polymer molecules. In this sense, it is possible to relate bulk
relaxation rate to crosslinker concentration to estimate the rate
law for the gelation process. Fig. 13 displays the change of
normalized bulk relaxation rate with time. These experiments
were conducted at 30oC and the gel formulations consisted on
40:1 polymer-to-chromium ratio and 1% of polymer
concentration, prepared in distilled water and synthetic brine.
The results, gathered in Fig. 13, demonstrate that the change
of bulk relaxation rate with time fits a straight line, thus
crosslinking reaction follows a second-order rate law. In
addition, Fig. 13 shows the influence of salinity on the
gelation reaction at constant crosslinker and polymer
concentration. The upper curve in Fig. 13 indicates that a gel
formulated in salt-free water crosslinks faster than a gel
formulated in synthetic brine.
Despite that our results are in agreement with previous
findings 7,9,21. Further research must be performed to
understand the relation between bulk relaxation rate and
crosslinking kinetics.
Additionally, activation energies for the first step of the
crosslinking reaction to the liquid-solid transition were
calculated using the Arrhenius-type law presented in equation
1 for some of the gels evaluated in this work. The values of
activation energy, given in Tables 7 an 8, are consistent with
previous activation energies values for similar acrylamide
systems reported by Eriksen et al. 32
Rheological measurements. In this work, we used the Tung
and Dynes method 36 to determine the liquid-solid transition
from dynamic viscoelastic data. In Fig.14 the storage modulus,
loss modulus and tan(δ) are plotted versus reaction time. The
gel formulation in the experiment illustrated in Fig. 14
consisted of 1 % polymer solution in synthetic brine and 40:1
polymer-to-chromium acetate ratio. In these series of
measurements the sample were subjected to steady strain of 40
% strain, 1Hz frequency, at 30oC. Measurements were started
after 6.52 minutes of polymer and crosslinker mixing, and
they were carried out at regular time intervals of 60 seconds.
As may be observed in Fig.14, the storage modulus and loss
modulus decay continuously up to a steady value during early
stages of gelation. Then, the storage modulus suddenly grows
intercepting the loss modulus curve. The intersection of the
two moduli curves (G’=G”) is related to the liquid-solid
transition. During our experimentation period, beyond the gel
point, the storage modulus (G’) keeps growing, while the loss
modulus (G”) remains constant. Fig. 14 shows that at the gel
point, the loss tangent, tanδ, (G”/G’= tan(δ)) is nearly 1. As
Suetmatsu 36 states, the loss tangent, which is the ratio of
energy lost to energy stored, measures the relative contribution
of viscosity to elasticity of a resin system. The loss tangent of
a viscous liquid therefore should be greater than unity, while
that of an elastic solid should be less that unity. The resin
systems proceed from a viscous liquid to an elastic solid. The
loss tangent of the systems, corresponding to the transition
state between viscous liquid and elastic solid, would therefore
be expected to be equal to 1. The complex viscosity behavior
for the gel system under evaluation is illustrated in Fig. 15.
The complex viscosity follows the same trend of storage
modulus, showing a rapid increase in viscosity at the gel point
location. The gel point for this system is reached after 223.2
min (3.72 hours) of polymer and crosslinker mixing (adding
the 6.52 minutes of mixing before loading the gel sample on
the rheometer plate). The equivalent liquid-solid transition
curve for the same system obtained using low field NMR was
presented previously in Fig. 12, where the middle curve shows
a gel point of 84 minutes. The large difference between the
two experimental procedures can be explained as Winter 42
states. Associated rheological experiments have been
successful in finding the approximate location of the gel point
by the divergence of the viscosity. However, as the
experimental times became longer and longer near the gel
point; shear viscosity measurements would result in large
stains which destroy the evolving microstructure
(mechanically induced anti-gelation). Numerous researchers
15,25,43
have investigated the effects of shear on the gelation
process. In light of these results, the next step in our
experiment was to avoid as much as possible to disrupt the
evolution of the gel network during the rheological
measurements. For that, we designed an experiment in which
polymer and crosslinker were mixed. Then, the mixture was
settled in the oven at 30oC during 74 min. Later on, about 10
minutes before the expected gel point, which is 84 minutes
from mixing, the gel sample was loaded on the rheometer
plate, carrying out measurements at regular time intervals of
60 seconds. Fig. 16 demonstrates this experiment. The
crossover point of the dynamic storage G’ and loss G” moduli
occurs after 508 s (8.5 min) after loading the sample in the
rheometer. The gel point in this case was reach at about 82.5
minutes after the beginning of the gelation reaction. This value
of gel point is consistent with the gel point value obtained
from bulk relaxation rates in the previous section. Therefore,
the mechanically induced anti-gelation is evident from
these results.
An additional gel formulation was evaluated; in this case the
gel composition consisted of 1.5 % polymer solution in
distilled water and 40:1 polymer-to-chromium acetate ratio. In
this experiment, the sample was subjected to steady strain of
40 % strain, 1Hz frequency, at 30oC. Measurements were
started after approximately 17 minutes of polymer and
crosslinker mixing, and they were also carried out at regular
time intervals of 60 seconds. Figures 17 and 18 depict this
experiment. G’ moduli displays a sudden rise after 1800 s of
sample loading in the rheometer configuration (Fig. 17), while
G” remains relatively constant. Fig. 18 shows that complex
viscosity follows the same fashion of G’ in Fig. 17.
Nevertheless, it is important to call attention to the fact that in
Fig. 17, we do not observe a crossover point of the dynamic
storage G’ and loss G” moduli. We may observe in Fig. 17,
that G’ module is higher than G” moduli since the beginning
of the test. This behavior can be explained if we look at Fig.
SPE 86548
19, which displays G’ and G” modulus curves for a polymer
solution 1.5 wt% concentrated in distilled water. These
measurements were performed using a Haake Rheometer
model RheoStress RS150 using the oscillatory mode. The
polymer samples were subjected to steady oscillatory stress of
2 Pa, 1Hz frequency, at 30oC. The higher value of G’ seen in
Fig. 19 indicates that the elastic modulus dominates over the
viscous modulus. In this case, the high concentration of
polymer in a salt free solution could encourage physical
crosslinking. Thus, physical junctions connect molecules into
large clusters and, eventually, into a sample spanning network
42
. Nevertheless, additional research must be performed to
understand the relation between dynamic rheological
measurements and bulk relaxation rate from low field NMR
observations.
Complex viscosity, (η*) versus NMR. We examined the
correlation between complex viscosity versus bulk relaxation
rate following equation 2, which was given in the literature
review section. Thus, in comparing these two parameters they
appear to qualitatively correlate with the complex modulus
(G*) but not with complex viscosity (η*). Nevertheless,
further research is planned to obtained an improved
correlation between complex viscosity and bulk relaxation rate
for polyacrylamide/Cr(III) acetate gels.
Conclusions.
Three different techniques, bottle testing, low field NMR, and
dynamic rheology have been applied to evaluate the
crosslinking process of polyacrylamide/chromium (III) acetate
systems. The main results are as follows:
• Although bottle testing represents a faster and inexpensive
method to monitor gelation of polyacrylamide/chromium
(III) acetate systems, the experimental observations obtained
from this technique have to be considered with caution
because it can lead to a subjective and mistaken
characterization of the system.
• It was demonstrated that low field NMR could be a useful
tool for monitoring the gelation process of
polyacrylamide/chromium (III) acetate.
• NMR is capable of observing shifts on gel properties as a
result changes in polymer concentration, crosslinker
concentration, and salinity of the polymers solutions. As
well as the onset and progression of syneresis as a function
of time.
• The detection of the liquid-solid transition and the
estimation of gel point using low field NMR seems to be
reliable, since this technique does not disrupt or influence in
any way the gelation process.
• Fitting the change of bulk relaxation rates with time in
chemical kinetics indicates that HPAm/Cr(III) acetate
crosslinking reaction follows a second-order rate law.
• In oil and gas field applications, the values of gel points
estimated using low field NMR should be taken as the
shortest period before network formation during field
operations for designing purposes. This is becaouse the
gelation process is not delayed or affected at all using
this technique.
• Under the appropriate experimental conditions, dynamic
rheological monitoring of the crosslinking reaction is
7
consistent with observations from low field NMR. Still,
more research is needed to establish correlations between
bulk relaxation rate and dynamic rheological parameters.
Nomenclature
AI = amplitude index
At = total NMR amplitude of the sample
Ea = activation energy (KJ/mole)
G* = complex modulus, Pa
G’ = elastic or storage modulus, Pa
G” = viscous or loss modulus, Pa
R = gas constant, 8.314 J/K mole
T = temperature, K
T2B = bulk relaxation time, ms
δ = phase shift or loss angle, o
η = viscosity, Pa-s
η* = complex viscosity, Pa-s
Acknowledgments
The authors wish to thank Drs. George Stastna and Giovanni
Polacco for fruitful discussions on gel systems rheology.
Financial support from the Alberta Energy Research Institute
through the COURSE program is gratefully appreciated.
Further financial support from the Canada Research Chair in
Energy and Imaging and its industrial affiliates (Nexen, Shell,
Albian Sands, Petro-Canada, Devon and CNRL) is also
gratefully appreciated.
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8 SPE 86548
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SPE 86548 9

9
Table 1. Sydansk gel-strength codes Table 5. Bottle testing: Crosslinker Concentration Effect
III
Crosslinker Concentration (PA:Cr ) →
Code Description
Time 130:1 60:1 40:1 20:1 10:1 5:1
A No detectable gel formed: The gel appears to have (hr) Gel Strength Code
the same viscosity (fluidity) as the original polymer 0 A A A A A A
solution and no gel is visually detectable. 6 B B B B B B
B Highly flowing gel: the gel appears to be only 48 B C D E H H
slightly more viscous than the initial polymer 57 B C D E H H
solution. 146 C D D G H H
C Flowing gel: most of the obviously detectable gel 217 C D E H H H
flows to the bottle upon inversion. 578 D D E H * *
D Moderately flowing gel: a small portion (about 5 to *Gel goes through syneresis
15%) of the gel does not readily flow to the bottle top
upon inversion. Table 6. Bottle testing: Salinity Effect
E Barely flowing gel: the gel can barely flow to the
bottle top and/or a significant portion (>15%) of the Polymer solution concentration (wt %)
gel does not flow upon inversion.
F Highly deformable non-flowing gel: the gel does 0.5 1.0 1.5
not flow to the bottle top upon inversion (gel flows to
Salinity
just short of reaching the bottle top).
Time
G Moderately deformable non-flowing gel: the gel
(hr) Brine DI W* Brine DI W Brine DI W
flows about half way down the bottle upon inversion.
0 A A A A A A
H Slightly deformable non-flowing gel: only the gel
6 A A B A C A
surface slightly deforms upon inversion.
48 A A D B G B
I Rigid gel: there is not gel-surface deformation upon
57 A A D B G B
inversion; and the gel is stable and clear.
146 B A D B H B
J Ringing rigid gel: a tuning-fork-like mechanical
vibration can be felt after tapping the bottle. 217 B A E B H B
578 C A E B H C
*Distilled water

Table 2. Synthetic Brine Composition (2.1 wt% TDS) Table 7. Activation Energy versus polymer concentration and gel
o
Components % time for polymer solutions prepared in synthetic brine at 30 C.
NaCl 1.7245
MgCl2:6H2O 0.094
CaCl2 0.325 Synthetic Brine
Polymer Gel time (2.1 wt% TSD)
Na2SO4 0.0095
Concentration (seconds) Activation Energy
Table 3. Physical Properties of Alcoflood 935 (KJ/mol)
(wt%)
Appearance White granular powder 0.5 3900 22.17
PH (1%solution) 6 1.0 5040 21.49
Specific Gravity 0.8 1.5 6600 20.84
Solubility in Water Soluble
Activity 100%
6
Molecular Weight ~ 6 x10 Daltons
Hydrolysis ~ 8 % Table 8. Activation Energy versus polymer concentration and gel
o
time for polymer solutions prepared in distilled water at 30 C.

Table 4. Bottle testing: Polymer Concentration Effect

Polymer Concentration (wt%) → Polymer Gel time Distilled Water (DIW)

Reaction Concentration (seconds) Activation Energy

0.5 1.0 1.5 (KJ/mol)
Time (wt%)
(hr) Gel Strength Code 0.5 3480 20.84
0 A A A 1.0 3720 20.72
6 A B C 1.5 3900 20.55
48 A C G
57 A D G
146 B D H
217 B E H
578 C E H
10 SPE 86548

14
Fig. 1- Schematic structure of partly hydrolyzed polyacrylamide, Fig. 4-Representation of Complex, Storage and Loss Modulus
the COOH groups are randomly distributed along the
3
polymer backbone

(a)

Fig. 2- Chromium acetate structures: (A) cyclic structure, (B)

10
linear structure

(b)

Fig. 5- Methods for estimation of gel point from dynamic rheology

36
data. (a) Tung and Dynes method . (b) Method of the
34
intersection of tan δ (t) at several frequencies .
21
Fig. 3- Crosslink structure in Cr(III)-HPAAm gels . Involving
coordinate-covalent bonding by the Cr(III) complex with
two carboxylate functional groups on two different
23
acrylamide polymer molecules .
SPE 86548 11

t=0 days -fresh gel t=4 days- gel t = 9 days- syneresed gel
0.01 t = 24 days-syneresed gel Cr(III) solution @ 16.7 % in Brine Polymer solution @ 1% in Brine
Gelation rate increases

10
Gel
Bulk Relaxation rate, 1/ T2 (ms-1)

9 Higher viscosities Aqueous solutions

Syneresed Gel
8 Solid network
Structures

Normalized Amplitude
7

6
0.001
5

4 Shrinked gel Free water

Polymer Concentration (wt%)
3
0.50% 1.0% 1.50%
2

1
0.0001
0
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00
10 100 1000 10000
Reaction time (hr) Relaxation time (ms)

Fig. 6-Bulk relaxation rate and polymer concentration versus Fig. 10-Amplitude index versus relaxation time
reaction time
0.5% Polymer in DI Water 1.0% Polymer in DI Water 1.5% Polymer in DI Water
0.1 0.010
Polyacrylamide-to-Chromium acetate ratio
130:1 60:1 40:1 20:1 10:1 5:1
Gelation rate increases

Bull Relaxation Rate,1/T2 (ms-1)

Bulk relaxation time (ms-1)

0.01

Gel point = 58 min

0.001

Gel point = 62 min

0.0001 Gel Point = 65 min

0 5 10 15 20 25 30 35 40 0.001
Reaction Time (hr) 10 100 1000
Reaction Time (min)

Fig. 7-Bulk relaxation and polyacrylamide-to-chromium acetate Fig. 11- Bulk relaxation rate versus reaction time in distilled water
ratio versus reaction time

Poplymer 0.5% in Brine Polymer 0.5% in DI Water 0.5% Polymer in Brine 1.0% Polymer in Brine 1.5% Polymer in Brine
Polymer 1% in Brine Polymer 1% in DI Water 0.01
Polymer 1.5% in Brine Polymer 1.5% in DI Water
Bulk Relaxation Rate, 1/T2 (ms-1)

0.01
Bulk relaxation rate (ms-1)

Gel point = 65 min

0.001
Delays gelation rate

Gel point = 84 min

Gel point = 110 min

0.001
1 10 100 1000
0.0001 Reaction Time (min)
0 10 20 30 40 50 60 70 80 90 100
Reaction time (hr)
Fig. 12- Bulk relaxation rate versus reaction time in brine
Fig. 8-Bulk relaxation, salinity and polymer concentration versus
reaction time
1% Polymer in Synthetic Brine 1% Polymer in DI Water
Polymer:Cr(III) = 5:1 Syneresed gel Polymer:Cr(III) = 40:1 Stable gel Linear (1% Polymer in Synthetic Brine) Linear (1% Polymer in DI Water)
1.45
0.1
1/ (Normalized bulk relaxation rate), dimensionless

1.4 y = 0.0000302434x + 1.0799161647

2
Syneresis starts R = 0.9651912980
Onset of phase separation Shrinked Gel + Free Water 1.35
Bulk relaxation (ms-1)

1.3
0.01
1.25

1.2

y = 0.0000225307x + 1.0158222032
1.15 2
R = 0.9961017713
0.001 Stable gel
1.1

1.05

1
4000 5000 6000 7000 8000 9000 10000 11000 12000 13000
0.0001 Reaction time (s)
0 100 200 300 400 500 600
Reaction time (hr)
Fig. 13. Normalized bulk relaxation rate versus time
Fig. 9- Bulk relaxation rate for two gel formulations versus time
12 SPE 86548

G' G" tan δ 0.58

Suddenly increase in
4.5
Viscosity
4
0.575
3.5
G' (Pa), G" (Pa), tan δ

0.57

(pa-s)
2.5

η∗
tan δ = 1
1.5 Liquid-Solid Transition 0.565
Gel point time = 13000s
1
Liquid-Solid Transition
Gel point time > 1800 s
0.5
0.56
0
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 11000 12000 13000 14000 15000 16000

Reaction Time (s)

0.555
Fig. 14- G’, G”, and tan(δ) versus reaction time 0 500 1000 1500 2000 2500 3000 3500
Reaction Time (s)

0.35 Fig. 18- Complex viscosity versus reaction time

0.3

G'-1.5% G"-1.5 %
25
0.25
η∗ (Pa-s)

0.2
20

Liquid-Solid Transition
0.15
Gel point time = 13000 s

G' (Pa), G"(Pa)

15

0.1

0.05 10

0
0 2000 4000 6000 8000 10000 12000 14000 16000 5
Reaction time (s)

Fig. 15- Complex viscosity versus reaction time 0

0 100 200 300 400 500 600

G' G" tan δ Time (s)

4
Fig. 19. G’ and G” versus time
3.5

3
G' (Pa). G" (Pa), tan δ

2.5

2 Liquid-Solid Transition
Gel Point= 508 s
1.5

0.5

0
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000

Reaction Time (s)

Fig. 16- G’, G”, and tan(δ) versus reaction time

G' G"
2.9
Liquid-Solid Transition
2.8 Gel point time> 1800 s

2.7

2.6
G' (Pa), G" (Pa)

2.5

2.4

2.3

2.2

2.1

2
0 500 1000 1500 2000 2500 3000 3500
Reaction time (s)

Fig. 17- G’ and G” versus reaction time