SPE 90840

Crosslinking of Guar and Guar Derivatives

*
Cuiyue Lei and Peter. E. Clark , Department of Chemical and Biological Engineering, The University of Alabama,
Tuscaloosa, AL
Copyright 2004, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in Houston, Texas, U.S.A., 2629 September 2004.

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Abstract
Crosslinking of guar and guar derivatives has played a major role in improving stimulation of oil and gas wells. While crosslinking
has been used for a number of years, many facets of crosslinked systems are still not well understood. Part of the problem is that the
traditional methods of determining the properties of crosslinked fluids work well for obtaining the data necessary for treatment design,
but yield little information about nature of the crosslinked system. A good example of this is found in the development of low polymer
concentration crosslinked gels. These gels are important because they lower costs and help to minimize formation damage. In this
paper, methods for predicting crosslinkability at low concentrations are reported.
The polymer literature is filled with methods for characterizing polymer solutions almost none of which find wide use in the
development of crosslinked fracturing fluids. Dawson, et. al.,1 first reported that the concentration at which a polymer solution
transitions from dilute to semidilute could be used as a method for determining the potential for low concentration crosslinking in
guar or guar derivative solutions. To say the least, this finding was controversial. To test this assertion, we have conducted a series of
experiments that not only show that the dilute-semidilute transition concentration is an important indicator, but also present a
framework for exploring the potential of other crosslinked systems. These experiments show conclusively that low polymer
crosslinking is determined by the value of the critical overlap concentration, c*. In addition, we show that the critical crosslinking
concentration for the range of polymer-crosslinking systems studied is correlated to the critical overlap concentration. A strong case is
presented for the ability to crosslink at low concentrations is only a function of the polymer and not the crosslinker type.
Introduction

Water-soluble polymers have been used for a number of years as thickening agents for stimulation fluids. Crosslinking was developed
in order to improve the performance of these materials without increasing polymer concentration. Over the years, a number of
different crosslinking agents have been used with success. There are several good discussions of polymer and crosslinking systems
available2, 3, and it is not the purpose of this paper to expand these discussions. Rather, we will approach the problem of crosslinking
from the prospective of the molecular or solution properties that control or influence crosslinking.
When a water-soluble polymer is hydrated, the viscosity of the resulting solution increases as a function of concentration. Starting
at low concentrations and building to high concentrations, the viscosity appears to exhibit an exponential increase. This phenomenon
has been studied for a wide range of polymersolvent systems and seems to be universal. Early work divided the viscosity
concentration curve into two regions4, 5 that were separated at a critical concentration labeled c*. As the understanding of polymer

*
Author to whom all correspondence should be addressed.
 2 [SPE 90840]

solution behavior developed and more sensitive instruments and experimental techniques were developed, the solution behavior was
determined to be more complex.
When a single polymer molecule dissolves in a good solvent, the molecule first swells as the solvent penetrates into the molecule
and eventually the polymer molecule will assume some conformation in space determined by the stiffness of the polymer backbone
and the goodness of the solvent. For random coil polymers, the volume of space occupied is roughly spherical. If a second polymer
molecule is added to the solution, the two polymer molecules will not interact and their effect on the solution viscosity will be strictly
hydrodynamic. As more and more molecules are added to the solution, a concentration is reached when the polymer molecules begin
to weakly interact and the slope of the viscosityconcentration curve changes (Fig. 1). This change is not abrupt, but it can be clearly
seen when the log of the specific viscosity is plotted against the log of the concentration. The specific viscosity is given by

" # "s
"sp = 0 (1)
"s

In this equation, 0 is the zero shear viscosity and s is the solvent viscosity.
Addition of more polymer molecules is accompanied by an increase in polymerpolymer interactions and a decrease in the
!
volume of space occupied by each polymer molecule. Eventually, the polymer molecules reach point where further contraction is not
possible and the only way to make room for additional polymer is for the molecules to begin to strongly interpenetrate. This point is
marked by another slope change and labeled c** (Fig. 1).

c**

log(sp) c* Concentrated

Dilute Semi-dilute

log(c)

Fig. 1. Specific viscosity versus concentration.

While there is some disagreement about the number of regimes6-8, the labeling and interpretation of the molecular interactions are
similar. It is also well accepted that crosslinking cannot occur below c* because there is simply not enough polymerpolymer
interaction to promote intermolecular crosslinking. Intramolecular crosslinking can occur below c*, but the result is normally a drop in
viscosity not an increase. The effectiveness of crosslinking between c* and c** increases dramatically as the concentration increases.
Somewhere between c* and c** there is a critical crosslinking concentration that denotes the minimum concentration needed for a full
three-dimensional crosslinked structure to develop. This concentration is probably not enough for use in fracturing, but it does form a
lower bound for crosslinking concentration.
Determining a value for the critical crosslinking concentration, also referred to as the gel point in the literature, presents some
problems. The gel point or sol-gel transition occurs when a three dimensional network pervades the whole solution and the effective
molecular weight approaches infinity. Rheological properties change radically near the gel point. The zero-shear viscosity diverges as
 [SPE 90840] 3

does the equilibrium modulus. Both could be used to quantify the gel point, but both are difficult to determine with any degree of
accuracy.
Dynamic (oscillatory) measurements provide information on both the viscous and elastic properties of fluids and gels. In these
measurements, an oscillatory stress or strain is applied to a sample and the phase shift and magnitude of the resulting strain or stress
are measured. From these data, the elastic storage modulus, G, viscous loss modulus, G, and the tangent of the loss angle, tan, are
derived. The phase shift is a function of the type of fluid. It is zero for a perfectly elastic material and 90 for a perfectly viscous fluid.
Gels exhibit a G that is nearly independent of frequency over a wide range, while viscoelastic fluids show a definite increase of G
with frequency. This means that it is possible to determine when the gel point is reached by observing the change in slope of the G
versus frequency curve. In practice, the changes are subtle and the gel point is difficult to determine in this manner. Tung and Dynes9
proposed using the crossover point in the storage and loss modulus versus frequency curve at low frequency. This method is
complicated by the fact that the viscous and loss modulus versus frequency curves cross for fluids that are not gels. Winter and
Chambon10 found that the tangent of the loss angle, tan = G/G, is independent of frequency at the gel point. Plots of tan (at
different frequencies) versus concentration will cross at the gel point. Curves generated in this manner can be curve fit and the point of
equivalency can be determined. This technique was used successfully by Power, et al.11-13 in studies of crosslinking of hydroxypropyl
guar.
The research reported here was inspired by a patent1 that used the critical overlap concentration as a predictor of crosslinkability at
low polymer concentration. While the work of Dawson et al.,1 resulted in a commercially viable product, there remained the question
of why the critical overlap concentration, c*, should be related to the ability to form useful gels at low concentration.
Experimentally, there are two problems that must be overcome. One, the determination of the critical concentration for gel
formation was solved by using the method of Winter and Chambon10. The other problem is the determination of the critical overlap
concentration. Over the years there have been a number of techniques used to determine c*. Since the critical overlap concentration is
related to the volume of space occupied by a polymer molecule, experimental methods that reflect molecular size can be used.
Theoretical methods can also be used, but care must be taken because not all polymers exhibit ideal behavior in solution.
Assuming that polymer chains move freely in solution and the average shape is spherical, c* can be calculated from

3M
c* = (2)
4 "N A Rg3

In this equation, M is the polymer molecular weight, NA is Avogadros number and Rg is the radius of gyration of the polymer.
!
Because c* is a function of the radius of gyration, light scattering can be used. However, it is an experimentally difficult technique that
is not in widespread use for this purpose.
!
Viscometric techniques are more widely used to determine c*. From an equipment standpoint, capillary viscometers are the
simplest. The intrinsic viscosity is obtained from the viscosityconcentration data and related to c* through an empirical equation or
from a specific viscosity versus concentration plot, similar to Fig. 1, and c* determined directly. This technique works for polymers
with a molecular weights of less than 106, but shear thinning in the capillary can introduce significant errors for higher molecular
weight molecules14. A more direct, but more expensive, method involves the use of a sensitive rheometer to determine the zero shear
viscosity. After calculating the specific viscosity, a plot similar to that shown in Fig. 1 is used to determine c*. Care must be taken
when using this method to obtain a sufficient number of points above and below c*. Since there are two transitions, it is relatively easy
to overlap into the second transition and thus bias the value of c* to higher values. While it is more work, the whole concentration
range (from 0.01 or less to 1.0 weight percent) should be studied. This is the technique used in this study.
 4 [SPE 90840]

Experimental
All polymers used in this study were obtained from the manufacturer (Aqualon) with the exception of the guar sample labeled GUAR-
3, which was obtained from BJ Services. The polymers did not contain free flow additive. The polymer solutions were prepared in a
blender by slowly adding the powder to distilled water while agitating the solution. Mixing continued for one hour and then the
appropriate salt was added. Salts used in this study were tetramethyl ammonium chloride (TMAC, 0.1 %) or potassium chloride (KCl,
2%). Urea and sugar were added to breakup intermolecular hydrogen bonds in one or two of the tests (not presented here). After
adding the salts, the solution was stirred for twenty minutes to one hour. The solution was allowed to age for twenty-four hours before
use. All dilutions were made by mixing a known weight of polymer solution with the appropriate amount of salt solution to achieve
the desired concentration. These samples were stirred periodically for twenty-four hours before use. Boric acid or zirconium chelates
(supplied by BJ Services) were used as crosslinkers and the pH was adjusted with laboratory grade sodium hydroxide. All crosslinked
solutions were prepared with a constant polymer to crosslinker ratio. This ratio was based on the crosslinker concentration used in
fracturing fluids made from the polymers.
Rheological measurements were carried out a room temperature. A Carrie-Med CS-100 controlled stress rheometer equipped with
a six centimeter, one degree cone was used to determine the zero-shear viscosities and creep data. All of the rate controlled and
oscillatory experiments were carried out with a Rheometrics Ares rheometer equipped with a five centimeter _______ cone.

Results and Discussion

In this study, guar, hydroxypropyl guar (HPG), carboxymethyl hydroxypropyl guar (CMHPG), carboxymethyl guar (CMG), and
GUAR-3 (a specially processed guar) were used. The two guars and HPG were crosslinked with borate, while CMHPG and CMG
were crosslinked with a zirconium chelate. To characterize the fluids before crosslinking, steady-shear, creep, and oscillatory tests
were run.
Polymer solution properties
Polymer molecules in very dilute solutions contribute individually to the viscosity of the solution. This can be described by a virial
type expansion (shown below)

( 2
" = "s 1+ ["]c + k H ["] c 2 + ...) (3)

In this equation, is the solution viscosity, s is the solvent viscosity, c is concentration, kH is the Huggins coefficient, and [] is the
!
intrinsic viscosity. Intrinsic viscosity measurements were derived from steady shear tests. To determine the intrinsic viscosity, the
zero-shear viscosity, 0, was used in combination with the equation above to yield

"0 # "s 2
= ["] + k H ["] c + ... (4)
"sc

Plots of (0 - )/sc versus concentration yield a straight line. Combining this with the Kraemer equation
!

# &
ln%"0 " ( #
$ s' 1& 2
= ["] + % k H ) (["] c + ... (5)
c $ 2'

!
[SPE 90840] 5

Where plots of ln(0/s)/c versus concentration extrapolated to zero concentration yield a straight line that intersects with the
extrapolated line from Huggins plot to yield the intrinsic viscosity. An example is shown in Fig. 2 for guar, and the data for all of the
rest of the polymers is summarized in Table 1.

30
Huggins plot
Kramer plot
25
kH = 0.77
!sp/c, ln(!r)/c

[!] = 12.75
20

15

10

0.00 0.01 0.02 0.03 0.04 0.05 0.06

Concentration (wt %)
Fig. 2 Determination of the intrinsic viscosity for guar.

The specific viscosity data was also used to determine the values of c* and c**. An example of the method is shown in Fig 3.
There are three data sets on this plot, so it is easy to see that the reproducibility of the data is good. Creep tests were also run on all of
the solutions. Analysis of creep data yields the zero shear viscosity (0) and these data were also used to determine the values of c*
and c**. The values were almost exactly the same as those derived from steady shear data indicating that the values presented in Table
1 are reasonable and accurate. All of the c* and c** for the polymer solutions are compiled in Table 1.

4
10

Run 1
Specific Viscosity ( !sp)

3
10
Run 2
Run 3 c* = 0.093
2
10

1
10

0
10 c** = 0.36

-1
10
2 3 4 5 6 7 8 2 3 4 5 6 7 8
0.01 0.1 1
Concentration (wt %)
Fig. 3. Determination of c* and c** for HPG.
6 [SPE 90840]

Another way of plotting the specific viscosity and concentration data uses the concentration times the intrinsic viscosity (c[]) on
the x-axis. Values of the intersection of the lines at the first slope change are therefore c*[]. This value has been associated with the
flexibility of the polymer chain in solution. These data are also compiled in Table 1.

Table 1. Polymer solution properties (all solutions contain TMAC).

Polymer Molecular Intrinsic Huggins c* c*[] c**
Weight Viscosity Coefficient wt% wt%
3
cm /g
6
Guar 2.7 x 10 12.75 0.77 0.078 0.97 0.26
GUAR-3 Not available 20.45 0.52 0.051 1.04 0.26
HPG Not available 11.02 0.83 0.093 1.02 0.36
6
CMG 1.8 x 10 31.74 0.88 0.054 1.84 0.42
6
CMHPG 2.2 x 10 18.93 0.93 0.068 1.4 0.39
3
Note: For low concentration polymer solutions, g/cm and weight percent are equivalent.
There are a number of conclusions that can be drawn from the information in Table 1. The intrinsic viscosity is an extrapolated
value that is indicative of the molecular size in solution. For the polymers studied the intrinsic viscosity increased in the order HPG,
Guar, CMHPG, GUAR-3, and CMG. Both CMG and CMHPG are charged species in solution. On the carboxylated polymers, the
negatively charged carboxymethyl groups attached at various points on the polymer will tend to repel each other and cause the
molecule to occupy a larger volume of space than it would in the absence of the charges. Deionized water maximizes the repulsion
and salts, which tend to shield the charges, lessen the repulsion. Salts with large, bulky cations will minimize the screening effect
while potassium and sodium salts are effective in screening the charges. For these studies, tetramethyl ammonium chloride was used
exclusively. Addition of this salt has no affect on the uncharged polymers. GUAR-3 is a specially processed guar that appears to
expand more in solution than the standard guar used in the industry. For this reason, it has the second highest intrinsic viscosity.
Molecular volume is directly related to the critical overlap concentration. Examining the c* values presented in Table 1, we find
that they increase in the order GUAR-3, CMG, CMHPG, Guar, and HPG. The list is almost the reverse order of the intrinsic viscosity
list with both GUAR-3 and CMG and guar and HPG exchanging places. Carboxymethyl guar is a more rigid molecule than GUAR-3
as indicated by the data in the c*[] column. In general, values of c*[] around one indicate a random coil polymer. Rigidity increases
with increasing values of c*[]. The extra rigidity and a small amount of intermolecular repulsion could explain the change in position
between GUAR-3 and CMG on the two lists. The exchange observed for HPG and guar is probably due to a change in polymer-
solvent inteaction and a change in the intermolecular interactions also due to the presence of the hydroxypropyl groups.
Oscillatory testing of polymer solutions yields information on the degree of entanglement in a solution. The data discussed in this
section was derived from tests on 0.5 weight percent polymer solutions. When an oscillatory stress or strain is imposed on a material
the response, either strain or stress, is offset or phase shifted. The degree of the phase shift can be related to the viscoelasticity of the
solution. Water, a purely viscous liquid, is phase shifted by 90 degrees while steel, a perfectly elastic solid, is phase shifted by 0
degrees. Viscoelastic fluids fall somewhere in between. From the phase shift () and the magnitude of the input signal, the viscous loss
modulus (G) and the elastic storage modulus (G) can be calculated. Both are a function of the oscillatory frequency. When G and
G are plotted as a function of angular velocity, plots similar to that shown in Fig. 4 are obtained. For fluids, G is initially larger in
magnitude, but there is almost always a crossover point where G becomes larger than G. The crossover is due to the failure of the
entanglements present in the solution to relax within the time frame of the oscillation. At an angular velocity above the crossover
point, the entanglements begin to act as temporary crosslink junctions. The inverse of the angular velocity of the crossover point can
[SPE 90840] 7

be used as a relaxation time. This relaxation time coupled with the value of G at the crossover point can be used as a metric for the
number and strength of the temporary crosslink junctions. The crossover point and G at the crossover points are tabulated in Table 2.

10
8
6 G'
4 G"
G', G" (Pa)

1 Crossover point
8
6

7 8 2 3 4 5 6 7 8 2 3 4 5 6 7 8
1 10 100
Angular Velociy (rad/s)
Fig. 4 Oscillatory test on 0.5 wt% guar solution.

Table 2. Crossover points for the five polymers at a concentration of 0.5 weight percent.
Polymer Zero Shear G=G G=G Gc @ G=G
Viscosity (rad/s) (s) (Pa)
(poise)

GUAR-3 19.2 10.23 0.09 5.61

Guar 15.27 13.25 0.075 3.36
HPG 5.25 22 0.045 3.09
CMHPG 6.10 20.05 0.05 3.13
CMG 5.56 23 0.043 3.12

It is easily seen from Table 2 that the relaxation times decrease in the order GUAR-3, Guar, CMHPG, HPG, and CMG. High
relaxation times and high values of G at the crossover point indicate that the strength of the polymerpolymer interactions decreases
in the same order. Since the concentration of the polymers was 0.5 weight percent, they were all above the c** values reported in
Table 1. Derivatization appears to play a large role in decreasing the strength of entanglements in guar systems.
Crosslinked gel systems
Crosslinking radically modifies the properties of water-soluble polymer solutions. These solutions go from weakly viscoelastic
fluids to strongly viscoelastic gels. In this study, guar, GUAR-3, and HPG were crosslinked with boric acid and CMG and CMHPG
were crosslinked with a zirconium chelate. In all of the experiments, the ratio of polymer to crosslinker was held constant, since the
question that we set out to answer was why do some polymers crosslink at lower concentrations than other polymers of the same
family.
Data shown in Fig 5 clearly indicate the change in the dynamic (oscillatory) measurements upon crosslinking a 0.5 weight percent
guar solution with borate. Values for the storage modulus increase dramatically and the dependence on angular velocity almost
disappears while the loss modulus decreases below that found in the non-crosslinked fluid. Note the extra consistency in the
crosslinked system made it possible to measure at lower frequencies. Similar results are obtained for the other polymercrosslinker
8 [SPE 90840]

systems. Dynamic testing can be used to probe crosslinked systems, unfortunately, the sensitivity of our measurement transducer made
it difficult to test concentrations much below the critical overlap concentration. Gels produced at concentrations above c* but below
the critical crosslinking concentration are not well formed and difficult to measure even though they are clearly different than non-
crosslinked fluids at the same concentration.

10
6
4
G', G" (Pa)

1
6
Non-crosslinked G'
4
Non-crosslinked G"
2 Crosslinked G'
Crosslinked G"
0.1

0.01 0.1 1 10 100

Angular Velocity (rad/s)
Fig. 5. Oscillatory tests on crosslinked and non-crosslinked 0.5 weight percent guar solution.

When the storage modulus is compiled for several concentrations of borate crosslinked guar it is easily seen that the dependence of
G on angular velocity decreases with increasing concentration indicating that the material is becoming increasingly gel-like (Fig 6).

100

10
G' (Pa)

0.1
0.20 0.25 0.30 0.50
0.23 0.28 0.40 0.60
0.01

0.01 0.1 1 10 100

Angular Velocity (rad/s)
Fig. 6. G versus frequency for different concentrations of crosslinked guar gels.

As mentioned previously, the technique suggested by Winter and Chambon10 can be used to determine the critical crosslinking
concentration (ccc). They indicate that the critical concentration can be found by plotting the tangent of the loss angle (tan = G/G)
versus concentration for several different angular velocities. The concentration at which all of the curves have the same value of tan
[SPE 90840] 9

is the critical crosslinking concentration. This is illustrated in Fig. 7 for guar. The critical crosslinking concentration for guar is 0.26
weight percent. Critical overlap and critical crosslinking concentrations for all of the polymers studied are compiled in Table 3.

10
4
Angular Velocity
2
0.04
1 0.1
0.25
tan!

2
0.63
1.0
0.1
2.5
4 3.0
2

0.01
2 3 4 5 6 7 8 9
0.1 1
Concentration (wt %)
Fig. 7. Critical crosslinking determination for guar.

Table 3. Critical overlap and crosslinking concentrations.

Polymer c* ccc Crosslinker
wt% wt%
GUAR-3 0.051 0.178 Borate
CMG 0.054 0.193 Zr-Chelate
CMHPG 0.068 0.22 Zr-Chelate
Guar 0.078 0.26 Borate
HPG 0.093 0.285 Borate

It is easy to see that the critical crosslinking and the critical overlap concentration increase in the same order (Table 3). Using a
relationship between the critical crosslinking concentration and the molecular weight proposed by Tanaka15 and the relationship
between the molecular weight and the critical crosslinking concentration a functional relationship can be derived16 to relate the two
concentrations (Eq. 1). Data shown in the plot shown in Fig. 8 can be used to evaluate the parameters in this equation

"
c cc = K (c *) (3)

!
 10 [SPE 90840]

0.30
Critical Crosslinking Concentration

0.25

0.20

0.15

0.10

0.05

0.00

0.00 0.02 0.04 0.06 0.08 0.10

Critical Overlap Concentration

Fig. 8. Correlation between c* and ccc.

The best-fit line for the experimental data (with a point added at (0,0) to anchor the fit) is shown in Eq 4. The correlation shown in
Fig. 8 is interesting because the critical crosslinking concentrations are derived from experiments using different crosslinkers. This
means that the critical crosslinking concentration is strong function of polymer properties and only a weak function of crosslinker
type. To say the least, this was unexpected.

0.78
c cc = 1.8(c *) (4)

!
[SPE 90840] 11

Dawson et al.,1 reported in their patent that crosslinking at low polymer concentration was possible for polymers having a c* about
0.06. At the time that the patent was written the only readily available polymer meeting this criteria was carboxymethyl guar.
Recently, a new guar, GUAR-3, has become available that can also be crosslinked at low concentrations. Both of these polymers
would have been predicted to be useful for use in low polymer concentration crosslinked systems using Eq. 2. The critical crosslinking
concentrations predicted by Eq. 2 provide a lower limit for the concentration that is useful for crosslinking. Since the tests run in this
study were at room temperature, practical crosslinked systems will necessitate higher concentrations but the method can be used to
find promising polymers for low-polymer concentration crosslinking. This method is useful for systems that are crosslinked with
borate and zirconium chelates. Extension of the method to crosslinkers that work by different crosslinking mechanisms will require
further testing.

Summary
Water-soluble polymers used in the oilfield vary widely in their ability to crosslink at low concentrations. In this paper, we report a
method of predicting the lower limit on the polymer concentration needed to produce a uniform crosslinked fluid. We also show that a
metric first proposed by Dawson1 does, in fact, work and it can be used to predict whether or not a fluid will make a good candidate
for a low polymer concentration crosslinked fluid. In addition, we show that the method of Winter and Chambon10 can be used to
establish the lowest polymer concentration that forms a stable crosslinked gel. We have also established an empirical relationship
between the critical overlap concentration and the critical crosslinking concentration that shows that the critical crosslinking
concentration is a strong function of the polymer type and only a weak function of crosslinker type. This work lays the groundwork
for finally establishing a firm basis for crosslinked fracturing fluid design engineering.

Acknowledgements
The authors thanks Jeff Dawson for many helpful suggestions and for providing samples of GUAR-3 and the zirconium crosslinkers.
They also thank Aqualon for generously supplying the other polymer samples. One of us (C.L.) thanks the University of Alabama and
the College of Engineering for generous support during her studies.

Nomenclature
c concentration
c* critical overlap concentration
c** second critical concentration that marks the transition between the semi-dilute and concentrated regions
ccc critical crosslinking concentration
G elastic storage modulus (Pa)
G viscous loss modulus (Pa)
K constant in the critical crosslinking correlation
kH Huggins coefficient
exponent in the critical crosslinking correlation
0 zero shear viscosity (Pas)
s solvent viscosity (Pas)
[] intrinsic viscosity (cm3/g)

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12 [SPE 90840]

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