SPE 90840

Crosslinking of Guar and Guar Derivatives

*

Cuiyue Lei and P. E. Clark , Department of Chemical Engineering, The University of Alabama, Tuscaloosa, AL
Copyright 2004, Society of Petroleum Engineers Inc.
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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
will be examined.
The polymer literature is filled with methods of
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 a guar or guar derivative
solutions. This finding was controversial, to say the least. To
test this assertion, we have conducted a series of experiments
that not only show that the transition concentration is an
important indicator, but also present a framework for
exploring the potential of other crosslinked systems.
Interestingly, polymers that crosslink well at low
concentrations do not always produce the best crosslinked gel
at higher concentrations. Based on our experiments, we will
present an explanation for this finding. This emphasizes the
importance of understanding the crosslinking process in order
to optimize the selection of a polymer for a particular
application.

Author to whom all correspondence should be addressed.

This paper examines guar and guar derivative systems

used in the industry and reports on a new guar that can be
successfully crosslinked at low concentrations. It also provides
a outline for studying crosslinking at low concentrations and
presents insights into the crosslinking process.
Introduction
Water-soluble polymers have been used for a number of years
as thickening agents for stimulation fluids. In order to improve
the performance of these materials without increasing the
concentration, crosslinking was developed. 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 versus concentration curve
appears to be exponental. This phenomenon has been studied
for a wide range of polymersolvent systems and appears to
be universal. Early work divided the viscosityconcentration
curve into two regions4,5 that were separated at a critical
concentration labeled c*. As the understanding of polymer
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 dissolves in a good solvent, the
molecule first swells as the solvent penetrates into the
molecule and eventually the polymer molecule will assume
some configuration in space determined by the stiffness of the
polymer backbone. 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, there is a point when the polymer
molecules begin to weakly interact and the slope of the
viscosityconcentration curve changes. 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

sp = 0 s
s

SPE 90840

where 0 is the zero shear viscosity and s is the solvent

viscosity.
Addition of more polymer molecules is accompanied by an
increase in polymerpolymer interaction and a decrease in
the volume of space occupied by each polymer molecule.
Eventually, the polymer molecules reach a minimum volume
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**
Concentrated

c*

log(sp)
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 field use, 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 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 and 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 research was inspired by a patent1 that used the
critical overlap concentration as a predictor of crosslinkability
at low 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
c* =

3M w
4 N A Rg3

where M w is the weight average 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 to use. 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 molar mass
of less than 106, but shear thinning in the capillary can
introduce significant errors for higher molecular weight
molecules11. 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

SPE 90840

less to 1.0 weight percent) should be studied. This is the

technique used in this study.

20
15
10
5
0
0

10

50

60x10

-3

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.
10
10

c* = 0.093
10
10
10
10

c** = 0.36

-1
2

= s 1 + []c + k H [] c + ... .
2 2

20
30
40
Concentration (wt %)

Fig. 2 Determination of the intrinsic viscosity for guar.

sp)(
Specific Viscosity

Results and Discussion

In this study, guar, hydroxypropyl guar (HPG), carboxymethyl
hydroxypropyl guar (CMHPG), carboxymethyl guar (CMG),
and GW-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 virial type expansion (shown below)

Huggins plot
Kramer plot
kH = 0.77
[] = 12.75

25
r)/c
/c, ln(

Experimental
All polymers used in this study were obtained from the
manufacturer (Aqualon) with the exception of the guar sample
labeled GW-3, which was obtained from BJ Services. The
polymers did not contain free flow additive. Standard mixing
techniques were used. Added salts 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). Boric acid or zirconium chelates (supplied by
BJ Services) were used as crosslinkers and the pH was
adjusted with laboratory grade sodium hydroxide.
Rheological measurements were carried out a room
temperature. A Carrie-Med CS-100 controlled stress
rheometer 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.

30

0.01

6 7 8

6 7 8

0.1
Concentration (wt %)

Fig. 3. Determination of c* and c** for HPG.

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

ln 0

1 2

s
= [] + k H [] c + ...

2
c
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 give 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.

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
Guar
GW-3
HPG
CMG
CMHPG

Intrinsic
Viscosity
12.75
20.45
11.02
31.74
18.93

Huggins
Coefficient
0.77
0.52
0.83
0.88
0.93

c*

c*[]

c**

0.078
0.051
0.093
0.054
0.68

0.97
1.04
1.02
1.84
1.4

0.26
0.26
0.36
0.42
0.39

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, GW-3, and CMG.

10
8
6

G', G" (Pa)

Both CMG and CMHPG are charged species in solution. 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
normally would. 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. GW-3 is a
specially processed guar that appears to have a higher
molecular weight than the standard guars 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 GW-3, CMG, CMHPG,
Guar, and HPG. The list is almost the reverse order of the
intrinsic viscosity list with both GW-3 and CMG and guar and
HPG exchanging places. Carboxymethyl guar is a more rigid
molecule than GW-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 GW-3 and CMG on the two lists. The exchange
observed for HPG and guar is probably due to the difference
in molecular weight caused by addition of the hydroxypropyl
groups 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 frequency 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.
Above the crossover point, the entanglements begin to act as
temporary crosslink junctions. The inverse of the frequency of
the crossover point can 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.

SPE 90840

Crossover point

8
6
4

2
7 8

5 6 7 8

10
Frequency (rad/s)

5 6 7 8

100

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
Viscosity
(poise)

G=G
(1/s)

G=G
(s)

Gc @ G=G
(Pa)

GW-3
Guar
HPG
CMHPG
CMG

19.2
15.27
5.25
6.10
5.56

10.23
13.25
22
20.05
23

0.09
0.075
0.045
0.05
0.043

5.61
3.36
3.09
3.13
3.12

It is easily seen from this table that the relaxation times

decrease in the order GW-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 decrease 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 seems to play a large role in decreasing the
strength of entanglements in guar systems.
Crosslinked gel systems
Crosslinking radically modifies the properties of watersoluble polymer solutions. These solutions go from weakly
viscoelastic fluids to strongly viscoelastic gels. In this study,
guar, GW-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. 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 frequency
dependence 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 systems. Dynamic
testing can be used to probe crosslinked systems,
unfortunately, the sensitivity of our measurement transducer
made it difficult to test concentrations close to 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

SPE 90840

clearly different than the non-crosslinked fluids at the same

concentration.
2

Non-crosslinked G'
Non-crosslinked G"
Crosslinked G'
Crosslinked G"

10
8
6
4

10
4

Frequency
0.04
0.1
0.25
0.63
1.0
2.5
3.0

2
2

1
1

tan

G', G" (Pa)

found to be 0.25 weight percent which is in good agreement

with the value obtained using the Winters and Chambon10
technique.

8
6

4
2

0.1
2
4

0.01

0.1

1
Frequency (rad/s)

10

100

0.01

Fig. 5. Oscillatory tests on crosslinked and non-crosslinked

0.5 weight percent guar solution.

0.1

1
Concentration (wt %)

Fig. 7. Critical crosslinking determination for guar.

When the storage modulus is compiled for several

concentrations of borate crosslinked guar it is easily seen that
the dependence of G on frequency decreases with increasing
concentration indicating that the material is becoming
increasingly gel-like (Fig 6).

0.20
0.23
0.25
0.28
0.30
0.40
0.50
0.60
0.80

0.1

0.01

c cc = K (c *)

0.8

0.1

1
Frequency (rad/s)

10

100

Fig. 6. G versus frequency for different concentrations of

crosslinked guar gels.

As mentioned previously, the technique suggested by

Winter and Chambon10 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 frequencies. The concentration at which all of the
curves have the same value of tan 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.
Table 3. Critical
concentrations.
Polymer
GW-3
CMG
CMHPG
Guar
HPG

c*
0.051
0.054
0.068
0.078
0.093

overlap
ccc
0.178
0.193
0.22
0.26
0.285

and

crosslinking

Crosslinker
Borate
Zr-Chelate
Zr-Chelate
Borate
Borate

Estimates of the critical crosslinking concentration can

also be obtained from creep experiments (not shown). From
these experiments, the critical crosslinking concentration is

Critical Crosslinking Concentrati

G' (Pa)

10

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 Tanaka12
and the relationship between the molecular weight and the
critical crosslinking concentration an equation can be
derived13 to relate the two concentrations (Eq. 1). Data shown
in the plot shown in Fig. 8 can be used to check the accuracy
of this equation
(1)

0.30

0.25

0.20

0.15

0.10

0.05

0.00
0

20

40
60
80
Critical Overlap Concentration

100x10

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 2. Comparing
the

c cc = 1.8(c *)

0.78

(2)

the exponents in Eqs. 1 and 2, it is easy to see that the

experimental exponent (0.78) is almost identical to the one
obtained from the derivation (0.8). 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

-3

only a weak function of crosslinker type. To say the least, this

was unexpected.
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, GW-3, has become
available that can also be crosslinked at low concentrations.
Both of these polymers would have been predicted to be
useful 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. This method is useful for systems
that are crosslinked with borate and zirconium chelates.
Extension to crosslinkers that work by different crosslinking
mechanisms will require further testing.
Summary
Water-soluble polymers exhibit two slope changes in the
specific viscosity versus concentration curves. The first slope
change (c*) is associated with the beginning of significant
polymerpolymer interactions while the second slope change
(c**) is associated with a dramatic increase in the strength of
these interactions. Crosslinking is not possible at
concentrations below c* and extremely weak until a critical
crosslinking concentration is reached (ccc). The critical
crosslinking concentration represents a lower limit to the
useful crosslinking concentration for oilfield applications. This
study provides a relationship that allows the prediction of the
critical crosslinking concentration for borate ion and
zirconium chelate crosslinked guar and guar derivatives. It
also shows that there is a definite relationship between c* and
the critical crosslinking concentration.
Acknowledgements
The authors thanks Jeff Dawson for many helpful suggestions
and for providing samples of GW-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
kH Huggins coefficient
0 zero shear viscosity (Pas)
s solvent viscosity (Pas)

SPE 90840

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