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Cuiyue Lei and P. E. Clark , Department of Chemical 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.
This paper was selected for presentation by an SPE Program Committee following review of
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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.
sp = 0 s
s
SPE 90840
c*
log(sp)
Dilute
Semi-dilute
log(c)
3M w
4 N A Rg3
SPE 90840
20
15
10
5
0
0
10
50
60x10
-3
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 %)
sp)(
Specific Viscosity
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 %)
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.
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
10
8
6
SPE 90840
Crossover point
8
6
4
2
7 8
5 6 7 8
10
Frequency (rad/s)
5 6 7 8
100
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
SPE 90840
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
8
6
4
2
0.1
2
4
0.01
0.1
1
Frequency (rad/s)
10
100
0.01
0.1
1
Concentration (wt %)
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
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
G' (Pa)
10
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0
20
40
60
80
Critical Overlap Concentration
100x10
c cc = 1.8(c *)
0.78
(2)
-3
SPE 90840
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