Al Muntasheri2014

PO169552 DOI: 10.
2118/169552-PA Date: 18-November-14
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A Critical Review of Hydraulic-Fracturing

Fluids for Moderate- to UltralowPermeability Formations Over the
Last Decade
Ghaithan A. Al-Muntasheri, Aramco Research CentersHouston and Saudi Aramco
Summary
Hydraulic fracturing is a well-established process to enhance productivity of oil and gas wells. Fluids are used in fracture initiation
and the subsequent proppant and/or sand transport. Several chemistries exist for these fluids. This paper summarizes the published
literature over the last decade (more than 100 technical articles)
and captures the advances in the design of water-based fracturing
fluids for fracturing ultralow- to moderate-permeability reservoirs
(nonfrac-pack applications).
Guar-based polymers are still being used in fracturing operations for wells at temperatures of less than 300 F (148.9 C). To
minimize the damage associated with this class of polymers, the
industry has attempted several approaches. These included the use
of a lower polymer concentration in formulating these fluids and
alteration of the crosslinker chemistry so that one can generate
higher viscosity values with lower polymer loadings. Moreover,
the industry shifted toward the use of cleaner guar-based polymers
because commercial guar contains a minimum of 5 wt% of residues, which can cause damage to proppant packs. The review has
also revealed that shear and pressure effects on the rheological
behavior of borate-crosslinked gels is significant. Although these
fluids recover their viscosity after shear, they have been observed
to lose a significant portion of their viscosity under high
pressures.
When fracturing deeper wells in hotter reservoirs, the need
arose for a new class of thermally stable polymers. Thus, the
industry shifted toward polyacrylamide- (PAM-) based polymers.
These synthetic polymers offer sufficient viscosity at temperatures
up to 450 F (232 C). Examples include 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and copolymers of partially hydrolyzed PAM-AMPS-vinyl phosphonate. To address the challenge
of high-pressure pumping requirements on the surface, high-density brines have been used to increase the hydrostatic pressure by
30%.
Breakers chemistry has seen introduction of new materials.
These breakers decrosslink the gel by reacting with the crosslinker. They form ligands with the metallic crosslinkers and displace them from the crosslinking bonds with the guar-based
polymers. Examples of these breakers include polysuccinimides
and lignosulfonates. To minimize the environmental impact of
using massive amounts of fresh water and to minimize costs associated with treating produced water, the use of produced water in
hydraulic-fracturing treatments has been reported. In addition, the
paper captures the advancements in the use of slickwater, which
uses drag-reducing agents (PAM-based polymers) to minimize
friction. The paper highlights the first use of breakers that were
introduced to improve the cleanup of these drag reducers.
For foamed fluids, new viscoelastic surfactants that are compatible with carbon dioxide are discussed. The paper also sheds
light on the use of emerging technologies, such as nanotechnolC 2014 Society of Petroleum Engineers
Copyright V
This paper (SPE 169552) was accepted for presentation at the SPE Western North
American and Rocky Mountain Joint Regional Meeting, Denver, 1618 April 2014, and
revised for publication. Original manuscript received for review 7 February 2014. Revised
manuscript received for review 7 August 2014. Paper peer approved 11 August 2014.
ogy, in the design of new, efficient hydraulic-fracturing fluids. For

example, nanolatex silica was used to reduce the concentration of
boron found in conventional crosslinkers. Another advancement
in nanotechnology was the use of 20-nm silica particles suspended
in guar gels. The paper provides a thorough review of all these
advancements.
Introduction
Hydraulic fracturing of oil and gas wells is a well-established
practice for productivity enhancement in petroleum reservoirs,
having been reported more than 60 years ago (Clark 1949; Padgett
1951; Grossman 1951; Clark and Fast 1952). At that time, despite
safety concerns, fluids that were based on a hydrocarbon phase
(kerosene, crude oil, or gasoline) were the preferred fluids for use
in hydraulic fracturing. At a later stage, fatty acids were used to
increase the viscosity of these oil-based fluids to initiate the fracture and transport sand (Hurst 1953; Ghauri 1960). With morefundamental understanding of the rock/fluid interactions, especially in clay-rich reservoirs (Black and Hower 1965), the use of
water-based fluids, such as guar-based polymers, emerged. Guar
is used to increase the viscosity of the fracturing fluid and help
transport the proppant. To generate more viscosity and minimize
leakoff, crosslinked guar-based fluids were introduced (Dysart
et al. 1969; Harris 1993). The low leakoff is needed for nonfracpack applications. In recent years, synthetic polyacrylamide polymers have also been reported as fracturing fluids for high-temperature applications up to 450 F (232 C) (Holtsclaw and
Funkhouser 2010). However, polymer-based fluids require breakers, which are used to improve the retained conductivity of the
fractures and to minimize the damage associated with the residues
left from these fluids (Small et al. 1991). As such, to minimize the
damage associated with the polymer-based fluids, viscoelastic surfactants were introduced (Samuel et al. 1999). However, their
temperature stability is an issue for reservoirs at temperatures of
more than 240 F (115 C), unless they are used at high concentrations. Moreover, these materials do not provide adequate leakoff
control, as will be discussed later in the paper.
In shale reservoirs (permeability in the nanodarcy range), the
need for a high-viscosity fluid to minimize leakoff is eliminated.
Thus, the industry made use of slickwater, in which the proppant
transport is governed by the high velocity of the injected water as
opposed to polymer-based fluids in which the viscosity is the
transporting mechanism. Note that slickwater is defined as water
with a drag reducer throughout the paper. However, slickwater
carries low concentrations of proppant that are approximately
0.25 to 3 lbm of proppants added per gallon (ppa/gal) of fracturing
fluid (Handren and Palisch 2009; Palisch et al. 2010). Note that
the literature reported significant use of hybrid technologies, in
which slickwater and polymer fluids are combined (Handren and
Palisch 2009; Coronado 2007; Robart et al. 2013). The polymerbased fluids used in these treatments are used to promote better
proppant transport (Sani et al. 2009). Energized fluids (fluids with
one compressible component such as nitrogen or carbon dioxide)
were also used (Tan et al. 1995; Cawiezel and Gupta 2010). The
use of the gas component helps reduce the hydrostatic pressure
and may eliminate the use of gas lift after the fracturing treatment.
November 2014 SPE Production & Operations

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PO169552 DOI: 10.2118/169552-PA Date: 18-November-14
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Polymer
Concentration
(pptg)
Crosslinker
Concentration (pptg)
Working Temporary
Range
PAM-based/zirconium
66
269449.6F
(132232C)
Holtsclaw and Funkhouser (2010)
PAM-based/zirconium and
activator
87
3.4 to 3.7
100.4269F
(38132C)
Holtsclaw and Funkhouser (2010)
Linear biopolymer
40 to 70
<200F (93C)
Walters et al. (2009)
CMHPG/zirconium
30
<300F (<149C)
Huang et al. (2005);

LeBas et al. (2013)
Not available
Not available
200275F
(93135C)
Weaver et al. (2002a, b)
AMPS-vinyl
phosphonate/zirconium
40
Not available
425F (218C)
Gupta and Carman (2011)
Linear guar
33
<175F (79C)
Fakoya and Shah (2013)
Guar/boronic acid-functionalized
nanoparticles
30
0.0166
100F (37C)
Lafitte et al. (2012)
Fluid Type
Low-molecular-weight HPG/borate
Reference
VES (quaternary ammonium)
Not applicable
Not applicable
<180F (82C)
Samuel et al. (1999, 2000)
VES (amidoamine oxide)
Not applicable
Not applicable
<250F (121C)
Huang and Crews (2008)
VES zwitterionic
Not applicable
Not applicable
<195F (90C)
Sullivan et al. (2006)
VES/carbon dioxide emulsion
Not applicable
Not applicable
230F (110C)
Chen et al. (2005)
Legend:
PAM = polyacrylamide.
CMHPG = carboxyymethylhydroxypropyl guar.
HPG = hydroxypropyl guar.
AMPS = 2-acrylamido-2-methylpropanesulfonic acid.
VES = viscoelastic surfactant.
Table 1Summary of fracturing fluids reviewed in this paper.
It also provides an easy-to-clean option from the formation after

the hydraulic fracture is created. Polymer-based fluids are still the
most commonly used type of fracturing fluids because of their
versatile properties and the extensive industry experience associated with their use. To the best of the authors knowledge, there is
no literature report that captures the advancements of the polymer-based fracturing fluids over the last decade. Therefore, the
objectives of this paper are to provide an overview of the available fracturing fluids, discuss their different chemistries, review
their breaker packages, and capture the new advancements
reported in the literature for these fluids over the past decade.
Discussion
This paper focuses on fluids for fracturing ultralow- to moderatepermeability reservoirs; frac-pack applications are beyond the
scope of this paper. In hydraulic fracturing of ultralow- to moderate-permeability reservoirs, a high-viscosity linear gel [10 to 103
cp polymer concentrations of 20 to 80 lbm per 1,000 gallons
(pptg), at 511 sec1 and 77 F] is injected under turbulent-flow conditions, where high friction and shear rate are encountered. In some
cases, crosslinked polymers are used to initiate the fracture. Once
the gel leaves the perforations (higher shear rate), the gel contacts
the formation face and starts building up pressure. The pressure
buildup continues until the fracturing point is reached. A fracture is
then generated, extending away from the wellbore into the formation. It propagates to provide maximum contact with the reservoir.
A crosslinker is then mixed with the linear gel, resulting in a substantial increase in the gel viscosity (can be more than 1,000 cp).
This crosslinking reaction can be controlled in such a way that it is
delayed, which, in many cases, is desired to minimize friction. At
the same time, this high viscosity of the crosslinked fracturing fluid
is exploited for transporting proppants. Once the proppant is successfully placed, the pressure is released, allowing the fracture to
close. Then, the well is flowed back for cleanup while the proppant
keeps an open channel for hydrocarbon production (Harris and
Heath 1998).
An ideal polymer-based fracturing fluid must possess certain
key physical properties during the previously mentioned process.
244
First, it must have a high shear resistance at which the gel does
not permanently lose viscosity upon high shearing in the pumping
equipment or in the piping system (well tubing and/or coiled tubing) and perforations. The highest shear rate is experienced at the
pumping equipment and at the perforations (Craigie 1983). At the
same time, the gel should provide minimal frictional losses during
injection through the well tubing. Second, the gel must provide
sufficient viscosity for proppant transport. If the viscosity is too
low, proppant screenout will result. Third, the gel should have
minimal leakoff into the adjacent matrix (except when fracturing
high-permeability reservoirs where leakoff is required). The leakoff is minimized in fracturing low-permeability reservoirs to
ensure that the fracture propagates deeper into the formation and
that minimal damage takes place at the adjacent matrix. Fourth,
the gel should be compatible with the formation materials, such as
clays, that are known to swell in the presence of water and cause
productivity loss. Fifth, the gel should be able to lose viscosity
(break) and clean up efficiently from the fracture face and the
proppant matrix.
Slickwater (which is water with a drag reducer), is used in
ultralow-permeability reservoirs (nanodarcy range). As such,
leakoff is not an issue. The proppant or sand is transported by the
high velocity of the slickwater. In this case, friction becomes high
and, hence, a drag reducer is added. Most drag reducers are based
on polymers; therefore, breakers have been added to improve the
cleanup of these fluids from shale reservoirs, as will be discussed
later in the paper. The following sections will provide information
on the available polymer-based and slickwater fracturing fluids in
light of the preceding requirements. A summary of all fluid systems reviewed in this paper is given in Table 1.
A valid question that may arise is how much of each fluid type
does our industry use? Patel et al. (2014) and Robart et al. (2013)
provided analysis of the hydraulic-fracturing trends in the US.
These two studies included analysis of the trends as percentages
of the types of fluids used, and covered the trends from the beginning of 2011 until the second quarter of 2013. Patel et al. (2014)
have shown that among 55,000 hydraulic-fracturing treatments
performed in the US, there has been a shift toward fewer
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O
O CH2COH
OH
CH2
OCH2CHCH3
CH2OH
OH
OH
CH
CH
CH
CH2
CH
O
O CH
CH
CH
CH
OH OH CH
CH
OH
OH
CH
CH
CH
OH CH
2
CH
OH CH
CH
OH
CH
CH
HOCCH2
CH2
OH
OH
CH
CH O
CH
CH
CH
O
CH2OH
CH2
CH
CH
CH OH
CH
CH
CH O
CH OH
CH O
CH
OH CH
CH OH OH
CH
OH
OH
OH CH2
CH
CH
CH
CH
CH
OCH2CHCH3
OH
CH
OCH2CHCH3
CH2OH
OH
CH
OH
OH CH
CH
CH
O
CH
OH
OH CH2
CH
CH O
CH
CH3HOCHCH2O
CH2
CH2
OH
CH
O
CH
CH
O
CH
CH
CH
CH
CH
OH
OH
CH
O
n
CH
CH2OH
CH
CH
OH
CH
CH2
CH2
OH
CH2
CH2
CH2
CH2
CH
(e) Carboxymethylhydroxyethyl cellulose

(CMHEC)
CH2
(d) Carboxymethylhydroxypropyl guar

(CMHPG)
CH
CH
OH
(f) Carboxymethyl cellulose (CMC)
CH2OH
OH
CH2OCH2CO2Na
CH
OH
CH
CH2
CH2
CH
CH
CH
CH
CH
CH
CH2
OH
CH
CH
CH2OCH2CO2Na
CH2OH
CH2CHCH
O
CH2
(c) Carboxymethyl guar (CMG)
OCH2CO2Na
OH
O CH COH
2
(b) Hydroxypropyl guar (HPG)
(a) Guar
CH2
O
CH
OH
CH
CH
CH
CH
OH
CH
CH
CH
CH2
OH
CH2
CH2CH2OH
n
(g) Hydroxyethyl cellulose (HEC)

Fig. 1Chemical structures of biopolymers used in hydraulic fracturing (Ely 1989; Montgomery 2013).
slickwater treatments and more hybrid treatments that use water,

a drag reducer, and a crosslinked gel. For example, the use of
slickwater has decreased from 46 to 19%, while the use of hybrid
treatments (slickwater with crosslinked fluids) has increased from
28 to 44%. The use of hybrid fluids that contain linear gels with
slickwater as well as treatments that use conventional crosslinked
fluids did not show large variations and remained at 14 to 17%
and 10 to 14%, respectively. Both studies have shown that the
number of oil rigs has increased (with a decrease in the number of
gas rigs) over the aforementioned period of time. Knowing that
fracturing oil wells requires larger-sized proppants (20/40 mesh)
than those used in gas wells (40/70 mesh) could explain the data
trend toward more-viscous fluids that have better proppant-carrying capacity (Robart et al. 2013).
Polymers
The use of biopolymers (such as guar and cellulose) in fracturing
fluids dates back to 1953, when they were used as fluid thickeners
in acid-fracturing treatments (Hurst 1953). Guar-based polymers
are the most commonly used type of polymers for hydraulic frac-
turing. Guar is a high-molecular-weight biopolymer consisting of

a chain of polysaccharide (mannose building block) with side
chains of galactose (Jennings 1996). It is a naturally occurring material that is produced from beans. Fig. 1a shows the chemical
structure of guar. In the presence of water, it hydrates, generating a
shear-thinning viscous fluid. In the field, it is prepared by dissolving solid guar in water at concentrations less than 40 pptg. For
high concentrations (more than 40 pptg), hydration of dry guar can
be difficult. As such, high-concentration slurries (4 lbm/gal) can
be used as a source of guar instead of solid guar, to minimize the
formation of fish eyes (Sarwar et al. 2011). The viscosity of this
fluid (linear gel) is a strong function of temperature, shear rate, and
polymer content. For example, the viscosity of linear guar gel can
drop by 90% (from 103 to 10 cp) upon the reduction of guar concentration from 80 to 20 pptg, maintaining the same shear rate and
temperature (at 511 sec1 and 77 F) (Ely 1989). Table 2 provides
the viscosity data of the linear gels reviewed in this paper. Despite
the different sources of these data for guar viscosity, they still
show good agreement. In the following subsections, the two major
polymer types used in hydraulic fracturingnamely, biopolymers
and synthetic polymerswill be discussed.

245
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Measurement Conditions
Concentration
(pptg)
Temperature
[F (C)]
Shear Rate
(sec1)
Viscosity
(cp)
Guar
80
77 (25)
511
103
Ely (1989)
Guar
45
77 (25)
511
42
Harris and Heath (1998)
Guar
20
77 (25)
511
10
Ely (1989)
Guar
25
77 (25)
50
50
Fischer et al. (2001)
Guar
20
77 (25)
50
15
25
(with 4:1 ratio of
guar to NAX)
77 (25)
50
110
Polymer Type
Guar/nonacetylyzed
xanthan (NAX)
Finely processed guar
Reference
37.6
150 (65.6)
170
>150
Qun et al. (2008)
Clean biopolymer
40 to 70
250 (121)
40
216
Clean biopolymer
40 to 70
96 (35)
40
352
Less residues polymer
25
150 (65.6)
100
580
Williams et al. (2012)
Less residues polymer
25
200 (93)
100
500
Williams et al. (2012)
Table 2Viscosity data of linear gels reported in this paper.
Biopolymers. Guar manufacturing involves the presence of insoluble residues (Sun and Qu 2011; Sarwar et al. 2011). These
residues can precipitate in the proppant pack, causing loss of productivity. This is in addition to solid residues resulting from inefficient breaking of the crosslinked gel, as will be discussed in the
coming sections. Moreover, thermal stability of the guar becomes
questionable at temperatures higher than 180 F. To address these
issues, the industry improved the thermal stability of guar by
introducing other forms of guar-based polymers such as HPG,
CMG, and CMHPG, shown in Figs. 1b through 1d, respectively
(Ely 1989; Montgomery 2013). Cellulose-based fluids are also
used in hydraulic fracturing. Examples are CMHEC, CMC, and
HEC, with the chemical structures shown in Figs. 1e through 1g,
respectively (Ely 1989).
In the early years of hydraulic fracturing, guar was used at
concentrations as great as 80 pptg. To minimize the damage associated with the guar-based gels, the industry reduced the concentration of guar to levels ranging from 15 to 25 pptg at lower
temperatures of 140 F (60 C) (Nimerick et al. 1997; Harris and
Heath 1998). When allowed more time for hydration, these fluids
were found to provide higher viscosity after crosslinking with
borate. Guo et al. (2012) reported on another low-polymer-content
fracturing gel. The gel is based on HPG and an additional additive
referred to as synthetic hydroxyl guar. The authors did not provide
details on the chemical nature of this material; however, the system gave, on average, 2.5 times more oil production when applied
during fracturing of 47 oil-producing wells in China that had bottomhole temperatures of 158 F (70 C).
Loveless et al. (2011) reported on a new system that is based
on ingredients used in the food industry. The system is said to
have a mixture of cellulose-based polymers and starch and is
crosslinked with Al3. Loveless et al. (2011) reported viscosity
data for this system at 140 F (60 C). Slot flow was used to investigate the ability of the system to transport sand without settlement in the vertical direction. The slot was 12 ft long and the sand
concentration ranged from 1 to 5 lbm/gal. The performance of the
system was compared with linear xanthan gel, a guar/borate gel,
and a viscoelastic-surfactants- (VES-) based system. The new
food-based system showed better results in terms of even distribution of the sand in the vertical direction. VES and the linear xanthan were the least-performing fluids. Static proppant-carrying
tests run for 300 minutes showed better results for the new fluid
and xanthan gel. Holtsclaw et al. (2011) reported on the fluid loss
and the retained-conductivity measurements of the system. The
retained-conductivity tests showed more than 80% retained conductivity. It should be mentioned that these tests used polymer
concentrations of 40 and 60 pptg at temperatures of 120 to 200 F
(48.9 to 93 C), respectively.
Qun et al. (2008) reported the use of what they referred to as
finely-processed guar for high-temperature applications of
246
302 F (150 C). The polymer loading was 0.45% (approximately

37.6 pptg). The finely processed guar is believed to have a low insoluble content of 1.6% compared with 16% in some types of
guar. This linear gel maintained more than 150 cp for more than 2
hours at 150 C and a shear rate of 170 sec1. The system was
implemented in gas-producing wells, where it gave 16 to 28 times
more gas after the treatments. It should be mentioned that, in addition to the use of the finely processed guar, the authors attributed
these successful treatments to a forced fracture-closure technique
in which the pumping schedule of the proppant was altered. In
this technique, the well was shut in, allowing the proppant to flow
from the low-permeability to the high-permeability zones. In a
similar approach, Williams et al. (2012) reported on the use of a
high-yield fast-hydrating guar polymer for use in fracturing applications. The polymer is thought to have fewer insoluble residues
compared with existing products. The authors observed higher
viscosity with the linear gels of this polymer compared with those
of standard guar polymers. For example, after 90 minutes, the
new polymer gave a viscosity of 580 cp compared with 420 cp (at
200 F and 100 sec1). The authors realized a 33% reduction in
polymer loading with the use of this polymer. The data are summarized in Table 3. It should be noted that this improvement in
viscosity results in part from the use of a size-designed, boratebased crosslinker.
Weaver et al. (2002a, b) reported a new approach to improve
polymer cleanup. The gel is mainly a low-molecular-weight guarbased polymer crosslinked with borate. The HPG is depolymerized to give low-molecular-weight segments (preferably between
100,000 and 250,000 Daltons). Then, the gel can form at pH values greater than 9. Upon contact with the formation, the pH drops
to less than 9; thus, the borate crosslinker does not become functional. This phenomenon, combined with the low-molecularweight nature of the segments, allows the gel to clean up without
the need for a breaker. The system was applied in gas and oil
shale wells. The authors claimed successful placement of the
proppant. Peles et al. (2002) reported another application of the
same system in the Springer Group reservoir of the Cement field
in Oklahoma. The treated wells had permeabilities ranging from
0.1 to 3.9 md. Production data were not reported. However, data
indicated that approximately 65% of the fracturing fluid was
recovered. In one of the treatments, the authors reported excessive
friction for this system, which hindered the placement of the proppant. Palmore et al. (2003) reported the application of this system
in wells of the Means San Andres field in Texas. The well treated
with this system showed better performance in terms of production rate (sustained 170 BOPD after 75 days of the treatment)
compared with a well that was treated with a conventional guarbased gelled system (100 BOPD after 75 days of the treatment).
Walters et al. (2009) reported the use of a linear gel (based on
a biopolymer) to carry proppants. The system requires neither
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Polymer
Loading
(pptg)
Temperature
[F (C)]
Shear Rate
(sec1)
Viscosity
(cp)
High-yield guar/new
borate crosslinker
25
150 (65.6)
100
580
Regular guar/regular
borate crosslinker
30
150 (65.6)
100
440
High-yield guar/new
borate crosslinker
25
200 (93)
100
500
Regular guar/regular
borate crosslinker
30
200 (93)
100
420
Polymer Type
Table 3Effect of the use of high-yield guar and the new crosslinker on the viscosity of crosslinked
gels (data extracted from Williams et al. 2012).
crosslinker nor a breaker. At 40 sec1 of shear rate, it gave viscosity values of 352 and 216 cp at 96 and 250 F, respectively. The
polymer concentration is believed to be between 40 and 70 pptg.
The authors did not provide information about the nature of the
fluid; however, it is claimed that the system retains 90% conductivity compared with 14% conductivity of borate-crosslinked gels
under the same conditions (200 F and 6,000-psi closure stress).
Note that the 14% regained conductivity of the run with boratecrosslinked gel is considered low, and, generally, this value is not
representative of borate-crosslinked gels because they can show
regained conductivity of 40 to 60%. This low regained conductivity could be a result of high polymer concentration, low breaker
concentration, and/or the testing method that has been implemented by the authors. The procedure by which the regained fracture conductivity was measured is as follows. First, potassium
chloride (KCl) was injected through the conductivity cell until a
stable pressure drop was obtained. This was repeated at different
closure pressures. Then, the gel was injected through the cell at
the desired closure pressure. After that, the cell was shut in for 24
hours. Finally, KCl was injected at the same desired closure pressure and the regained permeability was calculated by comparing
the conductivity after the gel injection with that before the gel
injection (Holtsclaw and Funkhouser 2010; personal communication with D.V.S. Gupta, Baker HughesHouston 2014; personal
communication with H.G. Walters, HalliburtonHouston 2014).
Another advancement was the use of a mixture of NAX gum
and guar (Fischer et al. 2001). NAX is a xanthan gum without the
acetyl acid group. The chemical structure of NAX is shown in
Fig. 2. The objective of the use of NAX was to obtain higher viscosity compared with a solution of guar alone. Table 2 provides
viscosity data at ambient temperature for this system. Clearly, the
introduction of NAX (at a ratio of 4:1) provided better viscosity
results than the use of guar or NAX alone. One drawback of this
CH2OH
CH2OH
O
O
OH
CH2OH
O
OH
CH2
OH
OH
OH
COOM+
O
OH
M+OOC
OCH2
OH
technology is its sensitivity to KCl. As such, alternatives to KCl,

such as tetra methyl ammonium chloride, should be used. There
are neither conductivity data nor field-application data for this
system. Tonmukayakul et al. (2011) reported the use of mixtures
of cellulose-based and xanthan or guar polymers. To the best of
the authors knowledge, no data are reported for the performance
of this system in terms of conductivity.
Note that most of the literature data of the rheological behavior of these guar-based fluids are reported under low pressures. In
the past few years, more emphasis was put on the effect of high
pressures (up to 10,000 psi) on the viscosity of these fluids (England and Parris 2010, 2011; Marquez et al. 2012). When highpressure viscosity measurements of linear guar gels, VES fluids,
and borate-crosslinked guars were performed, the borate-crosslinked guars were the only fluids that showed pressure-dependent
viscosity (England and Parris 2010). For example, England and
Parris (2011) reported that when a 25-pptg HPG was crosslinked
with a titanium complex crosslinker, the viscosity remained constant at 4,300 cp over the pressure range from atmospheric to
10,000 psi (at 70 F, 10 sec1). On the other hand, the authors
observed that the viscosity of a 30-pptg guar crosslinked with a
diboronic acid dropped from 9,500 cp at low pressures (ambient
pressure of approximately 14.7 psi) to 3,000 cp at 10,000 psi (10
sec1 and 72 F). Interestingly, the effect of pressure on viscosity
was reversible, with the fluid recovering its viscosity after the
pressure was lowered to the starting value. Parris et al. (2008)
studied the chemistry of these borate-crosslinked guar gels with
11
B by use of nuclear-magnetic-resonance spectroscopy. The
authors found that the crosslinking bond between the borate and
carbon on guar breaks at high pressures and that this break is reversible once the pressure is released to lower values.
One should note that gels produced by crosslinking biopolymers with borate-based crosslinkers do have better shear-resistance properties compared with those crosslinked with metallic
crosslinkers. This has been demonstrated experimentally by several researchers (Bjornen et al. 2011; Parris et al. 2009). One explanation for this advantage of borate-crosslinked gels is the fact
that the chemical bonding between the borate anion and the guar
polymer is reversible, enabling the gel to recover its crosslinks after shear is decreased (Harris 1993; Parris et al. 2008).
In summary, the major advancements in the use of biopolymers in fracturing were the use of cleaner fluids, in which the insoluble part of the guar was eliminated. At the same time,
mixtures of different polymers were attempted. Moreover, use has
been made of lower-molecular-weight segments that can be used
in low-permeability reservoirs in which leakoff is not an issue.
Finally, pressure was found to have a negative effect on the viscosity of borate-crosslinked guars. This effect was found to be reversible, with the gel recovering its viscosity upon lowering of the
pressure.
OH OH
H3C
O
Fig. 2Chemical structure of NAX (Fischer et al. 2001).
Synthetic Polymers. In recent years, the cost of guar beans

increased dramatically and became very volatile. Moreover, guar
is not stable at temperatures close to 400 F. Gupta and Carman

247
O
S
OH
NH2
Page: 248
Total Pages: 18
two wells in south Texas at 450 F (232 C) and 23,300 ft (Funkhouser et al. 2010). The data are summarized in Table 4. The
authors reasoned that the loss of production in Well 1 was caused
by the very low permeability of the reservoir (less than 10 ld).
Viscosity data for this system are summarized in Table 5. Note
that this table summarizes viscosity data of PAM-based polymers
reported in this paper.
Gupta and Carman (2011) reported on the use of another hightemperature fracturing gel, which is based on a copolymer of partially hydrolyzed PAM-AMPS vinyl phosphonate. The authors
did not report the content of each monomer in the copolymer
backbone. This copolymer is crosslinked by zirconium. The
authors reported high-temperature viscosity data, which are summarized in Table 5. The system maintained a 1,000-cp viscosity
after shearing at 100 sec1 for 2 hours at 425 F. The system at
3,000 psi of closure maintained more than 65% of conductivity at
the same temperature. The conductivity data are also summarized
in Table 6. It is worth mentioning that this system can also be
energized by the use of carbon dioxide (CO2). Note that energizing guar was limited to a temperature of 260 F because of compatibility issues between guar and CO2. The authors did not report
field-application data for this system. Acetic acid and sodium acetate buffers are used to maintain a low pH of 5, which is believed
to stabilize the gel.
Gaillard et al. (2013) reported the use of three PAM-based
polymers for use in hydraulic fracturing. These polymers are
high-molecular-weight (5 to 15 million g/gmol) PAM-based polymers. They all contain less than 1.5 mol% of a hydrophobic group
and have an acrylate content of 10 to 25 mol%. The third polymer
had a sulfonic monomer at a concentration of 10 to 25 mol%. The
polymers exhibited good proppant-settling properties; yet, their
viscosity at high shear rates and high temperatures is yet to be
investigated. Table 7 shows viscosity data for the three polymers
and guar as a function of shear rate at 194 F (90 C).
OH
Stage:
NH
Fig. 3Chemical structure of the partially hydrolyzed PAMAMPS copolymer (Holtsclaw and Funkhouser 2010).
(2011) reported 360 F (182 C) as the upper limit of guar use

while Harris and Sabhapondit (2009) reported 375 F (190 C).
With the cost-increase trends and the need to fracture wells with
temperatures greater than 375 F (190 C), the oil and gas industry
started developing alternatives. Synthetic polymers, such as polyacrylamide (PAM), have been widely used as friction reducers in
fracturing operations. They are usually added at concentrations of
1.25 to 2.5 pptg (Gaillard et al. 2013). Holtsclaw and Funkhouser
(2010) reported the use of a PAM-based polymer as a fracturing
fluid that can carry proppants. The system is based on a terpolymer of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and
acrylamide, with the structure shown in Fig. 3. Note that Funkhouser and Norman (2003) reported that the best performance of
this system is obtained with the use of 60% AMPS, 39.5% amide,
and 0.5% acrylate. Moreover, for these high temperatures, the
authors found that sodium bromate is the best breaker. Holtsclaw
and Funkhouser (2010) reported viscosity data of this copolymer
crosslinked with zirconium (Zr) [66 pptg of polymer and 3 gal per
thousand gallons (gptg) of Zr4], in which the system gave a viscosity of 700 cp for more than 1.5 hours at a temperature of 402 F
(204 C) under shear rate of 40 sec1. Under the same conditions,
a gel based on CMHPG and containing the same concentration of
polymer and crosslinker lost significant viscosity when, after 22
minutes of shear, its viscosity dropped to less than 50 cp. The
PAM-based polymer crosslinked with zirconium was applied in
High-Density Brines
A formation can be fractured only if the bottomhole pressure
exceeds the formation-breakdown pressure. Eq. 1 can be used to
calculate the surface treating pressure required for a fracturing
operation (Pandey and Robert 2002; Simms et al. 2008):
Proppant
Content
(lbm/gal)
Pad
Volume
(gallons)
Number
of
Fracture
Stages
PostTreatment
Gas Rate
(Mscf/D)
Well
Number
Reservoir
Depth (ft)
Reservoir
Temperature
[F (C)]
23,324
450 (232.2)
1 to 8
25,000
18,830
433 (222.7)
1 to 7.4
30,000
4,933
Table 4Field-application data of the PAM-based polymer crosslinked with zirconium (data extracted
from Funkhouser et al. 2010).
Polymer
Content (gptg)
Crosslinker
Content (gptg)
Temperature
[F (C)]
Shear
Rate
(sec1)
Viscosity
(cp)
66
0.5
399 (203.9)
100
200
Holtsclaw and
Funkhouser (2010)
66
1.5
399 (203.9)
100
450
Holtsclaw and
Funkhouser (2010)
40
Data not
available
400 (204.4)
100
1,020
Gupta and Carman

(2011)
40
Data not
available
425 (218.3)
100
1,000
Gupta and Carman

(2011)
50
Data not
available
450 (232.3)
100
200
Gupta and Carman

(2011)
Reference
Table 5Viscosity data of PAM-based high-temperature fracturing gels (after shearing at 100 sec21
for 2 hours with no breaker).
248

Stage:
Page: 249
Total Pages: 18
Polymer/Crosslinker Type
Polymer
Content
(pptg)
Breaker
Content
(gptg)
Closure
Stress (psi)
Shut-in
Time
(hours)
PAM-based/zirconium
87
5,000
48
399 (204)
68
Holtsclaw and
Funkhouser (2010)
PAM-based/zirconium and
activator
87
0.3 to 1.5
2,500
42 to 72
450 (232)
34 to 100
Holtsclaw and
Funkhouser (2010)
PAM-based/zirconium
66
4,000
71
399 (204)
43 to 73
Holtsclaw and
Funkhouser (2010)
PAM-based/zirconium
66
8,000
118
399 (204)
39 to 47
Holtsclaw and
Funkhouser (2010)
PAM-based/zirconium
66
10,000
165
399 (204)
37
Holtsclaw and
Funkhouser (2010)
Linear biopolymer
40 to 70
Not
needed
6,000
Not reported
200 (93.3)
90
6,000
Not reported
200 (93.3)
14
Guar/borate
Not
Not
applicable applicable
Temperature
Regained
[F (C)]
Conductivity (%)
Reference
AMPS-vinyl
phosphonate/zirconium
40
Not
applicable
3,000
24
425 (218)
64 to 69
Gupta and Carman

(2011)
AMPS-vinyl phosphonate/
zirconium
40
Not
applicable
3,000
24
385 (196)
83
Gupta and Carman

(2011)
Table 6Fracture-conductivity data of proppant packs.
Monomers Available
Hydrophobic
Sulfonic
Monomer
Acrylamide
Viscosity at 0.1
sec1 (cp)
Viscosity at 100
sec1 (cp)
40
Yes
Yes
Yes
8,000
Yes
No
Yes
5,000
40
Yes
No
Yes
900
40
Guar
Guar
Guar
80
10
Table 7Effect of shear rate on viscosity of associative PAM-based polymers at 194 F (90 C) (data
extracted from Gaillard et al. 2013).
PS PBH Pf Phydr ; . . . . . . . . . . . . . . . . . . . . . . 1
where PBH is the bottomhole treating pressure in psi, Pf is the friction pressure in psi, and Phydr is the hydrostatic pressure in psi.
Some unconventional reservoirs are located at depths up to
20,000 ft, and the reservoir temperature can be as high as 355 F
(179.4 C) (Bartko et al. 2009). Fracturing such wells requires bottomhole treating pressures of up to 20,000 psi. There are limitations on the pressure rating of some bottomhole completion
equipment. There could also be limitations on the pressure rating
of surface equipment and pumping equipment that do not exceed
15,000 psi (Qiu et al. 2009). From Eq. 1, increasing the hydrostatic pressure of the fluid will result in a decrease in the surface
treating pressure. To increase Phydr in Eq. 1 and address the
15,000-psi pumping-pressure limitation, a high-density brine
(11.4 lbm/gal) is used to prepare the fracturing gels. The density
of standard fracturing gels prepared in field brines is usually
approximately 8.7 lbm/gal (Simms et al. 2008). Thus, the use of
high-density brines can increase the hydrostatic pressure by 30%.
Bartko et al. (2009) reported the first field application of a
high-density brine in tight gas reservoirs in Saudi Arabia. This
system was based on a carboxymethylhydroxypropyl guar
(CMHPG) polymer crosslinked with a delayed zirconium- (Zr4-)
based crosslinker. The authors used NaBr with a density of 12.3
lbm/gal. Therefore, at a given depth, the use of this high-density
brine increases Phydr by 41%. As a result, the authors were able to
triple the pumping rate (10 to 30 bbl/min) with a wellhead-pressure increase of only 2,000 psi (from 9,500 to 11,500 psi). Nonetheless, the treatment was unsuccessful because of a mechanical
failure in which the liner collapsed.
Bu-Khamseen et al. (2010) reported the first successful field
application of this high-density CMHPG/Zr4 gel system in Saudi
Arabia. A well with a bottomhole temperature of 375 F (190 C)

was hydraulically fractured at an average depth of 18,300 ft. The
treatment used a high-strength 18/40 proppant. The lower part of
the formation was treated successfully. The gas rate increased
from 0.35 to 3.5 MMscf/D; yet, a failure in one of the upper completion pup joints caused a change in the direction of the treatment. This lower zone had to be isolated with a composite plug.
Then, the upper zone of the same formation was fractured. After
the second treatment, the plug was milled out. The total production rate was 2.8 MMscf/D.
Gupta et al. (2012) reported on the use of a different chemistry
to address the same challenge. The authors used a polyampholyte
and a surfactant. The mechanism by which the viscosity builds up
does not include a crosslinking reaction. The nature of this viscosity buildup is believed to be an interaction between the polyampholyte and the salts in the high-density brine. The authors
reported viscosity data and fracture-conductivity testing of this
system at temperatures up to 250 F (121 C). The system was
found to be compatible with various brines, including CaBr2 and
its mixtures with CaCl2 as well as NaBr and its mixtures with
NaCl. Conductivity data are shown in Table 8.
Crosslinkers
Polymer-based fracturing gels are crosslinked with one of two
major types of crosslinkersnamely, borate and metallic crosslinkers such as zirconium and titanium. In this section, light will
be shed on the advances in crosslinkers for polymer-based hydraulic-fracturing fluids. Note that the advancements were only limited
to borate-crosslinked gels. To the best of the authors knowledge,
the advancements in metallic crosslinkers were limited.
Sun and Qu (2011) reported on the development of a new class
of boron-based crosslinkers. The attempt was aimed at producing

249
Polymer
Content (pptg)
Salt Type
Brine Density
(lbm/gal)
Stage:
Page: 250
Closure Stress
(psi)
Temperature
(F (C)]
Total Pages: 18
Regained Gas
Conductivity (%)
Regained Water
Conductivity (%)
50
CaCl2
11
9,000
200 (93.3)
95
81
50
CaCl2
11
9,000
250 (121)
94
93
60
NaBr/NaCl
12
9,000
250 (121)
93
91
Table 8Fracture-conductivity data of proppant packs that use high-density polyamphoteric/surfactant gel (data extracted from Gupta et al.
2012).
OH
OH
HO
OH
OH
OH
HO
OH
(a) BDBA
(b) BPDPA
OH
OH
S
B
OH
OH
(c) TDBA
Fig. 4Chemical structures of larger-sized borate-based crosslinkers (Sun and Qu 2011).
crosslinkers that can generate higher viscosity with less polymer

content. The size of the crosslinker was the new parameter to
change. The authors used sources of boron other than boric acid.
These were thiophenediboronic acid (TDBA), benzenediboronic
acid (BDBA), and biphenyldiboronic acid (BPDPA). The chemical structures of these fluids are shown in Fig. 4. It has been found
that increasing the size of the crosslinker provides higher viscosity. The data are summarized in Fig. 5, where higher viscosity
values were obtained with these larger-sized crosslinkers compared with boric acid. Unfortunately, the cost associated with
making these crosslinkers makes them impractical. Thus, the
authors reported on the use of trimethylborates as a source of boron to react with amines. The amines that can be used include polyethyleneimine and 3-aminomethylbenzylamine, which are
shown in Fig. 6. The reaction yields cost-effective, large-sized
aminoborate compounds to crosslink guar-based polymers. The
700
600
Viscosity (cp)
500
400
300
TDBA
BPDBA
BDBA
Boric
acid
200
best results were obtained with tris(2-dimethoxyboronoaminoethylamine), which gave a viscosity of 900 cp compared with 700
cp from a conventional borate crosslinker at a temperature of
200 F (93 C) with 25 pptg of polymer. Legemah et al. (2013)
reported on the development of a crosslinking-delayed version of
the technology, which is covered in a subsequent section.
Loveless et al. (2012) reported on a similar approach. The
authors used a multifunctional boronic crosslinker that can crosslink at least two or more polymer molecules. Moreover, its chemical structure has spacers, enabling its chain to be large. The
authors used the measurement of the elastic modulus (G0 ) to test
the performance of this system. Note that G0 is a measure of how
much structure there is in a certain sample. As such, the measurement of G0 is one method for examining the suspension properties
of the gel. In an experiment to measure the G0 of gel samples prepared with this crosslinker, the authors realized a tenfold increase
in G0 (Sample 1) compared with a second sample that used the
conventional borate crosslinker. This is despite the fact that only
2.5 lmol of the multifunctional boronic crosslinker was used
compared with 400 lmol of the conventional borate crosslinker in
Sample 2. Neither the conductivity data of this gel nor its breaking behavior were reported.
Williams et al. (2012) reported on the use of a new crosslinking agent referred to as an efficient borate crosslinker. The
authors did not report on the chemical nature of the crosslinker. In
addition, it was combined with another improving factor, which is
the use of a high-yield, nonderivatized guar. Yet, some viscosity
data were reported from which incremental viscosity improvements were realized. The data are summarized in Table 3.
100
0
16
16
17
Polymer concentration (pptg)
24
Fig. 5Fann 35 viscosity data (300 rev/min, room temperature)

showing the effect of crosslinker size on viscosity (data
extracted from Sun and Qu 2011).
250
H2N
NH2
H2N
NH2
Fig. 6Chemical structures of polyethyleneimine (right) and

3-aminomethylbenzylamine (left) (Sun and Qu 2011).
Buffer
Loading
(gptg)
Crosslinker
Loading (gptg)
2.4
4.0
150
2.4
4.2
176
2.6
4.6
207
15
4.6
240
Table 9Effect of glyoxal on vortex-closure time for delayed

polyaminoborates crosslinking 25-pptg guar at room temperature
(data extracted from Legemah et al. 2013).
Total Pages: 18
14
Viscosity
1,200
12
Time
10
1,000
800
600
400
200
Delay Mechanisms
In many cases, it is desired to delay the crosslinking reactions of
fracturing gels to reduce frictional losses encountered during
pumping of these fluids under turbulent-flow conditions within
surface pumping equipment, well tubing, and perforations. Having
lower frictional losses reduces the pumping-pressure requirements
on the surface. For Zr4 and Ti3 crosslinked gels, another reason
to delay the crosslinking reaction is that these gels are shear sensitive and do not recover their viscosity upon shear reduction in the
formation. Thus, the chances of proppant screenout increase.
Delay agents are added to minimize viscosity buildup until the
fluid leaves the high-shear-rate regions of the wellbore and the perforation. Hence, the problem of the limited recovery of post-shear
viscosity for zirconium- (Zr4-) crosslinked gels is overcome. Ainley et al. (1993) and Legemah et al. (2013) give a comprehensive
list of patent literature resources on the delay methodologies used
over the years from 1987 through 2000.
Over the last decade, several advancements were captured. For
the new class of size-controlled borate crosslinkers that are based
on polyaminoborates, Legemah et al. (2013) reported the use of
four ligands as delay agentsnamely, sorbitol, pentaerythritol,
dipentaerythritol, and N-methylglucamine. These four ligands are
used in the synthesis of the polyaminoborate crosslinker to produce the delayed version of the technology. To quantify the delay
of these ligands on the crosslinking reaction of the guar with
delayed polyaminoborate, the authors made use of the vortex
time. This is performed experimentally by agitating the linear gel
at 1,500 rev/min with a three-blade blender. Then, a vortex is created. Upon the addition of the crosslinker, the viscosity of the
mixture increases and the vortex closes. Vortex time data ranged
from 1.5 to 4 minutes. The data are summarized in Table 9. It is
clear that adding more glyoxal enhances the crosslinking delay of
this system. However, field requirements for delay were not
discussed.
Putzig and St. Clair (2007) reported a new delay agent for metallic (Zr4 and titanium) crosslinked gels. The delay system is a
chelating agent containing alcohol, carboxylic acid, and amine
functional groups. The system was tested at temperatures up to
275 F (135 C). This delay agent was tested with various types of
crosslinkers, including nonaqueous Zr4 complexes such as triethanolaminozirconate, zirconium lactate, and triethanolaminotitanate. Some of the results from this study are reported in Fig. 7.
The data show that adding more delay agent retards the crosslinking reaction further; yet, the effect of these materials on final gel
viscosity is negative where the viscosity drops when more delay
agent is added. It is believed that the reason for this drop is the
interaction between the chelating agent and the multivalent cation. This reduces the concentration of the metal cations available
for crosslinking the polymer. However, the authors suggest the
use of more crosslinker concentration to offset this observation.
Kalgaonkar and Patil (2012) developed a new shear stabilizing
chemical for Zr4-crosslinked gels at high temperatures of 300 to
375 F (149 to 191 C). The system is believed to be based on a
combination of two bufferspotassium carbonate and sodium
carbonateadded at sufficient concentrations to raise the pH to
10.2. When sheared at 127 sec1 and 75 F (24 C), it took the stabilized gel 75 minutes to crosslink, and its viscosity remained
below 100 cp. After that, the temperature was increased to 350 F
Page: 251
1,400
VortexClosure Time
(seconds)
Maximum Viscosity (cp)
Glyoxal
Loading (%)
Stage:
0.25
Delay-Agent Concentration (mol/L)
0.75
Time To Generate
Maximum Viscosity (minutes)
Fig. 7Delay time and maximum-viscosity data for chelatingdelay agent (175 F, 40 pptg of carboxymethylhydroxypropyl
guar, 39 ppm of Zr41 from sodium zirconium lactate). (Data
extracted from Putzig and St. Clair 2007.)
(176 C) and the gel maintained a viscosity of more than 400 cp

for more than 1 hour. On the other hand, at 275 F (135 C), a gel
without the buffering system crosslinked in less than 5 minutes,
and its viscosity reached more than 500 cp.
Breaker Packages
Upon the completion of the fracture initiation in the reservoir and
the subsequent proppant placement, the used high-viscosity fluid
must be removed from the proppant matrix. In addition, the filter
cake it formed on the fracture face needs to be cleaned. Thus,
breakers are used to initiate a chemical reaction by which the viscosity is reduced. This chemical reaction is a function of temperature, concentration of the breaker, polymer concentration, and pH.
Note that studies pointed out that because of fluid leakoff, the
polymer concentration in the formed filter cake can be several
times larger than that of the polymer originally used (Reddy
2013). Several breaker packages exist in the market with their
own operating windows, as shown in Fig. 8 (Sarwar et al. 2011;
Brannon 1994; personal communication with J. Crews, Baker
HughesHouston 2013). Oxidizers (persulfates) degrade the
guar-based polymer by sulfate-free radical reaction. This reaction
defragments the polymer into shorter molecules, reducing its molecular weight and thus its viscosity. On the other hand, enzymes
degrade the polymer by hydrolysis of specific polymer units. For
example, hydrolase enzymes break both the mannose units and
the galactose side chains (Brannon 1994). Note that it is desirable
to break the linkages of the mannose building units before the galactose side chains. This is because the mannose blocks have low
solubility in water once the linkage with the side chain is broken
(Brannon 1994). Acids decrosslink the gel by lowering the pH
and are used mainly for borate-crosslinked gels that require high
pH for crosslinking.
Sarwar et al. (2011) investigated the effectiveness of oxidizers,
such as ammonium persulfate, sodium persulfate, sodium and calcium peroxides, and galactomannanase enzyme, over a wide temperature range from 75 to 300 F (24 to 149 C). The residue after
break was used as one measure of the effectiveness of the breaker.
All of the breakers generated residues from 5 to 7 wt%. The
enzyme was found to provide a more homogeneous break, leaving
less residue. The authors did not indicate whether the residue is a
result of impurities within the guar or is a residue of the unbroken
gel. However, it is believed that commercial guar contains up to
10 wt% of impurities (personal communication with H.A. NasrEl-Din, Texas A&M University, College Station, Texas, 2013).
Persulfates are very reactive at temperatures higher than 140 F
(60 C). At these temperatures, only low concentrations of these
materials can be used. For example, it has been reported that 0.5
pptg of ammonium persulfate at 160 F (71.1 C) and 0.1 pptg at
175 F (79.4 C) can produce the same viscosity drop of an

251
14
12
10
pH
8
6
4
LTE
LTO
MTO
HTE
HTO
0
0
50
100
150
200
250
300
350
Temperature (F)
LTE = low-temperature enzymes, HTE = high-temperature enzymes,
LTO = low-temperature oxidizers (sodium and potassium persulfates),
MTO = mid-temperature oxidizers (calcium and magnesium oxides),
HTO = high-temperature oxidizers (sodium and potassium bromates
(a) Enzymes and oxidizers

14
12
10
pH
8
6
4
EHTO
ELTO
EMTO
2
0
0
50
100
150
200
250
Temperature (F)
300
350
EHTO = encapsulated high-temperature oxidizers (bromates),

ELTO = encapsulated low-temperature oxidizer (persulfates),
EMTO = encapsulated mid-temperature oxidizer (metal peroxides)
(b) Encapsulated oxidizers

Fig. 8Various types of breakers with their operating conditions (Brannon 1994; Sarwar et al. 2011; Parker and Laramay
1992; personal communication with J. Crews, Baker HughesHouston 2013).
hydroxypropyl guar polymer (Gulbis et al. 1992). Thus, at highertemperature applications, the chances of a premature polymer
degradation and the subsequent proppant screenout can be high.
To provide a better control over the breaker activity and extend
Encapsulated
Breaker Type
Ammonium
persulfate
Page: 252
Temperature
[F (C)]
Time
(hours)
Breaker
Released (%)
Not reported
175 (79.4)
42
60
Not reported
Sodium
persulfate
Not reported
Polyvinylidene
Chloride
Total Pages: 18
the working temperature range of persulfates to higher than 140 F

(60 C), encapsulation was introduced (Gulbis et al. 1992; Powell
et al. 1997). The encapsulation takes more than nine forms (Lo
et al. 2002). For example, it can include a coating that dissolves,
slowly releasing the breaker (Lo et al. 2002). Another method is
the use of a barrier (shell) that allows diffusion of the aqueous medium to the core containing the breaker. Then, the breaker is dissolved into the fluid stream and diffuses back to the bulk fluid
(Patil et al. 2013). A third type is the use of particles that rupture
at the fracture closure where the stress increases significantly,
thus releasing the breaker afterward (Nolte 1985; Gulbis et al.
1992). Table 10 shows breaker-release data as a function of time
for various systems.
Patil et al. (2013) report the use of encapsulated persulfate oxidizers. The encapsulation was diffusion controlled such that the
breaker was distributed throughout a polymer matrix. The nature
of the polymer was not disclosed. Upon the encapsulation, it took
longer to decrease the viscosity of the gel to 50 cp. The data are
summarized in Fig. 9.
Because of safety concerns and their cost when encapsulated,
alternatives to oxidizers were sought. Hanes et al. (2006) introduced one of the new approaches during which the breaker decrosslinks the gel by competing with the guar polymer to crosslink the
metallic crosslinker. The authors used polyaspartate and polysuccinimide. Reddy (2013) also suggested that these materials can
even displace the guar from the already-existing guar/zirconium
(Zr4) crosslinks. Reddy (2013) reported laboratory data of the
polysuccinimide testing as a breaker for carboxymethylhydroxypropyl guar (CMHPG)/Zr4 gels. By use of 5-lm disks, it was
found that polysuccinimide did not produce a filter cake, whereas
the oxidizing breaker did form filter cake with a high polymer concentration ranging from 183 to 300 pptg, depending on shear. Note
that these experiments used an initial polymer concentration of 38
pptg and they were conducted at 200 F (93 C) by flowing the gel
through the disk under pressures ranging from 200 to 800 psi. The
author reported another class of decrosslinking agents that is based
on orthosubstituted aromatic lignosulfonates. These decrosslinking agents are thought to provide a delayed release of the breaker.
This is done by incorporating these materials as solid precipitate
within the filter-cake matrix. After the complete proppant placement, high pH conditions can then trigger the dissolution of the
solid breaker, which then degrades the filter cake from within. The
efficiency of these new breakers by use of conductivity measurements at high temperatures is yet to be reported.
Gunawan et al. (2012) reported on the development of a new
class of biobreakers that are nonenzyme-based and that can function at temperatures from 175 to 225 F (79 to 107 C). The chemistry of these breakers was not published; yet, they are believed to
degrade the polymer under alkaline conditions. These breakers
were efficient for use with derivatized guar such as CMHPG,
which is difficult to break by enzymes. The breakers reported in
this study showed a viscosity reduction to less than 50 cp at 100
Coating Type
Potassium
persulfate
Ammonium
persulfate (20%
coating)
Stage:
200 (93.3)
200 (93.3)
160 (71.1)
0.42
30
1.5
80
100
0.25
40
0.8
83
2.1
100
0.5
40
60
1.5
90
Reference
Norman et al.
(1995)
Patil et al.
(2013)
Patil et al.
(2013)
Gulbis et al.
(1992)
Table 10 Release data of various encapsulated breakers.

252

Time To Reach Viscoscity of 50 cp (minutes)
140
120
100
80
Encapsulated
sodium
persulfate
60
40
20
0
Encapsulated
sodium
persulfate
Neat sodium
persulfate
2.8
0.7
4.7
Breaker concentration (pptg)

Fig. 9Effect of encapsulation on sodium persulfate performance in breaking CMHPG/Zr41 gels at 200 F (93 C) (data
extracted from Patil et al. 2013).
sec1 for various polymers, including guar, high-yield guar crosslinked with borate, and CMHPG crosslinked with Zr4.
Reuse of Produced Water in Hydraulic Fracturing
A typical fracturing treatment requires the use of 4 to 6 million
gal of water. The transportation and processing of this water is
costly. Moreover, there are strict environmental regulations on the
injection of produced water that can cost from USD 0.75 to 1.0/
gal(LeBas et al. 2013). For these reasons, the industry started
making use of water produced from hydraulic-fracturing treatments. In some parts of the world where water is scarce, this
approach is even more needed.
Produced water contains high concentrations of salts [up to
270,000 ppm of total dissolved solids (TDS)] and may contain
hydrocarbons, suspended solids, and bacteria. The bacteria are responsible for generating enzymes that degrade the guar-based
polymers significantly. Thus, when fracturing gels are prepared in
produced waters, the resulting gels exhibit poor viscosity, as
shown in Table 11. Biocides, such as tetrakishydroxymethyl
phosphonium sulfate and quaternary ammonium compounds, are
used to suppress bacterial growth (Li et al. 2010; Paulus 2005).
These materials were successful in suppressing bacterial growth
in fresh water, but not in produced water, which can contain significant amounts of bacteria. This is because bacteria can grow by
more than 157 times in only 1 week (Li et al. 2009).
Huang et al. (2005) reported on the use of produced water in
New Mexico. The study used a carboxymethylhydroxypropyl guar
(CMHPG)/zirconium (Zr4) system prepared in a produced water
of 23,000 ppm of TDS. To suppress the bacterial growth, the produced water was treated with glutaraldehyde. The pH was found to
play a key role in the viscosity of the final gel. The best results were
Stage:
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achieved when the pH was approximately 5.7. At a pH of 7.2, the

weakest gel was obtained. A field application in the San Juan basin
of New Mexico in a gas-producing well resulted in 100% improvement in the gas-production rate, where the post treatment increased
to 100 Mscf/D from an initial rate of 50 Mscf/D.
Li et al. (2009) developed a new fluid stabilizer that is based
on organo-zirconium compounds such as sodium zirconium lactate, triethanolamine zirconium, zirconium tetrachloride, and zirconium acetate. The technology was used in fracturing 31 wells in
California. The produced water was first treated with 70 to 270
mg/L of the stabilizer for 20 minutes. Then, the water was used to
prepare the fracturing fluid. The reservoir had a temperature of
130 F (54 C). No gas-production data were reported; yet, the use
of produced water reduced the time it took to handle it by a factor
of six. Moreover, according to the author, approximately USD 1.5
million cost avoidance was realized. Another application at higher
temperatures from 197 to 225 F (92 to 107 C) in New Mexico
was highlighted by Li et al. (2010). The system was applied in
three vertical wells in New Mexico, with a total water requirement of 27,000 bbl. Another application was in six wells in the
Belmont offshore field in California, with a temperature of 190 to
210 F (88 to 99 C) and a total water requirement of 21,200 bbl.
The water analysis for both applications is reported in Table 12.
LeBas et al. (2013) reported the use of an electrocoagulation
method for treating produced water. The process is based on an
electric current applied across a solution of the produced water
such that hydrocarbons, solids, and other contaminants coagulate,
leaving a clear water solution. Part of the chemical analysis of
the produced water before and after this treatment is shown in Table 13. Note that the major reduction is in the amount of total suspended solids (TSS) and turbidity. The bacterial activity was not
reported as a concerning factor in this study. The treated water was
used to prepare a CMHPG/Zr4 gel that was applied in seven wells
with 97 fracturing stages. The authors reported significant cost
avoidance. The post-fracturing-treatment data were not reported.
In a study by Gupta and Hlidek (2010), flowback water from
fracturing treatments was recycled for use in other fracturing
treatments. The fracturing fluid was a foamed fluid that is based
on nitrogen (N2) or carbon dioxide (CO2). CO2 is used for deeper
wells, while N2 is used for shallower wells. Note that the use of
N2 is more cost-effective than CO2. The surfactant used in these
treatments was composed of anionic and cationic components.
When the charges become equal on both surfactants, lamellar
structures form that cause the viscosity to increase. The flowback
water flowed into large tanks and was then left for 24 hours,
allowing the solids to settle at the bottom of the tank and the residual oil to float to the top of the tank. Water was then extracted
3 ft (1 m) from the bottom of the tank, and filtered and used to
prepare the fracturing fluid. This technique was used in 5,000
treatments in Canada. The reservoir temperature ranges from 158
to 212 F (70 to 100 C).
Although the use of produced water represents a viable environmentally friendly approach, there are concerns with the use of
chemicals and their handling. It has been reported that up to 56%
Sample
Viscosity After
2 Hours (cp)
Shear Rate
(sec1)
Temperature
[F (C)]
740
100
125 (52)
Guar/borate gel prepared in

distilled water
50
100
125 (52)
Same as Sample 1, but with an

enzyme breaker
600
100
125 (52)
Same as Sample 2, but with a

stabilizer
320
100
135 (93)
Guar/borate gel treated with

stabilizer and then prepared in
produced water
50
100
135 (93)
Same as Sample 4, but with no

stabilizer
Comments
Table 11Effect of stabilizers and produced water on viscosity of borate-crosslinked gels (data
extracted from Li et al. 2009).
253
Stage:
Produced-Water Type
Page: 254
Total Pages: 18
Measurement
Before
Electrocoagulation
Treatment
Measurement
After
Electrocoagulation
Treatment
1.203
Component (mg/L)
Offshore Oil Field

in California, USA
Oil Field in New

Mexico, USA
Parameter
Sodium
9930
11 100
Specific gravity
1.2
Potassium
230
150
pH
4.83
Magnesium
970
450
Dissolved oxygen
8.24
8.45
Chloride
163,637
164,951
Calcium
260
1160
Chloride
18 400
20 740
Sulfate
40
38
Bicarbonate
100
170
Aluminum
1.42
2.28
Sulfate
>1600
<400
Table 12Chemical analysis of produced water used in preparing

fracturing gels (Li et al. 2010).
of the chemicals used in fracturing are hazardous to different

extents (Jacoby 2011). In addition, debates about the effect of
fracturing fluids on groundwater raise public concerns (Arthur
et al. 2011). Hepburn (2012) presents an example in which a scoring system was developed to assess the use of stimulation fluids in
the Eagle Ford formation in south Texas. The system examines
the health, safety, and environmental issues of these chemicals.
For example, in the health-hazards areas, a score is given to each
chemical in 10 health-hazard areas. Examples of these hazard
areas are toxicity, skin erosion, and carcinogenicity. The same
system is applied to physical health hazards and the environmental hazards.
In summary, the use of produced water represents a major
change to oil and gas hydraulic-fracturing operations because it
will require use of better handling and treating technologies of
produced water. Moreover, the use of produced water gives an
environmentally friendly approach to conserve water. However,
the environmental regulations for use of these chemicals are still
not global in all fields. A concern still exists about the effect of
these chemicals on the environment. Another issue is the fact that
borate-based gels are high-pH fluids and under these alkaline conditions, divalent cations (in produced waters) could precipitate out
of the solution, leading to formation damage. As such, more work
is needed in this area to resolve these issues.
Surfactants
An additional type of fracturing fluid is viscoelastic-surfactant(VES-) based fluid. These materials are believed to be less damaging to the proppant packs because they leave fewer residues. In
addition, they do not require crosslinkers, which means less complexity in the field. In water-sensitive formations, the use of VES
is preferred because it reduces the surface tension of the fracturing
fluid and thus helps in flowing water out of the pore space of the
rock. In fact, studies showed conclusive evidence that VES-based
fluids create less surface tension compared with borate-crosslinked gels (Nasr-El-Din et al. 2007). However, in high-permeability reservoirs (more than 200 md), VES-based fluids are
known to have high leakoff rates because they do not build a filter
cake on the fracture face (Crews et al. 2008). Other researchers
refer to the permeability threshold for the use of VES-based fluids
as 100 md (Sullivan et al. 2006). The reason for not building a filter cake is the lack of the crosslinking, as will be discussed later.
Moreover, their thermal stability is questionable at temperatures
greater than 275 F (135 C), unless a significant VES concentration is used (60 pptg) (Fontana et al. 2007). In this section, an
overview of the available surfactant technologies and their limitations will be presented.
Samuel et al. (1999, 2000) reported on the use of a VES for hydraulic fracturing. The system is based on a quaternary ammonium
salt that builds viscosity upon the interaction with inorganic salts.
The VES is a low-molecular-weight molecule having a hydrophilic head and a long hydrophobic tail. In the presence of salts,
such as potassium chloride, ammonium chloride, or ammonium nitrate, they form elongated micellar structures. With sufficient concentration of these micelles that is larger than their critical overlap
254
Barium
5.69
6.03
Calcium
29,222
28,845
Conductivity
(microS/cm)
257
258
Turbidity (NTU)
182
15.4
TDS (mg/L)
267,588
273,552
TSS (mg/L)
10 623
92
Table 13Chemical analysis of produced water (LeBas et al. 2013).
concentration, the micellar structures entangle to build viscosity.

Because this entanglement is not based on a chemical crosslinking
reaction (unlike the case with crosslinked polymer gels), these fluids have high leakoff rates. The high leakoff rate prevents their use
in reservoirs with high permeabilities (could be larger than 100
md). The authors reported case histories of the mentioned system.
It was applied in south Texas in wells with a bottomhole temperature of 180 F (82 C) and a reservoir permeability of 0.1 md. The
treatment used a maximum proppant content of 4 ppa/gal. The
well delivered almost tenfold more gas after the treatment.
Another treatment was conducted in a lower-permeability reservoir (0.03 to 0.05 md) in Wyoming. The reservoir temperature was
180 F (82 C). A maximum of 5 ppa/gal of proppant was placed.
The treatment was successful when the gas rate was 2.8 MMscf/D.
The authors claim that a similar treatment in the same field with a
borate-crosslinked gel gave only 1.3 MMscf/D.
VES-based fracturing fluids have a limitation when used in
reservoirs with permeabilities larger than 200 md because of their
high leakoff rate. The lack of structures in these fluids, unlike
polymer-based gels in which crosslinking provides a 3D structure
that forms a filter cake, leads to leakoff into the adjacent matrix.
Crews and Huang (2008), Huang and Crews (2008), and Huang
et al. (2010) reported on an improvement of the leakoff rate of
these fluids. The idea was to use nanoparticles that are less than
100 nm in size (35-nm-average-particle diameter). These are zinc
oxide particles. The particles crosslink the VES fluid, which
results in a crosslinked-like network. The network builds a filter
cake, which reduces leakoff. The nature of the crosslinking
between the particles and the VES fluid is believed to be a result
of van der Waals and electrostatic forces. The surfactant was an
amidoamine oxide. The particles were added at a concentration of
10 pptg. The surfactant concentration in the final solution was 2
vol%. Upon the addition of the nanoparticles, the zero shear viscosity was improved from 15 to 1,100 poise. It is claimed that the
nano-VES fluid improved the proppant settling time from 15
minutes to more than 90 minutes. To test the leakoff performance
of the nano-VES system, the fluid was forced through ceramic
disks (400 md, 0.25 in. thick) under 300-psi pressure drop. The
addition of the nanoparticles improved the leakoff rate significantly, with the leakoff volume dropping from 425 mL in 5
minutes to 80 mL in 70 minutes. However, a 30-pptg guar crosslinked with borate gave less leakoff (50 mL in 70 minutes). In
summary, the addition of nanoparticles improved the performance
of the VES-based fluid. It is worth mentioning that the authors
suggested the use of a hydrophobic breaker that is based on unsaturated fatty acids to break the viscosity of the VES nanofluids.
Sullivan et al. (2006) reported on the use of a zwitterionic surfactant in gravel-packing operations of reservoirs with permeabilities larger than 100 md in the Gulf of Mexico. A gas well was
hydraulically fractured to produce from a sandstone reservoir having a temperature of 195 F (90.5 C) and permeabilities ranging
from 100 to 420 md. The authors reported that the proppant was
placed successfully, but no gas-production data were presented.
Another well with a bottomhole temperature of 190 F (87.8 C)
and a permeability of 45 to 170 md was fractured with the zwitterionic VES system. No production data were reported for this well.
Moreover, the mechanism by which the leakoff control was
achieved was not reported.
Although VES fluids can break efficiently in the laboratory,
data indicated that 20% of field treatments using VES-based fluids
in the 1990s required the use of remedial actions to revive wells
fractured with these fluids (Crews et al. 2008). VES-based fluids
can break upon contact with hydrocarbons or when the salt content is reduced in the mixing brine. These two conditions may not
be met in all cases. For example, when reservoirs do not produce
hydrocarbons, then the VES does not break. Crews (2005)
reported the use of breakers with VES fluids. The VES system
reported by Crews (2005) was a nonionic VES. The author investigated four breakers that can be used over the temperature range
of 80 to 225 F (107 C). The chemistry of these breakers is
reported in patent literature (Crews 2009). The breaker is based
on a metal ion (such as iron), a reducing agent (such as ascorbic
acid), and a chelating agent (such as sodium citrate). The metal
attacks the micellar structure of the VES and breaks it. The chelating agent and the reducing agents are used to fine tune the breaking time. Reducing agents tend to reduce the required amount of
metal (can be a factor of 10) needed to break the VES. The breakers gave good results in the laboratory, where VES viscosity values were always reduced to below 20 cp.
Crews and Huang (2007) reported another breaker technology
for VES-based fluids in which two major mechanisms are used.
The first is by adding breakers that degrade the VES molecule
and, hence, prevent it from creating the micellar structures and
the subsequent viscosity generation. The second approach is by
adding materials that generate breakers that destroy the micellar
structures. Crews (2010) reported the chemistry involved in this
technology in which use is made of oils (soybean or fish oils) that
contain unsaturated fatty acids. Upon heating, the unsaturated
fatty acids produce fatty acids, aldehydes, and ketones. These
materials alter the micellar structure and break the VES. The
exact mechanism by which these materials function is still not
understood clearly.
To improve the cleanup of an amino oxide-based VES system,
Crews and Huang (2007) reported a study on the use of breakers
for this class of VES. The breaker is thought to be part of the VES,
enabling it to be in both the matrix (as a result of leakoff) and
within the proppant pack. The nature of this bonding between the
breaker and the VES is not reported. However, it is claimed that
the breaker does produce a hydrocarbon and thus initiates the VES
breakage. Gomaa et al. (2011) investigated the rheological behavior as well as the proppant-carrying capacity of this VES system. It
has been shown that increasing the total surfactant concentration
improves the viscosity of the system, with the viscosity increasing
from 10 to 100 cp (at 100 sec1) upon increasing the total surfactant concentration from 7.5 to 60.5 pptg. At the same time, it
improved the proppant-suspension capacity from 3 to 90% after 40
minutes of suspension. Similarly, the elastic modulus was found to
increase with the addition of more surfactant. However, data on
higher temperatures (greater than 60 C) were not reported.
Foamed Fluids
The term foamed fluids refers to fluids having at least one gas
component with a volume fraction (of the gas component) of at
least 52%. Note that this volume fraction is referred to as foam
quality. Similarly, energized fluids (dispersions) do have a gas
component; however, their quality does not exceed 52% (Hutchins and Miller 2005). Foamed fracturing fluids reduce the amount
of water to be used in the fracturing treatment. These fluids can
facilitate fluid flowback and thus are used in water-sensitive formations with high clay content. Riberio and Sharma (2013) pres-
Stage:
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ent a systematic approach on which energized fluid is to be used

under which conditions. Although these treatments can be costly,
they can show better performance than nonenergized fluids
(Burke et al. 2011). The most commonly used gases in these fluids
are either carbon dioxide (CO2) or nitrogen (N2). At temperatures
higher than 88 F (31 C) and pressures typical of those in fracturing treatments (greater than 1,000 psi), CO2 behaves as a supercritical fluid. In such a case, the energized fluid is considered an
emulsion. Quite often, the literature uses these two terms interchangeably (Gupta and Hlidek 2010; Arias et al. 2008). Note that
CO2 has more hydrostatic pressure than N2 and, therefore, it is
preferred in cases with high formation-breakdown pressure. This
section will report the major advancements in this class of fracturing fluids over the last decade.
Chen et al. (2005) reported on the development of a viscoelastic-surfactant (VES) system that is compatible with CO2.
Because CO2 is a nonpolar fluid, it has properties that are similar
to hydrocarbons, and therefore, it disturbs the worm-like micellar
structure, causing a drop in viscosity. The authors used a new concept in which additional surfactants are added to the mixture and
they stabilize the CO2 droplet within the VES solution. In this
case, the fluid is an emulsion rather than a foam. The system can
gel with 2% potassium chloride and has a maximum temperature
stability of 230 F (110 C). The best viscosity results were
obtained with CO2 qualities of 70%. The viscosity of the emulsion
was found to be 125 cp at 200 F (93 C) and 100 sec1. This compares with 50 cp with the straight VES without the CO2. The fluid
was tested in a reservoir in north Texas with an average bottomhole temperature of 150 to 170 F and a permeability of 0.01 to 0.1
md. Gas rates after these treatments were not reported. However,
for one of the treatments, the authors reported that pressure-transient analysis confirmed a 29% increase in productivity compared
with an offset well treated with a 40-pptg guar gel. Arias et al.
(2008) reported the use of the same system in fracturing wells in
Wyoming. The fluid was used to transport sand at concentrations
of 5 to 6 lbm/gal. The authors reported almost a 30% increase in
cumulative gas production of these wells when compared with
those fractured with a linear guar gel over a 6-month period.
Gupta et al. (2005) reported on the use of a surfactant that is
based on a mixture of anionic and cationic surfactants that form a
lamellar structure (and hence increase viscosity) if the charges on
both surfactants become equal. The surfactant can be foamed with
CO2 or N2 gases. The fluid was used in 3,100 oil wells in Canada,
where the maximum reservoir temperature was 212 F (100 C)
and the permeability ranged from 0.1 md to 10 darcies. Most of
these treatments used N2 gas to foam the surfactant. The fluid viscosity was sufficient to transport 5 to 6.7 lbm/gal of proppant. No
hydrocarbon data were reported in this paper to show the effectiveness of these treatments.
To address the thermal-stability issues of VES-foamed fluids,
Gupta and Carman (2011) reported on the use of associative polymers as an additional component to the VES-foamed fluid system.
The polymer is thought to have an advantage in treating clays.
The viscosity increase is because of the thermo-setting nature of
the polymer. This happens when it is heated to a certain temperature at which the thermo-sensitive blocks aggregate. The system
was able to maintain a viscosity of 150 cp at 260 F (126.7 C)
under a shear rate of 100 sec1.
Nanotechnology
Advancements in the field of nanotechnology have been used in
the oil field to resolve challenges related to many applications.
Nanotechnology provides an opportunity because of its welldesigned shapes, high surface/volume ratios, and its small size,
allowing its particles to propagate through reservoir rocks. In this
section, we present some of the recent literature that examines
nanotechnology for use in hydraulic fracturing. In the surfactant
section, some of the advancements that are related to viscoelastic
surfactants were already highlighted.
Fakoya and Shah (2013) studied the effect of adding silica particles to guar polymer gels, surfactants, and mixtures of

255
Stage:
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Total Pages: 18
60
Viscosity (cp)
50
N
H
40
Fig. 11Nanolatex silica synthesized with boronic acid (Lafitte
et al. 2012).
30
20
Shear Rate = 50 sec

Temperature = 175F (79C)
Guar Concentration = 33 pptg
10
0
0
0.1
0.2
0.3
0.4
0.5
Concentration of Nano SiO2 Particles (wt%)

Fig. 10Effect of nanomaterial on viscosity of 33-pptg guar linear gels (data extracted from Fakoya and Shah 2013).
surfactants and guar polymers. The authors used 20-nm silica particles. Upon the addition of more particles to a noncrosslinked
guar gel, the solution viscosity increased until it doubled by the
addition of 0.4-wt% particles. The data are summarized in Fig.
10. The mechanism by which the particles increase the viscosity
of the guar solution is believed to be by adsorption of the polymer
on the silica particles. Then, the polymer starts forming aggregates that increase its viscosity. More work is needed to quantify
the effects of these particles on viscosity of crosslinked gels and
their temperature stability.
Lafitte et al. (2012) introduced a new concept by which nanolatex silica is synthesized with boronic acid to yield what is known as
boronic-acid-functionalized nanoparticles. Fig. 11 shows the
chemical structure of the new crosslinker in which the blue ball
refers to the silica particle. The idea is to use these suspensions to
reduce the concentration of boron used in conventional systems.
For example, upon the addition of 2 ppm of boron to the guar polymer, the resulting gel had a viscosity of 800 to 2,000 cp, depending
on shear rate. It was observed that the maximum viscosity difference between the nanolatex-crosslinked gel and a conventional
borate-crosslinked gel takes place at guar concentrations less than
16 pptg at low shear rates. It should be mentioned that these particles have a size less than 30 nm, with a specific area of 300 m2/g.
One more advantage of these new crosslinkers is the independent
nature of their resulting gel viscosity compared with conventional
borates. The breaking mechanism of these suspension-based fluids
remains unanswered, along with their behavior at high temperatures; yet, they show a window of opportunity.
Fracturing of Shale Reservoirs
A major advancement in horizontal drilling and hydraulic fracturing allowed economical production of shale reservoirs. These reservoirs are characterized by nanodarcy permeabilities. Moreover,
some of them can contain water-sensitive clays such as smectite,
illite, or kaolinite (Maley et al. 2013). These clays can cause fines
migration upon contact with brine or can swell. In either case, the
permeability of the rock is compromised. Obviously, with these
low permeabilities, crosslinked fluids can cause seriously excessive productivity losses. Thus, use is made of water with a drag
reducer as a fracturing fluid. It is usually referred to as slickwater.
It is worth mentioning that water fracturing is not new. Several
papers report that it dates back to the 1950s (Wang and Miskimins
2010) and the 1970s (Grieser et al. 2003). Literature also reported
hybrid treatments in which slickwater is combined with low concentrations of polymers (Handren and Palisch 2009).
Unlike polymers, water has poor proppant-suspension properties because of lack of structure and viscosity. As such, very little
proppant can be transported. This is usually at a concentration of
0.25 to 2.5 ppa/gal of fracturing fluid (Palisch et al. 2010). To
256
B(OH)2
place large volumes of proppants, slickwater treatments are

injected at very high rates that can reach 120 bbl/min (Kaufman
et al. 2008). Obviously, with low quantities of proppant added,
these treatments will require very large volumes of water that can
reach 1 million gal. It has been thought that slickwater treatments
present a challenge when it comes to proppant placement in vertical fractures. It has been thought that because of the lack of suspension in water, proppants tend to settle, leaving portions of
fractures unpropped (Palisch et al. 2010). However, recent work
by Sahai et al. (2014) has shown experimentally (by use of vertical-slot flow experiments) that when the sand dunes in the nearwellbore region form, the area available for the slickwater flow
decreases. As such, the fluid velocity increases, which helps prop
the fracture more. This trend has proved to create greater propped
heights. Moreover, it is reported that seismic (when used to characterize hydraulically induced fractures) revealed more-complex
fractures upon the use of slickwater compared with other fluids
(Brannon and Bell 2011). It is believed that this is because of the
longer fracture length in the case of slickwater. In view of the
high rates encountered with these fluids in which very strong turbulent-flow conditions exist, friction reducers are added. This section will shed light on advancements related to the fluids used in
shale resources. These include new polymers as friction reducers
and new designs of slickwater treatments.
Sun et al. (2011) reported on the development and field application of a new friction reducer. The system is based on a synthetic polymer that can break efficiently with oxidizers. It is
believed that the polymer is polyacrylamide-based. It comes as a
water-in-oil emulsion. Upon contact with the fluid stream during
injection through the wellbore, the emulsion inverts and becomes
an oil-in-water emulsion. As such, the polymer is released and
hydrated in water to reduce friction. This process is very time sensitive. The authors reported an example in which it takes only 3
minutes for the fluid to reach the perforation (based on a well-tubing diameter of 5.5 in., a length of 15,000 ft, and an injection rate
of 100 bbl/min). Field data showed that the system requires a
maximum of 0.75 gptg compared with 1 to 1.25 gptg of similar
friction reducers. The system was used with an oxidizing breaker
package in oil- and gas-producing shales in a Texas-panhandle
field. The data indicated a 47% increase in oil cumulative production of the wells treated with the new polymer and the breaker.
For the gas wells, a 30% increase was realized.
Sun et al. (2013) reported on the use of a synthetic polymer as
a fracturing fluid in shale reservoirs. This was done to address the
challenges associated with the use of slickwater. Slickwater is
used at high rates, which translates into high velocities (100 bbl/
min through a 4-in.-diameter pipe translates into a velocity of 107
ft/s). The use of proppants at high velocities leads to blasting of
the pumping equipment. As such, polymers are used at low concentrations to substitute for slickwater. Guar has been used as a
replacement; yet, its increased cost in recent years posed a challenge. Therefore, the authors reported the use of a synthetic polymer with an oxidizing breaker. Their work shows that the system
can provide good suspension at low concentration of less than 3
gptg of polymer. The authors reported field applications of the
system in south Texas in the Eagle Ford shale. The comparison
data indicated that the system gives better results compared with
treatments using guar-based polymers. Kostenuk and Browne
(2010) reported a new approach by which the proppant settling is
reduced in slickwater fracturing. The idea is to coat the proppants
with a material that helps create bubbles around each grain. Thus,
the buoyancy of the proppant is increased and its settling
tendencies are reduced. The authors report approximately 23%

improvement in proppant settling with the new technique.
Conclusions
This paper presents a review of the available water-based fracturing fluids over the last decade for fracturing reservoirs with low to
moderate permeability (excluding frac-pack applications). The
review revealed the evolution of several developments. These
include use of cleaner guar-based polymers, use of synthetic polymers, and the use of larger-sized crosslinker molecules. In addition, the use of high-density brines as mixing fluids to reduce
surface pumping requirements is highlighted. Nanotechnology
can be a promising tool to present better-performing fluids. The
following major conclusions can be drawn.
1. The true zero-damaging fluid is still nonexistent.
2. Guar-based polymers are still being used for fracturing oil and
gas wells. This is because of their high shear stability and better cleanup compared with other systems.
3. When fracturing hot (400 F) reservoirs, synthetic polyacrylamide-based polymers can be used. However, their cleanup is
still in question.
4. The use of larger-sized boronic-based crosslinkers helped
reduce the concentration of polymers used in preparing fracturing fluids. However, no field application data have been
reported yet for this system.
5. Nanoparticles were used to improve leakoff of viscoelastic-surfactant-based fluids. They were also used to produce crosslinkers at lower concentrations. The use of these materials still
requires more research; however, the use of advances in nanotechnology provides a window of opportunity in the area of
fracturing fluids.
6. Produced water can present an opportunity to address environmental concerns about water preservation. This becomes very
important in shale reservoirs in which millions of gallons of
water are used. However, not all produced waters are compatible with fracturing fluids.
7. The environmental impact of fracturing-fluid chemicals
remains a major public concern.
Nomenclature
PBH bottomhole treating pressure, mL1t2, Pa
Pf friction pressure, mL1t2, Pa
Phydro hydrostatic pressure, mL1t2, Pa
PS surface treating pressure, mL1t2, Pa
Acknowledgments
The author would like to thank Ahmed Al Sarraj for his help with
the preparation of some of the figures presented in this paper. Jim
Crews, David Loveless, Satya Gupta, and Hisham Nasr-El-Din are
appreciated for many useful discussions. The technical editors of
this paper and the associate editor of SPE Production & Operations are highly appreciated for their valuable comments. Thanks
to Aramco Services Company and Saudi Aramco for permission to
publish this work.
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SI Metric Conversions
1 lbm/1,000 gal 0.119826427 kg/m3
1 bbl 42 gal
1 cp 1 mPas

F( F32)/1.8 C
Ghaithan A. Al-Muntasheri is a petroleum engineer working for
the US subsidiary of Saudi Aramco, Aramco Services Company
(ASC), in Houston, where he is the production technology
team lead. He has worked with Saudi Aramco for the last 13
years, and is still affiliated with the EXPEC Advanced Research
Center of Saudi Aramco in Dhahran, Saudi Arabia. He has
published 40 papers in refereed journals and international
conferences. Al-Muntasheri holds BS and MS degrees, both
with honors, in chemical engineering from King Fahd University
of Petroleum and Minerals, Dhahran, Saudi Arabia, and a PhD
degree (cum laude) in petroleum engineering from the Delft
University of Technology, Delft, The Netherlands. He is a member of SPE. Al-Muntasheri served as the chair of the SPE Saudi
Arabia Section for the 201112 term and as the chair of the
2011 Annual Technical Symposium & Exhibition in AlKhobar,
Saudi Arabia. He has received several awards, including the
2014 SPE Outstanding Young Member Service Award, the 2011
SPE Century Club Award, the 2011 SPE Outstanding Young
Member Regional Award, the 2011 World Oil Award for the
Best Production Chemical, the 2009 EXPEC ARC Award for the
Best Mentor, and the 2008 EXPEC ARC Award for the Best
Technical Presentation. Al-Muntasheri serves as a technical
reviewer for SPE Journal, the Journal of Canadian Petroleum
Technology, and the Arabian Journal for Science and Engineering. e-mail: ghaithan.muntasheri@aramcoservices.com.


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PO169552 DOI: 10.

2118/169552-PA Date: 18-November-14

A Critical Review of Hydraulic-Fracturing

ogy, in the design of new, efficient hydraulic-fracturing fluids. For

November 2014 SPE Production & Operations

PO169552 DOI: 10.2118/169552-PA Date: 18-November-14

Holtsclaw and Funkhouser (2010)

Holtsclaw and Funkhouser (2010)

Walters et al. (2009)

Huang et al. (2005);

Weaver et al. (2002a, b)

Gupta and Carman (2011)

Fakoya and Shah (2013)

Lafitte et al. (2012)

VES (quaternary ammonium)

Samuel et al. (1999, 2000)

VES (amidoamine oxide)

Huang and Crews (2008)

Sullivan et al. (2006)

VES/carbon dioxide emulsion

Chen et al. (2005)

Table 1Summary of fracturing fluids reviewed in this paper.

It also provides an easy-to-clean option from the formation after

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PO169552 DOI: 10.2118/169552-PA Date: 18-November-14

(e) Carboxymethylhydroxyethyl cellulose

(d) Carboxymethylhydroxypropyl guar

(f) Carboxymethyl cellulose (CMC)

(c) Carboxymethyl guar (CMG)

(b) Hydroxypropyl guar (HPG)

(g) Hydroxyethyl cellulose (HEC)

slickwater treatments and more hybrid treatments that use water,

turing. Guar is a high-molecular-weight biopolymer consisting of

November 2014 SPE Production & Operations

PO169552 DOI: 10.2118/169552-PA Date: 18-November-14

Harris and Heath (1998)

Fischer et al. (2001)

Fischer et al. (2001)

Fischer et al. (2001)

Qun et al. (2008)

Walters et al. (2009)

Walters et al. (2009)

Less residues polymer

Williams et al. (2012)

Less residues polymer

Williams et al. (2012)

Table 2Viscosity data of linear gels reported in this paper.

302 F (150 C). The polymer loading was 0.45% (approximately

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PO169552 DOI: 10.2118/169552-PA Date: 18-November-14

technology is its sensitivity to KCl. As such, alternatives to KCl,

Fig. 2Chemical structure of NAX (Fischer et al. 2001).

Synthetic Polymers. In recent years, the cost of guar beans

November 2014 SPE Production & Operations

PO169552 DOI: 10.2118/169552-PA Date: 18-November-14

(2011) reported 360 F (182 C) as the upper limit of guar use

Gupta and Carman

Gupta and Carman

Gupta and Carman

November 2014 SPE Production & Operations

PO169552 DOI: 10.2118/169552-PA Date: 18-November-14

Walters et al. (2009)

Walters et al. (2009)

Gupta and Carman