Phillip C.

Harris is a senior development chemist in the

Fracturing Group of the Stimulation Chemicals Section,
Chemical R&D Dept., Halliburton Services in Duncan, OK. He
obtained an MS degree in physical chemistry from Oklahoma
State U. in 1967. Before coming to Halliburton in 1979, Harris
worked for Eastman Kodak Co. during 1967-79. His primary
research interests are the chemical and physical properties of
two-phase fluids and continuous fracturing processes. He has
coauthored 14 SPE papers and holds four U.S. patents. Harris
currently serves on the Technical Review Committee.

sPEDistinguished
Author-sERIE$

Harris

Fracturing-Fluid Additives
Phillip C. Harris, SPE, Halliburton Services.

Summary. Fracturing-fluid additives serve two purposes: to enhance fracture creation and proppant-carrying capacity and to
minimize formation damage. Additives that assist fracture creation include viscosifiers, temperature stabilizers, pH-control agents,
and fluid-loss-control materials. Those used to minimize formation damage are gel breakers, biocides, surfactants, clay stabilizers,
and gases. This paper discusses the qualities and applications of each of these additives.
Introduction
Most wells drilled today are fracture-stimulated as part of the
completion process; if not fractured, these wells would not
sustain a commercial production rate. Fracturing fluids are
injected into a subterranean formation (1) to create a
conductive path from the wellbore extending into the formation
and (2) to carry proppant material into the fracture to create a
conductive path for produced fluids.
To create a fracture hydraulically, a fluid must be pumped at
high enough pressure to break down the rock and at high
enough rate to cause fracture extension. Although oil-based
fluids were the earliest used, more than 90% of today's fluids
are water-based. Aqueous fluids are economical and can
provide control of a broad range of physical properties as a
result of additives developed over the years.
Additives for fracturing fluids serve two purposes: to
enhance fracture creation and proppant-carrying capability and
to minimize formation damage. Additives that assist fracture
creation include viscosifiers, such as polymers and crosslinking
agents, temperature stabilizers, pH-control agents, and fluidloss-control materials. Formation damage is reduced with such
additives as gel breakers, biocides, surfactants, clay stabilizers,
and gases.
Viscosifiers
Much of the concern about fracture design in modern computer
simulators centers on the viscous nature of the fluid. Viscosity
affects both fracture geometry and proppant transport. More
viscous fluids generate wider and sometimes higher fractures
and allow less proppant settling during placement in the
formation. Water-soluble polymers from natural sources, guar
and cellulose, are used most often to prepare viscous fracturing
fluids. Chemical modification of these polymers has allowed a
broad range of physical properties to be attained. Derivatives,
such as hydroxypropyl guar, carboxymethyl hydroxypropyl
guar, or carboxymethyl hydroxyethyl cellulose provide
viscosity for fracturing wells with formation temperatures from
60 to more than 400F [16 to 204C].
Copyright 1988 Society of Petroleum Engineers

Journal of Petroleum Technology, October 1988

Wells with formation temperatures below about 150F

[66C] are successfully fractured with aqueous solutions of the
above polymers, often called base gel solutions. Sufficient
viscosity is generated from polymer concentrations of 30 to 50
Ibm/l,OOO gal [3.6 to 6 kg/m 3 ] to place low to moderate
proppant concentrations. For placement of high concentrations
of proppant, or for use in higher-temperature wells, additional
viscosity is needed. Higher viscosity incr~ases fracture width
in vertical fractures and improves proppant transport. Higher
viscosity is also needed to offset temperature-thinning effects
of polymer solutions at elevated temperature.
Crosslinkers
High viscosity may be attained by increasing polymer
conce~tration in the base gel solution or by crosslillking the
base gel. Increasing the polymer concentration is generally not
cost-effective and creates operational problems, such as sand
wetting and high pumping pressures. Crosslinking the base gel
polymer, usually with a transition-metal catiop., provides a
viscosity-multiplying effect at much lower cost than adding
more base polymer. Various crosslinking agents, such as
aluminum, antimony, borate, titanium, and zirconium, are
selected for compatibility with a particular base polymer and
its pH and thermal limitations. Profiles of fractp,ring-fluid
viscosity vs. increasing fluid temperature are shown in Fig.
for both base-gel-type fluids and typical delayed-action
crosslinked gelled fluids.
Crosslinking a polymer solution changes its nature from a
viscous fluid (like honey) to a viscoelastic fluid (like gelatin).
ViSCOelastic fluids may be degraded by pumping at highly
shearing conditions and are shear-history dependent.
Techniques have been developed to delay chemically or
theflually the onset of the crosslinking reaction until the highshear portion of the treatment in the tubing string has been
passed by the fluid. The viscosity increase resulting from
crosslinking may then occur when the fluid enters the lowsqear portion of the treatment in the fracture itself.
At temperatures above 225F [107C], guar and cellulose
derivatives chemically decompose owing to dissolved oxygen
1277

A. Base Gel Type Fluid

B. Delayed Crosslinked Gelled Fluid

1;
en

o
en
:>

Stimulation
Costs
Total Well Costs
Fig. 2-Well costs.

100

200

300

TEMPERATURE, of
Fig. 1-Fracturing-fluid viscosity profile vs. temperature.

in the treatment water. Because chemical breakdown will cause

reduction of viscosity, chemical stabilizers, such as methanol
or thiosulfate, are added. These stabilizers greatly slow down
the rate of viscosity loss at very high temperatures.

pH Control
Proper pH control is a key factor in gel properties. Fluid pH
affects initial polymer gelation rate, crosslinking properties,
viscosity stability, gel break properties, bacteria control, and
other properties. Fracturing fluids typically range from pH 3 to
10, although strong acids are sometimes used. Buffers, which
resist pH change, are prepared by combining a weak acid and
a weak base. Buffers cause pH to be maintained within a
narrow range so that desired fluid properties can be obtained.
FluldLoss Additives
Fluid-loss-control additives are materials added to the base
fracturing fluid to keep the fluid within the fracture. When
fluid leaks off into the rock matrix, it is no longer able to
generate additional fracture geometry or to transport proppant.
Because proppant remains within the fracture, loss of fluid will
cause an increase in proppant concentration. If the proppant
concentration gets too high, a bridge will form and fracture
propagation will cease.
Fluid leakoff is controlled by the formation of a gel filter
cake on the fracture faces. In low-permeability rocks, polymer
molecules are too large to enter the pore spaces in the rock, so
filtration occurs. Some volume of water, called spurt, is
initially lost to the formation before a gel filter cake is
established. Further loss of water is controlled by the
permeability and thickness of the gel filter cake. The rate of
deposition of gel filter cake increases with increasing polymer
concentration. In high-permeability formations, the amount of
spurt loss can be reduced by adding particulate materials with
a particle-size distribution similar to the size of the pore
openings in the rock matrix. Permeability of the gel filter cake
can also be reduced by adding a small concentration of suitable
hydrocarbon, well dispersed throughout the gelled fluid.
Gel Breakers
Once the fluid and proppant have been pumped into the
formation, the well usually is shut in for a period of time to
allow the fracture to close on the proppant and to allow the gel
to break. Chemical breakers are added to the gelled fluid to
1278

provide viscosity reduction for removal of the treating fluid.

Enzyme breakers are typically used below 140F [60C];
oxidizing breakers are used at higher temperatures.

Surfactants
Surfactants may be added for a variety of purposes. Surfactants
lower interfacial tension and hence capillary pressure. In lowpermeability formations, fluid is retained in very small pores
because of capillary pressure. Decreasing the capillary pressure
reduces the reservoir pressure needed to cause flowback of the
fracturing fluid. In cases where reservoir pressures are too low
to cause good recovery of fracturing fluids, gases, such as
nitrogen or CO 2 , may be added to assist the return of fluids.
The expansion of such gases from the formation into the
wellbore as the well is produced can improve fluid recovery
significantly.
Surfactants may be used with gases in high percentage (e.g.,
60 to 80%) to form foams. Foams produce high-viscosity
fluids for good proppant transport, contain very little water,
and provide excellent fluid recovery because most of the foam
is gas. Lower percentages of gas may also be used as a fluid
recovery aid to minimize formation damage. When less gas is
used, more liquid-phase viscosity is required either from more
base gel or from crosslinking the gel.
Surfactants also ease compatibility problems between the
fracturing and reservoir fluids. Potential emulsion formation
between aqueous fracturing fluid and reservoir oil can be
prevented by addition of a proper nonemulsifying surfactant.
Suspension of fines and dispersion of asphaltenes can also be
brought about with the proper surfactant.
Clay Stabilizers
Because formations may contain some clay minerals of either
swelling or migrating type, clay stabilizers may be added to
aqueous fracturing fluids. Clays in the rock exist in an aqueous
brine environment. Fracturing fluids must provide a
sufficiently high ionic strength that clays that are contacted by
the fluid will not undergo "ionic shock." Inorganic salts, such
as KCl, NaCl, NH 4 Cl, or CaCI 2 , are used to prevent shocking
the clays. In addition to salts, polymeric clay stabilizers are
often used. These polymers have multiple cationic groups
along the backbone of the polymer molecule that can attach to
anionic sites on clay surfaces. Such materials are also useful
for controlling fines migration.
Biocides
Biocides are additives developed to control growth of bacteria
in gelled fluids. Aerobic bacteria reproduce rapidly in warm
climates and can destroy the viscosity of a tank of gelled
fracturing fluid within a few hours. Anaerobic bacteria grow in
the absence of oxygen, a condition usually found in
hydrocarbon reservoirs. Inadvertent introduction of anaerobic
bacteria into a formation by a stimulation fluid may lead to
Journal of Petroleum Technology, October 1988

production of HzS within the reservoir. Biocides are available

to control both types of bacteria.

Design
The above discussion lists the major fracturing additives and
their overall purposes. Many variations in performance will
usually exist within a given class of additives. Proper selection
of additives depends on good information about formation
characteristics. Prestimulation testing of core samples or
formation fluids is often necessary for selection of the right
additives for a fracturing fluid. This fluid, when used with a
good pumping design, can produce a procedure for good
stimulation. A lack of knowledge of the formation only leads
to guesswork in choosing additives or calculation of a fracture
design that may be inappropriate. The cost of additives should
not be a factor in choosing fracturing fluid additives for the
design. As shown in Fig. 2, cost of the additive is insignificant
compared with the total cost of drilling and completing a well.
Because proper additive selection can "make or break" a
stimulation treatment, characteristics and performance of the
additives should be the prime considerations for selection.
A good stimulation design must then be executed properly
on location to achieve the desired stimulation of a well.
Additives must be metered at carefully controlled rates. Some
dry additives tend to lump when added to water, so solutions
or slurries are required for proper proportioning. Monitoring

Journal of Petroleum Technology, October 1988

of fluid viscosity and pH are needed to help ensure that

downhole properties obtained are those that were designed.
Good instrumentation and computer data acquisition of
important parameters undoubtedly help field personnel produce
a fracturing fluid with all the proper additives blended together
in the right proportions.

Review
Selection of fracturing-fluid additives and execution of a
stimulation design are key elements in well completion.
Commercial success of the well may depend on action taken
during this procedure. Considering the total investment in the
well, cost-cutting with respect to additives could result in false
economy.

51 Metric Conversion Factor

OF

CCF-32)/l.8

JPT
This paper is SPE 17112. Distinguished Author Series articles are general, descriptive
presentations that summarize the state of the art in an area of technology by describing
recent developments for readers who are not specialists in the topics discussed. Wrillen
by individuals recognized as experts in the area, these articles provide key references to
more definitive work and present specific details only to iliustrate the technology. Purpose:
To inform the general readership of recent advances in various areas of petroleum engi
neering. A softbound anthology, SPE Distinguished Author Series, Dec. 1981-Dec. 1983,
is available from SPE's Book Order Dept.

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