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Paper No.

03140
CORROSION 2003
Fluid Compatibility of Elastomers in Oilfield Completion Brines

J. Buc Slay and Thomas W. Ray


Halliburton Energy Services, Inc.
2601 Beltline Road
Carrollton, Texas 75006

ABSTRACT
Successful oilfield reservoir management includes the extraction of hydrocarbons from the earth using
metallic tools with elastomeric seals. During this extraction process, the seals are exposed to a wide
variety of media including diesel, oil- and water-based muds, strong bases, strong acids, solvents,
hydrogen sulfide (H2S), and corrosion inhibitors. Therefore, when selecting seal materials for oilfield
applications, it is critical that the compatibility of the elastomer and its environment as well as the
mechanical requirements of the completion equipment be considered.
This paper investigates the process of determining the fluid compatibility (FC) of elastomers and how
compatibility affects material selection for downhole applications. This paper focuses on the effects of
completion fluids (Bromides and Formates) on elastomers. Elastomer samples were conditioned at
temperatures between 175°F (80°C) and 380°F (193°C) for up to three weeks. Fluid compatibility was
characterized by measuring changes in hardness, thickness, and ASTM D412 tensile properties (TB, EB,
Mso, M loo).
Test results were modeled using the Arrhenius equation without entertaining an in-depth exposition of
the method.

KEY WORDS
Fluid compatibility, brine, completion fluid, zinc bromide, cesium potassium formate, elastomer, NBR,
HNBR, FKM, TFE/P, ETP

Copyright
2003 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are
solely those of the author(s) and not necessarily endorsed by the Association. Printed in U.S.A.

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Publication Right
Government work published by NACE International with permission of the author(s). Requests for permission to publish this manuscript in any form, in part
or in whole must be made in writing to NACE International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material
INTRODUCTION
Seal selection is one of the most important aspects to consider when planning the depletion of a
reservoir's hydrocarbon reserves. One must be able to recommend materials that will endure extreme
temperatures, pressures, and fluids over the life of short-term operations or for well completions that
might produce for more than 20 years. Wrong selections can lead to premature seal failure, lost rig time,
and lost profits for all companies involved.
Seals and seal materials are qualified for a particular application based on their initial mechanical
properties. These properties include resilience, extrusion resistance, explosive decompression
resistance, compliance at low temperature, good elongation, etc. For example, consider a three-piece
packer element. The center element must have good elongation and resilience to maintain a fluid/gas
tight seal between the mandrel and casing, while the end elements must provide extrusion resistance and
be stiff enough to contain the center element and energize the back-up system.
Mechanical-property changes that can be caused by incompatibility of elastomers with downhole
environments can lead to improper elastomer performance and failure. Tool manufacturers understand
how much variation in physical properties will be tolerable. Laboratory fluid compatibility (FC) tests
must be performed to simulate oilfield service with simple repeatable test methods even though these
tests do not exactly replicate stresses and strains experienced by seals in most cases. Fortunately,
changes in tensile properties also correlate well with changes in tear, compression set, and stress
relaxation. 1
Therefore, the objective of FC testing is to determine the long-term chemical and thermal stability of
elastomers using simple and repeatable test methods. This paper focuses on the effects of completion
fluids. Past efforts have focused on the effects of drilling fluids. 2'3

Modeling with the Arrhenius Equation


"For accelerated testing the most suitable model for making serious and convenient life-time predictions
for elastomers in various fluids; as for many chemical reactions of inorganic and organic materials like
oxidation (degradation) reactions in polymers, and physical processes like stabilizer migration in
,,~
polymers; is based on the law of Arrhenius.
The merits of the Arrhenius equation have been thoroughly reviewed in other publications, and this
technique will only be applied in this report. 1'4 FC tests are used to gather time to failure vs.
temperature data that are then used to determine the activation energy (AE) of a certain reaction. This
AE may be constant over a range of temperatures, fluid concentrations, and material thicknesses.
Therefore, AE may be used to predict time to failure for other conditions. The Arrhenius equation is
listed below as Equation 1.5

In K - lnA - ( Ea / R T ) (1)

K = time to failure criteria


A = frequency / concentration constant
Ea = Activation Energy (kJ / tool)
R = Universal gas constant = 8.31415 {J / (K tool)]
T = temperature (°K)

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A simple exponential relationship will be used to model reaction-rate relationships that do not
specifically involve a time to failure and temperature.

Elastomer Selection
Tests were performed with high durometer oilfield elastomers as shown in Error! Reference source
not found.. The rubber compounds represent materials, except ETP, that have been used in the field for
at least ten years and have well established material-property specifications. These materials are used in
many tools as thin cross section O-rings, bonded seals, V-packing and in thick cross-section packer
elements.
NBR. A copolymer of Butadiene and Acrylonitrile. NBR is the workhorse of the oil and gas
recovery industry. The NBR used in this study is sulfur cured and has a 40% Acrylonitrile content,
which gives the material good strength and oil resistance and is thermally stable for long-term use to
275oF (~35oc).
HNBR. A highly saturated NBR. HNBR has better thermal and chemical stability than standard
NBR because the double bonds have been removed through rehydrogenation. The HNBR used in this
study is sulfur cured and offers excellent extrusion resistance. HNBR can also be cured with peroxide to
get better chemical and thermal stability.
FKM. A fluorocarbon terpolymer of Vinylidene Fluoride and Hexafluoropropylene. These
materials have good inorganic acid resistance, poor base resistance, and if compounded properly, can
have exceptional high-temperature properties. They are susceptible to degradation by organic amine
corrosion inhibitors.
TFE/P. A copolymer of Tetrafluoroethylene and Propylene. TFE/P has good acid and base
resistance but will swell in oil-based muds (OBM) and aromatic solvents. Demanding oilfield
applications require the use of the 100H and 100S grade materials that offer excellent high- temperature
strength.
ETP. A terpolymer of Ethylene, Tetrafluoroethylene and Perfluoromethylvinyl ether. ETP
offers better base resistance than the FKM compounds but is still not considered a base resistant
material. The ETP has had limited oilfield use.

Fluid Selection
Oilfield fluid selection is based first on the impact the fluid will have on the reservoir, and second, on its
functionality. Fluids must have a certain viscosity, weight, chemical make-up, and may require
corrosion inhibitors, biocides, and oxygen scavengers to protect the metallic components. This work
focuses on two popular completion brine families known as Bromides and Formates. 6 The test
conditions for each fluid are listed in Error! Reference source not found..
Bromides. Bromides are generally acidic and have Bromine coupled with Zinc, Calcium, or
Sodium to add weight with ZnBr2 and CaBr2 being the heaviest and most acidic. These fluids are also
used as heat transfer media and can be very corrosive. Two different weight fluids were used in this
study.
Formates. Formates are generally basic and can be coupled with Potassium (KCOOH) or
Cesium (CsCOOH). Formates offer clean and solids-free completion brines with better HSE
characteristics than the Chlorides and Bromides. A single heavy 15.5 ppg Cesium Potassium Formate
was used for this study.
During an FC test, the active ingredients of the fluid can be depleted through absorption by the
elastomer, reaction with the elastomer, thermal degradation of the fluid, or secondary reactions in the

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fluid. This can lead to a plateau or even reversal in material property changes. As a result, fluids are
frequently replaced at 48-hour and one-week time periods. For example, alkaline brines may become
highly acidic in 48 hours (or less) when reacting with elastomers in the test chamber at elevated
temperatures. These fluid changes can falsify the final results. Polarity and pH of a fluid are good
initial indicators of their compatibility with elastomers.

Elastomer Characterization Methods


Modulus at 50%~ 100%~ and 200% (M50~ M100, M200). These values represent the stress at
50%, 100%, and 200% elongation respectively. This value represents the compliance of the material
and is much more repeatable than the TB and EB values. Because this measurement has good
repeatability and correlates well with compressive modulus and extrusion resistance, it the most valuable
tensile indicator of fluid compatibility.
Elonl~ation at Break (E~. The percent strain to break a tensile sample is highly affected by
internal flaws and irregularities in the surface of the sample and can easily have ___10% variation.
Because certain seal functionality relies heavily on good elongation, EB is the second most valuable
tensile indicator of fluid compatibility.
Tensile stress at Break (T~). This is the ultimate engineering stress required to break the tensile
sample. Because the ultimate strength is highly affected by internal flaws and irregularities in the
surface of the sample, these values can easily have _+10% variation. Ultimate tensile strength is the least
important tensile property measurement because it is not very repeatable, is least likely to change during
an FC study, and can be estimated by modulus and elongation values.
Hardness. Hardness is measured using a Shore A durometer mounted to a rack and pinion-
controlled stand according to ASTM D2240. A 0.200-in. (5 mm) thick, 90-durometer rubber pad is
placed below the tensile specimens to simulate a thick cross section. Hardness is measured in the center
of the grip region sitting closest to the bottom of the autoclave to improve repeatability. One must note
that hardness measurements rely on small scale surface strains and do not accurately measure the large
strain stiffness of an elastomer.
Thickness. The thickness of the tensile specimens is measured in the center of the gage region
to monitor swell across the thickness. Changes in thickness usually occur early in the FC testing.
Swelling of elastomers is often times reversible with no long-term effects. Shrinking of elastomers can
be caused by secondary crosslinking, crystallization, or additive extraction, which are not reversible.
Volume. Swell was not determined using volume change measurements in the work performed
for this paper but is recognized as the most accurate method of measuring swell in elastomers.
One must realize that sound material recommendations cannot be based solely on changes in hardness
and thickness properties but must also include tensile modulus, elongation, and strength measurements.
This concept is illustrated in Error! Reference source not found.. The data shows an NBR material
that appears to be compatible with this solution at 275°F when based on Hardness, Thickness, and TB
values. EB and modulus values reveal that the material is not compatible with this fluid at this
temperature and that the material will stiffen significantly in 3 weeks.
One must also consider that these FC tests are performed on very thin tensile specimens and that thicker
cross-section seals will require more time for the adverse effects of oilfield fluids to penetrate the
material, therefore increasing seal lifetime in some cases.

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EXPERIMENTAL
6-in.x 6-in.x 0.090-in. slabs were first molded and post-cured as needed, and then, stamped into standard
ASTM D412 Type II tensile specimens. Two specimens were used for each test-condition data point.
Unconditioned material properties were measured. Tensile specimens were hung unconstrained,
submerged completely in fluid, and sealed air tight in an autoclave during the conditioning process.
Samples were conditioned in 2 liters of fluid, and it was important that the fluid to elastomer volume
ratio was 25:1 or higher. The sealed autoclave was heated with heater bands to within _+0.2°F, and at
specific time intervals (24 hr, 48 hr, 1 wk, 2 wk, 3 wk), specimens were removed, cleaned, allowed to
return to room temperature, and properties measured. No additional pressure was added to the autoclave
during the conditioning process.
Individual tensile strength and elongation-to-break values may be thrown out or replicated, when
possible, if a specimen fails prematurely. In the event of premature failure due to an internal flaw and/or
artificial exterior crack, the modulus values up to the failure point may be retained.

RESULTS AND DISCUSSION

Bromide Exponential Relationships


Results for both test fluids show that the properties of fluorine containing materials ~ TFE/P, ETP, and
FKM (when compounded properly) changed less than _+15% during the tests. As a result, these
materials are recommended for long-term service in bromides at temperatures up to 325°F.
The NBR and HNBR are not generally compatible with ZnBr2, and this relationship is highly dependent
on concentration (fluid weight), temperature, and time. As a result, one can model the time- and
temperature-dependence using an exponential relationship so that concentration differences show up as a
curve shift. This point will be illustrated using M50 data.
The percent change in M50 (%AM50) data as a function of temperature for NBR and HNBR is shown in
Error! R e f e r e n c e s o u r c e not found, and Error! R e f e r e n c e source not found, respectively. Some of
the 275°F and 325°F data were not measurable because the samples experienced extreme degradation in
24 hours. These graphs show that as the temperature and fluid weight increased, the %AM50 values
increased with time. Therefore, the reaction rates or slopes increase as temperature and ZnBr2
concentration increase. The equations for each slope are noted on the graphs and also displayed in
Error! R e f e r e n c e source not found.. These slopes represent the time domain for failure since one can
choose an arbitrary failure criterion, and then, calculate the time required to reach that value using the
following equation:

Time- %AM50 (2)


Slope

For example, consider the failure criterion to be the time it takes for the M50 values to increase 30%.
Then, plug 30 into the above equation and divide by the slope to find the time it takes for a material in a
particular fluid at a certain temperature to reach the failure criterion time. The time in hours to reach
30%AM50 in each bromide fluid is listed in Error! R e f e r e n c e source not found..
The %AM50 vs. time slopes (d%AM50 / dt) for all material, fluid, and temperature conditions can be
represented in a single chart using an exponential relationship.
A simplified exponential relationship, which is the basis for the law of Arrhenius follows below"

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K = Ae x (3)

Taking the natural log of Equation 3 results in Equation 4 below:

ln(K) - m T + ln(A) (4)

ln(K) = In (d%AM50/dt)
m = dln(d%AM50) / c/I') / dI'
T = test temperature
Ln (A) = constant (y-intercept)

As seen in E r r o r ! R e f e r e n c e s o u r c e not found., the natural log of K was then plotted against test
temperature to reveal four simple relationships that define the fluid compatibility of HNBR and NBR in
ZnBr2. One can see that the two HNBR curves have very similar slopes (m = 0.257). This implies that
the degradation mechanisms do not change within the time, temperature, and concentration boundaries
of this experiment. One can also see that the curves shift to the right as the fluid weight decreases,
accurately predicting longer lifetimes. One can use this HNBR slope to predict performance across a
wide temperature range with other ZnBr2 fluid concentrations by running a single fluid compatibility test
at single test temperature. For example, one could predict M50 changes across the entire 175°F to 325°F
temperature range for a 16-ppg ZnBr2 by running a single test at 250°F and using Equation 4 with m =
0.257.
The complete 18.5 ppg NBR slope is steeper than the complete 17.5 ppg curve because the 18.5 ppg
curve only has two data points at 175°F and 225°F. This portion of the curve correlates well with the
175°F and 225°F data points from the 17.5 ppg curve. Therefore, a combination of the two curves was
used to estimate the slope of NBR in ZnBr2.

Bromide Arrhenius Relationship


To create a true Arrhenius relationship one must plot lifetime vs. temperature using the data from
E r r o r ! R e f e r e n c e s o u r c e n o t found., as seen in E r r o r ! R e f e r e n c e s o u r c e n o t found., that conform to
the following Arrhenius equation:

In K - l n A - ( E a / RT) (s)

K = time to reach a 30%AM50


lnA = frequency / concentration constant
Ea = Activation Energy of elastomers in ZnBr2
R = Universal gas constant
T = temperature

The slope of the Arrhenius plot in E r r o r ! R e f e r e n c e s o u r c e n o t found, equals - E a / R so that one can
solve for the activation energy (Ea) of the reaction. The activation energies for the reaction of HNBR
and NBR are listed in E r r o r ! R e f e r e n c e s o u r c e n o t found.. The activation energies for NBR and

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HNBR in ZnBr2 can be used to estimate lifetime (based on 30%AM50 data) for other concentrations of
similar fluids that maintain similar reaction kinetics.

Formates
As noted earlier, FKM materials are not base-resistant in fluids with a pH of 8 or more and at
temperatures above 200°F (93°C). As a result, FKM compatibility was so poor in the Formate
environments that the data did not merit further consideration.
ETP and TFE/P performance was mixed and highly dependent on test temperature. The changes in TB,
EB, and M50 are displayed in Error! Reference source not found., Error! Reference source not
found., and Error! Reference source not found, respectively. The 100% Modulus trend closely
resembled the 50% Modulus trend and is not displayed in this paper. The charts represent three test
conditions, which include changes after 1 week and 3 weeks at 325°F (163°C), and changes after 1 week
at 380°F (193°C). Hardness is not displayed because there was less than _+ 1.1% change in all three
conditions, which was not a significant measure of fluid compatibility in this case.
Error! Reference source not found, through Error! Reference source not found, reveals no
correlation or trends for data at different test temperatures. This illustrates the point that reactions are
highly temperature dependent and can completely change rather than simply accelerate at high
temperatures. Further testing and fluid analysis before and after testing will have to be performed to
pinpoint the changes in degradation mechanisms of the fluids and elastomers as the temperature
increases from 325°F (163°C) to 380°F (193°C). One must keep this point in mind when trying to make
lifetime predictions using time/temperature superposition.

CONCLUSIONS
Simple exponential relationships can be used to relate temperature and time to changes in
mechanical properties. Tensile modulus is the most valuable measure because it captures large-
scale strain and is not affected by internal and external flaws in the test sample. Elongation to
break is the next most significant tensile measurement.
Seal material recommendations and lifetime estimations can be made using the Arrhenius
equation and other exponential relationships when the fluid compatibility testing includes
measured changes and Hardness, Swell, and Tensile properties (TB, EB, MS0, M100).
Activation energy calculations should be based on tests performed at a minimum of three test
temperatures to ensure reliability of data. If activation energy is constant over a set temperature
range, superposition can be used to predict elastomer lifetimes in similar fluids with varying
concentrations or with materials of varying thickness.

REFERENCES

1. Schwarz, T., "Accelerated Testing for Lifetime Predictions for Sealing Materials in Drilling and
Completion Fluids." Corrosion 2001, Paper 01114.
2. Ray, T.W., Irby, R., "Elastomeric Material Considerations When Using Oil-base Drilling Fluids
in High Pressure/High Temperature (HP/HT) Environments." Paper #10, RAPRA, Oilfield
Engineering with Polymers 2001. London, UK.

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, Patel, A.D., "The Effects of Molecular Composition of Synthetic Base Fluids on Drilling
Elastomers." Corrosion 2001, Paper 01112.
° American Petroleum Institute, Bulletin on Testing of Oilfield Elastomers - A Tutorial, API
Bulletin 6J, First Edition, February 1, 1992.
5. Atkins, P., Physical Chemistry, Sixth Ed. W.H. Freeman and Company, New York, 1998.
6. Completion and Workover Fluids, 2lB.1 Revision No: A-0 / Revision Date: 03-31-98.

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