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Guidelines

for Selecting
Downhole Tubular
Materials for
Oil & Gas
Production Wells
(2000 Edition)
J W Martin
Major contributors: D Harrop, W Hedges
Sunbury Report No. S/UTG/023/00
dated February 2000

Main CD
Contents

S/UTG/023/00

Contents

CONTENTS
1. INTRODUCTION

2. BACKGROUND INFORMATION ON CORROSION ASPECTS.

3. INFORMATION REQUIRED TO ALLOW THE MATERIALS SELECTION TO BE


UNDERTAKEN.
5
4. USE OF MATERIALS SELECTION ROAD MAPS
5. QUESTIONS TO BE ASKED OF PROSPECTIVE SUPPLIERS.

7
11

6. PROPOSALS FOR TESTING CANDIDATE MATERIALS VIA REFERENCED


TEST PROTOCOLS.
12
APPENDIX A : GENERAL CORROSION RESISTANCE

13

APPENDIX B : CORROSION RESISTANCE OF CORROSION RESISTANT


ALLOYS

40

APPENDIX C : WHAT IS THE DEFINITION OF A "SOUR ENVIRONMENT"?

50

APPENDIX D : SULPHIDE STRESS CRACKING

52

APPENDIX E : WHAT OTHER FACTORS NEED TO BE CONSIDERED?

58

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Introduction

1. INTRODUCTION
Material selection of downhole tubulars is an important aspect of completion design. If the wrong
material is selected then premature failure can result, with considerable cost implications in both
replacing the tubulars and lost production.

The purpose of this document is to provide clear guidance that can be used by engineers to
carry out a first stage evaluation of the material requirements for the downhole tubulars. The
guidelines cover all aspects of corrosion and stress corrosion resistance, including sulphide
stress cracking in sour environments. Where the guidelines are unable to give unequivocal
recommendations on the material to be selected, test protocols are referenced which will allow
the choice of the optimum material for the intended duty.
Guidance is given on:
(a)

The information required to allow the assessment to be undertaken.

(b)

Materials selection for downhole tubulars, by the application of flow charts (road
maps) with references back to the text where necessary.

(c)

Questions to be asked of prospective suppliers.

(d)

Proposals for testing alternative materials via referenced test protocols

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Background Information on Corrosion Aspects

2. BACKGROUND INFORMATION ON CORROSION ASPECTS.


Background information on the various corrosion aspects relevant to the selection of materials
for downhole tubulars is contained in the Appendices. The subject matter of the appendices is
as follows:
Appendix A. Corrosion resistance of carbon/low alloy steels.
This appendix describes how the CO2 corrosion rate for carbon/low-alloy steel can be
estimated. A method for deciding whether the predicted corrosion rate will result in an
acceptable service life for carbon/low-alloy steel is indicated. Advice is given on what to do if
the corrosion rate estimates indicate that carbon/low-alloy steel would not give an adequate
life.
This appendix also includes a discussion on the use of downhole corrosion inhibition
programmes as a means of utilising carbon/low-alloy steel tubulars under corrosive conditions
where they would otherwise give an inadequate service life.
Appendix B. Corrosion resistance of corrosion resistant alloys (CRAs).
In this appendix the general and localised corrosion resistance of corrosion resistant alloys is
considered, particularly at the elevated temperatures often experienced downhole.
One of the most important aspects to be considered in selecting the right corrosion-resistant
alloy (CRA) for the intended application is the material's resistance to localised corrosion. The
two forms of localised corrosion of most relevance to downhole tubulars are pitting and
crevice corrosion. These aspects are considered in the appendix, with advice given on the
upper temperature limits for CRAs to avoid pitting corrosion and how to avoid crevice
corrosion.
Of the CRAs more commonly used for downhole tubulars, stress corrosion cracking is mainly
a concern with austenitic and duplex stainless steels. The mechanisms are discussed in the
appendix, together with advice on the application limits for the alloys to avoid stress corrosion
cracking in service.
Appendix C. What is the definition of a sour environment?
This appendix gives advice on how to determine if the service conditions should be considered
as "sour". This is based upon the definition of NACE Standard MR-0175 Standard Material
Requirements - Sulfide Stress Cracking Resistant Metallic Materials for Oilfield Equipment.
Appendix D. Sulphide Stress Cracking
This appendix describes the mechanism of sulphide stress cracking in sour conditions.
NACE Standard MR0175 is concerned with the resistance of materials to sulphide stress
cracking (SSC) in sour conditions. In some countries, such as the United States, the standard
is a legislative requirement, i.e. it must be applied there. Its application in materials selection is
discussed in the appendix.
It was recognised within BP some time ago that the use of the NACE Standard MR0175 alone
is not sufficient to allow the selection of the optimum material with adequate sulphide stress
cracking resistance. For example, the NACE Standard makes no reference to the in-situ pH,
which is known to affect the likelihood of sulphide stress cracking (SSC) of materials. In

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Background Information on Corrosion Aspects

addition, the testing solution used in assessing the acceptability of materials for sour service in
NACE is very severe (1 bar H2S, pH 2.8), meaning that the standard is very conservative
regarding which materials are acceptable for hydrogen sulphide service. Finally, there is
insufficient information in the NACE standard regarding the operating limits of many
corrosion-resistant alloys. Therefore, BP developed a methodology based upon laboratory test
results and some limited field experience, to allow the user to select the correct material for
the intended service. This methodology is discussed in the appendix.
Appendix E. What other factors need to be considered?
This appendix covers the issues of:
Mechanical Properties - limits on the maximum strength of materials to be used in sour
conditions are discussed, as are the effects of elevated temperature on the material strength
and isotropy in the cold worked duplex stainless steels.
Flow-Induced Damage - Erosion and Erosion-Corrosion - mechanisms of erosion and
erosion-corrosion are discussed, together with how to avoid and/or account for such attack in
downhole tubulars.
Galvanic Corrosion - the mechanism of galvanic corrosion is discussed, together with how to
avoid it in completion design.

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Information Required

3. INFORMATION REQUIRED TO ALLOW THE MATERIALS SELECTION TO


BE UNDERTAKEN.
A significant amount of information is required to fully establish the materials requirements for
downhole tubulars. However it is realised that, especially at the concept stage, the full suite of
required information may not be available. Therefore in the following listings two types of data
have been highlighted:
The minimum requirements to enable initial materials selection. This enables initial
materials selection for conceptual studies, order of magnitude estimates, etc.
Information required for final materials selection. This is required before preparing a final
specification for the downhole tubulars.
(1) Minimum Information Required
The design life in years
The type of well (i.e. whether oil or gas)
The partial pressure of H2S and CO2 in the gas phase
The operating and design temperatures/pressures (bottom hole, well head flowing/shut-in)
The bubble point pressure (i.e. for oil wells). Knowledge of this value is highly desireable
but not absolutely essential
The water composition (as complete as possible, but the levels of water salinity,
bicarbonate and organic acids as a minimum, to enable the in-situ pH to be estimated)
The material strength requirements
(2) Information Required for Final Materials Selection
The design life in years
The type of well (whether oil or gas)
The partial pressure of CO2 and H2S in a gas in equilibrium with the fluids (requires
knowledge of the bubble point pressure for oil wells)
The operating and design pressures/temperatures (bottom hole, well head flowing/shut-in)
The expected flow rates and regimes
The likelihood of sand production and likely rates (pptb [i.e. lbs/thousand barrels] for liquid
flows, lbs/mmscf for gaseous flows)
The water chemistry (to include full water analysis [Na+, Ca2+, K+, Mg2+, Fe2+, Ba2+, Sr2+,
Cl-, S2-, SO42-, HCO3-], amounts of fatty acids/salts [e.g. acetate, propionate, butyrite and
associated acids], pH)
Water Dewpoint Temperature for gas wells (if condensing water only is anticipated this
will help determine whether the downhole completion will be water wetted or not)

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Information Required

Predicted water cuts


Predicted changes in the field condition during service life of tubulars
Required material strength, pipe size, connection type.
Lowest ambient temperature (can be important when handling downhole equipment in
cold climes)

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Use of Materials Selection Road Maps

4. USE OF MATERIALS SELECTION ROAD MAPS


Three road maps have been developed for the selection of the optimum downhole tubular
material. These are:
(a) Materials Selection for Sweet Conditions - This should be used for well conditions
where there is no hydrogen sulphide present, or where only very low levels of hydrogen
sulphide are anticipated such that the conditions would not be considered sour (refer to
Appendix C for definitions of sour service).
(b) Materials Selection for Sour Conditions (Carbon/Low Alloy Steels) - This should be
used for sour conditions where the well fluid corrosivity is such that carbon/low alloy steels
are considered suitable (refer to Appendix A regards well fluid corrosivity).
(c) Materials Selection for Sour Conditions (Corrosion Resistant Alloys) - This should be
used for sour conditions where the well fluid corrosivity is such that carbon/low alloy steels
are not considered suitable.
The intention is that the Road Maps should be used in conjunction with these Guidelines.
They are not designed as stand alone documents.
Items dealt with in the Guidelines but not on the Road Maps that need to be considered in the
materials selection process for downhole tubulars include:
Use of carbon steel plus corrosion inhibition (Appendix A, Section 2)
Localised corrosion resistance of corrosion resistant alloys (Appendix B, Section 2)
Stress Corrosion Cracking of corrosion resistant alloys (Appendix B, Section 3)
Mechanical properties (Appendix E, Section 1)
Erosion and erosion-corrosion resistance (Appendix E, Section 2)
Galvanic Corrosion (Appendix E, Section 3)
It is not intended that the Road Maps/Guidelines should be all encompassing. The intention
is rather to flag the major considerations that need to be made in selecting downhole tubular
materials. With the very complex issues involved it is possible that there will be omissions.
Therefore it is incumbent upon the user of these Guidelines to ensure that all necessary aspects
of materials selection have been addressed before the final specification of materials.
In the road maps decision points at which it will be necessary to consult the relevant
specialist/s have been highlighted. The relevant specialists have not been identified in these
maps due to the likelihood of changes through the life of the document. If you are unsure who
the relevant specialist is, then advice on contacts should be available via the Corrosion &
Materials Networks.
In general, the road maps are intended to be self explanatory. If further information is
required on any of the aspects raised, the relevant specialist/s should be contacted.

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Use of Materials Selection Road Maps

MATERIALS SELECTION FOR SWEET CONDITIONS


NOTES
(1)
Gas fugacity should strictly be used which is what the corrosion Isoplots
are based on. The difference between fugacity and partial pressure
becomes significant at high pressures where simply using partial pressure
will result in over-estimating the corrosion rate and under-estimating the
pH.
(2)
If acetic acid is present in the produced water this can suppress formation
of potentially protective iron carbonate scales resulting in a higher than
predicted corrosion rate. This may also raise the value of Tscale and the
onset of the associated limiting corrosion rate condition; and how to view
the impact of erosion in the preence or absence of a protective scale. Care
must be exercised when applying the pH and CO 2 Corrosion Isoplots in the
presence of acetic acid and it is recommended that Specialist Advice is
sought under such circumstances.
(3)
It may be necessary to complete with a suitable CRA below the corrosion
inhibitor injection point if treating by continuous injection. See also the
section on Corrosion Inhibition in Appendix A.
(4)
If a corrosion inhibitor film and / or protective corrosion scale is present a
should be applied - is the fluid density in
limiting of velocity 200/
lbs/ft3 (1 kg/m3 = 0.06242). See also the Erosion Section in Appendix E.
(5)
The corrosion rate of 13%Cr does vary with T, PCO2 and pH in a similar
manner to carbon steel, although the corrosion rates are very much lower.
For information on calculating corrosion rates and on pitting behaviour for
13%Cr see Appendix B.
(6)
At high T and/or high chlorides 13%Cr will exhibit increased susceptibility
to pitting. Under such conditions Appendix B should be consulted. If in
any doubt Specialist Assistance should be sought.

INPUT

PCO2 / bara (1)


T oC

NO

CONSULT

in situ
pH?(2)

pH Isoplots

YES

H2S
present?

YES

q If PCO2 /PH2S 10 then pH Isoplot is affected by presence of H2S - Seek


Specialist Advice.
q H2S can reduce general corrosion rate by a factor 10 or more due to
formation of FeS - no account taken in CO2 Isoplots.
q H2S most likely to cause localised or pitting corrosion.
q Pitting rate taken as that from the relevant CO2 corrosion Isoplot; but
can get localised acidification inside a pit and galvanic affect of FeS film
accelerating pitting rate.

CONSULT
Materials Selection for
Sour Conditions Road
Maps

NO

Totally Solids Free

Solids
present?(2)

Yes/Dont
Know!

CONSULT

NO Specialist
Advice

Erosion Rate
0.1 mm/y

Erosion Section of
Appendix E

YES

YES

V > 13 m/s

CO 2 Corrosion Isoplots only strictly apply for


velocities 13 m/s - use with caution beyond this!
If in any doubt - Seek Specialist Advice.

NO

Detailed
analysis

CONSULT

NO

CO2 Corrosion Isoplots (2)

CR 0.1 mm/y

YES

Specialist
Advice

q Can use carbon or low alloy steels


q If H2S present note limits this may
impose - See Materials Selection for
Sour Conditions Road Map
q The affect of acetic acid can be
particularly pronounced here and
inhibition may be required(3, 4)

0.1mm/y<CR<10 mm/y
T 100oC

YES
q Carbon steel + corrosion
Inhibitor can be considered(3, 4)
q Check economics and logistics
against 13%Cr
q If H2S present consult Materials
Selection for Sour Conditions
Road Map

NO

0.1mm/y<CR<10 mm/y
T 150 oC

NO

YES
q Seek specialist advice on feasibility
of carbon steel + corrosion
inhibitor (3, 4)
q 13%Cr likely to be best option(5, 6) but
care needed above 120 oC
q If H2S present consult Sour Service
Road Map

CR>10mm/y
T 175 oC

T>175 oC

Specialist
Advice

YES
q 13%Cr should be considered(5, 6) but
care needed above 120 oC
q Super or Hyper grades 13%Cr for T
< 175 oC
q If H2S present consult Materials
Selection for Sour Conditions Road
Map

q GRE lined tubing is a possible alternative standalone option, but is not


commonly used for producing wells: main application is water injection.
Specialist advice should be sought if T > 80oC
q The economics of using CRA internally clad carbon steel over that for solid
CRA are questionable. There is limited experience with use of CRA clad
tubing.

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Use of Materials Selection Road Maps

MATERIALS SELECTION FOR TUBULARS - SOUR CONDITIONS- CARBON/LOW ALLOY STEELS


KNOWN DATA
THE CONDITIONS ARE SOUR WITHIN THE DEFINITIONS OF NACE MR-0175
CARBON/LOW ALLOY STEEL HAS ADEQUATE CO2 CORROSION RESISTANCE (SEE CHART I)
REQUIRED TUBULAR STRENGTH
IN-SITU pH AND pH2S
OPERATING & DESIGN TEMPERATURES

Apply Requirements
of NACE MR-0175

Yes

Is the
use of NACE MR-0175
a statutory requirement
for this
area?

No

Consider use of the


BP Amoco Methodology

Alternatively can use NACE MR-0175

Consideration can also be


given to using N80(Q+T),
C95 or proprietary Q+T
grades with a MAXIMUM
yield strength of 110ksi1

=>65oC

What is
the MINIMUM
exposure
temperature?

Establish required material


strength and downhole
pH and pH2S
<65oC

Sulphide Stress Cracking Performance Domain of


Sour Resistant Grade 110ksi Steel

Consideration can also be


given to using H40, N80,
P110 or proprietary Q+T
grades with a MAXIMUM
yield strength of 140ksi1

=<95ksi

Refer to Domain Diagram for the


material with adequate strength. If
no material with suitable pH/pH2S
resistance can be identified
apply requirements of
NACE MR-0175

What is
the required
material strength?

Solution pH

6.5

=>80oC

Acceptable
5.5

4.5
Unacceptable
3.5
0.003
0.001

=>107oC

Consideration can also be


given to using Q1251,2

0.1

1.0

10

Sulphide Stress Cracking Performance Domain of


Grade N80 Carbon Steel

Sulphide Stress Cracking Performance Domain of


Grade P110 Carbon Steel

>95ksi

6.5
Acceptable

Solution pH

Notes.
1. If temperatures below this minimum are expected, even for short
periods of time, then the higher temperature limit criteria for non-sour
grades should not be used.
2. Regardless of the requirements for the current edition of API Spec. 5CT,
the Q125 grades shall always (1) have a maximum yield strength of 150ksi;
(2) be quenched and tempered; (3) be an alloy based on Cr-Mo chemistry
(the C-Mn alloy chemistry is not acceptable).
3. For H40 material in sour conditions at temperatures less than 80oC
the maximum permissible yield strength is 80ksi

Consideration can be given


to using proprietary sour
resistant grades up to
110ksi SMYS
(Consult relevant specialists)

Solution pH

6.5

February 2000

0.01

pH2S (bara)

Consider API 5CT Grades


H403; J55; K55; L80 (Type 1)
C90 (Type 1); T95 (Type 1)

5.5

4.5

Acceptable
5.5

4.5
Unacceptable

Unacceptable
3.5

3.5

0.003

0.003
0.001

0.01

0.1

pH2S (bara)

1.0

10

0.001

0.01

0.1

1.0

10

pH2S (bara)

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Use of Materials Selection Road Maps

MATERIALS SELECTION FOR TUBULARS - SOUR CONDITIONS- CORROSION RESISTANT ALLOYS


KNOWN DATA
CRA GRADE REQUIRED TO OBTAIN ADEQUATE CO2 CORROSION RESISTANCE
(SEE CHART I)
REQUIRED TUBULAR STRENGTH
IN-SITU pH AND pH2S3
OPERATING & DESIGN TEMPERATURES
PRODUCED WATER CHEMISTRY (CHLORIDE LEVEL)

Notes:
1. Where more than one possible candidate material is identified,
the materials should be considered in terms of increasing
cost/corrosion resistance, i.e.

L80 13Cr Steel

95ksi and 110ksi Super 13Cr Alloys

22%Cr Duplex Stainless Steel

25%Cr Duplex Stainless Steel.


2. For the Super 13Cr Alloys Domain Diagrams have been
developed for high chloride (typical of produced water in oil/gas wells)
and low chloride (typical of condensing water in gas wells) conditions.
For intermediate chloride levels two courses of action are available:

Default to the high chloride domain diagram

Produce/use test data (pre-qualification) for the specific application that


demonstrates acceptability.
3. For high levels of H2S and/or for very high temperatures it may
be necessary to consider the use of highly alloyed austenitic stainless
steels (e.g. Sanichro 28, NIC-32, Incoloy 825) for temperatures below
175oC or nickel alloys (e.g. Hastelloy G3, Hastelloy C-276) for
temperatures aboove 175oC. Contact the relevant specialists.

Refer to Domain Diagram for the


materials with adequate strength and
corrosion resistance (Refer
to Chart I). Consider
in order of increasing cost/corrosion
resistance1 to select optimum
material

If
no material with suitable pH/pH2S
resistance can be identified
refer to relevant specialist

95ksi Super 13Cr Alloys2

22Cr Duplex Stainless Steel


6.5

110ksi Super 13Cr Alloys2


6.5

6.5

Acceptable
Further Assessment
Required

Solution pH

Acceptable
Acceptable

5.5

5.5

5.5

4.5

4.5

4.5
Further Assessment
Required

Unacceptable
3.5

Unacceptable

3.5

3.5

Unacceptable

0.02
0.001

0.01

0.1

1.0

10

0.001

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 22Cr Duplex Stainless Steel

L80 13Cr Steel

0.01

0.1

1.0

10

0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ski Super 13Cr Alloys in high Chloride (120,000 ppm Cl) Waters

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ski Super 13Cr Alloys in high Chloride (120,000 ppm Cl-) Waters

25Cr Duplex Stainless Steel


6.5

6.5

6.5

6.5

Solution pH

Solution pH

Acceptable
Acceptable

5.5

4.5

5.5

5.5
0.5

4.5

4.5

0.25

3.5

4.5

Further Assessment
Required

Unacceptable
Unacceptable

3.5

Further Assessment
Required

Acceptable

5.5

Acceptable

3.5

Unacceptable

3.5

Unacceptable

0.003
0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of API5CT L80 13Cr Steel

February 2000

0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 25Cr Duplex Stainless Steels

0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ski Super 13Cr Alloys in low Chloride (1000 ppm Cl-) Waters

0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ski Super 13Cr Alloys in low Chloride (1000 ppm Cl-) Waters

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Questions to be asked of Prospective Suppliers

5. QUESTIONS TO BE ASKED OF PROSPECTIVE SUPPLIERS.


In certain circumstances, for example if there is no 'standard' material that is suitable for the
intended duty, it may be necessary to consider the use of a 'proprietary' material outside the
scope of these Guidelines. In such circumstances there are a number of questions that the
prospective supplier should be asked to ascertain whether the proposed material may be
suitable for the intended duty. These include:
(a) Will the proposed material have adequate resistance to corrosion wastage, principally
general corrosion, pitting corrosion and crevice corrosion, under the anticipated service
conditions?
(b) Will the material have adequate resistance to sulphide stress cracking under all conditions
likely to be experienced during service?
(c) Will the material have an adequate combination of material strength and toughness under
the range of temperatures likely to be experienced? Is there any isotropy of the mechanical
properties in the material that need to be accounted for during completion design? Will the
material experience any loss of strength at the highest temperature anticipated in service? If so,
by how much?
(d) Is the material prone to stress corrosion cracking in the downhole environment (e.g. as a
result of chlorides)? If so, will it have adequate resistance under the expected service
conditions? (NB Remember to consider the issues for both the produced fluids and completion
brine environments, where appropriate)
(e) Is the proposed material compatible with other materials likely to be used downhole with
respect to galvanic corrosion? If not, what precautions will need to be taken?
(f) Has the material sufficient resistance to erosion and erosion-corrosion under the prevailing
conditions?

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Proposals for Testing Candidate Materials

6. PROPOSALS FOR TESTING CANDIDATE MATERIALS VIA REFERENCED


TEST PROTOCOLS.
In certain circumstances, for example if there is no 'standard' material that is clearly suitable for
the intended duty, it may be necessary to consider carrying out laboratory corrosion tests to
select the optimum material for the intended application. Aspects that need to be considered in
these corrosion tests, together with references to the preferred test protocols are as follows:
(a) Resistance to sulphide stress cracking.
A protocol has been developed based upon NACE TM-0177 smooth tensile tests, together
with constant extension rate tensile (CERT) and double cantilever beam (DCB) tests if
necessary. This is detailed in a separate Sunbury Report1.
An alternative simplified protocol is outlined in Appendix D.
(b) Resistance to stress corrosion cracking.
It is only necessary to consider other stress corrosion cracking issues for the corrosionresistant alloys, in particular the duplex and austenitic alloys. A testing protocol is outlined in
Appendix B.
(c) Resistance to general and pitting corrosion.
The resistance to general and/or pitting corrosion shall be determined using an "immersion
corrosion test". A testing protocol is outlined in Appendix B.

"Materials Assessment for Downhole Sour Service Applications; An overview", Sunbury Branch
Report PFB/135/124159, 14th May 1991.

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Appendix A

APPENDIX A : GENERAL CORROSION RESISTANCE


1. CO2 Corrosion
CO2 corrosion, or sweet corrosion, is the most prevalent form of attack associated with oil
and gas production and its understanding, prediction and control are key requirements to
sound design and subsequent assurance of operational integrity. The form of attack is often
localised - frequently referred to as Mesa attack - and, together with dissolved CO2 content
and temperature, is affected by flow, water chemistry, steel composition and the exposure to
mechanical damage of the surface corrosion scales often formed.
Several models are available to predict the CO2 corrosion rate for carbon and low alloy steels.
Of these the most commonly used is that of de Waard (Shell) et al which is empirical in origin
although its general applicability has been confirmed by test work in several independent
laboratories including BP Amoco, Sunbury. The basic equation relates corrosion rate to the
partial pressure of CO2 (PCO2), and temperature (T) with correction factors for pH and
formation of iron carbonate scale - both factors being affected by [HCO3-] (the concentration
of bicarbonate ions), PCO2 and T. The influence of flow - as mass transfer is a component in
the overall CO2 corrosion reaction - has been factored into the latest version of the de Waard
model on a semi-empirical basis. Correlation with field data generally shows the de Waard
model usually provides an acceptable prediction of the worst case situation.
The BP Amoco Corrosion Prediction Modelling guidelines2 use the latest versions of the de
Waard model adapted to include BPs experience and philosophy for application. These
guidelines provide a comprehensive approach to determining CO2 corrosion rate and the
application to detailed design.
No such models exist for Corrosion Resistant Alloys. However, standard grade 13% Cr does
exhibits a CO2 corrosion rate, albeit much lower than for carbon steel. Limited laboratory
work at BP Amoco, Sunbury(2) found that for a given set of conditions multiplying the
predicted CO2 corrosion for carbon steel by 0.0016 gave a reasonable estimate of that for 13%
Cr. Further information on the estimation of CO2 corrosion rates for 13%Cr steel is given in
Appendix B of these Guidelines. Duplex stainless steels and higher alloys are highly resistant
to purely CO2 corrosion and as such this is not a consideration in itself in determining the
suitability of these alloys. Chloride content, temperature, pH and presence of H2S are the key
factors which determine their acceptability where susceptibility to pitting corrosion and/or
cracking are the primary concerns (see Appendices B and D for further information).
There are no available CO2 corrosion models able to take direct account of the affect of H2S if
present- other than the small affect on pH. The presence of H2S may cause the models to over
predict the corrosion rate due to the presence of a highly protective FeS surface film.
However, this sulphide film can be susceptible to localised breakdown leading to severe pitting
corrosion under extreme conditions.
The other major complicating factor for predicting CO2 corrosion is the presence of acetic
acid. The influence of acetic acid is not well understood and is still being actively researched.
A primary role appears to be suppression of the formation of protective iron carbonate scale;
but there is also evidence of a direct affect on corrosion rate especially at low PCO2 where the
purely CO2 corrosion rate - ie. in the absence of acetic acid - would be acceptably low. As

Corrosion Prediction Modelling, Sunbury Report Number ESR.96.ER.066, November 1997.

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Appendix A

little as 10 ppm acetic acid can present a problem and Specialist Advice should be sought
where acetic acid is present.
Finally the presence of erosion, leading to erosion-corrosion, needs to be determined as under
certain conditions the CO2 corrosion rate is moderated by the presence of an iron carbonate
corrosion scale. If erosion is an issue this may lead to under prediction of the associated CO2
corrosion rate when simply applying the BP Amoco Guidelines(2). Erosion and erosioncorrosion are addressed in Appendix E of these Guidelines.
2. Materials selection for sweet conditions Road Map
The Materials Selection for Sweet Conditions Road Map is given in Section 4 of these
Guidelines. This is based primarily on consideration of the CO2 corrosion rate, but also takes
account of other key factors which will affect materials selection.
2.1. Use of the Road Map
The following text gives guidance on the use of the Road Map. The section headings in bold
letters refer to the various Information (indicated by a ) or Decision (indicated by a ) boxes
on the Road Map.

Input
The primary inputs are temperature (T in oC) and partial pressure of CO2 (PCO2 in bara)
defined as:
PCO2 = (mole % CO2 x Ptotal)/100.
The worst downhole conditions (upper limit) will be at the Bubble Point which defines
the maximum amount of dissolved CO2 and hence the maximum PCO2 in terms of CO2
corrosion rate. If the Bubble Point is not known the default should be the bottomhole
flowing or reservoir conditions - a conservative position. The lower limit will be
determined by the wellhead flowing conditions.
In situ pH?
For corrosion to occur free water must be present at the pipe wall. For a gas well
operating above the dew point corrosion should not be a concern. For oil wells the
water cut and flow regime will be critical to determining if the pipewall is waterwetted. A complicating factor for oil / water systems is the emulsion tendency of the
crude oil. For fully mixed flowing conditions the resulting emulsion will be water-inoil at low water cuts inverting to oil-in-water at high water cuts. The inversion point
will depend on the water cut, temperature and pressure and typically sits at about 30%
to 40% water. Exact determination will normally require measurement so the worst
case of water wetting should be assumed and refined later subject to specialist advice.
It should also be recognised that under certain specific conditions (e.g.
conditions/regions close to the gas break-out point) corrosion of carbon steel has been
experienced downhole even at very low water cuts (around 1% or even less).
Under multiphase conditions a range of flow regimes are possible - eg. for vertical
flow: bubble, churn and annular - which will depend on the superficial velocities of the
liquid and gas phases, the gas/liquid ratio (GLR) and the angle of inclination. Any
concerns should prompt specialist advice being sought. Again the worst case of water
wetting should be assumed for the first pass assessment.

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Appendix A

It is important to know the in situ pH at temperature and pressure. If a produced


water analysis is available this may well give a measured pH; however, care should be
taken to check that this is at temperature and pressure and not for the water after the
dissolved gases have been flashed off.
The pH Isoplots (in the absence of H2S - see next section for the case where H2S is
present) enable a ready estimate of what the in situ pH will be for a given T (up to
120oC - the limit of the pH model used) and PCO2. For gas wells with no production of
formation water the condensed water Isoplot should be used. For oil wells the other
Isoplots should be used which consider the affect of water salinity (at 3.5% and 10%)
and the presence of bicarbonate (50 to 1600 ppm which provides pH buffering) on pH.
If the produced water composition is not known then guidance from a Production
Chemist should be sought. If this is not immediately available then as an interim
position 10% brine with 50 ppm and 400 ppm bicarbonate should be considered.
It is also important to know if acetic acid is present in the water, something that is not
always analysed for: care also needs to be exercised in how acetic acid is measured in
the presence of bicarbonate Acetic acid can suppress the formation of potentially
protective iron carbonate scales (discussed later) and will affect the in situ pH. The
pH affect is not considered in the pH Isoplots and for any significant levels of acetic
acid present - in the range 10 to 100 ppm - a more exacting calculation of pH should
be undertaken. This is an area still not well understood and is still being researched to
develop better guidelines.
H2S Present?
A primary concern with the presence of H2S is susceptibility to Sulphide Stress
Cracking (SSC) and this is addressed in Appendix D.
For metal loss corrosion effected primarily by CO2 the presence of H2S, being and acid
gas, will affect the pH which in turn will affect corrosion rate. However, the effect on
pH is usually small. It is not possible to give generalised guidelines, and no corrosion
model exists which accounts for CO2 + H2S metal loss corrosion, but in conjunction
with the pH Isoplots the following may be applied in their use when H2S is present.
PH2S (bar)

PCO2 (bara) below which


the pH Isoplot is affected
by H2S

0.0001

Not affected

0.001

0.01

0.0034 (NACE sour service limit for


carbon steels, refer to Appendix C)

0.01

0.01

0.1

0.1

Where H2S is present below the above PCO2 limits increased acidification will result ie.
PCO2/PH2S 10. This can range between 0.5 and 3 pH units depending on the actual
PCO2/PH2S ratio and here pH modelling for the specific conditions is required.

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Appendix A

Once the pH has been fixed the CO2 Corrosion Isoplots can be consulted subsequent
to satisfying the remaining questions in the Road Map. For many cases where H2S is
present a protective iron sulphide film is readily formed often leading in practice to
very low corrosion rates below those given in CO2 Corrosion Isoplots. However,
should this protective film breakdown highly localised corrosion can result at rates at
least equal to those given in the Corrosion Isoplots: the risk will be greater where
erosion is a concern. Consequently, designing on the basis of achieving protection
from formation of an iron sulphide film is not recommended. Furthermore, subsequent
inspection and corrosion monitoring should pay particular attention to the possibility of
pitting corrosion being present.
Solids Present?
Here the principal concern is erosion-corrosion. Pure erosion provides a source of
metal wastage that will be at least additive to that due to the CO2 corrosion. Appendix
E provides guidelines for limiting the erosion rate to 0.1 mm/yr. It is considered that
as long as the rate of erosion can be limited to 0.1mm/yr or less then the risks of
unacceptable levels of erosion or of synergistic erosion-corrosion are acceptably low.
Carbon/Low Alloy steels
The presence / stability of a protective surface corrosion scale - iron carbonate
- on carbon and low alloy steels will be affected by erosion. A stable iron
carbonate scale forms when a critical temperature, Tscale, is exceeded for a
given PCO2. The CO2 corrosion model used to generate the Corrosion Isoplots
treats the influence of protective corrosion scale as being a limiting effect on
corrosion rate ie. for all temperatures > Tscale the corrosion rate is equal to that
at Tscale. The following graph shows how Tscale varies with PCO2.
230
210
190
170
150
130
110
90
70
50
0.0001

0.001

0.01

0.1

10

P C O 2 , bar

The nature of and long term dependence on such scale for protection is a
subject still being researched and one where there are conflicting results and
experience i.e. in practice corrosion rate often decreases for temperatures >
Tscale but there are some examples of the reverse effect. The BP Amoco
approach is therefore a pragmatic one for design purposes.

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Appendix A

As mentioned previously the presence of acetic acid can suppress the formation
of iron carbonate scales and /or maybe raise Tscale to a value higher than that
given above.
Erosion studies at Tulsa University have shown that where a protective iron
carbonate scale is formed but becomes damaged due to erosion rapid, highly
localised corrosion can result. Therefore if the erosion rate is > 0.1 mm/y
and the temperature is > Tscale Specialist Advice should be sought.
13%Cr Stainless Steel
Erosion, where the predicted rate is > 0.1 mm/y, will remove the naturally
forming surface oxide film which normally affords passivity to 13%Cr. (NB.
Film stability is temperature, pH and chloride ion concentration dependent.)
The resulting extent of corrosion will depend primarily on the speed at which
the 13%Cr is able to repassivate. For further information reference should be
made to Appendix E of these Guidelines and the BP Amoco Erosion Guidelines
Duplex Stainless Steels
These materials generally do not suffer from CO2 corrosion and so under
erosive conditions the wastage rate will equal the erosion rate.
u Flow Velocity > 13 m/s?
The 13 m/s limit applies only to carbon and low alloy steels and arises from the fact the
CO2 corrosion model used to generate the Corrosion Isoplots was developed from
corrosion data obtained at velocities up to 13 m/s. As the relationship is principally
empirical, extrapolation beyond this limit is questionable and Specialist Advice should
be sought.
The CO2 Corrosion Isoplots were in fact developed for a nominal fluid velocity of 3
m/s and pipe internal diameter of 4.5. While the CO2 corrosion rate is sensitive to
velocity - it has a mass transfer component to the reaction - for the purpose of this first
pass assessment the Corrosion Isoplots are acceptable up to 13 m/s.
n Consult CO2 Corrosion Isoplots
The CO2 Corrosion Isoplots provide a simple means of quickly estimating what the
corrosion rate for carbon and low alloy steels will be for the conditions of interest. For
13%Cr stainless steel refer to Appendix B. .
If you feel uncomfortable using this simplified approach, a more detailed analysis
maybe appropriate and can be acgieved using the CO2 corrosion model: this is best
done in consultation with Specialist Advice.
2.2. Corrosion Inhibition
This is covered in more detail later in this Appendix. BP Amoco experience and application
predominantly lies with flowlines and main export lines. The logistics, ease of deployment and
ability to effectively monitor performance downhole are important considerations which
generally have limited use of this approach for corrosion control downhole.
There are differences within the industry about how to account for inhibited corrosion rate at
the design stage. The BP Amoco Corrosion Prediction Guidelines2, for design purposes,

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Appendix A

assume for a correctly selected and applied corrosion inhibitor the inhibited corrosion rate will
be 0.1 mm/y. What then determines the acceptability over a given design / field / operational
life will be the time during which inhibitor is effectively deployed - due to upsets, under
injection, failed injections pumps etc. Applying this approach leads to a predicted effective
inhibited corrosion rate (CRinh) of:
CRinh = (0.1 x T + CRuninhib x (DL - T))/DL
where T is the time in years with effective inhibitor deployment (inhibitor availability), DL is
the design / field / operational life in years, (DL - T) is the time in years where effective
inhibitor depolyment is not achieved, and CRuninhib is the uninhibited CO2 corrosion rate taken
from the Corrosion Isoplots or from running a more detailed analysis using the BP Amoco
CO2 Corrosion model2. Inhibitor availability is normally taken as a maximum of 95% of DL
for design purposes.
2.3. Plastic Coated or Lined Tubing
This option is most commonly used for injection tubing. Uncertainties remain about the long
term performance when continuously exposed to hydrocarbons (plastic coated tubing) and
water (GRE lined tubing) and there is the risk of collapse under rapid decompression due to
gas permeating behind the coating / liner. In addition, the coatings/linings have upper
temperature limitations, the limiting temperature being dependant upon which coating/lining is
used. However, mechanical robustness is probably the most important consideration - during
handling / installation and subsequent running of downhole tools and wirelining operations.
Plastic coated tubing is particularly prone to mechanical damage, especially at joints, and as
such must be seriously questioned as a standalone corrosion control measure: the primary
benefit is more likely to lie with friction reduction. GRE lined tubing is therefore the only
standalone corrosion control option. Specialist advise should be sought for temperatures >
80oC for use of GRE lined tubing and 120oC for plastic coated tubing.
2.4. Corrosion Resistant Alloys
Where CO2 corrosion rates are unacceptably high, the use of 13%Cr stainless steel is often the
most cost effective and logistically attractive option. There are limitations with regard to H2S
- e.g. NACE limits the use of L80 13Cr steel to conditions where the partial pressure of H2S is
0.1bara or less and the pH is 3.5 or more - such that the presence or absence of H2S over life
needs to be rigorously questioned if considering this option (refer to Appendix D and the Sour
Condition Road Maps for further information) . The material also has limitations in terms of
pitting resistance which is temperature and chloride concentration dependent (refer to
Appendix B for further information: as a rule of thumb, its use is acceptable for chlorides <
50,000 ppm and temperatures 120oC. For temperatures > 120oC or chlorides above
50,000ppm refer to Appendix B and/or specialist advise should be sought.
The so called Hyper or Super grades of 13%Cr now available offer improved pitting and SCC
resistance, a higher temperature limit (ca. 175oC and no specific limit on chloride
concentration). However, they are not generic materials and performance is dependent on
composition, which differs from supplier to supplier, and specific application may require
laboratory testing to confirm suitability. Higher strength grades than API 5CT L80 13Cr steel
(i.e. 95ksi and 110ksi) are now readily available but resistance to H2S remains a major
limitation (refer to Appendix D). There also remains some question as to whether these alloys
are prone to chloride stress corrosion cracking (refer to Appendix D).
For use of higher CRAs - this will most commonly be duplex stainless steels - Specialist
Advise should be sought. Here there is a significant Capex cost penalty - duplex stainless steel
grades are typically 6 to 8 times the material cost of carbon steel; 13%Cr steel grades are

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Appendix A

typically 2.5 to 4 times the material cost of carbon steel. These penalties are significantly
lower when comparing installed costs.
3. Use of downhole corrosion inhibition programmes with carbon steel tubulars.
If a consideration of the available information indicates that specifying carbon steel is not
adequate to guarantee a suitable service life, alternatives will need to be sought. One such
alternative is to specify carbon steel, but add a suitable corrosion inhibitor to the fluids.
Generally the use of carbon steel with corrosion inhibition offers a cheap CAPEX option for
corrosion control. However, downhole corrosion inhibition is a complex issue, with the need
to consider many factors, e.g. type of inhibitor, application method, level of protection,
thermal stability, compatibility etc. In addition, there are many pitfalls with the application of
this method, i.e. sand production, flow rate, etc. can all affect the effectiveness of the
corrosion inhibitor programme, logistics of inhibitor supply to remote locations needs to be
considered (whether these are remote onshore locations or subsea well sites), etc. As a result,
great care needs to be taken in the design and operation of a downhole corrosion inhibition
scheme.
For these reasons it had not been common practice within BP to consider downhole corrosion
inhibition as a design strategy, rather this has been viewed as a corrective measure in
circumstances where the specified carbon steel proved inadequate, e.g. due to changing field
conditions. The preference within BP has been to use corrosion resistant alloys in
circumstances where carbon steel proved inadequate. However, given the ever changing face
of new field developments (e.g. the development of onshore gas and oil fields, the need to
minimise capex costs) it is likely that this option will be viewed more favourably in the future.
A very important question before deciding whether to consider a downhole corrosion
inhibition scheme is Does it provide the best whole life economic option ?
For pipelines over a few kilometres in length and all but the highest corrosion rates, inhibition
is usually the most economic option. For very short pipe sections the use of corrosion resistant
alloys is the best option.
For wells the answer is not always clear cut and is dependant on several factors. This usually
simplifies to a consideration of the risks involved in using inhibitors and the cost savings vs.
the cost of failure of the inhibitor approach. For offshore wells the high cost of getting
inhibition wrong usually results in corrosion resistant alloys being selected.
Benefits of Inhibition
Where practical, the use of Inhibitors allows the use of carbon steel and thus reduces
CAPEX.
If inhibitors are to be used in the flowline and pipeline systems then moving the location of
the injection point downhole essentially provides inhibition of the well without additional
inhibitor costs.
If the actual conditions differ from those predicted the type of inhibitor can be changed to
deal with them.
Concerns with Inhibition
If corrosion rates are high then any interruption in the scheduled treatment may result in
significant damage.

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Appendix A

Delivery of the chemicals downhole is more problematic than injection into pipe lines.
Installation of delivery systems can increase CAPEX.
Handling Chemicals
May cause operational problems ( e.g. foaming, emulsions )
Corrosion monitoring and/or inspection is essential (although inspection can be difficult)
Increased OPEX.
Treatment Options
There are two types of inhibitor treatment:
Batch Treatment
Periodic treatments with the chemical are applied to the metal surface. The inhibitor forms a
film on the surface which lasts until the next treatment. This method is not preferred, as its
effectiveness is dependant solely on film persistency (determines the time between treatments)
and it requires the well to be shut-in. It should only be used when the continuous method is
not practical.
Continuous Treatment
Inhibitor is continually injected into the fluids upstream of the location of corrosion. As the
fluids contact the metal surfaces the inhibitor adsorbs onto the surface to form a protective
film. Inhibitor must always be present in the fluid for the film and therefore the protection to
be maintained. This is the preferred method of inhibition.
3.1. Batch Treatment Methods
3.1.1. Tubing Displacement
This is the most common method of treating gas wells.
1. The well is shut in.
2. A concentrated solution (1 to 10%) of inhibitor is slowly pumped down the tubing to fill it
completely.
3. Care is taken to ensure the fluid does not enter the formation.
4. The fluid is allowed to contact the tubing for several hours ( 4 -24 )
5. The well is brought back onto production
6. Treatment is repeated every 2 to 12 weeks depending on conditions
This treatment is used successfully on low productivity wells such as rod pumped oil wells in
Texas, USA. Until 1998 BP Alaska used this method for their oil wells. The repeat interval
was 12 weeks. The treatment was stopped when the film life was determined to be less than
one week.

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Appendix A

In one variation on this theme a slug (sometimes called a pill) of inhibited solution is placed
in the tubing which is then pushed down to contact all of the tubing by a solvent. This
minimises the volume of inhibitor used and potential problems encountered when the well is
returned to service and the inhibitor flows back into the production stream.
In another variation the inhibitor is dissolved in a weighted carrier fluid such as a high
density brine. This allows the inhibitor to fall to the bottom of the well under the influence
of gravity and thus minimises the volume of solvents and intervention required. There is
insufficient evidence that this method works and hence it can not be recommended.
The following batch methods are designed to provide a continuos stream of inhibitor and may
be thought of as pseudo continuous methods. They can provide longer times between
treatments.
3.1.2. Formation Squeeze
1. The well is shut in.
2. A concentrated slug of inhibitor is pushed down the tubing and into the formation.
3. The inhibitor is allowed to contact the formation rock for several hours (4 to 24).
4. The well is brought back onto production.
5. Treatment is repeated every 3 to 12 months depending on conditions.
This method is used widely for scale control. For corrosion inhibitors the concern is with
plugging the formation and it is not recommended for low porosity (tight) formations.
3.1.3. Slow Release Inhibitors
The inhibitor is encapsulated in a slow release agent such as a wax, gel or capsule. This is
usually fabricated into spheres or sticks which are dropped or placed down the tubing where
they locate at the bottom of the well (in the rat hole).
In a variation on this method a container of inhibitor (a dump bailer ) is run on a wire line to
the bottom of the well. The bailer is tripped to release the product into the bottom of the well
There is little experience with such systems.
3.2. Continuous Treatment Methods
As already stated, continuous treatment is the preferred method. However, it is essential that
regular checks be made to ensure that:
1. The product is transported throughout the entire system to be protected.
2. The inhibitor is providing the required corrosion protection
3.2.1. Capillary String (Macaroni string)
A capillary string, typically 6mm ( ) diameter, is run from the wellhead and down the
annulus space to the bottom of the well, where it is connected to an injection valve into the
tubing. This location is usually just above the packer and so tubing below this must be
resistant to corrosion or be in non corrosive service.

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Appendix A

The capillary tubing is used to inject inhibitor into the bottom of the well.
This is probably the preferred method and is used in many locations.
Problems can occur with either the capillary tubing or the injection valve becoming blocked.
The capillary strings have a reputation for being difficult to install and retrieve ( e.g. Bruce,
June 1998 ).
3.2.2. Annulus Injection
In this method an injection valve is fitted at the bottom of the well just above the packer to
allow fluid in the annulus to be pumped into the tubing. The annulus is filled with a solution of
the inhibitor which is also pumped into it on a continuous basis. As the pressure in the annulus
rises it will exceed the differential setting on the valve and product will be injected into the
tubing.
Shell use this method on many of their gas wells around the world.
There have been problems with sludge formation in the annulus and blocking of the valves
(both open and closed ).
The valves usually sit in side pockets and can be removed using a wire line.

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Appendix A

pH ISOPLOTS

10

P CO2 , bara

0.1

0.01

0.001

0.0001
-4

-3

-2

-1

Log(Pco2)

Conversion of PCO2 to Log10 (PCO2) for use in subsequent pH Isoplots

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Appendix A

pH ISOPLOTS

Condensed Water

6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
3.00-3.50

6.50
6.00
5.50
5.00
4.50
4.00

-4

3.50

-3

3.00
120

-2
110

100

-1
90

80

Temperature, degC

70

Log(Pco2)

0
60

50

40

1
30

This case assumes no significant concentration of dissolved salts present and represents
water condensing from a wet gas.

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Appendix A

pH ISOPLOTS

3.5% Brine + 50 ppm Bicarbonate

8.00-8.50
7.50-8.00
8.50

7.00-7.50

8.00

6.50-7.00

7.50

6.00-6.50
5.50-6.00

7.00

5.00-5.50

6.50

4.50-5.00

6.00

4.00-4.50

5.50

3.50-4.00

5.00

3.00-3.50

4.50

-4

4.00
-3

3.50
3.00
120

-2
110

100

-1
90

80

70

Temperature, degC

Log(Pco2)

0
60

50

40

1
30

10% Brine + 50 ppm Bicarbonate

8.00-8.50
7.50-8.00
8.50

7.00-7.50

8.00

6.50-7.00

7.50

6.00-6.50
5.50-6.00

7.00

5.00-5.50

6.50

4.50-5.00

6.00

4.00-4.50

5.50

3.50-4.00

5.00

3.00-3.50

4.50

-4

4.00
-3

3.50
3.00
120

-2
110

100

-1
90

80

Temperature, degC

February 2000

70

Log(Pco2)

0
60

50

40

1
30

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Appendix A

pH ISOPLOTS

3.5% Brine + 100 ppm Bicarbonate

8.50-9.00
8.00-8.50
7.50-8.00

9.00

7.00-7.50

8.50

6.50-7.00

8.00

6.00-6.50

7.50

5.50-6.00

7.00
6.50

5.00-5.50
4.50-5.00

6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110

100

-1
90

80

70

Temperature, degC

Log(Pco2)

0
60

50

40

1
30

10% Brine + 100 ppm Bicarbonate

8.50-9.00
8.00-8.50
7.50-8.00

9.00

7.00-7.50

8.50

6.50-7.00

8.00

6.00-6.50

7.50

5.50-6.00

7.00
6.50

5.00-5.50
4.50-5.00

6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110

100

-1
90

80

Temperature, degC

February 2000

70

Log(Pco2)

0
60

50

40

1
30

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Appendix A

pH ISOPLOTS

3.5% Brine + 200 ppm Bicarbonate

8.50-9.00
8.00-8.50
7.50-8.00

9.00

7.00-7.50

8.50

6.50-7.00

8.00

6.00-6.50

7.50

5.50-6.00

7.00
6.50

5.00-5.50
4.50-5.00

6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110

100

-1
90

80

70

Temperature, degC

Log(Pco2)

0
60

50

40

1
30

10% Brine + 200 ppm Bicarbonate

8.50-9.00
8.00-8.50
7.50-8.00

9.00

7.00-7.50

8.50

6.50-7.00

8.00

6.00-6.50

7.50

5.50-6.00

7.00
6.50

5.00-5.50
4.50-5.00

6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110

100

-1
90

80

Temperature, degC

February 2000

70

Log(Pco2)

0
60

50

40

1
30

Page 27

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Appendix A

pH ISOPLOTS

3.5% Brine + 400 ppm Bicarbonate

9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00

9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110

100

-1
90

80

70

Temperature, degC

Log(Pco2)

0
60

50

40

1
30

10% Brine + 400 ppm Bicarbonate

8.50-9.00
8.00-8.50
7.50-8.00

9.00

7.00-7.50

8.50

6.50-7.00

8.00

6.00-6.50

7.50

5.50-6.00

7.00
6.50

5.00-5.50
4.50-5.00

6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110

100

-1
90

80

Temperature, degC

February 2000

70

Log(Pco2)

0
60

50

40

1
30

Page 28

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Appendix A

pH ISOPLOTS

3.5% Brine + 800 ppm Bicarbonate

9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00

9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110

100

-1
90

80

70

Temperature, degC

Log(Pco2)

0
60

50

40

1
30

10% Brine + 800 ppm Bicarbonate

9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00

9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110

100

-1
90

80

Temperature, degC

February 2000

70

Log(Pco2)

0
60

50

40

1
30

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Appendix A

pH ISOPLOTS

3.5% Brine + 1600 ppm Bicarbonate

9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00

9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110

100

-1
90

80

70

Temperature, degC

Log(Pco2)

0
60

50

40

1
30

10% Brine + 1600 ppm Bicarbonate

9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00

9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120

7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110

100

-1
90

80

Temperature, degC

February 2000

70

Log(Pco2)

0
60

50

40

1
30

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Appendix A

CO2 CORROSION ISOPLOTS


10

0.1

0.01

0.001

0.0001
-4

-3

-2

-1

L o g (P c o 2)

Conversion of PCO2 to Log10 (PCO2) for use in subsequent CO2 Corrosion


Isoplots

February 2000

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Appendix A

CO2 CORROSION ISOPLOTS


pH 3

55
50
45

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y

40
35
30
25
20
15

10

-1

0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 3

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix A

CO2 CORROSION ISOPLOTS


pH 3.5

45
40
35

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y

30
25
20
15

10
0

-1

0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 3.5

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix A

CO2 CORROSION ISOPLOTS


pH 4

40
35
30

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y

25
20
15
10

1
0

5
-1
0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 4

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix A

CO2 CORROSION ISOPLOTS


pH 4.5

30

25

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y

20

15

10
1
5

0
-1

0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 4.5

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix A

CO2 CORROSION ISOPLOTS


pH 5

25

20

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y

15

10

5
0
-1
0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 5

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix A

CO2 CORROSION ISOPLOTS


pH 5.5

20

15

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y

10

1
0
-1

0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 5.5

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix A

CO2 CORROSION ISOPLOTS


pH 6

15

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y

10

5
1
0
-1
0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 6

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix A

CO2 CORROSION ISOPLOTS


pH 6.5

10

n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
5

1
0
-1
0
30

Log(Pco2)

-2
40

50

60

70

-3

80

90

100

110

120

Temperature, degC

130

140

-4
150

pH 6.5

n
n
n
n
n
n
n
n
n
n

1.0
0.9
0.8
0.7
0.6
0.5
0.4

0.3

0.2

-1

0.1

-2

Log(Pco2)

-3

0.0
30

40

50

60

70

80

90

100

Temperature, degC

February 2000

0.9 - 1.0 mm/y


0.8 - 0.9 mm/y
0.7 - 0.8 mm/y
0.6 - 0.7 mm/y
0.5 - 0.6 mm/y
0.4 - 0.5 mm/y
0.3 - 0.4 mm/y
0.2 - 0.3 mm/y
0.1 - 0.2 mm/y
0.0 - 0.1 mm/y

110

120

130

-4
140

150

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Appendix B

APPENDIX B : CORROSION RESISTANCE OF CORROSION RESISTANT


ALLOYS
1. General corrosion resistance of corrosion-resistant alloys.
It should not be assumed that the corrosion-resistant alloys are immune to general corrosion in
CO2-containing environments. Specifically, it is known that 13%Cr steel is prone to general
corrosion at elevated temperatures. The rate of corrosion will be dependant on a number of
factors, including partial pressure of carbon dioxide, solution chemistry (particularly chloride
content), temperature. For many low temperature applications the rate of general corrosion
will be very low such that it will not be a concern. This led in the past to many steel
manufacturers putting a limit of 150oC on the use of 13%Cr steels. The origin of this limit
seems to be corrosion tests undertaken by the steel manufacturers in a 5% sodium chloride
solution with a CO2 partial pressure of 35bara. In these tests the acceptable corrosion rate was
considered to be 1 mm/yr, which occurred at 150oC. Clearly the use of a single 'blanket' figure
of this type will be unacceptable for many circumstances. Firstly, a wastage rate of 1 mm/yr
may not be acceptable, such that consideration will need to be given to other metallurgies.
Secondly, the conditions may be significantly less onerous than those used in the
manufacturers' tests, such that the 13%Cr steel can be used for temperatures in excess of
150oC.
A simple rule of thumb methodology has been established within BPX to obtain a first
order evaluation of the likely general corrosion rate for 13%Cr steel in sweet or mildly sour
conditions, as follows:
Establish the downhole pH (refer to Appendix A)
If the following criteria are met 13%Cr steel can be considered:
pH>4.0 and bottom hole temperature <120C
4.0>pH>3.5 and bottom hole temperature <95C
At temperatures greater than these limits, or for lower levels of pH, then to a rough first
approximation the corrosion rate of 13%Cr steel can be calculated using the following
formula:
Log10 (Vcorr) = 3.0 - 1710/(t+273) + 0.67log10 PCO2
Where:
Vcorr is the corrosion rate in mm/yr
t is the temperature in C
PCO2 is the partial pressure of CO2 in bara
If the value obtained from this analysis represents an acceptable corrosion rate (see
Appendix A for further details) then the use of 13%Cr steel can be considered.
For conditions beyond those for which the use of 13%Cr steel can be justified it has been
necessary to consider higher metallurgies with improved passive films and hence improved
general corrosion resistance (e.g. duplex stainless steel, austenitic stainless steel, nickel alloys).
However, in the past 2 to 3 years a new family of chromium steels have been developed for

February 2000

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Appendix B

downhole tubulars known as the alloyed martensitic 13%Cr steels. These alloys are a
development of the conventional 13%Cr steels (e.g. API 5CT L80 13%Cr steel) to which
alloying elements of nickel (typically 4 to 6%), molybdenum (typically 0.5 to 2.5%) and
possibly copper (up to 1.5%) have been added. These have a number of advantages over the
conventional 13%Cr steels, including:
Higher strength/toughness (available in strengths up to 110ksi)
Much better corrosion resistance at high temperatures (>120C)
Slightly better resistance to sulphide stress cracking under sour conditions (i.e. for
the same strength level)
These have been found to have good general (and pitting) corrosion resistance over a wide
range of conditions up to a temperature of 200C. Indeed, tests undertaken at BP Sunbury3
indicated good general (and pitting) corrosion resistance in a high chloride (120,000ppm)
solution at a pH of 3.5 and a temperature of 200C. Some manufacturers on the other hand
indicate that these alloys have good general/pitting corrosion resistance for all levels of
chlorides only up to a temperature of 175C. Therefore, given that this is a relatively new
family of materials with a potentially wide range of chemical compositions and that field
experience is relatively limited further laboratory testing will be required for specific field
applications.
2. Localised corrosion of corrosion-resistant alloys.
2.1. Pitting Corrosion.
Pitting corrosion occurs when certain regions on the metal surface become fixed anodic sites.
An example of this is the pitting of stainless steels in chloride-containing solutions. The
likelihood/rate of pitting corrosion is dependant on a number of factors, notably produced
water chemistry (particularly chloride content, pH), level of dissolved gases (CO2, H2S and
O2) and operating temperature.
However, the pitting process is strongly affected by temperature, with the propensity towards
pitting increasing with increasing temperature. The result is that for many CRAs a critical
temperature can be defined below which pitting corrosion will not be a significant risk. A
programme of work was undertaken within BP to develop a test protocol for determining the
temperature service limits for CRAs. This protocol was used to determine the temperature
service limits for two of the most commonly used CRAs for downhole tubulars, i.e. 13%Cr
steel (which has been found to be prone to pitting in the presence of hydrogen sulphide) and
25%Cr/7%Ni duplex stainless steel. Two temperatures were determined using different
techniques. In the first, an immersion test was used to determine the temperature at which pits
start to form, this was designated the onset of pitting temperature. However, it was
determined that there is a temperature range above the onset of pitting temperature over which
only non-propagating pits form, i.e. pits will form but they will not grow, such that they are
not normally harmful to the integrity of the tubulars. Therefore, an electrochemical noise
technique was developed to allow the determination of the temperature at which significant pit
growth will commence. This was designated the propagating pit temperature. Both these
temperature limits are quoted in Table B1 for a range of environments. These temperatures
can be used as the service limits for the material/environment combination, with the lower
3

Downhole Tubulars - Evaluation of the application regimes for super 13%Cr Alloys;
ESR.96.ER.008, January 1996.

February 2000

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Appendix B

(onset of pitting) temperature limit being used for conditions where even superficial pitting is
unacceptable and the upper temperature limit being used where superficial pitting is
acceptable, as long as it will not lead to perforation. Clearly, this is not the end of the story.
Even above the temperature at which propagating pits form there is likely to be a temperature
range over which the rate of pitting is acceptable, i.e. the required service life will be
achieved. For 13%Cr steel, as an initial rough estimate the possible rate of pitting can be
evaluated using the methodology outlined for general corrosion in Section 1 of this appendix
(Appendix B). However, given the different nature of the attack it is recommended that this is
confirmed via service experience under similar conditions or laboratory tests. In the case of
duplex stainless steels the evaluation of such situations is outside the scope of the present
guidelines. If it is intended to consider these materials for use in the pitting regime region, it
will be necessary to undertake service history evaluations/laboratory tests under the specific
field conditions, to demonstrate the acceptability of the candidate materials for the intended
service duty/life.
When using Table B1 for determining the acceptability of candidate materials for the intended
service it will be necessary to know the operating temperature, downhole pH (this can be
evaluated using the Methodology outlined in Appendix A) and equivalent chloride level.
Clearly, if the intended service conditions are less onerous than those quoted in Table B1, then
the material is acceptable up to the temperature given. It is possible that it will be acceptable
to even higher temperatures than those given, if the intended service conditions are
significantly less onerous. This can only be determined by service experience on similar
conditions or a series of laboratory evaluations using the test protocols outlined in Section 4 of
this appendix (Appendix B). In addition, the use of materials other than those stated in Table
B1 will require justification via documented good previous service experience or further
testing if there is a concern about pitting corrosion.
For the alloyed martensitic 13%Cr steels (such as Sumitomos Super 13Cr alloy) tests
undertaken at BP Sunbury indicated good general pitting corrosion resistance in a high
chloride (120,000ppm) solution at a pH of 3.5 and a temperature of 200C. However, given
that this is a relatively new family of materials with a potentially wide range of chemical
compositions and given that field experience is relatively limited it may well be that further
laboratory testing will be required for specific field applications
2.2. Crevice Corrosion.
Crevice corrosion is the localised damage that can result in a narrow gap or "crevice" between
two adjacent components. Examples of crevices that can occur in downhole tubulars are at
interfaces between two joints, under deposits, in contact with downhole jewellery, etc. The
local environment produced within the crevice can be quite different to the bulk fluid
environment, leading to corrosion damage which could not be predicted from the general fluid
composition. The likelihood and rate of crevice corrosion is dependant on a large number of
factors. These include solution chemistry and service temperature, as with pitting corrosion.
However, the factors also include crevice geometry and the changes in this geometry as the
crevice develops. This makes it extremely difficult to establish the "maximum service
temperatures" to avoid crevice corrosion. Therefore, in downhole tubular designs steps need
to be taken to ensure that crevices are, as far as possible, eliminated. In this way the risk of
crevice corrosion can be minimised so that the material can be used up to the service
temperature limit indicated from a consideration of pitting corrosion.
It is recommended that the following steps are taken to minimise the risk of crevice corrosion:
(i) Use only "premium" connections with CRAs. These connections have an energised
metal/metal seal on the inner diameter that minimises the size of any crevice so formed. Good
experience has been achieved with these types of joint and problems of crevice have only been

February 2000

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Appendix B

observed under conditions where an unsuitable material was chosen in the first place (e.g. the
use of 13%Cr steel for sea water containing oxygen, even at low levels).
(ii) Prevent significant scale build up. Significant scale build-up, as well as possibly affecting
the well productivity by affecting the throughput of the tubulars, can lead to crevices at the
scale/metal surface interface leading in turn to crevice corrosion. Therefore, if necessary, steps
should be taken to prevent significant scale build-up, e.g. by de-scaling treatments, use of scale
inhibitors, etc.
(iii) Ensure that due consideration is given to the potentially adverse effects of crevices in the
design of any downhole jewellery and that steps are taken to minimise the number of crevices.
3. Stress corrosion cracking of corrosion-resistant alloys.
(a) 13%Cr steel and alloys
The martensitic 13%Cr steels (e.g. API 5CT L80 13%Cr Steel) are not prone to stress
corrosion cracking in downhole environments. Hence there is no need to consider the stress
corrosion cracking behaviour of these materials for downhole applications.
There have been some indications in the literature that the alloyed martensitic 13%Cr steels
(such as Sumitomos Super 13Cr alloys) may be prone to chloride stress corrosion cracking
(CSC). However, tests undertaken at Sunbury4 did not reveal any signs of CSC under typical
produced water conditions. Therefore, it is not presently envisaged that CSC will be a
problem for produced fluids with this family of materials. However, given the limited test data
and service experience, care should be taken in their application in respect of the possibility of
CSC (e.g. check with the supplier/s and/or undertake evaluations if/when necessary). In
addition very recently (i.e. in 1999) there has been a case within BP Amoco of a 95ksialloyed
martensitic 13%Cr steel tubing string suffering from cracking. This initiated from the external
surface, i.e. the surface in contact with the completion brine. This incident is still be
investigated, but at the present the most likely cause is CSC in the calcium chloride high
density completion brine. Therefore, extra care needs to be exercised in the selection of
completion brines for use with this family of materials.
(b) Austenitic Stainless Steels
In principle, the austenitic stainless steels can be prone to CSC in typical downhole
environments. This type of cracking is exacerbated by increasing temperature. It is also known
that such cracking can be exacerbated by the presence of hydrogen sulphide. The possibility of
such cracking has meant that only alloys that are very resistant to it have been selected for
downhole applications in the past. For example, the NIC 32, Sanicro 28, type alloys are often
considered for downhole tubulars in place of the cheaper and more common AISI 300 series
stainless steels. These alloys have not been widely evaluated within BP Amoco. However,
there is some limited information available from the manufacturers. For example, NKK
indicate a temperature limit for NIC-32 (22%Cr, 4.5%Mo, 32%Ni) of 175C, if CSC is to be
avoided. It is recommended that if such alloys are being considered, the relevant specialist
should be consulted.

Downhole Tubulars - Evaluation of the Application Regimes for Super 13%Cr Alloys,
ESR.96.ER.008, January 1996.

February 2000

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Appendix B

(c) Duplex Stainless Steels


The duplex stainless steels are prone to some "unique" mechanisms of stress corrosion
cracking as a result of their duplex (ferrite/austenite) structure. Early work by Japanese steel
manufacturers showed that there was a possibility of stress corrosion cracking at elevated
temperatures in sodium chloride test solutions containing dissolved CO2 and H2S. The work
indicated that stress corrosion cracking was exacerbated by increasing levels of H2S,
decreasing pH and increasing chloride content. The cracking is thought to be the combination
of a chloride stress corrosion cracking mechanism and a hydrogen assisted mechanism
cracking (e.g. SSC) and/or selective corrosion of the ferrite phase leading to "crack-like"
defects. Many workers have indicated that this type of cracking is most severe in an
"intermediate" range of temperatures (e.g. 60 to 100C), such that tests are often carried out
at 80oC to represent a "worst case". However, work at Sunbury indicated that the
temperature range for most severe cracking is dependant on the type of duplex stainless steel
and test environment, with the most severe range being 20 to 60C in some circumstances.
Therefore, for any particular environment it is necessary to consider testing across the full
temperature range if the worst case for cracking is to be covered.
A series of stress corrosion cracking tests were undertaken at Sunbury to determine the
application limits for the two duplex stainless steels most commonly used for downhole
tubulars (22%Cr/5%Ni [UNS S31803] and 25%Cr/7%Ni [UNS S32750]). These have been
plotted in terms of pH v. PH2S plots, in a similar manner as for sulphide stress cracking (SSC)
resistance of ferritic/martensitic materials, as described in Appendix D. For ease of use these
have been included with the other Individual alloy go/no go charts at the end of these
Guidelines.
In addition very recently (i.e. in 1999) there has been a case of a 130ksi 25%Cr super duplex
stainless steel tubing string suffering from cracking. This initiated from the external surface,
i.e. the surface in contact with the completion brine. This incident is still be investigated, but at
the present the most likely cause is CSC at high temperature (around 130C) in the calcium
chloride high density completion brine. Therefore, extra care needs to be exercised in the
selection of completion brines for use with duplex stainless steel.
4. Test Protocols.
4.1. General/Localised Corrosion.
The following immersion test protocol can be used as part of the material pre-qualification
process to determine the suitability of a candidate material for the intended application with
regards to general/localised corrosion resistance:Specimen and Preparation The specimens shall be taken from the tube wall and shall
measure a minimum of 25mm x 50mm. Specimens shall be ground flat to a 600# paper finish
on one side and left as manufactured on the other side. Specimens shall be thoroughly
degreased, dried in a nitrogen gas stream, weighed and finally kept in a desiccator prior to
immersion.
Solutions
a) Prepare base solutions to represent the:
Produced Water Chemistry - for the case of oil wells or gas wells in which
produced water is anticipated.
and/or

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Appendix B

Condensed Water - for the case of gas wells. For the purpose of these tests distilled
water with 1000ppm of sodium chloride should be used.
b) Deaerate fully using oxygen free nitrogen prior to specimen immersion. Insert the
specimens, close the autoclave and re-deaerate fully by nitrogen. Purge the test solution using
the CO2 and/or H2S mixture for a period of at least one hour and then add CO2 and/or H2S up
to a suitable pressure such that at the test temperature the partial pressures of these gases
anticipated in service is achieved.
c) Heat to the test temperature (this should represent the anticipated bottom hole
temperature).
(Note: During the immersion, specimens should be kept away from direct contact with the
autoclave wall and other specimens.)
Reagents The reagents shall be high purity grades.
Acidic Gases High purity CO2 and H2S gas shall be used.
Solution Volume This shall be a minimum of 30 cc/cm2 of specimen.
Test Duration Test duration shall be kept to a minimum of 30 days.
Post Exposure Analysis The specimens shall be examined immediately after exposure and
their condition noted. They shall then be mechanically cleaned by scrubbing with a soft brush
under running water followed by the application of an appropriate cleaning solution (e.g.
inhibited acid) to remove any scale (refer to ASTM Standard G1, latest edition). Specimens
shall be dried and re-weighed to identify the weight loss. After weighing the specimens shall
be visually examined for corrosion/pitting with the aid of a stereo microscope at X40. In case
of pitting, all pits which are greater than 0.1mm diameter shall be reported. The report shall
include the number, maximum depth (mm), population per unit area of pits and pitting rate
(mm/yr).
4.2. Stress Corrosion Cracking.
The following test protocol can be used as part of the material pre-qualification process to
determine the suitability of a candidate material for the intended application with regards to
stress corrosion cracking resistance:Test Solution
The test solution shall consist of NaCl (at a concentration to simulate the level of Cl
anticipated in the produced water) + sodium acetate (CH3COONa, at a level sufficient to
buffer the pH, e.g. 0.86g/l has often been used in the past)5 in distilled or de-ionised water.
The procedure for solution preparation shall be as follows:a.

prepare a base solution of NaCl in distilled or de-ionised water

b.

Add the sodium acetate (CH3COONa)1

As an alternative to the acetate/hydrochloric acid buffering system, a bicarbonate/CO2 buffering


system may be offered for approval by BP Exploration.

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Appendix B

c.

Acidise using concentrated hydrochloric acid 1 down to a pH representative of the in


situ pH anticipated in the downhole tubulars.

d.

Introduce the solution into a test vessel, deaerate and saturate with a mixture of
CO2/H2S with the following gas ratios:

H2S at the partial pressure anticipated in the downhole tubulars, with the balance being CO2
up to the ambient test pressure (1 bar)
During the test the pH may alter, but shall not exceed a value 0.2 above the target figure. This
will be achieved through complete exclusion of oxygen and maintaining a sufficient solution
volume to test piece surface area ratio.
Test Temperature
The temperature shall be maintained at ambient (23oC)
Reagents
The reagents shall be in accordance with those specified in NACE TM0177-96 Section 3.
Acidic Gases
High purity H2S/CO2 gas mixtures shall be used. The test solution shall be purged with the gas
mixture throughout the test period.
Test pieces
All test pieces shall be machined from the pipe wall in the longitudinal direction
Test Vessels and Solution Volume
These shall be in accordance with those specified in NACE TM0177-96 and ISO 7539-1:
1987.
Number of Tests
A set shall comprise duplicate tests.
SSC Test Method
A smooth test piece tensile test shall be carried out in accordance with the procedures
specified in NACE TM0177-96 (Method A) and the additional requirements described in this
document.
Both types of stress fixtures and test containers used for stress corrosion testing are
acceptable; namely, constant load devices or sustained load (proof ring of spring loaded)
devices (ASTM G49-76).
Failure Appraisal
Total fracture of a test piece during the 720 hour test period shall be considered a failure.
To be considered a pass, the gauge length of the test piece shall be free from any signs of
fissure and/or cracks, after the exposure period. This may be assessed through visual

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Appendix B

examination of the gauge length (at a magnification of x10) plus one of the following
procedures: Metallographic examination of the gauge length by longitudinal sectioning and
polishing.
Fast fracturing of the test piece using a tensile test machine. Subsequent
visual examination of the gauge length for cracks. Analysis of the tensile test data and
fracture surfaces for evidence of embrittlement and/or brittle fracture.
Alternative methods may be offered for approval by BPX.
Applied Stress
The applied stress shall be 90% of the measured (actual) yield strength. The yield strength
shall be determined on a round bar test piece (Figure 4 of ASTM A370-94) using the 0.2%
offset method in ASTM A370-94.
Test pieces
The standard tensile test pieces shall be in accordance with those recommended in NACE
TM0177-96 (Method A). Where full-size test pieces can not be achieved then sub-size test
pieces in line with NACE TM-0177-96 may be used.
Test Duration
The test duration shall be 720 hours
Data Reporting
Data reporting shall include test piece geometry, test solution and conditions (temperature, gas
mixture), pH (initial and final), loading device used, test duration, test result (failure/pass) and
test piece surface appearance subsequent to test termination.

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Appendix B

TABLE B1. MAXIMUM SERVICE TEMPERATURE LIMITS FOR CORROSIONRESISTANT ALLOYS TO AVOID LOCALISED CORROSION
(a) 13% Chromium Steel
MATERIAL

13%Cr steel

13%Cr steel

13%Cr steel

13%Cr steel

13%Cr steel

13%Cr steel

13%Cr steel

13%Cr steel

13%Cr steel

WELL
CONDITIONS

6,000ppm Chloride
pH = 4.5*
pH2S = 0.001 bara
30,000ppm Chloride
pH = 4.5*
pH2S = 0.001 bara
120,000ppm Chloride
pH = 4.5*
pH2S = 0.001 bara
6,000ppm Chloride
pH = 4.5*
pH2S = 0.01 bara
30,000ppm Chloride
pH = 4.5*
pH2S = 0.01 bara
120,000ppm Chloride
pH = 4.5*
pH2S = 0.01 bara
6,000ppm Chloride
pH = 4.5*
pH2S = 0.1 bara
30,000ppm Chloride
pH = 4.5*
pH2S = 0.1 bara
120,000ppm Chloride
pH = 4.5
pH2S= 0.1bara

MAXIMUM
TEMPERATURE LIMITS
(oC)
Onset of
Pitting

Pit
Propagation

100

140 (GC**)

110

140 (GC**)

120

140 (GC**)

120

130 (P)

120

130 (P)

120

130 (P)

120

120 (P)

120

120 (P)

120

120 (P)

* Note that at pH levels lower than 4.5 13%Cr steels are liable to general corrosion over the
whole temperature range. In the case of general corrosion the likely rate of attack can be
assessed using the methodology outlined in Section 1 of Appendix B.
** For 13%Cr steel "significant attack" is likely to occur either as pitting corrosion (P) or
general corrosion (GC). The likely rate of general corrosion attack can be assessed using the
methodology outlined in Section 1 of Appendix B.

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Appendix B

(b) 25%Cr/7%Ni Duplex Stainless Steel

MATERIAL

25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel

February 2000

WELL
CONDITIONS

6,000ppm Chloride
pH = 3.5
pH2S = 0.001 bara
30,000ppm Chloride
pH = 3.5
pH2S = 0.001 bara
120,000ppm Chloride
pH = 3.5
pH2S = 0.001 bara
6,000ppm Chloride
pH = 3.5
pH2S = 0.01 bara
30,000ppm Chloride
pH = 3.5
pH2S = 0.01 bara
120,000ppm Chloride
pH = 3.5
pH2S = 0.01 bara
6,000ppm Chloride
pH = 3.5
pH2S = 0.1 bara
30,000ppm Chloride
pH = 3.5
pH2S = 0.1 bara
120,000ppm Chloride
pH = 3.5
pH2S = 0.1 bara

MAXIMUM
TEMPERATURE LIMITS
(oC)
Onset of
Pitting

Pit
Propagation

180

200

160

200

140

200

170

200

140

180

140

180

140

180

130

170

130

170

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Appendix C

APPENDIX C : WHAT IS THE DEFINITION OF A "SOUR ENVIRONMENT"?


A "sour environment" is defined in NACE Standard MR0175 as a fluid containing water as a
liquid, together with hydrogen sulphide at a level exceeding certain criteria, as detailed in
Figures C1 and C2. For convenience, these criteria are summarised in Tables C1 and C2. It
should be noted that only environments containing liquid water are classified as sour in the
context of the standard. Therefore dry gas would not be considered sour.
TABLE C1. DEFINITION OF SOUR SERVICE FOR A GAS WELL
Total System Pressure
(psia)

Partial Pressure of
Hydrogen Sulphide (psia)

Sour Environment
(YES/NO)

<65

<0.05

NO

<65

>0.05

NO

>65

<0.05

NO

>65

>0.05

YES

TABLE 2. DEFINITION OF SOUR SERVICE FOR AN OIL WELL


(oil/water or oil/water/gas)
Total System
Pressure (psia)

Partial Pressure of
Hydrogen Sulphide
in the gas phase
(psia)

Mol.-% H2S in the


gas phase

Sour Environment
(YES/NO)

<265

<0.05

<15

NO

<265

>0.05, <10

<15

NO

>265

<0.05

<15

NO

>265

>0.05

YES

>10

YES

>15

YES

From the Tables, it is clear that the definition of sour conditions is different for gas and oil
wells. For the purposes of this definition any well with a gas/oil ratio of greater than 5000
standard cubic feet per barrel of oil is taken as a gas well. It is also apparent from these Tables
that the definition of sour conditions is normally based upon the partial pressure of hydrogen
sulphide in the gas phase. To determine the partial pressure of hydrogen sulphide in the gas
phase certain field information is required.
Considering firstly a gas well, the information required is the bottom hole pressure and the
mole (or volume) fraction of hydrogen sulphide in the gas. The partial pressure is then

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Appendix C

calculated simply by multiplying the mole fraction of hydrogen sulphide in the gas by the
bottom hole pressure. For example, for a 5500m deep gas well with a bottom hole pressure of
14,000 psi and a hydrogen sulphide content of 5 ppm mole, the partial pressure of hydrogen
sulphide would be 0.07 psia (5/1,000,000 * 14,000), i.e. the well would be classified as sour.
For oil wells under circumstances where there is gas present (multiphase wells), the partial
pressure of hydrogen sulphide can be estimated by multiplying the total pressure by the mole
fraction of hydrogen sulphide. The situation for oil wells in which there is no gas phase
present under downhole conditions is somewhat different. The partial pressure of hydrogen
sulphide that needs to be calculated is that in a gas phase in equilibrium with that dissolved in
the well liquids (oil/water). An alternative description of this is the partial pressure of
hydrogen sulphide in the gas phase formed at its bubble point. Therefore, a "convenient"
method often used to calculate the partial pressure is to multiply the bubble point pressure by
the mole fraction of hydrogen sulphide in the gas phase.

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Appendix D

APPENDIX D : SULPHIDE STRESS CRACKING


1. Background.
Sulphide stress cracking occurs as a result of the entry of atomic hydrogen into the metal.
Aqueous corrosion will produce atomic hydrogen, which would normally tend to recombine
via the reaction:
2H+ + 2e H + H H2(gas)
These hydrogen gas molecules are too large to enter the metal and are thus not harmful to it.
However, hydrogen sulphide is thought to discourage the recombination of hydrogen atoms to
form H2 gas and hence encourage the entry of atomic hydrogen into the metal. Once in the
metal, the atomic hydrogen will diffuse to "trap" sites, where it will lead to a local increase in
the stress and/or a reduction in the strength of the metal lattice. For a material under load there
is evidence to suggest that the atomic hydrogen will concentrate near to stress concentrators
and may give rise to crack initiation at such points, hence leading to a brittle-like fracture. This
type of cracking can occur quite rapidly. Thus even if materials are only to be exposed to sour
conditions for short periods of time they must be resistant to SSC.
2. NACE Standard MR0175 (Standard Material Requirements - Sulfide Stress
Cracking Resistant Metallic Materials for Oilfield Equipment)
The NACE Standard MR0175 is concerned with the resistance of materials to sulphide stress
cracking (SSC) in sour conditions. In some countries, such as the United States, the standard
is a legislative requirement, i.e. it must be applied there. This document should be referred to
for initial information on materials with adequate resistance to SSC for sour conditions.
In particular, it should be noted that increasing the temperature reduces the likelihood of
sulphide stress cracking, particularly for low-alloy steels. Hence, NACE MR0175 allows the
use of materials with a specified minimum yield strength above that of the fully sour-resistant
grades under circumstances where the minimum operating temperature is above certain limits.
The information in Table D1 taken from NACE MR0175-99 details the acceptable tubular
material grades for different temperature ranges (refer to NACE MR0175-99 for the full
Table).

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Appendix D

TABLE D1. ACCEPTABLE API SPECIFICATIONS FOR TUBULAR GOODS


For all temperatures
(1)

For operating
temperatures 65oC
or greater (2)

For operating
temperatures
80oC or greater
(2)

For operating
temperatures
107oC or
greater (2)

API Spec. 5CT grades


H40 (3); J55; K55;
L80 (Type 1); C90
(Type1); T95 (Type1)

API Spec. 5CT grades


N80 (Q + T); C95

API Spec. 5CT


grades H40; N80;
P110

API Spec. 5CT


grade Q125. See
Note 4.

Proprietary grades
Per NACE MR-0175
Section 10.2.

Proprietary Q + T
grades with 110ksi or
less maximum yield
strength

Proprietary Q + T
grades with 140ksi
or less maximum
yield strength.

Notes to Table D1:


1. Impact resistance may be required by other standards and codes for low operating
temperatures.
2. Continuous minimum temperature; for lower temperatures, select from column 1.
3. For H40 material the maximum permissible yield strength is 80ksi.
4. Regardless of the requirements for the current edition of API Spec. 5CT, the Q125 grade
shall always (1) have a maximum yield strength of 150ksi; (2) be quenched and tempered;
(3) be an alloy based on Cr-Mo chemistry. The C-Mn alloy chemistry is not acceptable.
When using these criteria, it is important to bear in mind that SSC can occur within a relatively
short time span, so that periods of exposure to sour conditions at temperatures below those
stated in the Table could potentially lead to SSC problems. For this reason it is important to
note that the temperature levels quoted in Table D1 are the minimum operating temperature
the tubing will experience. If temperatures below this minimum are expected even for short
periods of time then the non-sour higher strength materials should not be used.
3. BP AMOCO Methodology for selecting materials with adequate SSC resistance.
It was recognised some time ago that the use of the NACE Standard MR0175 alone is not
sufficient to allow the selection of the optimum material with adequate sulphide stress cracking
resistance. For example, the NACE Standard makes no reference to the in-situ pH, which is
known to affect the likelihood of sulphide stress cracking (SSC) of materials. In addition, the
testing solution used in assessing the acceptability of materials for sour service in NACE is
very severe (1 bar H2S, pH 2.8), meaning that the standard is very conservative regarding
which materials are acceptable for hydrogen sulphide service. Finally, there is insufficient
information in the NACE standard regarding the operating limits of many corrosion-resistant
alloys. Therefore, BP AMOCO developed a methodology based upon laboratory test results
and field experience, to allow the user to select the most cost-effective material for the
intended service.
As a result of the concerns over the temperature conditions in Table D1, the decision was
made to carry out all testing for the BP AMOCO methodology under room temperature
conditions, i.e. the "worst case" scenario. Therefore, the methodology described here is

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Appendix D

applicable to all likely operating temperatures (Note: This methodology need not be applied to
the traditional sour-resistant grades in API 5CT [i.e. L80, C90, T95] which it is assumed are
suitable for all sour conditions on the basis of past experience and test data).
To apply the BP AMOCO methodology, it is necessary to know certain information about the
proposed well, i.e. the partial pressure of hydrogen sulphide in the gas phase, and the in-situ
pH of the water associated with the produced fluids. As an in-situ pH is not usually available,
the methodology outlined in Appendix A can be used to assess the in-situ pH on the basis of
certain well information.
Once the necessary information has been collected, the conditions can be plotted onto the
appropriate sulphide stress cracking performance domain charts for individual alloys at the
end of these Guidelines. There are two domains identified on the individual alloy go/no go
charts. If the operating conditions fall within the acceptable domain then the material can be
considered to have an acceptable resistance to SSC under the prevailing conditions. However,
if the operating conditions fall within the unacceptable domain then it will be necessary to
consider a material with greater SSC resistance.
Domain diagrams are included for 95ksi alloyed martensitic 13%Cr steels (e.g. Super 13Cr;
Hyper 13Cr). These alloys do not represent a distinct chemical composition, but rather are
comprised of a family of alloys with differing chemical compositions (varying between
manufacturers) and hence often having differing sour resistance. For this reason, it has not
been possible to develop a simple go no go domain chart. Therefore, for ease of
interpretation, charts with three domains have been developed. These three domains represent:
Acceptable (Green for go) - the material is satisfactory for the proposed
application.
Unacceptable (Red for no go) - the material is unsuitable for the proposed
application and an alternative material with greater SSC resistance should be
considered.
Further Assessment Required (Yellow for caution) - to assess whether the
material is suitable for the intended application or not, further assessment is required
in the form of consideration of specific pre-qualification data for the
alloy/manufacturer being considered, reference to relevant past test data (e.g. for a
similar application), application specific testing.
In addition, tests in BP Amoco have demonstrated that the level of chloride is very important,
as increased chloride levels significantly reduces the sulphide stress cracking resistance of the
materials. Therefore domain diagrams have been developed for both high chloride (typical of
produced water in oil/gas wells) and low chloride (typical of condensing water in gas wells)
conditions. For intermediate chloride levels two courses of action are available:
Default to the high chloride domain diagram
Produce/use test data (pre-qualification) for the specific application that
demonstrates acceptability.
With regards to the effect of chloride content, the present domain diagrams seem to infer that
the 110ksi materials perform better in condensing water conditions. This most probably
reflects the improvements in material chemistry and manufacturing methods between the two
sets of tests (the 95ksi materials were tested in 1995 and the 110ksi materials were tested in
1998, a time period which saw significant improvements in the manufacturing methods,

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Appendix D

control of chemistry for these materials). Instinctively, if anything, the 95ksi material should
outperform the 110ksi material. Therefore, it is recommended that manufacturers are
requested to retest the 95ksi materials in low (1000ppm) chloride conditions if intended for
use in gas wells where only condensing water will be present and where the partial pressure of
H2S is such that it would be in an acceptable regime on the attached Regime charts for the
110ksi material but not for the 95ksi material.
Given the wide range of proprietary 'super 13Cr alloys' now available on the market, it has not
been possible to test all those available. Rather, a few representative materials have been
tested. A Qualification Procedure has been developed on the basis of the present results6. It is
recommended that all manufacturers are requested to qualify their material using this
Qualification Procedure prior to using the material in BP Amoco. This will ensure that, as a
minimum, their material conforms with the attached Domain Diagrams. If uncertain whether
the prospective manufacturers material has already been pre-qualified contact the relevant
specialist within BP AMOCO.
It should be noted that the domain diagrams are not all encompassing, but only deal with
resistance to SSC. Before making the final selection of production tubular material, it will be
necessary to consider many other corrosion-related factors. For example, resistance to
general/localised corrosion, stress corrosion cracking resistance, etc. under the prevailing
conditions. These aspects are covered elsewhere in these Guidelines.
In addition, it should be noted that the assessment of the resistance of duplex stainless steels to
SSC and stress corrosion cracking (SCC) is considered further in Appendix B. As a result of
their unique duplex structure consisting of a combination of austenite and ferrite in
approximately equal volume fractions, they are prone to a number of unique cracking
mechanisms. These can consist of either a combination of sulphide stress corrosion cracking
(of the ferrite phase) and chloride stress corrosion cracking (of the ferrite and austenite
phases) or selective corrosion of the ferrite phase leading to crack-like defects.
4. Simplified Test Protocol.
The following test protocol can be used as part of the material pre-qualification process to
determine the suitability of a candidate material for the intended application with regards to
sulphide stress cracking resistance:Test Solution
The test solution shall consist of NaCl (at a concentration to simulate the level of Cl
anticipated in the produced water) + sodium acetate (CH3COONa, at a level sufficient to
buffer the pH, e.g. 0.86g/l has often been used in the past)7 in distilled or de-ionised water.
The procedure for solution preparation shall be as follows:a.

prepare a base solution of NaCl in distilled or de-ionised water

b.

Add the sodium acetate (CH3COONa)5

Super 13%Cr Alloy Seamless Tubing Pre-qualification Assessment, J W Martin & R G MacCuish,
April 1999.
7

As an alternative to the acetate/hydrochloric acid buffering system, a bicarbonate/CO2 buffering


system may be offered for approval by BP Exploration.

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Appendix D

c.

Acidise using concentrated hydrochloric acid 5 down to a pH representative of the in


situ pH anticipated in the downhole tubulars.

d.

Introduce the solution into a test vessel, deaerate and saturate with a mixture of
CO2/H2S with the following gas ratios:

H2S at the partial pressure anticipated in the downhole tubulars, with the balance being CO2
up to the ambient test pressure (1 bar)
During the test the pH may alter, but shall not exceed a value 0.2 above the target figure. This
will be achieved through complete exclusion of oxygen and maintaining a sufficient solution
volume to test piece surface area ratio.
Test Temperature
The temperature shall be maintained at ambient (23oC)
Reagents
The reagents shall be in accordance with those specified in NACE TM0177-96 Section 3.
Acidic Gases
High purity H2S/CO2 gas mixtures shall be used. The test solution shall be purged with the gas
mixture throughout the test period.
Test pieces
All test pieces shall be machined from the pipe wall in the longitudinal direction
Test Vessels and Solution Volume
These shall be in accordance with those specified in NACE TM0177-96 and ISO 7539-1:
1987.
Number of Tests
A set shall comprise duplicate tests.
SSC Test Method
A smooth test piece tensile test shall be carried out in accordance with the procedures
specified in NACE TM0177-96 (Method A) and the additional requirements described in this
document.
Both types of stress fixtures and test containers used for stress corrosion testing are
acceptable; namely, constant load devices or sustained load (proof ring of spring loaded)
devices (ASTM G49-76).
Failure Appraisal
Total fracture of a test piece during the 720 hour test period shall be considered a failure.

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Appendix D

To be considered a pass, the gauge length of the test piece shall be free from any signs of
fissure and/or cracks, after the exposure period. This may be assessed through visual
examination of the gauge length (at a magnification of x10) plus one of the following
procedures: Metallographic examination of the gauge length by longitudinal sectioning and
polishing.
Fast fracturing of the test piece using a tensile test machine. Subsequent
visual examination of the gauge length for cracks. Analysis of the tensile test data and
fracture surfaces for evidence of embrittlement and/or brittle fracture.
Alternative methods may be offered for approval by BPX.
Applied Stress
The applied stress shall be 90% of the measured (actual) yield strength. The yield strength
shall be determined on a round bar test piece (Figure 4 of ASTM A370-94) using the 0.2%
offset method in ASTM A370-94.
Test pieces
The standard tensile test pieces shall be in accordance with those recommended in NACE
TM0177-96 (Method A). Where full-size test pieces can not be achieved then sub-size test
pieces in line with NACE TM-0177-96 may be used.
Test Duration
The test duration shall be 720 hours
Data Reporting
Data reporting shall include test piece geometry, test solution and conditions (temperature, gas
mixture), pH (initial and final), loading device used, test duration, test result (failure/pass) and
test piece surface appearance subsequent to test termination.

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Appendix E

APPENDIX E : WHAT OTHER FACTORS NEED TO BE CONSIDERED?


Apart from the factors relating to corrosion discussed above, there are a number of other
factors that must be considered before finally selecting the material for downhole application.
Briefly, the main ones are as follows:
1. Mechanical Properties
Clearly it is necessary to ensure that the material selected for the downhole tubulars has
sufficient mechanical strength. There are a number of issues that need to be considered in
selecting the correct strength grade, i.e.:
(i) Maximum strength grade the can be used
There are a number of limits on the maximum strength of tubular that can be selected.
Principally:
(a) Low alloy steels.
The 155ksi grade low alloy steels (e.g. XT155) are unsuitable for sour service and should not
be considered.
(b)13%Cr steels.
Generally the highest acceptable strength level for 13%Cr steel is the C95 grade. At strength
levels higher than this it is difficult to ensure adequate toughness. Even at 95ksi the required
toughness can be difficult to achieve and it is important to ensure the correct requirements
(specification) are used.
(c) Alloyed Martensitic 13%Cr steels (e.g. Super 13Cr)
Presently available in two strength levels 95ksi and 110ksi.
(d) Duplex Stainless Steels.
Generally the highest acceptable strength level for the duplex stainless steels is 125ksi. There
is a possible reduction in corrosion/stress corrosion resistance above this level. Duplex
stainless steels with higher yield strength levels can be considered on the basis of specific
environmental testing for the intended application.
(ii) Directionality of mechanical properties
It is important to note that the cold worked duplex stainless steels can suffer from a degree of
directionality in their mechanical properties, as a result of isotropy induced by cold working
processes. This can result in a lower strength in the transverse direction than in the
longitudinal direction. The magnitude of this effect will be dependant on the manufacturing
process, but can be as high as 15% for high strength materials manufactured using the Pilger
process. Therefore, if specifying cold worked duplex stainless steel this issue should be
discussed with the supplier. However, for initial design purposes it is recommended that it is
assumed that the strength in the transverse direction is 5% lower than in the longitudinal
direction.

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Appendix E

(iii) Effect of elevated temperature on mechanical properties


The strength of many materials decreases with increasing temperature. It is important to take
such decreases into account in completion design. For the more commonly used downhole
tubular materials the magnitude of this affect is as follows:
(a) Carbon steel, 13%Cr steel and Super 13%Cr alloys
Over the range of temperatures likely to be experienced downhole the reduction in
strength is likely to be relatively small.
The present Casing Design Manual8 recommends that for low alloy steels up to and
including Q125 a yield strength temperature de-rating factor of 0.03% per F is
applied, with de-rating commencing at 68F.
Given the similarity in behaviour in this respect for low alloy steels and 13%Cr
steel/Super 13Cr alloys, it would be reasonable to assume a similar temperature derating factor for both 13%Cr steel and Super 13Cr alloys.
(b) Duplex stainless steel
The reduction in strength with increasing temperature is greater for duplex stainless
steels than for low alloy steels. This resulted in a design guideline for Miller that
assumed a 10% reduction in yield strength at 120oC. The magnitude of this affect is
likely to be different for different grades of duplex stainless steel and for tubulars made
by different manufacturing routes. Therefore, this aspect should be discussed with the
suppliers. However, for initial design purposes it is recommended that it is assumed
that the strength is reduced at a rate of 8% per 100oC.
Where design yield strength has a critical influence on weight or grade selection, and
conservative assumptions are economically undesirable, it will be necessary to ensure that
the actual yield strength at the required elevated temperature is adequate for the design by
undertaking mechanical tests. Tests should be undertaken both before (as a pre-qualification)
and during (as a quality control check) manufacture of the downhole tubulars.
2. Flow-Induced Damage: Erosion and Erosion-Corrosion Resistance
Erosion can defined as the mechanical loss of material by the impact of liquid droplets, gas
bubbles and/or solid particles (e.g. sand). The term erosion-corrosion is used to define the
conjoint action of erosion and corrosion.
Guidelines have been developed for the avoidance of erosion/erosion-corrosion problems9.
Amongst other things, these can be used to determine velocity limits for the avoidance of
erosion/erosion-corrosion damage. Different velocity limits apply in different situations,
depending on the fluids/flow regime (gas, liquid or multiphase gas and liquid), the environment
(corrosive or non-corrosive), the downhole tubular/equipment materials and whether or not
solids are present.

Casing Design Manual, Issue 2, BPA-D-003, September 1999

Erosion Guidelines Revision 2.1 (1999), J W Martin, Sunbury Report No. S/UTG/102/99, October
1999)

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Appendix E

Summary guidance for evaluating erosional velocity limits is given in Section 2.1. below.
These indicate the erosional velocity limits for which the rate of erosion will be 0.1mm/yr or
less. Three main categories for solids content are used in these guidelines:
Totally solids free The flow streams are such that there is no risk of solids being
transported in the fluids. It should be noted that even very low levels of solids can cause
significant wastage (erosion or erosion/corrosion) rates. Hence it is very important to be sure
there is no risk of solids entrainment before using these limits.
Nominally solids free less than 1pptb (lbs per thousand barrels) for liquid systems, less
than 0.1lb/mmscf for gas systems; no solids detectable.
Solids present Solids detectable in the system. In this case the levels of solids will need
to be known, or appropriate assumptions made regards their likely level.
2.1. Evaluation of Velocity Limits.
The following criteria indicate the maximum velocity limit to obtain an estimated rate of
erosion of 0.1 mm/yr. or less.
Totally Solids Free Duties:
Non Corrosive
Single Phase (liquid/gas) - no velocity limits for avoidance of erosion
Multiphase - limit velocity to 70m/s to avoid droplet/gas bubble impingement
erosion.

Corrosive
Single Phase Liquid - no velocity limits for avoidance of erosion
Un-inhibited wet gas/multiphase10 - limit velocity to 70m/s to avoid droplet/gas
bubble impingement erosion.
Inhibited carbon steel wet gas/multiphase - use the API RP14e11 equation with
C=200 or 20m/s (whichever is lower).
Nominally Solids Free Duties:
Single Phase Liquid - use the API RP14e7 equation with C=250 for carbon steel;
C=300 for 13Cr steel and C=450 for duplex stainless steel.
Multiphase - use the API RP14e7 equation with C=135 for carbon steel; C=300 for
13Cr steel and C=350 for duplex stainless steel.

10

For carbon steel it is assumed that the fluid has sufficiently low corrosivity to justify its use and is
un-filmed (i.e. no carbonate film). For carbonate filmed carbon steel (see Section ????) use the
inhibited flow velocity limits.
11

API RP14e equation is: Maximum Allowable Velocity (ft/sec) = C/(mixture density in lb/ft3)0.5

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Appendix E

Single Phase Gas - Evaluate using the Erosion Rate models in the Erosion
Guidelines5. Assume a solids production rate of 0.1lb/mmscf if no specific data
available.
Solids Containing Duties:
It is not possible to define a rational flow velocity for all possible operating conditions
below which the rate of erosion will be below 0.1 mm/yr. Therefore, it will be
necessary to undertake an assessment of the likely erosion rate/acceptable flow
velocities on a case by case basis using the relevant erosion rate models from the
Erosion Guidelines5.
If the anticipated maximum flow rate is less than the critical velocity calculated using the
information above, the effect of high fluid flow rates and/or sand erosion need not be
considered further. However, if the maximum flow rate is greater than the critical velocity then
significant wastage may result. In this case further consideration of the likely wastage rates
resulting from erosion/erosion-corrosion will be required. In the first instance reference should
be made to the BP Amoco Erosion Guidelines5.
3. Galvanic Corrosion
This is the preferential corrosion that can occur to one of the metals when two different metals
are electrically coupled in a corrosive environment. In such a couple one of the metals will act
as an anode (i.e. it will corrode at an enhanced rate) and the other will act as a cathode (i.e.
there will be a certain degree of protection). The susceptibility of a material couple towards
galvanic corrosion of the 'anodic' metal is influenced by a number of factors, such as the
conductivity of the corrosive medium, the relative surface area of the two metal components
and the magnitude of the potential difference between the two metals in the corrosive
environment.
In general, downhole tubular systems should be designed to eliminate galvanic cells where
possible. For the purposes of downhole materials selection galvanic corrosion should be
considered a potential problem if there is a corrosion-resistant alloy (CRA)/carbon steel
interface. However, if such interfaces do not occur then the problem of galvanic corrosion can
be discounted.
If galvanic corrosion between CRA jewellery and carbon steel tubulars is a concern,
consideration should be given to installing an internally coated CRA between the components.
In general, 9Cr-1Mo or 13%Cr steel against C-steel is not a concern, the major concern is for
the higher metallurgies, e.g. nickel alloys, against carbon steel.
If there is a concern about any material combination that occurs in a downhole tubular design
the relevant specialist/s should be consulted.

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Appendix E

INDIVIDUAL ALLOY "GO/NO GO" CHARTS SULPHIDE STRESS CRACKING AND STRESS CORROSION CRACKING
PERFORMANCE DOMAINS

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Appendix E

Sulphide Stress Cracking Performance Domain of


Sour Resistant Grade 110ksi Steel

Solution pH

6.5

Acceptable
5.5

4.5

Unacceptable
3.5

0.003
0.001

0.01

0.1

1.0

10

pH2S (bara)
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Appendix E

Sulphide Stress Cracking Performance Domain of


Grade N80 Carbon Steel

Solution pH

6.5

Suitable
Acceptable
5.5

4.5

Unsuitable
Unacceptable
3.5

0.003
0.001

0.01

0.1

1.0

10

pH2S (bara)
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Appendix E

Sulphide Stress Cracking Performance Domain of


Grade P110 Carbon Steel

Solution pH

6.5

Suitable
Acceptable
5.5

4.5

Unsuitable
Unacceptable
3.5

0.003
0.001

0.01

0.1

1.0

10

pH2S (bara)
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Appendix E

H2S Limits for


95ksi Super 13Cr Alloys

6.5

Solution pH

Acceptable
5.5

4.5

Further Assessment
Required
3.5

Unacceptable
0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ksi Super 13Cr Alloys in low Chloride (1000 ppm Cl-) Waters

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Appendix E

H2S Limits for


95ksi Super 13Cr Alloys

6.5

Solution pH

Acceptable
5.5

4.5

Further Assessment
Required

Unacceptable

3.5

0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ksi Super 13Cr Alloys in High Chloride (120,000 ppm Cl-) Waters

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Appendix E

H2S Limits for


22Cr Duplex Stainless Steel

Solution pH

6.5

Acceptable

5.5

4.5

Further Assessment
Required

Unacceptable

3.5

0.02
0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 22Cr Duplex Stainless Steel

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Appendix E

H2S Limits for


25Cr Duplex Stainless Steel

Solution pH

6.5

5.5

Acceptable
0.5

4.5

Further Assessment
Required

Unacceptable

0.25

3.5

0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 25Cr Duplex Stainless Steels

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Appendix E

H2S Limits for


110ksi Super 13Cr Alloys

6.5

Acceptable

Solution pH

Further Assessment
Required
5.5

4.5

3.5

Unacceptable

0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ksi Super 13Cr Alloys in High Chloride (120,000 ppm Cl) Waters

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Appendix E

H2S Limits for


110ksi Super 13Cr Alloys

Solution pH

6.5

5.5

Further Assessment
Required

Acceptable

4.5

3.5

Unacceptable
0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ksi Super 13Cr Alloys in Low Chloride (1000 ppm Cl-) Waters

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Appendix E

H2S Limits for


API5CT L80 13Cr Steel

Solution pH

6.5

Acceptable

5.5

4.5

Further Assessment
Required

Unacceptable

3.5

0.003
0.001

0.01

0.1

1.0

10

pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of API5CT L80 13Cr Steel

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