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NEW EVALUATION AND

QUALIFICATION PROTOCOL
FOR STAINLESS STEEL
TUBULARS FOR H2S/CO2
SERVICE
Russell Kane – iCorrosion LLC; Jim Skogsberg – Consultant;
John Meng and Brian Chambers – Honeywell Process Solutions
Organization
 Introduction
 Selection of materials for
evaluation and
qualification
 Evaluation of resistance
to H2S service
environments
 Use of electrochemical
methods and mini-roll
 Conclusions
Introduction
 When new alloys are introduced into the oil and
gas marketplace, a substantial time lag often
exists while each user company spends time
evaluating and qualifying the material for H2S
limits and corrosion performance.
 This slow process has been followed for many
currently available grades of stainless steels
tubulars.
 However, even after substantial evaluation,
questions often exist regarding localized corrosion
and stress corrosion cracking (SCC).
Introduction
 This presentation will:
 Discuss relevant corrosion issues
with stainless steel tubulars and an
alternative qualification approach.
 Review issues of characterization of
metallurgical, compositional and
mechanical properties of commercial
produced materials vs. manufacturing
and inspection specifications.
 Presents a test protocol for
evaluation and qualification of
martensitic stainless steel tubular
materials that includes:
 Localized corrosion assessment
 Consideration of SSC/SCC resistance
 Critical range of H2S, pH and chloride
A New Approach
 The approach involves the development of “project-ready” data for
manufacturers with third party assistance.
 Aid potential users of stainless alloy tubulars intended for sour oil
and gas production wells.
 “Project ready” data indicates that:
 A test protocol for evaluation and qualification be used, including…
 Carefully selected materials vs. manufacturing & QA specifications, and
 A critical set of tests be used that define the serviceability limits of the
materials with respect to both localized corrosion and SCC .
 Such data will serve as a foundation for users to proceed more
directly to alloy selection and purchase
 This should accelerate the acceptance cycle by minimizing the
amount of supplemental testing that is normally required to
establish confidence in the corrosion and SCC performance of the
material.
Example: Qualification of
Martensitic Stainless Steels
 New grades of high strength stainless alloys are still not
widely utilized for OCTG applications by oil and gas
companies.
 Some of these alloys are not included as acceptable alloys
with defined environmental serviceability limits in NACE
MR0175/ISO15156
 Example: New higher alloy and higher strength grades of
martensitic stainless steels represents a significant step-out
from 13Cr grades; now considering up to 125 ksi minimum
yield strength with 15Cr alloys.
 Some problems with previous generation 15Cr materials
 New controlled chemistry (low C, higher Cr, Ni, Mo)
 No performance database for critical materials at maximum
service conditions.
 Questions still persist about long term localized corrosion and
SSC/SCC resistance.
Selection of Materials for
Evaluation & Qualification
 The material must be selected
from production heats for
maximum risk of
corrosion/SCC
 Include multiple heats per

Cr + 0.2Ni + 0.25 Mo – 20 C
NACE MR0175/ISO15156.

Alloy Composition
 Near the maximum hardness

Cr+3.3Mo or
per applicable commercial
manufacturing specification.
 The chemistry must be
representative of the
commercial alloy, especially the
“lean side” of the specification.
 This material could be hard to
find and is why users often Mini-roll
conduct a mini-roll to produce target
worst-case material per the
manufacturing specification. Hardness
Selection of Materials for
Evaluation & Qualification – 2
 Need for representative materials
 The mechanical properties of yield strength, tensile
strength and hardness should be as indicated in the
commercial manufacturing and QA specifications, and
verified on test materials.
 For MSS alloys, delta ferrite and retained austenite
phases should be representative of the commercial
alloy; need to verify on test materials.
 Retained austenite may be around 20% in the
microstructure of some highly alloyed martensitic stainless
steel OCTG and to date is not normally controlled in
manufacturing and inspection specifications.
 Delta ferrite may also be present.
Selection of Materials for
Evaluation & Qualification – 3

Effect of delta ferrite in martensitic stainless steels – Effect of retained austenite in martensitic stainless steel
Delta ferrite in 13Cr steel reduces the passive region – Reduction in hydrogen content with increasing
leading to increased corrosion and cracking tendencies. retained austenite in modified 13Cr steel may lead to
reduced cracking tendencies
Selection of Test Environments
 Many potential oil and gas
service environments.
 For particular projects, the H2S
partial pressure, chloride
content of the produced water
phase and pH can be readily
obtained or conservatively
estimated from existing field
information.
 Environments for project-ready
data need to be critically
assessed based on
 Data from existing corrosion
research.
 The range of candidate oil and Laboratory SSC data for 15Cr-6Ni-2Mo martensitic
gas service environments for stainless steel at 23 C.
particular grades of material.
 Consideration of applicable
cracking mechanisms.
Selection of Test Conditions – 2
 Consideration of applicable
cracking mechanisms.
 SSC at lower temperatures.
 Chloride SCC at higher
temperatures (Ni content).
 Intermediate temperatures
should also be evaluated in
overlap region for SSC/SCC.
Selection of Test Conditions – 3
 The figure shows ranges of
conditions for typical gas well oil
wells
 Gas wells – low chloride and pH
 Oil wells – high chloride and pH 100 K Oil Well
Environments
 Limit max. chloride due to H2S Max. H2S

Chloride Concentration
solubility limit.

in Aqueous Phase
 The question is reduced to what is
the highest possible H2S level the
worst case material per the 10 K
specification can sustain without Gas Well
 Localized corrosion Environments
Max. H2S
 SSC/SCC
 Can assess major project 1K
conditions and “input data risk” to
assess test pH, H2S and chloride
level.
3 4 5
 Also need to have a fall-back
In-Situ pH of Aqueous Phase
condition if test failures are
observed during qualification.
Evaluation for Localized Corrosion
 Localized corrosion resistance is a critical and until
relatively recently, an underappreciated aspect of
evaluation of stainless alloys.
 Localized corrosion can be a precursor to
environmental cracking.
 Conventional methods include creviced coupons.
 Currently, no industry-wide standard or commonly
recognized evaluation approach.
 The lack of supporting data on localized corrosion
with emphasis on long term prediction capabilities
has been a barrier to wider utilization of stainless
alloys.
New Qualification Protocol for
Localized Corrosion
 Accelerated electrochemical testing
with applied anodic potentials has -0.20

been used for surface applications. 500 ppb O introduced


2

 ASTM G61 (cyclic polarization)

Potential (V vs. Ag/AgCl)


testing; developed for aerated, -0.25

chloride-containing solutions not


reducing H2S-containing
environments. -0.30

 Applied anodic potential can be


>350 mV vs. OCP.
 This protocol defined the severity of -0.35

service induced by anodic


Sour Gas Well @ 24 C
excursions from oxygen ingress. 1.5 psi H S
2
 Data suggests anodic hold at up to -0.40
0 500 1000 1500 2000 2500
100 mV vs. OCP while monitoring
corrosion current is a useful Time (s)
technique.
Effect of Applied Potential
 Electrochemical data show -1
10
different responses for Oil Well @ 200 F
martensitic stainless steel to a 100K ppm Cl/0.5 psi H S/pH 4.5
2

sour oilfield environment with -2

Current Density (A/cm )


10

2
100 mV OCP
applied potential of 50 and
100 mV. 10
-3

 Look for stable passive


conditions (low, uniform 10
-4

corrosion current – See data at


50 mV vs. OCP)
-5
 However, behavior at 100 mV 10 50 mV OCP
versus OCP shows rapid current
increase in corrosion current 10
-6

associated with pitting. 0 500 1000 1500 2000 2500 3000 3500 4000

 Data suggest potential issues Time (s)


with localized corrosion under
some test conditions.
Morphology of Localized Corrosion

 In addition to current monitoring, visual examination for


localized corrosion morphology is also important.
 Note: Local area corrosion (left) versus pitting (right)
Benefits of Mini-Roll in Qualification

 Available heats of material may not be sufficient to


cover range of materials made per manufacturing
specification.
 A mini-roll may be utilized to manufacture
additional material necessary for qualification at
expected allowable extremes: Maximum
hardness, section size or lean composition.
 Mini-roll can be witnessed by user
representatives.
 Materials produced in mini-roll can also be used
for supplemental testing for specific customer
needs.
Conclusions
 A test protocol for evaluation and qualification of
stainless steel tubular materials can accelerate the
qualification process and more rapidly gain their
acceptance by prospective users.
 It includes:
 Evaluation for localized corrosion and relevant
environmental cracking mechanisms.
 Selection of “worst case” materials for testing and
qualification.
 Consideration of service conditions and test environments
(for oil wells and gas wells, separately).
 Possible use of a mini-roll to examine extremes of
materials per the manufacturing & QA specification.