Professional Documents
Culture Documents
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
2
100 mV OCP
applied potential of 50 and
100 mV. 10
-3
associated with pitting. 0 500 1000 1500 2000 2500 3000 3500 4000