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RESEARCH NOTES

SUBJECT: SULFIDE STRESS CRACKING / HYDROGEN CRACKING

E/ECE/324 Rev.2/Add.109/Amend.1
E/ECE/TRANS/505
1 April 2003

AGREEMENT

CONCERNING THE ADOPTION OF UNIFORM TECHNICAL PRESCRIPTIONS


FOR WHEELED VEHICLES, EQUIPMENT AND PARTS WHICH CAN BE FITTED
AND/OR BE USED ON WHEELED VEHICLES AND THE CONDITIONS FOR RECIPROCAL RECOGNITION OF APPROVALS
GRANTED ON THE BASIS OF THESE PRESCRIPTIONS */

(Revision 2, including the amendments which entered into force on 16 October 1995)

"6.3.2.4. Sulfide Stress Cracking Resistance

If the upper limit of the specified tensile strength for the steel exceeds 950 MPa, the steel from a finished
cylinder shall be subjected to a sulphide stress cracking resistance test in accordance with appendix A to this
annex, item A.3. and meet the requirements listed therein."

"A.3.Sulphide Stress Cracking Test for Steel

Except as identified in the following, testing shall be conducted in accordance with Method A-NACE
Standard Tensile Test procedures, as described in NACE Standard TM0177-96. Tests shall be conduced on
a minimum of three tensile specimens with a gauge diameter of 3.81 mm (0.150 inches) machined from the
wall of a finished cylinder or liner. The specimens shall be placed under a constant tensile load equal to 60
per cent of the specified minimum yield strength of the steel, immersed in a solution of distilled water
buffered with 0.5 per cent (mass fraction) sodium acetate trihydrate and adjusted to an initial pH of 4.0, using
acetic acid.

The solution shall be continuously saturated at room temperature and pressure with 0.414 kPa (0.06 psia)
hydrogen sulphide (balance nitrogen). The tested specimens shall not fail within a test duration of 144 hours."

Hydrogen Damage in Steels


By
Khalid M. Al-Nabulsi

Sulfide Stress Corrosion Cracking (SSCC or SSC): In SSCC, the hydrogen atoms remain dissolved in the
steel, are highly mobile, and under the influence of stress, produce brittle cracking in susceptible steels or
hard areas. This mechanism is very dependent on the steel composition, microstructure, strength, and applied
and residual stress levels.

SULFIDE STRESS CORROSION CRACKING

A form of corrosion in which susceptible types of metals will break by a combination of stress within the
metal and the specific type of corrosion (anodic dissolution or oxidation).

The anodic dissolution reaction in steels:


Fe ↔ Fe++ + 2e-
In this model, propagation is controlled by anodic dissolution at the crack front, a process that is accelerated
by making the potential of the metal under attack more noble by impressed anodic current.

CONDITIONS WHICH PROMOTE SSCC

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RESEARCH NOTES

A higher tensile stress state, higher H2S concentrations, lower pH, higher pressure, higher chloride
concentration, lower temperature and harder material all promote SSC attack. Conversely, moving one or
more of these factors in the opposite directions will retard attack, other things equal.

NACE Standard MR0175, “Metals for Sulfide Stress Cracking and Stress Corrosion Cracking Resistance in Sour Oilfield
Environments,” was revised and reorganized over a seven-year period, resulting in the publication of the 2003 edition in February
2003. Because the changes were extensive, the Maintenance Panel formed to maintain this widely used standard, which will soon be
combined with ISO 15156 (based on MR0175), has received many questions regarding the requirements and revisions. Following are
the inquiries and responses provided thus far by the Maintenance Panel. Users of MR0175 who have questions are encouraged to review
these to determine whether your question may have been answered. Numbers are missing from the sequence because not all inquiries
have been answered; this information will be updated periodically as more replies are formulated by the Maintenance Panel. These
responses represent a consensus of the members of the Maintenance Panel and should not be construed to reflect the opinions of NACE
International, its officers, directors, or members.

QUESTION #1:
Paragraph 4.2—Austenitic Steels (say 316SS). One of the acceptance limits for these materials is a maximum
H2S partial pressure of 15 psia at a maximum of 140°F when no chlorides are present. Can I assume that I
can still use a material from this category at a higher temperature than 140°F if the partial pressure of H 2S is
lower than 15 psia?

ANSWER #1:
Please see attached ISO 15156 Table A.2, which is the correct interpretation of NACE MR0175 Paragraph
4.2.2. With the exception of Alloy UNS S20910, the temperature limit of the austenitic stainless steels is
140°F maximum for any H2S level within the scope of the document.

QUESTION:
In the past we have used 300 series SS pipes and valves in sour service. We are not sure of the implications
and use of SS in sour service according to NACE Standard
MR0175-2003. Could you please advise whether 300 series SS (304/316, etc.) can be used at lower H2S
partial pressures for temperatures above 60°C (140°F)?

ANSWER:
No, the maximum temperature for use of the austenitic stainless steels, as defined in NACE Standard
MR0175 Paragraph 4.2, is 60°C (140°F). Please see ISO 15156 Part 1 for guidance as to how to use field
experience or
laboratory data to qualify a material for H2S service.

QUESTION #1:
Paragraph 4.2.2 is new. Would you let us know which interpretation applies?

1. Paragraph 4.2.2 is intended to place a limit on acceptable H2S content under the conditions stated, i.e.,
when temperature does not exceed 60°C, when no elemental sulfur is present, but without restriction on
chlorides.
2. Paragraph 4.2.2 places a maximum temperature limit of 60°C on the use of austenitic stainless steel under
any conditions in which MR0175 applies, for example, at 0.1 psia H2S partial pressure with no chlorides
present.

ANSWER #1:
Please see the attached Table A.2 from the draft of ISO 15156 Part 3, which provides a clear interpretation
of NACE Standard MR0175-2003 Paragraph 4.2.2 for the use of austenitic stainless steels in sour service.

QUESTION #2:
In addition, please clarify the reason for the 60°C limit in Paragraph 4.2.2: We have noted that a limit of 60°C
is commonly cited with respect to chloride stress corrosion for austenitic SST in other publications, and that
chloride is mentioned in Paragraph 4.2.2. Are we correct in assuming, therefore, that the 60°C limit in

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Paragraph 4.2.2 is based on chloride stress corrosion concerns above 60°C when chloride concentrations
above 50 mg/L are present rather than H2S corrosion concerns?
That is, the first sentence of Paragraph 4.2.2 does not have a limit on chlorides but does have a temperature
limit, whereas the second sentence limits chlorides but does not have a temperature limit.

ANSWER #2:
Paragraph 4.2.2 limits austenitic stainless steels (as defined in Paragraph 4.2.1) to 60°C maximum when used
in hydrogen sulfide (H2S)-bearing hydrocarbon service. It allows a maximum H2S partial pressure of 100 kPa
abs (15 psia) with no restrictions on chlorides; or 350 kPa abs (50 psia) maximum H 2S partial pressure if
chlorides are less than 50 mg/L. In either case, there must be no elemental sulfur and the maximum
temperature is restricted to 60°C (140°F). The phrase in the sentence in Paragraph 4.2.2 “with no restrictions
on chlorides” means that any chloride concentration from nil to several thousand ppm chlorides (for example)
are acceptable up to 100 kPa H2S partial pressure up to a maximum temperature of 140°F.

See Paragraph 1.1 in NACE Standard MR0175-2003 for the scope of MR0175. The environmental
restrictions in Paragraph 4.2.2 were established to provide resistance to
sulfide stress cracking (SSC) and/or stress corrosion cracking (SCC) in austenitic stainless steels.

Corrosion Principles : Caproco Internal Corrosion Monitoring Specialists


http://www.caproco.com/corrosion/body.htm

7. Environmental Corrosion Cracking

Stress Corrosion Cracking


Stress corrosion occurs when a material is exposed to a corrosive media while a force (stress) or pressure is
applied. The material usually remains undamaged with the exception of cracks that grow through the material
matrix. These cracks are usually very fine, visible only under microscopic conditions, but often network
through the material, ultimately causing failure.

Hydrogen-Induced Cracking (HIC) and Sulfide Stress Cracking (SSC)


Hydrogen-induced cracking results from the combined action of a tensile stress and hydrogen in the metal.
It results in the brittle failure of otherwise ductile materials when exposed to an environment where hydrogen
can enter the metal. Sulfide stress cracking is a type of HIC in which sulfide is the primary poison for the
hydrogen evolution. SSC of medium-strength steels has been a continuing source of trouble in oil fields.

Liquid Metal Embrittlement (LME)


This is defined as the decrease in strength or ductility of a metal or alloy as a result of contact with a liquid
metal. Unlike fracture by SSC, cracking begins immediately upon the application of stress if the liquid metal
has wetted the solid material.

Evaluation of Geothermal Production for Sulfide Stress Cracking and Stress Corrosion Cracking
http://www.corrosionsource.com/events/intercorr/techsess/papers/session6/abstracts/rdkssc.html

SSC is a form of hydrogen embrittlement cracking commonly observed in high strength or high hardness
steels in which the hydrogen is generated by the sulfide corrosion process on the metal surface.

Corrosion Basics – An Introduction


NACE
Copyright 1984
p. 112 - 113

Some alloy/environment combinations seem to require stresses at or above the yield point (e.g. steel in
caustic). Others appear to have a definite threshold stress below which cracking will not occur. This is the

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RESEARCH NOTES

case for sulfide stress cracking (hydrogen embrittlement) of alloy steels, in which a hardness below about
Rockwell C22 seems to result in practical immunity to this type of crack.

Other systems seem to have no apparent minimum stress. For example, chloride stress corrosion cracking of
austenitic stainless steels has been reported at stresses as low as 1/10 th the yield strength. It should be noted,
however, that notches or stress raisers, even of a microscopic nature, can concentrate the apparent stresses
locally to a value several times the known macrostress. Laboratory work suggests that, at least in the region
in which the cracks originate, the stresses must be above the yield strength (i.e., the stress must produce some
plastic deformation of the material in that region, sometimes very small, at which cracking occurs).

Metals Handbook
Corrosion
P. 1277

…. Hydrogen stress cracking of embrittled metal is caused by static external stresses, transformation stresses
(for example, as a result of welding), internal stresses, cold working and hardening. As a rule, cracking does
not occur in ductile steels or in steels that have received a proper post weld heat treatment.

Hydrogen damage occurs primarily when steel is exposed to aqueous hydrogen sulfide solutions having low
pH values. Hydrogen sulfide, chemisorbed to the steel surface, partially poisons the reaction between
hydrogen atoms that yield molecular hydrogen. Aqueous hydrogen sulfide solutions having high pH values
can also cause hydrogen damage if cyanides are present. In the absence of cyanides, aqueous hydrogen sulfide
solutions with pH values above 8 do not corrode steel, because a protective iron sulfide film forms on the
surface.

Cyanides destroy this protective film and convert it into soluble ferrocyanide [Fe(CN) 6 –4] complexes. As a
result, the now unprotected steel can corrode very rapidly. For practical purposes, the corrosion rate depends
primarily on the bisulfide ion (HS-) concentration, and to a lesser extent, on the cyanide ion (CN -)
concentration. The more bisulfide ion that is present, the more cyanide that is required to destroy the iron
sulfide protective film. It has been shown experimentally that corrosion of steel in aqueous
ammonia/sulfide/cyanide solutions with pH values above 8 is always accompanied by hydrogen damage.

Metals Handbook
Corrosion
P. 1279

A large number of ferrous alloys, including the stainless steels, as well as certain nonferrous alloys, are
susceptible to hydrogen stress cracking. Cracking may be expected to occur with carbon and low alloy steels
when the tensile strength exceeds 620 MPa…..For other ferrous and nonferrous alloys used primarily in oil
field equipment, limits on hardness and /or heat treatment have been established in NACE MR-01-75.
Although oil fields environment can be more severe than those encountered during refining, the
recommendations can be used as a general guide for material selection.

Metals Handbook
Corrosion
P. 1279 - 1280

ON HYDROGEN ATTACK

The term hydrogen attack (or more specifically, high temperature hydrogen attack) refers to the deterioration
of mechanical properties of steels in the presence of hydrogen gas at elevated temperatures and pressures.
Although not a corrosion phenomenon in the usual sense, hydrogen attack is potentially a very serious
problem with regard to the design and operation of refinery equipment in hydrogen service. It is of particular

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concern in hydrotreating, reforming, and hydrocracking units at above roughly 260°C and hydrogen partial
pressure above 689 KPa. Under these conditions, molecular hydrogen dissociates at the steel surface to
atomic hydrogen, which readily diffuses into the steel. At grain boundaries, dislocations, inclusions, gross
discontinuities, laminations, and other internal voids, atomic hydrogen will react with dissolved carbon and
with metal carbides to form methane. The large size of its molecules precludes methane diffusion. As a result,
internal methane pressures become high enough to blister steel or to cause intergranular fissuring. If
temperatures are high enough, dissolved carbon diffuses to the steel surface and combines with atomic
hydrogen to evolve methane. Hydrogen attack now takes the form of overall decarburization rather than
blistering or cracking.

….. Stainless steels with chromium contents above 12% and, in particular, the austenitic stainless steels are
immune to hydrogen attack. It should be noted, however, that atomic hydrogen will diffuse through these
steels; as a result, they will not provide protection against hydrogen attack if applied as a loose lining or an
integral cladding over a nonresistant base steel.

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