Paper No.

CORROSION2004
04546
HYDROGEN EMBRITTLEMENT FROM CP ON SUPERMARTENSITIC STAINLESS STEELS –
RECOMMENDATIONS FOR NEW QUALIFICATION METHODS

Stein Olsen and S.M. Hesjevik

Statoil Research Centre
7005 Trondheim – Norway

ABSTRACT

Hydrogen Induced Stress Cracking is a well known failure mechanism for high strength
materials that are cathodically protected. Recently there are reports on failures on supermartensitic
and duplex stainless steels. Based on the general good field experience with these materials, it is
necessary to focus on utilisation and the local design. Allowable strain and stress should be defined
and special components should be given more attention in the design stage.
The results from charging experiments show that there is an effect of the hydrostatic pressure
and the electrolyte. Results from uniaxial tensile and four point bend testing are presented.

When defining a test method for qualification testing related to Hydrogen Induced Stress Cracking
from cathodic protection, it is necessary to address charging conditions, local stresses and dynamic
behaviour to simulate real life conditions. There is probably no single test method that can be used for
all materials and test conditions. Presently there is no practical standard or guideline that can be used as
basis for such testing.

Keywords: hydrogen embrittlement, cathodic protection, testing methods

INTRODUCTION

Hydrogen Induced Stress Cracking (HISC) is a well known failure mechanism for high
strength materials that are cathodically protected. The use of high strength steels in seawater
applications with Cathodic Protection (CP) is limited, and for special application, e.g. jack-up rigs,
reduced polarisation has been applied to avoid the problem. Recently there are some reports on HISC
failures on Supermartensitic Stainless Steels1 (SMSS) and Duplex Stainless Steels2 (DSS). The
general trend in the oil industry is to use more high strength steels in subsea application to enable
developments in deep waters and reduce capital cost. A way to solve the problem is to apply a
reduced potential, but this can be complicated and will increase cost.

Copyright
2004 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are
solely those of the author(s) and not necessarily endorsed by the Association. Printed in U.S.A.

1
Publication Right
Government work published by NACE International with permission of the author(s). Requests for permission to publish this manuscript in any form, in part
or in whole must be made in writing to NACE International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material
 The recent failures show that materials believed to be resistant to HISC from CP can crack
under specific conditions. In a subsea application not only straight pipes can be found, but every
system contain bends, flanges and complex geometries such as doubler plates that can lead to very
high local stresses. Moreover, forged components can contain large grains and precipitates that can
reduce the resistance to HISC. Furthermore, new design methods allow dynamic behaviour that can
influence initiation and propagation of cracks. A general qualification method involving all
conditions important to HISC from CP will probably disqualify many of the materials used over
many years with good experience. All these factors stress the need for methods to qualify materials
and components for specific applications. The future need for the industry will be procedures and
guidelines that describe in detail how such “fitness-for–purpose” qualification testing shall be
undertaken. In parallel it is necessary to focus on utilisation of the materials and the local design. By
increased awareness that materials like SMSS, DSS and Super Duplex Stainless Steel (SDSS) can
crack under unfavourable situations, maximum allowable strain and stress should be defined and
special components should be given attention to avoid unacceptable loading.

There are two official documents addressing the issue of HISC from CP. DNV recommended
Practice DNV RP B4013 is stating the following:
Section 5.5.2: “Ferrous and non-ferrous alloys with Specified Minimum Yield Strength up to 550
MPa are considered fully compatible with cathodic protection systems utilizing aluminium or zinc
based sacrificial anodes..”
Section 5.5.7: “Qualification testing should attempt to simulate the most severe loading condition and
environmental factors anticipated in service. Crack Tip Opening Displacement tests and Constant
Extension Rate Testing carried out in appropriate environment at controlled protection potentials are
relevant for this purpose..”
NORSOK Standard M-0014 is stating the following:
Section 6.1: “For submerged parts that may be exposed to cathodic protection, the following shall
apply: For carbon and low alloy steels, SMYS shall not exceed 700 MPa (725 MPa for bolts). The
actual yield strength shall not exceed 950 MPa. Alternatively, it may be verified that the actual
hardness in base materials does not exceed 295 HB. For carbon steel welds a max. limit of 350 HV10
applies. For stainless steels and non-ferrous materials, resistance against hydrogen embrittlement
shall be controlled by specifying that the actual hardness of the material shall be in accordance with
NACE MR01755, unless otherwise documented..”

Both these documents must be changed based on the current knowledge. SMYS below 550
MPa is no guarantee to avoid HISC and materials listed in MR01755 with no hardness restrictions
like duplex stainless steels, have cracked in specific situations.

For other cracking mechanisms such as sulphide stress cracking, there are international
standards defining how fitness-for-purpose testing shall be performed. It is now time to start the work
to define such test methods for HISC from CP.

2
 CRACKING MECHANISMS

HISC can occur provided that 3 conditions are fulfilled; there has to be a hydrogen source,
tensile stresses must be present and there has to be a susceptible metal micro structure.

For a cathodically protected material, a part of the cathodic reaction will produce
hydrogen that can either be gaseous hydrogen leaving the surface or hydrogen entering the metal
structure. There are two dominating cathodic reactions taking place; the oxygen reduction and the
direct water reduction, only the latter produces hydrogen. The oxygen reduction is the dominating
cathodic reaction for “higher” potentials normally obtained for large carbon steel structures that are
protected by zinc anodes, but for well coated components protected by aluminium anodes, the
electrochemical potential can be very close to the potential for the aluminium anode, i.e. –1050 mV
(SCE). At this potential the direct water reduction is the dominating reaction. When exposed in
seawater, calcareous deposits will be formed on the surface that will influence the cathodic reactions.
The part of the hydrogen actually entering the steel matrix will also depend on the surface properties,
the stress level and the hydrostatic pressure.

The hydrogen in a steel matrix is normally identified as diffusible hydrogen or trapped

hydrogen, and the traps can be reversible or irreversible. In an austenitic phase, the hydrogen
diffusion rate is very low, but the solubility of hydrogen is very high. On the other hand, in ferrite,
the diffusion is rather fast, but the solubility is low. For many Corrosion Resistant Alloys (CRA) the
ferrite-austenite balance is not exactly defined. In addition the extent of dislocations and various
precipitates in the material, where hydrogen can be stored, can vary, which means that generally
accepted critical hydrogen concentration cannot be defined. Presently there is still much fundamental
work to be done in order to understand the effect of hydrogen on the cracking resistance of a
material, particularly for new CRA’s.

HISC requires tensile stresses. Normally external stresses are required to get cracking, but
residual stresses can be significant and must be included in a total assessment of the stresses in a
component. The local geometry can introduce high stress concentrations that must be taken into
account. In a qualification for a specific application, the actual stresses must be simulated. In a real
system there is often a combination of load and deformation control. For low deformations it is
normally a load control, but for larger deformations it is often deformation control. This has to be
reflected in the test setup. Also stress variations due to temperature and pressure changes in operation
must be taken into account. To design a relevant test setup, it is important to identify all parameters
contributing to the resulting stress and strain state. Based on this and the knowledge about the
importance of each parameter, a test method can be designed.

Some materials are inherently more susceptible to HISC than others. Sulphide Stress
Cracking (SSC) has many similarities to HISC from CP because hydrogen is involved in both
mechanisms. The NACE MR 0175 Material Recommendation5 is addressing the issue on materials
properties and limitations to resist SSC. Some materials are inherently resistant to this cracking
mechanism, e.g. the high alloyed nickel alloys. The NACE document is using the hardness value as a
governing parameter, and the limits are defined for most materials where experimental data show a
relation between hardness and SSC resistance. Presently it is not possible to transfer the hardness
limits given by NACE for SSC to HISC from CP.

3
 Operating temperature is very important for HISC, as it is for SSC, and at elevated
temperatures the risk for HISC is dramatically reduced. However, for most subsea applications, the
temperature will approach the ambient temperature during a production shut down. Consequently the
ambient temperature must be used as basis for the qualification. In fact, cycling of the temperature
can lead to potentially the worst case scenario. The hydrogen is charged at elevated temperature, and
during a start up at low temperature, high concentrations of hydrogen combined with high stresses
and low temperature can promote crack initiation and propagation. As a consequence of this, a “soft”
start-up procedure may be recommended in order to raise the temperature prior to fully pressurising
the pipe.

TEST METHODS

Statoil has undertaken a test programme to study the susceptibility of welded SMSS material
against potential HISC from CP. This programme included hydrogen charging, uniaxial tensile (UT)
testing and Four Point Bend (FPB) testing.

Hydrogen charging

Hydrogen charging was undertaken on cylindrical specimens with a diameter of 4 mm and a

length of 50 mm. SMSS and SDSS were exposed in a 3.5% NaCl electrolyte and polarised with
standard aluminium anodes. In order to simulate the hydrostatic pressure, some specimens were also
exposed to a pressure of 25 bar using a test gas with 0.8% oxygen to give the correct value of solved
oxygen in the electrolyte. A few specimens were also mechanically stressed. The total hydrogen was
measured by melt extraction, which means that the diffusible and the trapped hydrogen could not be
separated.

A set of similar specimens were exposed in a field test to 620 m water depth for 54 days and
charged with aluminium anodes.

Uniaxial tensile tests

Smooth and notched UT specimens were tested in house in proof rings at ambient
temperature and pressure in a 3.5% NaCl solution. Cathodic polarization was obtained using
sacrificial anodes. Some of the specimens were notched. Standard UT specimens with 6.4 mm gauge
diameter were used and the stress level was 100% of Specified Minimum Yield Stress (SMYS) for
the materials. SMSS and SDSS base material and weld metal were tested. The full test matrix is
shown in Table 1.

Smooth SMSS base material UT specimens were tested in dead weight constant load by The
Welding Institute at ambient temperature in seawater and polarized to –1100 mV (SCE). Sub size
specimens with gauge diameter of approximately 3.3 mm were used. The test matrix is shown in
Table 2.

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FPB tests

FPB testing of welded SMSS was undertaken in house. The cap of the weld was maintained
as welded. The specimens were initially loaded to a total strain value of 0.35%. The specimens were
exposed in natural seawater at 40C and ambient pressure for 4 weeks. Cathodic polarization was
obtained by sacrificial anodes. The strain was then increased in steps up to 0.56% strain, which
corresponds to the 0.2% proof stress.

SINTEF Materials Technology carried out FPB testing of welded SMSS in 3.5% NaCl
solution at 4°C and 25 bar (0.8% oxygen). Cathodic polarization was obtained using sacrificial
anodes. All specimens were prior to machining strained to a level of 2 x 2.1% in order to simulate the
reeling process of pipes. Afterwards they were aged at 250 °C for 1 hour. Some specimens were
made from a weld with a normal and acceptable cap, some of these with a notch in the weld toe.
Some specimens were made from a “bad” weld that was deliberately made with a rough surface
geometry. The notch was made by use of spark eroding. Some of the test pieces were post weld heat-
treated (PWHT) at 630 °C for 5 minutes prior to corrosion testing. The specimens were loaded to
approximately 0.4% strain for 4 weeks. After inspection the deformation was increased by 20% on a
weekly basis until a total strain of 0.84% was reached. The test matrix is shown in Table 3.

FPB specimens were tested in a field exposure at 620 m water depth. Cathodic polarization
was obtained using sacrificial anodes. The specimens were pre-strained to different levels; no
straining, 2 x 1.6% and 2 x 2.8% straining to simulate a pipe reeling process. The specimens were
then strained to 0.66% and 0.85% in a FPB jig and exposed for 54 days.

TEST RESULTS

Hydrogen charging

The results from the hydrogen charging experiments are shown in Figure 1, 2, 3 and 4. The
results from testing at ambient temperature for ambient and 25 bar pressure are shown in Figure 1
and 2 for SMSS and SDSS materials respectively. A significant increase in the hydrogen content
could be observed when testing was undertaken at 25 bar total pressure. Two specimens that were
mechanically stressed contained more hydrogen than unstressed specimens charged under the same
conditions. The effect of temperature on the charging is shown in Figure 3 and 4. Also an increased
temperature increased the hydrogen content.

The total hydrogen content from the field test for SMSS and SDSS is shown in Table 4. It can
be observed that the hydrogen content is generally lower compared to the values obtained in a NaCl
solution.

Uniaxial tensile tests

The testing in the proof rings at 100% of SMYS gave no cracks in the specimens as shown in
Table 1. This included base material and welds and notched specimens. Testing of sub size base
material specimens in “dead weight” constant load gave no cracking at a stress level up to 15% above
the actual proof stress (Rp0.2).

5
FPB tests

FPB testing at 25 bars pressure with welded specimens stressed to the actual proof stress
(Rp0.2) gave no cracking. The results at different strain levels are shown in Table 3 and 5. For a
“normal” cap geometry, no cracking was observed until the total global straining reached 0.73% and
the highest global straining where no cracking has been observed is 0.62%.

The field test at 620 m water depth with different pre-straining and stressing level gave no
cracking in any of the specimens.

DISCUSSION OF THE TEST RESULTS

HISC from CP has been the potential cracking mechanism in focus for this test programme.

The hydrogen measurements show that there is a significant effect of the hydrostatic pressure
on the total hydrogen charged into the material. Testing at ambient pressure will thus not be
conservative. On the other hand the testing is carried out in a 3.5% NaCl solution and no carbonate or
hydroxide layers will be formed on the metal surface that can limit the hydrogen charging. This is
illustrated by the results from the field test at 620 m water depth where the total hydrogen content
was 2-3 times lower than the levels obtained in the laboratory with NaCl solution. Testing with NaCl
solution will in this respect be conservative. It is clearly preferable to undertake testing at ambient
pressure, but presently it is not verified if testing at ambient pressure in a NaCl solution will give the
same hydrogen charging as testing at actual pressure with natural seawater. For future testing this
should be studied more in detail.

The charging experiments gave somewhat unexpected results as charging of the SDSS
material occurred fairly rapidly and very high hydrogen concentrations could be found after a few
months. It is likely that the hydrogen is transported in the ferrite phase and in the grain boundaries
and stored in the austenite phase. A total hydrogen content of several hundreds of ppm is expected
after less than one year charging. In the SMSS material, the diffusion is rather fast and a steady state
concentration of approximately 10 ppm was reached after one month. As SMSS materials can
contain different amounts of retained austenite, it is likely that different charging times and hydrogen
levels can be observed for different materials.

For the UT specimens with welds, the stressing was applied in proof rings to 100% of SMYS
and no specimens failed, even not the notched specimens. Testing of smooth base material in the
“dead weight” constant load conditions gave no cracking for a stress 15% above the proof stress.
Based on these results, it seems like UT testing is not the preferred method to study HISC from CP in
a SMSS. This is, however, in contrast to what Woolin7 reported for testing of SDSS. In their case UT
testing was in fact the only method that reproduced the cracking observed in a field case. It may be
that testing of welded specimens in a “dead weight” constant load equipment would have given other
results, but UT specimens must be machined and given a smooth surface, which of course will
remove all local geometrical effects that may enhance the local stress.

FPB testing is a constant deflection method and any creep in the specimen will lead to stress
relaxation. From the results it can be concluded that giving a SMSS specimen a fixed deflection,
even though the total strain can be significantly higher than the strain at the proof stress, in most
cases will not lead to cracking with CP charging. This may not be true for a geometry with a very

6
high stress concentration factor, but for a specimen with a standard weld cap, this is probably the
case. In the testing with stepwise increase in the strain, cracking could be observed in specimens,
which show that a dynamic load normally is required to get cracking. In fact, almost all field cases
are reported to have failed during a “dynamic” situation, either during pressure testing or during a
start after a shut down. The first “normal” weld cap failed at 0.73% strain, but many specimens
strained to 0.86% did not crack. Based on these data, it seems like this stepwise FPB testing can be
used to identify the critical allowable tensile straining of this material as both the straining can be
controlled and the cap geometry can be maintained.

POTENTIAL TEST METHODS FOR NEW APPLICATIONS

Hydrogen charging

Hydrogen charging is required during HISC testing and normally this can be undertaken by
use of a standard anode or by a potensiostat. Recording of the cathodic current is recommended to
monitor that charging is taking place. A potential more negative than –1050 mV (SCE) is required to
reproduce conservative conditions with respect to hydrogen charging. Pre-charging prior to stressing
is normally not required, but on the other hand it is essential that charging is taking place during the
testing to provide local charging in the most stressed area and on the surface of the metal. As shown
above, there is a significant effect of the hydrostatic pressure on charging in a NaCl solution. On the
other hand testing in real seawater will form a carbonate layer that reduces the charging. For future
testing it is necessary to define charging conditions that can give realistic hydrogen flux into the
material. Preferably this should be done at ambient pressure for practical reasons.

Stressing of specimens

There are two important aspects related to how stressing of the specimens is undertaken. How
can we simulate local stresses and residual stresses, and how do we simulate the “dynamic”
behaviour.

Local stresses due to geometrical effects and residual stresses are normally not known and
only the global stresses are the basis for pipe design. However, local stresses are probably very
important, particularly for the initiation of cracking. Testing of stress corrosion cracking is thus
normally undertaken by applying a global stress at 90% or even 100% of the Actual Yield Stress
(AYS). This is based on the argument that local stresses in real life always will approach the AYS
due to residual stresses and local stress concentration factors. Applying a global stress at 90% of
AYS will, however, give different local stresses for a UT specimen and a FPB specimen with the
actual surface intact. For the UT specimen the stress is basically the same for the whole test section,
whereas for the FPB specimen, the local geometry can increase the local stress significantly. This
means that UT testing probably will be more reproducible, but FPB testing will be more realistic.
However, in a FPB specimen with the surface geometry intact, the results can vary due to variations
in the geometry.

Field data has shown that cracking occurs during a “quasi static” situation, and often when
the system is cooled down to the ambient temperature where the materials are generally most
susceptible to HISC. Pressure testing represents a situation with high hoop stress and potential lateral
displacement with associated axial stresses. Start up after a shutdown will lead to pressurising and a
temperature rise, both introducing stresses. These two conditions are probably the most critical with

7
respect to initiation and propagation of cracks. A test method should thus simulate such dynamic
behaviour. A UT test gives a constant load, and a dead weight system will ensure a constant load
independently of the straining. For some materials that are known to creep at low temperatures, e.g.
DSS and SDSS, constant load can lead to significant straining due to creep. There are not many real
systems with a constant load situation and such testing may be too conservative. In a FPB test, creep
will lead to stress relaxation and a non-conservative situation. A static FPB loading is thus not
recommendable. Stepwise straining in a FPB test with CP charging can be a way of simulating the
dynamic behaviour, but more work is needed to fully document that this can provide a realistic
simulation of the real life.

SUMMARY AND CONCLUSIONS

Hydrogen Induced Stress Cracking is a well known failure mechanism for high strength
materials that are cathodically protected. Recently, HISC failures on SMSS and DSS have been
reported. One way to solve the problem is to apply a reduced potential, but this can be complicated
and will increase cost.

The recent failures show that materials believed to be immune to HISC from CP can crack
under specific conditions. A general qualification with respect to HISC from CP will probably
disqualify many of the materials used over many years with good experience. This stresses the need
for methods to qualify materials and components for specific applications.

Based on the good field experience with SMSS and DSS materials, it is necessary to focus on
utilisation of the materials and the local design. By increased awareness that cracking can occur
under unfavourable situations, allowable strain and stress should be defined. Special components
should be given more attention in the design stage.

When defining a test method for fitness for purpose testing related to HISC from CP, it is
necessary to address charging conditions, local stresses and dynamic behaviour to simulate the real
conditions. Probably there is no single test that can be used for all materials and conditions. Presently
there is no practical standard or guideline that can be used as basis for such testing.

Stepwice FPB testing is one promising test method that combines testing of the actual surface
and “quasi-static” loading.

REFERENCES

1. S.M. Hesjevik, S. Olsen, “Hydrogen Embrittlement from Cathodic Protection on

Supermartensitic stainless steels – a Case History”, paper no 04545, CORROSION/04,
(NACE International, 2004)

2. L. Smith et.al. “A guideline to the successful use of duplex stainless steels for flowlines”,
Duplex America 2000 Conference.

3. Recommended Practice RP B401 Cathodic Protection Design, DNV 1993.

8
4. NORSOK STANDARD M-001, Materials selection, Rev. 3, 2002.
http://www.standard.no/standard/index.db2?id=1625

5. NACE Standard MR0175-2003, ”Metals for Sulfide Stress Cracking and Stress Corrosion
Cracking Resistance in Sour Oilfield Environments”.

6. European Federation of Corrosion Publications Number 16, 2nd edition, ”Guidelines on

Materials Requirements for Carbon and Low Alloy Steels for H2S-containing
Environments in Oil and Gas Production”.

7. P. Woolin and W. Murphy, “ Hydrogen Embrittlement Stress Corrosion Cracking of

Superduplex Stainless Steels”, paper no 01018, CORROSION/01, (NACE International,
2001)

TABLE 1
TEST MATRIX AND TEST RESULTS FOR UT TESTING WITH FULL SIZE SPECIMENS

Spec. # Material Weld Notch Load Time Result

1 SMSS 100% SMYS 32 days No Crack
2 SDSS “ “ “
3 SMSS X “ 67 day “
4 SDSS X “ 57 days “
5 SMSS X X “ 74 days “
6 SMSS X X “ “ “

TABLE 2
TEST MATRIX AND TEST RESULTS FOR UT TESTING OF SUB SIZE SPECIMENS

Spec. # Material Load Time Result

(x 0.2% proof stress) (h)
1 SMSS 0.95 >720 No crack
2 SMSS 1.0 “ “
3 SMSS 1.05 “ “
4 SMSS 1.1 “ “
5 SMSS 1.15 “ “

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 TABLE 3
TEST MATRIX AND TEST RESULTS FOR FPB TESTING. ALL SPECIMENS WERE
EXPOSED AT 0.4% STRAIN IN 4 WEEKS AND AT 0.51% STRAIN IN 1 WEEK PRIOR TO
FURTHER STRAINING.

Strain Terminated PWHT Cap Crack Test

% without size time
cracking (mm) (weeks)
0.62 No NO “Bad” 8.08 6
0.73 No NO “Bad” 7.78 7
No NO Normal 8.40
No NO Notched 7.06
No YES Normal 0.33
Yes NO Notched -
0.84 No NO Normal 8.22 8
Yes YES Notched -
Yes YES Normal -

TABLE 4
HYDROGEN CONTENT IN SPECIMENS CHARGED WITH ALUMINUM ANODES IN A
FIELD TEST AT 620 M WATER DEPTH FOR 54 DAYS

MATERIAL HYDROGEN (PPM)

SMSS 2.7 – 3.9
SDSS 31 – 40

TABLE 5
TEST RESULTS FOR FPB TESTING WITH INCREASED STRAIN

STRAIN RESULT
0.40 No cracks
0.51 No cracks
0.62 Crack found in one specimen with bad cap and no PWHT
0.73 Cracks found in:
one specimen with bad cap and no PWHT
one specimen with normal cap and no PWHT
one specimen with notch and no PWHT
One specimen with normal cap and PWHT
0.84 Crack fond in one specimen with normal cap and no PWHT

10
 14
1 bar
25 bar
12
600 MPa
10

ppm H
8

0
0 10 20 30 40 50 60 70 80
Time / days

FIGURE 1 – Hydrogen content in SMSS after charging at 1 bar and 25 bars with aluminum
anodes. Two specimens were mechanically stressed and exposed at ambient pressure.

100
90 1 bar
80 25 bar
550 MPa
70
60
ppm H

50
40
30
20
10
0
0 10 20 30 40 50 60 70 80
Time / days
FIGURE 2 – Hydrogen content in SDSS after charging at 1 bar and 25 bars with aluminum
anodes.

11
 14
4oC
25oC
12
50oC
10

ppm H
8

0
0 10 20 30 40 50 60 70
Time / days
FIGURE 3 – Hydrogen content in SMSS after charging at 1 bar at different temperatures.

100
90 4oC
25oC
80
50oC
70
60
ppm H

50
40
30
20
10
0
0 10 20 30 40 50 60 70
Time / days
FIGURE 4 – Hydrogen content in SDSS after charging at 1 bar at different temperatures.

12