Stainless Steels in

Oil and Gas Production

Introduction
Although oil is not corrosive in itself, production of this harmless (seen from the corrosion point of view) substance can involve highly corrosive environments because of
the presence of water and dissolved aggressive species such as chlorides, carbon dioxide,
hydrogen sulphide and oxygen. To a certain degree oil can in fact act as an inhibitor,
though it is somewhat unreliable when only a thin oil film is "isolating" the metal from
the corrosive water. Thick films of oil may totally inhibit corrosion.
Initially, mainly carbon steels were used in oil and gas production. However, because of the increasing amounts of corrosive agents after years of production in old wells
and the exploitation of more and more corrosive wells, stainless steels are used increasingly in the industry. Environmental considerations have also led to the increased use
of stainless steels, since carbon steel demands the addition of vast amounts of various
artificial corrosion inhibitors, even under fairly mild corrosive conditions, and most of
these inhibitors are more or less hazardous to the environment.
Looking at long term economics, by means of life cycle cost calculations, the use of
a stainless steel can often repay the initial extra investment cost, mainly through low
maintenance costs and weight savings since stainless steel components do not need to be
over-dimensioned to compensate for uniform corrosion as do carbon steel components.
Finally, longer lifetimes can be achieved with stainless steels than with carbon steels.

Environmental factors
"Sweet" or "Sour" environments

Production fluids and gases in the oil and gas industry are traditionally classified as
"sweet" or "sour" environments, depending on whether hydrogen sulphide is absent or
present in significant amounts respectively.
Sweet environments are those containing no or negligible amounts of hydrogen sul
phide. High amounts of carbon dioxide may be present in sweet environments, causing
accelerated corrosion on carbon steel. Sour environments are those containing significant
amounts of hydrogen sulphide. The main concern regarding H2S is its ability to embrittle metals thereby causing sulphide stress cracking (SSC), under certain conditions.
Hydrogen sulphide

Hydrogen sulphide is one of the main factors to consider when choosing a material
for oil and gas production equipment, because of the risk of sulphide stress cracking.
Sulphides, S2, HS or H2S adsorbed on the metal surface, catalyse the absorption of
hydrogen atoms by the metal, which may subsequently crack due to hydrogen induced
cracking (HIC) depending, among other factors, on the amount of hydrogen absorbed. It is this cracking which is usually termed sulphide stress cracking, SSC. The full
mechanism of hydrogen embrittlement by H2S is still under debate.
The hydrogen absorption caused by H2S may work synergistically with the factors
involved in chloride stress corrosion cracking, thereby increasing the risk of environ
mentally induced cracking. Hydrogen embrittlement seems to be the most active cracking mode at low temperatures, whereas chloride stress corrosion cracking predominates
at high temperatures. Consequently, the combined risk of cracking due to H2S and
chlorides tends to be most severe for the austenitic and duplex stainless grades at intermediate temperatures, approximately in the range 80-100C.

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Stainless Steels in Oil and Gas Production

When H2S is present, it is generally the risk of cracking that is of concern. However,
very small amounts of H2S should not necessarily be seen as a negative factor since
the presence of H2S guarantees a low redox potential in the environment and thereby
lowers the risk of chloride induced localised corrosion, e.g. stress corrosion cracking
(SCC), pitting and crevice corrosion. Actual limiting critical values of H2S partial pressures are difficult to give, due to several other factors - temperature, pH and chloride
concentration probably being the dominating ones.
Carbon dioxide

Stainless steels are not susceptible to uniform CO2 corrosion as are carbon steels. For
example, pipelines in carbon steel suffering CO2 corrosion have been replaced with
stainless steel and with very long service lives. However, CO2 can indirectly affect the
performance of stainless steels by dissociation of carbonic acid, which leads to a lowering of pH.
CO2 + H2O

H2CO3

H+ + HCO3

It is not surprising that a higher hydrogen ion activity will increase the driving force
for hydrogen being absorbed into the metal, so that the metal becomes more prone to
cracking (SSC). A significant hydrogen uptake is, however, still only possible when H2S
above a certain concentration is present.
It should be borne in mind that most actual systems have natural pH buffering systems such as that from the bicarbonate present initially. Therefore the full pH lowering
effect caused by CO2 may not be felt because of buffering action. So, in many practical
situations the system may not be as aggressive as expected from knowledge only of the
partial pressures of CO2 and H2S.
Chlorides

Chlorides are very often present in high concentrations in water associated with oil
and gas formations. Localised corrosion on stainless steels induced by chlorides is well
known. However, the oxygen content of these fluids is mostly extremely low and significantly higher chloride levels are therefore acceptable than under oxygen-saturated conditions. The main cathodic reaction in these systems is the reduction of hydrogen ions.
Oxygen

The corrosivitity of any chloride-containing aqueous phase present in systems for oil
and gas production depends to a large extent on the oxygen content. The presence of
oxygen results in an increase of the redox potential of the aqueous solution and thereby
also of the open circuit potential (OCP) of a stainless steel in contact with the solution.
Should the OCP exceed the critical potentials for pitting or crevice corrosion, the stainless steel will suffer from localised corrosion. The oxygen content of aqueous phases
handled in the oil and gas industry, e.g. formation waters, is often very low. However, it
has been shown, though, that for the effect of oxygen to be negligible the oxygen content needs to be down at the ppb level [1]. The polarising effect of oxygen increases with
decreasing pH. It is thus especially important to consider the oxygen content when
selecting material for systems with high contents of CO2.
Temperature

Normally the higher the temperature the more aggressive the environment with regard
to localised corrosion induced by chlorides. However, as mentioned above, non-ferritic
stainless steels seem to show their greatest sensitivity towards SSC at around 80 to
100C in terms of critical partial pressure of H2S. This effect is most pronounced in the
duplex stainless steels and lower alloyed austenitic stainless steels. This phenomenon is
thought to be explained by the opposite temperature dependency of sulphide induced
SSC and chloride induced SCC.

Stainless Steels in Oil and Gas Production

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Sulphur

The presence of elemental sulphur is very damaging for stainless steels and may reduce
the critical partial pressure of H2S appreciably. One possible explanation for the deleterious effect of elemental sulphur is that it can be reduced by hydrogen ions to form
H2S. However, elemental sulphur seems to be absent in most wells.
Hydrogen

In oil and gas production, stainless steel can be exposed to hydrogen when galvanically
coupled to carbon steel. Another source of hydrogen is cathodic protection. Subsea
stainless steels are typically exposed to cathodic protection as they are connected to
protected carbon steel structures. This will often result in full cathodic protection of
the stainless steel with regard to chloride induced localised corrosion. However, ferritic,
martensitic and duplex stainless steels may during long periods of exposure develop
galvanically-induced hydrogen stress cracking (GHSC) from the increase in the cathodic reaction (hydrogen ion reduction) on the stainless steel surface.
Artificial environments

In many cases the limiting environment with regard to corrosion may not be the gases
or formation waters present in the well. A number of chemicals are frequently added to
the well in order to optimize the productivity or as part of the initial drilling and set up
procedures.
Stimulation acids are widely used to increase formation permeability. These acids are
most often inhibited, however, many of these inhibitors have been developed for carbon
steel, and there is no guarantee that the inhibition is effective on stainless steels without
prior testing. Excessively large injections should be avoided. This will minimize the risk
of creating an unnecessarily aggressive local environment with low pH. It should be
recognized that even though the pH is lowered during acidifying, the concentration of
dissolved sulphides is also lowered by general dilution.
Completion fluids are sometimes used to counterbalance the formation pressure.
These fluids may contain high concentrations of chlorides or bromides which inherently introduce an enhanced risk of chloride (halide) induced localised corrosion.
Injected waters to help secondary recovery may be seawater in the case of offshore
production, or produced water in either onshore or offshore production. These waters
can be treated in various ways which influence their corrosivity like de-aeration (less
aggressive) or chlorination (more aggressive).
Seawater (Offshore production only)

Topside equipment may be exposed to seawater internally in the case of seawater being
used as a cooling liquid or used for the production of fresh water. In these cases, the
selection of a stainless steel grade should be based on the maximum temperature and
the condition (aerated and untreated, chlorinated, deaerated, etc.) of the seawater. The
superaustenitic stainless steel grades 254 SMO, 4565 and 654 SMO as well as the
25Cr duplex grade 2507 have shown excellent performance in many seawater environments, see also the article Some factors affecting stainless steel corrosion in seawater
in this handbook.
Unavoidable splashing from the marine environment causes external exposure of
topside equipment to seawater. In such cases, possible evaporative conditions resulting
in increased risk of chloride-induced localised corrosion should be considered.
Submerged pipelines are another example where the outside environment is sometimes potentially more aggressive than that on the inside.

Utilising stainless steels in oil and gas industry

Ferritic and martensitic stainless steels

Although ferritic stainless steels are very resistant to chloride-induced stress corrosion
cracking, they are fairly susceptible to SSC, especially in the cold worked condition.

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Stainless Steels in Oil and Gas Production

For common ferritic grades the resistance to chloride-induced pitting and crevice corrosion is also limited. Ferritic stainless steels have therefore found limited use in sour
production environments.
Martensitic stainless steels are used mainly when high strength is needed in sweet
environments, where they have shown to be cost effective in replacing carbon steel suffering from CO2 corrosion. The martensitic stainless steels have a fairly limited chloride
induced localised corrosion resistance, and they show a high susceptibility to SSC.
Austenitic stainless steels

Standard grade austenitic stainless steels, such as 4307 (304L) and 4404 (316L), are
being used for a large number of components. Especially grade 1.4404 and similar are
extensively used for such varying applications as flexible flowlines, explosion walls on
offshore platforms and tanks for various media. The standard austenitic grades are far
less prone to SSC than ferritic and martensitic alloys as long as they are in the annealed
condition. However, heavy cold work of these alloys does increase their susceptibility to
SSC even at ambient temperature. Stainless steel type 1.4301 (304) cold worked 30%
exhibits susceptibility to SSC even at very low chloride concentrations [2].
The superaustenitic 6Mo stainless steel grade 254 SMO is well known for high
resistance to pitting and crevice corrosion and it is widely used for seawater piping
and in heat exchangers where sea water or brackish water is used as coolant. The grade
also shows excellent resistance to SSC and SCC [3], which is important at the elevated
temperatures and corrosive conditions prevailing in many process pipe systems. Even
after cold work up to 80% and coupled to carbon steel, 254 SMO is highly resistant
to SSC. The carbon steel coupling increases the driving force for hydrogen induced
cracking as discussed above. Laboratory results documenting the high SSC resistance
of 254 SMO are shown in Table 1.
SSC test of 254 SMO at ambient temperature, p H2S =1 atm,
pH 3, (NACE solution), stress: 90% of Rp0.2 (4-point bend test).
Cold worked
condition

NaCl conc.

40%
50%
60%

Uncoupled

Table 1.

Coupled to carbon steel

5%
5%

0
0

2
2

0
0

2
2

5%

A= number of failed specimens

B= number of tested specimens

At high temperatures the high resistance to chloride induced SCC is a further argument for the widespread use of 254 SMO in oil and gas production.
The high-nitrogen austenitic grades 4565 and 654 SMO, which typically shows
chloride-induced localised corrosion resistance exceeding that of 254 SMO in combination with good resistance to SSC and high mechanical strength, are also interesting
grades for demanding oil and gas applications [3, 4].
Duplex stainless steels

The high strength of duplex stainless steels together with their high resistance to chlorideinduced SCC are important reasons for their popularity in oil and gas production.
Duplex grades are extensively used in applications such as solid and flexible flow-lines,
umbilicals, process piping and separators. The grade 2304 has been used successfully
for blast and firewalls on oil platforms, where it offers a resistance to marine atmospheres on a par with 1.4404 (316L), in combination with significant weight reduction due
to the high mechanical strength.

Stainless Steels in Oil and Gas Production

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However, it is necessary to observe some restrictions on the use of duplex grades in

severe sour environments, since laboratory investigations have indicated moderate SSC
susceptibility. It should be borne in mind, though, that pH and stresses in practical
applications can differ from laboratory tests. This is clearly illustrated by a number of
successful applications of duplex steels at far higher partial pressures of H2S than a
number of laboratory investigations have indicated should be possible [5].
Table 2 shows some results from laboratory testing of lean duplex stainless steel
LDX 2101 in sour environments. The results are compared with those of 13Cr super
martensitic stainless steel (SMSS).
LDX 2101 is a candidate for subsea oil and gas applications such as flow lines where
it can substitute SMSS.

Table 2.

Results from SSC testing of welded LDX 2101 and 13Cr SMSS
Grade

H 2S
(kPa)

Cl
(mg/l)

CO2

Temp.

Result*

Comment

13Cr

SMSS

100 000

Bal.

RT

6/6

Cracked

LDX 2101

LDSS

10

100 000

Bal.

RT

0/3

No cracks

Girth weld using GTAW with 2209 filler without post weld heat treatment. 4-point bend test at 100% of actual proof strength at room
temperature. CO2 balanced to 100 kPa (1 bar) total pressure and pH (start) 4.7.
*Number of cracked specimens/total number of specimens.

Environmental and metallurgical limits for some stainless steels when used for
any type of equipment or component according to NACE MR0175/ISO 15156-3:2003 [8].
Max.
temp.

Max.
p H2S

Max. Clconc.

(C)

(kPa)

(mg/l)

Ferritic stainless steels

1)

10

Martensitic stainless steels

1)

Austenitic stainless steels

Materials

Highly alloyed austenitic

stainless steels
(Ni+2Mo) > 30, Mo 2
Highly alloyed austenitic
stainless steels
PREN >40

pH

Remarks

1)

3.5

Shall be in the annealed condition and shall

have maximum hardness of 22 HRC.

10

1)

3.5

See standard for heat-treatment. Shall have a

maximum hardness of 22 HRC.

60

100

2)

2)

3)

3)

50

3)

Shall be in the solution-annealed and quenched condition, be free of cold work intended
to enhance their mechanical properties and
have a maximum hardness of 22 HRC.

60

100
50

2)

2)

3)

3)

100
50

2)

2)

3)

3)

3)

60
3)

121

700

5 000

4)

149
171

310
100

5 000
5 000

4)

Duplex stainless steels

30 PREN 40, Mo 1.5

232

10

2)

2)

Duplex stainless steels

40 PREN 45

232

20

2)

2)

Shall be in the solution-annealed conditions

Shall be in the solution-annealed conditions.

4)

Shall be solution annealed and liquid-quenched, have a ferrite content of between 35

and 65% and not have undergone ageing
heat-treatments.

Any combinations of temperature and chloride concentration occurring in production environments are acceptable.
Any combinations of chloride concentrations and in situ pH occurring in production environments are acceptable.
3)
These materials have been used without restrictions on temperature, p H2S , or in situ pH in production environments.
4)
The in situ pH values occurring in production environments are acceptable.
1)

2)

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Table 3.

Stainless Steels in Oil and Gas Production

In recent years some failures of cathodically protected duplex stainless steels in subsea
installations have been reported. These failures have involved materials with a large
grain size and/or intermetallic phases and/or high ferrite content in the weld metal, i.e.
an unfavourable microstructure, in combination with unusually high mechanical stresses [6]. A guideline has been published with recommendations regarding the austenite
spacing of duplex stainless steels and design criteria [7].

NACE MR0175/ISO 15156-3

Part 3 of the standard NACE MR0175/ISO 15156 gives requirements and recommendations for the selection and qualification of corrosion resistant alloys (including
stainless steels) for service in equipment used in oil and natural gas production [8]. It
addresses the resistance of these materials to damage caused by SSC, SCC and galvanically induced hydrogen stress-cracking (GHSC). Uniform corrosion resulting in mass
loss or localised corrosion is not addressed.
Materials selection tables show the environmental limits of the materials with the
respect to temperature, partial pressure H2S, chloride content and pH when used for
any equipment or component. For specific components less restrictive environmental
limits can also exist in some cases. There may also be metallurgical requirements such
as heat treatment and/or limitation of cold work, hardness and ferrite content. Table 3
gives some examples of environmental and metallurgical limits for some stainless steels
when used for any type of equipment or component.
NACE MR0175/ISO 15156-3 has adopted the following formula for PREN in oil and
gas production environments:
PREN = %Cr + 3.3 x (%Mo + 0.5 x %W) + 16 x %N
In Table 4 typical chemical compositions of some Outokumpu stainless steel grades are
given together with calculated PREN values.
As shown in Table 3, duplex stainless steels are included in MR0175/ISO 15156-3.
However, not all grades are covered; this is particularly true for the lean duplex grades.
Only duplex grades with PREN 30 and molybdenum content 1.5% are currently
included.

Typical composition and PREN values for

some Outokumpu stainless steel grades.
Steel grade

Table 4.

Typical composition, % by weight

Cr
Ni
Mo
N

Others

PREN1

Austenitic
4404

17.2

10.1

2.1

24

904L

20

25

4.3

1.5Cu

34

254 SMO

20

18

6.1

0.20

Cu

43

4565
654 SMO

24
24

17
22

4.5
7.3

0.45
0.50

5.5Mn
Mn, Cu

46
56

Duplex
LDX 2101

21.5

1.5

0.3

0.22

5Mn

26

2304

23

4.8

0.3

0.10

26

2205

22

5.7

3.1

0.17

35

2507

25

0.27

43

PREN = %Cr + 3.3 x (%Mo + 0.5 x %W) + 16 x %N.

Stainless Steels in Oil and Gas Production

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Generally the environmental limits in NACE MR0175/ISO 15156-3:2003 are worstcase conditions. Often these limits can be reconsidered after specific qualification if one
or several parameters, such as temperature, chloride content or pH, are favourable.
Welded joints may have a greater susceptibility to cracking than the base material.
Welding process and consumables should be selected in accordance with good practice
and in order to achieve the required corrosion and cracking resistances. After welding,
the hardness of the HAZ shall not exceed the maximum hardness allowed for the base
metal, and the hardness of the weld metal shall not exceed the maximum hardness
limit of the respective alloy used for the welding consumable. There are additional
requirement on welding of duplex stainless where there are limitation on the amount of
precipitates, intermetallic phases, nitrides and carbides. The ferrite content shall be in
the range of 30 70 % in duplex stainless steel welds.

References
1. T. Rogne, R. Johnsen, Corrosion 1992, Paper No. 295.
2. A.R. Troiano, R.E. Hehemann, Mat. Pen., January, (1979), pp 31-39.
3. C. Wolfe, P.-E. Arnvig, W. Wasielewska, A-COM No. 2-1997.
4. T.L. Ladwein et.al., Corrosion 2000, Paper No. 00148.
5. T. Cassagne, Corrosion 2005, Paper No. 05098.
6. NORSOK Worskshop Agreement M-WA-0, Design guideline to avoid hydrogen
induced stress crackin in subsea duplex stainless steel, (2005).
7. DNV-RP-F112, Design of duplex stainless steel subsea equipment exposed to
cathodic protection, (2008).
8. NACE MR0175/ISO 15156-3:2003, Petroleum and natural gas industries
Materials for use in H2S containing environments in oil and gas production
Part 3: Cracking-resistant CRAs (corrosion-resistant alloys) and other alloys.

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