Oil and Gas Market: Opportunities for Stainless Steel Long Products

Mercado do Setor de Petróleo e Gás Natural:

Oportunidades para Produtos Longos de Aço inoxidável

Diana Koschel1, Marc Mantel1 & Sophie Le Guennec2

1
Research Center, UGITECH, Schmolz + Bickenbach group.
2
Marketing Department , UGITECH, Schmolz + Bickenbach group.

Abstract:
A few current facts:
- Around 70% of the world oil&gas reserves are unconventional liquids, that is to say heavy,
viscous, bitumen fluids, often found in fields with a high H2S content
- Around 1/3 of the global production is coming from subsea reserves
- Drilling operations are more & more complex as we go deeper & deeper, onshore and
offshore

As a consequence, it appears clearly that oil&gas companies are faced to tougher and tougher
exploring conditions, that require more and more advanced technologies. In this respect,
materials are becoming a key issue. Owing to their specific properties (mechanical properties,
corrosion resistance properties, etc.) stainless steels long products have big opportunities in
oil&gas markets.
In this paper, after dealing with the main trends on oil&gas markets, we will introduce the
various oil&gas applications for stainless steel long products. Finally, we will also make a
specific focus on 2 grades, particularly suitable for oil&gas markets: XM19 and 1.4418.

Resumo:
Alguns fatos atuais:
- Cerca de 70% das reservas mundiais de petróleo e de gás natural são líquidos não
convencionais, isto é pesado, viscoso, de betume líquido, geralmente encontrados em áreas
com um elevado teor de H2S
- Cerca de 1/3 da produção mundial é proveniente de reservas submarinas
- As operações de perfuração são mais e mais complexas à medida são exigidas maiores
profundidades de perfuração, tanto onshore como offshore

Como conseqüência, parece claro que as companhias de petróleo e gás são confrontadas com
o agravamento das condições de exploração, que exigem tecnologias mais avançadas. Neste
contexto, os materiais estão se tornando uma questão fundamental. Devido às suas
propriedades específicas (propriedades mecânicas, resistência à corrosão, etc.), produtos de
aços inoxidáveis longos têm grandes oportunidades no mercado do petróleo & gás natural.
Neste artigo, depois de lidar com as principais tendências do mercado de petróleo & gás
natural, serão introduzidas diversas aplicações dos produtos longos de aço inoxidável neste
mercado. Finalmente, também serão focadas em específico duas classes de aço inoxidável
particularmente adequadas para petróleo e do gás: XM19 e 1.4418.
 1. Introduction

Oil & Gas markets are surfing on a skyrocketing changes wave. After the oil prices yoyo-
game known in 2008 and the global crisis in 2009, 2010 appears as a more stable year.
However, the storm is not that behind and the challenges these industries have to face are
tremendous in terms of, both, economics and technological breakthrough. In this paper, after
highlighting the main trends on oil&gas markets, we will focus on how these new challenges
may be opportunities for stainless steel long products. Particular attention will be paid to the
various types of oil&gas applications for stainless steel long products.
It is obvious, oil market is undergoing turbulence: prices are keeping falling down and
forecasts over the coming year remain modest. However, although the current world demand
for liquids is dampened in the near term, mainly as a result to the global economic recession, a
return to trend growth is expected over the long term as national economies recover. Indeed,
looking at the US Energy Information Administration global oil projections up to 2030,
liquid fuels remain the prevailing source of energy, with an expected increase in global oil
demand by 25%, equivalent to 107 million additional barrel/day.
Looking beyond the supply and demand sides, attention has to be paid to the available
reserves via the exhibition of two main current facts:
- Around 70% of the world oil&gas reserves are unconventional liquids, that is to say the
more often heavy, viscous, bitumen fluids, often found in fields with a high H2S content (Boy
de la Tour, 2004).
- Around 22% of the global reserves is coming from the subsea (Bauquis, 2005)

This implies that exploring and drilling operations are becoming more & more
complex as we need to go deeper & deeper, onshore and offshore, in harsher and harsher
environmental conditions, not to mention the necessity to secure people, supplies and
equipments. In this respect, the impact of an appropriate selection of technologies, equipments
and materials is obvious. The recent deepwater Horizon drilling accident in the US Gulf,
which has led to a major crude spill, namely because of defective valves, is a perfect example
of the technical constraints the oil companies have to observe, in order to operate in both
efficiency and safety.
Owing to their specific properties, particularly in terms of mechanical characteristics
and corrosion resistance, there is no doubt that stainless steel long products have tremendous
opportunities in oil and gas markets.
During any step of the oil&gas exploitation process, onshore or offshore, materials
and equipments are submitted to very severe environment and operating constraints : high
temperatures and pressures, presence of acid gas, humidity, salt and so on...It is then
absolutely indispensable to select materials with good thermal expansion resistance, corrosion
resistance, abrasion resistance and high mechanical & yield strength properties. Depending on
the environment and application concerned, stainless steels, from martensitics to austenitics
via duplex, offer a wide and perfectly relevant response to raise these challenges. We will
focus on stainless steel long products, that is to say on bars, wire rods and drawn wires.
As an illustration, you will find below some applications for oil&gas products, where
stainless steels long products are a key reference material
 Valves Wire lines
- Rings/bonnets/stems Super austenitics-super duplex
- Seals/fasteners
- Studs/bolts
- Bushes/springs Fittings
- Gaskets/flanges

Austenitics and superaustenitics, martensitics and duplex grades

Sand screen Pumps

filters - Seals All SS families
- Seats
- X trees
- Shafts/stems
- Flanges

Austenitics/Duplex Martensitics, austenitics and superaustenitics

Figure 1- Applications for stainless steel in oil and gas industry.

We will now present stainless steels technical grades used in oil and gas applications,
namely shafts and stems for pumps. The first grade is a high performance austenitic grade
XM19/UNS 20910 used for severe corrosive environment and when high mechanical
properties are required. Two other martensitic grades will also be described and compared in
terms of stress corrosion cracking, they are generally used in less severe conditions and when
economical aspects are a critical issue. The first one is the 1.4542 (17-4 PH) martensitic
stainless steel largely used in this kind of applications, but now limited by the NACE version
2003 to high pH (>4.5) and only for well head applications. The second grade is the 1.4418
martensitic stainless steel that could be an alternative for general use for oil and gas
applications.

2. Materials and Methods

Materials

The austenitic grade XM19 is an austenitic stainless steel with a high yield strength designed
for use in very severe corrosive environments. This grade also features excellent cryogenic
properties and very high, stable amagnetism. In accordance with NACE MR0175, this grade
can be used up to a hardness of 35HRC for applications in the oil industry in an H2S
environment. The yield strength of this grade is practically twice as high as that of type 316L.
The chemical composition and the mechanical properties are given in Table 1.

The first martensitic grade is the 1.4542 precipitation hardening martensitic stainless steel
which is frequently used in the oil and gas industry. The heat treatment consists of 3 steps.
The solution heat treatment is usually done between 1000 and 1100°C and leads to a
homogenous martensitic microstructure with some residual austenite. The first annealing
treatment which is done at either 760°C/2 hours to get the ASTM H1150M or at 620°C/4
hours for the ASTM H1150D will lead to the aging of the martensite and incoherent copper
precipitates are formed. This ε-Cu precipitation lead to hardening; highest strength can be
obtained between 450 and 480°C. A second heat treatment will than assure good toughness,
because fresh martensite from the unstable residual austenite will be tempered. This heat
treatment is at 620°C/4 hours for both conditions. The ASTM H1150M will lead to a lower
hardness due to more nucleation sites for the reversion austenite. The ASTM H1150M heat
treatment results in hardness values between HRC 26 to 31 while the ASTM H1150D gives
HRC≤33.

The second martensitic grade is the grade 1.4418, a high alloyed martensitic stainless steel
with high mechanical properties without precipitation hardening. This supermartensitic
stainless steel has 5% of nickel and 1% of molybdenum (Table 1) which increases the
resistance to local corrosion. A single heat treatment is done at 590°C for 2 hours. This
temperature is slightly higher than the Ac1 point which is around 520°C, which means that a
certain amount of reversion austenite is formed. The amount of reversion austenite formed at
his heat treatment was measured by X ray diffraction measurement and was found to be
approximately 12%. This grade is not yet integrated in the NACE but shows good corrosion
resistance and SSC resistance.

Table 1- Chemical composition of the studied materials (in mass %).

PREN Rp0.2 Rm
Heat C Si Mn Ni Cr Mo Cu N V Nb
(*) (MPa) (MPa)
XM19 0.03 0.66 5.03 12.06 21.60 2.06 0.27 0.28 0.22 0.12 32.8 534 812
1.4542
0.015 0.292 0.794 4.5180 15.317 0.159 3.104 0.031 0.077 0.208 16.3 762 872
(1150M)
1.4418 0.037 0.372 0.856 4.785 15.431 0.855 0.196 0.048 0.101 0.007 19.0 813 965
1.4006 0.1160 0.322 0.61 0.4.4 12.112 0.047 0.07 0.033 0.083 0.053 12.8 559 697
(*)PREN=Pitting Equivalent Resistance Number=%Cr+3.3%Mo+16N

Methods

Pitting corrosion test

The samples were taken in the traverse direction and polished with 1200 grit SiC paper. The
sample is placed in the test cell into the solution containing 0.02M NaCl at 23°C and pH=6.6.
The solution was deoxygenated before for minimum 1 hour with nitrogen. The
electrochemical potential is increased, when the current density reaches 100µA/cm² the
pitting potential is noted. The potential is then decreased until the current density diminishes
to 5µA/cm²; this potential is equivalent to the repassivation potential.

Sulphide stress cracking test

Tensile tests were carried out on smooth tensile specimens. The sulfide stress cracking test
was performed in accordance with NACE TM0177 method A. Proof rings are used to apply
the stress. The test solution was 5% NaCl + 2.5 %CH3COOH+0.41%CH3COONa for
pH=3.5. The pH4.5 contained the same solution but was adjusted with NaOH.
The sample specimen were cleaned and polished until 1200 grit SiC paper. The final
roughness Ra was measured and is situated at 0.2 µm.
Specimens subjected to the stress loading were immersed in this test solution at 23°C.
Deoxygenation procedure conform to the NACE specification was applied and the oxygen
level in the solution should be lower than 0.3ppm. After deoxygenation, the test gas is
introduced. The applied stress was set at 80% of the yield strength.
 Figure 2- Proof ring used for the stress cracking test.

3. Results and Discussion

We present the results concerning the pitting corrosion resistance and the sulphide stress
corrosion cracking resistance of the three mentioned grades. Stress corrosion cracking is a
complex phenomena which results from a corrosive media, applied stress and the susceptibility of
the material. From studies of service behavior and from extensive laboratory investigations, the
well-established term stress corrosion cracking (SCC) has been shown to relate to failure modes
classified as environment-sensitive fracture (Stansbury, 2000). The addition of stress to a
corrosive environment results in brittle fracture in otherwise ductile materials such as the stainless
steels. Fracture propagates at an advancing crack tip at which, simultaneously, the local stresses
can influence the corrosion processes, and the corrosion can influence the crack-opening
processes. In particular, stainless steels whose corrosion resistance depends on maintaining a
stable passive film undergo stress cracking in environment that causes local instabilities in the
film. For instance, potentials closed to pitting potential for austenitic stainless steels in chlorides or
sulfides plus chlorides may induce SCC (Béranger, 2002). A generalization relating to chloride
cracking of austenitic stainless steels is that it does not occur at stresses below one-half the yield
strength or below 60°C (Wallen, 1977). Temperature increase lowers the critical stress for failure
propagation. However, a cracking tendency may decrease with increasing temperature. This is the
case when cracking is due to hydrogen embrittlement or when an excessive uniform corrosion
takes place (Stansbury, 2000).
Hydrogen sulphide is not only responsible for the entry of hydrogen atoms into the metal but plays
as well an important role in the depassivation of the surface. Hydrogen sulphide encourage like
chloride ions, the localized corrosion, i.e. pitting and crevice corrosion (Enerhaug, 2001). Pitting
susceptibility is also dependent on oxygen levels in the solution.

3.1 XM 19 - UNS20910
Pitting corrosion

The critical pitting temperature of the XM19 according to G48 E was measured and compared to
two other austenitic grades generally used in oil and gas applications. The critical pitting
temperature of XM19 is much higher than a type 316 L grade and even higher than the 904L
(Figure 3). The good corrosion resistance is due to the higher content of Cr and N in the XM19
grade.
 Figure 3- Critical pitting temperature (CPT) according to ASTM G48 E in 6%
FeCl3.

Stress corrosion cracking

The resistance to H2S and a chloride containing environment was tested near the
utilization limits given by the NACE MR0175/ISO15156 (Figure 4). The usage limit for
XM19 at 1 bar of H2S in the NACE A solution is T= 66°C. The interest of this grade
compared to a type 316L is that it can be used at very high hardness’s, up to 35 HRC.

Figure 4- Stress corrosion cracking test in solution with 5.0 wt% NaCl at pH=3.5
at 80% of the Rp0.2; ●: no failure, ○: failure.

Figure 5 shows the surface of the tested specimen after the test duration of 720 hours. No
corrosion can be remarked at 60°C and 1 bar H2S, however at more severe conditions
corrosion occurs. Higher temperature which means higher chloride activity in the aqueous
solution seems to induce local corrosion which can be found all over the sample. Higher
partial hydrogen sulphide pressure seems to induce local corrosion near the waterline.
 T=60°C, P=1 bar H2S, NACE A T=70°C, P=1 bar H2S, NACE A

no corrosion can be observed  corrosion is observed all over the

sample
T=60°C, P=2 bars H2S, NACE A

 local corrosion on the sample is observed

Figure 5- Photo of samples after the stress corrosion cracking test XM19.

3.2 1.4542 and 1.4418

As mentioned in the introduction, the 1.4542 is facing for some years some limitations in the
NACE standard. This is due to some failures of this grade in oil and gas applications which
can be related to either mechanical failures or failures due to sulphide stress cracking.
Cassagne et alii., 2003, noted a mechanical failure of a 17-4 PH component because of
defective heat treatment. Raja and Rao,1995, noted a 17-4 PH steel mandrel tubing hanger
used in oil well drilling application failed prematurely even though it was given over aging
treatment and the hardness was even lower than the allowable hardness defined in NACE
standard.

Pitting corrosion

The pitting potential of the 1.4418 and the 1.4542 were measured. The average pitting
potential is given in Figure 6 and shows that the 1.4418 has a little higher pitting potential.
This can be attributed to the higher content of Mo. Copper doesn’t seem to have a positive
influence on the pitting resistance. The repassivation potential is higher for the 1.4418 and
little lower is the difference between the pitting and the repassivation potential. Copper and
Molybdenum are generally known to have a positive influence on the repassivation potential.
We can also note that the resistance to local corrosion of these two grades is much higher than
compared to a normal martensitic stainless steel like the 1.4006 (see chemical composition in
Table 1).
 Figure 6 - Average pitting potential Vpit (in grey) and repassivation potential
Vrep (in black) in 0.02M NaCl à 23°C (bars ∅ 40 à 70), transverse, pH=6.6.

Sulphide stress corrosion cracking

The following graph shows the results of the stress corrosion cracking test on 1.4418
and 1.4542. At pH=4.5, both grades do not show any cracking and the surface of the
specimens were brilliant even after the test (Figure 7).

Figure 7- Stress corrosion cracking test in test solution with 5.0 wt% NaCl at 80%
of the Rp0.2; ●: no failure, ○: failure.

No depassivation occurred. At pH=3.5, cracking of 1.4542 was observed. Two of the

four samples (each heat treatment were tested with 2 specimen) were depassivated and a black
surface layer mainly containing FeS (Figure 8) was noted on the specimen.
 SK
1300

1200

1100

1000

900

800

700

600

500
FeL
400 MnL

300 SK
200 CrL
OK CuL
NiL ClK
100 SiK
NaK ClK
0 keV
1 2 3 4 5

Figure 8- Chemical composition of the black surface layer

(analyzed by EBSD technique).

The first tests concerning the 1.4418 didn’t show cracking even at this very low pH.
Further tests need to be done in order to confirm these results. No depassivation occurred on
these samples.
Hashizume et al. 2000 studied the influence of pH on the hydrogen sulphide cracking
resistance of 13% Cr martensitic stainless steels. They showed experimentally that type
13%Cr-5%Ni-2%Mo stainless steel have a pH of depassivation between 3.5 and 3.8 in a
0.035atm H2S+0.0965 CO2 in 5%Nacl+0.5%CH3COOH solution. They took the formula
proposed by Ozaki et al. (Cr+2Mo+0.5N) who actually proposed it for sea water
environments and added the factor -12C to it. This coefficient was defined as the amount of
Cr combined as M23C6 in a tempered martensitic structure. Taking into account this formula
on the calculation of the depassivation pH for our two martensitic stainless steel grades, this
would lead to a little lower value for the 1.4418 compared to the 1.4542, however both are
closed to 3.5.
The better resistance of the 1.4418 could therefore be related to the higher PREN or to
the higher depassivation pH. Residual austenite has also been emphasized by some authors
concerning the SSC resistance. Cassagne et al. 2003 showed in his article concerning the
limitations of the 17-4 PH that the grade with the highest retained austenite has the highest
SSC resistance. Kimura 2000 showed as well that the SSC resistance for higher retained
austenite content steel was higher than that for lower retained austenite content steel. In fact,
the higher content of retained austenite reduced the amount of hydrogen in the steel and
therefore the susceptibility of the 13%Cr steel.
Concerning our both martensitic grades, work is actually in progress in order to study the
influence of retained austenite on the SSC resistance.
 4. Conclusions

The oil and gas market is getting more and more complex and this in terms of
environmental conditions but as well as due to the increasing security constraints. Due to their
specific properties, particularly the high mechanical characteristics and the good corrosion
resistance, stainless steel long products have remarkable opportunities in oil and gas markets.
The high nitrogen austenitic grade can for example easily substitute the 904L grade and offers
even higher mechanical and corrosion properties. Concerning the martensitic grades, the
1.4418 can be an alternative to the 1.4542 which showed in the recent years some mechanical
failures.

REFERENCES

Bauquis, P.R., Bauquis, E. Comprendre l’avenir :pétrole & gaz naturel, Editions Hirle, 2005.
Béranger G. and Mazille H. in Corrosion des métaux et alliages Lavoisier 2002 Lavoisier 75008 Paris.
Boy de la Tour, X.. Le Pétrole : au-delà du mythe, Editions Technip, Publication IFP, 2004
Cassagne, T., Bonis, M., Duret, C., Crolet, J.L. Limitations of 17-4 PH Metallurgical, Mechanical and
Corrosion Aspects. Corrosion 2003, Paper No. 03102, NACE Conference 2003.
Enerhaug J, Grong O, Steinsmo U M: 'Factors affecting initiation of pitting corrosion in
supermartensitic stainless steel weldments', Science and Technology of Welding and Joining, 2001,
Vol 6, No 5.
Hashizume, S., Inohara, Y., Masamura, K. Effects of pH, pH2S on SSC resistance of martensitic
stainless steel, Corrosion 2000, Paper No. 00130, NACE Conference 2000.
Kimura M., Miyata, Y., Toyooka, T. Effect of retained austenite on corrosion performance for
modified 13%Cr steel pipe, Corrosion 2000, Paper No. 00137, NACE Conference 2000.
Ozaki, T. and Ishikawa, Y. Boushoku-Gijyutsu, 38, 266, 1989.
Raja, K.S. and Prasad Rao, K. Environmental cracking behavior of the precipitation hardened
stainless steel, 17-4PH, under applied potential. 1995
Stansbury E.E. and Buchanan R.A. in Fundamentals of Electrochemical Corrosion ASM
International,Materials Park, Ohio 44073-0002 (July 2000)
Wallen B. and Olsson J., Handbook of Stainless Steels, D. Pecker and I.M. Bernstein, Ed.,McGraw
Hill Book Co., 1977 P16-1 to 16-89.

Corresponding author: Marc Mantel (marc.mantel@ugitech.com)