Beruflich Dokumente
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Development of
acom
Superaustenitic Stainless Steels
by
Mats Liljas, Avesta Sheffield, R&D, S-774 80 Avesta, Sweden
and Si were used at an early stage to addition of various trace elements stress corrosion cracking as did 904L
improve the corrosion resistance to and the alloy is still used extensively and Alloy 20 (3). This alloy has been
acids, one important industry being for sulphuric acid service (Carpenter used extensively in the form of pipes
the pulp and paper industry (sulfite 20Cb-3), see Table 1 (2)1. Alloy B6, and tubes in phosphoric and
industry), Increased Cr levels were more known today as 904L, came to sulphuric acid environments but also
used to get a better high temperature a very widespread use starting from as casing and liners in deep sour gas
oxidation resistance. Type 310, with the 1970s in applications such as wells.
about 25% Cr and 20% Ni, was pulp and paper and also chemical Alloy 20 and 904L formed a base
produced already in the 1930s. industry. One reason for the in- for further development of super-
The driving force for development creased use was improved produc- austenitic steels. In the 1960s, an
of the austenitic stainless steels has tion capability through the introduc- alloy that showed high resistance to
been the need from the end user side tion of new refining technologies, e.g. seawater with a Mo content
for materials that are resistant to such as AOD (Argon Oxygen above 5%, NSCD, was introduced by
increasingly harsh environments. A Decarburisation) in the early 1970s. Ugine (4). In 1967, INCO applied for
particular medium that gave rise to These technologies allowed a better a patent of an alloy containing 14-
development of special stainless steel control of alloy additions and im- 21% Cr, 20-40% Ni and 6-12% Mo
alloys already in the 1930s is proved the removal of detrimental with enhanced resistance to corrosion
sulphuric acid. In Europe (France) tramp elements considerably. Thus, in chloride media such as seawater
Uranus B6, with approximately 20% the possibility to produce extra low (5). A steel according to this patent,
Cr, 25% Ni, 4.5% Mo and 1.5% Cu carbon (ELC) steels was improved introduced in the early 1970s, was
was developed and in USA, Alloy 20, drastically. AL-6X with 20% Cr, 25% Ni and 6%
containing 20% Cr, 30% Ni, 2.5% Mo In the 1970s a special high alloy Mo. In 1975 Allegheny Ludlum made
and 3.5% Cu, was developed. Alloy austenitic stainless steel was devel- a patent application on the same
20 had, due to the high alloy content, oped for phosphoric acid service. The alloy ranges in the INCO patent but
poor hot workability and therefore grade, Sanicro 28, contained high Cr claimed improved hot workability
limited availability in wrought form. and Ni amounts (Table 1) and through controlled additions of Ce
This was later remedied by the showed also a high resistance to (6). AL-6X was mainly used in thin
Table 1.
Compositions of austenitic stainless steels for wet corrosion applications.
Alloy Cmax Mn Cr Ni Mo Cu N Other PRE EN UNS Trademark
304 0.08 18 9 18 1.4301 S30400
316L 0.03 17 12 2 24 1.4404 S31603
Alloy 20 0.05 20 30 2.5 3.5 32 - -
20 Cb-3 0.06 20 34 2.5 3.5 Nb, Ta 32 - N08020 Carpenter Technology
B6, 904L 0.02 20 25 4.5 1.5 35 1.4539 N08904
Sanicro 28 0.02 27 31 3.5 1 39 1.4563 N08028 Sandvik
NSCD 0.03 17 16 5.5 2.5 35 - - Ugine
AL-6X 0.03 20 25 6 40 - N08366 Allegheny Ludlum
AL-6XN 0.03 20.5 24 6.3 0.22 45 - N08367 Allegheny Ludlum
1.4439 0.03 17 14 4 0.15 33 1.4439 S31726
2RE69 0.02 25 22 2 0.12 37 1.4466 S31050 Sandvik
ASN 7W 0.04 18 16 7 2 0.15 43 - - Böhler
VEW 963 0.03 17 16 6.3 1.6 0.15 40 - - VEW
Antinit 3974 0.03 6 23 17 3 0.40 0.2Nb 39 - - Thyssen
254 SMO 0.02 20 18 6.1 0.7 0.2 43 1.4547 S31254 Avesta Sheffield
1925hMo 0.02 20 25 6.2 0.7 0.2 44 1.4529 N08925 VDM
SX 0.02 17.5 20 1 2 5 Si 21 - S32615 Sandvik
Alloy 31 0.02 27 31 6.5 1.2 0.2 52 1.4562 N08031 VDM
934LN 0.02 10 20 15 4.5 0.4 41 - -
1.4565 0.03 6 24 18 4.5 0.4 45 1.4565 S34565
654 SMO 0.02 3 24 22 7.3 0.5 0.5 56 1.4652 S32654 Avesta Sheffield
1
Commercial Trademarks used in this paper are attributed once in Tables 1 and 2.
2
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walled condenser tubing for seawater AL-6XN and Cronifer 1925hMo, see development of 654 SMO, with just
cooled power plants. The high alloy Table 1. Common for this family of so 3% Mn and still 0.5% N as listed in
content made the steel prone to called 6Mo super austenitic steels is a Table 1 (18). 654 SMO is one of the
precipitation of intermetallic phases very high resistance to pitting and most highly alloyed superaustenitic
preventing fabrication in heavier crevice corrosion. Therefore, they stainless steels produced to date and
sections. have been used extensively in the as a consequence, it has a corrosion
In the late 1960s it was shown that offshore and desalination industries resistance on level with the best
N addition retards both carbide and for seawater handling, in chlorine nickel-base alloys, as will be shown
intermetallic phase precipitation in and chlorine dioxide stages in bleach below.
austenitic steels (71. The German plants, and in flue gas desulphuriza- Parallel to the evolution of austenitic
grade 1.4439 (∼317 LMN) with tion plants. stainless steels there was also an
minimum 4% Mo and 0.15% N was A special development in the 1970s early development of austenitic
an example of a steel where this was a high Si austenitic stainless steel nickel-base alloys for corrosive en-
knowledge was used. This grade has for use in sulphuric acid at high vironments. Thus for example various
since been used in many applications temperature and concentrations and Hastelloys were developed in the
with severe corrosion environments highly concentrated nitric acid. 1920s and 1930s. The production
such as heat exchangers, flue gas Avesta Jernverk and Sandvik Steel was made in quite a small scale
desulphurization (FGD) and pulp and jointly developed and patented this during the first decades. As with the
paper bleach plants. A further alloy (13). It was later denominated austenitic stainless steels, the intro-
development of 1.4439 was Böhler SX and contains as high as 5% Si duction of new refining technologies
Antinit ASN 7W with as high as 7% and 2% Cu (Table 1) providing the such as electroslag remelting (ESR),
Mo, see Table 1 (8). This alloy did for steel excellent properties for those vacuum arc remelting (VAR) and AOD
some reason not see any important special environments. resulted in increased yields and
commercial use and a successor with Further developments in the 1980s improved production economy.
lower molybdenum content, VEW have been to use the Sanicro 28 base An evolution has also occurred
A963 (Table 1), was presented later and add more alloying elements. during the years of heat resisting
(9). Also, other higher alloyed Alloy 31 is one example where the austenitic stainless steels. A deter-
austenitic steels were developed Mo content has been increased and mining factor for this field of applica-
where the strong austenitizing effect N addition has been practised, see tion is the fact that the austenitic
of N was utilized to an even greater Table 1 (14). This grade has, due to structure implies a high creep strength.
extent. To achieve higher N solubility its very high Cr level, a higher pitting Types 309 and 310 were thus used
and thereby even higher N levels, Mn resistance than the current 6Mo early for high temperature service due
alloying was practised. This resulted grades. to both high oxidation resistance and
in highly alloyed austenitic grades The concept of N alloying auste- creep strength. For more critical
with high corrosion resistance as well nitic grades has been used for applications nickel-base alloys with
as a much improved strength. One decades and very high N levels, up ∼20% Cr and up to ∼70% Ni were
example was Amaganit 3974 with the to about 1%, have been achieved used. They contained various other
composition as shown in Table 1. The (15). Well known commercial grades additions for improved high tempera-
grade was used in non-magnetic are for example the Nitronic series ture performance. Austenitic stainless
submarines as one example. from Armco. The positive influence of steel grades with ∼20% Cr and 30-
Another development in the early Mn on N solubility has been used in 40% Ni have also been available
1970s using N addition was an alloy many developments but Cr and Mo since the early 1920s as oxidation
intended for urea production. The have similar and maybe synergetic resistant alloys for use in furnace
alloy, 2RE69 (Table 1), with high Cr effects. In the 1980s alloys, high in parts and heating elements. Due to
and Ni levels, showed excellent these three elements, and with very nickel shortage in the early 1950s,
corrosion resistance also in nitric acid high N levels were developed in INCO introduced Incoloy 800, con-
and chloride environments (10, 11). Sweden and Germany (16, 17). Both taining about 20% Cr and 30-35%
In 1976 Avesta Jernverks AB grades, 934LN and 1.4565, con- Ni (19). The alloy also contained Al
patented and introduced 254 SMO, tained about 0.4% N, as seen in and Ti additions that were found to
a 6Mo superaustenitic stainless steel Table 1. These grades show similar improve the high temperature prop-
with a balanced composition corrosion resistance but superior erties considerably. Later, several
containing 20% Cr, 18% Ni, 6% Mo, strength compared to the 6Mo steels. modified versions have resulted in
0.7% Cu and 0.2% Ni (12). The The use of thermodynamic databases Alloy 800 representing a family of
addition of N made the precipitation to predict the N solubility in high materials with a range of properties.
of intermetallic phases more sluggish, alloy austenitic steels has resulted in Minor alloy additions to the high
facilitating production of heavier further development. If the alloying temperature materials have been
gauges. It also improved the mechan- levels of Cr and Mo are further used to improve the scaling resistance
ical and corrosion properties. Later, increased, even higher N contents and creep strength. Elements most
other 6% Mo steels followed this N can be reached yet with quite low commonly used to reduce the scale
alloying approach. Examples include Mn addition. This was utilized in the formation are Al and Si but trace
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4
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Uniform corrosion Pitting and crevice corrosion CPT values for a number of austenitic
Uniform corrosion on stainless steels Pitting and crevice corrosion are two stainless steels are plotted against the
occurs mainly in acids and hot closely related types of corrosion that PRE value using a factor for N of 16.
alkaline solutions that are able to regularly cause failures on stainless The 6Mo steels, represented by
destroy the passive layer. The most steels exposed to chloride containing 254 SMO, show quite high PRE num-
important alloying additions to in- environments. It is also a well known bers and CPT values. This family of
crease the passivity of a stainless fact that increased contents of Cr and superaustenitic stainless steels has
steel are Cr and Mo. Thus, the alloys Mo enhance the pitting corrosion also been used extensively in appli-
very high in these elements show resistance. By adopting a pitting cations where a high pitting resist-
excellent corrosion resistance in many index or pitting resistance equivalent ance is required. The highest PRE
solutions. Ni increases the resistance (PRE) the influence of various elements values are reached in Alloy 31 and,
in some non-oxidizing acids and in on the chloride pitting corrosion particularly, in 654 SMO. With these
certain environments additions such resistance can be estimated. The PRE high values the pitting resistance is on
as Si, Cu and W give increased is the result of application of linear the level with many high performance
resistance. Corrosion data for various regression mathematics to the values nickel-base alloys. The ranking of the
steels could be presented as cor- of a particular corrosion result as a crevice corrosion resistance is largely
rosion rates in mm/year or in iso- function of the composition of the similar as that of pitting resistance.
corrosion diagrams covering different grades tested. The most current PRE
concentrations and temperatures of a expression involves Cr, Mo and N, as
certain chemical. Such information is shown below, but also other elements Stress corrosion cracking
available for example in Avesta could have some effect on pitting (SCC)
Sheffield Corrosion Handbook (22). In resistance. Stress corrosion cracking is caused by
Figure 1, an iso-corrosion diagram for a combination of tensile stresses and
a number of austenitic stainless steels PRE = % Cr + 3.3 x % Mo + k x % N,
corrosive environment. For stainless
in sulphuric acid is shown. The higher where k is reported as between steels, SCC occurs mainly in chloride
alloyed steels show a superior resist- 13 and 30. environments above about 50°C. The
ance in a wide range of concentra- standard austenitic stainless steels are
tions than the standard grades 304 A positive factor has been pro- more prone to SCC than ferritic and
and 316. The diagram also shows posed for W and a strong negative duplex stainless steels. However,
that the high silicon steel, SX, has a factor has been reported for S (23). when it comes to superaustenitic
very high resistance to concentrated The pitting indices, using a factor for stainless steels, very high resistance
sulphuric acid. The iso-corrosion dia- N of 16, are listed in Table 1. A can be obtained, in many instances
gram in hydrochloric acid is shown in common laboratory test method for superior to the duplex grades. This is
Figure 2. Also here, the great advan- ranking different alloys is a modified illustrated in Figure 4 (page 6), where
tage of using a high alloy superaus- ASTM G48 test where a critical the threshold stresses for SCC, under
tenitic grade is apparent. In sulphuric pitting temperature (CPT) can be severe evaporative conditions, deter-
and hydrochloric acid the very high assessed in a ferric chloride solution. mined by the drop evaporation test
alloyed grade 654 SMO shows The CPT is normally defined as the are shown. Increased risk of attack is
superior corrosion resistance at most lowest temperature where a pitting encountered if hydrogen sulphide
concentrations. attack occurs. In Figure 3 (page 6) the (H2S) is present, as common in oil and
Figure 1. Figure 2.
Isocorrosion diagram, 0.1 mm/year, in sulphuric acid. Isocorrosion diagram, 0.1 mm/year, in hydrochloric acid.
5
acom No. 2-95
Figure 3. Figure 4.
Plot of CPT in Ferric chloride versus PRE for several austenitic grades. Threshold stresses determined by the drop evaporation test.
gas wells. Such wells are currently carbide precipitation followed by susceptibility. Although having an
called sour wells. Superaustenitic susceptibility to intergranular cor- austenitic solidification, 6Mo grades
stainless steels show high resistance rosion of the heat affected zone. This exhibit less sensivitiy. However, the
in sour environments while the duplex problem is today eliminated by nickel-base fillers that are normally
stainless steels are more prone to control of the carbon levels in the used for this group of steels may
cracking due to hydrogen embrittle- steels. Due to a stable structure there bring the deposit to a more suscep-
ment of the ferrite phase. In the most is no need to preheat or post weld tible composition. To avoid or reduce
severe oil and gas environments with heat the weldment. Normally, there is the hot cracking, welding should be
high hydrogen sulphide contents, no minimum heat input limitation and done with low arc energy and with
austenitic alloys are the optimal quite high arc energies can be used joints giving low restraints.
choice of material. without any adverse effects. One alloying element in steels with
The general observation is that the For the more highly alloyed super- a high tendency to segregate during
high alloy superaustenitic steels show austenitic grades, particular concern solidification is molybdenum. Ac-
superior resistance to all four corro- has to be paid to two phenomena cordingly, superaustenitic grades with
sion types described above. There- related to the solidification, namely high molybdenum levels such as the
fore a single alloy can be used in those of hot cracking and elemental 6Mo steels show large molybdenum
many harsh environments which is of segregation. Hot cracking occurs microsegregations in autogenous
great importance in some industries. either directly during the solidification, weld metals. The areas depleted in
The evolution has been that super- and is referred to as solidification molybdenum have a lower local
austenitic grades can serve as multi- cracking, or upon reheating of suc- pitting index and are thus less resis-
purpose grades similarly to the role of cessive weld runs and is then con- tant to chloride pitting corrosion. To
316L for less severe conditions. Thus sequently called reheat cracking. overcome this reduction in corrosion
317L and 904L have been multi- Both types of cracking are related to resistance, fillers overalloyed with
purpose grades for the pulp and the solidification mode of the weld molybdenum, preferably nickel-base
paper industry for many years. This deposit and presence of certain alloys, are used. Alternatively, a post
role has today been overtaken by the impurities such as sulphur and phos- weld solution heat treatment can
6Mo grades. phorous. A primary ferritic solidifica- restore the pitting resistance of auto-
tion as is the case in standard aus- genous welds. Another possibility is
tenitic grades such as 304 and most welding with nitrogen addition to the
316 gives high crack resistance. shielding gas that enhances the
Welding Superaustenitic stainless steels that nitrogen level in the weld to such a
The welding of common austenitic normally have fully austenitic solid- degree that improved pitting resist-
stainless steels is very well established ification are therefore more prone to ance is achieved. This, however, may
and is generally considered to give both types of cracking. A classical not be fully sufficient to restore the
very few problems provided appro- case is grade 310 showing a well- pitting resistance.
priate procedures and recommended known susceptibility to hot cracking.
consumables are used. One classical Some of the highly alloyed, heat
problem is that of weld decay due to resistant grades have a similar
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acom No. 2-95
Although Avesta Sheffield has made every effort to ensure the accuracy of this publication, neither it nor any contributor can accept any legal
responsibility whatsoever for errors or omissions or information found to be misleading or any opinions or advice given.
7
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