An Introduction to Duplex and
Super Duplex Stainless Steels
Summary Duplex stainless steels
• provide high levels of yield strength and good levels of impact strength
• achieve excellent levels of corrosion resistance in a wide variety of mediums
• can be confidently specified for applications between -50˚C and +250˚C
• are resistant to stress corrosion cracking
• can be readily machined, fabricated and welded with the correct tooling and procedures
• offer unbeatable levels of cost competitiveness versus more expensive alloys
Introduction (and therefore the properties and characteristics) of a given
alloy from the chart below.
Duplex stainless steels are so-called due to their combination
of austenitic and ferritic microstructures, in an approximately
50:50 ratio. The microstructure of an alloy is another way to
i) Alloy costs
describe the crystal structure of the atoms, and it is important One obvious feature of the Schaeffler diagram is how close a
as it defines many of the alloy’s properties. Whereas the most number of the most common (3xx and 4xx) alloys are to the
common 3xx and 4xx stainless steels are exclusively austenitic boundaries of a particular microstructure. As the different
or ferritic in structure respectively, duplex stainless steels elements used can vary considerably in cost, an important
combine the most attractive features of both. aspect of alloy design is maintaining the favourable properties
without compromising cost. Therefore 304/316 will use the
A family of duplex stainless steels minimum amount of expensive nickel in order to remain fully
austenitic. Ferritic (4xx) and martensitic (17/4 PH) grades
The Schaeffler diagram is a useful tool that indicates the follow a similar pattern, albeit with different elements.
microstructure of an alloy based upon its chemical
composition. The presence of elements such as chromium, An important feature of duplex and super duplex stainless
silicon, molybdenum, niobium and tungsten (chrome steels is their ability to achieve excellent levels of strength and
equivalent content) tend to favour the existence of a ferritic corrosion resistance in addition to competitive costs. The
microstructure, whilst the presence of carbon, nickel, widespread use of nitrogen as an alloying addition was one of
manganese, copper and nitrogen (nickel equivalent content) the main drivers for their development. Not only does this
tend to favour the existence of an austenitic microstructure. element improve the overall corrosion resistance, but it also
acts as a nickel-equivalent - substituting a high-cost element
Adding together the content of the nickel - and chrome- with a low-cost element.
equivalent elements allows the reader to predict the structure
30
Increasing ‘Nickel Equivalent’ content %
[Ni + Co + 0.5Mn + 0.3Cu + 25N + 30C]
6Mo
Austenitic Grades
904L Duplex Grades
316
304 Hyper Duplex 27% Cr
Super Duplex 25% Cr
Duplex 22% cr
17/4 PH
Martensitic Grades
Ferritic Grades
410 440
0 40
Increasing ‘Chrome Equivalent’ content %
[Cr + 1.5Mo + 5V + 5.5AI + 1.75Nb + 1.5Ti + 0.75W]
Figure 1. Schaeffler Diagram, highlighting the position of duplex alloys.
Ferritic Austenitic Duplex Martensitic
HHH Standard HH
HHH HHHHH
HHHHH Super HHH
Corrosion resistance
Stress Corrosion Cracking HHHHH HH HHHH HHHH
Strength HHH HH HHHHH HHHHH
Tough (low temps) HH HHHHH HHH HH
Formality HH HHHH HHH HH
Weldability H HHHHH HHHH H
Non-magnetic H HHHHH HHH H
Figure 2. An overview of stainless steel properties depending upon microstructure (1=low, 5=high)
ii) Alloy types Duplex Stainless Steels
At a very simplistic level the high-level properties of each Duplex stainless steels were originally developed in the 1930’s
microstructure are summarised in the table. The table above is for application in paper and pulp manufacture, based around a
perhaps the clearest way to see how duplex stainless steels 22% Cr composition. Compared with the more common 3xx
capture the most favourable aspects of both austenitic and grades they replaced, these early duplex stainless steels offered
ferritic microstructures. twice the strength and a significant uplift in corrosion resistance.
Rather confusingly, there are two different designations for
iii) Corrosion resistance the most common type of duplex stainless steel. When
Pitting Resistance Equivalent number (PREN) is a helpful originally developed, the grade was identified as UNS S31803
theoretical way of comparing the pitting corrosion resistance (F51). However, in order to enhance the resistance to pitting
of various types of metals based on their chemical corrosion, steel manufacturers started to produce this grade
compositions. The most widely accepted version of the PREN with the composition of the key alloy additions at or near the
formula utilises the content of chromium, molybdenum and maximum levels. In order to differentiate this enhanced
nitrogen as: PREN = %Cr + 3.3x %Mo + 16x %N. product from the standard product it was re-designated as
UNS S32205 (F60). As such S32205 meets the requirements of
The progression from duplex to super duplex to hyper duplex S31803 but not vice-versa.
stainless steels can be clearly seen on the Schaeffler diagram.
Increasing an alloy’s content of chromium, molybdenum and Sandvik’s Sanmac 2205 offers ‘enhanced machinability as
nitrogen will increase its resistance to pitting corrosion. standard’ compared with standard duplex grades, through
Duplex alloys typically have a PREN of >34, super duplex alloys careful control of the composition and production processes.
are >40 and hyper duplex grades approach 50. Whilst it is not The distribution of inclusions encourages chip-breaking,
an exact science, and will depend upon the exact operating resulting in improved tool life and productivity gains.
environment and product form, it is a
helpful tool. The changes in Super Duplex Stainless Steels
composition also improve the
strength of these alloys too. Whilst concepts like the Schaeffler diagram and PREN
equation suggest it is relatively easy to develop new and
improved alloys, the complexities of production should not be
understated. The desire to create higher performance alloys
partly-coincided with the development of off-shore oil and
gas exploration. Combining high strength to limit the weight
of suspended components, with excellent corrosion resistance
to operate in the UK’s North Sea, were important objectives.
Ferralium (UNS S32550, 1.4507, F61) is the original super
duplex stainless steel, patented by Langley Alloys in 1967 and
launched in 1969. As such it was the very first alloy to be
captioned as ‘super duplex’ and based around a 25%
chromium content. Compared with later alternatives, it is the
only grade to exceed a minimum yield strength of 85ksi, with
an increased copper content for superior pitting corrosion
resistance.
Alloy 32760 (UNS S32760, Zeron 100, 1.4501, F55) was
developed in the 1980’s by Mather & Platt (UK) around the
same 25% chromium basis. However, it contains less copper
but a deliberate addition of tungsten instead, claimed to
selectively improve corrosion resistance.
The final grade most commonly stocked as solid bar is Alloy
32750 (UNS S32750, 1.4410, F53) which is promoted by
Sandvik as SAF2507 (Alloy 2507). It contains neither copper
nor tungsten as significant additions.
Composition of Duplex and Super Duplex
Stainless Steels
As duplex and super duplex alloys have gained acceptance in
the marketplace, the number of specifications has tended to
proliferate. So-called lean duplex grades aim to match the
performance of duplex grades, but reducing the content of
Compared with the
expensive elements such as nickel. At the other extreme,
hyper duplex stainless steels have been developed by Sandvik
to rival the corrosion resistance of much more expensive
nickel alloys. In all cases, mill- and customer-specific grades
more common 3xx
have been created, some more widely adopted in a particular
product form i.e. as sheet or tubes only.
Both lean duplex and hyper duplex stainless steels are not
grades they
commonly available in bar form.
The most common duplex stainless steel offered in bar form is
S32205, which can be dual-certified as S31803. This accounts
replaced, these
for around 2-3% of the global market for stainless steel bars.
The most common super duplex stainless steels in bar form
are S32750, S32760 and Ferralium 255. These account for up to
early duplex
2% of the global market for stainless steel bars.
The most noticeable differences in the composition of these
three alloys is in the level of deliberate additions of copper
stainless steels
and tungsten. Copper is widely recognised as improving the
corrosion resistance to acids such as sulphuric acid,
phosphoric acid and nitric acid. Ferralium 255 typically
offered twice the
contains 2.0% copper, and as a consequence is highly
specified in a number of chemical process industries, such as
fertiliser and urea manufacture that use these acids within
their process.
strength and a
In addition, Ferralium 255 is specified with much lower levels
of phosphorus and sulphur. This reduces the incidence and
size of any inclusions, which if present at the surface of a
significant uplift in
component would be a potential source for pitting corrosion.
It therefore contributes to the improved corrosion resistance
of Ferralium 255 in practice.
corrosion resistance.
UNS Grade Tradename Cr Ni Mo N C Mn P S Si Cu Other
22.0 - 1.0 - 0.05 - 4.0 -
S32001 0.6 0.03 0.04 0.03 1 1
Lean 23.0 3.0 0.17 6.0
Duplex 21.5 - 3.0 - 0.05 - 0.05 - 0.05 -
S32304 2304 0.03 2.5 0.04 0.03 1
24.5 5.5 0.60 0.20 0.60
24.0 - 5.5 - 1.2 - 0.14 -
S31200 0.03 2 0.045 0.03 1
26.0 6.5 2.0 0.20
24.0 - 5.5 - 2.5 - 0.1 - 0.2 - W 0.1 -
S31260 0.03 1 0.03 0.03 0.75
26.0 7.5 3.5 0.20 0.8 0.2
Duplex
21.0 - 4.5 - 2.5 - 0.08 -
S31803 0.03 2 0.03 0.02 1
23.0 6.5 3.5 0.20
22.0 - 4.5 - 3.0 - 0.14 -
S32205 2205 0.03 2 0.03 0.02 1
23.0 6.5 3.5 0.20
24.0 - 5.5 - 3.0 - 0.20 - 0.5 -
S32520 255 0.03 1.5 0.035 0.02 0.8
26.0 8.0 4.0 0.35 2.0
24.0 - 4.5 - 2.9 - 0.10 - 1.5 -
S32550 255 0.04 1.5 0.04 0.03 1
27.0 6.5 3.9 0.25 2.5
Ferralium 24.5 - 5.5 - 3.1 - 0.20 - 0.80 - 1.5 -
0.025 0.025 0.005 0.7
Super 255 26.5 6.5 3.8 0.25 1.20 2.0
Duplex 24.0 - 6.0 - 3.0 - 0.24 -
S32750 SAF 2507 0.03 1.2 0.035 0.02 0.8 0.5
26.0 8.0 5.0 0.32
24.0 - 6.0 - 3.0 - 0.20 - 0.5 - W 0.5 -
S32760 Zeron 100 0.03 1 0.03 0.01 1
26.0 8.0 4.0 0.30 1.0 1.0
23.0 - 2.5 - 1.0 -
S32900 329 0.75 0.06 1 0.04 0.03
28.0 5.0 2.0
S32707 SAF 2707 27 6.5 4.8 0.4 0.03 1.5 0.035 0.01 0.5 Co 1.0
Hyper
Duplex
S33207 SAF3207 32 7 3.5 0.5 0.03 1.5 0.035 0.01 0.8
Yield Strength Ultimate tensile
UNS Grade Tradename Elongation (%)
(ksi) Strength (ksi)
S32001 65 90 25
Lean Duplex
S32304 2304 65 90 25
S31200 65 100 25
S31260 65 100 25
Duplex
S31803 65 90 25
S32205 2205 65 90 25
S32520 255 80 109 25
S32550 255 80 109 25
Ferralium 255 85 115 25
Super Duplex
S32750 SAF 2507 80 109 15
S32760 Zeron 100 80 109 25
S32900 329 65 90 20
S32707 SAF 2707 101 116 25
Hyper Duplex
S33207 SAF3207 101 123 25
in ‘sour’ fields can greatly exacerbate the corrosivity of natural
seawater due to its acidic nature. Stress corrosion cracking can
be avoided by using austenitic alloys of high corrosion
resistance, but these will tend to be highly-alloyed, and
therefore highly expensive. Alternatively, the mix of austenitic
and ferritic grains within a duplex alloy slows and prevents the
propagation of cracks within duplex and super duplex
stainless steels. The most popular duplex and super duplex
stainless steels are listed in NACE MR 0175 / ISO 15156 as
being suitable for sour service.
Duplex and super duplex stainless steels can be widely used in
operating temperatures from -50ºC to +250ºC. At the lower
temperature, impact strength will fall away sharply, as it
undergoes a ductile-brittle fracture transition. At the higher
temperature, continuous service above this range will result in
the precipitation of deleterious phases that impact
mechanical properties and corrosion resistance.
Machining and Welding
Duplex and super duplex stainless steels require more care
when machining than standard stainless steels. They are
obviously higher strength, which puts greater stress on
tooling and machinery. In addition, the chip formed is strong
Figure 3. Sanmac 2205 offers ‘enhanced machinability as and abrasive to tooling. The absence of sulphur or other free-
standard’ with improved chip-breaking properties. machining additives means that chip breaking is also more
difficult too. Therefore, it is recommended to use tooling with
carbide inserts and a positive chip-breaking geometry.
Mechanical Properties of Duplex and The phenomenon of ‘movement’ is also anecdotally reported
Super Duplex Stainless Steels for these grades. The presence of residual stresses within the
original bar can lead to distortion, which is thought to be
The yield and tensile strength of this family of alloys will influenced by the mixed ‘duplex’ microstructure. Setting aside
generally increase as you progress from duplex to super partly-machined components for any residual stresses to ‘relax’
duplex to hyper duplex variants. Duplex stainless steels are between passes can help to minimise the extent of any
the logical next-step when looking for improved performance movement. Stress relieving heat treatments can also be used
over standard 304/316 austenitic alloys, whilst super duplex for more challenging components such as long pump shafts.
stainless steels are close enough to the most popular nickel However, it should be noted that this operation may reduce
alloys to make them worthy of consideration. the impact strength and corrosion resistance.
Through careful control of the composition and processing Welding has historically been a limitation for duplex and super
conditions, Ferralium 255 is able to achieve a higher yield duplex stainless steels, but should not be a concern as long as
strength compared with S32750 and S32760 (85ksi vs. 80ksi). effective weld procedures are adopted. These grades are
This increase can be beneficial in components where weight is prone to the formation of harmful phases when exposed to
an issue, such as in suspended loads. It can also be used to elevated temperatures for a period of time. In poorly welded
reduce the size of critical components. components, corrosion has been observed in the heat
Stress corrosion cracking occurs when metal components are affected zone (HAZ) exposed to such undesirable conditions.
exposed to a combination of tensile stresses and a corrosive The answer is to avoid excessive temperatures by controlling
environment. It is particularly relevant to alloys used in oil and weld speed, plus limiting the inter-pass temperature in multi-
gas applications, as the presence of hydrogen sulphide (H2S) run welds.
Applications for Duplex and Super Duplex f ) vegetable processing – a less obvious application has
been in the construction of equipment for processing
Stainless Steels grains and vegetables, The severe wear and corrosion
Since their development in the 1930’s, duplex stainless steels (‘erosion corrosion’) conditions involved in sugar cane
have been widely used in a variety of industrial processes processing, mixers and centrifuges, have been well-served
where 304/316 grades are not sufficiently robust. Aside from in Ferralium 255.
paper and pulp manufacture, other common applications can g) water treatment – associated applications such as sewage
be found in water treatment, architecture and marine treatment, desalination and swimming pools all use super
hardware. duplex grades to resist the threat of corrosion from
Given the additional performance of super duplex stainless seawater, contaminated or brackish solutions.
steels, they are used in many demanding applications, h) paper and pulp – most components throughout the
including: production processes of pulp and paper can make use of
a) Oil & Gas – downhole tooling, wellhead and subsea super duplex alloys. Duplex and lean duplex grades are
equipment, pumps and valves all make use of super duplex typically specified where possible on grounds of cost, but
alloys. As a family, these alloys are included in NACE super duplex grades will be used in areas of greatest risk of
MR1075 / EN15156-3 as being suitable for use in H2S- failure.
containing environments i.e. sour service wells. i) pump shafts – this is a ‘sweet spot’ for super duplex
b) bolts and fasteners – are a very common application of stainless steels, exploiting the combination of high
super duplex stainless steels, due to their very high starting strength, wear and corrosion resistance.
strength and the possibility to work harden them to even
higher strength levels.
c) pollution control scrubbers – this has been a successful
application for super duplex stainless steels in the
fabrication of precipitators, fans and pumps. These grades
strongly resist corrosion in such environments; seawater is
frequently used as a coolant, and acids such as sulphuric
acid are formed from the emissions of the burnt fuel.
The recent application of marine scrubbers are
unable to exploit the excellent properties of
these alloys, and are having to use more
expensive super austenitic stainless steels
instead. Legislation is forcing such vessels to
selectively employ their scrubber systems in
certain locations. When not in use, the scrubber
will see temperatures beyond the sensible
working range for duplex and super duplex
alloys.
d) marine applications – propellers, shafts,
rudders and seals are frequently supplied in
super duplex grades, when austenitic stainless
steels such as XM-19 are not deemed
acceptable on the grounds of either corrosion
resistance or strength.
e) chemical process industry – a large number
of processes will utilise sulphuric acid, nitric
acid and phosphoric acid, such as in the
production of PP, PVC, TiOx, dyes and
agrochemicals. Fortunately, super duplex
stainless steels are generally resistant to
reducing acids, as well as offering good abrasion
and wear resistance.
Ferralium 255 is widely specified in the production of
fertilisers, as mixers, tanks and vessels, pumps and valves,
as it strongly resists corrosion from the acids used
(sulphuric, phosphoric or nitric acid) and the mechanical
impact of ‘phos rock’.
Unique metals for your demanding applications
UK Singapore US - Portland US - Houston
The Wharf 9B Jalan Ampas Langley Alloys 300 Hilbig Rd Super-Duplex
504-506 Lowfield Dr Singapore 12323 NE 99th Street Conroe, Texas 77301-1458
Newcastle, Staffordshire 329517 Vancouver WA 98682 United States
Duplex
ST5 0UU Tel: +65 6254 1139 Tel: 800-878-3675 Tel: 281 819 5588 Stainless
Tel: +44 (0)1782 610250
[email protected] Tel: (360)-883-0569
[email protected] Copper Alloys
Fax: +44 (0)1782 612219 Fax: 360-883-0764 Nickel Alloys
[email protected] [email protected] www.langleyalloys.com
While care has been taken to ensure that the information contained in this publication is accurate, Langley | 01/2020 | Issue 1
Alloys does not accept responsibility or liability for errors or for information which is found to be misleading.
