Duplex Stainless Steels for Sea Water Service

Introduction
1. Duplex stainless steels were developed in the early thirties in Sweden and in France.
The driving force to the development was the sensitivity to intergranular corrosion of existing
austenitic steels which often contained 0.08-0.10% carbon. The duplex steels had the same
carbon content but proved much less sensitive to this type of corrosion. Over the last several
decades, there has been an increased interest in the use of duplex stainless steel
for pumps used in marine environments. The synergistic effect of increased levels of
chromium, molybdenum and nitrogen have been shown to provide outstanding
benefits for localized corrosion resistance of the duplex alloys comparable to those
of the highly alloyed austenitic alloys. Today both the super-austenitic and super-
duplex stainless steels are widely
being utilized in seawater pumps.

2. Duplex Stainless Steels have a structure that contains both ferrite and austenite. Duplex
alloys have higher strength and better stress corrosion cracking resistance than most austenitic
alloys and greater toughness than ferritic alloys, especially at low temperatures. It has been
noted for many years that it is mainly the lack of localized corrosion (i.e. pitting and
crevice corrosion) resistance that has limited the suitability of stainless steels for
seawater services. This understanding has provided the motivation for developing
more highly alloyed duplex stainless steels that offer superior corrosion resistance
in seawater and other chloride media.

3. None of the earlier first or second-generation duplex stainless steels were

resistant enough for seawater use until nitrogen and higher molybdenum alloying
was introduced, and the so-called super-duplex stainless steels were made
available.

4. The corrosion resistance of duplex alloys depends primarily on their composition,

especially the amount of chromium, molybdenum, and nitrogen they contain. The chemical
composition based on high contents of Cr and Mo, improves intergranular and pitting corrosion
resistance, respectively. Additions of nitrogen can promote structural hardening by interstitial
solid solution mechanism, which raises the yield strength and ultimate strength values without
impairing toughness. Moreover, the two-phase microstructure guarantees higher resistance to
pitting and stress corrosion cracking in comparison with conventional stainless steels. Modern
seawater resistant duplexes usually contain at least 25% chromium and have
increased levels of molybdenum and nitrogen alloying over the standard duplex
offerings such as wrought UNS S32900 (AISI Type 329), and cast UNS J93370 (ACI
Type CD4Mcu).

5. Duplex alloys are often divided into three sub-classes: Lean Duplex (AL 2003™ alloy),
Standard Duplex (AL 2205™ alloy), and Superduplex (AL 255™ Alloy and UNS S32760), as
described in Table 1.
 Table 1.
Duplex steel types.

Stainless Steel - Duplex

Alloy Density Tensile 0.2% Yield Elong-
(UNS Composition lb/in3 Strength Strength ation
Designation) End Use nominal wt% Specifications (g/cm3) ksi. (MPa) ksi. (MPa) % Hardness

AL 2003™ Piping, tubing in C 0.03 max, Mn 2.0 ASTM A-240 0.279 100 min 70 min 25 31
S32003 general corrosion and max, Si 1.0 max, Cr ASME Code (7.72) (sheet) / (sheet) / min Rockwell
choride environments, 19.5-22.5, Ni 3.0-4.0, Case 2503 95 min 65 min C max
architectural Mo 1.5-2.0, N 0.14-0.2, (plate) (plate)
structures, roofing, Fe Balance (690min (485 min
topside applications (sheet) / (sheet) /
on oil platforms 655 min 450 min
(plate) (plate)

AL 2205™ Pipe, Tubing in C 0.03 max, Mn 2.0 ASTM A-240 0.280 90 min 65 min 25 31
S31803/S32205 general corrosion and max,Si 1.0 max, Ni ASME SA-240 (7.75) (31803) / (450 min) min Rockwell
chloride stress 4.5-6.5, S31803: Cr 95 min C max
corrosion 21.0-23.0, Mo 2.5-3.5, (32205)
environments N 0.08-0.20, S32205: (620 min
Cr 22.0-23.0, Mo 3.0- (31803) /
3.5, N 0.14-0.20, Fe 655 min
Balance (32205))

AL 255™ Pipe, containers for C 0.04 max, Mn 1.5 ASTM A240 0.279 110 min 80 min 15 32
S32550 CPI, Oil & Gas max, P 0.04 max, S (7.73) (760 min) (550 min) min Rockwell
0.03 max, Si 1.0 max, C max
Cr 24.0-27.0, Ni 4.5-
6.5, Mo 2.9-3.9, N 0.1-
0.25, Cu 1.5-2.5, Fe
Balance

Benefits
6. The benefits of these steels over Austenitic or Martensitic steels can be summarized as
follows:

• High strength
• High resistance to pitting, crevice corrosion resistance
• High resistance to stress corrosion cracking, corrosion fatigue and erosion
• Good sulfide stress corrosion resistance
• Low thermal expansion and higher heat conductivity than austenitic steels
• Good workability and weldability
• High energy absorption

Factors Affecting Seawater Resistance

7. From a corrosion viewpoint, seawater may be considered a neutral chloride
salt solution that promotes localized corrosion in stainless steels. In saline waters or
seawater environments at or near neutral pH levels the protective passive film on
stainless steels renders them virtually immune to general corrosion. Unfortunately,
this passive film can break down locally in certain environments containing
chlorides. At the intermediate temperatures existing in many seawater pumps,
crevice and pitting corrosion are the major forms of corrosion damage most often
observed.

8. Over the past 25 years, a number of highly alloyed duplex stainless steels
offering superior corrosion resistance have been introduced for seawater service.
Many researchers and much of the materials/corrosion literature indicates that
excellent resistance to localized corrosion can be achieved in neutral and acid
chloride containing media by increasing chromium, molybdenum and nitrogen
content in these materials. In addition more noble values are exhibited in seawater
with increases of these key elements.

9. Increased nitrogen content has led to improved corrosion resistance due to a

better balance of alloying elements between the dual austenite and ferrite phases,
resulting in a decreased susceptibility towards alloy partitioning between these two
phases.

10. Regarding other alloying elements, it should be noted that some duplex
stainless steels contain tungsten additions in the range of 0.5 % to 2.0 %. Tungsten
additions have been shown to improve crevice corrosion resistance, with benefits
similar to that of molybdenum. Copper additions in certain duplex alloys along the
order of 0.5 % to 3.25 % are used primarily to extend the application to include
sulfuric acid service, and offer better resistance in polluted seawater that contains
hydrogen sulfide or other reducing reactants.

Pitting Resistance Equivalent

11. A familiar aspect of these newer seawater worthy duplex stainless steels is a high
content of the alloying elements chromium, molybdenum, and nitrogen. Attempts have been
made to establish a measure of the localized corrosion resistance by assessing the relative
effect of these important alloying elements in a weighted form. This calculated sum is often
referred to as the PRE (pitting resistance equivalent) or PREN factor (when nitrogen is
included), with a common expression for the austenitic and duplex steels as follows:

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

12. The passive film on stainless steels is significantly improved in seawater services when
the alloy composition contains higher levels of these key elements and provides a PREN value
of at least 38 or more. Long-term exposure in natural stagnant seawater has determined that
only the higher molybdenum and nitrogen bearing duplex stainless steels with a PREN greater
than 40 are highly resistant to localized (pitting & crevice) corrosion. Those super-duplex alloys
with PREN greater than 40 successfully compete with the most resistant super-austenitic 6%
molybdenum alloys such as UNS S31254 (Alloy 254SMO) and UNS N08367 (Alloy AL6XN),
and are considered to be most suitable for seawater service. It should be noted that it is only
those alloys offering a PREN value of 40 and greater that are usually referred to as "super"
stainless steels. Several of these are listed as cast alloy grades in the ASTM Duplex Standard
Specification (i.e. ASTM A890 (2) as grades 1C, 5A and 6A). Table 2 summarizes some of the
various cast duplex stainless steels that are suitable for seawater service.
Importance of Nitrogen and Phase Balancing
13. As mentioned earlier, the two phases in duplex stainless steel have different
compositions, resulting in a different resistance to localized corrosion in seawater. The austenite
phase generally is less resistant to localized corrosion than the ferrite phase. This is because
the chromium and molybdenum are more concentrated in the ferrite phase; while the nickel and
nitrogen are more concentrated in the austenite phase. This is known as alloy partitioning, and
one of the drawbacks of dual phase or duplex alloy systems.

15. Nitrogen enhancement is beneficial to increase localized corrosion resistance of the

austenite where it is mainly concentrated, and it also reduces the partitioning of chromium and
molybdenum between the two phases. The only way to make the austenite phase as resistant
as the ferrite phase in a duplex stainless is to alloy the material with high amounts of nitrogen.
Since nitrogen helps to maintain higher levels of chromium and molybdenum in the austenite, it
improves its corrosion resistance. Therefore, duplex stainless steel enhancement due to
nitrogen is mainly due to the improved corrosion resistance of the austenite.

16. In low-nickel duplex stainless steels, the diffusion of nitrogen into austenite is possible
due to its large diffusion coefficient, but molybdenum and chromium (small diffusion coefficients)
cannot be significantly redistributed, so they are unevenly distributed (higher in ferrite) between
the ferrite and austenite phases. The main role of nickel is to control the ferrite/austenite phase
ratio and the partitioning of the alloying elements between the two phases.

17. An optimum range of nickel content is about 4 to 8% in a 25% Chromium duplex

stainless steel. Increasing nickel content above this optimum increases the austenite ratio in
such a way that the dilution of nitrogen in larger volumes of austenite would be detrimental and
lowers its resistance to pitting and crevice corrosion.

18. Increasing the chromium content raises the pitting potential, and is beneficial in both
phases. The trend in materials development seems to be towards moving from the 25% to 27%
Chromium duplex alloys for increased corrosion resistance. Molybdenum content well in excess
of 3% is needed within a 25% Cr nitrogen enhanced duplex to be fully resistant to pitting and
crevice corrosion in seawater. Molybdenum content cannot be increased indefinitely because of
severe problems with intermetallic phase precipitation, and it rarely exceeds 4.5 to 5.0% in even
the highest alloyed duplex stainless steels.

Applications
19. Duplex steels find application typically in:

• Heat exchangers, tubes and pipes for production and handling of gas and oil
• Heat exchangers and pipes in desalination plants
• Pressure vessels, pipes, tanks and heat exchangers for processing and transport of various
chemicals
• Pressure vessels, tanks and pipes in process industries handling solutions containing chlorides
• Rotors, fans, shafts and press rolls where the high corrosion fatigue strength can be utilized
• Cargo tanks, piping and welding consumables for chemical tankers.

Summary and Recommendations

20. To summarise, for seawater services the duplex alloy selected should have a balanced
nitrogen enhanced composition to provide for a PREN greater than 38 or higher to ensure
freedom from localized corrosion. Those duplex alloys that offer PREN values of 40 or more are
ideal for pumps and valves and are highly recommended for use in seawater. An excellent way
to specify any duplex alloy intended for seawater service would be to request that the chemical
composition be balanced to provide a PREN greater than or equal to 40 as a minimum using the
pitting resistance equivalent expression given above. This will ensure that the alloy selected has
the optimum chemistry control to provide adequate localized corrosion resistance in the
seawater environment.

21. Highly alloyed 25% Chromium duplex stainless alloys such as Goulds Code 1338
(Modified Cast Alloy CD4MCuN with 3% molybdenum), Goulds Code 1384 (ASTM A890 Grade
1C - CD3MCuN), or Goulds Code 1361 (ASTM A890 Grade 5A - CE3MN) are logical choices
for sea water services.

References:

(1) Bengt Walle'n, “Corrosion of Duplex Stainless Steels In Seawater,” Avest Sheffield AB, Research and
Development, acom 1-1998, SE-77480 Avesta, Sweden
(2) ASTM A890, “Standard Specification for Castings, Iron-Chromium-Nickel-Molybdenum Corrosion -
Resistant, Duplex (Austenitic-Ferritic) for General Application,” Annual Book of ASTM Standards 2002,
Volume 01.02.

(3) Stephen Morrow, “Duplex Stainless Steels – Several Generations In The Making,” PUMPLINES –
Spring 2000 issue, ITT Industries- Industrial Products Group, Seneca Falls, NY
Duplex Stainless Steel
Triplex Plunger Pump

New 60 Frame Reciprocating Triplex Plunger Pump

offers added corrosion resistance with Duplex
Stainless Steel Head. CAT PUMPS dependable
Nickel Aluminum Bronze Model 6767 and 316
Stainless Steel Model 6761 triplex pumps have
delivered exceptional life in seawater desalination
systems for many years. The new Model 6762
features a Duplex Stainless Steel head and valve
assemblies providing added corrosion resistance,
higher strength and extended life in aggressive
applications like seawater desalination.
Duplex UNS S31803 Technical Information

Overview
Duplex is an austenitic ferritic Iron Chromium-Nickel alloy with Molybdenim
addition. It has good resistance to pitting, a high tensile strength and higher
resistance to stress corrosion cracking at moderate temperatures to that of
conventional austenitic stainless steels.

Duplex is a material having an approximate equal amount of austenite and ferrite.

These combine excellent corrosion resistance with high strength. Mechanical
properties are approximately double those of singular austenitic steel and
resistance to stress corrosion cracking is superior to type 316 stainless steel in
chloride solutions. Duplex material has a ductile / brittle transition at approximately
-50°C. High temperature use is usually restricted to a maximum temperature of
300°C for indefinite use due to embrittlement.

Benefits
There are several benefits of Duplex including:

• High Strength
• High resistance to pitting, crevice corrosion resistance
• High resistance to stress corrosion cracking, fatigue and erosion
• Excellent resistance to Chloride stress corrosion cracking
• Low thermal expansion and higher heat conductivity than Austenitic steels
• High energy absorption
• Good workability and weldability

Applications

Pipe – ASTM A790

The method of manufacture can be either seamless or automatic welding, with no

addition of filler metal. Pipe may be hot or cold finished but must always be
furnished in the heat treated condition.
BUTT WELD – ASTM A815

This class covers the class of WP, made up of 4 categories and meet the
requirements of ANSI B16.9. Pressure ratings are the same compatability of
matching pipe.

Categories :-

• WP-S : Seamless Construction

• WP-W : Welded Construction where construction welds are radiographed
• WP-WX : Welded Construction where all welds are radiographed
• WP-WU : Welded Construction where al welds are Ultrasonically Tested.

Flanges ASTM A182

ASTM specifications regulate approved raw materials from which flanges can be
made. Forged or rolled alloy steel pipe flanges, forged fittings and valves for high
temperature applications.

Technical Details

CHEMICAL COMPOSITION (All values are maximum unless stated otherwise)

%C %Cr %Ni %Mo %Mn %S %P %Si %N

0.03 21.0-23.0 4.5-6.5 2.5-3.5 2.00 0.020 0.030 1.00 0.08-0.20

MECHANICAL PROPERTIES

Yield Tensile Elongation Reduction of Area Hardness

Strength Strength (Minimum) (Minimum) (Maximum)*

(Ksi) (Mpa) (Ksi) (Mpa) (Bhn)

65 450 90 620 20 - 290

* (N.A.C.E. MR-01-75 latest revision may limit hardness in certain applications)

PREn (PITTING RESISTANCE EQUIVALENT) - (%Cr) + (3.3 x %Mo) + (16 x

%N)

HEAT TREATMENT: SOLUTION ANNEALED AT 1020 DEG C - 1100 DEG C WATER

QUENCH

EQUIVALENT GRADES

FRANCE
UNS BS EN SWEDEN SS GERMANY DIN SANDVIK +
AFNOR

X2 CrNiMoN Z2 CND
31803 1.4462 2377 SAF 2205
22.5.3 22.05.03

19. Are there temperature limits, low and high, on the use of duplex stainless steels?
The toughness of the duplex stainless steel mill plate does not undergo an abrupt ductile-brittle transition.
Rather it decreases gradually from its high shelf energy to a very low impact energy as temperature
decreases from about ambient to temperatures in the range of -45 to -75° C (-50 to -100° F). So the
minimum application temperature is determined in accordance with the tough of the duplex stainless steel.
To date, there have been few applications with minimum design metal temperature below -40° C (-40° F).

The maximum temperature for ASME Code applications is 315° C (600° F). The temperature was chosen
because it represents the lowest temperature for the transformation curve for 475° C (885° F)
embrittlement. Below that temperature, the steel will not be embrittled by this reaction in many years of
exposure. In non-Code applications, it would be possible to consider use of 2205 in applications where there
are limited excursions in the range just slightly above the limiting temperature. However, the embrittling
reaction is real and exceptions to the 315° C (600° F) limit should not be undertaken without full knowledge
and evaluation.

20. How do the properties of duplex stainless steels affect wall thickness, thermal
expansion, and heat transfer in comparison to austenitic stainless steels?
Although it is generally correct to say that the yield strengths of the duplex stainless steels are twice that of
the common austenitic stainless steels, that relationship does not imply that the thickness of the duplex
stainless steel will be simply half that of the austenitic stainless steel in the same design. The higher
strength of the duplex grades is reflected in higher allowable design stresses in the ASME Code. Depending
on the shape of the construction, it is possible to reduce significantly the thickness of the material required
when using duplex stainless steel, an opportunity for cost savings.
The thermal expansion of a duplex stainless steel is intermediate to that of carbon steel and austenitic
stainless steels. This difference can be an advantage in structure with cyclic heating because there is less
necessity to accommodate the large expansions associated with the austenitic materials. On the other hand,
using duplex stainless steel within a construction of austenitic stainless steel may create problems when the
duplex steel does not expand to the same extent. The combination of high strength and lower expansion
may mean that the duplex stainless steel will impose high stresses at the point where it is joined to the
austenitic structure.

Because the duplex stainless steel has a ferritic matrix, it is more efficient in heat transfer than the
austenitic stainless steels. This property, combined with the thinner material that results from economical
use of the higher strength of the duplex grades, can be used to significant advantage in heat transfer
applications.

Duplex Stainless Steel

These grades combine high strength with excellent
corrosion resistance, especially to chloride stress
corrosion cracking, however a tendency to brittleness
limits their use to approx 300 to 315oC maximum, sub-zero
use is also restricted to approx 50oC because of brittleness
due to the ferrite content. Main uses include offshore piping, chemical tanks, flue gas scrubbers and chimneys.

Super Duplex Stainless Steel

Similar qualities and limitations to duplex grades above.
These grades are widely used to handle seawater and
other brackish waters, marine pumps, oil and gas
production and desalination plants are typical applications.