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— P A P E R 1 D —

Advantages of a Super
Duplex Stainless Steel for
Various Industries

DAVID R. HASEK have enjoyed great success in the equipment’s overall weight and
MANAGER, ATI OIL & GAS European markets, only now have further enhancing the cost
ATI Allegheny Ludlum duplex alloys gained more effectiveness.
1300 Pacific Avenue international attention by fabricators SDSS continue to build upon an
Natrona Heights, Pennsylvania 15065 and end users as a result of the excellent track record in markets
USA advantages in strength, corrosion such as Oil and Gas, Desalination,
T: 724-226-6581 resistance and in some economic and Pollution Control, and therefore
F: 724-226-6452 periods, reduced raw material costs are gaining increased awareness for
E: david.hasek@ATImetals.com as compared to traditional austenitic other end uses such as in the
stainless alloys. Chemical Process Industry. This
In the late 1980s, further trend is projected to continue with
Co-author development led to more highly expanded knowledge and availability
alloyed Super Duplex Stainless Steels in all product forms. Design
JOHN J. DUNN (SDSS). These alloys came in the engineers have found greater ease
DIRECTOR, ATI OIL & GAS form of castings, forgings, hot-rolled in working with SDSS while meeting
ATI Allegheny Ludlum long products, wire, seamless tubing, budgetary constraints in a fluctuating
1300 Pacific Avenue hot-rolled flat products (i.e. plates), raw materials market.
Natrona Heights, Pennsylvania 15065 and more recently, cold-rolled flat
USA products (sheet and strip). This paper
T: 724-226-6538 addresses some applications for flat- KEYWORDS
F: 724-226-5976 rolled products of one SDSS known • super duplex stainless steels
E: john.dunn@ATImetals.com commercially as ZERON ® 100 alloy • SDSS
(UNS S32760). • oil and gas
Among the advantages of SDSS • pollution control
ABSTRACT alloys over standard 6Mo alloys are • desalination
Demand for new duplex stainless their higher mechanical strength. • sulfuric acid production
products has been driven primarily This has permitted thinner cross- • mining
by the developing offshore oil and sections in the design of pressure • chemical process industry
gas industry in the North Sea. vessels and other process • UNS S32760
Although duplex stainless products equipment thereby reducing the • ZERON ® 100

*Zeron® is a registered trademark of Rolled Alloys Ltd.


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40 1D — ADVANTAGES OF A SUPER DUPLEX STAINLESS STEEL FOR VARIOUS INDUSTRIES

INTRODUCTION Table 1. Duplex stainless steel primary families: Lean, Standard, and 25 Cr Super Duplex.
Duplex Stainless Steels (DSS) are
Cr-Ni-Fe alloys which may also
contain molybdenum, copper,
tungsten, and other alloying
elements. Their name is derived
from the fact that they develop a
microstructure containing similar
amounts of austenite and ferrite
phases. DSS are stronger than their
austenitic stainless steel
counterparts when comparing them
in solution annealed conditions.
Similarly, DSS can have corrosion
resistance advantages with regards
to pitting, crevice corrosion, and
especially stress corrosion cracking.
While DSS have enjoyed success in
Europe for a number of years, they
are now gaining more global
attention and acceptance.
DSS can be broken into three
primary families, as shown in Table
1. The balance of this paper will
focus on the end uses for flat-rolled
(UNS S32760), also known as Rolled Alloys, Incorporated product’s application and post weld
ZERON ® 100 SDSS. international supply chain. Wrought heat treatment options.
Just as DSS can have products are available as long Flat-rolled SDSS are generally
advantages over austenitic grades, products (rod, bar, wire seamless produced with finishes suitable for
SDSS can have advantages over pipe, and tube), forged products the end use. Plate is produced with
DSS and 6 Mo super austenitic (fittings, flanges, valves, etc.), and a #1 finish that involves steel shot
alloys. These include: rolled products (Sheet, Strip, and blasting followed by acid pickling.
Plate). Due to processing difficulties, Lighter gage cold-rolled products
• Higher strength only recently were flat-rolled coil can be produced in finishes that are
• High resistance to pitting and products available in the form of common in the stainless steel
crevice corrosion (vs. DSS) continuous plate and cold-rolled industry. Even precision rolled light
• Excellent resistance to sheet. ATI Allegheny Ludlum, in gage strip (0.3 mm) has been
chloride stress corrosion working with Weir Materials, commercially produced by ATI
cracking developed a commercial product in Allegheny Ludlum.
• Improved sulfide stress the form of ZERON ® 100 flat-rolled ATI Allegheny Ludlum’s quality
corrosion resistance (vs. DSS) sheet and strip as well as quarto standards and systems along with
• Lower raw material costs (vs. plate. This subsequently afforded the production and testing methods
6 Mo alloys). the supply of welded pipe and tube employed to manufacture coiled
to the market place. UNS S32760 (including CMP, Sheet,
Welded pipe and tube can have and Strip) have been audited by and
PRODUCTS MADE FROM advantages over seamless have been granted NORSOK M-650
FLAT-ROLLED SDSS products, such as the availability of accreditation [1,2] . This stringent
Cast and wrought products have longer lengths, better wall thickness Norwegian Oil and Gas Quality
been commercially available in uniformity and potential for lower Standard is often mandated by the
SDSS from companies like Weir costs. While thin walled seam welds Offshore Oil and Gas Industry.
Materials, who have produced are generally made autogenously Mechanical testing tends to
ZERON ® 100 since the mid 1980s. and get subsequently annealed, show somewhat higher properties
Today RA Materials have assumed thicker sections can be welded with as cold-rolled thicknesses are
the trade name of ZERON® 100 and either a matching or over matching reduced. Microstructural differences
will supply the product through filler wire, depending on the end are also observed on lighter gages,
*Zeron® is a registered trademark of Rolled Alloys Ltd.
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1D — ADVANTAGES OF A SUPER DUPLEX STAINLESS STEEL FOR VARIOUS INDUSTRIES 41

as the amount of ferrite tends to be Traditionally, in high-pressure burst tests, and for this reason has
increased. This phenomenon is the applications, seamless SDSS tubing been granted NORSOK M-650
result of faster cooling of thin is employed in such umbilicals. accreditation [1,3]. In burst tests run
sections which avoids reformation Seam welded SDSS umbilical tubing to failure, it should be noted that the
of austenite after solution annealing. made from cold-rolled UNS S32760 failure occurred in the base metal
This is a commonly observed strip can provide the benefit of much and not in the seam weld, the orbital
phenomenon in 22 Cr duplex longer segment lengths between weld, nor in the heat affected zone.
stainless (UNS S31803 / 32205) as orbital welds, as compared to the Another sub-sea application is
well. Generally, it is not a problem seamless tubing. This provides a the line pipe or flexible flow line,
for a fabricator, and does not significant advantage to the used to transport oil and natural gas
jeopardize the end use, but can be umbilical manufacturer by reducing from wells located in deep and ultra-
an attribute where increased the number of orbital welds required deep water. These flow lines utilize
strength is desirable. For this reason, and hence, the total weld time to high-strength SDSS to combat the
provisions in specifications are fabricate these multi-tube lines. crushing pressures of deepwater
generally made for duplex stainless Another benefit of producing seam while providing corrosion resistance
grades that reflect the strength welded tubing from cold-rolled against the effect of sour oil and gas
differences between plate, cold- SDSS strip is the consistency of the on the interior and seawater on the
rolled sheet, and light gage strip. wall dimensions which are very exterior. Today, SDSS are the choice
tightly controlled when the strip is to provide the increased strength
cold--rolled. required not only for deeper water,
END USES FOR FLAT-ROLLED The continuous seam weld in but also higher well stream
SDSS this tubing is solution annealed then pressures. SDSS strip is also a
rapidly quenched, so as to eliminate candidate for marine banding straps
Oil and Gas the possibility of deleterious phases and buckles used to attach
For years, UNS S32760 has been at the weld and in the Heat Affected buoyancy modules or strakes to
used in offshore topsides and sub- Zones (HAZ). The seam welded these flow line risers or to secure
sea applications in the Oil and Gas tubing must meet the same criteria pipes to saddles. The yield strength
Industry. On offshore platforms, as seamless tubes for umbilical of the SDSS strip surpasses that of
SDSS are employed in process applications. To that end, seam the nickel alloy UNS N06625 which
equipment such as vessels, piping, welded UNS S32760 tubes have is widely used in these applications.
and tubing. Examples of some of satisfied mechanical tests, corrosion
the processing equipment include tests (i.e. ASTM G48 and ASTM Pollution Control
produced water separators, A923), and manipulation tests such The burning of coal to generate
manifolds, sub-sea flow lines, risers, as the flare test and reverse electricity in power plants across the
seawater cooling pipework, and flattening test (ASTM A370), along globe produces undesirable by-
heat exchangers. SDSS has also with accumulated strain tests and products such as NO x , SO 2,
been used in process pipework,
pumps and valves, and for
Figure 1. Schematic of a flue gas desulfurization (FGD) system.
desalination units to generate
drinking water for the occupants of
these platforms. Additionally, it can
find use in certain structural
portions, such as connecting
bridgework, due to its high
strength-to-weight ratio and
excellent chloride resistance.
In sub-sea applications, an
umbilical line (made up of a number
of tubes and / or cables) is used to
control the operations of the wells
and manifolds by supplying
hydraulic and electrical power, as
well as chemicals to enhance and
maintain the flow of oil and natural
gas, and inhibit corrosion.

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42 1D — ADVANTAGES OF A SUPER DUPLEX STAINLESS STEEL FOR VARIOUS INDUSTRIES

particulates, and other pollutants of Flue Gas Desulfurization (FGD). suited to scrubbing the high volume
that contaminate the environment. There are several FGD methods of flue gas emitted by large power
Pollution control legislation by world available; examples include various plants. A schematic of an FGD
governments has mandated a dry scrubbing methods, sea water system is shown in Figure 1.
significant reduction in emissions scrubbing, and wet scrubbing with Material choices for an FGD
from these power plants. The most lime or limestone. The majority of system are extremely important
effective way to significantly reduce the scrubbers currently being because the corrosive conditions
emissions of SO 2, and in some installed use the wet limestone are so complex, with many factors
cases mercury, is through the use technology. This method is best contributing to the severity of the
environment. The selection of an
Figure 2. Iso-corrosion curves (0.1 mm/y) for some stainless steels in suphuric acid. appropriate material will depend on
the operating parameters of the
system, the type of coal being
burned, as well as the environment
surrounding the specific
components. The most important
corrosive species generated during
the combustion of coal are chlorides
and fluorides along with sulfur
bearing species. Contributing to the
corrosive environment is the
temperature, acid dew point, pH,
crevice forming deposits, erosion,
etc. Typically, several alloys are used
in a system, which will be matched
to the conditions under which a
component is operating.
Fortunately, extensive operating
experience has been generated
which can be used as a guide to
selecting appropriate materials of
construction.
The excellent corrosion
Figure 3. Pin erosion rig test results in a simulated flue gas desulfurization (FGD) slurry. resistance of UNS S32760,
combined with its high-strength
makes it suitable for a wide range
of applications in FGD scrubbers.
UNS S32760 is highly resistant to
halides, and thus, is an excellent
choice for absorber components.
The alloy also has good resistance
to sulfuric acid, which makes it a
viable candidate for outlet ducting
where chlorides carry over and acid
condensation are a concern. The
resistance of UNS S32760 to
sulfuric acid is shown in Figure 2.
The high-strength and hardness
of the alloy result in excellent erosion
and erosion corrosion resistance of
the alloy, making UNS S32760 an
ideal candidate for slurry piping,
pumps, and agitators. Erosion
testing results for a simulated FGD
slurry can be seen in Figure 3.

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A partial experience list for Table 2. Partial experience list for applications of UNS S32760 in flue gas
applications of UNS S32760 in FGD desulfurization (FGD) systems.
systems is shown in Table 2. UNS
S32760 has been used successfully
for the slurry pumps, gas distribution
plates, and agitator stools at the
Drax FGD plant in the UK. These
pumps are lasting 30,000 to 40,000
hours between major overhauls. The
slurry centrifuges at Ratcliffe FGD
plant were supplied in UNS S32760.
After two years operation, they are
in excellent condition. After a short
time of operation, the GRP slurry
return lines at Ratcliffe FGD plant
were suffering severe erosion. These
have now been replaced with spools Table 3. Pipe wall thickness calculated per ASME B31.3, internal pressure 100 bars
in UNS S32760 and have given no (1450 psi), at 40°C (100°F).
further problems.

Desalination
The desalination market is another
key area of use for SDSS. ZERON ®
100 SDSS is being used in
increasing quantities for the high-
pressure seawater intake and reject
brine pipework in Sea Water
Reverse Osmosis (SWRO)
desalination plants which
traditionally employed 6Mo and
904L austenitic alloys. savings have become more and S32760 already has been used by
The initial driving force behind more important in the viability of many manufacturers of specialized
the change was the extra strength these larger projects. equipment in sulfuric acid
of SDSS over the austenitic stainless Recent work by Miyasaka[5] has environments for applications such
alloys, which allowed the reduction concluded that SDSS are required as agitators, stirrers, and
in wall thickness and schedule size for warm seawater and perform very centrifuges. The high-strength and
in certain sizes of pipe. Initially, well when compared to the 6Mo excellent fatigue resistance make it
ZERON ® 100 also replaced a alloys. Additionally it is thought that very cost effective for these and
number of lower alloy systems that SDSS can be cost effective for use other rotating applications.
were experiencing extensive as 0.3 mm welded, thin walled Additionally, it is ideal for use in tube
corrosion as detailed by G. Byrne et tubes for Multiple Effect Distillation and shell heat exchangers. The
al [4] . With the escalation of raw (MED) and Multiple Stage Flash excellent resistance of UNS S32760
material costs, SDSS became the (MSF) desalination plants, and to chlorides means that it can
choice of the industry. development is underway. confidently be used for heat
A typical SWRO plant will work exchangers using seawater or
at 70 bar (1015 psi) and will use Sulfuric Acid Production brackish water as a cooling medium.
Schedule 40S NB pipework. By With the good acid corrosion UNS S32760 can be
changing from an austenitic resistance of UNS S32760 (as particularly effective in the high
stainless steel to a SDSS, material shown in Figure 2) and its availability temperature heat recovery sections
savings as evidenced in Table 3, can in the form of flat rolled products, of sulfuric acid plants. In one field
be achieved. tube, pipe, and a variety of other test, a spool of UNS S32760 was
In recent years, technology has forms, its use should be considered exposed for 18 months in
allowed for a rapid increase in the in sulfuric acid plants. Applications concentrated acid at 200°C (392°F).
size and output of SWRO include vessels, pipework systems, The corrosion rate was <0.2
desalination plants and so the valves, pumps, and fasteners. UNS mm/year. The end user has
*Zeron® is a registered trademark of Rolled Alloys Ltd.
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44 1D — ADVANTAGES OF A SUPER DUPLEX STAINLESS STEEL FOR VARIOUS INDUSTRIES

subsequently fitted a UNS S32760 aggressiveness, but UNS S32760 is Annealed Super Duplex
filter in front of a sulfuric acid pump still performing well[7]. Stainless Steel Tubing for
operating at high temperatures Umbilical Service,” Webco
~200°C (~392°F). After 18 months Industries, Inc., QTR W004,
in service, the filter is in excellent CONCLUSIONS Rev. 1, Alloy Zeron ®100 (UNS
condition. This is a substantial Many industries have found the S32760), May 3, 2007.
improvement over the 310 stainless benefits of Super Duplex Stainless 4. G. Byrne, R. Francis, G.
steel filter used previously [6]. Steels in some of the most Warburton, R. J. Bullock, and
aggressive environments. The C. Kuzler, “The Selection
Mining improved availability of flat-rolled Design, Fabrication and
The excellent acid corrosion products such as plate, strip, and Performance of ZERON 100 in
resistance and erosion resistance sheet, compliment a full list of other SWRO Applications,” IDA
properties of UNS S32760 can also product forms. This has opened the Conference, 2003.
be used in the mining sector. door to new applications in a variety 5. M. Miyasaka, “Designing
There have been many of industries where SDSS products Pumps to Combat Seawater
applications in acid leaching can provide solutions through Corrosion”, Yakura Ebara
extraction processes, and to date, improved strength, enhanced Research Co. Ltd., Japan,
the alloy has been used in the corrosion resistance, operating cost The International Desalination
mining and extraction of nickel (from reductions, and even shortened and Water Reuse Quarterly,
oxide or sulfide ores), gold, uranium, deliveries [8]. a Volume 18, No. 1, p 33-38,
zinc, and also copper. The alloy has May 2008.
been used in pumps, pipework, 6. “The Performance of ZERON
sparge pipes, and vessels in North REFERENCES 100 Super Duplex Stainless
America, South America, and 1. “Qualification of Manufacturers Steel in Sulfuric Acid,” RA
Australasia with excellent results. of Special Materials”, Materials Internal Report,
The same properties also allow NORSOK Standard M-650, TN1290R4.
for its use in the production of potash Rev. 3, April 2004. 7. “ZERON 100 Super Duplex
where excellent experience has been 2. “NORSOK Accreditation for Stainless Steel in the Mining
gained in plants in both Canada and Hot and Cold Rolled Strip Industry,” RA Materials
the United States. The UNS S32760 Produced from Continuous Internal Report, TN1346R3.
pumps have given excellent service. Coil,” ATI Allegheny Ludlum, 8. D. Hasek, G. Warburton, J.
In Canada, mixtures of KCl and NaCl QTR 1562-1, Rev.1, Alloy Dunn, and C. Stinner,
(~300 g/l) are handled at about 80°C Zeron ®100 (UNS S32760), “Applications for a Flat Rolled
(176°F), with some sand. The fluids December 6, 2007. Super Duplex Stainless Steel,”
in United States potash mines also 3. “NORSOK Accreditation for Stainless Steel World
contain H 2S, which increases the Laser Seam Welded and Conference 2008.

*Zeron® is a registered trademark of Rolled Alloys Ltd.

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