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PAST, PRESENT AND FUTURE OF THE DUPLEX STAINLESS STEELS

Dr. J.CHARLES
ARCELOR MITTAL STAINLESS / UGINE&ALZ /Dir. I-R&D 5-7, rue Luigi Cherubini, 93210 LA PLAINE SAINTDENIS Cdx, FRANCE.
E-mail address: jacques.charles@arcelor.com -Tel: 0033171920650

ABSTRACT
Stainless Steels world wide crude steel production is close to 30 millions of tons. The average
annual growth since 30 years is 6%, much more than others materials including wood, aluminum,
copper, steel.This results from there very attractive properties resulting from multi-grades offer
making it possible to cover a wide range of corrosion resistance and mechanical properties.
Furthermore when properly selected, they are almost maintenance free and secure materials.
The main stainless steels families are the austenitic and the ferritic ones. They cover more than 95%
of the global stainless steel production. Recently among the austenitic, due to a sharp increase of the
Ni cost, austenitic grades with partial substitution of Nickel by manganese additions have been
developed (the 200 series).
Duplex grades production, worldwide, represent less than 200KT i.e. less than 1% of the total
stainless steel production although the production has growth of more than 100% in the latest
decade. Most of the production concerns the so-called quarto plates i.e. wide more than 2M- and
thick more than 6mm- plates. For those productions weight savings are often obtained taking
advantage of their high mechanical properties. Most of the applications concerns highly corrosion
resistance properties encountered in process industry. (Chemical, petrochemical, off-shore,
chemical tankers, pulp and paper industry, pollution control equipments-FGD-, desalination, seawater applications...).
The paper presents present also the new trends in alloying duplex grades including the new low
alloying grades so-called lean duplex- as well as new grades with specific properties. The extended
duplex family with new grades makes it possible to extend the applications areas including in huge
markets requiring less corrosion resistance properties than process industry. One of the main
challenges is the industrialization of thinner gauges. The possible new offer of duplex grades is also
optimized in alloying cost with some new grades with partial replacement of nickel by manganese
additions. The target to be more cost competitive than 304 austenitic is now achieved at least for the
quarto plates. The next target is the thinner gauges.
Duplex developments are nowadays extremely dynamic with high potential of successes in many
new markets. They offer the right answer with a unique combination of high mechanical properties,
appropriate corrosion resistance properties and optimum alloying costs. For all this reasons a yearly
growth with two digits may be expected.
KEYWORDS
Duplex, Markets and applications, Chemistries, Mechanical Properties, Corrosion resistance.
INTRODUCTION
The first international duplex conferences ( St LOUIS/USA/82 and Den HAGUE/NL/86 ) were
mainly focused on scientific aspects since they appeared very attractive for the metallurgical
aspects including phase precipitations (structures, kinetics,), corrosion resistance, mechanical
properties. The world wide industrial production in that time was almost marginal and
standardization has still to come.
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BEAUNE 91/France conference was the first duplex conference with a mix between scientific and
market applications. The new grades with increased nitrogen additions were presented. Duplex
grades gained in structure stability, weld ability and corrosion resistance properties! New standards
were proposed. The duplex family included the popular 2205 grades with increased nitrogen
additions (0.16/0.18%N instead of 0.12/0.15%N) and optimized Mo contents. PREN values were
proposed between 33 and 36 with a most common value 34/35. Sigma free grades were
recommended as well as a minimum Mo level of 3%.
Grade 2304 was already developed but for marginal applications. Several super duplex grades were
also promoted SAF 2507, UR 52N+, Zeron 100 - for the most severe applications including offshore. Those super duplex grades were also redesigned before the BEAUNE91 conference in order
to have a PREN value minimum of 40 and a nitrogen level minimum of 0.25 %.
The grades were mainly produced with EF + VOD or AOD + continuous casting devices i.e. the
most efficient stainless steels tools.
First extensive applications were reported as well as new areas of developments. Confidence in
duplex grades gained the end-users and the cost savings aspects partially obtained through the high
mechanical properties were expected. New codes for duplex grades had to come. The potential
growth of the grades was clearly emphasized. All this partially has explained the extremely wide
audience of the BEAUNE91 conference.
York94, Maestricht97 and Venice2000 conferences were also successful conferences with
increasing return of information on practical experiences. Most of the applications still concerned
the quarto plates and tubing. The first lean duplexes appeared. More concerning the technical
content of those conferences will be discussed in this article.
STAINLESS FAMILIES and ALLOYING COSTS.

Figure 1 : Schaeffler diagram.

Although Schaeffler diagram is mainly used for welded structures, it is very useful to illustrate the
different areas of stability for the stainless steel microstructures. The classical austenitic grades
the so called 300 series- contains a minimum of 9/10%Ni while the more alloyed grades in Cr
and/or Mo needs even more Ni to stabilise the austenitic phase. The most popular stainless steel
the 304 is the lowest alloying grade of the austenitic area.
Ferritic stainless may be produced when Ni content is almost 0% and Cr minimum content 12%
Most of the ferritic grades have a Cr content included in the 12/18% range. More recently >20%Cr
grades with Ti+Nb or Cu+Nb are developed to extend the Mo-free ferritic family.
Between the austenitic and the ferritic areas, we obtain a mixed ferrite + austenite microstructure.
Most of the duplex industrial grades have a typical 50%ferrite/50%austenite microstructure. The
three main families of duplex grades are plotted in the Schaeffler diagram. As observed it is almost
impossible to develop duplex grades having less than 19%Cr without formation of martensite.
With the extreme volatility of alloying element costs ( Figure 2 ) Ni for example has increased of
more than 500% this latest 3 years - new grades have been introduced recently in the market. This
concerns austenitic grades with partial replacements of Ni by combined Mn and N additions. Such
grades were already developed on a marginal production since more than 50 years. The newly
developed grades have Cu additions and often lower Cr contents in order to reduce the interstitial
elements like C and N. Those grades are softer than the former 200 grades and make it possible to
utilise the same tools to manufacture equipments - drawings for ex - than those used for 304
grades (Table I and Figure 3).
Typical mechanical properties of the different stainless steel families are presented Figure 4.
Mechanical properties of the different stainless steels are directly linked to the nitrogen + carbon
contents and microstructure. Ferritics have slightly higher yield strength than austenitics at room
temperature but can not be strengthen by interstitial additions. (lack of solubility) The duplex
grades have the highest mechanical properties due to a grain refining effect obtained by the two
phase microstructure. This will be very useful for the design of pressure vessels where weight
reductions can be expected when properly designed.

52 000 $/T 04/2007


Chromium

LME Ni Evolutions

0.9 $/lb

34 000 $/T

0.8 $/lb

29 000 $/T

0.7 $/lb

24 000 $/T

0.6 $/lb

19 000 $/T

0.5 $/lb
14 000 $/T

0.4 $/lb

9 000 $/T

0.3 $/lb
0.2 $/lb

02

03

04

05

06

4 000 $/T

02 03 04 05 06

Figure 2 : Cr and Ni volatility this latest years..


TABLE I : Typical chemistry of several stainless steels.
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FAMILY

AISI(USA)

EURONORM

Cr

Mo

Ni

Mn

304L
316L
904LN

1.4307
1.4401
1.4339

18
17
20

0
2
4

9
11
25

1
1
1

DUPLEX

2101
2304
2205
2507

1.4162
1.4362
1.4462
1.4410

21
23
22
25

0
0
3
3,5

2
4
6
7

5
1
1
1

0,2
0,13
0,17
0,25

1.4016
1.4510

400

430
439
445
434
444

17
17
21
18
19

0
0
0
1
2

0
0
0
0
0

0
0
0
0
0

0
0
0
0
0

201
204

1.4372

16,5
15,5

0
0

5
2

6
9

0,15
0,2

NO
NO
NO

17
15
15

0
0
0

4,8
4
1

3,7
7
9

2
1,6
1,7

300

200

200New

A
B
C

1.4113

Cu

Others

0
0
0,1 1,5 Cu

Ti;Nb
Ti;Nb
Ti;Nb
Ti;Nb

0,12
0,05
0,1 C=0,1

PRE PREN
18
24
32

18
24
36

21
23
32
37

24
25
35
41

17
17
20
22
26

17
17
20
22
26

16
15

18
18

17
15
16

18
16
17

PRE = %Cr + 3.3%Mo ; PREN = %Cr + 3.3%Mo + 16%N

Figures 3 and 4 : Stainless Steel families and mechanical properties


STAINLESS CRUDE WORLDWIDE PRODUCTION AND CONSUMPTION.
Figure 5 presents the worldwide yearly crude steel production for flat stainless steels. An average
growth of about 6% is observed since many decades. Figure 6 shows that if the nowadays biggest
geographic area of consumption is located in Europe, in the future most of the growth is expected to
take place in Asia. Production capacities are booming mainly in China and are expected to come in
India. Asia witch has since many years imported part of their needs will be soon able to export
stainless steel due to possible overcapacities. The booming demand in Asia particularly in China
and a certain lack of regulations made it possible to develop new grades with less alloying elements.
China and India are the countries where the new 200 series were developed. More recently China
has used more than 1 million of tons of those new grades which do not have specific norms.
(Figures 7 and 8)
Austenitics remains the most popular grades thanks to their unique combination of high ductility,
high potential of strengthening, weld ability, toughness even at extra-low temperatures and of
course corrosion resistance.(Figures 9 and 10) Ferritics represent about 25% of the total production
and

Kmt
20 000
6% / year INCREASE
15 000

10 000

19
7
19 8
7
19 9
8
19 0
8
19 1
8
19 2
8
19 3
8
19 4
8
19 5
8
19 6
8
19 7
8
19 8
8
19 9
9
19 0
9
19 1
9
19 2
9
19 3
9
19 4
95
19
9
19 6
9
19 7
9
19 8
9
20 9
0
20 0
0
20 1
0
20 2
0
20 3
04

5 000

Figure 5 :Flat Stainless Steel Crude worldwide production.

Figure 6 : Flat Stainless Steel worldwide 2002 consumption and 2010 expectations.

63.1

65.5

60

68.0

70.8

71.5

70

72.2

80

50

40

5.7

7.4

9.4

9.8

9.0

23.0

5.3

10
0

24.8

23.0

21.8

22.1

20

23.2

30

2001

2002

2003

2004

2005

2006 (e)

CrNi
CrMn
Cr

Figures 7 and 8 : Stainless Steel crude steel production (2001-2006) by grades. (ISSF documents)
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11%

2%1%
304
316

7%

>Mo AUST
200OLD
200NEW

11%

12CR FERR

58%

17CR FERR

1%
1%

Mo FERR
DUPLEX

8%

Figures 9 and 10 : Stainless worldwide crude production in 2004 by grades.


due to welding aspects and toughness properties, they are restricted to thinner gauges even if they
are often the cost saving grades. Duplex grades cover about 1% of the total production. The recent
evolutions of raw material costs particularly Ni have a drastic impact on 304 and 316 alloy
surcharges. They are nowadays higher than the base material price!! As a result differences of
several thousands of euros per ton are observed for the 300 series prices in a few years. Of course
ferritic steels are almost not affected by those effects. Replacement of 304 grades by ferritic grades
containing some molybdenum is nowadays cost savings solutions! This concerns particularly thin
gauges applications. Duplex grades start to be very cost competitive answers for thicker gauges and
particularly for very corrosive applications. Replacements of 316 grades by 2205 duplex grades are
now to be considered: cheaper grade for much more corrosion resistance properties and high
mechanical properties! Same results are observed for 2304 duplex versus 304 and 904L versus
superduplex grades!!! This provides new powerful driving forces for a further increase duplex uses
in new applications!

304L

8000

316L
7000
6000
5000
4000

Ni
6
10
14
30
52

1
2
3
4
5

Mo
7
17
35
40
42

Cr
0,8
1
1,5
1,5
1,5

2101
2304
2205
2507
430
439
445

3000

434
444

2000

201
204

1000

17 5 Cu
0

15 1 Cu
1

Figure 11 : Evolutions of raw material costs ( 2004/2007).


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DUPLEX STAINLESS STEELS IN THE FUTURE.


Some new duplex grades have been introduced in the market or are concerned by R&D activities.
Nowadays the main target is the development of so-called lean duplex having much less alloying
elements than the standard 2205 duplex grade. There targets is the replacement of 316 and even 304
grades. Some of those chemistries are presented Table II. Chromium contents are in the range
20/22 while Ni additions are reduced by further increase of Mn contents.
For some more corrosion resistance applications Mo contents are considered. Table II presents also
Table II : Chemical analysis of duplex grades.
FAMILY

USA EURONORM

Cr

Mo

Ni

Mn

Cu
0
0
1,5

0,1

0,7
1,5

0,13
0,17
0,27
0,27
0,25

304L
316L
904LN

1.4307
1.4401
1.4339

18
17
20

0
2
4

9
11
25

1
1
1

Standard
DUPLEX
(1996)

S 32304
S 32205
S 32750
S 32760
S 32520

1.4362
1.4462
1.4410
1.4501
1.4507

23
22
25
25
25

0
3
3,5
3,8
3,5

4
6
7
7
7

1
1
1
1
1

New
DUPLEX
(EX)

S 31500
S 32101
S 32001
S 32003
S 31260
S 39274
S 32906

18,5
21
20
20
27
25
29

2,7
0
0,3
1,7
3
3
2

5
1,5
1,7
3,5
7
7
6

1
5
5
2
1
1
1

300

1.4162

1.4362

0,3
0,5
0,6

N Others PRE PREN

0,1
0,2
0,15
0,15
0,16
0,27
0,4

0,7W

0,3W
2W

18
24
33
0
23
32
37
38
37

18
24
35
0
25
35
41
42
41

27
21
21
26
37
35
36

29
24
23
28
39
39
42

PRE = %Cr + 3.3%Mo ; PREN = %Cr + 3.3%Mo + 16%N

Figure 12 : Pitting resistance corrosion of stainless steels.


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some R&D or ongoing work on new grades. Alloying with copper and tungsten are also considered.
Those developments may boost the developments of duplex grades in the future. The real huge
boost in duplex production is still pending upon the successful industrialisation of thinner gauges!
Duplex grades, particularly the lower alloying grades are know to have poor hot workability
properties. Production of wide hot coils free of defects remains a technical challenge! In case of
success, taking in to account their corrosion resistance properties and alloying costs they have
promising future even we can not expect for thin gauges weight savings due to their improved
mechanical properties. Typical corrosion resistance properties and PREN ranking are presented
figures 12 and 13.
PREN =
%Cr +
3,3 x %Mo
+ 16 x %N

6Mo
904
317LNM
317LN

35
30

446

25

444

20

434

15

201-202

430

316
304

2507
2205+
2205
2003
2304
2101

Most severe
conditions
( acids, temperature.)

Standard grades

2XX

409
200 AUST. FERRITIC 300 AUST. DUPLEX
Figure 13 : PREN ranking and stainless steels families.
DUPLEX STAINLESS STEELS AND MARKET APPLICATIONS.

Figure 14 and 15 : Main duplex production and market applications.(ISSF documents)


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Most of the duplex grades in services are 2205 hot rolled products. In the recent past strong demand
and developments concerns cold finished flat products and hot finished long products ( rebars).
Typical applications are presented Figures 16 to 19.

Figure 16 York millennium bridge

Figure 17 : La grande Arche La dfense - Paris


Figure 19 : Chemical tanker.

Figure 18 : Arco project Figure 20 : Pollution controll

CONCLUSIONS
The paper has presented the impressive growth of stainless steels grades in the latest decades. An
average yearly growth of 5/6 % is observed.
Among the stainless steel grades the austenitics and particularly the 304 grades are the most popular
ones. They cover more than 80% of the total stainless steel market.
In the recent past since 2000- a huge increase of new austenitic grades has been observed
particularly in Asia. Those grades replace partially Ni by combined Mn, N and Cu additions.
The real cost savings grades are the ferritic grades since they do not contain Nickel additions but
heir uses are restricted to the thinner gages due to welding and toughness aspects. There formability
when considering complex shapes is also reduced when compared to austenitic
Finaly, duplex grades which still covers nowadays less than 1% of the worldwide stainless markets
may presents a very attractive answer taking in to account their lower alloying cost than austenitic
and their exceptional combination of corrosion resistance and mechanical properties.
Already for the most severe corrosive conditions superduplex grades are the cost saving grades;
they are economical substitutions to some Ni grades, 6 Mo grades and even 904 grade. They
targeted applications are still marginal when considering the stainless steel markets.
Duplex 2205 grade is now a standard which is widely used for the severe corrosion applications like
pulp and paper, chemical tankers, desalination plants, petrochemical industry, phosphoric acid
production plants, pollution control equipments energy including sour gas applications. The
grades are cost savings when considering the alternative solutions like 904LN grades and even
316L even when weight savings are obtained ( pressure vessels..).Duplex 2205 grades represent
nowadays about 85% of the total duplex production.
The new coming duplex grades are designed to replace 304L grades. Their Ni and Mo contents are
decreased. Further cost savings with partial replacement of Ni by combined Mn and N additions are
are even considered! The grades nevertheless are more difficult to manufacture. The targeted
markets are huge! This is particularly through when thinner gauges applications are also considered.
Technical improvements are still to come.
Duplex family is now an industrial success and represents about one percent of the total stainless
steel market. The next steps are duplex grades to replace 304 grades and the developments of
thinner gauges for new markets. An annual growth of more than 10% is expected.
REFERENCES :
1) J.CHARLES and S.BERNHARDSON Duplex Stainless Steels 91 Conference Beaune, France
2) R.ROBERI and A.TAMBA Duplex conference 2000 Venezia, Italy AIM
3) P.LOVLAND Duplex Stainless Steels 97 The Hague, NL Stainless Steel World
4) J.A.ODRIOZOLA and A.PAUL Stainless Steel 05 Sevila, Spain
5) D.LEANER Stainless Steels 2003 Maastricht, NL pp115-121
6) Y.YAMADA at all Stainless Steels 2003 Maastricht, NL pp 164-170
7) J.J.DUNN at all all Stainless Steels 2003 Maastricht, NL pp 415-422
8) W.SCUMACKER at all. Stainless Steel USA 2002 Houston USA pp 130-136.
9) C.ERICKSSON at all. Stainless Steel USA 2002 Houston USA pp 423-431.
10) J.W.ENERWAY. Stainless Steel USA 2002 Houston USA pp 92-122.
11) J.W.ENERWAY. Stainless Steels 2001 The Hague, NL pp 245-264.
12) P.JOHANSSON 4th Stainless Steel Steels science and Markets Paris France 2002,pp153-163.
13) L.COUDREUSE 4th Stainless Steel Steels science and Markets Paris France 2002,pp120-125
14) C.ERICSON Stainless Steels America 2004 pp 230-240
15) S.AMcCOY Stainless Steels America 2004 pp 374-379.
16) J.CHARLES Duplex conference 2000 Venezia, Ilaly pp 1-12.

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