CA2519786A1

CA2519786A1 - Duplex stainless steel alloy for use in seawater applications

Info

Publication number: CA2519786A1
Application number: CA002519786A
Authority: CA
Inventors: Ann Sundstrom; Pasi Kangas
Original assignee: Individual
Current assignee: Sandvik Intellectual Property AB
Priority date: 2003-03-02
Filing date: 2004-02-19
Publication date: 2004-09-16
Also published as: SE0300574L; AU2004217572A1; KR20060056886A; NO20054105D0; US20070089810A1; WO2004079027A1; SE527178C2; EP1599612A1; SE0300574D0; NO20054105L; CN100457953C; CN1768156A; EA200501409A1; EA009108B1; JP2006519313A

Abstract

The present invention relates to a stainless steel alloy, more precisely a duplex stainless steel alloy having ferritic-austenitic matrix and having high corrosion resistance in combination with good structural stability and hot-workability, in particular a duplex stainless steel having a ferrite content of 40-65 % and a well-balanced composition, which gives the material corrosion properties making it more suitable for use in chloride-containing environments than what has been found possible previously. The material according to the present invention has, in view of the high alloy content thereof, extraordinarily good workability, in particular hot-workability, and should thereby be very suitable to be used for, for instance, the manufacture of bars, pipes, such as welded and weld less pipes, weld material, construction parts, such as, for instance, flanges and couplings. These objects are met according to the present invention with duplex stainless steel alloys, which contain (in % by weight): C more than 0 and up to max 0,03 Si up to max 0,5 Mn 0-3,0 2 0 Cr 24,0-30,0 Ni 4,9-10,0 Mo 3,0-5,0 N 0,28-0,5 B 0-0,0030 25 S up to max 0,010 Co 0-3,5 W 0-3,0% Cu 0-2,0 Ru 0-0,3 3 0 Al 0-0,03 Ca 0-0,010%, balance Fe together with inevitable contaminations.

Description

DUPLEX STAINLESS STEEL ALLOY FOR USE IN SEAWATER APPLICATIONS.
Technical Field of the Invention The present invention relates tca a stainless steel alloy, more precisely a duplex stainless steel alloy having ferritic-austenitic matrix and having high corrosion resis-tance in combination with go~d structural stability and hot workability, in particular a duplex stainless steel having a ferrite content of 4~0-65 °/~ by volume and a well-bal-anced composition that gives the material corrosion pr0perfiies making it more suit-1o able for use in chloride-containing environments than what has previously been found possible.
Background of the Invention i5 In oil production in the sea, holes are drilled down from the bottom of the sea to the oil deposit. At the bottom of the sea, a unit is installed for control of the flow of the crude oil and further transportation to the units that are to handle and refine the crude oil to useful products or semi-finished products. At the unit on the bottom of the sea there is, among other things, valves that control extraction, pressure, flow

2 o rate, etc., and couplings to pipes with possibility of injecting chemicals into the oil well. Frequently, methanol is used for injection with the object of avoiding that crude oil coagulates and causes undesired stops in the production pipes.
Valves and couplings on the unit at the bottom of the sea are controlled hydraulically 25 and electrically from a platform, a production ship or another unit on the surface of the sea or on land. An umbilical cord pipe, a so-called umbilical, couples together the guiding unit with the units on the bottom of the sea. The part of the umbilical that lies on the bottom of the sea, for instance, between two underwater units on different extraction sites, is called static umbilical since the same only to a relatively small

3 o extent is effected by the motions of the sea. The part of the umbilical, that is situated between the bottom of the sea and the surface, is called dynamic umbilical and is effected to a large extent by motions in the water and on the surface.
Examples of such motions are flows in the water, wave motions as well as motions of the platform and the production ship.
The demands that are made on the pipes in an umbilical are foremost related to cor-rosion and mechanical properties. The pipe material has to be resistant to corrosion in sea water, which surrounds the outer surface of the pipes. This property is what is regarded as being most important, since sea water has a very corrosive impact on stainless steel. Furthermore, the material has to have high corrosion resistance to the possible corrosive solutions that are injected in the oil well. The material has to be compatible with hydraulic liquids without contaminating the liquid.
Possible con-tamination may affect the service function of the control unit at the bottom of the sea very negatively.
The mechanical properties of the used pipe material are very important for the appli-cation of umbilical pipes. Since the depth may be considerable on the site of the oil production, the dynamic part of the umbilical generally becomes long, and thereby Zo heavy. The weight has to be carried by the platform or the floating production ship. In practice, there is two ways to decrease the weight of an umbilical having a given configuration. It is possible to choose a lighter material or a material having the same density but having higher tensile yield limit and ultimate tensile strength.
By choosing a material having higher strength, pipes having thinner wall may be used, and thereby the total mass of the umbilical is reduced. The deeper the sea at the site of extraction, the more important the total weight per unit of length of umbilical of the material will be.
During the most recent years, when the environments in which corrosion-resistant 2 o metallic materials are used have become more heavy-duty, the requirements on the corrosion properties of the materials as well as on their mechanical properties have increased. Duplex steel alloys that were established as an alternative to hitherto used types of steel, such as, for instance, ferritic steel that previously were used in this application, nickel base alloys or other high-alloy steels, are not excepted from this development.
Furthermore, the latest development on the market for umbilical pipes implies addi-tionally increased demands on the performance of the materials. The demands that hitherto have been made regarding strength and corrosion resistance have been 3 o able to be met by existing alloys. The new demands that are made on construction materials in the future for umbilicals mean, however, considerable exacting demands on corrosion resistance, by virtue of plants being projected in warmer waters as well as by virtue of process solutions in the umbilical will have higher temperatures. The new demands that are made may involve that the alloy must have resistance to crevice corrosion in sea water at temperatures up to i0-90 °C. Today's construction materials do not meet these requirements with sufficient reliability against corrosion.
It is this problem that has to be solved. However, hitherto all feasible alloys that have been evaluated, have had a weak point. An alloy of higher resistance to chloride-induced corrosion that also meets other demands such as increased strength and good structural stability, would, on the other hand, mean greater possibilities to meet the new demands made on umbilical pipes.
A recognized measure for the corrosion resistance in chloride-containing environ-manta is the so-called Pitting Resistance Equivalent (abbreviated PRE), being defined as PRE=°/~Cr+3,3°/~Mo+16°/~i~
where the percentage figures of each element refer to percentage by weight.
~o A higher numerical value indicates a better corrosion resistance, in particular to pit-ting. The principal alloying elements that affect this properly are, according to the formula, Cr, Mo, N. An example of such a steel grade is seen in EP 0 220 141, which through this reference hereby is included in this description. This steel grade, having the trade mark of SAF 2507 (UNS S32750), 'has essentially been alloyed with high 15 contents of Cr, Mo and N. Thus, it is developed towards this property with, above all, good corrosion resistance in chloride environments. Recently, also the elements Cu and W have turned out to be efficient alloying additives for additional optimization of the corrosion properties of the steel in chloride environments. The element W
has, on that occasion, been used as substitution for a part of Mo, as for instance in the 2 o commercial alloys DP3W (UNS S39274) or Zeron100, which contain 2,0 % and 0,7 % of W, respectively. The latter also contains 0,7 % of Cu with the purpose of increasing the alloy's corrosion resistance in acid environments.
Addition of tungsten led to a further development of the measure for the corrosion 25 resistance, and thereby the PRE formula to the PREW formula, which also eluci-dates the relation between the impact of Mo and W on the corrosion resistance of the alloy:
PREW = % Cr + 3,3(% Mo + 0,5 % W) + 16 % N, as described, for instance, in EP 0 545 753, which relates to a duplex stainless alloy 3 o having generally improved corrosion properties.
The above-described steel grades have a PRE number, irrespective of method of calculation, which is above 40 but the PRE number is limited upwards to about since higher values mean that the alloys obtain inferior structural stability.
A higher 35 degree of alloying increases the risk of precipitation of intermetallic phase, and therefore the level of alloying in duplex steel is regarded as limited to achieve PRE
values around a maximum of about 43, irrespecfiive of method of calculation.

4 Of the alloys having good corrosion resistance in chloride environments, SAF

should also be mentioned, the composition of which is seen in EP 0 708 845.
This alloy, which is characterized by higher contents of Cr and N in comparison with, for instance, SAF 2507, has turned out to be especially suitable for use in environments where the resistance to intercrystwlline corrosion and corrosion in ammonium carba mate is of imporkwnce, but it has also a high corrosion resistance in chloride-con twining environments.
The wlloy has a corrosion resistwnce in chloride environment corresponding to the so alloy UNS 532750, but simultwneously a higher yield point in tensi~n Rp~,2.
This makes that this alloy has advantages in compwrison with UNS 532750 as umbilical material, since lower weight of the umbilical can be obtained. The corrosion resis-tance gi~res, however, no improvements in comparison with UNS S32750, which means considerable limitations in umbilical pipes that are exposed to higher tem-peratures in future plants.
The alloy 19D (UNS S32001 ) is a duplex alloy characterized by the composition 19,5-21,5 % of Cr, 0,05-0,17 % of N and max 0,6 % of Mo. This alloy has a PRE
number of about 22, and therefore the alloy is unsuitable in sea-water applications 2 o such as umbilicals. Accordingly, in order to achieve a sufficient corrosion resistance in this alloy, a cathode protection has to be applied in the form of a zinc layer on the outer surface of the umbilical pipe. If the zinc layer is consumed or if a greater sur-face becomes damaged, the corrosion protection is, however, ruined and a fast cor-rosion process may occur, which means expensive repairs and down periods.
A problem with the above-described alloys, all having high PRE numbers, is the appearance of hard and brittle intermetallic precipitations in the steel, such as, for instance, sigma phase, especially after heat treatment, such as, for instance, upon welding during later working. This results in a harder material having worse workabil-3 o ity and finally a deteriorated corrosion resistance.
Another group of alloys having good corrosion resistance is austenitic steels, with PRE numbers of up to 55 having been made possible by the addition of high con-tents of Cr, f~lo and N combined with high contents of Ni. Said alloys should work very well to the new tougher corrosion conditions in umbilicals. The disadvantage of the swore alloys is that they have considerably lower yield point in tension than duplex steel and are, furthermore, considerably more expensive to manufacture, foremost by virtue of their high percentage of Ni, which is an expensive alloying material. Examples of austenites having good resistance in chloride environment are UNS S32654 having a PRE number of about 55, and UNS S34565 having a PRE
number of about 45. These have, however, too low a strength and high a cost in order to be a realistic alternative for umbilical pipes.

5 In order to additionally improve, among other things, the pitting resistance of duplex stainless steel, an increase of the PRE number is required in both the ferrite please and the austenite phase without, because of this, jeopardizing the structural stability or the workability of the material. If the composition in the two phases is not equiva-lent in respect of the active alloying components, one of fibs phases becomes more 1 o susceptible to pitting and crevice corrosion. Thus, the more corrosion-susceptible phase controls the resistance of the alloy, while the structural stability is controlled by the highest alloyed phase.
The demands that may be made on an alloy that shall meet the requirements in the future for umbilical pipes, can be summarized in table 1, with examples of the best various alternative alloys existing on the market in the present situation being included. It is clear that all existing alloys on at least one point do not meet the new stiffer demands that are made on umbilical pipes.
2 o Table 1 Property Demands = UNS UNS UNS UNS

alloy accordingS32750 S32906 S32654 S32001 to the invention PRE Min 46 42,5 42 55 22 Yield point 720 550 650 430 450 in tension Rpo,2 (N/mm2) Pitting CPT > 90 C 50 50 >95 <20 in C

Crevice corro-60 C 35 35 60 <20 sion CCT in C

Structural Max 0,5 /~ ~K ~K ~K OK
sta-bility sigma phase Manufacture Vveldable ~l~ ~I~ ~t< ~t~
by means of con-ventional tech-nique Summary of the Invention

6 Therefore, it is an object of the present invention to provide a duplex stainless steel alloy, which has high corrosion resistance in combination with improved mechanical properties and simultaneously having good structural stability and that is most suit-able for use in envir~nments where a high resistance is reguired t~ general corrosion and local corrosion, such as, f~r insiance, in chloride-containing environments.
It is an additional object of the present invenfiion to provide a duplex stainless steel alloy having a Critical Pitting Corrosion Temperature (henceforth abbreviated CPT) 1 o value greater than 90 °C, preferably greater than 95 °C and a Critical Crevice Corro-sion Temperature (henceforth abbreviated CCT) value of at least 60 °C
in 6 °/~ FeCl3.
It is an additional object of the present invention to provide an alloy having an impact resistance of at least 100 J at room temperature and a yield point in tension Rpo,2 of 15 at least 720 N/mm2 and an elongation upon tensile testing of at least 25 %
at room temperature.
The material according to the present invention has, in view of the high alloy content thereof, extraordinarily good workability, in particular hot-workability, and should 2 o thereby be very suitable to be used for, for instance, the manufacture of bars, pipes, such as welded and seamless pipes, weld material, construction parts such as, for instance, flanges and couplings.
These objects are met according to the present invention by means of duplex stain-25 less steel alloys, which contain (in % by weight) C more than 0 up to max 0,03 Si up to max 0,5 M n 0-3, 0 Cr 24,0-30,0 3 o Ni 4,9-10,0 %

Mo 3,0-5,0 N 0,28-0,5 /~

S 0-0,0030 /~

S up to max 0,010 /~

3 5 Co 0-3, 5 %

V1I 0-3, 0 Cu 0-2,0 %

Ru 0-0,3 AI 0-0, 03

7 PCT/SE2004/000223 Ga 0-0,010 balance Fe together with inevitable contaminations.
Srief Description of the Figures Figure 1 shows CPT values from tesfi of the ea;perimental charges in the modified R,STM G43C test in the "Green Death" solution in comparison with the duplex steels S~F 2507, SP~F 2906.
Figure 2 shows CPT values produced by means of the modified ~4STM G43C test to in "Green Death" solution for the experimental charges in comparison with the duplex steel SAF 2507 as well as SAF 2906.
Figure 3 shows the mean value of the corrosion in mm/year in 2 °/~ HCI
at the temperature of 75 °C.
Figure 4 shows the results from hot ductility test for most of the charges.
Detailed Description of the Invention A systematic development work has surprisingly shown that by a well balanced com-bination of the elements Cr, Mo, Ni, N, Mn and Co, an optimum distribution of the 2 o elements in the ferrite and in the austenite can be obtained, which enables a very corrosion resistant material having only a negligible quantity of sigma phase in the material. The material also gets good workability, which enables the extrusion to weldless pipes. In order to obtain the combination of high corrosion resistance in connection with good structural stability, a very narrow combination of the alloying elements in the material is required. Therefore, the alloy according to the invention contains (in % by weight):
C more than 0 up to max 0,03 Si up to max 0,5 3 o M n 0-3, 0 Cr 24,0-30,0 Ni 4,9-10,0 Mo 3,0-5,0 %

N 0,23 -0,5 /~

B 0-0,0030 S up to max 0,010 °/~
Co 0-3, 5 °/~
W 0-3, 0 Cu 0-2,0

8 Ru 0-0, 3 AI 0-0,03 Ca 0-0, 010 balance Fe together with normally occurring contaminations and additives, the ferrite content being 40-65 °/~ by volume.
The impact of the alloying elements is described in the following:
Carbon (C) has limited solubility in both ferrite and austenite. The limited solubility to means a risk of precipitation of chromium carbides and therefore the content should not exceed 0,03 °/~ by weight, preferably not exceed 0,02 °/~ by weight.
Silicon (Si) is utilized as deoxidizer in the steel production and increases fihe flowabil-ity in production and upon welding. However, too high contents of Si lead to precipi-tation of undesired intermetallic phase, and therefore the content should be limited to max 0,5 % by weight, preferably max 0,3 % by weight.
Manganese (Mn) is added in order to increase the solubility of N in the material However, it has turned out that Mn only has a limited impact on the solubility of N in 2 o the alloy type in question. Instead, there are other elements having higher impact on the solubility. Furthermore, Mn may in combination with high sulphur contents give rise to the formation of manganese sulphides, which work as initiation spots for pit-ting. Therefore, the content of Mn should be limited to between 0-3,0 % by weight, preferably 0,5-1,2 % by weight.
Chromium (Cr) is a very active element in order to improve the resistance to the majority of corrosion types. Furthermore, a high chromium content means that a very good solubility of N is obtained in the material. Thus, it is desirable to hold the con-tent of Cr as high as possible in order to improve the corrosion resistance.
For very 3 o good values of the corrosion resistance, the chromium content should be at least 24,0 % by weight, preferably 27,0-29,0 % by weight. However, high contents of Cr increases the risk of intermetallic precipitations, and therefore the chromium content has to be limited upwards to max 30,0 °/~ by weight.
Nickel (Ni) is used as austenite-stabilizing element and is added in suitable contents so that the desired ferrite content is attained. In order to achieve the desired relation between the austenitic and the ferritic phase of between 40-65 % by volume of fer-rite, an addition of between 4,9-10,0 % by weight of nickel is required, preferably 4,9-9,0 % by weight, in particular 6,0-9,0 % by weight.

9 Molybdenum (Mo) is an active element that improves the corrosion resistance in chloride environments as well as preferably in reducing acids. Too high a content of Mo, in combination with the contents of Cr being high, means that the risk of inter-s metallic precipitations increases. The content of Mo in the present invention should be in the interval of 3,0-5,0 % by weight, preferably 3,6-4,9 °/~ by weight, in particu-lar q.,4-4,9 °/~ by weight.
Nitrogen (N) is a very active element that increases the corrosion resistance, the Zo structural stability as well as the strength of the material. Furthermore, a high content of N improves the reformation of austenite after welding, which gives good properties of welded joints. In order to achieve a good effect from N, at least 0,23 °/~ by weight of N should be added. At high contents of N, the risk of precipitation of chromium nitrides increases, especially when the chromium content simultaneously is high.
15 Furthermore, a high content of N means that the risk of porosity increases by virtue of the solubility of N in the charge being exceeded. The content of N should, for these reasons, be limited to max 0,5 % by weight, preferably is >0,35-0,45 %
by weight of N added.
2 o Too high a chromium as well as a nitrogen content result in the precipitation of Cr2N, which is to be avoided since it deteriorates the properties of the material, especially upon heat treatment, for instance welding.
Boron (B) is added in order to increase the hot workability of the material.
At too high 25 a boron content, the weldability and the corrosion resistance may be deteriorated.
Therefore, the boron content should be greater than 0 and up to 0,0030 % by weight.
Sulphur (S) affects the corrosion resistance negatively by forming easily soluble sul-phides. Furthermore, the hot workability is deteriorated, and therefore the sulphur 3 o content is limited to max 0,010 % by weight.
Cobalt (Co) is added foremost in order to improve the structural stability as well as the corrosion resistance. Co is an austenite stabilizer. In order to have an effect, at least 0,5 % by weight, preferably at least 1,0 °/~ by weight should be added. Since 35 cobalt is a relatively expensive element, the cobalt addition is therefore limited to max 3,5 °/~ by weight.
Tungsten increases the resistance to pitting and crevice corrosion. But addition of too high contents of tungsten in combination with the contents of Cr and contents of Mo being high, means that the risk of intermetallic precipitations increases.
The content of W in the present invention should be in the interval of 0-3,0 % by weight, preferably between 0-1,8 % by weight.
s C~er is added in order to improve the corr~sion resistance in acid envir~nments such as sulphuric acid. Cu also affects the strucfiural stability. However, high contents of Cu means tl-rat the solid solubility is exceeded. Therefore, the content of Cu is lim-iced to max 2,0 °/~ by weight, preferably between 0,1 and 1,5 °/~ by weight.
so Ruthenium (Ru) is added in order to increase the corrosion resistance.
Ruthenium is a very expensive element, and therefore the content is limited to max 0,3 °/~ by weight, preferably greater than 0 and up to 0,1 °/~ by weight.
Aluminium (AI) as well as Calcium (Ca) are utilized as deoxidizers in the steel pro-duction. The content of AI should be limited to max 0,03 % by weight in order to limit nitride formation. Ca has a favourable effect on the hot ductility but the content of Ca should, however, be limited to 0,010 % by weight in order to avoid undesired quantity of cinder.
2 o The ferrite content is important in order to obtain good mechanical properties and corrosion properties as well as good weldability. From a corrosion and a weldability point of view, it is desirable having a ferrite content of between 40-65 % in order to obtain good properties. Furthermore, high ferrite contents means that the low-tem-perature impact resistance as well as the resistance to hydrogen embrittlement risk 2 s being deteriorated. Therefore, the ferrite content is 40-65 % by volume, preferably 42-60 % by volume, in particular 45-55 % by volume.
Description of Preferred Embodiment Examples 3 o In the examples below, the composition of a number of experimental charges is given, which illustrate the impact of various alloying elements on the properties.
Charge 605182 represents a reference composition and is accordingly not included in the field of this invention. Neither should other charges be regarded as limiting the invention but only states examples of charges that illustrate the invention according to the claims.
Given PRE numbers or values always relate to values calculated according to the PREW formula, even if not explicitly stated.

Example 1 Experimental charges according to this example were produced by laboratory casting of 170 kg of ingot that was hot-forged into round bar. The same was hot extruded into bar (round bar as well as flafi bar), where test material was sampled from round s bar. Furkhermore, flat bar was annealed before cold rolling took place, and then additional test material was sampled. The process may, from a material technology point of view, be regarded as representative for the manufacture on a larger scale, for instance for the manufacture of seamless pipes by means of the extrusion method followed by cold rolling. Table ~ shows composition of experimental charges l o of the first batch.
Table 2 Charge Mn Cr Ni Mo W Co v La Ti N

605193 1,0327,908,80 4,000,01 0,020,04 0,010,01 0,36 605195 0,9727,909,80 4,000,01 0,970,55 0,010,35 0,48 605197 1,0728,408,00 4,001,00 1,010,04 0,010,01 0,44 605178 0,9127,947,26 4,010,99 0,100,07 0,010,03 0,44 605183 1,0228,716,49 4,030,01 1,000,04 0,010,04 0,28 605184 0,9928,097,83 4,010,01 0,030,54 0,010,01 0,44 605187 2,9427,744,93 3,980,01 0,980,06 0,010,01 0,44 605153 2,7827,856,93 4,031,01 0,020,06 0,020,01 0,34 605182 0,1723,487,88 5,750,01 0,050,04 0,010,10 0,26 With the purpose of examining the structural stability, samples from each charge 15 were annealed at 900-1150 °C with steps of 50 °C and were quenched in air and water, respectively. At the lowest temperatures, intermetallic phase was formed. The lowest temperature where the amount of intermetallic phase became negligibly small, was determined by means of studies in light-optical microscope. New samples from the respective charge were then annealed at said temperature during five min-e o utes, and then the samples were cooled down by the constant cooling rate of -140 °C/min to room temperature. The area fraction of sigma phase in the materials was then determined by means of digital image processing of images recorded by means of back-scattered electrons in scanning electron microscope. The results are seen in Table 3.
Tma,~ sigma is calculated by means of Thermo-Calc (T-C version f~ the thermody_ namic database of steel TCFE99) based on guiding values of all stated elements in the different variants. TmaX sigma is the resolution temperature of the sigma phase, with high resolution temperature indicating lower structural stability.

Table 3 Charge Heat treatmentQuantity of 6 Tmax [% by vol.] a 605193 1100 C, 7,5 % 1016 min 605195 1150 C, 32 /~ 1047 5 min 605197 1100 C, 18 /~ 1061 5 min 605178 1100 C, 14 % 1038 5 min 605183 1050 C, 0,4 % 997 5 min 605184 1100 C, 0,4 % 999 5 min 605187 1050 C, 0,3 % 962 5 min 605153 1100 C, 3,5 % 1032 5 min 605182 1100 C, 2,0 % 1028 5 min The object of this investigation is to be able to rank materials in respect of the struc-tural stability, i.e. this is not the actual content of sigma phase in the test pieces that have been heat treated and quenched before, for instance, corrosion test. It is evi-dent that TmaX sigma that has been calculated by means of Thermo-calc does not directly corresponds with measured quantity of sigma phase, but in this investigation it is, however, clear that the experimental charges having the lowest calculated Tmax ~ o sigma contain the lowest quantity of sigma phase.
The pitting properties of all charges have been tested for ranking in the so-called "Green Death" solution that consists of 1 % FeCl3, 1 % CuCh, 11 % H2S04, 12 HCI . The test procedure corresponds to the pitting testing according to ASTM
G48C, but is carried out in the more aggressive "Green Death" solution. Furthermore, some charges have been tested according to ASTM G48C (2 experiments per charge).
Also electrochemical testing in 3 % NaCI (6 experiments per charge) has been car-ried out. The results in the form of critical pitting temperature (CPT) from all experi-ments are seen in Table 4, such as the PREW number (Cr + 3,3(Mo + 0,5 W) + 16 2 o N) of the total alloy composition as well as of austenite and ferrite. The indexing alpha relates to ferrite and gamma relates to austenite.
Table 4~
Charge PRE PRE PRE ~y/PREPRE CPT C CPT C RSTMCPT C 3%
a ~y c~

Modified G48C 6% NaCI (600 my ASTM G48C FeCl3 SCE

Green Death 605193 51,3 49,0 0,9552 46,9 90/90 64 Charge PRE PRE'yPRE ~y/PREPRE CPT C CPT C ASTMCPT C 3%
a a Modified G48C 6% NaCI (600 ASTM G48C FeCl3 my Green ~eath SCE

605195 51,5 48,9 0,94.95 48,7 90/90 95 605197 53,3 53,7 1,0075 50,3 90/90 >95 >95 605178 50,7 52,5 1,0355 49,8 75/80 94~

605183 48,9 48,9 1,0000 46,5 85/85 90 93 605184 48,9 51,7 1,0573 48,3 80/80 72 605187 48,0 54,4 1,1333 48,0 70/75 77 605153 49,6 51,9 1,0464 48,3 80/85 85 90 605182 54,4 46,2 0,8493 46,6 75/70 85 62 SAF2507 39,4 42,4 1,0761 41,1 70/70 80 95 SAF2906 39,6 46,4 1,1717 41,0 60/50 75 75 It is recognized that there is a linear relation between the lowest PRE value in the austenite or the ferrite and the CPT value in duplex steels, but the results in Table 4 show that the PRE number not solely explains the CPT value.
It is clear from these results that all test materials have better CPT in the modified ASTM G48C than SAF 2507 and SAF 2906. Test charge 605 183 alloyed with cobalt shows good structural stability at controlled cooling rate (-140 °C/min), in spite of it 2o containing high contents of chromium as well as molybdenum, has better results than SAF 2507 as well as SAF 2906. In this investigation, it is seen that a high PRE
not solely explains the CPT values, but the ratio of PRE austenite/PRE ferrite is of utmost importance for the properties of higher alloyed duplex steels, and a very nar-row and accurate levelling between the alloying elements is required in order to 15 obtain this optimal ratio, which is between 0,9-1,15; preferably 0,9-1,05 and simul-taneously obtain PRE values above 46. The ratio of PRE austenite/PRE ferrite ver-sus CPT in the modified ASTM G48C test for the experimental charges are accounted for in Table 4.
2 o The strength at room temperature (RT), 100 °C and 200 °C and the impact resis-tance at room temperature (RT) have been determined for all charges and are sh~wn as mean value of three experiments.

Tensile test pieces (DR-5C50) were produced from extruded bars Q~ 20 mm, which avers heat treated at temperatures according to Table 2 for 20 min followed by cool-ing down in either air or water (605 195, 605 197, 605 184). The results of the inves-tigation are presented in Tables 5 and 6. The results of the tensile strength investi-gation show that the contents of chromium, nitrogen and tungsten str~ngly affect the tensile strength in the material. III charges except 505 153 meet the requirement on a 25 ~/~ elongation upon tensile testing at room temperature (RT).
Teble 5.
Charge Tempera~urRPp RPO,~ Rm A5 G

(MPG)(MPa) (MPa)(/~) (%) 605193 RT 652 791 916 29,7 38 100 C 513 646 818 30,4 36 200 C 511 583 756 29,8 36 605195 RT 671 773 910 38,0 66 100 C 563 637 825 39,3 68 200 C 504 563 769 38,1 64 605197 RT 701 799 939 38,4 66 100 C 564 652 844 40,7 69 200 C 502 577 802 35,0 65 605178 RT 712 828 925 27,0 37 100 C 596 677 829 31,9 45 200 C 535 608 763 27,1 36 605183 RT 677 775 882 32,4 67 100 C 560 642 788 33,0 59 200 C 499 578 737 29,9 52 605184 RT 702 793 915 32,5 60 100 C 569 657 821 34,5 61 200 C 526 581 774 31,6 56 605187 RT 679 777 893 35,7 61 100 C 513 628 799 38,9 64 200 C 505 558 743 35,8 58 605153 RT 715 845 917 20,7 24 100 C 572 692 817 29,3 27 200 C 532 G11 749 23,7 31 605182 RT 627 754 903 28,4 43 100 C 493 621 802 31,8 42 Tabell 6.
Charge AnnealingCooling Impact Annealing[C/Cooling Impact [C/min] down resistancemin] down resistance [J] [J]

605193 1100/20 Air 35 1100/20 Water 242 605195 1150/20 Water 223 605197 1100/20 Water 254 1130/20 Water 259 605178 1100/20 Air 62 1100/20 Water 234.

605183 1050/20 Air 79 1050/20 Water 244.

605184 1100/20 Water 81 1100/20 Air 78 605187 1050120 Air 51 1100/20 Water 95 605153 1100/20 Air 50 1100/20 Water 246 605182 1100/20 Air 22 1100/20 Water 324 This investigation shows very clearly that water quenching naturally is required in 5 order to obtain the best structure and accordingly good impact resistance values.
The requirement is 100 J upon testing at room temperature and this do all charges manage except charge 605 184 and 605 187, where, however, the last-mentioned one is very near the requirement.
1o Table 7 shows results from Tungsten Inert Gas remelting test (henceforth abbrevi-ated TIG), with the charges 605 193, 605 183, 605 184 as well as 605 253 having a stable structure in the heat affected zone (henceforth abbreviated HAZ). The Ti-containing charges have TiN in HAZ.
15 Table 7 Charge Precipitations Protective gas Ar (99,99 %) 605193 HAZ:OK

605195 HAZ: Large amounts of TiN and o' phase 605197 HAZ: Small amounts of Cr2N in 8 grains, however not much 605178 HAZ: Cr~N in 8 grains, otherwise OK

605183 HAZ:OK

605184 HA~:OI<

605187 HAS: Cr2N fairly close to the melting b~undary, no precipitations farther ~ut 605153 HAZ:OK

605182 HAS: TiN as well as decorated grain boundaries S/8.

Example 2 In the example below, the composition is given of an additional number of experi-mental charges manufactured with the intention of finding the optimal composition.
Said charges are modified, based on the properties of the charges having good structural stability as well as high corrosion resistance, from the results that were shown in Example ~ . III charges in Table ~ are comprised of the composition according to the present invention, with charges ~-~ being included in a statistical experimental plan, while charges a to n are additional experimental alloys within the scope of this invention.
so A number of experimental charges were produced by seating a X70 I<g casting, which was hot-forged into round bar. This was extruded to bar, from which test materials were sampled. Then the bar was annealed before cold rolling of flat bar took place and then additional test materials were sampled. Table ~ shows the composition of the same experimental charges.
Table 8 Charge Mn Cr Ni Mo W Co Cu Ru B N

1 605258 1,129,0 6,54,23 1,5 0,00180,46 2 605249 1,028,8 7,04,23 1,5 0,00260,38 3 605259 1,129,0 6,84,23 0,6 0,00190,45 4 605260 1,127,5 5,94,22 1,5 0,00200,44 5 605250 1,128,8 7,64,24 0,6 0,00190,40 6 605251 1,028,1 6,54,24 1,5 0,00210,38 7 605261 1,027,8 6,14,22 0,6 0,00210,43 8 605252 1,128,4 6,94,23 0,5 0,00180,37 a 605254 1,126,9 6,54,8 1,0 0,00210,38 f 605255 1,028,6 6,54,0 3,0 0,00200,31 g 605262 2,727,6 6,93,9 1,0 1,0 0,00190,36 h 605263 1,028,7 6,64,0 1,0 1,0 0,00200,40 i 605253 1,028,8 7,04,16 1,5 0,00190,37 j 605266 1,130,0 7,14,02 0,00180,38 k 605269 1,028,5 7,03,97 1,0 1,0 0,00200,45 I 605268 1,128,2 6,G4,0 1,0 1,01,0 0,00210,43 m 605270 1,028,8 7,04,2 1,5 0,1 0,00210,41 n 605267 1,129,3 6,54,23 1,5 0,00190,38 The distribution of alloying elements in the ferrite and austenite phase was examined by means of micro probe analysis, the result is seen in Table 9.
Tebell 9 Cherge Phese Cr fVin~Li fVi~1/U C~ Cu i~

605258 Ferric 29,8 1,3 4,8 5,0 1,4 0,11 Austenit28,3 1,4 7,3 3,4 1,5 0,60 605249 Ferrit 29,8 1,1 5,4 5,1 1,3 0,10 Austenite27,3 1,2 7,9 3,3 1,6 0,53 605259 Ferrite 29,7 1,3 5,3 5,3 0,5 0,10 Austenite28,1 1,4 7,8 3,3 0,58 0,59 605260 Ferrite 28,4 1,3 4,4. 5,0 1,4 0,08 Austenite26,5 1,4 6,3 3,6 1,5 0,54 605250 Ferrite 30,1 1,3 5,6 5,1 0,46 0,07 Austenite27,3 1,4 8,8 3,4 0,53 0,52 605251 Ferrite 29,6 1,2 5,0 5,2 1,3 0,08 Austenite26,9 1,3 7,6 3,5 1,5 0,53 605261 Ferrite 28,0 1,2 4,5 4,9 0,45 0,07 Austenite26,5 1,4 6,9 3,3 0,56 0,56 605252 Ferrite 29,6 1,3 5,3 5,2 0,42 0,09 Austenite27,1 1,4 8,2 3,3 0,51 0,48 605254 Ferrite 28,1 1,3 4,9 5,8 0,89 0,08 Austenite26,0 1,4 7,6 3,8 1,0 0,48 605255 Ferrite 30,1 1,3 5,0 4,7 2,7 0,08 Austenite27,0 1,3 7,7 3,0 3,3 0,45 605262 Ferrite 28,8 3,0 5,3 4,81,4 0,9 0,08 Austenite26,3 3,2 8,1 3,00,85 1,1 0,46 605263 Ferrite 29,7 1,3 5,1 5,11,3 0,91 0,07 Austenite27,8 1,4 7,7 3,20,79 1,1 0,51 605253 Ferrite 30,2 1,3 5,4 5,0 1,3 0,09 Austenite27,5 1,4 8,4 3,1 1,5 0,48 605266 Ferrite 31,0 1,4~5,7 4,8 0,09 Austenite29,0 1,5 8,4~ 3,1 0,52 605269 Ferrite 28,7 1,3 5,2 5,11,4 0,9 0,11 Austenite26,6 1,4 7,8 3,20,87 1,1 0,52 605268 Ferrite 29,1 1,3 5,0 4,71,3 0,910,84 0,12 Austenite26,7 1,4 7,5 3,20,97 1,0 1,2 0,51 605270 Ferrite 30,2 1,2 5,3 5,0 1,3 0,11 ChargePhase Cr Mn Ni Mo W Co Cu N

Austenite27,7 1,3 8,0 3,2 1,4 0,47 605267Ferrite 30,1 1,3 5,1 4,9 1,3 0,08 Austenite27,8 1,4 7,6 3,1 1,8 0,46 The pitting properties of all charges have been tested in the "Green Death"
solution (1 °/~ FeCl3, 1 % CuCl2, 11 °/~ H2S~~, 1,2 % HCl) for ranking.
The test procedure is the same as pitting testing according to AST~tt G48C, but the testing is carried out in a more aggressive solution than 6 °/~ FeCI~, the so-called "Green Death" solution.
Also general corrosion test in 2 °/~ HCI (2 experiments per charge) has been carried out for ranking before dew point testing. The results from all experiments are seen in Table 10, Figure 2 and Figure 3. All tested charges perForm better than SAF
2507 in 1 o the Green Death solution. All charges are within the identified interval of 0,9-1,15;
preferably 0,9-1,05 as regards the ratio PRE austenite/PRE ferrite at the same time as PRE in both austenite and ferrite is higher than 44 and for most of the charges also substantially higher than 44. Some of the charges even reach the limit total PRE
50. It is very interesting to note that charge 605 251, alloyed with 1,5 % by weight of 15 cobalt, performs almost equivalent to charge 605 250, alloyed with 0,6 % by weight of cobalt, in "Green Death" solution, in spite of the lower chromium content in charge 605 251. It is particularly surprisingly and interesting when charge 605 251 has a PRE number of approx. 48, which is higher than any commercial super duplex alloy today at the same time as the TmaX sigma value below 1010 °C indicates a good 2 o structural stability based on the values in Table 2 in example 1.
In Table 10, also the PREW number (% Cr + 3,3 °/~(Mo + 0,5 % W) + 16 % N) is given for the total alloy composition and PRE in austenite as well as ferrite (rounded) based on phase composition being measured by means of micro probe. The ferrite 25 content is measured after heat treatment at 1100 °C followed by water quenching.
Table 10 Charge~ contentPREW TotalPRE PRE PRE~y/PREaCPT C the Green a ~y Death 60525848,2 50,3 48,1 4.9,1 1,021 65/70 60524959,8 48,9 48,3 46,6 0,967 75/80 60525949,2 50,2 48,8 48,4 0,991 75/75 60526053 4~ 4.8,5 4.6,14.7,0 1,019 75/80 60525053,6 49,2 48,1 46,8 0,974 95/80 60525154,2 48,2 48,1 46,9 0,976 90/80 Chargea contentPREW TotalPRE PRE PREyIPREaCPT C the Green a y Death 60526150,8 48,6 45,2 46,3 1,024 80/70 60525256,6 48,2 48,2 45,6 0,946 80/75 60525453,2 48,8 48,5 46,2 0,953 90/75 60525557,4 4.6,9 46,9 44,1 0,94.0 90/80 60526257,2 4.7,9 48,3 45,0 0,931 70/85 60526353,6 49,7 49,8 4'x,80,959 80/75 60525352,6 48,4. 4.8,2 4.5,40,942 85/75 60526662,6 49,4 48,3 47,6 0,986 70/65 60526952,8 50,5 49,6 4.6,90,945 80/90 60526852,0 49,9 48,7 47,0 0,965 85/75 60527057,0 49,2 48,5 45,7 0,944 80/85 60526759,8 49,3 47,6 45,4 0,953 60/65 ChargeCPT AverageCCT AverageRP0,12 Rm RT A Z
RT RT RT

In order to more closely examine the structural stability, the samples were annealed for 20 min at 1080 °C, 1100 °G and 1150 °C, and then they were quenched in water.

The temperature where the amount of intermetallic phase became negligibly small was determined by means of investigations in light-optical microscope. A
comparison of the structure of the charges after annealing at 1080 °C followed by water quench-ing indicates which of the charges that are more inclined to contain undesired sigma phase. The results are seen in Table 11. Structural control shows that the charges 605 249, 605 251, 505 252, 605 253, 505 254, 505 255, 505 259, 505 260, 605 as well as 605 267 are free frorn undesired sigma phase. Furthermore, charge 605 249, alloyed with 1,5 % by weight of cobalt, is free from sigma phase, while charge 605 250, alloyed with 0,6 °/~ by weight of cobalt, contains a little sigma phase.
to both charges are alloyed with high percentage of chromium, almost 29,0 °/~ by weight, as well as molybdenum content of almost 4,25 °/~ by weight.
When the com-positions of the charges 605 249, 605 250, 605 251 and 605 252 are compared considering the sigma phase content, it is very clear that the composition interval for the optimal material in respect of, in this case, structural stability, is very narrow.
15 Furthermore, it is evident that charge 605 268 contains only occasional sigma phase in comparison with charge 605 263, which contains much sigma phase. What essentially separates these charges, is addition of copper to charge 605 268.
In charge 605 266 as well as 605 267, the sigma phase is free in spite of high chro-mium content, the later charge is alloyed with copper. Furthermore, the charges 2 0 605 262 and 605 263, having the addition of 1,0 % by weight of tungsten, have a structure with much sigma phase, while it is interesting to note that charge 605 269, also having 1,0 % by weight of tungsten but of a higher nitrogen content than 605 262 and 605 263, has a considerably smaller quantity of sigma phase. Thus, a very well-adjusted balance between the various alloying elements is required at 2s these high alloy contents for, e.g. , chromium and molybdenum, in order to obtain good structural properties.
Table 12 shows the results from the light optical investigation after annealing at 1080 °C, 20 min, followed by water quenching. The amount of sigma phase is indi-3 o Gated by means of values from 1 to 5, with 1 representing that no sigma phase has been detected upon the investigation, while 5 representing that a very high percent-age of sigma phase has been detected upon the investigation.
Table 12 ChargeSigma phaseGr Nio W Go Cu P~ Ru 60524.91 28,8 4,23 1,5 0,38 6052502 28,8 4,24 0,6 0,40 6052511 28,1 4,24 1,5 0,38 6052521 28,4 4,23 0,5 0,37 ChargeSigma phaseCr Mo W Co Cu N Ru 6052531 28,8 4,16 1,5 0,37 6052541 26,9 4,80 1,0 0,38 6052551 28,6 4,04 3,0 0,31 6052582 29,0 4,23 1,5 0,46 6052591 29,0 4.,23 0,6 0,45 6052601 27,5 4,22 1,5 0,44 6052612 27,8 4,22 0,6 0,43 6052624 27,6 3,931,0 1,0 0,36 6052635 28,7 3,961,0 1,0 0,40 6052661 30,0 4,02 0,38 6052671 29,3 4,23 1,50,38 6052682 28,2 3,981,0 1,0 1,00,43 6052693 28,5 3,971,0 1,0 0,45 6052703 28,8 4,19 1, 0,41 0,1 In Table 13, results are shown from impact resistance testing of some of the charges. The results are very good, which indicates a fine structure after annealing at 1100 °C followed by water quenching and the requirement of 100 J is met by a large margin by all tested charges.
Table 13 ChargeAnnealing Cooling Impact Impact resistanceImpact resistance [C/min] down resistance jJ] [J]
[J]

6052491100/20 Water >300 >300 >300 6052501100/20 Water >300 >300 >300 6052511100/20 Water >300 >300 >300 6052521100/20 Water >300 >300 >300 6052531100/20 Water 258 267 257 6052541100/20 Water >300 >300 >300 6052551100/20 Water >300 >300 >300 Figure 4 shows the results from hot ductility test of most of the charges. ~4 good worl<ability is naturally crucial in order to be able to manufacture the material into product shapes such as bars, pipes, such as welded and seamless pipes, thread, weld material, construction parts such as, for instance, flanges and couplings. The charges 605 249, 605 250, 605 251, 605 252, 605 255, 605 266 as well as 605 267, most having a nitrogen content of around 0,38 % by weight, have somewhat better hot ductility values.
The strain controlled fatigue properties give information about how much, and how many times, a material may be elongated, before strain controlled fatigue cracks arise in the material. Since umbilical pipes are welded together into long lengths, are reeled on drums before the are twisted into the umbilical, it is not unusual that a number of operations occurs where certain plastic deformation arises before the to umbilical starts function. The strain controlled fatigue data that has been established emphasise that the risk of rupture as a consequence of strain controlled fatigue in an umbilical pipe borders on zero.
Summary The demands that are made on umbilical pipes in the future and that are met by an optimised alloy according to above, is that PRE of min 46 in the alloy combined with the fact that PRE in austenite or ferrite exceeds 45 is required in order to obtain suf-ficiently good pitting and crevice corrosion properties. Thus, it is required that:
CPTin6%FeCl3 >90°C
CCT in 6 % FeCl3 >_ 60 °C
The strength that is required for being able to substantially reduce the weight of an umbilical is:
field point in tension Rpo,2 min 720 N/mm2 In order to be able to manufacture umbilical pipes and in order to guarantee that pit-3 o ting and crevice corrosion resistance as well as mechanical properfiies being pre-served, the following is required regarding the structural stability:
~ The alloy shall be weldable by means of conventional welding methods f~laximally 0,5 °/~ sigma phase in the structure o fVllaxim~am resolution temperattare of sigma phase is 1010 °C
The material according to the present invention has, in view of the high alloy content thereof, extraordinarily good workability, in particular hot-workability, and should thereby be very suitable to be used for, for instance, the manufacture of bars, pipes, such as welded and weldless pipes, weld material, construction parts, such as, for instance, flanges and couplings.

Claims

1. Ferrite-austenitic duplex stainless steel alloy having the following com-position (in % by weight):
C more than 0 and up to max 0,03%
Si up to max 0,5%
Mn 0-3,0 %
Cr 24,0-30,0%
Ni 4,9-10,0%
Mo 3,0-5,0%
N 0,23-0,5%
B 0-0,0030%
S up to max 0,010%
Co 0-3,5%
W 0-3,0%
Cu 0-2,0%
Ru 0-0,3%
AI 0-0,03%
Ca 0-0,010%
as well as balance Fe together with normally occurring contaminations and additives, the ferrite content being 40-65 % by volume and the relation PRE = % Cr + 3,3%
Mo + 16 % N exceeding 46 for the total composition of the alloy, as well as that PRE
in austenite and ferrite phase exceeds 45 as well as that the yield point in tension Rp0,2 of the alloy exceeds 720 N/mm2, as well as that CPT >90 °C as well as CCT >=
60 °C.

2. Alloy according to claim 1, characterized in that the chromium content is between 26,5 and 29,0 % by weight.

3. Alloy according to claim 1 and 2, characterized in that the manganese content is between 0,5 and 1,2 % by weight.

4. Alloy according to claim 1-3, characterized in that the nickel content is between 5,0 and 8,0 % by weight.

5. Alloy according to claim 1-4, characterized in that the molybde-num content is between 3,6 and 4,9 % by weight.

6. Alloy according to claim 1-5, characterized in that the nitrogen content is between 0,35 and 0,45 % by weight.

7. Alloy according to claim 1-6, characterized in that the ruthenium content is between 0 and 0,3 % by weight, preferably greater than 0 and up to 0,1 %
by weight.

3. Alloy according to claim 1-7, characterized in that the cobalt content is between 0,5 and 3,5 % by weight, preferably between 1,0 and 3,0 %
by weight.

9. Alloy according to claim 1-3, characterized in that the copper content is between 0,5 and 2,0 % by weight, preferably between 1,0 and 1,5 %
by weight.

10. Alloy according to claim 1-9, characterized in that the ferrite content is between 42 and 60 % by volume, preferably between 45 and 55 % by volume.

11. Alloy according to claim 1-9, characterized in that the total PRE
or PREW value of the alloy exceeds 46, wherein PRE = % Cr + 3,3 % Mo + 16 N
and PREW = % Cr + 3,3 (% Mo + 0,5 % W) + 16 N, wherein % relates to % by weight.

12. Alloy according to claim 11, characterized in that the PRE or PREW value of both the ferrite and austenite phase is greater than 45 and the PRE
or PREW value of the total alloy composition is greater than 46.

13. Use of an alloy according to claim 1 as umbilical cord pipe in chloride-containing environments, in particular sea-water environments.

14. Use of an alloy according to any one of claims 1-13 for the manufacture of bars, pipes, such as welded and weldless pipes, weld material, construction parts, such as, for instance, flanges and couplings.