Title of Invention	FERRITE-AUSTENITIC DUPLEX STAINLESS STEEL ALLOY FOR USE IN SEA WATER APPLICATIONS
Abstract	The present invention relates to a stainless steel alloy, more precisely a duplex stainless steel alloy having ferritic-austenitic matrix and high corrosion resistance in combination with good structural stability and hot workability, in particulars 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 hotworkability, 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 duples stainless steel alloys, which contain (in % by weight): C more that 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.

Title of Invention

FERRITE-AUSTENITIC DUPLEX STAINLESS STEEL ALLOY FOR USE IN SEA WATER APPLICATIONS

Abstract

The present invention relates to a stainless steel alloy, more precisely a duplex stainless steel alloy having ferritic-austenitic matrix and high corrosion resistance in combination with good structural stability and hot workability, in particulars 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 hotworkability, 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 duples stainless steel alloys, which contain (in % by weight): C more that 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.

Full Text	Technical Field of the Invention The present invention relates to a stainless steel alloy, more precisely a duplex stainless steel alloy having ferritic-austenitic matrix and having high corrosion resis- tance in combination with good structural stability and hot workability, in particular a duplex stainless steel having-a ferrite content of 40-65 % by volume and a well-bal- anced composition that gives the material corrosion properties making it more suit- able for use in chloride-containing environments than what has previously been found possible. Background of the Invention 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 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 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 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 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 naving 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 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 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 70-90 °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- ments is the so-called Pitting Resistance Equivalent (abbreviated PRE), being defined as PRE =%Cr+ 3,3 % Mo + 16 % N where the percentage figures of each element refer to percentage by weight. A higher numerical value indicates a better corrosion resistance, in particular to pit- ting. The principal alloying elements that affect this property 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 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 commercial alloys DP3W (UNS S39274) or ZeronlOO, 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 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 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 43 since higher values mean that the alloys obtain inferior structural stability. A higher 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, irrespective of method of calculation. Of the alloys having good corrosion resistance in chloride environments, SAF 2906 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 intercrystalline corrosion and corrosion in ammonium carba- mate is of importance, but it has also a high corrosion resistance in chloride-con- taining environments. The alloy has a corrosion resistance in chloride environment corresponding to the alloy UNS S32750, but simultaneously a higher yield point in tension Rpo.2. This makes that this alloy has advantages in comparison with UNS S32750 as umbilical material, since lower weight of the umbilical can be obtained. The corrosion resis- tance gives, 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 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- 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, Mo 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 same alloys is that they have considerably lower yield point in tension than duplex steel ai d 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. 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 phase 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 the phases becomes more susceptible to pitting and crevice corrosion. Thus, the more corrosion-susceptible phase controls the resistance bf 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. 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 suitable for use in environments where a high resistance is required to general corrosion and local corrosion, such as, for instance, in chloride-containing environments. It is an additional object of the present invention to provide a duplex stainless steel alloy having a Critical Pitting Corrosion Temperature (henceforth abbreviated CPT) value greater than 90°C, preferably greater than 95°C and a Critical Crevice Corrosion Temperature (henceforth abbreviated CCT) value of at least 60°C in 6% FeCI3. 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 Rp0.2 of 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 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. The objects are met according to the present invention by means of 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 % Cr 24. 0-30. 0 % Ni 4.9-10.0% Mo 3.0-5.0 % N 0.28-0.5% B 0-0.0030 % S up to max 0.010% Co 0.5-3.5 % W 0-3.0 % Cu 0-2.0% Ru 0-0.3 % Al 0-0.03 % Ca 00,01030 balance Fe together with inevitable contaminations. Brief Description of the Figures Figure 1 shows CPT values from test of the experimental charges in the modified ASTM G48C test in the "Green Death" solution in comparison with the duplex steels SAF 2507, SAF 2906. Figure 2 shows CPT values produced by means of the modified ASTM G48C test 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 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 % Mn 0-3,0 % Cr 24,0-30,0 % Ni 4,9-10,0% Mo 3,0-5,0 % N 0,28 -0,5 % B 0-0,0030 % S up to max 0.010 % Co 0-3,5 % W 0-3,0% CU 0-2,0 % Ru 0-0,3 % Al 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 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 the 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 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 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 90 by weight. 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-metallic precipitations increases. The content of Mo in the present invention should be in the interval 3.0 - 5.0% by weight, preferably 3.6 - 4.9% by weight, in particular 4.4 - 4.9% by weight. Nitrogen (N) is a very active element that increases the corrosion resistance, the 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 0.28% 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. 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 greater than 0.35 and up to 0.45% by weight of N added. 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 a boron content, the weldablity 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 negativity by forming easily soluble sulphides. Furthermore, the hot workability is deteriorated, and therefore the sulphur 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 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 intermetaliic 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. Copper is added in order to improve the corrosion resistance in acid environments such as sulphuric acid. Cu also affects the structural stability. However, high contents of Cu means that the solid solubility is exceeded. Therefore, the content of Cu is lim- ited to max 2,0 % by weight, preferably between 0,1 and 1 ,'5 % by weight. 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 (Al) as well as Calcium (Ca) are utilized as deoxidizers in the steel pro- duction. The content of Al 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. 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 being deteriorated. Therefore, the ferrite content is 40-65 % by volume, preferably 42-60 % by volume, in particular 45-55 % bv volume. Description of Preferred Embodiment Examples 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 flat bar), where test material was sampled from round bar. Furthermore, 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 2 shows composition of experimental charges of the first batch. With the purpose of examining the structural stability, samples from each charge 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- 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. Tmax sigma is calcul ted by means of Thermo-Calc (T-C version N 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. 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 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 % FeCI3,1 % CuCI2,11 % H2SO4,12 % 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 carried 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 N) of the total alloy composition as well as of austenite and ferrite. The indexing alpha relates to ferrite and gamma relates to austenite. 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 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 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. 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 shown as mean value of three experiments. Tensile test pieces (DR-5C50) were produced from extruded bars 0 20 mm, which were heat treated at temperatures according to Table 2 for 20 min followed by cool- ing down in either air of 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 strongly affect the tensile strength in the material. All charges except 605 153 meet the requirement on a 25 % elongation upon ten.sile testing at room temperature (RT). This investigation shows very clearly that water quenching naturally is required in 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. 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. 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 1. All charges in Table 8 are comprised of the composition according to the present invention, with charges 1-8 being included in a statistical experimental plan, while charges e to n are additional experimental alloys within the scope of this invention. A number of experimental charges were produced by casting a 270 kg 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 8 shows the composition of the same experimental charges. 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. The pitting properties of all charges have been tested in the "Green Death" solution (1 % FeCI3, 1 % CuCI2,11 to H2SO4,1,2 % HCI) for ranking. The test procedure is the same as pitting testing according to ASTM G48C, but the testing is carried out in a more aggressive solution than 6 % FeCI3, 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 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 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 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 content is measured after heat treatment at 1100 °C followed by water quenching. In order to more closely examine the factural stability, the samples were annealed for 20 min at 1080 °C, 1100 °C 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, 605 252, 605 253, 605 254, 605 255, 605 259,605 260, 605 266 as well as 605 267 are free from 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. 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. 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 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 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- cated 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. 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. Figure 4 shows the results from hot ductility test of most of the charges. A good workability 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 instruction 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 umbilical starts function. The strain controlled fatigue data that has been established emphasize 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: CPT in 6 % 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: Yield 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- ting and crevice corrosion resistance as well as mechanical properties being pre- served, the following is required regarding the structural stability: • The alloy shall be weldable by means of conventional welding methods • Maximally 0,5 % sigma phase in the structure e Maximum resolution temperature 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. WE CLAIM: 1. Ferrite-austenitic duplex stainless steel alloy having the following composition (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 0.28-0.5% B 0-0.0030% S up to max 0.010% Co 0.5-3.5% W 0-3.0 % Cu 0-2.0% Ru 0-0.3 % Al 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 RpO,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, wherein the chromium content is between 26.5 and 29.0 % by weight. 3. Alloy according to claim 1 and 2, wherein the manganese content is between 0.5 and 1.2 % by weight. 4. Alloy according to claim 1-3, wherein the nickel content is between 5.0 and 8.0% by weight. 5. Alloy according to claim 1 -4, wherein the molybdenum content is between 3.6 and 4.9 % by weight. 6. Alloy according to claim 1-5, wherein the nitrogen content is between 0.35 and 0.45 % by weight. 7. Alloy according to claim 1 -6, wherein the ruthenium content is between 0 and 0.3 % by weight, preferably greater than 0 and up to 0.1 % by weight. 8. Alloy according to claim 1-7, wherein the cobalt content is between 1.0 - 3.0% by weight. 9. Alloy according to claim 1-8, wherein 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, wherein the ferrite content is between 42 and 60 % by volume, preferably between 45 and 55 % by volume. 11. Alloy according to claim 1-9, wherein 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, wherein the PRE or PREW value of both the ferrite and austenite phase is exceeding 45 and the PRE or PREW value of the total alloy composition is exceeding 46. 13. Alloy according to claim 1 adapted for umbilical cord pipe in chloride-containing environments, in particular sea-water environments. 14. Alloy according to any one of claims 1-13 adapted for manufacture of bars, pipes, such as welded and weldless pipes, weld material, construction parts, such as, for instance, flanges and couplings. The present invention relates to a stainless steel alloy, more precisely a duplex stainless steel alloy having ferritic-austenitic matrix and high corrosion resistance in combination with good structural stability and hot-workability, in particulars 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 hotworkability, 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 duples stainless steel alloys, which contain (in % by weight): C more that 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.

Full Text

Technical Field of the Invention
The present invention relates to a stainless steel alloy, more precisely a duplex
stainless steel alloy having ferritic-austenitic matrix and having high corrosion resis-
tance in combination with good structural stability and hot workability, in particular a
duplex stainless steel having-a ferrite content of 40-65 % by volume and a well-bal-
anced composition that gives the material corrosion properties making it more suit-
able for use in chloride-containing environments than what has previously been
found possible.
Background of the Invention
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
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
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
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
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 naving 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
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
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 70-90 °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-
ments is the so-called Pitting Resistance Equivalent (abbreviated PRE), being
defined as
PRE =%Cr+ 3,3 % Mo + 16 % N
where the percentage figures of each element refer to percentage by weight.
A higher numerical value indicates a better corrosion resistance, in particular to pit-
ting. The principal alloying elements that affect this property 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
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
commercial alloys DP3W (UNS S39274) or ZeronlOO, 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
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
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 43
since higher values mean that the alloys obtain inferior structural stability. A higher
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, irrespective of method of calculation.
Of the alloys having good corrosion resistance in chloride environments, SAF 2906
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 intercrystalline corrosion and corrosion in ammonium carba-
mate is of importance, but it has also a high corrosion resistance in chloride-con-
taining environments.
The alloy has a corrosion resistance in chloride environment corresponding to the
alloy UNS S32750, but simultaneously a higher yield point in tension Rpo.2. This
makes that this alloy has advantages in comparison with UNS S32750 as umbilical
material, since lower weight of the umbilical can be obtained. The corrosion resis-
tance gives, 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
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-
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, Mo 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 same alloys is that they have considerably lower yield point in tension than
duplex steel ai d 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.
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 phase
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 the phases becomes more
susceptible to pitting and crevice corrosion. Thus, the more corrosion-susceptible
phase controls the resistance bf 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.
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 suitable for use in
environments where a high resistance is required to general corrosion and local corrosion,
such as, for instance, in chloride-containing environments.
It is an additional object of the present invention to provide a duplex stainless steel alloy
having a Critical Pitting Corrosion Temperature (henceforth abbreviated CPT) value
greater than 90°C, preferably greater than 95°C and a Critical Crevice Corrosion
Temperature (henceforth abbreviated CCT) value of at least 60°C in 6% FeCI3.
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 Rp0.2 of 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 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.
The objects are met according to the present invention by means of 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 %
Cr 24. 0-30. 0 %
Ni 4.9-10.0%
Mo 3.0-5.0 %
N 0.28-0.5%
B 0-0.0030 %
S up to max 0.010%
Co 0.5-3.5 %
W 0-3.0 %
Cu 0-2.0%
Ru 0-0.3 %
Al 0-0.03 %
Ca 00,01030
balance Fe together with inevitable contaminations.
Brief Description of the Figures
Figure 1 shows CPT values from test of the experimental charges in the modified
ASTM G48C test in the "Green Death" solution in comparison with the
duplex steels SAF 2507, SAF 2906.
Figure 2 shows CPT values produced by means of the modified ASTM G48C test
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
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 %
Mn 0-3,0 %
Cr 24,0-30,0 %
Ni 4,9-10,0%
Mo 3,0-5,0 %
N 0,28 -0,5 %
B 0-0,0030 %
S up to max 0.010 %
Co 0-3,5 %
W 0-3,0%
CU 0-2,0 %
Ru 0-0,3 %
Al 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
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 the 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
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
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 90 by weight.
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-metallic
precipitations increases. The content of Mo in the present invention should be in the
interval 3.0 - 5.0% by weight, preferably 3.6 - 4.9% by weight, in particular 4.4 - 4.9% by
weight.
Nitrogen (N) is a very active element that increases the corrosion resistance, the 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 0.28% 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. 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
greater than 0.35 and up to 0.45% by weight of N added.
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 a
boron content, the weldablity 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 negativity by forming easily soluble sulphides.
Furthermore, the hot workability is deteriorated, and therefore the sulphur 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 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 intermetaliic 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.
Copper is added in order to improve the corrosion resistance in acid environments
such as sulphuric acid. Cu also affects the structural stability. However, high contents
of Cu means that the solid solubility is exceeded. Therefore, the content of Cu is lim-
ited to max 2,0 % by weight, preferably between 0,1 and 1 ,'5 % by weight.
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 (Al) as well as Calcium (Ca) are utilized as deoxidizers in the steel pro-
duction. The content of Al 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.
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
being deteriorated. Therefore, the ferrite content is 40-65 % by volume, preferably
42-60 % by volume, in particular 45-55 % bv volume.
Description of Preferred Embodiment Examples
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 flat bar), where test material was sampled from round
bar. Furthermore, 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 2 shows composition of experimental charges
of the first batch.
With the purpose of examining the structural stability, samples from each charge
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-
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.
Tmax sigma is calcul ted by means of Thermo-Calc (T-C version N 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.
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
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 % FeCI3,1 % CuCI2,11 % H2SO4,12 %
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 carried
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
N) of the total alloy composition as well as of austenite and ferrite. The indexing
alpha relates to ferrite and gamma relates to austenite.
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
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
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.
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
shown as mean value of three experiments.
Tensile test pieces (DR-5C50) were produced from extruded bars 0 20 mm, which
were heat treated at temperatures according to Table 2 for 20 min followed by cool-
ing down in either air of 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 strongly affect the
tensile strength in the material. All charges except 605 153 meet the requirement on
a 25 % elongation upon ten.sile testing at room temperature (RT).
This investigation shows very clearly that water quenching naturally is required in
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.
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.
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 1. All charges in Table 8 are comprised of the composition
according to the present invention, with charges 1-8 being included in a statistical
experimental plan, while charges e to n are additional experimental alloys within the
scope of this invention.
A number of experimental charges were produced by casting a 270 kg 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 8 shows the composition of
the same experimental charges.
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.
The pitting properties of all charges have been tested in the "Green Death" solution
(1 % FeCI3, 1 % CuCI2,11 to H2SO4,1,2 % HCI) for ranking. The test procedure is
the same as pitting testing according to ASTM G48C, but the testing is carried out in
a more aggressive solution than 6 % FeCI3, 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
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
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
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
content is measured after heat treatment at 1100 °C followed by water quenching.
In order to more closely examine the factural stability, the samples were annealed
for 20 min at 1080 °C, 1100 °C 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, 605 252, 605 253, 605 254, 605 255, 605 259,605 260, 605 266
as well as 605 267 are free from 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.
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.
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
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
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-
cated 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.
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.
Figure 4 shows the results from hot ductility test of most of the charges. A good
workability 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 instruction 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
umbilical starts function. The strain controlled fatigue data that has been established
emphasize 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:
CPT in 6 % 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:
Yield 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-
ting and crevice corrosion resistance as well as mechanical properties being pre-
served, the following is required regarding the structural stability:
• The alloy shall be weldable by means of conventional welding methods
• Maximally 0,5 % sigma phase in the structure
e Maximum resolution temperature 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.
WE CLAIM:
1. Ferrite-austenitic duplex stainless steel alloy having the following composition (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 0.28-0.5%
B 0-0.0030%
S up to max 0.010%
Co 0.5-3.5%
W 0-3.0 %
Cu 0-2.0%
Ru 0-0.3 %
Al 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 RpO,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, wherein the chromium content is between 26.5
and 29.0 % by weight.
3. Alloy according to claim 1 and 2, wherein the manganese content is
between 0.5 and 1.2 % by weight.
4. Alloy according to claim 1-3, wherein the nickel content is between 5.0 and 8.0% by weight.
5. Alloy according to claim 1 -4, wherein the molybdenum content is between
3.6 and 4.9 % by weight.
6. Alloy according to claim 1-5, wherein the nitrogen content is between 0.35
and 0.45 % by weight.
7. Alloy according to claim 1 -6, wherein the ruthenium content is between 0
and 0.3 % by weight, preferably greater than 0 and up to 0.1 % by weight.
8. Alloy according to claim 1-7, wherein the cobalt content is between 1.0 - 3.0% by weight.
9. Alloy according to claim 1-8, wherein 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, wherein the ferrite content is between 42
and 60 % by volume, preferably between 45 and 55 % by volume.
11. Alloy according to claim 1-9, wherein 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, wherein the PRE or PREW value of both the
ferrite and austenite phase is exceeding 45 and the PRE or PREW value of the total
alloy composition is exceeding 46.
13. Alloy according to claim 1 adapted for umbilical cord pipe in chloride-containing
environments, in particular sea-water environments.
14. Alloy according to any one of claims 1-13 adapted for manufacture of bars, pipes,
such as welded and weldless pipes, weld material, construction parts, such as, for
instance, flanges and couplings.
The present invention relates to a stainless steel alloy, more precisely a duplex
stainless steel alloy having ferritic-austenitic matrix and high corrosion resistance
in combination with good structural stability and hot-workability, in particulars 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 hotworkability,
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 duples stainless steel alloys,
which contain (in % by weight): C more that 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.

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Patent Number

224141

Indian Patent Application Number

01733/KOLNP/2005

PG Journal Number

40/2008

Publication Date

03-Oct-2008

Grant Date

01-Oct-2008

Date of Filing

31-Aug-2005

Name of Patentee

SANDVIK INTELLECTUAL PROPERTY AB

Applicant Address

S-811 81 SANDVIKEN

Inventors:

#	Inventor's Name	Inventor's Address
1	SUNDSTROM, ANN	BARRSATRAGATAN 71, S-811 36, SANDVIKEN
2	KANGAS, PASI	KARLAVAGEN 37, S-811 36, SANDVIKEN

PCT International Classification Number

C22C 38/44

PCT International Application Number

PCT/SE2004/000223

PCT International Filing date

2004-02-19

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0300574-1	2003-03-02	Sweden