WO2023198720A1 - Nouvel acier inoxydable duplex - Google Patents

Nouvel acier inoxydable duplex Download PDF

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Publication number
WO2023198720A1
WO2023198720A1 PCT/EP2023/059457 EP2023059457W WO2023198720A1 WO 2023198720 A1 WO2023198720 A1 WO 2023198720A1 EP 2023059457 W EP2023059457 W EP 2023059457W WO 2023198720 A1 WO2023198720 A1 WO 2023198720A1
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stainless steel
duplex stainless
content
weight
max
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PCT/EP2023/059457
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English (en)
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Mats HÄTTESTRAND
Ulf KIVISÄKK
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Alleima Tube Ab
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Publication of WO2023198720A1 publication Critical patent/WO2023198720A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/02—Hardening by precipitation
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
    • C21D8/105—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to a duplex stainless steel having a high Cr-, W- and N-content.
  • umbilical Today the pressure of an oil well is increasing and there are plans to develop wells with pressures of 20 kpsi.
  • a long liner also known as an umbilical, usually link the surface and seafloor equipment.
  • umbilicals contain tubing for both hydraulic and chemical injection to the subsea but also signal lines for providing electric and fiber-optics signals and electric power.
  • the tubing of umbilicals consists of long tubes which may be welded together.
  • Super duplex stainless steels i.e., an austenitic-ferritic iron chromium nickel alloy with molybdenum addition with PRE above 40, have been used as these steels will provide enough pitting resistance and mechanical strength for traditional subsea wells.
  • the umbilicals have to withstand higher internal pressure.
  • the wall thickness of the tube of the umbilicals has to be increased in order to withstand the higher pressure.
  • these tubes will suffer from an increased weight which will increase the likelihood of failure as the duplex stainless steels of today do not have enough strength to carry their own weight if the wall thickness is increased to meet the higher pressure demands.
  • duplex stainless steels of today may not possess enough corrosion resistance and may also have problems with formation of sigma phase during welding, especially in the heat affected zone. This will be very problematic when manufacturing umbilicals as these tubes may contain a lot of weld joints where cracks may be formed.
  • FIGURE 1A shows a LOM picture of Heat 7 in a representative site of 0.05 mm 2 ;
  • FIGURE IB shows the same LOM picture as Figure 1 A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm 2 ;
  • FIGURE 2A shows a LOM picture of Heat 8 in a representative site of 0.05 mm 2 ;
  • FIGURE 2B shows the same LOM picture as Figure 2A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm 2 ;
  • FIGURE 3 A shows a LOM picture of Heat 13 in a representative site of 0.05 mm 2 ;
  • FIGURE 3B shows the same LOM picture as Figure 3 A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm 2 ;
  • FIGURE 4A shows a LOM picture of Heat 14 in a representative site of 0.05 mm 2 ;
  • FIGURE 4B shows the same LOM picture as Figure 4A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm 2
  • FIGURE 5A shows a LOM picture of Heat 9 in a representative site of 0.05 mm 2 ;
  • FIGURE 5B shows the same LOM picture as Figure 5 A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm 2 .
  • the present disclosure provides a duplex stainless steel having a combination of high strength and excellent corrosion resistance as it contains a low coverage of quenched-in nitrides in the ferrite grain boundaries in its final form and will essentially not contain any sigma phase in the steel as such and in the heat affected zone when exposed to welding.
  • the low coverage of quenched-in nitrides in the ferrite grain boundaries will increase the corrosion resistance and the impact resistance. Additionally, the low content of sigma phase will increase the corrosion resistance. Both these properties are important for the endurance of products in operation, such as when used for tubes in umbilicals.
  • final form is meant that the present duplex stainless steel has been exposed to the metallurgy processes necessary for being used in different applications.
  • the present duplex stainless steel as defined hereinafter will contain low amounts of or essentially no sigma phase both in the duplex stainless steel as such and in the Heat Affected Zone (HAZ) after welding and additionally will have low coverage of quenched-in nitrides in the ferrite grain boundaries after being subjected to solution annealing and quenching.
  • HZ Heat Affected Zone
  • the present disclosure therefore relates to a duplex stainless steel having the ranges of elements as disclosed hereinbelow.
  • the inventors have carefully adapted both which elements and which ranges of these elements to be used in order to obtain a duplex stainless steel having the properties as mentioned hereinabove or hereinafter.
  • the present duplex stainless steel therefore comprises the following elements in weight%: C max 0.030;
  • the ferrite content is of 40-60 vol%; and wherein the duplex stainless steel fulfills the requirements of: a. [Cr] + 4.0*[Mo] + 2.0*[W] ⁇ 42.5 wherein the values of [Cr], [Mo] and [W] are in weight%; and b) having less than 10% coverage of quenched-in nitrides in the ferrite grain boundaries when in solution annealed condition.
  • the present duplex stainless steel will have a low coverage of quenched-in nitrides in the ferrite grain boundaries after solution annealing followed by quenching.
  • the coverage of quenched-in nitrides in the ferrite grain boundaries is measured as described in the method of the Example, Example 4.
  • the present duplex stainless steel will, due to its composition, have resistance against formation of sigma phase in the Heat Affected Zone (HAZ) and will therefore essentially not contain any sigma phase.
  • HAZ Heat Affected Zone
  • solution annealed condition is intended to mean the condition obtained after subjecting the present duplex stainless steel to a heat treatment, for the purpose of solution annealing, followed by cooling from the solution annealing temperature to a temperature of about 900 to about 1000 °C, and thereafter quenching.
  • solution annealing is intended to include both heat treatment and cooling from the solution annealing temperature to a temperature between about 900 to about 1000 °C.
  • quenched-in nitrides refers to the nitrides which are formed at the ferrite grain boundaries when a steel is cooled fast as the elements will have no time to migrate between the phases and therefore will be precipitated in the ferrite grain boundaries.
  • the coverage of quenched-in nitrides in the ferrite grain boundaries is measured as according to the method as described in the Example.
  • the inventors have found that it is important, in order to obtain the properties of the present duplex stainless steel, to balance the elements having an impact on the sigma phase formation during welding, as the sigma phase has a negative impact on the strength.
  • the inventors have thus found that if the following condition is fulfilled:
  • equation 1 may also fulfill the following: 40 ⁇ [Cr] +4.0* [Mo] + 2.0* [W] ⁇ 42.
  • the ferrite content of the present duplex stainless steel is between 40-60 vol%, the reminder is essentially composed of austenite. If the ferrite content is too low, the mechanical strength will be too low and if the ferrite content is too high, the corrosion properties will deteriorate. For example, the resistance to hydrogen induced cracking will deteriorate if the ferrite content is too high. According to embodiments, the ferrite content is at least 44 vol%, the reminder being essentially austenite.
  • the phase balance is important in duplex stainless steels as it helps to obtain the optimum mechanical properties and corrosion resistance. Additionally, the ferrite content of the present duplex stainless steel has been adapted so that phase balance is still within acceptable ranges in the heat affected zone. This is important as the ferrite content in the heat affected zone is often increase, which will have a negative impact on the mechanical properties and corrosion resistance.
  • the quenched-in nitrides formed in the ferrite grain boundaries will as, mentioned above, have a negative impact on both corrosion resistance and mechanical properties. It is therefore important to avoid formation of these quenched-in nitrides.
  • the present inventors have found that the present duplex stainless steel having the specified element ranges as defined hereinabove or hereinafter will have a low coverage of quenched-in nitrides in the ferrite grain boundaries (less than 10%) in a solution annealed condition.
  • a low coverage of quenched-in nitrides in the ferrite grain boundaries is meant that the percentage of ferrite grain boundaries covered with quenched-in nitrides is less than 10%.
  • a 10% coverage of ferrite grain boundaries with quenched-in nitrides will correspond to a very low fraction of quenched-in nitrides in the material as a whole. Therefore, less than 10% of ferrite grain boundaries covered with quenched-in nitrides is considered to be a low coverage of quenched-in nitrides.
  • weight% and “wt%” are used interchangeably herein.
  • HAZ heat affected zone
  • Chromium is an essential element, and the range has been selected in order to have good strength and corrosion resistance of the present duplex stainless steel. In order to have good strength properties and resistance to corrosion, the content of chromium should be at least
  • the chromium content of the present duplex stainless steel is therefore 28.5 to 30.5 weight%.
  • the chromium content may be 29.0 to 30.5 wt%, such as
  • the chromium content may be from 29.1, 29.2, 29.3, 29.4 or 29.5 to 29.6, 29.7, 29.8, 29.9, 30.0, 30.1, 30.2, 30.3, 30.4 or 30.5 wt%.
  • Ni is used as an austenite-stabilizing element.
  • the content of nickel should be at least 6.0 weight%. Additionally, if you have a too high Ni content, the austenite content will be increase which will lead to lowers strength.
  • the highest content of nickel is 8.0 weight%.
  • the content of Ni may be less than 7.9, 7.8, 7.7 or 7.6 weight%.
  • the lowest amount of Ni may be 6.0 weight%.
  • the range may be between 6.0 to 7.6 wt%.
  • Mo is an active element which improves the strength and resistance to corrosion in chloride environments as well as in reducing acids.
  • Molybdenum may sometimes be replaced with tungsten. It is generally accepted in the art that replacement of molybdenum with tungsten may be performed in such a ratio that 1 weight% of Mo would be replaced by 2 weight% of W. However, if the present duplex stainless steel contains too low amounts of Mo, too much quenched-in nitrides in the ferrite grain boundaries will be formed during solution annealing with subsequent quenching.
  • the content of Mo should be in the range of at least 0.70 weight% and the content of Mo should be no more than 3.00 wt%.
  • the content of Mo may be from at least 0.70 to 2.00 wt%., such as from at least 0.70 to 1.70 wt%, such as from at least 0.90 to 1.70 wt%.
  • W will improve the resistance to corrosion in chloride environments as well the resistance to pitting and crevice corrosion.
  • a too high W content in combination with a high Cr content increase the risk of precipitation of sigma phase.
  • the W-content is therefore 2.00 to 4.40 wt%. According to ethe present disclosure, the content of W may be 2.50 to 4.40 wt%, such as 3.00 to 4.00 wt%. Nitrogen (N)
  • N is a very active element which increases the resistance to corrosion as well as the strength of the duplex stainless steel. In order to obtain a good effect at least 0.30 weight % N should be added.
  • the range of N must be carefully selected as too high content of N will increase the risk of precipitation of chromium nitrides, especially when the content of chromium is also high.
  • the N-content should therefore be limited to maximum 0.55 weight%.
  • the content of nitrogen is 0.30 to 0.55 weight%.
  • the content of N may be from 0.35 to 0.55 wt%; such as 0.38 to 0.55 wt%, such as 0.38 to 0.50 wt%.
  • Mn is added in order to increase the solubility of N in the steel.
  • Mn may also form manganese sulphides, which act as initiation points for pitting corrosion.
  • the content of Mn is therefore greater than or equal to 0.20 weight% but equal to or less than 2.50 weight %. According to the present disclosure, the content of Mn may be 0.30 to 2.00 weight%.
  • Si is frequently utilized as a deoxidizer during steel production. However, it is known that high silicon content stabilizes the sigma phase. The content of silicon should therefore be limited to max 0.30 weight%. According to the present disclosure, the content of silicon may be 0. 10 to 0.30 weight%.
  • Carbon is an element which is very difficult to completely avoid in a duplex stainless steel. Striving towards very low carbon contents would unduly increase the manufacturing costs. Therefore, carbon may be present in an amount of at least 0.005 weight% at least for cost reasons. C strengthens stainless steel but also promotes the formation of chromium carbides which are harmful to corrosion. Carbon has also a limited solubility in both ferrite and austenite. The carbon content should therefore be limited to max 0.030 weight%, such as max 0.025 weight%.
  • Cu may be added in order to improve resistance to certain corrosive environments such as acid environments and it also decreases susceptibility to stress corrosion cracking. Furthermore, Cu will increase the strength and also reduce the formation of sigma phase.
  • Cu will have a negative effect on nitrogen solubility as less nitrogen is solved in the stainless steel and formation of chromium nitrides will therefore be increase.
  • the content of Cu is therefore limited max 0.50 wt%, such as less than 0.50 wt%.
  • Cu is added, and the content of Cu is between 0.15 to ⁇ 0.50 wt%, According embodiments, the Cu content may be 0.25 to 0.45 wt%.
  • Sulfur is an impurity element normally contained in duplex stainless steel.
  • the sulfur content should not be more than 0.030 wt% as it will have an impact on the hot workability above said range.
  • Phosphorus is also an impurity element normally contained in duplex stainless steel.
  • the phosphorus content should not be more than 0.030 wt% as it will have an impact on the hot workability above said range.
  • the balance of present duplex stainless steel is iron (Fe) and unavoidable impurities.
  • the unavoidable impurities are elements which are not added on purpose but may be in the present steel due to the scrap and/or manufacturing process used for providing the duplex stainless steel. Examples but not limited to such elements are Co, V, Ti, Nb, Pb, Sn and Ce.
  • the combined content of these elements is less than 1.0 wt%
  • the present duplex stainless steel may optionally comprise one or more, elements which may have been added in order to improve the manufacturing process. Examples but not limiting to such manufacturing process improving elements are Aluminium (Al), Magnesium (Mg), Calcium (Ca) and Boron (B).
  • the combined content of these improving elements is less than 0.50 weight%, such as less than 0.30 weight% with the condition that content of Al cannot be more the 0.050 weight% and with the condition that the content of B cannot be more than 0.050 weight%.
  • the present duplex stainless steel may comprise or consist of the elements mentioned herein in any of the ranges of the specific elements mentioned herein and fulfilling the requirements mentioned herein.
  • the present disclosure related to an object comprising or consisting of the duplex stainless steel as defined hereinabove or hereinafter.
  • the object is made of the duplex stainless steel as defined hereinabove or hereinafter.
  • the object is in solution annealed condition.
  • the present disclosure relates to an object comprising a duplex stainless steel wherein said duplex stainless steel comprising the following elements in weight%:
  • the ferrite content is of 40-60 vol%; and wherein the duplex stainless steel fulfills the requirements of: a) [Cr] + 4.0*[Mo] + 2.0*[W] ⁇ 42.5 wherein the values of [Cr], [Mo] and [W] are in weight%; and b) having less than 10% coverage of quenched-in nitrides in the ferrite grain boundaries when in solution annealed condition.
  • the present object may have Rp0.2 higher than 650 MPa, ISO 6892-1, 2019, measured in room temperature.
  • the present disclosure also relates to an object comprising or consisting of duplex stainless steel comprising the following elements in wt%:
  • the present disclosure also relates to an object comprising a duplex stainless steel wherein said duplex stainless steel comprising the following elements in weight%:
  • a Rp0.2 higher than 650 MPa, ISO 6892-1,2019, in room temperature means that the object of the present duplex stainless steel can be used in applications where the material is exposed to the high internal pressures, such as the pressures which can be found in the new developments where exploration recently started at a higher well pressure of 20 ksi and will also be able to have a strength high enough to carry its own weight.
  • the object is a tube or a pipe, such as a seamless tube or a coiled tube or one or several tubes welded together to one long tube.
  • the object is a longitudinally welded tube or welded pipe.
  • the object is a hollow or a billet.
  • the object may be a strip or a wire.
  • the present disclosure also relates to a process for manufacturing an object, such as a tube, of the duplex stainless steel defined hereinabove or hereinafter, wherein said process comprises the steps of:
  • the melting may be performed by a high frequency induction furnace or an arc furnace.
  • the hot working may be performed by forging and/or rolling and/or extrusion.
  • Cold working may be performed by forging and/or rolling and/or extrusion.
  • the cold working may be performed by rolling or pilgering.
  • Solution annealing is performed at a temperature range of to about 1000 to about 1200°C, such as about 1050 to about 1150°C;
  • Cooling may be performed in room temperature and the cooling may be performed in air.
  • the cooling is performed from the solution annealing temperature to a temperature of about 900 to about 1000 °C Quenching;
  • the quenching may be performed in water.
  • the quenching should be performed so that the formation of sigma phase is avoided.
  • steps may be performed such as straightening, machining and the like.
  • a duplex stainless steel comprising the following elements in weight%:
  • the ferrite content is of 40-60 vol%; and wherein the duplex stainless steel fulfills the requirements of: a) [Cr] + 4.0*[Mo] + 2.0*[W] ⁇ 42.5 wherein the values of [Cr], [Mo] and [W] are in weight%; and b) having less than 10% coverage of quenched-in nitrides in the ferrite grain boundaries when in solution annealed condition.
  • duplex stainless steel according to item 1 wherein the content of Cr is 29.0 to 30.5 wt%.
  • duplex stainless steel according to any one of items 1 to 3, wherein the content of Ni is from 6.0 to 7.6 wt%.
  • duplex stainless steel according to any one of items 1 to 4, wherein the content of Mo is at least 0.70 to 2.00 wt%.
  • duplex stainless steel according to any one of item 1 to 5, wherein the content of W is from 2.50 to 4.40 wt%,
  • duplex stainless steel according to any one of items 1 to 8, wherein the content of Si is 0.10 to 0.30 weight%.
  • duplex stainless steel according to any one of items 1 to 9, wherein the content of Cu is 0.15 to 0.50 weight%.
  • duplex stainless steel according to any one of items 1 to 10, wherein the content of N is from 0.35 to 0.55 weight%.
  • duplex stainless steel according to any one of items 1 to 11, wherein the content of N is from 0.38 to 0.55 weight%.
  • duplex stainless steel according to any one of items 1 to 12, wherein the content of N is from 0.38 to 0.50 weight%.
  • An object comprising or consisting of the duplex stainless steel according to any one of items 1 to 13.
  • the object according to claim 14 having a Rp0.2 higher than 650 MPa, ISO 6892-1, 2019, in room temperature.
  • the present disclosure also relates to a solution annealed condition object comprising or consisting of any or a combination of the features 1 to 15.
  • the present disclosure also relates to a processed duplex stainless steel comprising or consisting of any or a combination of the features 1 to 13.
  • the duplex stainless steel has been processed as described hereinabove or hereinafter.
  • Heats having a chemical composition according to Table 1 were melted in a high frequency induction furnace as 50 kg heats or 270 kg heats and then cast to ingots using a mold.
  • the obtained ingots were forged or hot rolled to billets.
  • the obtained billets were if needed machined to smaller billets.
  • the billets were cold rolled to 7 to 10 mm samples and then solution annealed in a temperature of 1050 to 1150°C and then cooled in room temperature to a temperature between 950 to 1000 °C and subsequent water quenched.
  • Samples were taken after solution annealing and quenching. After that and in order to simulate the environment of a heat affected zone, the samples were heated to about 1100°C. The cooling of the samples was controlled, and the cooling rate was 40 °C/min from about 1100 °C to room temperature.
  • the fraction of sigma phase formed during cooling was measured using SEM and image analysis evaluation of ten image fields covering a total area of 0.4 mm 2 2 of the sample. As this test simulates the reality for welding operations, a product can be welded with low formation of sigma phase in the HAZ if containing no or low sigma phase. As stated before, if no or low sigma phase can be found, there will be the corrosion resistance as well as the impact toughness will be excellent.
  • Rp0.2 was measured according to ISO 6892-1,2019, in room temperature.
  • All the inventive stainless steels heats have a RpO.2 higher than 650 MPa, such as higher than 660 MPa.
  • Table 2 The table shows the sigma phase content of each alloy and the RpO.2. The heats marked with are inventive heats.
  • Example 4 Measurement of the coverage of quenched-in nitride in the ferrite grain boundaries
  • LOM Light Optical Microscopy
  • the percentage of ferrite grain boundaries covered with quenched-in nitrides was calculated by dividing the number of intercepts between test lines and ferrite grain boundaries covered with quenched-in nitrides with the total number of intercepts between test lines and ferrite grain boundaries. Examples of this is shown in FIGURES 1 A to 5B and the result from these calculations is shown in Table 3.
  • Table 3 Heats having less than 10% coverage of quenched-in nitrides in ferrite grain boundaries as measured as described in Example 4. The heats marked with are inventive heats.
  • the ferrite amount was measured using LOM and manual point counting according to ASTM E562. The reminder is essentially austenite. The ferrite was measured on cold rolled and solution annealed and quenched samples.
  • Table 4 The result of the samples ferrite amount - the reminder is essentially austenite, The heats marked with are inventive heats.
  • the heats marked with are inventive heats.
  • the other heats are comparative heats.
  • Balance for each heat is Fe and unavoidable impurities. Note that some of impurites are also mentioned in the table.

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Abstract

La présente invention concerne un acier inoxydable duplex comprenant les éléments suivants en pourcentages pondéraux: C max 0,030; Si max 0,30; Mn 0,20 à 2,50; P max 0,030; S max 0,030; Cr 28,5 à 30,5; Ni 6,0 à 8,0; Mo 0,70 à 3,00; W 2,00 à 4,40; Cu ≤ 0,50 ; N 0,30 à 0,55; le reste étant du Fe et des impuretés inévitables; et la teneur en ferrite étant de 40 à 60 % en volume ; et l'acier inoxydable duplex satisfaisant aux exigences de: a. [Cr] + 4,0*[Mo] + 2,0*[W] < 42,5, les valeurs de [Cr], [Mo] et [W] étant en % en poids; et b. ayant moins de 10% de couverture de nitrures trempés dans les limites de grain de ferrite lorsqu'il est dans un état recuit en solution. La présente invention concerne également des objets constitués de l'acier inoxydable duplex de la présente invention ayant un Rp0.2 supérieur à 650 MPa, ISO 6892-1 2019.
PCT/EP2023/059457 2022-04-12 2023-04-11 Nouvel acier inoxydable duplex WO2023198720A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1117848A1 (fr) * 1999-06-29 2001-07-25 Sandvik AB (publ) Acier inoxydable duplex
JP2002241838A (ja) * 2001-02-13 2002-08-28 Sumitomo Metal Ind Ltd 二相ステンレス鋼管の製造方法
US20030155046A1 (en) * 2002-02-05 2003-08-21 Yoshimi Yamadera Duplex stainless steel for urea manufacturing plants
US20080138232A1 (en) * 2004-11-04 2008-06-12 Pasi Kangas Duplex Stainless Steel
WO2017013181A1 (fr) * 2015-07-20 2017-01-26 Sandvik Intellectual Property Ab Nouvelle utilisation d'un acier inoxydable duplex
EP3712289A1 (fr) * 2017-11-15 2020-09-23 Nippon Steel Corporation Acier inoxydable biphasique et procédé de fabrication d'acier inoxydable biphasique
US20210108295A1 (en) * 2017-12-22 2021-04-15 Tubacex Innovación A.I.E. Duplex stainless steel resistant to corrosion

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1117848A1 (fr) * 1999-06-29 2001-07-25 Sandvik AB (publ) Acier inoxydable duplex
JP2002241838A (ja) * 2001-02-13 2002-08-28 Sumitomo Metal Ind Ltd 二相ステンレス鋼管の製造方法
US20030155046A1 (en) * 2002-02-05 2003-08-21 Yoshimi Yamadera Duplex stainless steel for urea manufacturing plants
US20080138232A1 (en) * 2004-11-04 2008-06-12 Pasi Kangas Duplex Stainless Steel
WO2017013181A1 (fr) * 2015-07-20 2017-01-26 Sandvik Intellectual Property Ab Nouvelle utilisation d'un acier inoxydable duplex
EP3712289A1 (fr) * 2017-11-15 2020-09-23 Nippon Steel Corporation Acier inoxydable biphasique et procédé de fabrication d'acier inoxydable biphasique
US20210108295A1 (en) * 2017-12-22 2021-04-15 Tubacex Innovación A.I.E. Duplex stainless steel resistant to corrosion

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