EP2843068B1 - Eine methode zur herstellung eines cr-haltigen stahlrohrs für ein leitungsrohr mit hervorragender beständigkeit gegen interkristalline spannungsrisskorrosion der wärmebeeinflussten schweiszzone - Google Patents

Eine methode zur herstellung eines cr-haltigen stahlrohrs für ein leitungsrohr mit hervorragender beständigkeit gegen interkristalline spannungsrisskorrosion der wärmebeeinflussten schweiszzone Download PDF

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EP2843068B1
EP2843068B1 EP12875045.2A EP12875045A EP2843068B1 EP 2843068 B1 EP2843068 B1 EP 2843068B1 EP 12875045 A EP12875045 A EP 12875045A EP 2843068 B1 EP2843068 B1 EP 2843068B1
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steel pipe
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resistance
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content
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EP2843068A1 (de
EP2843068A4 (de
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Yukio Miyata
Mitsuo Kimura
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JFE Steel Corp
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JFE Steel Corp
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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
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • 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
    • C21D9/50—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for welded joints
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • 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
    • 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
    • C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0226—Hot rolling
    • 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
    • C21D8/0263—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment following hot rolling

Definitions

  • the present invention relates to a method of making a Cr containing steel pipe which is suitable as a steel pipe for linepipe to be used for transporting crude oil or natural gas which are produced at an oil well or a gas well, in particular, having excellent resistance to intergranular stress corrosion cracking (or resistance to IGSCC) in a welded heat affected zone.
  • oil wells and gas wells are generally arranged deep in the ground and in an intensely corrosive environment, for example, in a high temperature atmosphere containing carbon dioxide gas CO 2 , chloride ions Cl - , and so forth.
  • oil wells and gas wells which are arranged in a severe drilling environment, for example, at the bottom of the ocean are also being actively developed.
  • Patent Literature 1 describes a martensitic stainless steel pipe with excellent resistance to IGSCC in a welded heat affected zone which is suitably used as a linepipe without performing a post weld heat treatment.
  • the martensitic stainless steel pipe described in Patent Literature 1 has a chemical composition containing, by mass%, C: less than 0.0100%, N: less than 0.0100%, Cr: 10% to 14%, Ni: 3% to 8%, Si: 0.05% to 1.0%, Mn: 0.1% to 2.0%, P: 0.03% or less, S: 0.010% or less, and Al: 0.001% to 0.10%, and further containing at least one selected from Cu: 4% or less, Co: 4% or less, Mo: 4% or less, and W: 4% or less, and at least one selected from Ti: 0.15% or less, Nb: 0.10% or less, V: 0.10% or less, Zr: 0.10% or less, Hf: 0.20% or less, and Ta
  • Patent Literature 1 since formation of Cr carbides at prior-austenite grain boundaries is prevented by controlling the Csol, which is effective for forming Cr carbides, to be less than 0.0050%, formation of Cr depleted zones which causes IGSCC in a welded heat affected zone is prevented without performing - a post weld heat treatment.
  • Patent Literature 3 describes a Cr containing steel pipe for linepipe having high strength of X65 to X80 grade, and excellent in toughness, corrosion resistance, resistance to sulfide stress cracking, and resistance to IGSCC in a welded heat affected zone.
  • the Cr containing steel pipe for linepipe described in Patent Literature 3 has a chemical composition containing, by mass%, C: 0.001% to 0.015%, Si: 0.05% to 0.50%, Mn: 0.10% to 2.0%, Al: 0.001% to 0.10%, Cr: 15.0% to 18.0%, Ni: 2.0% to 6.0%, Mo: 1.5% to 3.5%, V: 0.001% to 0.20%, and N: 0.015% or less, under the condition that Cr+Mo+0.4W+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N is 11.5 to 13.3.
  • a microstructure in a welded heat affected zone which is subjected to heating up to a temperature range for forming ferrite single phase of 1300°C or higher and to cooling when welding is performed, is formed such that 50% or more of prior-ferrite grain boundaries, in a ratio with respect to the total length of the prior-ferrite grain boundaries, is occupied by martensite phase and/or austenite phase and formation of Cr carbide depleted zones is suppressed, a steel pipe having significantly increased resistance to IGSCC in a welded heat affected zone can be obtained, which results in a significant decrease in construction period of a welded steel pipe structure due to a post weld heat treatment being unnecessary.
  • Patent Literature 2 describes a high-strength stainless steel pipe for linepipe with excellent corrosion resistance.
  • the high-strength stainless steel pipe described in Patent Literature 2 has a chemical composition containing, by mass%, C: 0.001% to 0.015%, N: 0.001% to 0.015%, Cr: 15% to 18%, Ni: 0.5% or more and less than 5.5%, Mo: 0.5% to 3.5%, V: 0.02% to 0.2%, Si: 0.01% to 0.5%, Mn: 0.1% to 1.8%, P: 0.03% or less, S: 0.005% or less, N: 0.001 to 0.015% and O: 0.006% or less, under the condition that Cr+0.65Ni+0.6Mo+0.55Cu-20C ⁇ 18.5, Cr+Mo+0.3Si-43.5C-0.4Mn-Ni-0.3Cu-9N ⁇ 11.5, and C+N ⁇ 0.025 are satisfied at the same time.
  • Patent Literature 2 by maintaining a ferrite-martensite dual phase microstructure containing an appropriate amount of ferrite phase and by controlling Cr content to be in a rather high range from 15% to 18%, a steel pipe having excellent hot workability, excellent low temperature toughness, and sufficient strength for linepipe, and further having excellent corrosion resistance in a corrosive high temperature environment of 200°C containing carbon dioxide gas and chloride ions is obtained.
  • Patent literature 4 describes a high chromium-welded steel pipe excellent in the weld zone toughness of the seam weld zone and excellent in corrosion resistance and stress corrosion cracking resistance in the carbon dioxide environment and hydrogen sulfide environment.
  • the weld metal of the seam weld zone has a chemical composition of, by weight, ⁇ 0. 02% C, ⁇ 1.0% Si, ⁇ 2.0% Mn, ⁇ 0.03% P, ⁇ 0.005% S, ⁇ 300 ppm N, 3.0 to 7.0% Ni, 10 to 14% Cr, 200 to 400 ppm oxygen and ⁇ 8 cc/100 g diffusible hydrogen
  • Patent Literature 1 In an intensely corrosive environment, even with the steel pipe described in Patent Literature 1, there is a problem in that IGSCC occurring in a welded heat affected zone cannot be completely suppressed, and IGSCC occurring in a welded heat affected zone is at present prevented by performing a post weld heat treatment.
  • the steel pipe described in Patent Literature 1 was previously developed by the present inventors, and the steel pipe according to Patent Literature 1 is a martensitic stainless steel pipe whose microstructure does not include ferrite phase.
  • An object of the present invention is, by solving the problems in conventional arts described above, to provide a method of making a Cr containing steel pipe for linepipe having desired high strength, and excellent in toughness, corrosion resistance, resistance to sulfide stress cracking, and resistance to IGSCC in a welded heat affected zone.
  • the steel pipe which the present invention is intended for is a steel pipe of X65 to X80 grade (steel pipe having a yield strength (YS) of 448 to 651 MPa).
  • excellent toughness refers to a case where absorbed energy E -40 (J) at -40°C in a Charpy impact test is 50 J or more
  • excellent corrosion resistance refers to a case where a corrosion rate (mm/y) is 0.10 mm/y or less in a 200 g/liter NaCl aqueous solution at a temperature of 150°C in which carbon dioxide gas of 3.0 MPa is dissolved in the saturated state.
  • steel pipe includes not only seamless steel pipe and but also welded steel pipe.
  • the present inventors in order to achieve the object described above, diligently conducted investigations regarding various factors having influences on resistance to IGSCC in a welded heat affected zone of a ferritic-martensitic stainless steel pipe in a corrosive high temperature environment containing carbon dioxide gas and chloride ions.
  • the present inventors found that, in the case of this kind of steel, if almost all the grain boundaries of the ferrite grains having a large grain diameter is occupied by austenite phase at least by inducing ferrite ( ⁇ ) to austenite ( ⁇ ) transformation at the grain boundaries before Cr carbides are precipitated at the grain boundaries, precipitation of Cr carbides at the grain boundaries is prevented, and thus formation of Cr depleted zones is suppressed, which allows IGSCC to be prevented.
  • the present invention has been completed on the basis of the findings described above and further investigations. To solve the above object, the present invention proposes a method according to claim 1.
  • a Cr containing steel pipe for linepipe excellent in resistance to IGSCC in a welded heat affected zone can be manufactured at low cost without performing a post weld heat treatment, which results in a great industrial effect.
  • steel pipe structures such as pipelines can be constructed without performing a post weld treatment, there is also a merit of significantly decreasing construction cost due to, for example, a decrease in construction period.
  • C is a chemical element which contributes to an increase in strength, and it is necessary that the C content be 0.001% or more in the present invention.
  • the C content is set to be 0.001% to 0.010%, preferably 0.002% to 0.010%.
  • Si is a chemical element which functions as a deoxidizing agent and increases strength due to solid solution hardening, and it is necessary that the Si content be 0.05% or more in the present invention.
  • the Si content is set to be 0.05% to 0.50%, preferably 0.10% to 0.40%.
  • Mn contributes to an increase in strength due to solid solution hardening and is an austenite forming element which increases the toughness in both a base steel and a welded heat affected zone by suppressing formation of ferrite phase.
  • the Mn content is set to be 0.10% to 2.0%, preferably 0.20% to 1.5%.
  • the P content is a chemical element which deteriorates corrosion resistances such as CO 2 corrosion resistance and resistance to sulfide stress cracking, it is preferable that the P content be as small as possible in the present invention, but there is an increase in manufacturing cost in the case where the P content is excessively decreased.
  • the P content is set to be 0.020% or less, preferably 0.015% or less.
  • the S content is as small as possible, but, since it is possible to manufacture a pipe using an ordinary process in the case where the S content is 0.010% or less, the S content is set to be 0.010% or less, preferably 0.004% or less.
  • Al is a chemical element which is strongly effective as a deoxidizing agent, and it is necessary that the Al content be 0.001% or more in order to realize this effect, but there is a negative effect on toughness in the case where the Al content is more than 0.10%. Therefore, the Al content is set to be 0.10% or less, preferably 0.05% or less.
  • Cr is a chemical element which increases corrosion resistance such as CO 2 corrosion resistance and resistance to sulfide stress cracking as a result of forming a protective surface film. It is necessary in the present invention that the Cr content be 14% or more in order to increase corrosion resistance in an intensely corrosive environment. On the other hand, in the case where the Cr content is 15% or more excessively, it is necessary that large amount of other alloy elements such as Ni be added in order to control the value of P 1 to be within the specified range, and there is a significant increase in material cost. Therefore, the Cr content is set to be more than 14% and less than 15%.
  • Ni is a chemical element which increases corrosion resistance such as CO 2 corrosion resistance and resistance to sulfide stress cracking as a result of strengthening a protective surface film and contributes to an increase in strength. It is necessary that the Ni content be 2.0% or more in order to realize these effects, but, in the case where the Ni content is more than 5.0%, there is a tendency for hot workability to deterioration and there is a significant increase in material cost. Therefore, the Ni content is set to be 2.0% to 5.0%, preferably 2.5% to 5.0%.
  • Mo is a chemical element which is effective for increasing resistance to pitting corrosion caused by Cl - (chloride ions). It is necessary that the Mo content be 1.5% or more in order to realize this effect. On the other hand, in the case where the Mo content is more than 3.5%, there is a deterioration in hot workability and there is a significant increase in manufacturing cost. Therefore, the Mo content is set to be 1.5% to 3.5%, preferably 1.8% to 3.0%.
  • V 0.001% to 0.20%
  • V is a chemical element which contributes to an increase in strength and is effective for increasing resistance to stress corrosion cracking. These effects are markedly realized in the case where the V content is 0.001% or more, but there is a deterioration in toughness in the case where the V content is more than 0.20%. Therefore, the V content is set to be 0.001% to 0.20%, preferably 0.010% to 0.10%.
  • N is effective for increasing pitting corrosion resistance
  • N is a chemical element which significantly deteriorates weldability
  • the N content be as small as possible in the present invention.
  • the N content is set to be 0.015% or less.
  • the chemical composition described above is a basic chemical composition
  • at least one selected from Cu: 0.01% to 3.5% and W: 0.01% to 3.5%; and/or at least one selected from Ti: 0.01% to 0.20%, Nb: 0.01% to 0.20%, and Zr: 0.01% to 0.20%; and/or at least one selected from Ca: 0.0005% to 0.0100% and REM: 0.0005% to 0.0100% may be selectively added if necessary.
  • Cu is, moreover, also a chemical element which contributes to an increase in strength. It is preferable that the Cu content be 0.01% or more in order to realize these effects, but, since the effects become saturated in the case where the Cu content is more than 3.5%, effects corresponding to the content cannot be expected, which results in an economic disadvantage. Therefore, in the case where Cu is added, it is preferable that the Cu content be 0.01% to 3.5%, more preferably 0.30% to 2.0%.
  • W is, moreover, also a chemical element which increases resistance to stress corrosion cracking, resistance to sulfide stress cracking, and pitting corrosion resistance. It is preferable that the W content be 0.01% or more in order to realize these effects, but, since the effects become saturated in the case where the W content is more than 3.5%, effects corresponding to the content cannot be expected, which results in an economic disadvantage. Therefore, in the case where W is added, it is preferable that the W content be 0.01% to 3.5%, more preferably 0.30% to 2.0%.
  • Ti, Nb, and Zr are all chemical elements which tend to form carbides more than Cr, these chemical elements are effective for suppressing Cr carbides from being precipitated at the grain boundaries in a cooling process. Therefore, at least one of these chemical elements may be selectively added if necessary. It is preferable that the contents of these chemical elements be respectively Ti: 0.01% or more, Nb: 0.01% or more, and Zr: 0.01% or more in order to realize this effect, but there is a deterioration in weldability and toughness in the case where the contents of these chemical elements are respectively Ti: more than 0.20%, Nb: more than 0.20%, and Zr: more than 0.20%.
  • the contents of these chemical elements be respectively Ti: 0.01% to 0.20%, Nb: 0.01% to 0.20%, and Zr: 0.01% to 0.20%, more preferably Ti: 0.020% to 0.10%, Nb: 0.020% to 0.10%, and Zr: 0.020% to 0.10%.
  • Ca and REM are both chemical elements which increase hot workability and manufacturing stability in a continuous casting process as a result of controlling the form of inclusions, these chemical elements may be selectively added if necessary. It is preferable that the contents of these chemical elements be respectively Ca: 0.0005% or more and REM: 0.0005% or more in order to realize these effects, but there is an increase in the amount of inclusions in the case where the contents of these chemical elements are respectively Ca: more than 0.0100% and REM: more than 0.0100%, which results in a deterioration in the cleanliness of steel.
  • the contents of these chemical elements be respectively Ca: 0.0005% to 0.0100% and REM: 0.0005% to 0.0100%, more preferably Ca: 0.0010% to 0.0050% and REM: 0.0010% to 0.0050%.
  • the contents of chemical elements are controlled under the condition that P 1 defined by equation (1) below is 11.5 or more and 13.3 or less and that P 2 defined by equation (2) below is 0 or more :
  • P 1 Cr + Mo + 0.4 W + 0.3 Si ⁇ 43.5 C ⁇ 0.4 Mn ⁇ Ni ⁇ 0.3 Cu ⁇ 9 N (where Cr, Mo, W, Si, C, Mn, Ni, Cu, N: the contents (mass%) of the chemical elements represented respectively by the corresponding atomic symbols),
  • P 2 0.5 Cr + 5.0 ⁇ P 1 (where Cr: Cr content (mass%)).
  • P 1 is an index for evaluating hot workability and resistance to IGSCC, and in the present invention, the contents of chemical elements are controlled to be within the ranges described above so that P 1 is 11.5 to 13.3. In the case where P 1 is less than 11.5, since hot workability is insufficient for the manufacture of seamless steel pipes, it is difficult to manufacture seamless steel pipes. On the other hand, in the case where P 1 is more than 13.3, there is a deterioration in resistance to IGSCC as described above. Similarly, in the case where P 2 is less than 0, there is a deterioration in resistance to IGSCC. Therefore, the contents of chemical elements are to be controlled to be within the ranges described above and to satisfy the conditions that P 1 : 11.5 to 13.3 and P 2 : 0 or more.
  • the balance of the chemical composition other than the chemical elements described above consists of Fe and inevitable impurities.
  • inevitable impurities O: 0.010% or less is acceptable.
  • the steel pipe according to the present invention has the chemical composition described above, and, moreover, has a microstructure including martensite phase as a base phase and including, at volume percentage, 10% to 35% of ferrite phase and 30% or less of austenite phase.
  • the martensite phase includes tempered martensite phase. It is preferable that the volume percentage of martensite phase be 40% or more in order to achieve desired strength.
  • the volume percentage of ferrite phase be 10% or more in order to increase workability.
  • austenite phase increases toughness. It is preferable that the volume percentage of austenite phase be 15% or more in order to achieve sufficient toughness. However, in the case where the volume percentage of austenite phase is more than 30%, it is difficult to achieve sufficient strength.
  • austenite phase there is a case where austenite phase does not altogether undergo transformation to martensite phase when quenching is performed and some portion of austenite phase is retained, and there is a case where some portions of martensite phase and ferrite phase undergo reverse transformation when tempering is performed and are stabilized so as to be retained as austenite phase even after cooling.
  • a microstructure in a welded heat affected zone which is subjected to heating up to a temperature range for forming ferrite single phase of 1300°C or higher and to cooling when welding is performed, is formed such that 50% or more of prior-ferrite grain boundaries, in a ratio with respect to the total length of the prior-ferrite grain boundaries, is occupied by martensite phase.
  • molten steel having the chemical composition described above be smelted with an ordinary smelting method such as one using a converter, an electric furnace, or a vacuum melting furnace and that the molten steel be made into a steel material such as a billet with an ordinary method such as a continuous casting method or a slabbing mill method for rolling an ingot. Subsequently, the steel material is heated and hot rolled into a seamless steel pipe having a desired size using a Mannesmann-plug mill method or a Mannesmann-mandrel mill method.
  • the seamless steel pipe after hot rolling be cooled down to a room temperature by an accelerated cooling at a cooling rate equal to or larger than an air-cooling rate, preferably at an average cooling rate of 0.5°C/s or more from 800°C to 500°C.
  • a microstructure having martensite phase as a base phase as described above can be obtained.
  • the cooling rate is less than 0.5°C/s
  • a microstructure having martensite phase as a base phase as described above cannot be obtained.
  • "a microstructure having martensite phase as a base phase” means a microstructure in which martensite has the largest volume percentage or in which martensite has almost the same volume percentage as another phase which has the largest volume percentage.
  • reheating followed by quenching and tempering may be performed.
  • quenching it is preferable that the seamless steel pipe be reheated up to a temperature of 800°C or higher and held for 10 minutes or more and that the reheated pipe be cooled down to a temperature of 100°C or lower at a cooling rate equal to or larger than an air-cooling rate or at an average cooling rate of 0.5°C/s or more from 800°C to 500°C.
  • the reheating temperature is lower than 800°C, desired microstructure having martensite phase as a base phase cannot be achieved.
  • the quenched pipe be heated up to a temperature of 500°C or higher and 700°C or lower, preferably 500°C or higher and 680°C or lower, and held for a specified time and that the heated pipe be air-cooled.
  • an electric resistance welded steel pipe or a UOE steel pipe may be manufactured using an ordinary process and used as a steel pipe for linepipe.
  • the quenching and tempering described above be performed to have the microstructure described above.
  • a welded structure may be constructed by welding the steel pipes according to the present invention described above.
  • welding of the steel pipes according to the present invention includes welding of the steel pipes according to the present invention with other kinds of steel pipes.
  • Such a welded structure which is constructed by welding the steel pipes according to the present invention have a welded zone in which a welded heat affected zone, which is subjected to heating when welding is performed, preferably up to a temperature range for forming ferrite single phase of 1300°C or higher and to cooling, has a microstructure in which 50% or more of prior-ferrite grain boundaries, in a ratio with respect to the total length of the prior-ferrite grain boundaries, is occupied by martensite phase and/or austenite phase.
  • test sample (steel pipe) was cut out of the obtained seamless steel pipe, and the test sample (steel pipe) was subjected to quenching and tempering under the conditions given in Table 2.
  • Test specimens were cut out of the test sample (steel pipe) which had been subjected to quenching and tempering, and were subjected to microstructure observation, tensile test, impact test, corrosion test, sulfide stress test and U-bent test. The microstructure observation and the test methods will be described hereafter.
  • test specimen for microstructure observation was cut out of the obtained test sample (steel pipe). After polishing and etching the test specimen, the microstructure was identified by taking photographs using an optical microscope (at a magnification ratio of 1000 times), and then the percentages of ferrite phase and martensite phase of the base steel were determined using an image analyzer. Here, the amount of ⁇ phase was determined using an X-ray diffraction method.
  • a V-notch test specimen having a thickness of 5.0 mm was cut out of the obtained test sample (steel pipe) in accordance with JIS Z 2242. After performing a Charpy impact test using the test specimen, absorbed energy v E -40 (J/cm 2 ) at -40°C was determined in order to evaluate the toughness of the base steel.
  • test specimen for a corrosion test having a thickness of 3 mm, a width of 25 mm, and a length of 50 mm was cut out of the obtained test sample (steel pipe) by performing mechanical working. After performing a corrosion test using the test specimen, corrosion resistance (CO 2 corrosion resistance and pitting corrosion resistance) was evaluated.
  • corrosion resistance CO 2 corrosion resistance and pitting corrosion resistance
  • a four-point bending test specimen having a thickness of 4 mm, a width of 15 mm, and a length of 115 mm was cut out of the obtained test sample (steel pipe).
  • resistance to sulfide stress cracking resistance to SSC was evaluated by observing where or not cracks occurred.
  • a test solution consisting of 50 g/liter NaCl + NaHCO 3 pH: 4.5 was used, and a mixed gas consisting of 1 vol% H 2 S + 99 vol% CO 2 was flowed during the test.
  • Applied stress was equal to the YS (yield strength) of the base steel and the test period was 720 hours (hereinafter, abbreviated as h).
  • YS yield strength
  • h yield strength
  • a test specimen having a thickness of 4 mm, a width of 15 mm, and a length of 115 mm was cut out of the obtained test sample (steel pipe), and the welding thermal cycle illustrated in Fig. 1 was applied to the central portion of the test specimen.
  • the test specimen was polished and etched for microstructure observation in order to investigate whether or not there were transformation phases (martensite phase and/or austenite phase) produced from prior-a grain boundaries. And determining the length of the prior-a grain boundaries occupied by the transformation phases (martensite phase and/or austenite phase), a grain boundary occupancy ratio was calculated with respect to the total length of the prior-a grain boundaries.
  • test specimen having a thickness of 2 mm, a width of 15 mm, and a length of 75 mm was cut out of the central portion of the specimen which had been subjected to the welding thermal cycle, and subjected to a U-bent test using the jig illustrated in Fig. 2 .
  • the test specimen was bent in a U-shape having an internal radius of 8.0 mm and immersed in a corrosive solution. Two kinds of corrosive solution below were used:
  • test period was 168 h.
  • All of the examples of the present invention were excellent in terms of hot workability, and had high strength, that is, YS: 450 MPa or more, high toughness, that is, v E -40 : 50 J/cm 2 or more, high corrosion resistance, that is, corrosion rate: 0.10 mm/y or less, and further, had no SSC and no IGSCC in HAZ which had been subjected to heating up to a temperature of 1300°C or higher, which means that these pipes were excellent in terms of resistance to IGSCC in HAZ.
  • Example I 0.009 0.41 0.42 0.012 0.002 0.022 14.5 4.5 2.0 1.02 1.03 0.045 Zr/0.045 - 0.011 11.57 0.68
  • Inventive Example J 0.010 0.16 0.54 0.012 0.001 0.015 14.2 4.2 2.3 - - 0.020 - Ca/0.0023 0.012 11.59 0.51
  • Inventive Example K 0.009 0.20 0.49 0.011 0.001 0.027 13.5 3.1 1.9 - - 0.016 - REM/0.0044 0.009 11.69 0.06
  • Example L 0.012 0.21 0.89 0.014 0.002 0.020 13.4 2.4 2.5 3.2 - 0.045 - Ca/0.0046 0.012 11.62 0.08
  • Example M 0.006 0.19 0.61 0.008 0.002 0.015 14.7 4.6 2.0 - 1.15 0.023 Ti/0.098 Ca/0.0034 0.012 12.00 0.35
  • Inventive Example N 0.010 0.21 0.53 0.013 0.00

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Claims (1)

  1. Verfahren zum Herstellen eines Cr-haltigen Stahlrohrs für Leitungsrohr, wobei das Stahlrohr eine chemische Zusammensetzung hat, die in Masse-% aus 0,001 % bis 0,010 % C, 0,05 % bis 0,50 % Si, 0,10 % bis 2,0 % Mn, 0,020 % oder weniger P, 0,010 % oder weniger S, 0,001 % bis 0,10 % Al, mehr als 14 % und weniger als 15 % Cr, 2,0 % bis 5,0 % Ni, 1,5 % bis 3,5 % Mo, 0,001 % bis 0,20 % V, 0,015 % oder weniger N, optional wenigstens ein Element ausgewählt aus 0,01 % bis 3,5 % Cu, 0,01 % bis 3,5 % W, 0,01 % bis 0,20 % Ti, 0,01 % bis 0,20 % Nb, 0,01 % bis 0,20 % Zr, 0,0005 % bis 0,0100 % Ca, sowie 0,0005 % bis 0,0100 % REM besteht, wobei der Rest Fe und unvermeidbare Verunreinigungen sind, unter der Bedingung, dass Pi, definiert durch Gleichung (1) unten, 11,5 bis 13,3 beträgt und dass P2, definiert durch Gleichung (2) unten, 0 oder mehr beträgt, und
    wobei bei diesem Verfahren ein Mikrogefüge in einer geschweißten Wärmeeinflusszone, die, wenn Schweißen durchgeführt wird, Erwärmung bis auf einen Temperaturbereich zum Ausbilden einer ferritischen Einzelphase von 1300 °C oder darüber und Abkühlen unterzogen wird, durch das Schweißen so ausgebildet wird, dass 50 % oder mehr der ehemaligen Ferrit-Korngrenzen in einem Verhältnis in Bezug auf die Gesamtlänge der ehemaligen Ferrit-Korngrenzen von martensitischer Phase eingenommen wird, Pi = Cr + Mo + 0,4 W + 0,3 Si − 43,5 C − 0,4 Mn − Ni − 0,3 Cu − 9 N
    Figure imgb0007
     P 2 = 0,5 Cr + 5,0 − Pi
    Figure imgb0008
     wobei Cr, Mo, W, Si, C, Mn, Ni, Cu, N die Gehalte in Masse-% der chemischen Elemente sind, die jeweils durch die entsprechenden Elementsymbole dargestellt werden.
EP12875045.2A 2012-04-26 2012-04-26 Eine methode zur herstellung eines cr-haltigen stahlrohrs für ein leitungsrohr mit hervorragender beständigkeit gegen interkristalline spannungsrisskorrosion der wärmebeeinflussten schweiszzone Active EP2843068B1 (de)

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JP4462005B2 (ja) 2003-10-31 2010-05-12 Ｊｆｅスチール株式会社 耐食性に優れたラインパイプ用高強度ステンレス鋼管およびその製造方法
BRPI0416001B1 (pt) * 2003-10-31 2017-04-11 Jfe Steel Corp tubo de aço inoxidável sem costura para tubulações de condução
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JP4400423B2 (ja) 2004-01-30 2010-01-20 Ｊｆｅスチール株式会社 マルテンサイト系ステンレス鋼管
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