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WO2013161089A1 - TUBE D'ACIER CONTENANT DU Cr DESTINÉ À UN TUBE DE CANALISATION EXCELLENT EN TERMES DE RÉSISTANCE À LA FISSURATION INTERGRANULAIRE PAR CORROSION SOUS TENSION D'UNE ZONE SOUDÉE TOUCHÉE PAR LA CHALEUR - Google Patents

TUBE D'ACIER CONTENANT DU Cr DESTINÉ À UN TUBE DE CANALISATION EXCELLENT EN TERMES DE RÉSISTANCE À LA FISSURATION INTERGRANULAIRE PAR CORROSION SOUS TENSION D'UNE ZONE SOUDÉE TOUCHÉE PAR LA CHALEUR Download PDF

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Publication number
WO2013161089A1
WO2013161089A1 PCT/JP2012/061699 JP2012061699W WO2013161089A1 WO 2013161089 A1 WO2013161089 A1 WO 2013161089A1 JP 2012061699 W JP2012061699 W JP 2012061699W WO 2013161089 A1 WO2013161089 A1 WO 2013161089A1
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Prior art keywords
steel pipe
stress corrosion
corrosion cracking
less
affected zone
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PCT/JP2012/061699
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English (en)
Japanese (ja)
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宮田　由紀夫
木村　光男
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Ｊｆｅスチール株式会社
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Priority to BR112014025818-0A priority Critical patent/BR112014025818B1/pt
Priority to CN201280072699.1A priority patent/CN104254625A/zh
Priority to PCT/JP2012/061699 priority patent/WO2013161089A1/fr
Priority to EP12875045.2A priority patent/EP2843068B1/fr
Publication of WO2013161089A1 publication Critical patent/WO2013161089A1/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
    • C22C38/58—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 is suitable as a steel pipe for line pipe used in a pipeline for transporting crude oil or natural gas produced in an oil well or a gas well. It is related to Cr-containing steel pipes (Cr-containing steel pipes), and in particular, it is related to the resistance to intergranular stress corrosion cracking cracking cracking resistance of the welded heat affected zone (welded heat affected zone).
  • Pipelines for transporting crude oil and natural gas produced in such oil and gas fields have high strength, high toughness, excellent corrosion resistance, and laying of pipelines From the viewpoint of reducing the cost of laying, it is required to use a steel pipe that also has excellent weldability.
  • Patent Document 1 discloses an intergranular stress corrosion crack (intergranular stress cracking) that occurs in a weld heat affected zone without performing post-weld heat treatment suitable for a line pipe.
  • a martensitic stainless steel pipe that can prevent corrosion cracking (abbreviated as IGSCC) and is excellent in intergranular stress corrosion cracking resistance of a weld heat-affected zone.
  • the martensitic stainless steel pipe described in Patent Document 1 is mass%, C: less than 0.0100%, N: less than 0.0100%, Cr: 10-14%, Ni: 3-8%, Si: 0.05 to 1.0%, Mn: 0.1 to 2.0%, P: 0.03% or less, S: 0.010% or less, Al: 0.001 to 0.10%, and One or more selected from Cu: 4% or less, Co: 4% or less, Mo: 4% or less, W: 4% or less, and 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, Ta: 0.20% or less.
  • Csol which is an effective content of dissolved carbon (Csol) that effectively acts on the formation of Cr carbide
  • Csol dissolved carbon
  • Patent Document 3 contains Cr for line pipes with high strength of X65 to X80, excellent toughness, corrosion resistance, and sulfide stress corrosion cracking resistance, and excellent resistance to intergranular stress corrosion cracking in the weld heat affected zone. Steel pipes are described.
  • the Cr-containing steel pipe for line pipe described in Patent Document 3 is 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: 0.00.
  • the welding heat-affected zone heated to 1300 ° C. or more in the ferrite single-phase temperature range at the time of welding and cooled is a ratio to the total length, and 50% or more of the old ferrite grain boundaries are martensite phase and / or austenite phase. It becomes an occupied structure, the formation of a Cr carbide-deficient layer is suppressed, and a steel pipe with markedly improved intergranular stress corrosion cracking resistance of the weld heat affected zone is obtained. There is no need to perform heat treatment after welding, and the construction period of the welded steel pipe structure can be greatly shortened.
  • Patent Document 2 describes a high-strength stainless steel pipe for line pipes having excellent corrosion resistance.
  • the high-strength stainless steel pipe described in Patent Document 2 is mass%, C: 0.001 to 0.015%, N: 0.001 to 0.015%, Cr: 15 to 18%, Ni: 0.00.
  • JP 2005-336601 A (WO 2005/073419 A1) JP 2005-336599 A Unexamined-Japanese-Patent No. 2011-241477 (WO2011-132765 A1)
  • the present invention solves the problems of the prior art, and has the desired high strength, toughness, corrosion resistance, resistance to sulfide stress corrosion cracking, and intergranular stress resistance of the weld heat affected zone. It aims at providing the Cr containing steel pipe for line pipes excellent in corrosion cracking property.
  • the steel pipe targeted by the present invention is an X65 to X80 grade steel pipe (steel pipe having a yield strength (YS) of 448-651 MPa).
  • “excellent toughness” means that the absorbed energy E ⁇ 40 (J) at ⁇ 40 ° C. in the Charpy impact test is 50 J or more.
  • the term “excellent in corrosion resistance” as used herein means that the corrosion rate (mm / y) in a 200 g / liter NaCl aqueous solution at 150 ° C. saturated with 3.0 MPa of carbon dioxide gas is 0.10 mm / y or less. It shall mean a certain case.
  • the “steel pipe” includes a seamless steel pipe and a welded steel pipe.
  • the inventors of the present invention have provided a ferrite-martensitic stainless steel pipe with intergranular stress corrosion cracking of a weld heat-affected zone in a high-temperature corrosive environment containing carbon dioxide and chlorine ions.
  • intergranular stress corrosion cracking is caused by the formation of coarse ferrite grains during the heating cycle during welding, followed by a cooling cycle. It has been found that Cr carbide precipitates at the grain boundaries of the coarse ferrite grains and a Cr-depleted layer is formed at the grain boundaries.
  • the present inventors have found that at least the ferrite ( ⁇ ) ⁇ austenite ( ⁇ ) from the grain boundary before Cr carbide precipitates at the grain boundary of coarse ferrite grains. If transformation can be caused and most grain boundaries can be occupied by austenite, precipitation of Cr carbides at the grain boundaries can be prevented, formation of Cr-deficient layers can be suppressed, and the occurrence of intergranular stress corrosion cracking can be prevented. I came up with it.
  • P 1 is 13.3 or less
  • a composition such as P 2 becomes 0 or more, difficult to precipitate carbides (Cr carbides) is the grain boundary, thus It has been newly found that formation of a Cr-deficient layer is difficult to occur and it is possible to prevent intergranular stress corrosion cracking.
  • P 1 is 13.3 or less as described above, when the proportion of ferrite forming elements is low composition, upon circumferential weld, such as during laying of the pipeline (girth welding), at the time of heating, melting point A coarse ferrite phase single phase structure is formed in a region exposed to a high temperature exceeding 1200 ° C.
  • the composition of the ferrite-forming element when the composition of the ferrite-forming element is high such that P 1 exceeds 13.3, the formed coarse ferrite phase single phase structure undergoes ⁇ ⁇ ⁇ transformation during subsequent cooling. Since it does not occur and reaches room temperature as it is, Cr carbide precipitates at the grain boundary, a Cr-deficient layer is formed, and intergranular stress corrosion cracking is likely to occur. If the composition can be adjusted so that P 1 becomes 13.3 or less and P 2 becomes 0 or more even if Cr and further Ni are reduced by further study, the above-mentioned is described. We obtained the knowledge that it was possible to ensure the structural change and prevent the intergranular stress corrosion cracking of the weld heat affected zone.
  • composition in addition to the above-mentioned composition, it is further one of mass%, selected from Cu: 0.01 to 3.5%, W: 0.01 to 3.5%, or 2 A Cr-containing steel pipe for line pipes, characterized by comprising a seed-containing composition.
  • mass% selected from Cu: 0.01 to 3.5%, W: 0.01 to 3.5%, or 2 A Cr-containing steel pipe for line pipes, characterized by comprising a seed-containing composition.
  • a Cr-containing steel pipe for a line pipe excellent in resistance to intergranular stress corrosion cracking in a weld heat-affected zone can be produced at low cost without performing post-weld heat treatment, and a remarkable industrial effect can be achieved.
  • steel pipe structures, such as a pipeline can be constructed without performing post-weld heat treatment, and there is also an effect that construction costs can be significantly reduced, such as shortening the construction period.
  • C 0.001 to 0.015%
  • C is an element that contributes to an increase in strength. In the present invention, it is necessary to contain 0.001% or more. On the other hand, if the content exceeds 0.015%, the toughness of the weld heat affected zone is deteriorated. If it is contained in a large amount, it becomes difficult to prevent intergranular stress corrosion cracking in the weld heat affected zone. For this reason, C is limited to the range of 0.001 to 0.015%. Preferably, the content is 0.002 to 0.010%.
  • Si 0.05 to 0.50%
  • Si is an element that acts as a deoxidizing agent and increases the strength by solid solution. In the present invention, it is necessary to contain 0.05% or more. However, a large content exceeding 0.50% lowers the toughness of the base metal and the weld heat affected zone. For this reason, Si was limited to the range of 0.05 to 0.50%. Note that the content is preferably 0.10 to 0.40%.
  • Mn 0.10 to 2.0%
  • Mn is a solid solution that contributes to increasing the strength of the steel and is an austenite-generating element that suppresses the formation of ferrite and improves the toughness of the base material and the weld heat affected zone.
  • Such an effect requires the content of 0.10% or more, but even if the content exceeds 2.0%, the effect is saturated and an effect commensurate with the content cannot be expected. For this reason, Mn was limited to the range of 0.10 to 2.0%.
  • the content is preferably 0.20 to 1.5%.
  • P 0.020% or less
  • P is an element that deteriorates corrosion resistance such as carbon dioxide corrosion resistance (CO 2 corrosion resistance) and sulfide stress corrosion cracking resistance, and can be reduced as much as possible in the present invention. Although desirable, extreme reduction results in increased manufacturing costs.
  • P is limited to 0.020% or less as a range that can be industrially implemented at a relatively low cost and does not deteriorate the corrosion resistance. In addition, Preferably it is 0.015% or less.
  • S 0.010% or less
  • S is an element that significantly deteriorates the hot workability in the pipe manufacturing process, and is preferably as small as possible, but if it is reduced to 0.010% or less, the pipe in the normal process Since production is possible, S is limited to 0.010% or less. In addition, Preferably it is 0.004% or less.
  • Al: 0.001 to 0.10% Al is an element having a strong deoxidizing action, and in order to obtain such an effect, it is necessary to contain 0.001% or more. However, if it exceeds 0.10%, the toughness is adversely affected. Effect. For this reason, Al was limited to 0.10% or less. In addition, Preferably it is 0.05% or less.
  • Cr 13% or more and less than 15% Cr is an element that forms a protective surface film and improves corrosion resistance such as carbon dioxide corrosion resistance and sulfide stress corrosion cracking resistance.
  • the content of 13% or more is required for the purpose of improving the corrosion resistance in a severe corrosive environment.
  • Cr was limited to the range of 13% or more and less than 15%. More preferably, it is more than 14% and less than 15%.
  • Ni 2.0-5.0%
  • Ni is an element that has a function of strengthening the protective coating, enhances corrosion resistance such as carbon dioxide corrosion resistance and sulfide stress corrosion cracking resistance, and contributes to an increase in strength.
  • the content of 2.0% or more is required.
  • the content exceeds 5.0%, the hot workability tends to decrease and the material cost increases. .
  • Ni was limited to the range of 2.0 to 5.0%.
  • the content is 2.5 to 5.0%.
  • Mo 1.5-3.5%
  • Mo is an element that has an effect of increasing resistance to pitting corrosion caused by Cl ⁇ (chlorine ions) and effectively acts to improve corrosion resistance. In order to acquire such an effect, it is necessary to contain 1.5% or more. On the other hand, if the content exceeds 3.5%, the hot workability is lowered and the production cost is increased. For this reason, Mo was limited to the range of 1.5 to 3.5%. Note that the content is preferably 1.8 to 3.0%.
  • V 0.001 to 0.20%
  • V is an element that contributes to an increase in strength and has an effect of improving stress corrosion cracking resistance. Such an effect becomes remarkable when the content is 0.001% or more, but the content exceeding 0.20% lowers the toughness. For this reason, V is limited to a range of 0.001 to 0.20%. Note that the content is preferably 0.010 to 0.10%.
  • N 0.015% or less N is an element that has an effect of improving pitting corrosion resistance but significantly reduces weldability. In the present invention, N can be reduced as much as possible. Although desirable, extreme reduction results in increased manufacturing costs.
  • the upper limit was set to 0.015% as a range that can be industrially implemented at a relatively low cost and does not deteriorate the weldability.
  • the above-mentioned components are basic components, but in addition to the basic composition, Cu: 0.01 to 3.5%, W: 0.01 to 3.5% 1 is selected as a selective element.
  • Two or more kinds and / or one or two kinds selected from Ca: 0.0005 to 0.0100% and REM: 0.0005 to 0.0100% can be selected and contained as necessary. .
  • Cu 0.01 to 3.5%
  • W 0.01 to 3.5%
  • Cu and W are both elements that improve the corrosion resistance of carbon dioxide gas. , And can be selected and contained as necessary.
  • Cu is an element that further contributes to an increase in strength. In order to obtain such an effect, it is desirable to contain 0.01% or more, but even if it exceeds 3.5%, the effect is saturated, and an effect commensurate with the content cannot be expected, and it is economical. Disadvantageous. For this reason, when it contains, it is preferable to limit Cu to 0.01 to 3.5% of range. More preferably, it is 0.30 to 2.0%.
  • W is an element that further improves stress corrosion cracking resistance, sulfide stress corrosion cracking resistance, and pitting corrosion resistance. In order to obtain such an effect, it is desirable to contain 0.01% or more, but even if it exceeds 3.5%, the effect is saturated, and an effect commensurate with the content cannot be expected, and it is economical. Disadvantageous. For this reason, when contained, W is preferably limited to a range of 0.01 to 3.5%. More preferably, it is 0.30 to 2.0%.
  • Ti, Nb, Zr are Both are elements that have a strong tendency to form carbides compared to Cr, have the effect of suppressing the precipitation of Cr carbides at grain boundaries during cooling, and can be selected as needed to contain one or more. .
  • Ti 0.01-0.20%
  • Nb 0.01-0.20%
  • Zr 0.01-0.20%
  • Ti is 0.020 to 0.10%
  • Nb is 0.020 to 0.10%
  • Zr is 0.020 to 0.10%.
  • Ca and REM are both hot through the control of the form of inclusions. It is an element that improves processability and production stability during continuous casting, and can be selected and contained as necessary. In order to obtain such an effect, it is desirable to contain Ca: 0.0005% or more and REM: 0.0005% or more, respectively, but Ca: 0.0100% and REM: more than 0.0100%, respectively. Inclusion increases the amount of inclusions and lowers the cleanliness of the steel. For this reason, when it contains, it is preferable to limit to Ca: 0.0005-0.0100% and REM: 0.0005-0.0100%, respectively. More preferably, Ca: 0.0010 to 0.0050%, REM: 0.0010 to 0.0050%.
  • P 1 is an index for evaluating hot workability, and further resistance to intergranular stress corrosion cracking, and in the present invention, each element of P 1 satisfies the range of 11.5 to 13.3.
  • the content is adjusted within the above range.
  • P 1 is less than 11.5, the hot workability is insufficient, can not secure the necessary sufficient hot workability in the production of seamless steel pipe, it is difficult to manufacture a seamless steel pipe.
  • P 1 exceeds 13.3, as described above, the intergranular stress corrosion cracking resistance decreases.
  • P 2 is intergranular stress corrosion cracking resistance is lowered below the 0. For this reason, the content of each element is adjusted so as to satisfy the above-described range and satisfy P 1 : 11.5 to 13.3 and P 2 : 0 or more.
  • the balance other than the components described above consists of Fe and inevitable impurities.
  • the steel pipe of the present invention has a structure having the above-described composition, further comprising a martensite phase as a base phase, a ferrite phase having a volume ratio of 10 to 35%, and an austenite phase having a volume ratio of 30% or less.
  • the martensite phase includes a tempered martensite phase (tempered martensite phase).
  • the martensite phase is preferably contained in a volume ratio of 40% or more in order to secure a desired strength.
  • the ferrite phase is a soft structure that improves workability, and is preferably contained in a volume ratio of 10% or more from the viewpoint of improving workability. On the other hand, if it exceeds 35%, the desired high strength (X65) cannot be secured.
  • the austenite phase is a structure that improves toughness. From the viewpoint of securing toughness, 15% or more is preferable. However, when the austenite phase exceeds 30%, it is difficult to ensure the strength.
  • the austenite phase does not completely transform into a martensite phase during the quenching process, and a part of the austenite phase remains, and a part of the martensite phase and the ferrite phase during the tempering process reversely transforms and stabilizes. After cooling, it may remain as an austenite phase.
  • the weld heat-affected zone that is heated and cooled to a ferrite single-phase temperature range of 1300 ° C.
  • the ratio of the former ferrite grain boundaries to the total length of the prior ferrite grain boundaries is a structure in which 50% or more of the old ferrite grain boundaries are occupied by the martensite phase.
  • molten steel having the above composition is melted by a conventional melting method such as a converter, an electric furnace, a vacuum melting furnace, and the like, and a continuous casting method. It is preferable to use a steel material such as a billet by a conventional method such as (continuous casting method) or a slabbing-mill method for rolling an ingot. Subsequently, these steel materials are heated and hot-rolled using a normal Mannesmann-plug mill method or Mannesmann-mandrel mill method manufacturing process. The pipe is made into a seamless steel pipe having a desired size.
  • the seamless steel pipe after pipe forming is subjected to accelerated cooling (air-cooling rate) or higher, preferably cooled to room temperature at an average cooling rate of 0.5 ° C./s or higher at 800 to 500 ° C. It is preferable to apply.
  • air-cooling rate air-cooling rate
  • tissue based on a martensite phase as mentioned above.
  • the cooling rate is less than 0.5 ° C./s, it becomes impossible to obtain a structure based on the martensite phase as described above.
  • the structure based on the martensite phase is a structure in which the martensite phase has the largest volume ratio or has a volume ratio substantially equal to the volume ratio of another structure having the largest volume ratio.
  • reheating quenching
  • tempering tempering
  • the quenching treatment it is reheated to 800 ° C. or higher, held at that temperature for 10 minutes or more, and then cooled to 100 ° C. or lower at a cooling rate of 0.5 ° C./s or higher on average by air cooling or 800 to 500 ° C. It is preferable to set it as a treatment.
  • the reheating temperature is less than 800 ° C., it becomes impossible to secure a structure based on a desired martensite phase.
  • the tempering treatment after the quenching treatment, heating to a temperature of 500 ° C. or more and 700 ° C. or less, preferably 500 ° C. or more and 680 ° C. or less, holding for a predetermined time, and air cooling is preferable. Thereby, desired high strength, desired high toughness, and desired excellent corrosion resistance can be combined. So far, the seamless steel pipe has been described as an example, but the present invention is not limited to this.
  • a steel pipe material (steel plate) having the above-described composition an electric-welded steel pipe and a UOE steel pipe can be manufactured by a normal process to obtain a steel pipe for a line pipe.
  • the above-described steel pipe of the present invention can be welded to form a welded structure (steel pipe structure).
  • the welding joining of this invention steel pipe shall include the case where welding joining of this invention steel pipe and another kind of steel pipe is included.
  • the welded heat-affected zone heated to a ferrite single-phase temperature range of 1300 ° C. or higher and preferably cooled at the time of welding is compared with the total length of the old ferrite grain boundary. In terms of the ratio, 50% or more of the prior ferrite grain boundaries have welds that have a structure occupied by the martensite phase and / or austenite phase. Thereby, intergranular stress corrosion cracking is suppressed, and the intergranular stress corrosion cracking resistance of the weld heat affected zone is improved without performing post-weld heat treatment.
  • Molten steel having the composition shown in Table 1 was melted and degassed in a vacuum melting furnace, cast into a 100 kgf steel ingot, and made into a steel pipe material of a predetermined size by hot forging. These steel pipe materials are heated and then piped by hot working using a model seamless mill (small seamless mill for experiments) to produce a seamless steel pipe (outer diameter 72 mm ⁇ x wall thickness 5.5 mm). ). About the obtained seamless steel pipe, the presence or absence of the crack generation
  • test material was collected from the obtained seamless steel pipe, and the test material (steel pipe) was quenched and tempered under the conditions shown in Table 2.
  • a test piece is taken from a test material (steel pipe) that has been subjected to quenching treatment and tempering treatment, and the structure is observed (microstructure observation), tensile test (impact test), impact test (corrosion test), and corrosion test (corrosion test).
  • a sulfide stress corrosion cracking test and a U bending stress corrosion cracking test were conducted.
  • the test method was as follows. (1) Structure observation A test piece for structure observation was collected from the obtained test material (steel pipe).
  • SSC Sulfide stress corrosion cracking
  • the applied stress was YS (yield strength) of the base material, and the test period was 720 hour (hereinafter abbreviated as h).
  • the broken piece was evaluated as x, and the broken piece was evaluated as o.
  • tissue observation was extract
  • the U bending stress corrosion cracking test was a test in which a test piece was bent into a U shape with an inner radius of 8.0 mm and immersed in a corrosive solution using the jig shown in FIG.
  • the following two types of corrosive liquids were used.
  • the test period was 168h.
  • each of the inventive examples is excellent in hot workability, high strength of YS: 450 or more, high toughness of vE- 40 : 50 J / cm 2 or more, and corrosion rate; High corrosion resistance of 10 mm / y or less, no occurrence of sulfide stress corrosion cracking, no occurrence of intergranular stress corrosion cracking in the welding heat affected zone heated to 1300 ° C. or higher, The steel pipe has excellent intergranular stress corrosion cracking resistance.
  • Comparative examples outside the scope of the present invention have reduced hot workability, reduced toughness, reduced corrosion resistance, or reduced resistance to sulfide stress cracking. Or the IGSCC resistance of the weld heat affected zone is reduced.
  • Tube No. In No. 26 since the range of C exceeds the upper limit of the present invention, the toughness is lowered.
  • Tube No. 28 to 30 correspond to F steel, K steel, and M steel in the examples of Patent Document 1, respectively, but the Cr range is less than the lower limit of the present invention, and the Ni range is the upper limit of the present invention.
  • the ferrite phase has a structure fraction of 0%, and the intergranular stress corrosion cracking resistance of the weld heat-affected zone has a more severe corrosion solution (2). In this case, the intergranular stress corrosion cracking resistance of the weld heat affected zone is lowered.

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Abstract

L'invention concerne un tube en acier contenant du Cr destiné à un tube de canalisation, montrant une haute résistance de classe X65 à X80, une ténacité et une résistance à la corrosion excellentes et une excellente résistance à la fissuration par corrosion sous tension due au sulfure et assurant une excellente résistance d'une zone soudée touchée par la chaleur à la fissuration intergranulaire par corrosion sous tension. En particulier, le présent tube en acier présente une composition qui contient, en pourcentage massique, 0,001 à 0,015 % de C, 0,05 à 0,50 % de Si, 0,10 à 2,0 % de Mn, 0,001 à 0,10 % d'Al, 13 à moins de 15 % de Cr, 2,0 à 5,0 % de Ni, 1,5 à 3,5 % de Mo, 0,001 à 0,20 % de V, et jusqu'à 0,015 % de N de manière à satisfaire à la relation : P1 = 11,5 à 13,3 et P2 = (0,5Cr+5,0) - P1 ≥ 0. Lorsque le tube d'acier est soumis à un procédé de soudage, qui comprend le chauffage jusqu'à une zone de température de phase unique de ferrite de 1300°C ou supérieure, puis un refroidissement, la zone soudée touchée par la chaleur résultante présente une structure telle que : la martensite représente au moins 50 % de la limite de grains de ferrite préalable en termes de rapport à la longueur globale de la frontière de grains; et la formation de zones épuisées en carbure de Cr est minimisée. Par conséquent, la zone soudée touchée par la chaleur montre une résistance considérablement améliorée à la fissuration intergranulaire par corrosion sous tension. La présente invention peut se passer de traitement thermique post-soudage et présente ainsi un effet de raccourcissement considérable de la période de construction d'une structure en tubes d'acier soudés.
PCT/JP2012/061699 2012-04-26 2012-04-26 TUBE D'ACIER CONTENANT DU Cr DESTINÉ À UN TUBE DE CANALISATION EXCELLENT EN TERMES DE RÉSISTANCE À LA FISSURATION INTERGRANULAIRE PAR CORROSION SOUS TENSION D'UNE ZONE SOUDÉE TOUCHÉE PAR LA CHALEUR WO2013161089A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR112014025818-0A BR112014025818B1 (pt) 2012-04-26 2012-04-26 TUBO DE AÇO CONTENDO Cr PARA TUBULAÇÃO.
CN201280072699.1A CN104254625A (zh) 2012-04-26 2012-04-26 焊接热影响部的耐晶界应力腐蚀破裂性优良的管线管用含Cr钢管
PCT/JP2012/061699 WO2013161089A1 (fr) 2012-04-26 2012-04-26 TUBE D'ACIER CONTENANT DU Cr DESTINÉ À UN TUBE DE CANALISATION EXCELLENT EN TERMES DE RÉSISTANCE À LA FISSURATION INTERGRANULAIRE PAR CORROSION SOUS TENSION D'UNE ZONE SOUDÉE TOUCHÉE PAR LA CHALEUR
EP12875045.2A EP2843068B1 (fr) 2012-04-26 2012-04-26 PROCÉDÈ DE FABRICATION D'UN TUBE D'ACIER CONTENANT DU Cr DESTINÉ À UN TUBE DE CANALISATION EXCELLENT EN TERMES DE RÉSISTANCE À LA FISSURATION INTERGRANULAIRE PAR CORROSION SOUS TENSION D'UNE ZONE SOUDÉE TOUCHÉE PAR LA CHALEUR

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PCT/JP2012/061699 WO2013161089A1 (fr) 2012-04-26 2012-04-26 TUBE D'ACIER CONTENANT DU Cr DESTINÉ À UN TUBE DE CANALISATION EXCELLENT EN TERMES DE RÉSISTANCE À LA FISSURATION INTERGRANULAIRE PAR CORROSION SOUS TENSION D'UNE ZONE SOUDÉE TOUCHÉE PAR LA CHALEUR

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