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WO2017149571A1 - Tuyau en acier sans soudure, à haute résistance, faiblement allié pour puits de pétrole - Google Patents

Tuyau en acier sans soudure, à haute résistance, faiblement allié pour puits de pétrole Download PDF

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Publication number
WO2017149571A1
WO2017149571A1 PCT/JP2016/004915 JP2016004915W WO2017149571A1 WO 2017149571 A1 WO2017149571 A1 WO 2017149571A1 JP 2016004915 W JP2016004915 W JP 2016004915W WO 2017149571 A1 WO2017149571 A1 WO 2017149571A1
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steel pipe
stress
steel
mpa
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Japanese (ja)
Inventor
岡津　光浩
正雄 柚賀
石黒　康英
太田　裕樹
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JFE Steel Corp
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JFE Steel Corp
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Priority to JP2017513268A priority Critical patent/JP6152929B1/ja
Priority to EP16892416.5A priority patent/EP3425076B1/fr
Priority to BR112018017250-2A priority patent/BR112018017250B1/pt
Priority to US16/078,924 priority patent/US20190048444A1/en
Priority to NZ74466816A priority patent/NZ744668A/en
Priority to MX2018010363A priority patent/MX386977B/es
Publication of WO2017149571A1 publication Critical patent/WO2017149571A1/fr
Anticipated expiration legal-status Critical
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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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • 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
    • C22C38/02—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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium 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
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B17/00—Drilling rods or pipes; Flexible drill strings; Kellies; Drill collars; Sucker rods; Cables; Casings; Tubings
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/002—Bainite
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/004—Dispersions; Precipitations
    • 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
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • 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

Definitions

  • the present invention relates to a high-strength seamless steel pipe excellent in sulfide stress corrosion cracking resistance (SSC resistance) for oil wells and gas wells, particularly in a sour environment containing hydrogen sulfide.
  • SSC resistance stress corrosion cracking resistance
  • high strength refers to the case where the yield strength is 861 MPa or more (125 ksi or more).
  • Patent Document 1 discloses that, in weight%, C: 0.2 to 0.35%, Cr: 0.2 to 0.7%, Mo: 0.1 to 0.5 %, V: Low well steel containing 0.1 to 0.3%, which defines the total amount of precipitated carbides and the proportion of MC type carbides in them. Steel for use is disclosed.
  • Patent Document 2 by mass, C: 0.15 to 0.30%, Si: 0.05 to 1.0%, Mn: 0.10 to 1.0%, P: 0.025 %: S: 0.005% or less, Cr: 0.1-1.5%, Mo: 0.1-1.0%, Al: 0.003-0.08%, N: 0.008%
  • B 0.0005 to 0.010%
  • Nb 0.05% or less
  • Zr 0.0.
  • V For steel inclusions containing one or more selected from 0.30% or less, the maximum length of continuous non-metallic inclusions and the number of particles having a particle size of 20 ⁇ m or more An oil well steel material excellent in sulfide stress corrosion cracking resistance is disclosed.
  • Patent Document 3 in mass%, C: 0.15 to 0.35%, Si: 0.1 to 1.5%, Mn: 0.1 to 2.5%, P: 0.025%
  • An oil well steel having excellent resistance to sulfide stress corrosion cracking in which the hardness of the composite oxide and the steel is defined by HRC is disclosed.
  • the resistance to sulfide stress corrosion cracking of steels of the techniques disclosed in these Patent Documents 1 to 3 refers to a round bar tensile test piece defined in NACE (abbreviation of National Association of Corrosion Engineering) TM0177 method A. This means the presence or absence of SSC when immersed for 720 hours in a test bath described in NACE TM0177 under constant stress.
  • NACE abbreviation of National Association of Corrosion Engineering
  • K stress intensity factor K under a hydrogen sulfide corrosion environment obtained by performing a DCB (Double Cantilever Beam) test prescribed in NACE TM0177 method D for the purpose of ensuring further safety of steel pipes for oil wells. It is being demanded that the ISSC value satisfies a specified value or more.
  • the above prior art does not disclose a specific measure for improving such a K ISSC value.
  • Patent Document 4 by mass, C: 0.2 to 0.35%, Si: 0.05 to 0.5%, Mn: 0.05 to 1.0%, P: 0.025 %: S: 0.01% or less, Al: 0.005 to 0.10%, Cr: 0.1 to 1.0%, Mo: 0.5 to 1.0%, Ti: 0.002 to [211] of steel containing 0.05%, V: 0.05 to 0.3%, B: 0.0001 to 0.005%, N: 0.01% or less, O: 0.01% or less
  • a steel for low alloy oil country tubular goods having a yield strength of 861 MPa or more and excellent in resistance to sulfide stress corrosion cracking is disclosed by defining a formula consisting of a half width of a crystal plane and a hydrogen diffusion coefficient to a predetermined value.
  • K ISSC values are also described.
  • B bath 0.5 mass% acetic acid aqueous solution
  • resistance to sulfide stress corrosion cracking resistance increases as the hydrogen sulfide gas saturation partial pressure increases.
  • the present invention has been made in view of such problems, and has a high strength of a yield strength of 861 MPa or more and a higher hydrogen sulfide gas saturation environment, specifically, a hydrogen sulfide gas partial pressure of 0.02 MPa.
  • An object of the present invention is to provide a low-strength, high-strength seamless steel pipe for oil wells exhibiting excellent sulfide stress corrosion cracking resistance (SSC resistance) under the following sour environment, in particular, a stable and high KISSC value.
  • the present inventors first made a seamless steel pipe having various chemical compositions and microstructures of steel with a yield strength of 861 MPa or more based on NACE TM0177 method D, with a thickness of 10 mm, Three or more DCB test pieces each having a width of 25 mm and a length of 100 mm were sampled and subjected to a DCB test.
  • the test bath for the DCB test was a mixed aqueous solution of 0.5 mass% CH 3 COOH + CH 3 COONa at 24 ° C. saturated with 0.2 atm (0.02 MPa) hydrogen sulfide gas.
  • FIG. 1 is a schematic diagram of a DCB test piece.
  • h is the height of each arm of the DCB test piece
  • B is the thickness of the DCB test piece
  • Bn is the web thickness of the DCB test piece.
  • the target of the K ISSC value was set to 26.4 MPa ⁇ m or more (24 ksi ⁇ inch or more) based on the assumed maximum notch defect of the oil well pipe and the load weighting condition.
  • FIG. 2 shows a graph in which the obtained K ISSC values are arranged by the average hardness (Rockwell C scale hardness) of the seamless steel pipe provided with the test piece.
  • the K ISSC value obtained in the DCB test tended to decrease as the hardness of the seamless steel pipe increased, but it was found that the numerical values varied greatly even at the same hardness.
  • FIG. 3 shows an example of a stress-strain curve.
  • the stress-strain curves (solid line A and broken line B) of the two steel pipes shown in FIG. 3 do not change the stress value of 0.5 to 0.7% strain corresponding to the yield stress, but one (broken line B) is continuous. Yield is occurring, and the other (solid line A) has an upper yield point. It was also found that the steel exhibiting a continuous yield type stress-strain curve (broken line B) has a larger variation in KISSC values.
  • the inventors of the present invention conducted further research and found that the variation in the K ISSC value was determined by comparing the stress at the time of 0.7% strain with respect to the stress at the time of 0.4% strain ( ⁇ 0.4 ) of the stress-strain curve. (sigma 0.7) performs organized by the value ( ⁇ 0.7 / ⁇ 0.4) of the ratio of, as shown in FIG. 4, the ⁇ 0.7 / ⁇ 0.4 of seamless steel pipe 1.02 It has been found that the variation in K ISSC value can be reduced to about half by setting the following as compared with the case of exceeding 1.02.
  • the fact that is about half the variation in K ISSC value means that the hardness of the steel as a lower limit of the variation in hardness -K ISSC value K ISSC values in the correlation extends to high hardness side.
  • the Rockwell C scale hardness is as low as 30.2.
  • the stress-strain curve should not be a continuous yield type.
  • the precipitation Mo which precipitated before hardening is made into a primary precipitate, and it melts at the time of hardening, and Mo which precipitated after tempering is made into a secondary precipitate.
  • the quenching temperature is lower.
  • DQ is hot At the end of rolling, it indicates that quenching is performed immediately from a state where the steel pipe temperature is still high.
  • the present invention has been completed based on these findings and comprises the following gist.
  • C 0.25 to 0.31%, Si: 0.01 to 0.35%, Mn: 0.45 to 0.70%, P: 0.010% or less, S: 0.001% or less, O: 0.0015% or less, Al: 0.015 to 0.080%, Cu: 0.02 to 0.09%, Cr: 0.8 to 1.5%, Mo: 1.1 to 1.6%, V: 0.01 to 0.06%, Nb: 0.005 to 0.015%, B: 0.0015 to 0.0030%, Ti: 0.005 to 0.020%, N: 0.005% or less, Containing
  • Ti 0.005 to 0.020%, N: 0.005% or less, Containing
  • the value of the ratio of Ti content to N content (Ti / N) is 3.0 to 4.0, Having a composition consisting of the balance Fe and inevitable impurities, In the stress-strain curve, the ratio of the stress at 0.7% strain to the stress at 0.4% strain ( ⁇
  • a low-alloy high-strength seamless steel pipe for oil wells [2] In addition to the above composition, W: 0.1-0.2% Zr: 0.005 to 0.03% The low-alloy high-strength seamless steel pipe for oil wells according to [1], containing one or two selected from among the above. [3] In addition to the above composition, Ca: 0.0005 to 0.0030% In addition, the number of non-metallic inclusions in the oxide-based steel composed of Ca and Al having a major axis of 5 ⁇ m or more and satisfying the following formula (1) in mass% is 20 or less per 100 mm 2 The low alloy high-strength seamless steel pipe for oil wells according to [1] or [2]. (CaO) / (Al 2 O 3 ) ⁇ 4.0 (1)
  • high strength means that the yield strength is 861 MPa or more (125 ksi or more).
  • the upper limit of yield strength is not particularly limited, but is preferably 960 MPa.
  • the low-alloy high-strength seamless steel pipe for oil wells of the present invention is excellent in sulfide stress corrosion cracking resistance (SSC resistance), and is excellent in sulfide stress corrosion cracking resistance based on NACE TM0177 methodD.
  • SSC resistance sulfide stress corrosion cracking resistance
  • NACE TM0177 methodD sulfide stress corrosion cracking resistance
  • an excellent sulfide stress resistance in a high hydrogen sulfide gas saturation environment specifically, a sour environment with a hydrogen sulfide gas partial pressure of 0.02 MPa or more while having a high yield strength of 861 MPa or more. It is possible to provide a low-alloy high-strength seamless steel pipe exhibiting corrosion cracking resistance (SSC resistance), in particular, a stable high KISSC value.
  • SSC resistance corrosion cracking resistance
  • K is a diagram showing stress-strain curves of steel pipes with different variations in ISSC value. It is a figure which shows that the dispersion
  • the steel pipe of the present invention is, in mass%, C: 0.25 to 0.31%, Si: 0.01 to 0.35%, Mn: 0.45 to 0.70%, P: 0.010% or less S: 0.001% or less, O: 0.0015% or less, Al: 0.015 to 0.080%, Cu: 0.02 to 0.09%, Cr: 0.8 to 1.5%, Mo: 1.1 to 1.6%, V: 0.01 to 0.06%, Nb: 0.005 to 0.015%, B: 0.0015 to 0.0030%, Ti: 0.005 to 0.020%, N: 0.005% or less, the ratio of Ti content to N content (Ti / N) is 3.0 to 4.0, the balance Fe and inevitable impurities having a composition consisting of, stress - the ratio of the value of 0.7% strain when the stress to 0.4% strain at the stress at strain curve ( ⁇ 0.7 / ⁇ 0.4) is 1.02 or less , And the yield strength is low alloy high strength seamless steel pipe for oil well is at least 861MPa.
  • C 0.25 to 0.31%
  • C is an element that has an effect of increasing the strength of steel and is important for ensuring a desired high strength, and in order to achieve a high yield strength of 861 MPa or more, it is 0.25% or more.
  • C content is required.
  • the content of C exceeding 0.31% causes a significant increase in ⁇ 0.7 / ⁇ 0.4 and increases the variation of the K ISSC value. Therefore, C is set to 0.25 to 0.31%.
  • C is 0.27% or more.
  • C is 0.30% or less.
  • Si 0.01 to 0.35%
  • Si is an element that acts as a deoxidizer and has a function of increasing the strength of the steel by dissolving in steel and suppressing rapid softening during tempering. In order to obtain such an effect, it is necessary to contain 0.01% or more of Si. On the other hand, the inclusion of Si exceeding 0.35% forms coarse oxide inclusions and increases the variation of the K ISSC value. For this reason, Si is made 0.01 to 0.35%. Preferably, Si is 0.01 to 0.04%.
  • Mn 0.45 to 0.70%
  • Mn is an element that has the effect of increasing the strength of steel through the improvement of hardenability and binding to S to fix S as MnS, thereby preventing grain boundary embrittlement due to S.
  • the content of Mn exceeding 0.70% causes a significant increase in ⁇ 0.7 / ⁇ 0.4 and increases the variation of the K ISSC value. Therefore, Mn is set to 0.45 to 0.70%.
  • Mn is 0.50% or more.
  • Mn is 0.65% or less.
  • P 0.010% or less
  • P has a tendency to segregate at grain boundaries in the solid solution state and cause grain boundary embrittlement cracks, etc., and is desirably reduced as much as possible in the present invention. acceptable. Therefore, P is set to 0.010% or less.
  • S 0.001% or less S is mostly present as sulfide inclusions in steel, and lowers corrosion resistance such as ductility, toughness, and resistance to sulfide stress corrosion cracking.
  • a part of S may exist in a solid solution state, but in this case, it segregates at the grain boundaries and tends to cause grain boundary embrittlement cracks. For this reason, it is desirable to reduce S as much as possible in the present invention. However, excessive reduction increases the refining cost. For this reason, in the present invention, S is set to 0.001% or less where the adverse effect is acceptable.
  • O (oxygen) 0.0015% or less
  • O (oxygen) is present as an inevitable impurity in the steel as an oxide such as Al or Si.
  • O (oxygen) is made 0.0015% or less to which the adverse effect is allowable.
  • O (oxygen) is 0.0010% or less.
  • Al acts as a deoxidizer and combines with N to form AlN and contribute to the reduction of solid solution N. In order to acquire such an effect, Al needs to contain 0.015% or more. On the other hand, when Al is contained exceeding 0.080%, oxide inclusions increase and the variation in K ISSC value increases. For this reason, Al is made 0.015 to 0.080%. Preferably, Al is 0.05% or more. Preferably, Al is 0.07% or less.
  • Cu 0.02 to 0.09%
  • Cu is an element that has the effect of improving corrosion resistance. When added in a trace amount, a dense corrosion product is formed, and the formation and growth of pits starting from SSC is suppressed, and the resistance to sulfide stress corrosion cracking. In the present invention, it is necessary to contain 0.02% or more of Cu. On the other hand, when it contains Cu exceeding 0.09%, the hot workability at the time of the manufacturing process of a seamless steel pipe will fall. For this reason, Cu is made 0.02 to 0.09%.
  • Cu is 0.03% or more.
  • Cu is 0.05% or less.
  • Cr 0.8 to 1.5% Cr is an element that contributes to an increase in the strength of steel through an increase in hardenability and improves the corrosion resistance. Also, Cr combines with C during tempering to form carbides such as M 3 C, M 7 C 3 and M 23 C 6 systems, and especially M 3 C carbides improve temper softening resistance. Reduces strength change due to tempering and contributes to improved yield strength. In order to achieve a yield strength of 861 MPa or more, it is necessary to contain 0.8% or more of Cr. On the other hand, even if Cr is contained exceeding 1.5%, the effect is saturated, which is economically disadvantageous. Therefore, Cr is set to 0.8 to 1.5%. Preferably, Cr is 0.9% or more. Preferably, Cr is 1.1% or less.
  • Mo 1.1-1.6%
  • Mo is an element that contributes to an increase in the strength of steel through an increase in hardenability and improves the corrosion resistance.
  • the present inventors particularly focused on the point of forming M 2 C-based carbides.
  • Mo 2 C carbides that are secondarily precipitated after tempering improve resistance to temper softening, reduce strength change due to tempering, contribute to improvement of yield strength, and change the stress-strain curve of steel from a continuous yield type. The present inventors have found that a yield type shape can be obtained.
  • a specific amount of Mo is effective for achieving both high yield strength and K ISSC value in a sour environment with a hydrogen sulfide gas partial pressure of 0.2 atm (0.02 MPa) or more as described above.
  • Mo is set to 1.1 to 1.6%.
  • Mo is 1.2% or more.
  • Mo is 1.5% or less.
  • V 0.01 to 0.06%
  • V is an element that forms carbides or nitrides and contributes to the strengthening of steel. In order to obtain such an effect, the V content of 0.01% or more is required. On the other hand, when V is contained exceeding 0.06%, the V-based carbide becomes coarse and becomes the starting point of sulfide stress corrosion cracking, rather, the K ISSC value decreases. Therefore, V is set to 0.01 to 0.06%.
  • V is 0.03% or more.
  • V is 0.05% or less.
  • Nb 0.005 to 0.015%
  • Nb delays recrystallization in the austenite ( ⁇ ) temperature range, contributes to the refinement of ⁇ grains, and acts extremely effectively on the refinement of the substructure (eg, packets, blocks, lath) of steel immediately after quenching. Element. In order to obtain such an effect, it is necessary to contain 0.005% or more of Nb. On the other hand, the effect is saturated even if it contains Nb exceeding 0.015%. For this reason, Nb is made 0.005 to 0.015%.
  • a packet is defined as a region composed of a group of laths having the same crystal habit plane arranged in parallel, and a block is composed of a group of laths parallel and in the same orientation.
  • Nb is 0.009% or more.
  • B 0.0015 to 0.0030%
  • B is an element that contributes to improving the hardenability when contained in a very small amount.
  • B needs to contain 0.0015% or more of B.
  • the effect is saturated or the formation of Fe boride (Fe-B) makes it impossible to expect the desired effect, which is economically disadvantageous. .
  • B is made 0.0015 to 0.0030%.
  • B is 0.0020 to 0.0030%.
  • Ti forms a nitride and reduces the surplus N in the steel to make the effect of B described above effective.
  • Ti is an element that contributes to prevention of coarsening due to the pinning effect of austenite grains during steel quenching. In order to obtain such an effect, it is necessary to contain 0.005% or more of Ti.
  • the Ti content exceeding 0.020% promotes the formation of coarse MC-type nitride (TiN) during casting, and causes coarsening of austenite grains during quenching. For this reason, Ti is made 0.005 to 0.020%.
  • Ti is 0.008% or more.
  • Ti is 0.015% or less.
  • N 0.005% or less N is an unavoidable impurity in steel and forms MN-type precipitates by combining with nitride-forming elements such as Ti, Nb, and Al. Further, the remaining surplus N that forms these nitrides combines with B to form BN precipitates. At this time, since the effect of improving hardenability due to the addition of B is lost, it is preferable to reduce surplus N as much as possible, and N is set to 0.005% or less.
  • Ti / N Value of ratio of Ti content to N content (Ti / N): 3.0 to 4.0
  • Ti / N is defined.
  • surplus N is generated, and as a result of the formation of BN, the solid solution B at the time of quenching is insufficient, so that the microstructure at the end of quenching is martensite and bainite, or martensite and ferrite.
  • Ti / N is set to 3.0 to 4.0.
  • the balance other than the above components is Fe and inevitable impurities.
  • W 0.1-0.2%
  • Zr 0.005-0
  • One or two selected from 0.03% may be selected and contained.
  • from Ca and Al containing 0.0005 to 0.0030% Ca, mass%, composition ratio (CaO) / (Al 2 O 3 ) ⁇ 4.0, and having a major axis of 5 ⁇ m or more.
  • the number of non-metallic inclusions in the oxide-based steel may be 20 or less per 100 mm 2 .
  • W 0.1-0.2% W, like Mo, forms carbides and contributes to an increase in strength by precipitation hardening, and also forms a solid solution, segregates at the prior austenite grain boundaries, and contributes to an improvement in resistance to sulfide stress corrosion cracking.
  • Zr 0.005 to 0.03%
  • Zr is effective in suppressing austenite grain growth during quenching by forming a nitride and pinning the same as Ti.
  • Zr is set to 0.005 to 0.03%.
  • Ca 0.0005 to 0.0030%
  • Ca is effective in preventing nozzle clogging during continuous casting, and in order to obtain a necessary effect, it is desirable to contain 0.0005% or more of Ca.
  • Ca forms oxide-based non-metallic inclusions complexed with Al.
  • Ca exceeds 0.0030%, a large number of coarse substances exist, and resistance to sulfide stress corrosion cracking is present. Reduce.
  • the major axis has a particularly adverse effect, so that the major axis is 5 ⁇ m or more.
  • the number of inclusions satisfying the expression (1) is 20 or less per 100 mm 2 .
  • the number of inclusions is obtained by taking a sample for a scanning electron microscope (SEM) having a cross section orthogonal to the longitudinal direction of the pipe from an arbitrary circumferential position on the end of the steel pipe. At least the outer surface of the pipe, the center of the wall, It can be calculated from the SEM observation of inclusions at three locations on the surface and the analysis result of the chemical composition with the characteristic X-ray analyzer attached to the SEM. Therefore, when Ca is contained, the Ca content is set to 0.0005 to 0.0030%.
  • the number of non-metallic inclusions in the oxide-based steel composed of Ca and Al having a major axis of 5 ⁇ m or more satisfying the following formula (1) in mass% is 20 or less per 100 mm 2.
  • Ca is 0.0010% or more.
  • Ca is 0.0016% or less.
  • the number of inclusions described above is to control the amount of Al input during Al deoxidation treatment after decarburization refining and to add an amount of Ca according to the analytical values of Al, O, and Ca in the molten steel before Ca addition. Can be controlled.
  • the manufacturing method of the steel pipe material having the above composition is not particularly limited, but the molten steel having the above composition is melted by a generally known melting method such as a converter, an electric furnace or a vacuum melting furnace. It is preferable to produce a steel pipe material such as billet by a conventional method such as continuous casting or ingot-splitting rolling.
  • the steel pipe material is formed into a seamless steel pipe by hot forming.
  • hot forming method after piercer drilling, after forming to a predetermined thickness using any one of mandrel mill rolling and plug mill rolling, hot rolling is performed until appropriate diameter reduction rolling. In order to stabilize ⁇ 0.7 / ⁇ 0.4 to 1.02 or less, it is desirable to perform direct quenching (DQ) after hot rolling.
  • DQ direct quenching
  • the microstructure at the end of DQ becomes a composite structure such as martensite and bainite or martensite and ferrite, the crystal grain size of steel after the quenching and tempering heat treatment, 2 It is necessary to prevent the next precipitation amount from becoming heterogeneous and the value of ⁇ 0.7 / ⁇ 0.4 from exceeding 1.02. Therefore, it is preferable that completion
  • the temperature of the steel pipe at the end of DQ is preferably 200 ° C. or lower.
  • the steel pipe is quenched (Q) and tempered (T) in order to achieve a target yield strength of 861 MPa or more.
  • the quenching temperature at this time is preferably 930 ° C. or lower from the viewpoint of crystal grain refinement.
  • the quenching temperature is preferably 860 to 930 ° C.
  • the tempering temperature In order to avoid austenite retransformation, the tempering temperature needs to be Ac 1 temperature or less, but if it is less than 600 ° C., the secondary precipitation amount of Mo or the like cannot be secured. For this reason, the tempering temperature is preferably at least 600 ° C. or higher.
  • the value ( ⁇ 0.7 / ⁇ 0.4 ) of the ratio of the stress at the time of 0.7% strain ( ⁇ 0.7 ) to the stress at the time of 0.4% strain ( ⁇ 0.4 ) in the stress-strain curve is 1.02 or less
  • the variation of the K ISSC value varies greatly depending on the shape of the stress-strain curve of the steel.
  • the value ( ⁇ 0 ) of the ratio of the stress at the time of 0.7% strain ( ⁇ 0.7 ) to the stress at the time of 0.4% strain ( ⁇ 0.4 ) .7 / ⁇ 0.4 ) was found to be approximately halved in variation in K ISSC value when 1.02 or less.
  • ⁇ 0.7 / ⁇ 0.4 is set to 1.02 or less.
  • the yield strength, the stress at 0.4% strain ( ⁇ 0.4 ), and the stress at 0.7% strain ( ⁇ 0.7 ) are measured by a tensile test based on JIS Z2241. be able to.
  • microstructure of the present invention is not particularly limited, but the main phase is martensite, and the other remaining structures are one type or two types or more of ferrite, retained austenite, pearlite, bainite, etc. And if it is 5% or less, the objective of this invention can be achieved.
  • the bloom slab was formed into a billet with a round cross section by hot rolling. Furthermore, using this billet as a raw material, after heating to the billet heating temperature shown in Table 2, Mannesmann piercing-plug mill rolling-reducing rolling was performed hot, and rolling was completed at the rolling end temperatures shown in Table 2 and Table 3. And formed into a seamless steel pipe.
  • the steel pipe is cooled to the room temperature (below 35 ° C.) by direct quenching (DQ) or air cooling (0.2 to 0.5 ° C./s), and then the steel pipe heat treatment conditions (Q1 temperature) shown in Table 2 and Table 3 1st quenching temperature, T1 temperature: 1st tempering temperature, Q2 temperature: 2nd quenching temperature, T2 temperature: 2nd tempering temperature).
  • Q1 temperature 1st quenching temperature
  • T1 temperature 1st tempering temperature
  • Q2 temperature 2nd quenching temperature
  • T2 temperature 2nd tempering temperature
  • the DCB test was implemented based on NACETM0177 methodD using the extract
  • the test bath for the DCB test was a mixed aqueous solution of 0.5 mass% CH 3 COOH + CH 3 COONa at 24 ° C. saturated with 0.2 atm (0.02 MPa) hydrogen sulfide gas. After immersing the DCB test piece in which the wedge was introduced into this test bath under predetermined conditions for 336 hours, the length a of the crack generated in the DCB test piece during the immersion and the wedge opening stress P were measured, and the following equation (2 ) To calculate K ISSC (MPa ⁇ m).
  • h is the height of each arm of the DCB test piece
  • B is the thickness of the DCB test piece
  • Bn is the web thickness of the DCB test piece.
  • Steel pipes 1 to 7 whose chemical composition and ⁇ 0.7 / ⁇ 0.4 were within the scope of the present invention were all hydrogen sulfide having a yield strength of 861 MPa or more and a DCB test bath of 0.2 atm (0.02 MPa).
  • a DCB test bath 0.2 atm (0.02 MPa).
  • the K ISSC value obtained in each of the three DCB tests does not vary greatly, and the target is 26.4 MPa. Satisfied all over ⁇ m.
  • Comparative Example 8 (steel No. G) in which C of the chemical composition was below the lower limit of the scope of the present invention
  • Comparative Example 9 (steel No. H) in which Mn was below the lower limit of the scope of the present invention, and Cr was within the scope of the present invention
  • Comparative Example 10 (steel No. I), which was less than the lower limit, could not achieve the target yield strength of 861 MPa or more.
  • Comparative Example 11 (steel No. J) in which Mo of the chemical composition was below the lower limit of the range of the present invention and Comparative Example 12 (steel No. K) in which the upper limit was exceeded were all in the three DCB tests. Neither book satisfied the target of 26.4 MPa ⁇ m or more.
  • Comparative Example 13 (steel No. L) in which Nb of the chemical composition was below the lower limit of the range of the present invention
  • Comparative Example 14 (steel No. M) in which B was lower than the lower limit of the range of the present invention were ⁇ 0.7
  • the K ISSC values varied greatly, and two of the three DCB tests did not satisfy the target of 26.4 MPa ⁇ m or more.
  • Comparative Example 16 (steel No. O) in which the Ti / N ratio exceeded the upper limit of the range of the present invention also has a large K ISSC value as a result of ⁇ 0.7 / ⁇ 0.4 being out of the range of the present invention. Variations did not satisfy the target of 26.4 MPa ⁇ m or more, one of the three DCB tests.
  • Comparative Example 17 which had a low final tempering temperature, showed that ⁇ 0.7 / ⁇ 0.4 was outside the scope of the present invention. The target of 26.4 MPa ⁇ m or more was not satisfied. Similarly, in Comparative Example 18 in which the quenching temperature before the final tempering was low, ⁇ 0.7 / ⁇ 0.4 was out of the range of the present invention. As a result, the K ISSC value varied greatly, and three DCB tests Two of them did not satisfy the target of 26.4 MPa ⁇ m or more.
  • the bloom slab was formed into a billet with a round cross section by hot rolling. Further, using this billet as a raw material, after heating to the billet heating temperature shown in Table 5, hot Mannesmann piercing-plug mill rolling-reducing rolling was performed, and rolling was completed at the rolling completion temperature shown in Table 5 and seamlessly performed. Molded into a steel pipe.
  • the steel pipe is cooled to the room temperature (below 35 ° C.) by direct quenching (DQ) or air cooling (0.2 to 0.5 ° C./s), and then the heat treatment conditions (Q1 temperature: first time) shown in Table 5 , T1 temperature: first tempering temperature, Q2 temperature: second quenching temperature, T2 temperature: second tempering temperature).
  • DQ direct quenching
  • T1 temperature first tempering temperature
  • Q2 temperature second quenching temperature
  • T2 temperature second tempering temperature
  • the DCB test was implemented based on NACETM0177 methodD using the extract
  • the test bath for the DCB test was a mixed aqueous solution of 0.5 mass% CH 3 COOH + CH 3 COONa at 24 ° C. saturated with 0.2 atm (0.02 MPa) hydrogen sulfide gas. After immersing the DCB test piece into which the wedge was introduced into this test bath under predetermined conditions for 336 hours, the length a of the crack generated in the DCB test piece during the immersion and the wedge opening stress P were measured. K ISSC (MPa ⁇ m) was calculated.
  • the steel pipes 2-1 to 2-4 whose chemical composition, number of inclusions and ⁇ 0.7 / ⁇ 0.4 were within the range of the present invention, all had a yield strength of 861 MPa or more, and were obtained by three DCB tests. All of the obtained K ISSC values satisfied the target of 26.4 MPa ⁇ m without greatly varying.
  • Comparative Example 2-5 (steel No. T) in which the upper limit of Ca exceeded the upper limit of the range of the present invention, the K ISSC value greatly varied, and one of the three DCB tests was targeted at 26.4 MPa. ⁇ m was not satisfied.
  • Comparative Example 2-6 (steel No. U), considering that the amount of Ca in the molten steel before addition of Ca is high due to impurities Ca contained in the alloy iron of other elements added during secondary refining.
  • Ca was within the scope of the present invention because Ca was added, but the number of non-metallic inclusions in the oxide-based steel composed of Ca and Al with a major axis of 5 ⁇ m or more and satisfying formula (1) was The upper limit of the invention range was exceeded, the K ISSC value varied greatly, and one of the three DCB tests did not satisfy the target of 26.4 MPa ⁇ m.

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Abstract

La présente invention concerne un tuyau en acier sans soudure, à haute résistance, faiblement allié pour un puits de pétrole qui présente une excellente résistance SSC. Ce tuyau d'acier présente une composition qui contient, en % en masse, C : 0,25 à 0,31 %, Si : 0,01 à 0,35 %, Mn : 0,45 à 0,70 %, P : 0,010 % ou moins, S : 0,001 % ou moins, O: 0,0015 % ou moins, Al : 0,015 à 0,080 %, Cu : 0,02 à 0,09 %, Cr : 0,8 à 1,5 %, Mo : 1,1 à 1,6 %, V : 0,01 à 0,06 %, Nb : 0,005 à 0,015 %, B : 0,0015 à 0,0030 %, Ti : 0,005-0,020 % et N : 0,005 % ou moins, la valeur du rapport (Ti /N) de la teneur en Ti et la teneur en N étant de 3,0 à 4,0, et le reste étant Fe et des impuretés inévitables, et la valeur du rapport (σ0.7/σ0.4) de la contrainte à 0,7 % de déformation à la contrainte à 0,4 % de déformation sur la courbe contrainte-déformation étant de 1,02 ou moins, et la limite d'élasticité étant de 861 MPa ou plus.
PCT/JP2016/004915 2016-02-29 2016-11-18 Tuyau en acier sans soudure, à haute résistance, faiblement allié pour puits de pétrole Ceased WO2017149571A1 (fr)

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JP2017513268A JP6152929B1 (ja) 2016-02-29 2016-11-18 油井用低合金高強度継目無鋼管
EP16892416.5A EP3425076B1 (fr) 2016-02-29 2016-11-18 Tube en acier faiblement allié sans soudure, à haute résistance pour produits tubulaires pour puits de pétrole
BR112018017250-2A BR112018017250B1 (pt) 2016-02-29 2016-11-18 Tubo de aço sem costura de alta resistibilidade de baixa liga para produtos tubulares petrolíferos
US16/078,924 US20190048444A1 (en) 2016-02-29 2016-11-18 Low alloy high strength seamless steel pipe for oil country tubular goods
NZ74466816A NZ744668A (en) 2016-02-29 2016-11-18 Low alloy high strength seamless steel pipe for oil country tubular goods
MX2018010363A MX386977B (es) 2016-02-29 2016-11-18 Tubo de acero sin costura de alta resistencia y baja aleación para productos tubulares para la industria petrolera.

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WO2024209921A1 (fr) * 2023-04-06 2024-10-10 日本製鉄株式会社 Matériau d'acier
WO2025033002A1 (fr) * 2023-08-07 2025-02-13 日本製鉄株式会社 Matériau d'acier
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JP5943164B1 (ja) 2014-12-24 2016-06-29 Ｊｆｅスチール株式会社 油井用高強度継目無鋼管およびその製造方法
BR112018017191B8 (pt) 2016-02-29 2022-09-20 Jfe Steel Corp Tubo de aço sem costura de alta resistência e de baixa liga para produtos tubulares de campos de petróleo
NZ744616A (en) * 2016-02-29 2019-11-29 Jfe Steel Corp Low alloy high strength thick-walled seamless steel pipe for oil country tubular goods
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WO2019198459A1 (fr) * 2018-04-09 2019-10-17 日本製鉄株式会社 Tuyau d'acier et procédé de production de tuyau d'acier
JPWO2019198459A1 (ja) * 2018-04-09 2021-01-14 日本製鉄株式会社 鋼管、及び、鋼管の製造方法
WO2024209921A1 (fr) * 2023-04-06 2024-10-10 日本製鉄株式会社 Matériau d'acier
JP7633586B1 (ja) * 2023-04-06 2025-02-20 日本製鉄株式会社 鋼材
WO2025033002A1 (fr) * 2023-08-07 2025-02-13 日本製鉄株式会社 Matériau d'acier
JPWO2025033002A1 (fr) * 2023-08-07 2025-02-13
JPWO2025033003A1 (fr) * 2023-08-07 2025-02-13
WO2025033003A1 (fr) * 2023-08-07 2025-02-13 日本製鉄株式会社 Matériau d'acier
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JP7759015B2 (ja) 2023-08-07 2025-10-23 日本製鉄株式会社 鋼材

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AR107720A1 (es) 2018-05-23
NZ744668A (en) 2019-11-29
BR112018017250B1 (pt) 2021-10-05
US20190048444A1 (en) 2019-02-14
MX2018010363A (es) 2018-12-06
EP3425076A1 (fr) 2019-01-09
EP3425076B1 (fr) 2021-11-10

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