US20050224143A1 - High strength martensitic stainless steel excellent in carbon dioxide gas corrosion resistance and sulfide stress-corrosion cracking resistance - Google Patents

High strength martensitic stainless steel excellent in carbon dioxide gas corrosion resistance and sulfide stress-corrosion cracking resistance Download PDF

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US20050224143A1
US20050224143A1 US11/149,320 US14932005A US2005224143A1 US 20050224143 A1 US20050224143 A1 US 20050224143A1 US 14932005 A US14932005 A US 14932005A US 2005224143 A1 US2005224143 A1 US 2005224143A1
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steel
tempering
carbon dioxide
dioxide gas
martensitic stainless
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Hideki Takabe
Masakatsu Ueda
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Nippon Steel Corp
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Assigned to SUMITOMO METAL INDUSTRIES, LTD. reassignment SUMITOMO METAL INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAKABE, HIDEKI, UEDA, MASAKATSU
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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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • 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
    • 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
    • C22C38/02—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
    • C22C38/50—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
    • 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

Definitions

  • the present invention relates to a steel material suitable for its use in severe corrosion environment containing corrosive materials such as carbon dioxide gas, hydrogen sulfide, chlorine ions and the like.
  • the present invention relates to a steel material for a seamless steel tube and a seam welded steel tube such as an electric resistance welding steel tube, a laser welding steel tube, a spiral welding tube or the like, which is used in applications for petroleum or natural gas production facilities, facilities for eliminating carbon dioxide gas, or for geo-thermal power generation, or for a tank for liquid containing carbon dioxide gas, especially to a steel material for oil well tubes for oil wells or gas wells.
  • the SUS 420 steel has excellent corrosion resistance to carbon dioxide gas, it has poor corrosion resistance to hydrogen sulfide. Thus, the SUS 420 steel is liable to generate sulfide stress-corrosion cracking (SSCC) under the environment containing carbon dioxide gas and hydrogen sulfide simultaneously.
  • SSCC sulfide stress-corrosion cracking
  • Japanese Patent No. 2861024, Japanese Patent Application Publication No. 05-287455, and Japanese Patent Application Publication No. 07-62499 disclose steel having improved corrosion resistance by reducing carbon content of the SUS 420.
  • Japanese Patent Appilcation Publication No. 2000-192196 discloses steel of a martensitic single phase structure containing Co: 0.5-7% and Mo: 3.1-7% having high strength and excellent sulfide stress-corrosion cracking resistance.
  • the invention described in the publication is a steel containing Co in the above-mentioned range to suppress the generation of retained austenite during cooling so that the structure is made to be a martensitic single phase.
  • Co is an expensive element, it is desirable not to use.
  • the present invention was made in consideration of the above-mentioned circumstances.
  • the object of the present invention is to provide a martensitic stainless steel having sufficient strength to use for oil well tubes for a deep well, that is high strength of a proof stress of 860 MPa or more, and excellent carbon dioxide as corrosion resistance and sulfide stress-corrosion cracking resistance whereby it an be used even under the environment containing carbon dioxide gas, hydrogen ulfide or chlorine ions or two or more of them.
  • the symbols of the respective lements in the following expression show the content (mass %) of each element.
  • the gist of the present invention is high strength martensitic stainless steels described in the following (a) and (b).
  • a high strength martensitic stainless steel excellent in carbon dioxide gas corrosion resistance and sulfide stress-corrosion cracking resistance and having 0.2% proof stress of 860 MPa or more which comprises including, by mass %, C: 0.005-0.04%, Si: 0.5% or less, Mn: 0.1-3.0%, P: 0.04% or less, S: 0.01% or less, Cr: 10-15%, Ni: 4.0-8%, Mo: 2.8-5.0%, Al: 0.001-0.10% and N, 0.07% or less, Ti: 0-0.25%, V: 0-0.25%, Nb: 0-0.25%, Zr: 0-0.25%, Cu: 0-1%, Ca: 0-0.005%, Mg: 0-0.005%, La: 0-0.005%, and Ce: 0-005%, and the balance Fe and impurities; and satisfying the expression (1) given below wherein the microstructure mainly comprises tempered martensite, carbide precipitated during tempering, and intermetallic compounds such as Laves phase, ⁇ phase and the like
  • the gist of the present invention is martensitic stainless steels containing at least one of alloying elements selected from at least one group consisting of the following a first group, a second group and a third group, in addition to the components described in the above mentioned (a).
  • this steel said expression (1) is also satisfied and the microstructure is the same as mentioned above.
  • Second group . . . Cu 0.05-1%
  • a high strength martensitic stainless steel excellent in carbon dioxide gas corrosion resistance and sulfide stress-corrosion cracking resistance and having 0.2% proof stress of 860 MPa or more which comprises the compositions defined in any one of (a); being subjected to tempering in which (20+log t)(T+273) satisfies 13500-17700 when, after quenching the steel at a quenching temperature of 880° C.-1000° C., a range of a tempering temperature is set to 450° C.-620° C., a tempering temperature is set to T (° C.) and tempering time is set to t (hour); and satisfying the above mentioned expression (1) wherein the microstructure of said steel mainly comprises tempered martensite, carbide precipitated during tempering, and intermetallic compounds such as a Laves phase, a ⁇ phase and the like finely precipitated during tempering.
  • FIG. 1 is a view showing relationships between Mo contents of various types of steels tested in examples and the right side in the expression (1), that is “2.3-0.89 Si+32.2 C” (IM value).
  • FIG. 2 is a view for explaining tempering conditions defined in the present invention, which shows relationships between 0.2% proof stress obtained by changing values of (20+log t)(T+273) while changing tempering temperatures in 400-650° C. after quenching steel at 920° C., and the (20+log t)(T+273).
  • C carbon
  • C carbon
  • proof stress does not reach 860 Mpa or more.
  • the lower limit of the C content was set to 0.005%.
  • the C content exceeds 0.04%, the hardness of the tempered steel becomes hard excessively, the steel has high sulfide stress-corrosion cracking sensibility. Accordingly, the C content was set to 0.005-0.04%.
  • Si is an alloying element necessary as a deoxidizer.
  • An amount of Si retained in the steel may be a level of impurities.
  • the Si content is set to 0.01% or more.
  • the Si content exceeds 0.5%, the toughness of the steel is decreased and the workability of the steel is also decreased. Accordingly, the Si content was set to 0.5% or less.
  • Mn Manganese
  • Mn content 0.1% or more is needed.
  • the Mn content exceeds 3.0%, the effect is saturated resulting in an increase in cost. Accordingly, the Mn content was set to 0.1-3.0%.
  • P Phosphorus
  • the P content is better as low as possible. Particularly, if the P content exceeds 0.04%, the sulfide stress-corrosion cracking resistance is remarkably decreased. Accordingly, the P content was set to 0.04% or less.
  • S is an impurity element contained in the steel and the S content is better as low as possible. Particularly, if the S content exceeds 0.01%, the hot workability, corrosion resistance and toughness are remarkably decreased. Accordingly, the S content was set to 0.01% or less.
  • Cr Chromium
  • Cr Chromium
  • Ni Ni (Nickel) is an alloying element, which is necessary for making the microstructure of tempered steel a martensite phase mainly.
  • the Ni content is 4.0% or less, a number of ferrite phases were precipitated in the microstructure of tempered steel and the microstructure of tempered steel does not become a martensite phase mainly.
  • the Ni content exceeds 8%, the microstructure of tempered steel becomes an austenite phase mainly. Accordingly, the Ni content was set to 4.0-8%. More preferably the Ni content was set to 4-7%.
  • Mo Mo is an effective alloying element to enhance the sulfide stress-corrosion cracking resistance for a high strength material. To obtain this effect Mo content of 2.8% or more is needed. However, if the Mo content exceeds 5.0%, this effect is saturated, resulting in an increase in cost. Accordingly, the Mo content was set to 2.8-5.0%.
  • Al is an alloying element, which is used as a deoxidizer in a melting process. To obtain this effect Al content of 0.001% or more is needed. However, if the Al content exceeds 0.10%, many inclusions are formed in the steel so that the corrosion resistance is lost. Accordingly, the Al content was set to 0.001-0.10%.
  • N is an impurity element contained in the steel and the N content is better as low as possible. Particularly, if the N content exceeds 0.07%, many inclusions are formed so that the corrosion resistance is lost. Accordingly, the N content was set to 0.07% or less.
  • One of martensitic stainless steels according to the present invention consists the above-mentioned chemical composition as well as the balance Fe and indispensable impurities.
  • Another martensitic stainless steel according to the present invention further contains, in addition to the above-mentioned components, at least one alloying element selected from at least one group consisting of a first group, a second group and a third group shown as follows. The components (elements) of the respective groups will be described below.
  • one or more selected from these elements may be optionally contained. However, if any one of the elements is less than 0.005%, the above-mentioned effect cannot be obtained. On the other hand, if any one of the elements exceeds 0.25%, the microstructure of the steel cannot become a martensite phase mainly so that highly strengthening of the steel with a proof stress of 860 MPa or more cannot be attained. Accordingly, the respective contents in selectively containing these elements were set to 0.005-0.25%.
  • Cu is an effective element to make the microstructure of tempered steel a martensite phase mainly like Ni.
  • the Cu content may be 0.05% or more.
  • the Cu content exceeds 1%, the hot workability of the steel is lowered. Accordingly, when Cu is contained in the steel the Cu content was set to 0.05-1%.
  • Ca, Mg, La and Ce are effective elements to enhance the hot workability of the steel, one or more selected from these elements may be optionally contained. However, if any one of the elements is less than 0.0002%, the above-mentioned effect cannot be obtained. On the other hand, if any one of the elements exceeds 0.005%, coarse oxide is formed in the steel whereby the corrosion resistance of the steel is decreased. Accordingly, the respective contents in selectively containing these elements were set to 0.0002-0.005%. Particularly, it is preferred to contain Ca and/or La in the steel.
  • the steel according to the present invention should have the above-mentioned chemical composition and satisfy the following expression (1). This is because, if the steel satisfies the expression (1), strength of the steel can be enhanced to proof stress of 860 Mpa or more without deteriorating sulfide stress-corrosion cracking resistance. Mo ⁇ 2.3 ⁇ 0.89 Si+32.2 C (1) wherein the symbols of the respective elements in the expression (1) show the content (mass %) of each element.
  • FIG. 1 is a view showing relationships between Mo contents of various types of steels tested in examples, which will be described later, and the right side in the expression (1), that is “2.3 ⁇ 0.89 Si+32.2 C” (IM value).
  • the results shown in FIG. 1 are based on steels of the present invention and comparative steels (test Nos. 18-21).
  • the mark “ ⁇ ” shows an example that did not generate rupture in a sulfide stress-corrosion cracking test, and the mark “x” shows an example that generated rupture therein. Even if the Mo content exceeds 2.8%, if the Mo content does not satisfy the expression (1), the steel has a poor sulfide stress-corrosion cracking resistance.
  • the 0.2% proof stress of the steel is less than 860 Mpa. Further, even if Mo content is in a range (that is 2.8-5%) defined in the present invention, if the Mo content does not satisfy the above-mentioned expression (1), the 0.2% proof stress of the steel is less than 860 Mpa.
  • the steel according to the present invention should be in a range of said chemical composition and satisfy the above-mentioned expression (1).
  • the present inventors have checked the influences of microstructure. As a result the present inventors have found that if the microstructure is a structure mainly comprising tempered martensite, carbide precipitated during tempering, and intermetallic compounds such as Laves phase, ⁇ phase and the like finely precipitated during tempering, the strength of the steel can be enhanced without deteriorating sulfide stress-corrosion cracking resistance.
  • mainly comprising tempered martensite means that a 70 vol % or more of the microstructure of the steel is a tempered martensitic structure, and a retained austenitic structure and/or a ferritic structure other than a tempered martensitic structure may be present.
  • intermetallic compounds such as Laves phase, ⁇ phase and the like
  • the microstructure of the steel according to the present invention contains carbide precipitated during tempering.
  • carbide is an effective microstructure to ensure the strength of the steel, high strength of proof stress of 860 Mpa or more cannot be realized by only carbide contained in the steel. Accordingly, in the present invention precipitation of carbide as well as fine precipitation of intermetallic compounds such as the above-mentioned Laves phase, ⁇ phase and the like are needed.
  • Heat treatment for the steel of the present invention is typical quenching-tempering. To precipitate fine intermetallic compounds during tempering it is necessary to sufficiently dissolve the intermetallic compounds during quenching.
  • the quenching temperature is preferably 880-1000° C.
  • conditions in which intermetallic compounds such as a fine Laves phase, ⁇ phase and the like are precipitated and 0.2% proof stress of 860 Mpa or more can be obtained resides in a case where when a temperature range for tempering is 450-620° C., as well as the tempering temperature is set to T(° C.) and the tempering time is set to t (hour), (20+log t)(T+273) can satisfy 13500-17700.
  • FIG. 2 is a view for explaining tempering conditions defined in the present invention.
  • FIG. 2 shows relationships between 0.2% proof stress obtained by changing values of (20+log t)(T+273) while changing tempering temperatures in 400-650° C. after quenching steel at 920° C., and the (20+log t)(T+273).
  • the steel of the present invention should have the above-mentioned chemical compositions and satisfy the expression (1) and the microstructure of the steel should be mainly comprising tempered martensite, carbide precipitated during tempering, and intermetallic compounds such as a Laves phase, ⁇ phase and the like finely precipitated during tempering.
  • IM value shows (2.3 ⁇ 0.89 Si + 32.2C)
  • Mo ⁇ IM value shows a calculated value of (Mo content ⁇ IM value), and if this value is 0 or more, it satisfied the expression (1) defined in the present invention.
  • IM value shows (2.3 ⁇ 0.89 Si + 32.2C)
  • Mo ⁇ IM value shows a calculated value of (Mo content ⁇ IM value), and if this value is 0 or more, it satisfied the expression (1) defined in the present invention.
  • test pieces each having a thickness of 3 mm, a width of 20 mm and a length of 50 mm were taken from the respective testing steel plates and these testing pieces were polished with a No. 600 emery paper and degreased and dried. Then the obtained testing pieces were immersed into 25% NaCl water solution saturated with 0.973 Mpa CO 2 gas and 0.0014 Mpa H 2 S gas (temperature: 165° C.) for 720 hours.
  • the corrosion rate of the steel according to the present invention is 0.5 mm/year or less, and no local corrosion on its surface could be found.
  • examples Nos. 1 to 17 of the present invention each have 0.2% proof stress of 860 Mpa or more and excellent carbon dioxide gas corrosion resistance and sulfide stress-corrosion cracking resistance.
  • the martensitic stainless steel according to the present invention can have high strength of 0.2% proof stress of 860 Mpa or more and excellent carbon dioxide gas corrosion resistance and sulfide stress-corrosion cracking resistance by limiting the steel composition of specified elements and defining Mo content in the steel by relationships with IM values as well as by forming microstructure of the steel with tempered martensite mainly, carbide precipitated during tempering, and intermetallic compounds such as a Laves phase, a ⁇ phase and the like.
  • the martensitic stainless steels of the present invention can be applied to practical steels, which can be widely used in oil well tubes and the like under environment including carbon dioxide gas, hydrogen sulfide, chlorine ions or two or more of them, in wide fields.

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  • Metallurgy (AREA)
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US11/149,320 2002-12-20 2005-06-10 High strength martensitic stainless steel excellent in carbon dioxide gas corrosion resistance and sulfide stress-corrosion cracking resistance Abandoned US20050224143A1 (en)

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JP5145793B2 (ja) * 2007-06-29 2013-02-20 Ｊｆｅスチール株式会社 油井管用マルテンサイト系ステンレス継目無鋼管およびその製造方法
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