WO2006054430A1 - Acier inoxydable martensitique - Google Patents

Acier inoxydable martensitique Download PDF

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Publication number
WO2006054430A1
WO2006054430A1 PCT/JP2005/019685 JP2005019685W WO2006054430A1 WO 2006054430 A1 WO2006054430 A1 WO 2006054430A1 JP 2005019685 W JP2005019685 W JP 2005019685W WO 2006054430 A1 WO2006054430 A1 WO 2006054430A1
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Prior art keywords
stainless steel
martensitic stainless
content
less
tempering
Prior art date
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PCT/JP2005/019685
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English (en)
Japanese (ja)
Inventor
Hideki Takabe
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Sumitomo Metal Industries, Ltd.
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Filing date
Publication date
Application filed by Sumitomo Metal Industries, Ltd. filed Critical Sumitomo Metal Industries, Ltd.
Priority to EP05799225A priority Critical patent/EP1826285B1/fr
Priority to US11/791,015 priority patent/US20080213120A1/en
Publication of WO2006054430A1 publication Critical patent/WO2006054430A1/fr

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Classifications

    • 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
    • C22C38/02—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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • the present invention relates to martensitic stainless steel, and more particularly to martensitic stainless steel used in a corrosive environment containing corrosive substances such as hydrogen sulfide, carbon dioxide, and chlorine ions.
  • martensitic stainless steel used as oil well steel materials such as oil well pipes is required to have high strength and high toughness. Therefore, a martensitic stainless steel with a yield stress (0.2% resistance) strength of 758 to 860 MPa (hereinafter referred to as “l lOksi class”) and a martensitic stainless steel with a high strength of 1 lOksi class or higher have been developed. It has been.
  • Martensitic stainless steel for oil wells is also required to have high corrosion resistance such as SCC (Stress Corrosion Cracking) resistance and SSC (Sulfide Stress Cracking) resistance.
  • Oil and gas wells are corrosive environments and contain corrosive substances such as hydrogen sulfide, carbon dioxide, and chlorine ions.
  • martensitic stainless steel for oil wells is required to have high strength, high toughness and high corrosion resistance.
  • Japanese Unexamined Patent Publication No. 2003-3243 is disclosed as a martensitic stainless steel having high strength and high corrosion resistance.
  • the martensitic stainless steel disclosed in this document has higher SSC resistance than conventional martensitic stainless steel by setting the Mo content to 1.5% by mass or more.
  • Fig. 1 shows the relationship between the yield stress and the tempering temperature of martensitic stainless steel with a high Mo content (hereinafter referred to as high Mo martensitic stainless steel).
  • High Mo martensitic stainless steel of FIG. 1 the mass 0/0 0.016% of. 11.8% Cr, 7.2% Ni 2 2.9% Mo, the balance being Fe and impurities.
  • the yield stress ranges from 758 to 860 MPa. Tempering curve in the box The gradient of CIO is large.
  • the tempering temperature must be set within the range of about 580 to about 600 ° C in order to increase the strength of high Mo martensitic stainless steel to the lOksi class.
  • the tempering temperature range ⁇ for making the strength l lOksi grade is very small.
  • the tempering temperature range ⁇ T is small, the productivity decreases.
  • high Mo martensitic stainless steel is produced continuously for several hundred tons.
  • high Mo martensitic stainless steel is produced from multiple heats (molten steel obtained in a single steelmaking process), but the chemical composition of each heat does not completely match and varies slightly.
  • the tempering temperature range ⁇ is small, the tempering temperature must be changed each time the chemical composition changes to make the steel strength l lOksi grade. In short, it is necessary to change the tempering temperature setting for each heat in order to make the strength l lOksi class. Changing the tempering temperature setting reduces productivity.
  • An object of the present invention is to provide a martensitic stainless steel having a large tempering temperature range in which a yield stress of 758 to 860 MPa is obtained.
  • the tempering temperature range of 758 to 860 MPa becomes even wider.
  • the higher the C content the larger the tempering curve gradient within the yield stress range of 758 to 860 MPa.
  • the symbol in the formula is the content (% by mass) of each element.
  • left side of equation (1) F1
  • left side of equation (1) F1
  • F1 is an equation for predicting the A transformation point of the martensitic stainless steel of the present invention.
  • Formula (2) is a formula for martensiticizing the steel after tempering. If the content of C, Mn, Ni, which are austenite forming elements, and the content of Si, Cr, Mo, which are ferrite forming elements, satisfy the relationship of formula (2), the structure becomes martensite, and ⁇ ferrite Can be prevented. Therefore, strength reduction can be prevented and high toughness can be maintained.
  • Martensitic stainless steel according to the invention, the mass 0/0, C: 0.001 ⁇ 0.01% , S i: 0.5% or less, Mn:. 0 1 ⁇ 3.0%, P: 0.04% or less, S: 0.01% or less, Cr: 10-15%, Ni: 4-8%, Mo: 2.8-5.0%, A1: 0.001-0.10%, N: 0.07% or less, Ti: 0-0.25%, V: 0 ⁇ 0.25%, Nb: 0 ⁇ 0.25%, Zr: 0 ⁇ 0.25%, Cu: 0 ⁇ 1.0%, Ca: 0 ⁇ 0.005%, Mg: 0 ⁇ 0.005%, La: 0 ⁇ 0.005%, Ce: The content is 0 to 0.005%, the balance is made of Fe and impurities, satisfies the formulas (1) and (2), and has a yield stress of 758 to 860 MPa.
  • the symbol in the formula represents the content (% by mass) of each element.
  • “Ti” and “Cu” in formulas (1) and (2) are “0”.
  • the yield stress is 0.2% proof stress.
  • the gradient of the tempering curve can be reduced by making the C content 0.01% or less. Furthermore, by satisfying equation (1), A
  • the cl transformation point can be made higher than before. Therefore, the slope of the tempering curve is reduced and the yield stress is 7
  • the tempering temperature range of 58 to 860 MPa is larger than before.
  • the strength can be prevented from becoming less than llOksi and high toughness can be maintained.
  • it has high corrosion resistance due to its high Mo content.
  • the martensitic stainless steel according to the present invention has Ti: 0.005 to 0.25%,
  • V 0.005 to 0.25%
  • Nb 0.005 to 0.25%
  • Zr One or more of 0.005 to 0.25%.
  • the martensitic stainless steel according to the present invention contains Cu: 0.05-1.0%.
  • the martensitic stainless steel according to the present invention includes Ca: 0.0002 to 0.005%, Mg: 0.0002 to 0.005%, La: 0.0002 to 0.005%, Ce : 0.0002 ⁇ 0.005
  • FIG. 1 is a graph showing the relationship between yield stress and tempering temperature of conventional high Mo martensitic stainless steel.
  • FIG. 2 is a graph showing the relationship between yield stress and tempering temperature of Specimen 1 and Specimen 14 in an example of the present invention.
  • % related to elements means “% by mass”.
  • the C content is less than 0.001%, the production cost increases. Therefore, the C content is 0.0
  • Si is effective as a deoxidizer.
  • Si hardens the steel, so if the Si content is too high, the toughness and cacheability of the steel will deteriorate.
  • Si content should be 0.5% or less.
  • a preferable Si content is 0.3% or less.
  • Mn contributes to the improvement of hot workability of steel. Furthermore, Mn is an austenite forming element And contribute to the organization's martensite. However, if Mn is contained excessively, the toughness will decrease. Therefore, the Mn content is set to 0.1 to 3.0%. The preferred Mn content is 0.3 to L 0%.
  • P is an impurity. Since P generates SSC, the P content is limited to a very low level. Specifically, the P content is set to 0.04% or less.
  • S is an impurity. S decreases hot workability. Therefore, the S content is limited to a very low level. Specifically, the S content is set to 0.01% or less.
  • Cr contributes to the improvement of corrosion resistance in a wet carbon dioxide environment.
  • Cr since Cr is a ferrite-forming element, if it is excessively contained, tempered martensite is difficult to form, and strength and toughness are reduced. Therefore, Cr content should be 10-15%. The preferred Cr content is 11-14%.
  • Ni is an austenite-forming element and is necessary to make the structure after tempering martensite.
  • the Ni content is too low, the structure after tempering contains a large amount of ferrite.
  • the Ni content is too high, the structure after tempering contains a large amount of austenite. Therefore, the Ni content should be 4-8%.
  • the preferred Ni content is 4-7%.
  • Mo is an important element that contributes to the improvement of SSC resistance and strength.
  • the lower limit of the Mo content is set to 2.8% in order to obtain high SSC resistance.
  • the upper limit of Mo content is set to 5.0%.
  • a preferable Mo content is 2.8 to 4.0%.
  • A1 is effective as a deoxidizer.
  • the A1 content should be 0.001-0.10%.
  • the Al content is 0.001 to 0.06%.
  • N 0.07% or less
  • N forms nitrides and reduces corrosion resistance. Therefore, N content should be 0.07% or less.
  • the balance is composed of Fe and impurities. Impurities are included due to various factors in the manufacturing process.
  • the martensitic stainless steel according to the present embodiment further includes Ti, V,
  • Ti, V, Nb and Zr are selective elements. These elements fix C and reduce strength variations. On the other hand, when these elements are contained excessively, the structure after tempering is prevented from becoming martensite. Therefore, the content of these elements is 0 to 0.25%. A preferable content is 0.005-0.25%, respectively, and a more preferable content is 0.005-0.20% respectively.
  • the martensitic stainless steel according to the present embodiment further contains Cu as necessary.
  • Cu is a selective element.
  • Cu like Ni, is an austenite-forming element and is effective for martensite formation after tempering.
  • the Cu content is set to 0 to 1.0%.
  • a preferable Cu content is 0.05 to 1.0%.
  • the martensitic stainless steel according to the present embodiment further includes Ca, Mg as necessary.
  • Ca, Mg, La, and Ce are all selective elements. These elements contribute to the improvement of hot workability. On the other hand, if these elements are contained excessively, coarse oxides are formed and the corrosion resistance is lowered. Therefore, the content of these elements is set to 0 to 0.005%. Preferable contents are 0.0002 to 0.005%, respectively.
  • Ca and La are elements that particularly contribute to the improvement of hot workability.
  • the steel having the above chemical composition is melted and refined by a well-known refinement process. Subsequently, the molten steel is made into a continuous forging material by a continuous forging method. For example, slabs and blooms are billets. Alternatively, the molten steel is made into an ingot by the ingot-making method.
  • Slabs, blooms, and ingots are hot-worked into billets.
  • the billet may be formed by hot rolling, or may be formed by hot forging.
  • a billet obtained by continuous forging or hot working is hot worked into an oil well pipe.
  • Mannesmann method is implemented as hot working.
  • hot working hot extrusion such as a Eugene Selgene method may be performed, or a forged pipe manufacturing method such as an Erhardt method may be performed.
  • the quenching process is performed by a well-known method.
  • the quenching temperature is 900 to 950 ° C. However, other temperature ranges may be used.
  • the lower limit of the tempering temperature is preferably 500 ° C.
  • the preferable upper limit of the tempering temperature is 600 ° C.
  • martensitic stainless steel according to the embodiment of the present invention satisfies the following formulas (1) and (2).
  • Equation (1) If Equation (1) is satisfied, the A transformation point becomes high, so the yield stress is in the range of 758 to 860 MPa. The slope of the tempering curve at can be reduced. Also, if the formula (2) is satisfied, the organization can be promoted to martensite. Therefore, if the formulas (1) and (2) are satisfied, the tempering temperature range in which a yield stress of 758 to 860 MPa can be obtained can be made larger than before. Therefore, it is possible to suppress a decrease in productivity due to a change in the setting of the tempering temperature during operation.
  • a force obtained by using martensitic stainless steel as a steel pipe may be martensitic stainless steel.
  • F1 and F2 of each test material were obtained with Fl on the left side of Equation (1) and F2 on the left side of Equation (2).
  • “Ti” in F1 is set to “0” for specimens that do not contain Ti
  • “Cu” in F2 is set to “0” for specimens that do not contain Cu. It was.
  • Specimen 1 to Specimen 11 both had F1 and F2 within the scope of the present invention. Specifically, F1 was 600 or more and F2 was 0 or more.
  • the F1 value was less than 600.
  • the C content exceeded the upper limit of the present invention.
  • the specimen 14 had an F1 value of less than 600
  • the specimen 15 had an F2 value of less than 0.
  • Specimens 1 to 16 molten steel was forged into continuous forged materials.
  • the manufactured continuous forging material was hot forged and hot rolled into a plurality of steel plates 15 mm thick, 120 mm wide and 1000 mm long.
  • the steel sheet after hot forging and hot rolling was air-cooled to room temperature. The following tests were conducted using the obtained steel plate.
  • the obtained plurality of steel plates were quenched.
  • the quenching temperature was set to 910 ° C.
  • tempering was performed on the quenched steel sheet.
  • the tempering temperature was changed within a temperature range of 450 to 650 ° C.
  • Tensile tests were performed using steel plates that had been tempered at each tempering temperature. Specifically, a round bar test piece having a parallel part diameter of 6.35 mm and a parallel part length of 25.4 mm was prepared. A tensile test was performed at room temperature based on JIS Z2241 using the prepared round bar test piece, and the yield stress was determined. After the tensile test, the tempering temperature range ⁇ where the yield stress was in the range of 758 to 860 MPa was determined for each specimen. The yield stress was 0.2% resistance.
  • Table 2 shows the tempering temperature range in which the yield stress of each specimen is 758 to 860 MPa.
  • ⁇ in Table 2 is a difference value between the highest temperature and the lowest temperature among the tempering temperatures at which the yield stress of each specimen becomes 758 to 860 MPa.
  • the unit is ° C.
  • Specimens 1 to L 1 all had a ⁇ repulsive force of 0 ° C or higher.
  • specimens 12 and 13 had an F1 value of less than 600, so the ⁇ repulsive force was less than 0 ° C.
  • specimens 14 had a high C content and an F1 value of less than 600, so the ⁇ repulsive force was less than 0 ° C.
  • Specimens 15 and 16 had a high C content, so the ⁇ repulsive force was less than 0 ° C.
  • FIG. 2 shows the relationship between the tempering temperature and the yield stress in Sample 1 and Sample 14.
  • the tempering curve C1 of Specimen 1 with an F1 value of 600 or more had a tempering temperature range ⁇ 1 of 110 ° C with a small gradient in the yield stress range of 758 to 860 MPa.
  • the slope of the tempering curve C2 in the yield stress range of 758 to 860 MPa for specimen 14 with an F1 value of less than 600 was large, and the tempering temperature range ⁇ 2 was as low as 20 ° C.
  • Table 3 shows the results of determining the toughness value of each specimen.
  • the toughness test was performed as follows. The obtained steel sheet was quenched at 910 ° C. and subsequently tempered so that the yield stress was as shown in Table 3. From tempered steel sheet
  • a 10 mm wide V-notch specimen based on JISZ2202 was prepared.
  • a Charpy impact test was performed at -40 ° C based on JIS Z2242 using the manufactured V-notch test piece, and the absorbed energy was obtained.
  • the unit of absorbed energy in Table 3 is ⁇ ⁇ .
  • Corrosion resistance in a wet carbon dioxide environment was evaluated by carrying out the following carbon dioxide corrosion test.
  • a test piece having a width of 20 mm, a thickness of 3 mm, and a length of 50 mm was cut out for a steel plate that had been quenched and tempered under the same conditions as in the toughness evaluation.
  • the surface of the cut specimen is 60
  • the corrosion weight loss of the test piece was determined. Specifically, the value obtained by subtracting the weight of the test piece after the test from the weight of the test piece before the test was taken as the corrosion weight loss. Furthermore, the surface of the test piece is visually The presence or absence of local corrosion was confirmed. If the corrosion weight loss was less than 7.7 g and local corrosion did not occur, it was judged that the corrosion resistance in a wet carbon dioxide environment was high.
  • the test piece was immersed in the aqueous solution for 720 hours.
  • the pH of the aqueous NaCl solution was 4.5, and the temperature of the aqueous solution was maintained at 25 ° C during the test. After the test, the presence or absence of cracks was confirmed visually.
  • Table 4 shows the results of the corrosion resistance test.
  • “ ⁇ ” in the carbon dioxide corrosion test in the table indicates that the corrosion weight loss is less than 7.7 g and no local corrosion has occurred.
  • “ ⁇ ” in the SSC corrosion test indicates that cracking has occurred.
  • the specimens 1-1 were high in deviation and corrosion resistant.
  • the martensitic stainless steel according to the present invention can be used as a steel material used in a corrosive environment containing corrosive substances such as hydrogen sulfide, carbon dioxide gas, and chlorine ions.
  • it can be used for steel materials for production facilities, steel materials for geothermal power generation facilities, steel materials for carbon dioxide gas removal equipment, and steel pipes used as oil well pipes in wet sulfur and hydrogen environments such as oil wells and gas wells. .

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  • Mechanical Engineering (AREA)
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Abstract

L’invention concerne un acier inoxydable martensitique dont la composition chimique, en pourcentages massiques, est la suivante : C : de 0,001 à 0,01 %, Si : 0,5 % ou moins, Mn : de 0,1 à 3,0 %, P : 0,04 % ou moins, S : 0,01 % ou moins, Cr : de 10 à 15 %, Ni : de 4 à 8 %, Mo : de 2,8 à 5,0 %, Al : de 0,001 à 0,10 %, N : 0,07 % ou moins, Ti : de 0 à 0,25 %, V : de 0 à 0,25 %, Nb : de 0 à 0,25 %, Zr : de 0 à 0,25 %, Cu : de 0 à 1,0 %, Ca : de 0 à 0,005 %, Mg : de 0 à 0,005 %, La : de 0 à 0,005 %, Ce : de 0 à 0,005 %, le reste consistant en fer et impuretés, à la condition que les formules (1) et (2) suivantes soient vérifiées. Ledit acier a une limite de contrainte de 758 à 860 MPa. 922,6 - 554,5C - 50,9Mn + 2944,8P + 1,056Cr - 81,1Ni + 95,8Mo - 125,1Ti - 1584,9Al - 376,1N ≥ 600 (1) 30C + 0,5Mn + Ni + 0,5Cu - 1,5Si - Cr - Mo + 7,9 ≥ 0 (2) La limite de contrainte de l’acier inoxydable martensitique ci-dessus peut atteindre 758 à 860 MPa, la plage de température de trempe étant plus étendue que dans le cas d’un acier inoxydable martensitique traditionnel.
PCT/JP2005/019685 2004-11-19 2005-10-26 Acier inoxydable martensitique WO2006054430A1 (fr)

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Application Number Priority Date Filing Date Title
EP05799225A EP1826285B1 (fr) 2004-11-19 2005-10-26 Acier inoxydable martensitique
US11/791,015 US20080213120A1 (en) 2004-11-19 2005-10-26 Martensitic Stainless Steel

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JP2004-335241 2004-11-19
JP2004335241A JP4337712B2 (ja) 2004-11-19 2004-11-19 マルテンサイト系ステンレス鋼

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JP (1) JP4337712B2 (fr)
CN (1) CN100549204C (fr)
WO (1) WO2006054430A1 (fr)

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CN113939607B (zh) * 2019-07-24 2022-06-28 日本制铁株式会社 马氏体系不锈钢钢管和马氏体系不锈钢钢管的制造方法
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EP2128278A1 (fr) * 2007-03-26 2009-12-02 Sumitomo Metal Industries Limited Procédé de production d'un tube coudé pour tube de canalisation et tube coudé pour tube de canalisation
EP2128278A4 (fr) * 2007-03-26 2010-12-01 Sumitomo Metal Ind Procédé de production d'un tube coudé pour tube de canalisation et tube coudé pour tube de canalisation
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JP2022501515A (ja) * 2018-09-28 2022-01-06 コーニング インコーポレイテッド オーステナイト変態温度を上昇させた合金金属、及びこれを含む物品

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JP4337712B2 (ja) 2009-09-30
EP1826285A1 (fr) 2007-08-29
CN100549204C (zh) 2009-10-14
CN101061245A (zh) 2007-10-24
JP2006144069A (ja) 2006-06-08
EP1826285B1 (fr) 2012-10-03
US20080213120A1 (en) 2008-09-04
EP1826285A4 (fr) 2009-04-08

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